JP6536158B2 - 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 in 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 production process of the resin substrate, after the resin composition is formed into a sheet, the sheet-like resin composition (resin sheet) is cured and reacted. Thereby, the resin substrate containing the hardening reaction product (resin cured material) of a resin composition is manufactured.

  Various proposals have already been made regarding the composition and the like of this resin composition. Specifically, a brominated epoxy resin is used to improve impact resistance and the like (see, for example, Patent Document 1).

Patent No. 5396721 specification

  However, there is room for improvement because sufficient thermal characteristics have not yet been obtained for resin substrates.

  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 which can obtain excellent thermal characteristics.

The resin composition of the present invention comprises an epoxy compound containing bromine (Br) as a constituent element and containing two or more epoxy groups in one molecule, and a triphenylbenzene compound represented by the following formula (1) And is included.

（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、反応基である。Ｒ６〜Ｒ１０のうちの少なくとも１つは、反応基である。Ｒ１１〜Ｒ１５のうちの少なくとも１つは、反応基である。）

(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₎ However, at least one of R 1 to R 5 is a reactive group, at least one of R 6 to R 10 is a reactive group, and at least one of R 11 to R 15 is a reactive group .)

  The resin sheet of the present invention contains a resin composition, and the resin composition has the same configuration as the above-described resin composition of the present invention.

  The cured resin of the present invention contains a cured reaction product of the resin composition, and the resin composition has the same configuration as the above-described resin composition of the present invention.

  The resin substrate of the present invention contains one or more curing reaction products of resin sheets, the resin sheet contains a resin composition, and the resin composition has the same configuration as the above-described resin composition of the present invention It is a thing.

According to the resin composition of the present invention, an epoxy compound containing two or more epoxy groups in one molecule together with bromine containing as an element, and a triphenyl benzene compound shown in Formula (1) Therefore, excellent thermal characteristics can be obtained. 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 further another 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. It is sectional drawing for demonstrating the manufacturing method of the resin substrate shown in FIG.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. The order to be described 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. Hardened resin 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 describing the present invention. Thus, the present invention is not limited to only one embodiment described herein. An embodiment of the present invention can be changed to various embodiments without departing from the scope 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 to manufacture a resin sheet, a resin cured product, a resin substrate, and the like described later. However, the application of the resin composition may be another application.

<1-1. Configuration>
This resin composition contains an epoxy compound containing bromine as a constituent element (hereinafter referred to as "brominated 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。）

(Each of R 1 to R 15 is either a hydrogen group or a reactive group, and the reactive group is any of a hydroxyl group and an amino group, provided that at least one of R 1 to R 15 is , Reactive groups.)

  As described above, the resin composition described here is used to produce an intermediate product such as a resin sheet and to produce a final product (cured resin) 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. In addition, the “final product” means a substance in a state where the curing reaction of the resin composition is substantially completed, as described later.

  The brominated epoxy compound which is a thermosetting resin is a so-called main ingredient. On the other hand, a triphenylbenzene compound which is used together with a brominated epoxy compound and contains a reactive group is a so-called curing agent. This curing agent is used to advance the crosslinking reaction of the brominated epoxy compound using the reactive group.

  The resin composition contains the triphenylbenzene compound together with the brominated epoxy compound because the resin cured product has improved flame retardancy and peel resistance while maintaining high thermal conductivity.

  Specifically, when a brominated epoxy compound is used as the main agent and another compound other than the triphenylbenzene compound is used as the curing agent, the cured resin is difficult to burn, but the thermal conductivity and peeling of the cured resin are Strength decreases. Thus, the tendency for the peel strength of the cured resin to decrease is remarkable particularly when the cured resin is left to stand (so-called high temperature standing) in a high temperature environment. The “other compound” is a compound which does not contain 1,3,5-triphenylbenzene as a skeleton, and is, for example, other curing agent such as phenol and amine described later.

  On the other hand, when using an epoxy compound other than a brominated epoxy compound as the main agent and using a triphenylbenzene compound as the curing agent, the peel strength of the cured resin is increased, but the cured resin is easily burned. Become. In addition, "another epoxy compound" is an epoxy compound which does not contain bromine as a constitutent element, for example, is other epoxy compounds, such as a glycidyl ether type epoxy compound mentioned below.

