JP6907504B2 - Resin composition, resin sheet, cured resin, and resin substrate - Google Patents

Description

The present invention relates to a resin composition containing an epoxy compound, and a resin sheet, a cured resin product, and a resin substrate using the resin composition.

Various electronic components tend to be widely used in high-temperature environment applications such as automobiles. For this reason, research and development have been actively conducted on the thermal properties of resin substrates used for electronic components.

In the process of manufacturing a resin substrate, the resin composition is formed into a sheet, and then the sheet-shaped resin composition (resin sheet) is cured. As a result, a resin substrate containing a curing reaction product (resin cured product) of the resin composition is produced.

Various proposals have already been made regarding the composition of this resin composition and the like. Specifically, an epoxy resin having a mesogen group is used as a monomer in order to obtain excellent thermal conductivity (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 11-323162

When examining the thermal characteristics of each of the resin composition and the resin substrate (resin cured product), not only the thermal conductivity characteristics of the resin substrate are taken into consideration, but also the resin composition is used to manufacture the resin substrate. It is also important to consider the moldability.

The present invention has been made in view of such problems, and an object of the present invention is to provide a resin composition, a resin sheet, a cured resin product, and a resin substrate capable of obtaining excellent thermal properties.

The resin composition of the present invention contains an epoxy compound, a first trinaphthylbenzene compound represented by the following formula (1), and a second trinaphthylbenzene compound represented by the following formula (2). The ratio M (mol%) represented by the following mathematical formula (A) is 0.2 mol% or more and 16.4 mol% or less.

（Ｒ１〜Ｒ２１のそれぞれは、水素基（−Ｈ）および水酸基（−ＯＨ）のうちのいずれかである。ただし、Ｒ１〜Ｒ２１のうちの少なくとも１つは、水酸基である。）

(Each of R1 to R21 is either a hydrogen group (-H) or a hydroxyl group (-OH). However, at least one of R1 to R21 is a hydroxyl group.)

（Ｒ３１〜Ｒ５１のそれぞれは、水素基、水酸基およびアルコキシ基のうちのいずれかである。ただし、Ｒ３１〜Ｒ５１のうちの少なくとも１つは、水酸基であると共に、Ｒ３１〜Ｒ５１のうちの少なくとも１つは、アルコキシ基である。）

(Each of R31 to R51 is one of a hydrogen group, a hydroxyl group and an alkoxy group. However, at least one of R31 to R51 is a hydroxyl group and at least one of R31 to R51. Is an alkoxy group.)

M (mol%) = (M1 / M2) × 100 ... (A)
M1: Number of moles of alkoxy groups contained in the second trinaphthylbenzene compound (mol)
M2: The number of moles of hydroxyl groups contained in the first trinaphthylbenzene compound (mol), the number of moles of hydroxyl groups contained in the second trinaphthylbenzene compound (mol), and the number of moles of hydroxyl groups contained in the second trinaphthylbenzene compound. Sum with the number of moles (mol) of the alkoxy group

The resin sheet of the present invention contains the above-mentioned resin composition of the present invention.

The cured resin product of the present invention contains the cured reaction product of the above-mentioned resin composition of the present invention.

The resin substrate of the present invention contains the above-mentioned curing reaction product of the resin sheet of the present invention.

Here, the "hydroxyl group" contained in each of the first trinaphthylbenzene compound and the second trinaphthylbenzene compound is a reaction (crosslinking reaction) between the epoxy compound and the first trinaphthylbenzene compound and the second trinaphthylbenzene compound. ) Is a group (reactive group) for advancing. On the other hand, the "alkoxy group" contained in the second trinaphthylbenzene compound is a group for adjusting the reaction rate of the above-mentioned epoxy compound with the first trinaphthylbenzene compound and the second trinaphthylbenzene compound. (Reaction regulator). This "adjusting the reaction rate" means intentionally slowing down the reaction so that the reaction does not proceed too rapidly.

The resin composition of the present invention contains an epoxy compound, a first trinaphthylbenzene compound represented by the formula (1), and a second trinaphthylbenzene compound represented by the formula (2), and is represented by the formula (A). Since the ratio M is 0.2 mol% or more and 16.4 mol% or less, excellent thermal characteristics can be obtained. Further, the same effect can be obtained with the resin sheet, the cured resin product, and the resin substrate of the present invention.

It is sectional drawing which shows the structure of the resin sheet using the resin composition of this invention. It is sectional drawing which shows the other structure of the resin sheet using the resin composition of this invention. It is sectional drawing which shows the other structure of the resin sheet using the resin composition of this invention. It is sectional drawing which shows the structure of the resin substrate using the resin cured product of this invention. It is sectional drawing which shows the other structure of the resin substrate using the resin cured product of this invention. It is sectional drawing which shows the other structure of the resin substrate using the cured resin product of this invention. It is sectional drawing which shows the other structure of the resin substrate using the cured resin product of this invention. It is sectional drawing for demonstrating the manufacturing method of the resin substrate shown in FIG.

Hereinafter, one embodiment of the present invention will be described in detail with reference to the drawings. The order of explanation is as follows.

1. 1. Resin composition 1-1. Configuration 1-2. Manufacturing method 1-3. Action and effect 2. Resin sheet 2-1. Configuration 2-2. Manufacturing method 2-3. Action and effect 3. Hardened resin 3-1. Composition 3-2. Manufacturing method 3-3. Actions and effects 4. Resin substrate 4-1. Configuration 4-2. Manufacturing method 4-3. Action and effect

One embodiment of the present invention described below is an example for explaining the present invention. Therefore, the present invention is not limited to only one embodiment described herein. One embodiment of the present invention can be changed to various embodiments without departing from the gist of the present invention.

<1. Resin composition>
First, the resin composition of one embodiment of the present invention will be described.

The resin composition is used for producing a resin sheet, a cured resin product, a resin substrate, and the like, which will be described later. However, the resin composition may be used for other purposes.

<1-1. Configuration>
This resin composition contains an epoxy compound, a first trinaphthylbenzene compound represented by the following formula (1), and a second trinaphthylbenzene compound represented by the following formula (2).

（Ｒ１〜Ｒ２１のそれぞれは、水素基および水酸基のうちのいずれかである。ただし、Ｒ１〜Ｒ２１のうちの少なくとも１つは、水酸基である。）

(Each of R1 to R21 is either a hydrogen group or a hydroxyl group. However, at least one of R1 to R21 is a hydroxyl group.)

（Ｒ３１〜Ｒ５１のそれぞれは、水素基、水酸基およびアルコキシ基のうちのいずれかである。ただし、Ｒ３１〜Ｒ５１のうちの少なくとも１つは、水酸基であると共に、Ｒ３１〜Ｒ５１のうちの少なくとも１つは、アルコキシ基である。）

(Each of R31 to R51 is one of a hydrogen group, a hydroxyl group and an alkoxy group. However, at least one of R31 to R51 is a hydroxyl group and at least one of R31 to R51. Is an alkoxy group.)

As described above, the resin composition described here is used for producing an intermediate product such as a resin sheet and for producing a final product (resin cured product) such as a resin substrate. As will be described later, this "intermediate product" means a substance in a state in which the curing reaction (crosslinking reaction) of the resin composition is not substantially completed. Further, the “final product” means a substance in a state in which the curing reaction of the resin composition is substantially completed, as will be described later.

The epoxy compound, which is a thermosetting resin, is a so-called main agent. On the other hand, the first trinaphthylbenzene compound, which is used together with the epoxy compound and contains a reactive group (hydroxyl group), is a first curing agent for advancing the cross-linking reaction of the epoxy compound using the reactive group as described above. be. Further, the second trinaphthylbenzene compound, which is used together with the epoxy compound and contains a reactive group (hydroxyl group) and a reaction adjusting group (alkoxy group), proceeds with the cross-linking reaction of the epoxy compound using the reactive group as described above. It is a second curing agent for adjusting the rate of the cross-linking reaction of the epoxy compound (intentionally slowing down the rate of the cross-linking reaction) by using the reaction adjusting group.

