JP6696283B2 - 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 resin cured product, and a resin substrate using the resin composition.

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

  In the process of manufacturing a resin substrate, after the resin composition is molded into a sheet shape, the sheet-shaped resin composition (resin sheet) is subjected to a curing reaction. As a result, a resin substrate containing a cured reaction product (resin cured product) of the resin composition is manufactured.

  Various proposals have already been made regarding the composition of this resin composition. Specifically, in order to obtain excellent thermal conductivity, an epoxy resin having a mesogenic group is used as a monomer (see, for example, Patent Document 1). Further, in order to achieve both high thermal conductivity and solubility in an organic solvent, a reaction product of a specific epoxy compound and a specific phenol compound is used as an epoxy resin (for example, refer to Patent Document 2). ..

JP, 11-323162, A JP 2004-002573 A

  When considering the thermal characteristics of the resin composition and the resin substrate (resin cured product), not only considering the thermal conductivity characteristics of the resin substrate, but also manufacturing the resin substrate using the resin composition. It is also important to consider moldability.

  The present invention has been made in view of such problems, and an object thereof is to provide a resin composition, a resin sheet, a resin cured product, and a resin substrate that can obtain excellent thermal characteristics.

The resin composition of the present invention contains an epoxy compound having two or more epoxy groups in one molecule and a triphenylbenzene compound represented by the following formula (1).

（Ｒ１〜Ｒ１５のそれぞれは、水素基（−Ｈ）および反応基のうちのいずれかであり、その反応基は、水酸基（−ＯＨ）およびアミノ基（−ＮＨ₂ ）のうちのいずれかである。ただし、Ｒ１〜Ｒ５のうちの少なくとも１つは反応基であり、Ｒ６〜Ｒ１０のうちの少なくとも１つは反応基であり、Ｒ１１〜Ｒ１５のうちの少なくとも１つは反応基であると共に、Ｒ３、Ｒ８およびＲ１３のうちの少なくとも１つは水素基である。）

(Each R1～R15, are any of a hydrogen group (-H) and reactive groups, the reactive group is in any of the hydroxyl groups (-OH) and amino groups (-NH ₂₎ Provided that at least one of R1 to R5 is a reactive group, at least one of R6 to R10 is a reactive group, and at least one of R11 to R15 is a reactive group, and R3 , at least one of R8 and R13 is water containing 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 curing reaction product of the resin composition of the present invention described above.

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

Since the resin composition of the present invention contains the triphenylbenzene compound represented by the formula (1) together with the epoxy compound , excellent thermal characteristics can be obtained. Moreover, the same effect can be obtained also in the resin sheet, the resin cured product, and the resin substrate of the present invention.

It is sectional drawing showing the structure of the resin sheet using the resin composition of this invention. It is sectional drawing showing the other structure of the resin sheet using the resin composition of this invention. It is sectional drawing showing the other structure of the resin sheet using the resin composition of this invention. It is sectional drawing showing the structure of the resin substrate using the resin cured material of this invention. It is sectional drawing showing the other structure of the resin substrate using the resin cured material of this invention. It is sectional drawing showing the further another structure of the resin substrate using the resin cured material of this invention. It is sectional drawing showing the further another structure of the resin substrate using the resin cured material of this invention. FIG. 9 is a cross-sectional view for explaining the method of manufacturing the resin substrate shown in FIG. 7. It is a figure showing the relationship between the viscosity of a resin composition, and heating temperature.

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

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. Resin cured product 3-1. Configuration 3-2. Manufacturing method 3-3. Action and effect 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 invention is not limited to only one embodiment described herein. One embodiment of the present invention can be modified into various embodiments without departing from the gist of the present invention.

<1. Resin composition>
First, a resin composition according to an embodiment of the present invention will be described.

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

<1-1. Composition>
This resin composition contains an epoxy compound and a triphenylbenzene compound represented by the following formula (1).

（Ｒ１〜Ｒ１５のそれぞれは、水素基および反応基のうちのいずれかであり、その反応基は、水酸基およびアミノ基のうちのいずれかである。ただし、Ｒ１〜Ｒ１５のうちの少なくとも１つは、反応基であると共に、Ｒ３、Ｒ８およびＲ１３のうちの少なくとも１つは、水素基である。）

(Each of R1 to R15 is one of a hydrogen group and a reactive group, and the reactive group is one of a hydroxyl group and an amino group. Provided that at least one of R1 to R15 is , And at least one of R3, R8 and R13 is a hydrogen 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. The “intermediate product” means a substance in a state where the curing reaction (crosslinking reaction) of the resin composition is not substantially completed, as described later. Further, the "final product" means a substance in a state where the curing reaction of the resin composition is substantially completed, as described later.