  On the other hand, when a brominated epoxy compound is used as the main agent and a triphenylbenzene compound is used as the curing agent, the synergy between the two can maintain high thermal conductivity and high peel strength in the resin cured product. , Hardened resin cured product is difficult to burn.

  In this case, in particular, even when the cured resin is left at a high temperature, the thermal conductivity and the peel strength hardly change before and after the high temperature storage. That is, even when the resin cured product is heated, the thermal conductivity does not easily decrease, and the peel strength also does not easily decrease.

  The resin composition may be in the form of a solid such as powder or bulk, or in the form of liquid, or both may be mixed. The state of the resin composition is appropriately determined according to the application and the like.

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

[Brominated epoxy compound]
The main component brominated epoxy compound is any one kind of compounds containing one or more bromines as one of its constituent elements and one or more epoxy groups (-C ₃ H ₅ O) in one molecule. Or two or more. Among them, the brominated epoxy compound preferably contains two or more epoxy groups in one molecule. This is because the brominated epoxy compound and the triphenylbenzene compound easily react.

  The type of brominated epoxy compound is not particularly limited as long as it is a compound that contains one or more bromines as a constituent element and also contains one or more epoxy groups, as described above. When the brominated epoxy compound contains a skeleton and one or more substituents introduced into the skeleton, bromine may be contained as a constituent element in the skeleton, and the bromine may be contained in a substituent. It may be contained as an element, or may be contained as a constituent element in both the skeleton and the substituent.

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

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

  In particular, since the scattering phenomenon of lattice vibration of the above-mentioned molecule is a major factor to lower the thermal conductivity, the reduction of the thermal conductivity is remarkably suppressed by suppressing the scattering phenomenon of lattice vibration of the molecule. .

  Second, in brominated epoxy compounds and triphenylbenzene compounds, the benzene ring contained in the mesogen skeleton of the brominated epoxy compound and the skeleton (1,3,5-triphenylbenzene) of the triphenylbenzene compound It becomes easy to overlap with the benzene ring. Therefore, high thermal conductivity can be obtained for the same reason as in the case where benzene rings easily overlap each other in the brominated epoxy compounds described above.

  The “mesogenic framework” is a generic 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 in which the benzene rings are linked via either a single bond or a non-single bond.

  In addition, when three or more benzene rings are couple | bonded, the directionality of the coupling | bonding is not specifically limited. That is, three or more benzene rings may be linked so as to be linear, may be linked so as to bend once or more along the way, or linked so as to branch in two or more directions. May be

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

  The mesogen 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 a kind of bond between benzene rings. . Moreover, the number of types of non-single bond may be one, or two or more.

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

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

  Specific examples of brominated epoxy compounds are EPICLON series of DIC Corporation (flame retardant epoxy resin based on tetrabromobisphenol A) and the like. In addition, specific examples of the brominated epoxy compound are Nippon Kayaku Co., Ltd.'s BREN series (heat and flame retardant epoxy resin), BROC series (reactive flame retardant) and BR series (reactive flame retardant).

[Triphenylbenzene compound]
The triphenyl benzene compound which is a hardening | curing agent is one or more types in any one of the compounds containing frame | skeleton (1, 3, 5- triphenyl benzene) and a reactive group. That is, in the triphenylbenzene compound, 1,3,5-triphenylbenzene is contained as a skeleton in one molecule, and a reactive group is introduced into the skeleton.

  This skeleton (1,3,5-triphenylbenzene) comprises one centrally located benzene ring (central benzene ring) and three benzene rings (peripheral benzene rings) located around the central benzene ring. It contains.

  In the following, the peripheral benzene ring into which R 1 to R 5 is introduced is referred to as “first peripheral benzene ring”, the peripheral benzene ring into which R 6 to R 10 is introduced is referred to as “second peripheral benzene ring”, and R 11 to R 15 are introduced. The surrounding benzene ring is called "third peripheral benzene ring".