The fact that the resin composition contains the first trinaphthylbenzene compound and the second trinaphthylbenzene compound together with the epoxy compound improves the moldability of the cured resin while ensuring the thermal conductivity of the cured resin. Because.

Specifically, a resin composition is used by using a first trinaphthylbenzene compound containing a skeleton having excellent thermal conductivity (1,3,5-trinaphthylbenzene) and a reactive group that promotes a crosslinking reaction. As the cured resin product is produced, the thermal conductivity of the cured resin product is improved.

In this case, by using the second trinaphthylbenzene compound containing the above-mentioned first trinaphthylbenzene compound and the reaction group for advancing the cross-linking reaction and the reaction adjusting group for adjusting the rate of the cross-linking reaction. The number of reaction points (crosslink points) can be suppressed so as not to become too large. In this case, since the curing reaction rate is suppressed so as not to become too high during the curing reaction, the melt viscosity of the resin composition also decreases. As a result, the fluid state of the resin composition is easily maintained even during the curing reaction, so that the cured resin product can be easily molded.

In particular, the second trinaphthylbenzene compound contains a skeleton (1,3,5-trinaphthylbenzene) similar to that of the first trinaphthylbenzene compound. In this case, even in the skeleton contained in the second trinaphthylbenzene compound, excellent thermal conductivity can be obtained as in the skeleton contained in the first trinaphthylbenzene compound. Therefore, even if the first trinaphthylbenzene compound and the second trinaphthylbenzene compound are used in combination, the moldability of the cured resin product is improved without lowering the thermal conductivity.

However, the ratio M (mol%) represented by the following mathematical formula (A) is 0.2 mol% to 16.4 mol%.

M (mol%) = (M1 / M2) × 100 ... (A)
M1: Number of moles of alkoxy groups contained in the second trinaphthylbenzene compound (mol)
M2: The number of moles of hydroxyl groups contained in the first trinaphthylbenzene compound (mol), the number of moles of hydroxyl groups contained in the second trinaphthylbenzene compound (mol), and the number of moles of hydroxyl groups contained in the second trinaphthylbenzene compound. Sum with the number of moles (mol) of the alkoxy group

The ratio M, that is, the ratio of the total number of moles of reaction adjusting groups (M1) to the sum (M2) of the total number of moles of reaction groups (hydroxyl groups) and the total number of moles of reaction adjusting groups (alkoxy groups) is within the above range. This is because the balance between the number of hydroxyl groups that promote the cross-linking reaction and the number of reaction-regulating groups that regulate the rate of the cross-linking reaction is optimized. As a result, as described above, the curing reaction rate is appropriately suppressed and the melt viscosity of the resin composition is lowered, so that the fluid state of the resin composition is maintained even during the curing reaction, and the curing reaction is utilized. The cured resin product can be produced.

Specifically, when the ratio M is smaller than 0.2 mol%, the number of reaction adjusting groups is too small, and therefore, even though the second trinaphthylbenzene compound containing the reaction adjusting groups is used, at the time of the curing reaction, The rate of the cross-linking reaction is not slow enough. In this case, since the melt viscosity of the resin composition does not sufficiently decrease, the fluid state of the resin composition is not sufficiently maintained during the curing reaction. Therefore, the thermal conductivity is improved, but the moldability is insufficient.

Further, when the ratio M is larger than 16.4 mol%, the number of reaction adjusting groups is too large, so that the first trinaphthylbenzene compound containing a reactive group and the second trinaphthylbenzene compound containing a reactive group are used. Nevertheless, the cross-linking reaction does not proceed sufficiently during the curing reaction. Therefore, it is difficult to produce a cured resin because the resin composition does not sufficiently cure.

On the other hand, when the ratio M is 0.2 mol% to 16.4 mol%, the cross-linking reaction proceeds sufficiently during the curing reaction, and the rate of the cross-linking reaction is suppressed so as not to become too fast. In this case, the resin composition sufficiently cures while the melt viscosity of the resin composition is sufficiently lowered. Therefore, both improvement of thermal conductivity and ensuring moldability can be achieved at the same time.

Above all, the ratio M is preferably 0.2 mol% to 5.1 mol%. This is because the balance between the number of hydroxyl groups that promote the cross-linking reaction and the number of reaction-regulating groups that adjust the rate of the cross-linking reaction is more optimized. As a result, the thermal conductivity is further improved while ensuring the moldability.

Here, the procedure for obtaining the ratio M is, for example, as follows.

In order to obtain the ratio M, the resin sheet or the like which is the above-mentioned intermediate product may be used, or the resin cured product (resin substrate or the like) which is the above-mentioned final product may be used. The type of the resin sheet may be any of the resin sheets 10, 20, and 30 described later, and the type of the resin substrate may be any of the resin substrates 40, 50, 60, and 70 described later. Hereinafter, a cured resin product will be described as an example.

(Procedure 1)
First, a cured resin product is produced using only the first trinaphthylbenzene compound as a curing agent, and then a reaction reagent is added to the cured resin product. Subsequently, the cured resin product was rapidly heated (temperature = 445 ° C., time = 6 seconds) using a thermal decomposition apparatus (Curie Point Pyrolyzer JHP-5 manufactured by Nippon Analytical Industry Co., Ltd.). As a result, the cured resin product was thermally decomposed, so that a thermal decomposition reaction product was obtained. This thermal decomposition reaction product is a compound in which a reaction product of an epoxy compound and a first trinaphthylbenzene compound is dissociated. Subsequently, the thermal decomposition reaction product was mass-analyzed using a gas chromatograph mass spectrometer (GCMS-QP5050A manufactured by Shimadzu Corporation). In this case, the column temperature was raised from 40 ° C. to 320 ° C. at a heating rate of 10 ° C./min, and then the column temperature was maintained at 320 ° C. for 15 minutes. As a result, the retention time of the reaction product derived from the first trinaphthylbenzene compound is confirmed.

(Procedure 2)
Next, a cured resin product was produced and the second trinaphthyl was produced by the same procedure as in step 1 above, except that the second trinaphthylbenzene compound was used instead of the first trinaphthylbenzene compound as the curing agent. Check the retention time of the reaction product derived from the benzene compound.

(Procedure 3)
Next, using only the first trinaphthylbenzene compound as the curing agent, a plurality of cured resin products having different contents of the first trinaphthylbenzene compound are produced. Subsequently, the retention time of the reaction product derived from the first trinaphthylbenzene compound is confirmed by the same procedure as in step 1 described above except that a plurality of cured resin products are used. Based on this confirmation result, a calibration curve for the peak area of the reaction product is created.

(Procedure 4)
Next, a cured resin product is produced by the same procedure as in step 1 above, except that the first trinaphthylbenzene compound and the second trinaphthylbenzene compound are used as the curing agent, and then the first trinaphthylbenzene compound is obtained. The retention time of the derived reaction product is confirmed, and the retention time of the reaction product derived from the second trinaphthylbenzene compound is confirmed. The cured resin product produced here is a sample for which a ratio M is required (hereinafter, simply referred to as "sample").

Subsequently, from the ratio of the peak area at the holding time confirmed in step 1, the peak area at the holding time confirmed in step 2, and the peak area at the holding time confirmed in step 4, the first in the sample. The abundance ratio of the trinaphthylbenzene compound and the second trinaphthylbenzene compound is calculated.

Subsequently, the content of the first trinaphthylbenzene compound in the sample is calculated using the calibration curve prepared in step 3. Subsequently, the number of hydroxyl groups contained in the first trinaphthylbenzene compound, the number of hydroxyl groups and the number of alkoxy groups contained in the second trinaphthylbenzene compound, and the first trinaphthylbenzene compound and the second trinaphthylbenzene compound. Based on the abundance ratio of the first trinaphthylbenzene compound and the content of the first trinaphthylbenzene compound in the sample, the number of moles of hydroxyl groups (mol) contained in the first trinaphthylbenzene compound and the content of the second trinaphthylbenzene compound. After calculating the number of moles of hydroxyl groups (mol) and the number of moles of alkoxy groups (mol), the sum of the number of moles M2 (mol) is obtained.