  The epoxy compound, which is a thermosetting resin, is a so-called base resin. On the other hand, a triphenylbenzene compound used together with an epoxy compound and containing a reactive group is a so-called curing agent. This curing agent is used to promote the crosslinking reaction of the epoxy compound using the reactive group.

  The reason why the resin composition contains the triphenylbenzene compound together with the epoxy compound is that high heat conductivity and high heat resistance can be obtained in a resin cured product while ensuring the moldability of the resin composition. The detailed reason why such an advantage is obtained will be described later.

  The resin composition may be in a solid state such as a powder or a lump, a liquid state, or a state in which both are mixed. The state of this resin composition is appropriately determined according to the application.

  The mixing ratio of the epoxy compound and the triphenylbenzene compound is not particularly limited. However, when the epoxy compound containing an epoxy group and the triphenylbenzene compound containing a reactive group undergo a crosslinking reaction, generally, one epoxy group reacts with one active hydrogen in the reactive group. Therefore, in order to increase the reaction efficiency between the epoxy compound and the triphenylbenzene compound, the total number of epoxy groups contained in the epoxy compound and the total number of active hydrogen contained in the triphenylbenzene compound are 1: 1. It is preferable to set the mixing ratio so that

[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). Above all, the epoxy compound preferably contains two or more epoxy groups in one molecule. This is because the epoxy compound and the triphenylbenzene compound are 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 cycloaliphatic epoxy compound and a long chain aliphatic 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. The novolac type epoxy compound is, for example, a cresol novolac type epoxy compound and a phenol novolac type epoxy compound. 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). The fact that the type is not limited as long as it contains a specific structure is the same as in specific examples of other epoxy compounds such as glycidyl ester type epoxy compounds.

  Among them, the epoxy compound preferably contains a mesogenic skeleton in one molecule. The reason is as follows.

  First, in the molecules of the epoxy compound, the benzene rings are easily overlapped with each other, so that the distance between the benzene rings is reduced. Thereby, in the resin composition, the density of the epoxy compound is improved. Further, in the resin cured product, since the lattice vibration of molecules is less likely to be scattered, high thermal conductivity can be obtained.

  In particular, since the scattering phenomenon of the lattice vibration of the molecule is a large factor that lowers the thermal conductivity, the scattering phenomenon of the lattice vibration of the molecule is suppressed, and thus the reduction of the thermal conductivity is significantly suppressed. ..

  Secondly, in the epoxy compound and the triphenylbenzene compound, the benzene ring contained in the mesogen skeleton of the epoxy compound and the benzene ring contained in the skeleton of the triphenylbenzene compound (1,3,5-triphenylbenzene) The ring easily overlaps. Therefore, high thermal conductivity is obtained for the same reason as in the case where the benzene rings are likely to overlap with each other in the molecules of the epoxy compound described above.

  This "mesogenic skeleton" is a general term for an atomic group having two or more aromatic rings and having rigidity and orientation. Specifically, the mesogenic skeleton is, for example, a skeleton that includes two or more benzene rings and that the benzene rings are bonded to each other through either a single bond or a non-single bond.

  In addition, when three or more benzene rings are bonded, the direction of the bonding is not particularly limited. That is, three or more benzene rings may be linearly bonded, may be bent one or more times in the middle, or may be branched in two or more directions. May be.

  The "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, for example, one or more kinds of constituent elements such as carbon (C), nitrogen (N), oxygen (O), and hydrogen (H). .. In addition, the non-single bond includes, as a multiple bond, one or both of a double bond and a triple bond.

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

  Specific examples of the non-single bond include a bond represented by each of the following formulas (2-1) to (2-10). In addition, the arrow shown in each of Formula (2-6) and Formula (2-10) represents the coordinate bond.

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

[Triphenylbenzene compound]
The triphenylbenzene compound that is the curing agent is any one kind or two or more kinds of the compounds including the skeleton (1,3,5-triphenylbenzene) and the reactive group. That is, in a triphenylbenzene compound, 1,3,5-triphenylbenzene is contained in one molecule as a skeleton, and a reactive group is introduced into the skeleton.

  This skeleton (1,3,5-triphenylbenzene) has one benzene ring (central benzene ring) located at the center and three benzene rings (peripheral benzene rings) located around the central benzene ring. Contains.

  In the following, the peripheral benzene ring in which R1 to R5 are introduced is the "first peripheral benzene ring", the peripheral benzene ring in which R6 to R10 is introduced is the "second peripheral benzene ring", and R11 to R15 are introduced. The surrounding benzene ring is referred to as the “third peripheral benzene ring”.

  Each kind of R1 to R15 is not particularly limited as long as it is either a hydrogen group or a reactive group. That is, each of R1 to R15 may be a hydrogen group or a reactive group.