  The type of each of R1 to R15 is not particularly limited as long as it is any one of a hydrogen group and a reactive group. That is, each of R1 to R15 may be a hydrogen group or a reactive group.

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

  However, one or more of R1 to R15 are reactive groups. In order for the triphenylbenzene compound to function as a curing agent, the triphenylbenzene compound must contain one or more reactive groups. As long as this condition is satisfied, the number of reactive groups and the position of introduction are not particularly limited. Among them, two or more of R1 to R15 are preferably reactive groups. This is because the brominated epoxy compound and the triphenylbenzene compound easily react.

  In particular, with regard to the types of R1 to R15, it is preferable that one or more of the following three conditions be satisfied.

  As the first 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 the case where the total number of reactive groups is three or more, the introduction positions of the three or more reactive groups are dispersed in each of the first to third peripheral benzene rings, thereby reducing the influence of steric hindrance. is there. This facilitates the reaction between the brominated epoxy compound and the triphenylbenzene compound.

  As the second condition, it is preferable that one of R 1 to R 5 is a reactive group, one of R 6 to R 10 is a reactive group, and one of R 11 to R 15 is a reactive group. In the case where the total number of reactive groups is three, the introduction positions of the three reactive groups are dispersed in each of the first to third peripheral benzene rings, so that the influence of steric hindrance is further alleviated. Thereby, the brominated epoxy compound and the triphenylbenzene compound are easily reacted.

  As the third condition, each of R1 to R15 is preferably any one of a hydrogen group and a hydroxyl group, and each of R1 to R15 is preferably any one of a hydrogen group and an amino group. That is, the triphenylbenzene compound preferably contains only one of a hydroxyl group and an amino group as a reactive group. This is because sufficient reactivity is obtained in the triphenylbenzene compound and the triphenylbenzene compound is easily synthesized.

  Specific examples of the triphenylbenzene compound are compounds represented by the following formulas (1-1) and (1-2). This is because the first to third conditions described above are satisfied.

  The compound shown in Formula (1-1) is 1,3,5-tris (4-hydroxyphenyl) benzene. This compound contains only a hydroxyl group as a reactive group, and the number of the hydroxyl group is three. The compound shown in Formula (1-2) is 1,3,5-tris (4-aminophenyl) benzene. This compound contains only amino groups as reactive groups, and the number of amino groups is three.

[Other material]
The resin composition may contain one or more of other materials, in addition to the brominated epoxy compound and the triphenylbenzene compound described above.

  The type of the other material is not particularly limited, and examples thereof include additives, solvents, other epoxy compounds, 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 derivatives thereof, and derivatives of the imidazole are, 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 brominated epoxy compound and the triphenylbenzene compound in the liquid resin composition. The solvent is any one or more of organic solvents, etc. Specific examples of the organic solvent are methyl ethyl ketone, methyl cellosolve, methyl isobutyl ketone, dimethylformamide, propylene glycol monomethyl ether, toluene, xylene, And acetone, 1,3-dioxolane, N-methyl pyrrolidone and γ-butyrolactone.

  Another epoxy compound is an epoxy compound which does not contain bromine as a constituent element. Specific examples of this other epoxy compound are glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, novolac type epoxy compounds, cyclic aliphatic type epoxy compounds, long chain aliphatic type epoxy compounds, etc. . The glycidyl ether type epoxy compound includes, for example, a bisphenol A epoxy compound and a bisphenol F epoxy compound. The novolac epoxy compounds include, for example, cresol novolac epoxy compounds and phenol novolac epoxy compounds. In addition, the type of epoxy compound may be, for example, a flame retardant epoxy compound, a hydantoin epoxy resin, an isocyanurate epoxy compound, or the like.

  In addition, the specific example of a glycidyl ether type epoxy compound will not be specifically limited if it is a compound containing the structure (group) of a glycidyl ether type. As described above, the kind is not limited as long as the specific structure is included, and the same applies to specific examples of other epoxy compounds such as glycidyl ester type epoxy compounds.

