JP2019163440A - Resin composition, resin sheet, resin cured product and resin substrate - Google Patents

Abstract

To provide a resin composition having high thermal conductivity.SOLUTION: A resin composition contains an epoxy compound represented by formula (1), another epoxy compound represented by formula (2) or (8), and a curing agent containing hydroquinone, where, a molar ratio between the epoxy compound and the other epoxy compound (the other epoxy/epoxy) is 0.05 or more and less than 2.34.SELECTED DRAWING: Figure 1

Description

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

  In recent years, due to the downsizing of electronic devices, higher functionality and higher density mounting of components have been promoted, and the amount of heat generated from the components has increased.

  Heat generated from electronic components and the like is radiated to the outside mainly through the substrate. Among them, the laminated substrate for power supply with laminated resin substrates has low thermal conductivity compared to metal substrates, etc., so it is possible to conduct heat conduction by adding inorganic particles such as aluminum oxide, boron nitride and magnesium oxide into the resin. Increases sex.

  However, if the content of inorganic particles in the resin composition is increased in order to improve the thermal conductivity, a problem arises in the fluidity of the paint during molding of the resin substrate. Therefore, even if the content of the inorganic particles in the resin composition is suppressed and the fluidity of the coating is ensured, a resin that can obtain a cured resin having high thermal conductivity so that a resin substrate having high heat dissipation can be obtained. Development is underway.

  Epoxy resins are often used as laminated substrate applications because they have excellent moldability and high electrical properties. The thermal conductivity of the cured epoxy resin is not determined only by the structure of the epoxy main agent, but is determined by a combination of a curing agent, a catalyst, and curing conditions.

  In an insulator, atomic vibrations called phonons are responsible for heat transport. Since these phonons are vibrations, they have the property of being scattered when propagating through an irregular structure. For this reason, the more regular the structure, the more the scattering is suppressed and the higher the thermal conductivity.

  For the above reasons, a method for aligning polymer chains by introducing a liquid crystal structure in the resin (a method for increasing regularity) has been proposed as a method for developing a high thermal conductivity in a cured epoxy resin. (Non-Patent Document 1). The most common method for introducing a liquid crystal structure into a resin is to impart liquid crystallinity by imparting a mesogen to an epoxy main agent. Mesogen is a relatively rigid rod-like or plate-like functional site, which is a necessary element for the expression of liquid crystallinity. And it is reported that the epoxy resin hardened | cured material of high heat conductivity is obtained by hardening this epoxy main ingredient and hardening | curing agent in the temperature range which a liquid crystal phase expresses.

  Among such epoxy resins having mesogens, 4,4'-biphenol diglycidyl ether is widely used because it is inexpensive (Patent Document 1). However, 4,4'-biphenol diglycidyl ether still has problems of low solubility in solvents, high melting point, and low thermal conductivity of the resulting cured resin.

  Therefore, in order to solve these problems, an epoxy resin in which an alkyl chain is extended asymmetrically has been proposed, which can lower the melting point, improve the solubility, and improve the thermal conductivity. Has been reported (Patent Document 2).

JP-A-11-323162 JP 2013-209631 A

Takezawa Yoshitaka, Polymer 65, February, p65-67, 2016

  However, Patent Document 2 studies using biphenol which is an inexpensive raw material containing mesogen, but its thermal conductivity is not low enough.

  When such a cured resin product made of a raw material imparted with liquid crystallinity is cured without performing a special alignment treatment such as stretching or magnetic field orientation, the cured product is macroscopically isotropic. However, microscopically, polymer chains oriented in various directions form domains to form a structure like a polycrystal. This domain has a very high thermal conductivity in the direction in which the polymer chain is oriented, while the thermal conductivity in the direction perpendicular to the direction in which the polymer chain is oriented is very low. . Therefore, phonon scattering occurs between domains. The scattering between the domains is suppressed because the domain boundary included per volume decreases as the domain size increases. Therefore, as the domain size increases, the thermal conductivity tends to work more advantageously.

  When an epoxy main agent composed of biphenol, an epoxy group, and an alkylene chain as described in Patent Document 2 is used, the nucleation rate of the domain is the nucleation rate of the domain because of the high symmetry of the oligomer generated during the polymerization process. As a result, the domain size becomes smaller and the thermal conductivity becomes lower.

  Therefore, in order to obtain a resin composition having high thermal conductivity, it is necessary to increase the growth rate of the domains relative to the generation rate of the domains.

  The present invention has been made in view of such problems, and the object thereof is to provide a resin composition, a resin sheet, and a resin cured product that can realize high thermal conductivity by forming a large domain while using an inexpensive biphenol skeleton. And providing a resin substrate.