  This reactive group is either a hydroxyl group or an amino group. That is, the triphenylbenzene compound may contain only a hydroxyl group, an amino group alone, or both a hydroxyl group and an amino group as a reactive group.

  However, regarding the types of R1 to R15, the following two conditions are satisfied.

  As a first condition, one or more of R1-R15 are reactive groups. That is, the triphenylbenzene compound contains one or more reactive groups in one molecule. The number of the reactive groups may be one, two, three or more. Therefore, 1,3,5-triphenylbenzene and the like in which all of R1 to R15 are hydrogen groups are excluded from the triphenylbenzene compound described here. Among them, it is preferable that two or more of R1 to R15 are reactive groups. This is because the epoxy compound and the triphenylbenzene compound are likely to react with each other.

  As a second condition, one or more of R3, R8 and R13 is a hydrogen group. That is, focusing on R3, R8, and R13, whether each of R3, R8, and R13 is a hydrogen group or a reactive group is classified into three modes. In the first aspect, all of R3, R8 and R13 are hydrogen groups. In the second aspect, one of R3, R8, and R13 is a hydrogen group, and the remaining two are reactive groups. In the third aspect, two of R3, R8, and R13 are hydrogen groups, and the remaining one is a reactive group. Therefore, compounds in which all of R3, R8, and R13 are reactive groups and all other hydrogen groups are excluded from the triphenylbenzene compound described herein.

  As long as these two conditions are satisfied, the number of reactive groups in each of the first to third peripheral benzene rings and the introduction position are not particularly limited.

  Here, the above two conditions are satisfied because the number and positions of the reactive groups (reaction points) are optimized as compared with the case where the two conditions are not satisfied. As a result, the crosslink density is ensured during the reaction between the epoxy compound and the triphenylbenzene compound, so that the glass transition point of the cured resin increases and the thermal conductivity of the cured resin also increases. Moreover, since the melt viscosity of the resin composition becomes low in a wide temperature range, the fluidity is ensured in a wide temperature range when the resin composition is used.

  The case where the above two conditions are not satisfied is, for example, the following case. The first condition is satisfied, but the second condition is not satisfied. The first condition is not satisfied, but the second condition is satisfied. This is a case where both the first and second conditions are not satisfied.

  Among them, regarding the types of R1 to R15, it is preferable that one or more of the following three conditions are further satisfied.

  As a third condition, at least one of R1 to R5 is a reactive group, at least one of R6 to R10 is a reactive group, and at least one of R11 to R15 is a reactive group. Is preferred. In this case, the total number of reactive groups is 3 or more. Even if the total number of reactive groups is large, the introduction positions of the reactive groups are dispersed in each of the first to third peripheral benzene rings, so that the epoxy compound and the triphenylbenzene compound easily react with each other.

  In this case, if at least one of R1 to R5 is a reactive group, the position at which the one or more reactive groups are introduced into the first peripheral benzene ring is not particularly limited. As described above, when the number of the reactive groups is one or more, the introduction position of the one or more reactive groups is not limited, and the position of the one or more reactive groups introduced into the second peripheral benzene ring is not limited. Is similar to the above, and the same applies to the positions of one or more reactive groups introduced into the third peripheral benzene ring.

  As the fourth condition, it is preferable that one of R1 to R5 is a reactive group, one of R6 to R10 is a reactive group, and one of R11 to R15 is a reactive group. In this case, the total number of reactive groups is three. Even if the total number of reactive groups is three, the introduction positions of the reactive groups are dispersed in each of the first to third peripheral benzene rings, so that the epoxy compound and the triphenylbenzene compound easily react with each other.

  In this case, if one of R1 to R5 is a reactive group, the position where the one reactive group is introduced into the first peripheral benzene ring is not particularly limited. As described above, in the case where the number of the reactive groups is one, the introduction position of the one reactive group is not limited, and the same applies to the position of the one reactive group introduced into the second peripheral benzene ring. At the same time, the same applies to the position of one reactive group introduced into the third peripheral benzene ring.

  As the fifth condition, the type of reactive group is preferably only a hydroxyl group or only an amino group. This is because it is easy to synthesize a triphenylbenzene compound.

  Specific examples of the triphenylbenzene compound include compounds represented by the following formulas (1-1) to (1-6). These series of compounds satisfy the first to fifth conditions described above.

  The compounds represented by formulas (1-1) to (1-3) each contain only a hydroxyl group as a reactive group, and the total number of hydroxyl groups in each compound is three. The compounds shown in formulas (1-4) to (1-6) each contain only an amino group as a reactive group, and the total number of amino groups in each compound is three.