  Other curing agents are compounds which do not contain 1,3,5-triphenylbenzene as backbone but contain one or more reactive groups. Specific examples of this other curing agent are phenol, amine and acid anhydride.

The inorganic particles are any one or more types of 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 produced, for example, by the following procedure.

  In the case of obtaining a solid resin composition, a brominated epoxy compound and a triphenylbenzene compound are mixed. When using a brominated epoxy compound such as bulk, the brominated epoxy compound may be ground before mixing. The fact that grinding may be carried out before mixing is also the same for triphenylbenzene compounds. Thereby, a solid resin composition containing a brominated epoxy compound and a triphenylbenzene compound is obtained.

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

  When a liquid resin composition is to be obtained, a solvent is added to the mixture of the brominated epoxy compound and the triphenylbenzene compound described above, and then the solvent is stirred using a stirring apparatus such as a mixer. Thereby, the brominated epoxy compound and the triphenylbenzene compound are dispersed or dissolved in the solvent. Thus, a liquid resin composition containing a brominated epoxy compound and a triphenylbenzene compound is 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, a melt of the resin composition may be molded using a mold or the like, and then the melt may be cooled.

  In addition, as epoxy compounds, such as a brominated epoxy compound, you may use solid compounds, such as powdery form and a lump, a liquid compound may be used, and you may use both together. Similarly, as a curing agent such as a triphenylbenzene compound, a powdery compound or a solid compound such as a block may be used, a liquid compound may be used, or both may be used in combination. . What has been described here is the same for the other materials described above.

<1-3. Action and effect>
According to this resin composition, the brominated epoxy compound and the triphenylbenzene compound shown in Formula (1) are contained. In this case, as described above, the synergistic effect of the brominated epoxy compound and the triphenylbenzene compound improves the flame retardancy and the peel resistance while maintaining high thermal conductivity in the cured resin. Thus, excellent thermal characteristics can be obtained.

  In particular, in the formula (1), one or more of R 1 to R 5 is a reactive group, one or more of R 6 to R 10 is a reactive group, and one or more of R 11 to R 15 is a reactive group In this case, since the brominated epoxy compound and the triphenylbenzene compound are easily reacted, higher effects can be obtained. In this case, 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, the effect is similarly enhanced. You can get it.

  Furthermore, in the formula (1), higher effects are obtained if each of R1 to R15 is any of a hydrogen group and a hydroxyl group, or each of R1 to R15 is any of a hydrogen group and an amino group. You can get

  Further, if the triphenylbenzene compound contains one or both of the compounds shown in each of Formula (1-1) and Formula (1-2), higher effects can be obtained.

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

  The resin sheet contains the resin composition of the present invention. The configuration of the 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 be equipped with other components together with the resin composition, or may be equipped with other components together with the resin composition.

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

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

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

  The core material 2 contains, for example, any one or two or more of a fibrous substance and a non-fibrous substance, and is formed into a sheet. 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, woven fabric and non-woven fabric and the like. Specific examples of synthetic fibers are 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. A specific example of the polymer compound is polyethylene terephthalate (PET) or the like.

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

  The resin composition layer 1 used for the resin sheet 30 may be only one layer or two or more layers. As described above, one or two or more layers may be used in the core material 2 as well.

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

2-2. Manufacturing method>
When manufacturing the resin sheet 10, the procedure similar to the manufacturing method of the resin composition of this invention is used, for example.

  Specifically, in the case of using a solid resin composition, the resin composition is molded into a sheet 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. In the case of molding a melt, first, the solid resin composition is heated to melt the resin composition. Subsequently, after molding a melt of the resin composition, the molded article 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. Thus, 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. Thus, the resin composition layer 1 is formed. Thereafter, the resin composition layer 1 is peeled off from the support.

  When manufacturing the resin sheet 20, the formation procedure of the above-mentioned 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 being heated if necessary. Thereby, the resin composition layers 1 adhere to 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. Thereby, two resin composition layers 1 are formed so as to sandwich the core material 2. In the application step of 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 liquid material is used. A portion of the resin composition impregnates the inside of the core material 2. 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 to only 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 dipped in the molten material. In this case, after the core material 2 is taken out of the melt, the core material 2 is cooled. Thereby, the resin composition layer 1 is formed on both surfaces of the core material 2.