(Procedure 5)
Finally, based on the number of moles M1 (mol) of the alkoxy group contained in the second trinaphthylbenzene compound and the sum M2 (mol) of the number of moles described above, the ratio M (A) is used. mol%) is calculated.

This resin composition may be in a solid state such as powder or lump, in a liquid state, or in a state in which both are mixed. The state of this resin composition is appropriately determined depending on the intended use and the like.

The mixing ratio of the epoxy compound, the first trinaphthylbenzene compound, and the second trinaphthylbenzene compound is not particularly limited. However, when an epoxy compound containing an epoxy group and a first trinaphthylbenzene compound containing a reactive group undergo a cross-linking reaction, generally one epoxy group reacts with one active hydrogen in the reactive group. The reaction of one epoxy group with one active hydrogen in the reactive group in this way is the same for the second trinaphthylbenzene compound containing the reactive group. Therefore, in order to increase the reaction efficiency between the epoxy compound and the first trinaphthylbenzene compound and the second trinaphthylbenzene compound, the total number of epoxy groups contained in the epoxy compound and the first trinaphthylbenzene compound and the first trinaphthylbenzene compound and the first. It is preferable to set the mixing ratio so that the total number of active hydrogens contained in each of the two trinaphthylbenzene compounds is 1: 1.

[Epoxy compound]
Epoxy compounds which are main component is either one or more kinds of the compounds containing one or more epoxy groups in one molecule (-C 3 H _{5 O).} Among them, the epoxy compound preferably contains two or more epoxy groups in one molecule. This is because the epoxy compound and the first trinaphthylbenzene compound are more likely to react with each other, and the epoxy compound and the second trinaphthylbenzene compound are more likely to react with each other.

The type of the epoxy compound is not particularly limited, but for example, a glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, a glycidyl amine type epoxy compound, a novolac type epoxy compound, a cyclic aliphatic type epoxy compound and a long chain aliphatic type epoxy compound. And so on.

The glycidyl ether type epoxy compound is, for example, a bisphenol A type epoxy compound and a bisphenol F type epoxy compound. Novolac-type epoxy compounds include, for example, cresol novolac-type epoxy compounds and phenol novolac-type epoxy compounds. In addition, the type of epoxy compound may be, for example, a flame-retardant epoxy compound, a hydantoin-based epoxy resin, an isocyanurate-based epoxy compound, or the like.

The specific example of the glycidyl ether type epoxy compound is not particularly limited as long as it is a compound containing a glycidyl ether type structure (group). As described above, the type is not limited as long as it contains a specific structure, and the same applies to specific examples of other epoxy compounds such as glycidyl ester type epoxy compounds.

Above all, the epoxy compound preferably contains a mesogen skeleton in one molecule. The reason is as follows.

First, in the molecules of the epoxy compound, the benzene rings tend to overlap each other, so that the distance between the benzene rings becomes small. As a result, the density of the epoxy compound is improved in the resin composition. Further, in the cured resin product, the lattice vibration of the molecules is less likely to be scattered, so that high thermal conductivity can be obtained.

In particular, since the scattering phenomenon of the lattice vibration of the molecule described above is a major factor for lowering the thermal conductivity, the reduction of the thermal conductivity is remarkably suppressed by suppressing the scattering phenomenon of the lattice vibration of the molecule. ..

Secondly, in the epoxy compound and the first trinaphthylbenzene compound, the benzene ring contained in the mesogen skeleton of the epoxy compound and the skeleton of the first trinaphthylbenzene compound (1,3,5-trinaphthylbenzene) are contained. It is easy for the benzene ring to overlap. The fact that the benzene rings are likely to overlap with each other is the same for the epoxy compound and the second trinaphthylbenzene compound. Therefore, high thermal conductivity can be obtained for the same reason as in the case where the benzene rings are likely to overlap each other in the above-mentioned molecules of the epoxy compound.

This "mesogen skeleton" is a general term for atomic groups containing two or more aromatic rings and having rigidity and orientation. Specifically, the mesogen skeleton is, for example, a skeleton containing two or more benzene rings and having benzene rings bonded to each other via either a single bond or a non-single bond.

When three or more benzene rings are bonded, the direction of the bond is not particularly limited. That is, three or more benzene rings may be bonded so as to be linear, may be bonded so as to be bent once or more in the middle, or may be bonded so as to branch in two or more directions. You may.

"Non-single bond" is a general term for divalent groups containing one or more constituent elements and one or more multiple bonds. Specifically, the non-single bond contains any one or more of the constituent elements such as carbon (C), nitrogen (N), oxygen (O) and hydrogen (H). .. In addition, the non-single bond includes one or both of a double bond and a triple bond as a multiple bond.

The mesogen skeleton may contain only a single bond, a non-single bond, or both a single bond and a non-single bond as the type of bond between the benzene rings. .. Further, the type of non-single bond may be only one type or two or more types.

Specific examples of non-single bonds include bonds represented by the following formulas (3-1) to (3-10). The arrows shown in each of the formulas (3-6) and (3-10) represent coordination bonds.

Specific examples of the mesogen skeleton are biphenyl and terphenyl. The terphenyl may be o-terphenyl, m-terphenyl, or p-terphenyl.

[1st trinaphthylbenzene compound]
The first trinaphthylbenzene compound, which is the first curing agent, is any one or more of the compounds containing a skeleton (1,3,5-trinaphthylbenzene) and a reactive group (hydroxyl group). That is, in the first trinaphthylbenzene compound, 1,3,5-trinaphthylbenzene is contained as a skeleton in one molecule, and a hydroxyl group is introduced into the skeleton.

This skeleton (1,3,5-trinaphthylbenzene) consists of one central benzene ring (central benzene ring) and three naphthalene rings (peripheral naphthalene rings) located around the central benzene ring. Includes.

In the following, the peripheral naphthalene rings in which R1 to R7 are introduced are introduced as "first peripheral naphthalene ring", the peripheral naphthalene rings in which R8 to R14 are introduced are introduced as "second peripheral naphthalene ring", and R15 to R21 are introduced. The peripheral naphthalene ring is referred to as the "third peripheral naphthalene ring". This also applies to the second trinaphthylbenzene compound described later.

Each type of R1 to R21 is not particularly limited as long as it is any one of a hydrogen group and a hydroxyl group. That is, each of R1 to R21 may be a hydrogen group or a hydroxyl group.

However, one or more of R1 to R21 are hydroxyl groups. This is because, in order for the first trinaphthylbenzene compound to proceed with the cross-linking reaction using a reactive group (hydroxyl group), the first trinaphthylbenzene compound must contain one or more hydroxyl groups. As long as this condition is satisfied, the number of hydroxyl groups, the introduction position, and the like are not particularly limited. Above all, it is preferable that two or more of R1 to R21 are hydroxyl groups. This is because the epoxy compound and the first trinaphthylbenzene compound are likely to react with each other.

In particular, with respect to the types of R1 to R21, it is preferable that one or both of the following conditions are further satisfied.

As the first condition, it is preferable that one or more of R1 to R7 is a hydroxyl group, one or more of R8 to R14 is a hydroxyl group, and one or more of R15 to R21 is a hydroxyl group. Even if the total number of hydroxyl groups is three or more, the introduction positions of the three or more hydroxyl groups are dispersed in each of the first to third peripheral naphthalene rings, so that the epoxy compound and the first trinaphthylbenzene compound can easily react with each other. Because.