[Other materials]
This resin composition may contain any one kind or two or more kinds of other materials together with the above-mentioned epoxy compound and triphenylbenzene compound.

  The type of other material is not particularly limited, and examples thereof include additives, solvents, other curing agents, and inorganic particles.

  The additives are, for example, a curing catalyst and a coupling agent. Specific examples of the curing catalyst are phosphine, imidazole and their derivatives, and the imidazole derivative is, for example, 2-ethyl-4-methylimidazole. 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 and the triphenylbenzene compound in the liquid resin composition. This solvent is any one kind or two or more kinds among 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, Such as acetone, 1,3-dioxolane, N-methylpyrrolidone and γ-butyrolactone.

  Other hardeners are compounds that do not contain 1,3,5-triphenylbenzene as a skeleton, but do contain one or more reactive groups. Specific examples of other curing agents include phenols, amines and acid anhydrides.

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

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

  When obtaining a solid resin composition, an epoxy compound and a triphenylbenzene compound are mixed. When using an epoxy compound in a lump form, the epoxy compound may be pulverized before mixing. The fact that the triphenylbenzene compound may be pulverized before mixing is also the same. As a result, a solid resin composition containing the epoxy compound and the triphenylbenzene compound is obtained.

  In addition, after obtaining the solid resin composition, the resin composition may be molded using a mold or the like, if necessary.

  To obtain a liquid resin composition, a solvent is added to the above-mentioned mixture of the epoxy compound and the triphenylbenzene compound, and then the solvent is stirred using a stirring device such as a mixer. As a result, the epoxy compound and the triphenylbenzene compound are dispersed or dissolved in the solvent. Therefore, a liquid resin composition containing an epoxy compound and a triphenylbenzene compound can be obtained.

  In addition to this, 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 and the melt may be cooled.

  As the epoxy compound, a solid compound such as powder and lump may be used, a liquid compound may be used, or both may be used in combination. Similarly, as the curing agent such as a triphenylbenzene compound, a solid compound such as powder and lump may be used, a liquid compound may be used, or both may be used in combination. .. What has been described here also applies to the other materials described above.

<1-3. Action and effect>
This resin composition contains the triphenylbenzene compound represented by the formula (1) together with the epoxy compound. In this case, as described above, as compared with the case where the resin composition does not contain a triphenylbenzene compound, the crosslink density is secured during the reaction between the epoxy compound and the triphenylbenzene compound, so that the resin curing As the glass transition point of the product increases, the thermal conductivity of the resin cured product increases. Moreover, since the melt viscosity of the resin composition becomes low in a wide temperature range, the fluidity is ensured in a wide temperature range when the resin composition is used. Therefore, excellent thermal characteristics can be obtained.

  The case where the resin composition does not contain the triphenylbenzene compound represented by the formula (1) is, for example, the case where the resin composition contains another compound. The other compound is, for example, a compound represented by each of the following formula (3-1) and formula (3-2).

  The compound represented by the formula (3-1) is 1,3,5-tris (4-hydroxyphenyl) benzene. In this compound, R3, R8, and R13 shown in Formula (1) are all reactive groups (hydroxyl groups), and all other groups are hydrogen groups. Therefore, among the above-mentioned first and second conditions, the first condition is satisfied, but the second condition is not satisfied.

  The compound represented by the formula (3-2) is 1,3,5-tris (4-aminophenyl) benzene. In this compound, R3, R8, and R13 shown in Formula (1) are all reactive groups (amino groups), and all other groups are hydrogen groups. Therefore, among the above-mentioned first and second conditions, the first condition is satisfied, but the second condition is not satisfied.

  Particularly, in the resin composition, in the formula (1), one or more of R1 to R5 are reactive groups, one or more of R6 to R10 are reactive groups, and one of R11 to R15. When one or more is a reactive group, the epoxy compound and the triphenylbenzene compound are likely to react with each other, so that a higher effect can be obtained.

  Further, if one of R1 to R5 is a reactive group, one of R6 to R10 is a reactive group, and one of R11 to R15 is a reactive group, an epoxy compound and a triphenylbenzene compound are obtained. Can be more easily reacted, and a higher effect can be obtained.

  Further, if the type of the reactive group is only a hydroxyl group or an amino group, a triphenylbenzene compound can be easily synthesized, and a higher effect can be obtained.

  Further, if the triphenylbenzene compound is a compound represented by each of formulas (1-1) to (1-6), the first to fifth conditions are satisfied, and thus a higher effect can be obtained.

<2. Resin sheet>
Next, the resin sheet of one embodiment of the present invention will be described. Below, the resin composition already explained is called "the resin composition of this invention."

  The resin sheet contains the resin composition of the present invention. The constitution 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 have other constituent elements together with the resin composition, or may have other constituent elements together with the resin composition.