  Here, in the case where a liquid resin composition is used to manufacture the resin sheets 10 to 30, as described above, the liquid resin composition is filmized (solidified) in the drying step. However, “film formation (solidification)” described here means that a substance in a fluid state (liquid state) changes to a self-supportable state (solid state), and so-called semi-hardening Also includes the state. That is, when the liquid resin composition forms a film, since the curing reaction is not substantially completed, the resin composition is in a substantially uncured state. For this reason, it is preferable that the drying conditions at the time of forming a 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, and the drying temperature is 70 ° C. to 120 ° C. and the drying time is 3 minutes to 90 minutes It is more preferable that

  The fact that the conditions that do not substantially complete the curing reaction as described above is preferable as in the case of using a solid resin composition melt to produce the resin sheets 10 to 30. That is, it is preferable that the heating conditions (heating temperature and heating time) at the time of melting the solid resin composition be conditions in which the curing reaction is not substantially completed.

<2-3. Action and effect>
According to this resin sheet, since the above-described resin composition of the present invention is contained, excellent thermal characteristics can be obtained for the same reason as the resin composition. The other functions and effects are the same as those of the resin composition of the present invention.

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

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

<3-2. Manufacturing method>
In the case of producing the cured resin, the resin composition is heated. Thereby, since the resin composition undergoes a curing reaction, a cured resin product which is a curing reaction product is obtained.

  Although the heating conditions such as the heating temperature and the heating time are not particularly limited, it is preferable that the conditions allow the curing reaction to substantially proceed, unlike the above-described method for producing a resin sheet.

<3-3. Action and effect>
According to this resin cured product, since the cured reaction product of the above-described resin composition of the present invention is contained, excellent thermal characteristics can be obtained for the same reason as the resin composition. The other functions and effects are the same as 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. Below, the resin sheet demonstrated already is called "the resin sheet of this invention", and a resin cured material is each called "the resin cured material of this invention."

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

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

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

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

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

  The number (the number of stages) in which the above-described three-layer structure can be stacked 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 have a metal layer. The metal layer is provided, for example, on the surface of the uppermost resin cured material layer 3 and on the surface of the lowermost resin cured material layer 3.

  The metal layer contains, for example, any one or more of copper, nickel, and aluminum. The metal layer contains, for example, one or more of metal foils and metal plates, and may be a single layer or multiple layers. The thickness of the metal layer is not particularly limited, and is, for example, 3 μm to 150 μm. The resin substrate 70 provided with the metal layer is a so-called metal-clad substrate.

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

  The resin substrate 70 provided with the metal layer may be subjected to one or more kinds of various treatments such as an etching treatment and a drilling treatment, as needed. In this case, a multilayer substrate may be formed by overlapping the resin substrate 70, the metal layer subjected to the various treatments described above, and one or more of the resin sheets 10 to 30.

  As described above, the provision of the metal layer or the multi-layer substrate is not limited to the resin substrate 70, and the same applies to the resin substrates 40 to 60 described above.

<4-2. Manufacturing method>
When manufacturing the resin substrate 40, the resin sheet 10 is heated. Thereby, as described above, since the curing reaction of the resin composition is substantially completed in the resin composition layer 1, as shown in FIG. The object layer 3 is formed.

  When manufacturing the resin substrate 50, the resin sheet 20 is heated. Thereby, as described above, since the curing reaction of the resin composition is substantially completed in each resin composition layer 1, as shown in FIG. 5, the curing reaction products of the plurality of resin composition layers 1 are used. A certain plurality of cured resin layers 3 are formed.

  When manufacturing the resin substrate 60, the resin sheet 30 is heated. Thereby, as described above, since the curing reaction of the resin composition is substantially completed in each resin composition layer 1, as shown in FIG. A cured resin layer 3 which is a curing reaction product is formed.