In this case, if one or more of R1 to R7 are hydroxyl groups, the position where the one or more hydroxyl groups are introduced into the first peripheral naphthalene ring is not particularly limited. As described above, when the number of hydroxyl groups is one or more, the introduction position of the one or more hydroxyl groups is not limited, and the same applies to the positions of the one or more hydroxyl groups introduced into the second peripheral naphthalene ring. The same applies to the positions of one or more hydroxyl groups introduced into the third peripheral naphthalene ring.

As a second condition, it is preferable that one of R1 to R7 is a hydroxyl group, one of R8 to R14 is a hydroxyl group, and one of R15 to R21 is a hydroxyl group. When the total number of hydroxyl groups is three, the introduction positions of the three hydroxyl groups are dispersed in each of the first to third peripheral naphthalene rings, so that the epoxy compound and the first trinaphthylbenzene compound can easily react with each other. Because.

In this case, if one of R1 to R7 is a hydroxyl group, the position where the one hydroxyl group is introduced into the first peripheral naphthalene ring is not particularly limited. As described above, when the number of hydroxyl groups is one, the introduction position of the one hydroxyl group is not limited, the same applies to the position of the one hydroxyl group introduced into the second peripheral naphthalene ring, and the first The same applies to the position of one hydroxyl group introduced into the peripheral naphthalene ring.

Specific examples of the first trinaphthylbenzene compound are compounds represented by the following formulas (1-1) and (1-2), respectively. The compound represented by the formula (1-1) has three hydroxyl groups, and the compound represented by the formula (1-2) has six hydroxyl groups.

Of these, the compound represented by the formula (1-1) is preferable. This is because the above-mentioned first and second conditions are satisfied.

[Second trinaphthylbenzene compound]
The second trinaphthylbenzene compound, which is the second curing agent, is any one of compounds containing a skeleton (1,3,5-trinaphthylbenzene), a reactive group (hydroxyl group) and a reaction regulating group (alkoxy group). Type or two or more types. That is, in the second trinaphthylbenzene compound, 1,3,5-trinaphthylbenzene is contained as a skeleton in one molecule, and a hydroxyl group and an alkoxy group are introduced into the skeleton.

As described above, the first trinaphthylbenzene compound contains a reactive group (hydroxyl group) but does not contain a reaction regulating group (alkoxy group). On the other hand, the second trinaphthylbenzene compound contains a reactive group (hydroxyl group) and also contains a reaction adjusting group (alkoxy group).

Each type of R31 to R51 is not particularly limited as long as it is any one of a hydrogen group, a hydroxyl group and an alkoxy group. That is, each of R31 to R51 may be a hydrogen group, a hydroxyl group, or an alkoxy group. When the second trinaphthylbenzene compound contains a plurality of alkoxy groups, the types of the plurality of alkoxy groups may be the same or different. Of course, some of the plurality of alkoxy groups may be of the same type.

As described above, the alkoxy group, which is the reaction adjusting group, suppresses the number of reaction points (crosslinking points) from becoming too large in order to prevent the crosslinking reaction from becoming too fast during the curing reaction. Fulfill function.

Specific examples of the alkoxy group include a methoxy group (-OCH ₃ ), an ethoxy group (-OC ₂ H ₅ ) and a propoxy group (-OC ₃ H ₇ ), and other groups may be used. Of these, a methoxy group and an ethoxy group are preferable. This is because the second trinaphthylbenzene compound can be easily synthesized and the reaction adjusting group can exert a sufficient function. The propyl group (-C ₃ H ₇ ) in the propoxy group may be a normal propyl group (-CH ₂ CH ₂ CH ₃ ) or an isopropyl group (-CH (CH ₃ ) ₂ ).

However, one or more of R31 to R51 are hydroxyl groups. This is because the second trinaphthylbenzene compound must contain one or more hydroxyl groups in order for the second trinaphthylbenzene compound to proceed with the cross-linking reaction using hydroxyl groups. As long as this condition is satisfied, the number of hydroxyl groups, the introduction position, and the like are not particularly limited.

Further, one or more of R31 to R51 are alkoxy groups. This is because in order for the second trinaphthylbenzene compound to adjust the rate of the cross-linking reaction using an alkoxy group, the second trinaphthylbenzene compound must contain one or more alkoxy groups. As long as this condition is satisfied, the number of alkoxy groups, the introduction position, and the like are not particularly limited.

In particular, regarding the types of R31 to R51, it is preferable that one or two or more of the following three conditions are satisfied.

As a third condition, it is preferable that one of R31 to R37 is an alkoxy group, and each of R38 to R51 is a hydrogen group and a hydroxyl group, respectively. That is, it is preferable that an alkoxy group is introduced into one peripheral naphthalene ring and no alkoxy group is introduced into the remaining two peripheral naphthalene rings among the first to third peripheral naphthalene rings. This is because the minimum number of alkoxy groups is used, so that the rate of the cross-linking reaction does not decrease too much.

As a fourth condition, one of R31 to R37 is an alkoxy group, one of R38 to R44 is an alkoxy group, and each of R45 to R51 is either a hydrogen group or a hydroxyl group. Is preferable. That is, of the first to third peripheral naphthalene rings, one alkoxy group is introduced into each of the two peripheral naphthalene rings, and no alkoxy group is introduced into the remaining one peripheral naphthalene ring. preferable. This is because when the number of alkoxy groups is two, the introduction positions of the two alkoxy groups are dispersed in the two peripheral benzene rings, so that steric hindrance of the alkoxy groups is less likely to occur. Moreover, since the number of hydroxyl groups is not too large, the rate of the cross-linking reaction is sufficiently slow even if the content of the second trinaphthylbenzene compound is small.

As a fifth condition, in the second trinaphthylbenzene compound (one molecule), the sum of the number of hydroxyl groups and the number of alkoxy groups is preferably 3. That is, since the number of hydroxyl groups is one or more and the number of alkoxy groups is one or more, the number of hydroxyl groups is one and the number of alkoxy groups is two, or the number of hydroxyl groups is two. It is preferable that the number of alkoxy groups is one. This is because the minimum number of hydroxyl groups and the minimum number of alkoxy groups are secured in order to achieve both the progress of the crosslinking reaction and the adjustment of the rate of the crosslinking reaction.

Specific examples of the second trinaphthylbenzene compound are compounds represented by the following formulas (2-1) to (2-6). This is because the compounds represented by the formulas (2-1), (2-3) and (2-5) satisfy the above-mentioned third and fifth conditions. This is because the compounds represented by the formulas (2-2), (2-4) and (2-6) each satisfy the above-mentioned fourth and fifth conditions. The number of alkoxy groups is one in each of the compounds represented by the formulas (2-1), (2-3) and (2-5). In the compounds represented by the formulas (2-2), (2-4) and (2-6), the number of alkoxy groups is two.

In each of the formulas (2-1) to (2-6), the case where each of the hydroxyl group and the alkoxy group is introduced at the 6-position in each peripheral naphthalene ring is shown. However, the position where each of the hydroxyl group and the alkoxy group is introduced into each peripheral naphthalene ring is not limited to the 6-position, and may be another substitution position.

[Other materials]
This resin composition may contain any one or more of the other materials together with the above-mentioned epoxy compound, the first trinaphthylbenzene compound and the second trinaphthylbenzene compound.

The types of other materials are not particularly limited, but are, for example, additives, solvents, other curing agents and inorganic particles.

Additives are, for example, curing catalysts and coupling agents. Specific examples of the curing catalyst are phosphine, imidazole and derivatives thereof, and the derivative of the imidazole is, for example, 2-ethyl-4-methylimidazole and the like. Specific examples of the coupling agent include a silane coupling agent and a titanate coupling agent.

The solvent is used to disperse or dissolve the epoxy compound, the first trinaphthylbenzene compound and the second trinaphthylbenzene compound in the liquid resin composition. This solvent is one or more of any one or more of organic solvents, and specific examples of the organic solvent include methyl ethyl ketone, methyl cellosolve, methyl isobutyl ketone, dimethylformamide, propylene glycol monomethyl ether, toluene, xylene, and the like. Acetone, 1,3-dioxolane, N-methylpyrrolidone and γ-butyrolactone and the like.