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

  FIG. 2 shows a 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 resin composition layers 1 laminated (the number of laminated layers) is not particularly limited as long as it is two or more layers. In FIG. 2, for example, the case where the number of laminated resin composition layers 1 is 3 is shown. In addition, 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, some of the plurality of resin composition layers 1 may have the same resin composition structure in the resin composition layers 1.

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

  The core material 2 contains, for example, one kind or two or more kinds of a fibrous substance and a non-fibrous substance, and is formed into a sheet shape. The fibrous substance is, for example, glass fiber, carbon fiber, metal fiber, natural fiber and synthetic fiber, and the fibrous substance formed into a sheet shape is, for example, woven fabric or 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 shape is, for example, a polymer film. A specific example of the polymer compound is polyethylene terephthalate (PET).

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

  The resin composition layer 1 used for the resin sheet 30 may be one layer or two or more layers. The same applies to the core material 2 as described above, in which one layer or two or more layers may be used.

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

<2-2. Manufacturing method>
When the resin sheet 10 is manufactured, for example, the same procedure as the method for manufacturing 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 a melt of the solid resin composition may be molded. When molding the melt, first, the solid resin composition is heated to melt the resin composition. Subsequently, after molding a 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 is volatilized, so that the resin composition is formed into a sheet on the surface of the support. That is, the resin composition forms a film on the surface of the support. Therefore, the resin composition layer 1 is formed. Then, the resin composition layer 1 is peeled off from the support.

  When the resin sheet 20 is manufactured, the above-described procedure for forming the resin composition layer 1 is repeated to stack a plurality of resin composition layers 1. 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 being heated if necessary. Thereby, the resin composition layers 1 are in close contact with each other.

  When manufacturing 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. Thereby, 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 coated with the liquid resin composition and the liquid material A part of the resin composition is impregnated into the core material 2. Alternatively, when the core material 2 contains a non-fibrous substance, the surface of the core material 2 is coated with the liquid resin composition.

  Of course, when manufacturing the resin sheet 30 having a two-layer structure, the liquid resin composition may be applied to only one surface of the core material 2.

  When the resin sheet 30 is manufactured, for example, the solid resin composition may be heated to melt the resin composition, and then the core material 2 may be dipped in the melt. In this case, after taking out the core material 2 from the melt, 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 to manufacture the resin sheets 10, 20, and 30, the liquid resin composition is formed into a film (solidified) in the drying step as described above. However, "film formation (solidification)" described here means that a substance in a fluid state (liquid state) changes to a self-sustainable state (solid state). Including state. That is, when the liquid resin composition forms a film, the curing reaction is not substantially completed, and thus the resin composition is in a substantially uncured state. For this reason, 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, it is preferable that the drying temperature is 60 ° C. to 150 ° C. and the drying time is 1 minute to 120 minutes, and the drying temperature is 70 ° C. to 120 ° C. and the drying time is 3 minutes to 90 minutes. More preferably.

  The fact that the conditions in which the curing reaction is not substantially completed is preferable in this way also applies to the case where a melt of the solid resin composition is used for producing the resin sheets 10, 20, 30. That is, the heating conditions (heating temperature and heating time) for melting the solid resin composition are preferably conditions that do not substantially complete the curing reaction.

<2-3. Action and effect>
Since this resin sheet contains the above-described resin composition of the present invention, excellent thermal characteristics can be obtained for the same reason as that of the resin composition. Other functions and effects are similar to those of the resin composition of the present invention.

<3. Cured resin>
Next, a cured resin product of one embodiment of the present invention will be described.

<3-1. Composition>
The resin cured product contains the curing reaction product of the resin composition of the present invention described above, and more specifically, the curing reaction product of the epoxy compound and the triphenylbenzene compound. In this curing reaction product, the epoxy group contained in the epoxy compound and the reactive group contained in the triphenylbenzene compound undergo a crosslinking reaction, so that a so-called crosslinked network is formed.

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

  Moreover, the physical properties of the cured resin are not particularly limited. Specifically, the resin cured product may have a property (rigidity) that does not easily deform according to an external force, or has a property (flexibility or flexibility) that easily deforms according to an external force. May be.

<3-2. Manufacturing method>
When producing this resin cured product, the resin composition is heated. As a result, the resin composition undergoes a curing reaction, so that a cured resin product that is a curing reaction product is 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 the resin sheet, it is preferable that the curing reaction substantially progresses.

<3-3. Action and effect>
Since this cured resin product contains the curing reaction product of the resin composition of the present invention described above, excellent thermal properties can be obtained for the same reason as for the resin composition. Other functions and effects are similar to those of the resin composition of the present invention.