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

  Here, when using a melt of a resin composition to produce the resin sheets 10 to 30, as described above, it is avoided that the curing reaction is substantially completed when the resin composition is melted. For this reason, it is preferable to lower the temperature at which the resin composition is heated to obtain a melt, 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, generally, the maximum value (maximum temperature) of the heating temperature at the time of molding is about 250 ° C. Therefore, the melting temperature of the resin composition is preferably lower than 250 ° C., and more preferably 200 ° C. or less.

  The “melting temperature” described here is a temperature at which the resin composition changes from a solid state to a fluid (melted) state while avoiding that the curing reaction of the resin composition is substantially completed. In order to specify this melting temperature, for example, while heating the resin composition using a heating device such as a hot plate, the state of the resin composition is visually observed. In this case, the heating temperature is gradually raised while mixing the resin composition with a spatula or the like. Thereby, the temperature at which the resin composition has begun 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 the molding is 50 ° C. or more higher than the melting temperature of the resin composition, specifically 100 ° C. to The temperature is set to 250 ° C., and the heating time is set to about 1 minute to 300 minutes. Since the resin composition is sufficiently heated at a temperature at which the curing reaction is substantially completed, the curing reaction proceeds uniformly.

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

  In particular, when manufacturing the resin substrate 70, it is preferable to heat the laminate while pressing the laminate in the laminating direction of the resin sheet 30. This is because the adhesion between the resin sheets 30 is improved. The heating condition and the pressurizing condition 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 pressure is 0.5 MPa to 8 MPa.

<4-3. Action and effect>
According to this resin substrate, since the resin cured product of the present invention is contained, excellent thermal characteristics can be obtained for the same reason as the resin cured product. The other functions and effects are the same as those of the resin cured product of the present invention.

  The embodiments of the present invention will be described in detail.

(Experimental examples 1 to 7)
Two types of resin substrates 50 and 70 were manufactured according to the procedure described below. The content (parts by mass) described below is a value converted to solid content.

  First, as shown in FIG. 5, a resin substrate 50 which is a laminate in which a plurality of cured resin layers 3 are laminated was manufactured. First, the epoxy compound, the curing agent, and the additive (curing catalyst) were mixed. In this case, the mixing ratio of the epoxy compound and the curing agent is set so that the ratio of the number of epoxy groups contained in the epoxy compound to the number of active hydrogens contained in the curing agent is 1: 1. It was adjusted.

  The types of epoxy compound and curing agent and the contents (parts by mass) in the mixture are as shown in Table 1. As the epoxy compound, EPICLON 152 (Chemical A) manufactured by DIC Corporation, BREN 105 (Chemical B) manufactured by Nippon Kayaku Co., Ltd., and 1001 (Chemical C) manufactured by Mitsubishi Chemical Corporation were used. As a curing agent, a compound (THPB) shown in Formula (1-1), a compound (TAPB) shown in Formula (1-2), and HE-200 (BA) manufactured by Air Water Co., Ltd. were used. . While 2-ethyl-4-methylimidazole is used as a curing catalyst, the amount of the curing catalyst added is 1% by mass with respect to the total of the epoxy compound and the curing agent. In Table 1, the presence or absence of “Br” indicates whether the epoxy compound contains bromine as a constituent element, and the presence or absence of “TPB skeleton” indicates that the curing agent is 1,3,5-trido It indicates whether or not it contains phenylbenzene.

  Subsequently, the mixture was poured into a solvent (methyl ethyl ketone), and then the solvent was stirred. As a result, since the epoxy compound and the curing agent were dissolved in the solvent, a liquid resin composition was obtained. In this case, the concentration of solid content (epoxy compound and curing agent) was 65% by mass.

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

  Subsequently, ten resin sheets 10 were stacked to produce a resin sheet 20 (the number of laminated layers of the resin composition layer 1 = 10) 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 ( The pressure was 4 MPa and the time was 1 hour. In this heating step, since the curing reaction of the resin composition is substantially completed in each resin composition layer 1, the cured resin layer 3 containing the curing reaction product of the resin composition was formed. Thereby, the resin substrate 50 (the number of laminated layers of the resin cured material layer 10 = 10 layers, thickness = 0.9 mm) was completed.