Other curing agents are compounds that do not contain 1,3,5-trinaphthylbenzene as the skeleton but contain one or more reactive groups, wherein the reactive groups described herein are, for example, hydroxyl groups and aminos. One or both of the groups. Specific examples of other curing agents include phenols, amines and acid anhydrides.

From the viewpoint of the effect, the curing agent containing 1,3,5-trinaphthylbenzene is the active hydrogen of the curing agent containing 1,3,5-trinaphthylbenzene with respect to the number of epoxy groups of the epoxy resin. It is preferably contained so that the number is at least 50% or more.

The inorganic particles are any one or more of the particulate inorganic materials. Specific examples of these inorganic particles are magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), boron nitride (BN) and the like.

<1-2. Manufacturing method>
This resin composition is produced, for example, by the following procedure.

When a solid resin composition is obtained, the epoxy compound, the first trinaphthylbenzene compound, and the second trinaphthylbenzene compound are mixed. When an epoxy compound such as a lump is used, the epoxy compound may be crushed before mixing. The fact that the mixture may be pulverized before mixing is the same for the first trinaphthylbenzene compound and the second trinaphthylbenzene compound. As a result, a solid resin composition containing an epoxy compound, a first trinaphthylbenzene compound, and a second trinaphthylbenzene compound can be obtained.

After obtaining the solid resin composition, the resin composition may be molded by using a mold or the like, if necessary.

When obtaining a liquid resin composition, a solvent is added to the mixture of the above-mentioned epoxy compound, the first trinaphthylbenzene compound and the second trinaphthylbenzene compound, and then the solvent is added using a stirrer such as a mixer. Stir. As a result, the epoxy compound, the first trinaphthylbenzene compound and the second trinaphthylbenzene compound are dispersed or dissolved in the solvent. Therefore, a liquid resin composition containing an epoxy compound, a first trinaphthylbenzene compound, and a second trinaphthylbenzene compound can be obtained.

In addition, when a liquid resin composition is obtained, the solid resin composition may be heated to melt the resin composition. In this case, if necessary, the melt of the resin composition may be molded using a mold or the like, and then the melt may be cooled.

As the epoxy compound, a solid compound such as a powder or a lump may be used, a liquid compound may be used, or both may be used in combination. Similarly, as the curing agent such as the first trinaphthylbenzene compound and the second trinaphthylbenzene compound, a solid compound such as a powder or a lump may be used, or a liquid compound may be used. However, both may be used together. The same applies to the other materials described above.

<1-3. Actions and effects>
According to this resin composition, the epoxy compound, the first trinaphthylbenzene compound represented by the formula (1), and the second trinaphthylbenzene compound represented by the formula (2) are contained, and the ratio M is It is 0.2 mol% to 16.4 mol%. In this case, as described above, the moldability of the cured resin product is improved while ensuring the thermal conductivity of the cured resin product. Therefore, excellent thermal properties can be obtained.

In particular, when the ratio M is 0.2 mol% to 5.1 mol%, the thermal conductivity is further improved while ensuring the moldability, so that a higher effect can be obtained.

Further, in the formula (1), if one or more of R1 to R7 are hydroxyl groups, one or more of R8 to R14 are hydroxyl groups, and one or more of R15 to R21 are hydroxyl groups. , Since the epoxy compound and the first trinaphthylbenzene compound are easily reacted, a higher effect can be obtained. In this case, if one of R1 to R7 is a hydroxyl group, one of R8 to R14 is a hydroxyl group, and one of R15 to R21 is a hydroxyl group, a higher effect can be obtained. ..

Further, if the first trinaphthylbenzene compound contains the compound represented by the formula (1-1), a higher effect can be obtained.

Further, in the formula (2), if one of R31 to R37 is an alkoxy group and each of R38 to R51 is one of a hydrogen group and a hydroxyl group, the epoxy compound and the second trinaphthylbenzene compound are used. Is more responsive, so a higher effect can be obtained.

Further, if one of R31 to R37 is an alkoxy group, one of R38 to R44 is an alkoxy group, and each of R45 to R51 is one of a hydrogen group and a hydroxyl group, the second tri Even if the content of the naphthylbenzene compound is small, the rate of the crosslinking reaction is sufficiently slowed down, so that a higher effect can be obtained particularly from the viewpoint of moldability.

Further, in the second trinaphthylbenzene compound (one molecule), if the sum of the number of hydroxyl groups and the number of alkoxy groups is 3, a higher effect can be obtained.

Further, if the second trinaphthylbenzene compound contains one or more of the compounds represented by the formulas (2-1) to (2-6), a higher effect can be obtained. can.

The type of reaction adjusting group is not limited to the above-mentioned alkoxy group, and is a group capable of suppressing the number of reaction points (crosslinking points) from becoming too large during the curing reaction, that is, the rate of the crosslinking reaction. Is not particularly limited as long as it is a group capable of suppressing the speed from becoming too fast. This reaction adjusting group may be a group that does not participate in the cross-linking reaction, that is, a group that is not used in the reaction between the epoxy compound and the second trinaphthylbenzene compound.

<2. Resin sheet ＞
Next, the resin sheet of one embodiment of the present invention will be described. Hereinafter, the resin composition already described is referred to as "the resin composition of the present invention".

The resin sheet contains the resin composition of the present invention. The structure of this resin sheet is not particularly limited as long as it contains the resin composition of the present invention. That is, the resin sheet may not include other components together with the resin composition, or may include other components together with the resin composition.

<2-1. Configuration>
FIG. 1 shows the cross-sectional structure of the resin sheet 10. The resin sheet 10 is a resin composition (resin composition layer 1) molded into a sheet shape, and more specifically, it is a single layer body composed of one resin composition layer 1. The thickness of the resin sheet 10 is not particularly limited. The structure of the resin composition layer 1 is the same as that of the resin composition of the present invention, except that it is molded into a sheet shape.

FIG. 2 shows the cross-sectional structure of the resin sheet 20. The resin sheet 20 is a laminated body in which a plurality of resin composition layers 1 are laminated. In the resin sheet 20, the number of layers of the resin composition layer 1 (number of layers) is not particularly limited as long as it is two or more layers. FIG. 2 shows, for example, a case where the number of layers of the resin composition layer 1 is three. In the resin sheet 20, the configuration of each resin composition layer 1 is not particularly limited. That is, the composition of the resin composition in each resin composition layer 1 may be the same or different. Of course, among the plurality of resin composition layers 1, the composition of the resin composition in some of the resin composition layers 1 may be the same.

FIG. 3 shows the cross-sectional structure of the resin sheet 30. The resin sheet 30 includes a core material 2 together with a resin composition (resin composition layer 1) molded into a sheet shape. For example, the core material 2 is sandwiched between two resin composition layers 1. It has a three-layer structure.

The core material 2 contains, for example, any one or more of fibrous substances and non-fibrous substances, and is formed into a sheet shape. The fibrous material is, for example, glass fiber, carbon fiber, metal fiber, natural fiber, synthetic fiber and the like, and the fibrous material formed into a sheet is, for example, a woven fabric and a non-woven fabric. Specific examples of synthetic fibers include polyester fibers and polyamide fibers. The non-fibrous substance is, for example, a polymer compound, and the non-fibrous substance formed into a sheet is, for example, a polymer film. Specific examples of the polymer compound are polyethylene terephthalate (PET) and the like.

The thickness of the core material 2 is not particularly limited, but is preferably 0.03 mm to 0.2 mm, for example, from the viewpoint of mechanical strength and dimensional stability.

The resin composition layer 1 used in the resin sheet 30 may be only one layer or two or more layers. The fact that one layer or two or more layers may be used is the same for the core material 2.