  In order to solve the above-mentioned problems, the present inventor has intensively studied as described below. As a result, the resin composition which concerns on following [1]-[7] was discovered. That is, the present invention relates to the following inventions.

［２］：式（１）で表される第１のエポキシ化合物と、式（２）で表される第２のエポキシ化合物と、式（８）で表される第３のエポキシ化合物と、ヒドロキノンを含む硬化剤と、を含み、前記第１のエポキシ化合物と前記第２のエポキシ化合物と前記第３のエポキシ化合物と、のモル比をａ：ｂ：ｃ（第１のエポキシ：第２のエポキシ：第３のエポキシ）とした際に、三成分の組成図上（ａ、ｂ、ｃ）の組成の範囲が、Ａ（０．３０、０、０．７０）と、Ｂ（０．９５、０、０．０５）と、Ｃ（０．９５、０．０５、０）と、Ｄ（０．３０、０．７０、０）と、Ｅ（０、０．７０、０．３０）と、Ｆ(０、０．３０、０．７０）と、で囲まれる領域である、樹脂組成物。（但し、点ＡＢＣＤＥＦで囲まれる領域とは、点ＡＢＣＤＥＦで決められる六角形の線上を含まない。）

［３］：式（２）で表されるエポキシ化合物と、式（８）で表される他のエポキシ化合物と、ヒドロキノンを含む硬化剤と、を含み、前記エポキシ化合物と前記他のエポキシ化合物とのモル比（他のエポキシ／エポキシ）が、０．４以上、２．３４未満である樹脂組成物。
［４］：前記硬化剤はメチルヒドロキノンを含み、前記ヒドロキノンと前記メチルヒドロキノンとのモル比（ヒドロキノン／メチルヒドロキノン）が、０．４〜１９．０である［１］〜［３］の何れかに記載の樹脂組成物。
［５］：［１］〜［４］の何れかに記載の樹脂組成物を硬化して得られる樹脂硬化物。
［６］：［１］〜［４］の何れかに記載の樹脂組成物を含む樹脂シート。
［７］：［６］に記載の樹脂シートを１枚または複数枚積層して成形硬化することにより得られる樹脂基板。 [1]: An epoxy compound represented by the formula (1), another epoxy compound represented by the formula (2) or (8), and a curing agent containing hydroquinone, the epoxy compound and the other The resin composition whose molar ratio (other epoxy / epoxy) with an epoxy compound is 0.05 or more and less than 2.34.

[2]: The first epoxy compound represented by formula (1), the second epoxy compound represented by formula (2), the third epoxy compound represented by formula (8), and hydroquinone A molar ratio of the first epoxy compound, the second epoxy compound, and the third epoxy compound is a: b: c (first epoxy: second epoxy). : Third epoxy), the composition ranges of (a, b, c) on the three-component composition diagram are A (0.30, 0, 0.70) and B (0.95, 0, 0.05), C (0.95, 0.05, 0), D (0.30, 0.70, 0), E (0, 0.70, 0.30), A resin composition which is a region surrounded by F (0, 0.30, 0.70). (However, the region surrounded by the point ABCDEF does not include the hexagonal line determined by the point ABCDEF.)

[3]: An epoxy compound represented by the formula (2), another epoxy compound represented by the formula (8), and a curing agent containing hydroquinone, the epoxy compound and the other epoxy compound, The resin composition whose molar ratio (other epoxy / epoxy) is 0.4 or more and less than 2.34.
[4]: Any of [1] to [3], wherein the curing agent contains methylhydroquinone, and a molar ratio of the hydroquinone to the methylhydroquinone (hydroquinone / methylhydroquinone) is 0.4 to 19.0. The resin composition described in 1.
[5]: A cured resin obtained by curing the resin composition according to any one of [1] to [4].
[6]: A resin sheet comprising the resin composition according to any one of [1] to [4].
[7]: A resin substrate obtained by laminating one or more of the resin sheets according to [6] and molding and curing.

  The resin composition of the present invention can suppress the nucleation rate of the domain and relatively increase the nucleation rate of the domain by mixing similar resin components that are easy to form an orientation. Large domains can be generated, and as a result, thermal conductivity can be increased.