  Further, as shown in FIG. 6 and FIG. 7, a resin substrate 70 which is a laminated body in which a plurality of resin substrates 60 are laminated was manufactured. In this case, the same manufacturing procedure as the resin substrate 50 described above was used except for the procedure described below.

After the inorganic particles were added to the solution in which the mixture was dissolved by the solvent, the solution was stirred. As the inorganic particles, aluminum oxide (Al ₂ O ₃ , manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size = 40 μm to 50 μm) was used. The average particle size is a median diameter D50. As a result, since the inorganic particles were dispersed in the solution, a liquid resin composition containing the inorganic particles was obtained. The content of the inorganic particles was 230 parts by mass with respect to the total of the epoxy compound and the curing agent.

Subsequently, a liquid resin composition is applied to both surfaces of core material 2 (glass fiber woven fabric, thickness = 0.05 mm, cloth weight = 50 g / m ² ), and then the liquid resin composition is dried. (Temperature = 100 ° C). Thereby, since the resin composition layer 1 was formed on both surfaces of the core material 2, the resin sheet 30 (cloth weight = 350 g / m ² ) was obtained.

  Subsequently, six resin sheets 30 were stacked to produce a laminate (the number of steps of the resin sheet 30 = 6) 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 ( The pressure was 4 MPa and the time was 1 hour. In this heating step, since the curing reaction of the resin composition is substantially completed in each resin composition layer 1, the cured resin layer 3 containing the curing reaction product of the resin composition was formed. Thus, the resin substrate 70 (the number of steps of the resin substrate 60 = 6 steps) shown in FIG. 7 is completed.

  The thermal characteristics of the resin substrates 50 and 70 (cured resin layer 3) were examined, and the results shown in Table 1 were obtained. Here, the flame retardancy and the peel resistance were examined using the resin substrate 70, and the thermal conductivity was examined using the resin substrate 50.

  In the case of examining the flame retardancy, the flammability test in accordance with UL 94 was conducted to determine the flame retardancy class. In this case, the flammability test was performed using five measurement samples as one set of five measurement samples.

  When investigating peeling resistance, the peeling test based on JISC6481 was implemented. In this case, first, a metal-clad substrate was produced. This metal-clad substrate is a resin substrate 70 in which a copper foil (thickness = 35 μm), which is a metal layer, is provided on the surface of the uppermost resin cured material layer 3. Subsequently, a peeling test was performed in a normal temperature environment (temperature = 23 ° C.) to measure the peeling strength (kN / m). Subsequently, after leaving untested measurement samples in a high temperature environment (temperature = 180 ° C., time = 1000 hours), the peel strength test was performed again to measure the peel strength (kN / m). . Finally, change rate (%) = [(Peeling strength after high temperature standing-peeling strength before high temperature standing) / Peeling strength before high temperature standing] × 100 The rate of change in peel strength before and after high temperature storage was calculated.

In the case of examining the thermal conductivity, first, the thermal conductivity (W / (m · K)) of the measurement sample was measured in a normal temperature environment (temperature = 23 ° C.). Specifically, the resin substrate 50 was cut to prepare a circular measurement sample (diameter = 10 mm, thickness = 0.9 mm). Subsequently, the sample for measurement was analyzed using a thermal conductivity measuring device (TC series manufactured by Advance Riko Co., Ltd. (old ULVAC Riko Co., Ltd.)) to measure a thermal diffusion coefficient α (m ² / s). Further, using sapphire as a standard sample, the differential scanning calorimetry (DSC) was used to measure the specific heat Cp of the measurement sample. Furthermore, the density r of the sample for measurement was measured using the Archimedes method. Subsequently, 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), r is density (kg / m ³ ) .)

  Subsequently, the measurement sample was left in a high temperature environment (temperature = 180 ° C., time = 1000 hours), and then the thermal conductivity (W / (m · K)) was measured again. Finally, based on the formula expressed by the following equation: change rate (%) = [(thermal conductivity after high temperature storage-thermal conductivity before high temperature storage) / thermal conductivity before high temperature storage] × 100 The rate of change of the thermal conductivity before and after

  The flame retardant class, peel strength and thermal conductivity varied greatly depending on the composition of the resin composition.