Further, the resin sheet 30 is not limited to a three-layer structure in which the core material 2 is sandwiched between the two resin composition layers 1, but also has a two-layer structure in which the resin composition layer 1 and the core material 2 are laminated. You may. In addition, two or more resin sheets 30 may be laminated.

<2-2. Manufacturing method>
When producing the resin sheet 10, for example, the same procedure as the method for producing the resin composition of the present invention is used.

Specifically, when a solid resin composition is used, the resin composition is molded into a sheet shape to form the resin composition layer 1. In this case, the solid resin composition may be molded as it is, or the melt of the solid resin composition may be molded. When molding a melt, first, the solid resin composition is heated to melt the resin composition. Subsequently, after molding the melt of the resin composition, the molded product is cooled.

When a liquid resin composition is used, the liquid resin composition is applied to the surface of a support such as a polymer film, and then the liquid resin composition is dried. As a result, the solvent contained in the liquid resin composition volatilizes, so that the resin composition is formed into a sheet on the surface of the support. That is, the resin composition is filmed on the surface of the support. Therefore, the resin composition layer 1 is formed. After that, the resin composition layer 1 is peeled off from the support.

When the resin sheet 20 is manufactured, the above-mentioned procedure for forming the resin composition layer 1 is repeated, and a plurality of resin composition layers 1 are laminated. In this case, after forming a laminated body in which a plurality of resin composition layers 1 are laminated, the laminated body may be pressurized while heating as necessary. As a result, the resin composition layers 1 are brought into close contact with each other.

In the case of producing the resin sheet 30 having a three-layer structure, for example, a liquid resin composition is applied to both surfaces of the core material 2, and then the liquid resin composition is dried. As a result, the two resin composition layers 1 are formed so as to sandwich the core material 2. In the step of applying the liquid resin composition, when the core material 2 contains a fibrous substance, the surface of the core material 2 is covered with the liquid resin composition and the core material 2 is in a liquid state. A part of the resin composition impregnates the inside of the core material 2. Alternatively, when the core material 2 contains a non-fibrous substance, the surface of the core material 2 is covered with the liquid resin composition.

Of course, in the case of producing the resin sheet 30 having a two-layer structure, the liquid resin composition may be applied only to one side of the core material 2.

In the case of producing the resin sheet 30, for example, the solid resin composition may be heated to melt the resin composition, and then the core material 2 may be immersed in the melt. In this case, the core material 2 is taken out from the melt, and then the core material 2 is cooled. As a result, the resin composition layer 1 is formed on both surfaces of the core material 2.

Here, when the liquid resin composition is used for producing the resin sheets 10, 20 and 30, the liquid resin composition is filmed (solidified) in the drying step as described above. However, the "film formation (solidification)" described here means that a substance in a fluid state (liquid state) changes to a self-sustaining state (solid state), so-called semi-curing. Including the state. That is, when the liquid resin composition is filmed, the curing reaction is not substantially completed, so that the resin composition is in a substantially uncured state. Therefore, it is preferable that the drying conditions for forming the liquid resin composition into a film are conditions that do not substantially complete the curing reaction. Specifically, the drying temperature is preferably 60 ° C. to 150 ° C. and the drying time is preferably 1 minute to 120 minutes, the drying temperature is 70 ° C. to 120 ° C., and the drying time is 3 minutes to 90 minutes. More preferably.

The condition that the curing reaction is not substantially completed as described above is preferable even in the case where the melt of the solid resin composition is used for producing the resin sheets 10, 20 and 30. That is, it is preferable that the heating conditions (heating temperature and heating time) when melting the solid resin composition are conditions that do not substantially complete the curing reaction.

<2-3. Actions and effects>
Since this resin sheet contains the above-mentioned resin composition of the present invention, excellent thermal properties can be obtained for the same reason as the resin composition. Other actions and effects are the same as those of the resin composition of the present invention.

<3. Resin cured product>
Next, the cured resin product according to the embodiment of the present invention will be described.

<3-1. Configuration>
The cured resin product contains the cured product of the resin composition of the present invention described above, and more specifically, a cured product of an epoxy compound and a first trinaphthylbenzene compound and a second trinaphthylbenzene compound. Includes. In this curing reaction product, the epoxy group contained in the epoxy compound and the hydroxyl group contained in each of the first trinaphthylbenzene compound and the second trinaphthylbenzene compound undergo a cross-linking reaction, so that the so-called cross-linking network Is formed.

The shape of the cured resin product is not particularly limited. Specifically, the cured resin product may or may not be molded so as to have a desired shape.

Further, the physical characteristics of the cured resin product are not particularly limited. Specifically, the cured resin product may have a property (rigidity) that is difficult to deform in response to an external force, or has a property (flexibility or flexibility) that is easily deformed in response to an external force. You may.

<3-2. Manufacturing method>
When producing this cured resin product, the resin composition is heated. As a result, the resin composition undergoes a curing reaction, so that a cured resin product, which is a curing reaction product, can be obtained.

The heating conditions such as the heating temperature and the heating time are not particularly limited, but unlike the above-mentioned method for producing a resin sheet, it is preferable that the conditions are such that the curing reaction substantially proceeds.

<3-3. Actions and effects>
Since this cured resin product contains the cured reaction product of the resin composition of the present invention described above, excellent thermal properties can be obtained for the same reason as that of the resin composition. Other actions and effects are the same as those of the resin composition of the present invention.

<4. Resin substrate ＞
Next, the resin substrate of one embodiment of the present invention will be described. Hereinafter, the resin sheet already described will be referred to as "the resin sheet of the present invention", and the cured resin product will be referred to as "the cured resin product of the present invention".

The resin substrate is one of the above-mentioned application examples of the cured resin product of the present invention, and contains the cured resin product of the present invention. The resin substrate described here contains, for example, a curing reaction product of the resin sheet of the present invention, and the configuration of the resin substrate is not particularly limited as long as it contains the curing reaction product of the resin sheet of the present invention.

The description regarding the physical properties (presence or absence of rigidity) of the cured resin product is the same for the physical properties of the resin substrate.

That is, the resin substrate may have rigidity, or may have flexibility or flexibility. Therefore, the resin substrate described here includes, for example, a curing reaction product having rigidity as well as a curing reaction product having flexibility or flexibility in the case of a curing reaction product of a resin sheet. The flexible or flexible curing reaction product is, for example, an adhesive tape which is a sheet-like adhesive.

Further, the number of curing reactants of the resin sheet contained in the resin substrate is not particularly limited. That is, the number of the curing reactants of the resin sheet may be only one or two or more. When the number of the curing reactants of the resin sheet is two or more, the curing reactants of the two or more resin sheets may be laminated.

<4-1. Configuration>
FIG. 4 shows the cross-sectional structure of the resin substrate 40. The resin substrate 40 is a curing reaction product of the resin sheet 10 shown in FIG. That is, the resin substrate 40 is a curing reaction product (resin cured product layer 3) of the resin composition layer 1, and more specifically, it is a single layer body composed of one resin cured product layer 3.

FIG. 5 shows the cross-sectional structure of the resin substrate 50. The resin substrate 50 is a curing reaction product of the resin sheet 20 shown in FIG. 2, and more specifically, it is a laminate in which a curing reaction product (resin cured product layer 3) of a plurality of resin composition layers 1 is laminated. The body. The number of layers of the cured resin layer 3 (number of layers) is not particularly limited as long as it is two or more layers. FIG. 5 shows, for example, a case where the number of layers of the cured resin layer 3 is three.

FIG. 6 shows the cross-sectional structure of the resin substrate 60. The resin substrate 60 is a cured product of the resin sheet 30 shown in FIG. 3, and more specifically, has a three-layer structure in which one core material 2 is sandwiched between two cured resin layers 3. ing.