It is sectional drawing showing the structure of the resin sheet using the resin composition which concerns on one Embodiment of this invention. It is sectional drawing showing the other structure of the resin sheet using the resin composition which concerns on one Embodiment of this invention. It is sectional drawing showing the other structure of the resin sheet using the resin composition which concerns on one Embodiment of this invention. It is sectional drawing showing the structure of the resin substrate using the resin cured material which concerns on one Embodiment of this invention. It is sectional drawing showing the other structure of the resin substrate using the resin cured material which concerns on one Embodiment of this invention. It is sectional drawing showing the other structure of the resin substrate using the resin cured material which concerns on one Embodiment of this invention. It is sectional drawing showing the other structure of the resin substrate using the resin cured material which concerns on one Embodiment of this invention. It is sectional drawing for demonstrating the manufacturing method of the resin substrate shown in FIG. It is a three-component composition figure which shows the preferable composition of the epoxy resin which concerns on 4th Embodiment.

  Hereinafter, embodiments according to the present invention will be described in detail with reference to the drawings as appropriate. In the drawings used in the following description, in order to make the characteristics of the embodiments according to the present invention easier to understand, there are cases where the characteristic parts are enlarged for convenience. Therefore, the dimensional ratios of the components described in the drawings may be different from actual ones. The materials, dimensions, and the like exemplified in the following description are examples, and the present invention is not limited to them, and can be changed to various embodiments without departing from the gist thereof.

<First Embodiment>
First, the resin composition according to the first embodiment of the present invention will be described.

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

  The resin composition according to the present embodiment includes a compound described in Formula (1) (hereinafter, Compound 1) and a compound described in Formula (2) (hereinafter, Compound 2) as an epoxy resin, and a curing agent including hydroquinone. It is characterized by including these.

  As described above, the resin composition described here is used for producing an intermediate product such as a resin sheet and also 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 will be 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 will be described later, and a curing agent containing Compound 1 and Compound 2 and hydroquinone, Includes a combined structure.

  When trying to increase the thermal conductivity of the cured product by orienting the polymer chain, the thermal conductivity of the cured epoxy resin is not determined only by the structure of the epoxy main agent, but is determined by the combination of the curing agent and the curing conditions. This is because the thermal conductivity of the cured resin is not determined only by the molecular arrangement of the micro polymer chains, but is strongly influenced by the macro structure in which they are assembled.

  When orientation occurs in a polymer system containing a rod-shaped mesogen such as biphenol in the main chain, the polymer chain is oriented in the same direction as the major axis direction of the mesogen. Therefore, although the thermal conductivity in the direction along the polymer chain shows a high value, the thermal conductivity in the direction orthogonal to the polymer chain is the same level as that of the non-oriented resin. This oriented polymer chain forms a domain over a wide scale of nm to μm, and exhibits a very high thermal conductivity in the orientation direction of the polymer chain within this domain. However, in a bulk resin cured product that has not been subjected to special orientation treatment, the domains are in random directions, and phonons are scattered at the domain-domain interface. The value is lower than the single orientation direction. Therefore, the decrease in the thermal conductivity between the single domain and the bulk is strongly influenced by the macro structure rather than the micro structure. That is, the larger the size of the domain contained in the cured product, the more phonon scattering at the domain-domain interface is suppressed, and thus the thermal conductivity in the bulk state increases.

  Therefore, by containing a mixture obtained by adjusting Compound 1 and Compound 2 in a specific composition range as an epoxy resin, and obtaining a resin composition containing hydroquinone as a curing agent, while maintaining the orientation of the cured resin, By suppressing the nucleation rate of the domain and relatively increasing the nucleation rate of the domain, larger domain growth can be promoted, and a highly thermally conductive resin cured product can be obtained.

  Compound 1 and Compound 2 are selected as the epoxy resin that is a constituent element of the resin composition. These two types have the effect of forcibly breaking the aggregation of the biphenyl moiety when the polymer chain is formed by reacting with hydroquinone, since the number of methylene groups is different one by one around the biphenol moiety. That is, when the polymer chain is oriented, the strong cohesive force of the mesogen part is adjusted by shifting the biphenyl part in the extending direction of the polymer chain as shown in the following formula (7), and the effect of suppressing the nucleation rate of the domain is suppressed. is there.

  When only the compound 2 is used as the epoxy resin, or when the ratio of the compound 2 is too large, a decrease in the thermal conductivity of the cured product is caused, which is not desirable. On the other hand, when the compound 2 is not included, the nucleation rate of the domain is too high, so that the thermal conductivity of the cured product is lowered. Therefore, the molar ratio of Compound 2 / Compound 1 is preferably 0.05 or more and less than 2.34, more preferably 0.11 to 1.00, and 0.25 to 0.67. Most preferred.