  In detail, when triphenylbenzene compound was used as the curing agent but brominated epoxy compound was not used as the epoxy compound (Experimental example 5), the peel strength and thermal conductivity were high and low after leaving at high temperature. Although neither changed, the resin substrate 70 burned.

  In addition, when a brominated epoxy compound was used as the epoxy compound but a triphenylbenzene compound was not used as the curing agent (Experimental Examples 6 and 7), a good judgment (V-0) regarding the flame retardancy class Although obtained, both the peel strength and the thermal conductivity decreased significantly.

  On the other hand, when a brominated epoxy compound is used as the epoxy compound and a triphenylbenzene compound is used as the curing agent (Experimental Examples 1 to 4), a good determination (V-0) regarding the flame retardancy class The respective reductions in peel strength and thermal conductivity were significantly suppressed. In this case, in particular, the decrease in the thermal conductivity was significantly suppressed, and in some cases, the thermal conductivity did not change before and after the high temperature storage.

  From the results shown in Table 1, when the resin composition contains a brominated epoxy compound and the triphenylbenzene compound shown in Formula (1), it is difficult to maintain high thermal conductivity in the resin cured product. The flammability and peel resistance was improved. Thus, excellent thermal characteristics were obtained.

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

  1 ... resin composition layer, 2 ... core material, 3 ... cured resin layer, 10, 20, 30 ... resin sheet, 40, 50, 60, 70 ... resin substrate.

Claims (8)

An epoxy compound containing bromine (Br) as a constituent element and containing two or more epoxy groups in one molecule ,
The resin composition containing the triphenyl benzene compound represented by 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₎ However, at least one of R 1 to R 5 is a reactive group, at least one of R 6 to R 10 is a reactive group, and at least one of R 11 to R 15 is a reactive group .) One of R 1 to R 5 is the reactive group,
One of R 6 to R 10 is the reactive group,
One of R 11 to R 15 is the reactive group,
Claim 1 Symbol placement of the resin composition. Each of R1 to R15 is any one of a hydrogen group and a hydroxyl group,
Alternatively, each of R 1 to R 15 is any one of a hydrogen group and an amino group,
The resin composition of Claim 1 or Claim 2 . The triphenylbenzene compound contains at least one of the compounds represented by each of the following formula (1-1) and formula (1-2):
The resin composition according to any one of claims 1 to 3 .

Containing a resin composition,
The resin composition is
An epoxy compound containing bromine as a constituent element and containing two or more epoxy groups in one molecule ;
And triphenylbenzene compounds represented by the following formula (1):
Resin sheet.

(Each of R 1 to R 15 is either a hydrogen group or a reactive group, and the reactive group is any of a hydroxyl group and an amino group, provided that at least one of R 1 to R 5 is And at least one of R6 to R10 is a reactive group, and at least one of R11 to R15 is a reactive group. Containing the curing reaction of the resin composition,
The resin composition is
An epoxy compound containing bromine as a constituent element and containing two or more epoxy groups in one molecule ;
And triphenylbenzene compounds represented by the following formula (1):
Hardened resin.

(Each of R 1 to R 15 is either a hydrogen group or a reactive group, and the reactive group is any of a hydroxyl group and an amino group, provided that at least one of R 1 to R 5 is And at least one of R6 to R10 is a reactive group, and at least one of R11 to R15 is a reactive group. Containing one or more cured reactants of resin sheet,
The resin sheet contains a resin composition,
The resin composition is
An epoxy compound containing bromine as a constituent element and containing two or more epoxy groups in one molecule ;
And triphenylbenzene compounds represented by the following formula (1):
Resin substrate.

(Each of R 1 to R 15 is either a hydrogen group or a reactive group, and the reactive group is any of a hydroxyl group and an amino group, provided that at least one of R 1 to R 5 is And at least one of R6 to R10 is a reactive group, and at least one of R11 to R15 is a reactive group. The curing reaction products of the two or more resin sheets are laminated,
The resin substrate according to claim 7 .

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