FIG. 7 shows the cross-sectional structure of the resin substrate 70. In this resin substrate 70, the curing reactants of two or more resin sheets 30 are laminated. Here, for example, the curing reactants of the three resin sheets 30 are laminated. That is, a three-layer structure in which one core material 2 is sandwiched between the two cured resin layers 3 is formed, and the three-layer structure is stacked in three stages.

The number of layers (number of stages) of the above-mentioned three-layer structure is not limited to three stages, and may be two stages or four or more stages. This number of stages can be appropriately set based on conditions such as the thickness and strength of the resin substrate 70.

Although not shown here, the resin substrate 70 may include a metal layer. This metal layer is provided, for example, on the surface of the uppermost resin cured product layer 3 and on the surface of the lowermost resin cured product layer 3.

The metal layer contains, for example, any one or more of copper, nickel, aluminum and the like. Further, the metal layer includes, for example, any one type or two or more types of a metal foil, a metal plate, and the like, and may be a single layer or a multi-layer. The thickness of the metal layer is not particularly limited, but is, for example, 3 μm to 150 μm. The resin substrate 70 provided with this metal layer is a so-called metal-clad substrate.

The metal layer may be provided only on the surface of the uppermost resin cured product layer 3, or may be provided only on the surface of the lowermost resin cured product layer 3.

If necessary, the resin substrate 70 provided with the metal layer may be subjected to any one or more of various treatments such as etching treatment and drilling treatment. In this case, the resin substrate 70, the metal layer subjected to the above-mentioned various treatments, and any one or more of the resin sheets 10, 20, and 30 can be laminated to form a multilayer substrate. good.

As described above, the fact that the metal layer may be provided and the multilayer substrate may be used is not limited to the resin substrate 70, but the same applies to the resin substrates 40, 50, and 60 described above.

<4-2. Manufacturing method>
When the resin substrate 40 is manufactured, the resin sheet 10 is heated. As a result, as described above, the curing reaction of the resin composition in the resin composition layer 1 is substantially completed. Therefore, as shown in FIG. 4, the resin curing reaction product of the resin composition layer 1 is cured. The material layer 3 is formed.

When the resin substrate 50 is manufactured, the resin sheet 20 is heated. As a result, as described above, the curing reaction of the resin composition is substantially completed in each resin composition layer 1. Therefore, as shown in FIG. 5, the curing reactions of the plurality of resin composition layers 1 are used. A plurality of cured resin layers 3 are formed.

When the resin substrate 60 is manufactured, the resin sheet 30 is heated. As a result, as described above, the curing reaction of the resin composition is substantially completed in each resin composition layer 1. Therefore, as shown in FIG. 6, the resin composition layer 1 is formed on both sides of the core material 2. The resin cured product layer 3 which is a curing reaction product is formed.

FIG. 8 shows a cross-sectional configuration corresponding to FIG. 7 for explaining a method of manufacturing the resin substrate 70. When manufacturing this resin substrate 70, first, as shown in FIG. 8, three resin sheets 30 are laminated. As a result, a laminated body of three resin sheets 30 is obtained. After that, the laminate is heated. As a result, in each resin sheet 30, the curing reaction of the resin composition is substantially completed in each resin composition layer 1. Therefore, as shown in FIG. 7, the resin composition is formed on both sides of each core material 2. The resin cured product layer 3 which is the curing reaction product of the layer 1 is formed.

Here, when the melt of the resin composition is used for producing the resin sheets 10, 20, and 30, as described above, it is avoided that the curing reaction is substantially completed when the resin composition is melted. do. Therefore, it is preferable that the temperature at which the resin composition is heated in order to obtain the melt is lower than the temperature at which the curing reaction of the resin composition is substantially completed. In other words, the melting temperature of the resin composition is preferably lower than the temperature at which the curing reaction of the resin composition is substantially completed.

As an example, in the molding process using a mold, the maximum value (maximum temperature) of the heating temperature at the time of molding is generally about 250 ° C. Therefore, the melting temperature of the resin composition is preferably lower than 250 ° C, more preferably 200 ° C or lower.

The “melting temperature” described here is a temperature at which the resin composition changes from a solid state to a flowing (melting) state while avoiding substantially completing the curing reaction of the resin composition. In order to specify the melting temperature, for example, the state of the resin composition is visually observed while heating the resin composition using a heating device such as a hot plate. In this case, the heating temperature is gradually raised while mixing the resin composition with a spatula or the like. As a result, the temperature at which the resin composition begins to melt is defined as the melting temperature.

As described above, when the maximum temperature at the time of molding is about 250 ° C., for example, the heating temperature at the time of molding is 50 ° C. or more higher than the melting temperature of the resin composition, specifically, 100 ° C. to 100 ° C. The temperature is set to 250 ° C., and the heating time is set to about 1 minute to 300 minutes. As a result, the resin composition is sufficiently heated at a temperature at which the curing reaction is substantially completed, so that the curing reaction proceeds uniformly.

In the molding process using a mold, the resin composition may be pressurized using a press machine or the like, or the pressure in the environment in which the resin composition is present may be increased or decreased, if necessary. ..

In particular, when the resin substrate 70 is manufactured, it is preferable to heat the laminated body while pressurizing the laminated body in the laminating direction of the resin sheet 30. This is because the adhesion between the resin sheets 30 is improved. The heating conditions and pressurizing conditions in this case are not particularly limited. As an example, the heating temperature is 100 ° C. to 250 ° C., the heating time is 1 minute to 300 minutes, and the pressurizing pressure is 0.5 MPa to 8 MPa.

<4-3. Actions and effects>
Since this resin substrate contains the cured resin product of the present invention, excellent thermal properties can be obtained for the same reason as the cured resin product. Other actions and effects are the same as those of the cured resin product of the present invention.

Examples of the present invention will be described in detail.

(Examples 1 to 10, Comparative Examples 1 to 4)
As shown in FIG. 5, a resin substrate 50 made of a laminated body in which a plurality of cured resin layers 3 are laminated was manufactured by a procedure described below. The content (parts by mass) described below is a value converted into a solid content.

When producing the resin substrate 50, first, an epoxy compound, a first curing agent, a second curing agent, and an additive (curing catalyst) were mixed. In this case, the ratio of the number of epoxy groups contained in the epoxy compound to the number of active hydrogens contained in each of the first curing agent and the second curing agent is 1: 1. The mixing ratio of the epoxy compound, the first curing agent, and the second curing agent was adjusted.

The presence / absence, type, and content (parts by mass) of the epoxy compound, the first curing agent, and the second curing agent in the mixture are as shown in Table 1. As the epoxy compound, a biphenyl type epoxy resin (YL6121H: manufactured by Mitsubishi Chemical Corporation) was used. As the first curing agent, the compound represented by the formula (1-1) and 1,5-diaminonaphthalene (manufactured by Tokyo Kasei Co., Ltd.) were used. As the second curing agent, the compounds represented by the formulas (2-1), formulas (2-2), formulas (2-3), and formulas (2-5) were used. The presence or absence of the "TNB skeleton" shown in Table 1 indicates whether or not the first curing agent contains 1,3,5-trinaphthylbenzene as the skeleton. 2-Ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei Co., Ltd.) was used as the curing catalyst, and the amount of the curing catalyst added was 1% by mass with respect to the total of the epoxy compound and the curing agent.

In this case, the proportion M (mol%) was adjusted by changing the type and content of each of the first curing agent and the second curing agent. The ratio M (mol%) is as shown in Table 1.

Subsequently, the mixture was added to a solvent (methyl ethyl ketone), and the solvent was stirred. The amount of the curing catalyst added was 1% by mass with respect to the total of the epoxy compound and the curing agent. As a result, the epoxy compound, the first curing agent and the second curing agent were dissolved in the solvent, so that a liquid resin composition was obtained. In this case, the concentration of the solid content (epoxy compound, first curing agent and second curing agent) was set to 65% by mass.