<4. Resin substrate>
Next, a resin substrate according to an 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 resin cured product will be referred to as the “resin cured product of the present invention”.

  The resin substrate is one of application examples of the resin cured product of the present invention described above, and includes the resin cured product of the present invention. The resin substrate described here contains, for example, the 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 of the physical properties of the resin cured product (presence or absence of rigidity) applies to the physical properties of the resin substrate.

  That is, since the presence or absence of rigidity regarding the resin substrate is not limited, 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 as long as it is 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 reaction products of the resin sheet contained in the resin substrate is not particularly limited. That is, the number of curing reaction products of the resin sheet may be only one, or may be two or more. In addition, when the number of curing reaction products of the resin sheet is two or more, the curing reaction products of the two or more resin sheets may be laminated.

<4-1. Composition>
FIG. 4 shows a 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 cured reaction product (resin cured product layer 3) of the resin composition layer 1, and more specifically, is a single layer body including one cured resin product layer 3.

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

  FIG. 6 shows a cross-sectional structure of the resin substrate 60. This resin substrate 60 is a curing reaction 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 resin cured product layers 3. ing.

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

  The number of stacked three-layered structures (the number of steps) is not limited to three and may be two or four or more. The number of steps 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, one kind or two or more kinds of copper, nickel, aluminum and the like. Further, the metal layer includes, for example, one kind or two or more kinds of a metal foil and a metal plate, and may be a single layer or a multilayer. 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 lowermost resin cured product layer 3.

  The resin substrate 70 provided with this metal layer may be subjected to any one kind or two or more kinds of various kinds of processing such as etching processing and punching processing, if necessary. In this case, the resin substrate 70, the metal layer that has been subjected to the various treatments described above, and one or more of the resin sheets 10, 20, and 30 are stacked to form a multilayer substrate. Good.

  Thus, not only the resin substrate 70 but also the above-mentioned resin substrates 40, 50, 60 may be formed by providing the metal layer and the multilayer substrate.

<4-2. Manufacturing method>
When manufacturing the resin substrate 40, 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 which is the curing reaction product of the resin composition layer 1 is completed. Material layer 3 is formed.

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

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

  FIG. 8 shows a sectional configuration corresponding to FIG. 7 in order to explain the method for manufacturing the resin substrate 70. When manufacturing this resin substrate 70, first, as shown in FIG. 8, three resin sheets 30 are laminated. Thereby, a laminate of the three resin sheets 30 is obtained. Then, the laminated body is heated. As a result, in each resin sheet 30, the curing reaction of the resin composition in each resin composition layer 1 is substantially completed. Therefore, as shown in FIG. A resin cured product layer 3 which is a cured reaction product of the layer 1 is formed.

  Here, when the melt of the resin composition is used to manufacture 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. To do. For this reason, it is preferable to lower the temperature for heating the resin composition to obtain the melt, rather 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 heating temperature during molding (maximum temperature) is generally about 250 ° C. Therefore, the melting temperature of the resin composition is preferably lower than 250 ° C, and 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, 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 using a spatula or the like. Thus, the temperature at which the resin composition begins to melt is taken as the melting temperature.

  As described above, when the maximum temperature during molding is about 250 ° C., for example, the heating temperature during molding is higher than the melting temperature of the resin composition by 50 ° C. or more, specifically from 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 step using a mold, the resin composition may be pressurized using a pressing 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 manufacturing the resin substrate 70, it is preferable to heat the laminated body while pressing the laminated body in the laminating direction of the resin sheets 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. For 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. Action and effect>
Since this resin substrate contains the resin cured product of the present invention, excellent thermal characteristics can be obtained for the same reason as the resin cured product. Other functions and effects are similar to those of the cured resin product of the present invention.

  Embodiments of the present invention will be described in detail.

(Experimental Examples 1-10)
By the procedure described below, as shown in FIG. 5, a resin substrate 50 made of a laminated body in which a plurality of resin cured material layers 3 were laminated was manufactured. The content (parts by mass) described below is a value converted into solid content.

  When manufacturing the resin substrate 50, first, an epoxy compound, a curing agent, and an additive (curing catalyst) were mixed. In this case, the mixing ratio of the epoxy compound and the curing agent is adjusted so that the ratio of the number of epoxy groups contained in the epoxy compound and the number of active hydrogen contained in the curing agent is 1: 1. It was adjusted.

  The respective types (parts by mass) of the epoxy compound and the curing agent in the mixture and the mixture are as shown in Table 1.