  Further, methylhydroquinone may be included as a curing agent in addition to hydroquinone. In particular, methylhydroquinone is useful because it can form different structures in the polymer chain depending on the direction of the methyl group when reacted with the main agent as shown in formulas (3) and (4). That is, when methylhydroquinone is bonded between A and B having different arrangements of the constituent elements in the polymer chain, two patterns are generated when the methyl group faces the A direction and when the methyl group faces the B direction. Since this acts as a mixture having a similar structure during the resin curing process, it has the effect of suppressing the nucleation rate of the domain by the melting point lowering phenomenon.

  An excessively high ratio of methylhydroquinone in the curing agent is undesirable because it causes a decrease in thermal conductivity and a decrease in the heat resistance of the cured product. Therefore, the hydroquinone / methylhydroquinone molar ratio is preferably 0.43 to 19.0, more preferably 0.66 to 4.0, and most preferably 1.0 to 2.34. .

  When these resin compositions are cured to obtain an oriented structure, the curing temperature is important. If the curing temperature is too high, the alignment structure is destroyed, and the thermal conductivity and heat resistance are greatly reduced. On the other hand, if it is too low, the curing reaction does not proceed completely, resulting in an incomplete cured product. Therefore, the curing temperature is preferably 100 ° C. to 200 ° C., more preferably 110 ° C. to 160 ° C., and most preferably 120 ° C. to 140 ° C.

  A mixture of an epoxy resin containing compound 1 and compound 2 and a curing agent containing hydroquinone has fluidity if it is 100 ° C. or higher due to a melting point drop, so that the process temperature can be lowered, and further a highly thermally conductive resin cured product Therefore, it is highly applicable to various processes and useful.

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

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

  Examples of the additive include a curing catalyst and a coupling agent. Specific examples of the curing catalyst include imidazoles and tertiary amines. Specific examples of the coupling agent include a silane coupling agent and a titanate coupling agent.

  The solvent is used for dispersing or dissolving the epoxy resin and the curing agent. This solvent is one or more of organic solvents, and specific examples of the organic solvent include methyl ethyl ketone, methyl cellosolve, methyl isobutyl ketone, dimethylformamide, propylene glycol monomethyl ether, toluene, xylene, Acetone, 1,3-dioxolane, N-methylpyrrolidone and γ-butyrolactone.

  The other curing agent is a compound containing one or more reactive groups, and the reactive groups described here are, for example, a hydroxyl group, an amino group, and a carboxyl group. Specific examples of other curing agents are phenol, amine and carboxylic acid.

  From the viewpoint of effect, it is preferable that more than half of the epoxy groups contained in the resin composition are occupied by a mixture of Compound 1 and Compound 2, and more than half of the curing agent is occupied by hydroquinone, or more than half. It is preferably occupied by a mixture of hydroquinone and methylhydroquinone. Moreover, it is preferable that the number of active hydrogens of a hardening | curing agent is contained so that it may become 50% or more with respect to the number of epoxy compounds, and it is more preferable that it is 80% or more.

The inorganic particles are one kind or two or more kinds of particulate inorganic materials. Specific examples of the inorganic particles include magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), aluminum hydroxide (Al (OH) ₃ ), boron nitride (BN), aluminum nitride ( AlN), silicon nitride (Si ₃ N ₄ ), and the like. Among them, the higher the thermal conductivity of the inorganic particles, the more advantageous it is to improve the thermal conductivity of the composite. Therefore, the thermal conductivity of the inorganic particles is desirably 30 W / (m · K) or more. Specific examples include magnesium oxide, aluminum oxide, boron nitride, silicon carbide, and silicon nitride. Among these, magnesium oxide and boron nitride are preferable as inorganic particles to be added because they are excellent in chemical stability and workability.

  This resin composition is manufactured, for example, by the following procedure.

  An epoxy compound containing compounds 1 and 2 and a curing agent containing hydroquinone are mixed. When the epoxy compound is in a lump shape, it may be pulverized before mixing. As described above, the curing agent may be pulverized before mixing. Thereby, a predetermined resin composition is obtained.

  You may use it, adding a solvent to the resin composition obtained in this way. In this case, after adding a solvent to said resin composition, a solvent is stirred using stirring apparatuses, such as a mixer. Thereby, an epoxy resin and a hardening | curing agent are disperse | distributed or melt | dissolved in a solvent.

  In addition, the resin composition may be used after being melted by heating, and if necessary, a resin composition melt may be formed using a mold or the like, and the melt may be cooled.

  According to the resin composition which concerns on this embodiment, as above-mentioned, the resin cured material which has the outstanding heat conductivity can be obtained.

    Next, the resin sheet of one embodiment of the present invention will be described. Below, the resin composition already demonstrated is called "resin composition of this invention."

  The resin sheet contains the resin composition of the present invention. The structure of this resin sheet will not be specifically limited if the resin composition of this invention is included. That is, the resin sheet may not include other components together with the resin composition, or may include other components together with the resin composition.