Subsequently, a liquid resin composition was applied to the surface of the support (PET film, thickness = 0.05 mm), and then the liquid resin composition was dried (temperature = 100 ° C.). As a result, the resin composition layer 1 was formed on the surface of the support, so that the resin sheet 10 (thickness = 0.1 mm) which was the single layer shown in FIG. 1 was obtained. After that, the resin sheet 10 was peeled off from the support.

Subsequently, 10 resin sheets 10 were laminated to prepare a resin sheet 20 (the number of layers of the resin composition layer 1 = 10 layers), which is the laminated body shown in FIG. Finally, the laminate is heated (temperature = 170 ° C.) and pressurized (pressure = 1 MPa, time = 20 minutes) using a flat plate press, and then the laminate is further heated (temperature = 200 ° C.) and pressurized (temperature = 200 ° C.). Pressure = 4 MPa, time = 1 hour). In this heating step, since the reaction of the resin composition was substantially completed in each resin composition layer 1, the resin cured product layer 3 containing the cured product of the resin composition was formed. As a result, the resin substrate 50 (the number of layers of the cured resin layer 3 = 10 layers, the thickness = 0.9 mm) was completed.

When the thermal properties of the resin composition, the resin sheet 20 (resin composition layer 1) and the resin substrate 50 (resin cured product layer 3) were examined, the results shown in Tables 1 and 2 were obtained. .. Here, the moldability of the resin composition and the resin sheet 20 was examined, and the thermal conductivity of the resin substrate 50 was examined.

When examining the moldability, the minimum melt viscosity (mPa · s) of the resin sheet 20 was measured using a viscoelasticity measuring device. In this case, the resin sheet 20 was molded to prepare a circular measurement sample (diameter = 20 mm, thickness = 1.8 mm). After that, using a viscoelasticity measuring device (Rheo Stress 6000 manufactured by Thermo Scientific Co., Ltd.), a sample for measurement was used under the conditions of a starting temperature of 100 ° C., a heating rate of 2.5 ° C./min, and a frequency of 1 Hz. Was heated and the minimum melt viscosity was measured. In this case, the viscosity decreased as the sample for measurement melted, and then increased as the curing reaction proceeded, so that a downwardly convex viscosity curve was obtained. The lowest value of this viscosity curve was defined as the lowest melt viscosity.

When examining the thermal conductivity, the thermal conductivity (W / (m · K)) of the resin substrate 50 was measured. Specifically, first, the resin substrate 50 was cut to prepare a circular measurement sample (diameter = 10 mm, thickness = 0.9 mm). Subsequently, the measurement sample was analyzed using a thermal conductivity measuring device (TC series manufactured by Advance Riko Co., Ltd. (formerly ULVAC Riko Co., Ltd.)), and the thermal diffusivity α (m ² / s) was measured. In addition, using sapphire as a standard sample, the specific heat Cp of the measurement sample was measured using differential scanning calorimetry (DSC). Furthermore, the density r of the measurement sample was measured using the Archimedes method. Finally, the thermal conductivity λ (W / (m · K)) was calculated based on the following mathematical formula (B).

λ = α × Cp × r ・ ・ ・ (B)
(Λ is the thermal conductivity (W / (m · K)), α is the thermal diffusivity (m ² / s), Cp is the specific heat (J / kg · K), and r is the density (kg / m ³ ). .)

The minimum melt viscosity and thermal conductivity varied greatly depending on the presence or absence of the TNB skeleton and the proportion M.

Specifically, when the first curing agent contains a TNB skeleton and the ratio M is 0.2 mol% or more and 16.4 mol% or less (Examples 1 to 10), high thermal conductivity is maintained. However, the minimum melt viscosity became sufficiently low.

In particular, when the ratio M was 0.2 mol% or more and 5.1 mol% or less (Examples 1 to 3, 9, and 10), higher thermal conductivity was obtained while the minimum melt viscosity was sufficiently low.

On the other hand, when the ratio M was smaller than 0.2 mol% (Comparative Examples 1 and 2), sufficient thermal conductivity was obtained, but the minimum melt viscosity was remarkably high. Further, when the ratio M was larger than 16.4 mol% (Comparative Example 3), the minimum melt viscosity was sufficiently low, but the thermal conductivity was lowered.

Further, when the first curing agent did not contain TNB (Comparative Example 4), the thermal conductivity decreased and the minimum melt viscosity also increased remarkably.

This result shows that when the ratio M is optimized when the resin composition contains the first curing agent and the second curing agent together, the thermal conductivity related to the thermal conductivity is improved and the moldability is improved. It shows that the improvement of the minimum melt viscosity involved is compatible.

From the results shown in Table 1, the resin composition contains the epoxy compound, the first trinaphthylbenzene compound represented by the formula (1), and the second trinaphthylbenzene compound represented by the formula (2), and the proportion thereof. When M was within an appropriate range, both thermal conductivity and moldability were compatible. Therefore, excellent thermal properties were obtained.

Although the present invention has been described above with reference to embodiments and examples, the present invention is not limited to the embodiments described in the embodiments and examples, and various modifications are possible.

1 ... Resin composition layer, 2 ... Core material, 3 ... Resin cured product layer, 10, 20, 30 ... Resin sheet, 40, 50, 60, 70 ... Resin substrate.

Claims (11)

Epoxy compounds and
The first trinaphthylbenzene compound represented by the following formula (1) and
Including the second trinaphthylbenzene compound represented by the following formula (2),
The ratio M (mol%) represented by the following mathematical formula (A) is 0.2 mol% or more and 16.4 mol% or less.
Resin composition.

(Each of R1 to R21 is either a hydrogen group (-H) or a hydroxyl group (-OH). However, at least one of R1 to R21 is a hydroxyl group.
One or more of R1 to R7 are hydroxyl groups,
One or more of R8 to R14 are hydroxyl groups,
One or more of R15 to R21 is a hydroxyl group. )

(Each of R31 to R51 is one of a hydrogen group, a hydroxyl group and an alkoxy group. However, at least one of R31 to R51 is a hydroxyl group and at least one of R31 to R51. Is an alkoxy group.)
M (mol%) = (M1 / M2) × 100 ... (A)
M1: Number of moles of alkoxy groups contained in the second trinaphthylbenzene compound (mol)
M2: The number of moles of hydroxyl groups contained in the first trinaphthylbenzene compound (mol), the number of moles of hydroxyl groups contained in the second trinaphthylbenzene compound (mol), and the number of moles of hydroxyl groups contained in the second trinaphthylbenzene compound. Sum with the number of moles (mol) of the alkoxy group The ratio M is 0.2 mol% or more and 5.1 mol% or less.
The resin composition according to claim 1. The alkoxy group is one of a methoxy group (-OCH ₃ ), an ethoxy group (-OC ₂ H ₅ ) and a propoxy group (-OC ₃ H ₇ ).
The resin composition according to claim 1 or 2. One of the R31 to R37 is an alkoxy group.
Each of the R38 to R44 is one of a hydrogen group and a hydroxyl group.
The resin composition according to any one of claims 1 to 3. One of the R31 to R37 is an alkoxy group.
One of the R38 to R44 is an alkoxy group.
Each of R45 to R51 is one of a hydrogen group and a hydroxyl group.
The resin composition according to any one of claims 1 to 3. The sum of the number of hydroxyl groups contained in the second trinaphthylbenzene compound (one molecule) and the number of alkoxy groups is 3.
The resin composition according to any one of claims 1 to 5. The second trinaphthylbenzene compound contains at least one of the compounds represented by the following formulas (2-1) to (2-6).
The resin composition according to any one of claims 1 to 6.

The resin composition according to any one of claims 1 to 7.
Resin sheet. A cured reaction product of the resin composition according to any one of claims 1 to 7.
Resin cured product. The curing reaction product of the resin sheet according to claim 8 is included.
Resin substrate. Containing two or more curing reactants of the resin sheet,
The curing reactants of the two or more resin sheets are laminated.
The resin substrate according to claim 10.

Images