  As the epoxy compound, a biphenyl type epoxy resin (BER: YL6121H manufactured by Mitsubishi Chemical Corporation) was used. As the curing agent, the compounds represented by the formulas (1-1) to (1-6), (3-1) and (3-2), and 4,4′-diamino-p-terphenyl. (DAT) and 1,5-diaminonaphthalene (DAN) were used. The presence or absence of the "TPB skeleton" shown in Table 1 indicates whether or not the curing agent contains 1,3,5-triphenylbenzene as the skeleton. Further, the “reactive group (introduction position)” represents the type of the reactive group (introduction position of the reactive group in the formula (1)). 2-Ethyl-4-methylimidazole was used as the curing catalyst, and the addition amount of the curing catalyst was 1% by mass based on the total amount of the epoxy compound and the curing agent.

  Subsequently, the mixture was put into a solvent (methyl ethyl ketone), and then the solvent was stirred. The amount of the curing catalyst added was 1% by mass based on the total amount of the epoxy compound and the curing agent. As a result, the epoxy compound and the curing agent were dissolved in the solvent, so that a liquid resin composition was obtained. In this case, the concentration of solids (epoxy compound and curing agent) was 65% by mass.

  Subsequently, the 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, since the resin composition layer 1 was formed on the surface of the support, the resin sheet 10 (thickness = 0.1 mm) as the single-layer body shown in FIG. 1 was obtained. After that, the resin sheet 10 was peeled from the support.

  Subsequently, 10 resin sheets 10 were stacked to form a resin sheet 20 (the number of laminated resin composition layers 1 = 10 layers) which is the laminated body shown in FIG. 2. Finally, after heating (temperature = 170 ° C) and pressurizing (pressure = 1 MPa, time = 20 minutes) the laminate using a flat plate press, the laminate is further heated (temperature) = 200 ° C and pressurizing ( Pressure = 4 MPa, time = 1 hour). In this heating step, since the reaction of the resin composition in each resin composition layer 1 was substantially completed, the resin cured product layer 3 containing the curing reaction product of the resin composition was formed. As a result, the resin substrate 50 (the number of laminated resin cured material layers 3 = 10 layers, thickness = 0.9 mm) was completed.

  When the thermal characteristics of the resin sheet 20 (resin composition layer 1) and the resin substrate 50 (resin cured material layer 3) were examined, the results shown in Table 1 were obtained. Here, the moldability of the resin sheet 20 was examined, and the heat resistance and thermal conductivity of the resin substrate 50 were examined.

  When examining the moldability, the lower limit temperature (° C.) and the upper limit temperature (° C.) of the resin sheet 20 at the time of melting were examined while heating the resin sheet 20 using a viscoelasticity measuring device. The lower limit temperature is a temperature at which the melt viscosity of the resin sheet 20 becomes 1 Pa · s or less, and the upper limit temperature is a temperature at which the melt viscosity of the resin sheet 20 becomes 1 Pa · s or more. In this case, the resin sheet 20 was compression-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 measurement sample under the conditions of starting temperature = 100 ° C., temperature rising rate = 2.5 ° C./min and frequency = 1 Hz. Was heated.

  Here, FIG. 9 represents the measurement results of the melt viscosity regarding Experimental Example 1 as a representative of Experimental Examples 1 to 10. In FIG. 9, the horizontal axis represents the heating temperature (° C.) and the vertical axis represents the melt viscosity (Pa · s).

  When the resin sheet 20 is heated while increasing the temperature, the melt viscosity of the resin sheet 20 changes so as to draw a downward convex curve as the heating temperature rises. That is, in the first half when the temperature rises, the resin sheet 20 gradually melts in response to heating, so the melt viscosity of the resin sheet 20 gradually decreases as the heating temperature rises. On the other hand, in the latter half of the temperature rise, the curing reaction gradually progresses in the resin sheet 20 in response to heating, so that the melt viscosity of the resin sheet 20 gradually increases as the heating temperature rises. From the measurement results of the melt viscosity, the temperature at which the melt viscosity becomes 1 Pa · s or lower in the first half of the temperature rise (lower limit temperature) and the temperature at which the melt viscosity becomes 1 Pa · s or higher in the latter half of the temperature rise (upper limit temperature) Is required.

  When examining the heat resistance, the glass transition point (° C.) of the resin substrate 50 was measured using a dynamic viscoelasticity measuring device (DMA). Specifically, first, the resin substrate 50 was cut to prepare a rectangular measurement sample (3 mm × 25 mm). Then, the storage elastic modulus was measured using a dynamic viscoelasticity measuring device (DVE-V4 type manufactured by Rheology Co., Ltd.) while heating the measurement sample. In this case, the heating rate was 5 ° C./min and the heating temperature was raised from 25 ° C. to 300 ° C. Finally, the heating temperature corresponding to the inflection point of the storage elastic modulus was taken as the glass transition point.

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). Then, the measurement sample was analyzed using the thermal conductivity measuring device (TC series manufactured by Advance Riko Co., Ltd. (former ULVAC Riko Co., Ltd.), and the thermal diffusion coefficient α (m ² / s) was measured. Further, the specific heat Cp of the measurement sample was measured using differential scanning calorimetry (DSC) using sapphire as a standard sample. 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 formula (A).

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

  The thermal conductivity, the glass transition point, the lower limit temperature, and the upper limit temperature did not depend on the type of epoxy compound, but varied greatly depending on the type of curing agent.

  Specifically, when the curing agent did not contain the TPB skeleton (Experimental Examples 9 and 10), the resin composition did not fundamentally melt. In this case, the thermal conductivity and the glass transition point could not be fundamentally measured, or even if the thermal conductivity and the glass transition point could be measured, both the thermal conductivity and the glass transition point were extremely low.

  On the other hand, when the curing agent contained a TPB skeleton (Experimental Examples 1 to 8), a clear difference was observed depending on the structure of the curing agent.

  When the introduction position of the reactive group was not proper (Experimental Examples 7 and 8), both the thermal conductivity and the glass transition point were higher than those in the case where the curing agent did not contain the TPB skeleton. , The upper limit temperature did not become high enough.

  In this way, the upper limit temperature does not become sufficiently high means that the temperature range between the lower limit temperature and the upper limit temperature is narrow, so that the margin of the heating temperature at which the resin composition is in a fluid state suitable for molding is narrow. Is represented. In this case, in the molding step of the resin composition, it is desired to increase the heating temperature in order to improve the fluidity of the resin composition, but increasing the heating temperature rather causes the fluidity due to the curing reaction. descend. This makes it difficult to control the heating temperature, making it difficult to handle the resin composition in molding applications.

  On the other hand, when the introduction position of the reactive group is proper (Experimental Examples 1 to 6), the same thermal conductivity is obtained as compared with the case where the introduction position of the reactive group is not proper. , The glass transition point became equal or higher. Moreover, the upper limit temperature became sufficiently high while the lower limit temperature was maintained.

  In this way, the upper limit temperature is sufficiently high means that the temperature range between the lower limit temperature and the upper limit temperature is expanded in the high temperature direction, so that the heating temperature of the resin composition becomes a fluid state suitable for molding. This means that the margin is wide. In this case, unlike the case where the margin of the heating temperature is narrow, the resin composition can be heated to a high temperature while suppressing the decrease in the fluidity due to the curing reaction, so that the temperature range of the high temperature is wide. In the above, the resin composition can be brought into a fluid state suitable for molding. This makes it easy to control the heating temperature, which makes it easier to handle the resin composition in molding applications.

  In particular, when the introduction position of the reactive group is proper, only the upper limit temperature is increased while suppressing the decrease of both the thermal conductivity and the glass transition point as described above. Therefore, it is possible to improve the moldability of the resin composition and the heat resistance and the thermal conductivity of the cured resin.

  From the results shown in Table 1, when the resin composition contains the epoxy compound and the triphenylbenzene compound represented by the formula (1), the moldability of the resin composition is improved and the resin substrate (resin The heat resistance and thermal conductivity of the cured product) were also improved. Therefore, excellent thermal characteristics were obtained.

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

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

Claims (8)

An epoxy compound containing two or more epoxy groups in one molecule ,
A resin composition containing a triphenylbenzene compound represented by the following formula (1).

(Each R1～R15, are any of a hydrogen group (-H) and reactive groups, the reactive group is in any of the hydroxyl groups (-OH) and amino groups (-NH ₂₎ Provided that at least one of R1 to R5 is a reactive group, at least one of R6 to R10 is a reactive group, and at least one of R11 to R15 is a reactive group, and R3 is , at least one of R8 and R13 is water containing group.) One of the R1 to R5 is the reactive group,
One of the R6 to R10 is the reactive group,
One of the R11 to R15 is the reactive group,
Claim 1 Symbol placement of the resin composition. Each of R1 to R15 is one of a hydrogen group and a hydroxyl group,
Alternatively, each of R1 to R15 is either a hydrogen group or an amino group,
The resin composition according to claim 1 or 2 . The triphenylbenzene compound contains at least one compound represented by each of the following formulas (1-1) to (1-6),
The resin composition according to any one of claims 1 to 3 .

A resin composition according to any one of claims 1 to 4 ,
Resin sheet. A curing reaction product of the resin composition according to any one of claims 1 to 4 ,
Resin cured product. A curing reaction product of the resin sheet according to claim 5 ,
Resin substrate. Including two or more curing reaction products of the resin sheet,
The curing reaction products of the two or more resin sheets are laminated,
The resin substrate according to claim 7 .

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