  FIG. 1 shows a 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 of the resin sheet 10 is not particularly limited. The configuration of the resin composition layer 1 is the same as the configuration of the resin composition of the present invention except that it is formed into a sheet shape.

  FIG. 2 shows a cross-sectional configuration of the resin sheet 20. 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 of laminated resin composition layers 1 (the number of laminated layers) is not particularly limited as long as it is two or more. In FIG. 2, the case where the number of lamination | stacking of the resin composition layer 1 is 3 layers is shown, for example. In addition, in the resin sheet 20, the structure of each resin composition layer 1 is not specifically limited. That is, the structure of the resin composition in each resin composition layer 1 may be the same or different. Of course, the structure of the resin composition in some resin composition layers 1 among the plurality of resin composition layers 1 may be the same.

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

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

  In addition, the resin composition layer 1 used for the resin sheet 30 may be only one layer or two or more layers. It is the same for the core material 2 that one layer or two or more layers may be used.

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

  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, the resin composition is formed so as to be in a sheet shape, and the resin composition layer 1 is formed. In this case, a melt of the resin composition may be molded. When molding a melt, first, the resin composition is heated to melt the resin composition. Subsequently, after molding a melt of the resin composition, the molded product is cooled.

  When using the resin composition which added the solvent, after apply | coating a resin composition on the surface of support bodies, such as a polymer film, a solvent is volatilized. Thereby, the resin composition is shape | molded in the sheet form in the surface of a support body. That is, the resin composition forms a film on the surface of the support. Therefore, the resin composition layer 1 is formed. After that, the resin composition layer 1 is peeled from the support.

  When manufacturing the resin sheet 20, the formation procedure of the above-mentioned resin composition layer 1 is repeated, and the several resin composition layer 1 is laminated | stacked. 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 as necessary. Thereby, the resin composition layers 1 adhere to each other.

  When manufacturing the resin sheet 30 having a three-layer structure, for example, the resin composition to which a solvent is added is applied to both surfaces of the core material 2 and then the solvent is volatilized. Thereby, the two resin composition layers 1 are formed so as to sandwich the core material 2. In this coating step, when the core material 2 contains a fibrous material, the surface of the core material 2 is covered with the resin composition, and a part of the resin composition is impregnated inside the core material 2. To do. Or when the core material 2 contains a non-fibrous substance, the surface of the core material 2 is coat | covered with the liquid resin composition.

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

  In addition, when manufacturing the resin sheet 30, for example, the resin composition may be heated to melt the resin composition, and then the core material 2 may be immersed in the melt. In this case, after the core material 2 is taken out from 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, when using the resin composition which added the solvent in order to manufacture the resin sheets 10-30, as mentioned above, in a solvent volatilization process, a liquid resin composition film-forms (solidifies). However, “film formation (solidification)” described here means that a substance having fluidity changes to a self-supporting state, and includes a so-called semi-cured state. That is, when the liquid resin composition forms a film, since the curing reaction is not substantially completed, the resin composition is substantially in an uncured state. For this reason, it is preferable that the solvent volatilization conditions at the time of film-forming the resin composition to which the solvent is added are conditions that do not substantially complete the curing reaction. Specifically, the drying temperature is preferably 50 ° C. to 100 ° C. and the drying time is preferably 1 minute to 120 minutes. The drying temperature is 50 ° C. to 80 ° C. and the drying time is 3 minutes to 90 minutes. More preferably.

  The conditions that do not substantially complete the curing reaction are preferable 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) for melting the resin composition are conditions that do not substantially complete the curing reaction.

  According to this resin sheet, since the above-described resin composition of the present invention is included, excellent thermal conductivity can be obtained for the same reason as that of the resin composition. Other operations and effects are the same as those of the resin composition of the present invention.

  Next, the cured resin according to an embodiment of the present invention will be described.

  The resin cured product includes a curing reaction product of the above-described resin composition, and more specifically includes a curing reaction product of Compound 1, hydroquinone, and methylhydroquinone. That is, it is characterized by including a polymer chain having a repeating structure represented by the following formula (5).

（式中のｎは２以上の整数を示し、ｍは０、または１、もしくは３を示す。式中Ｒは両方とも水素または、いずれか片方がメチル基、残りの片方が水素である。）

(In the formula, n represents an integer of 2 or more, and m represents 0, 1, or 3. In the formula, both R are hydrogen, or one of them is a methyl group and the other is hydrogen.)

  In producing this cured resin, the resin composition is heated. Thereby, since a resin composition raise | generates hardening reaction, the resin hardened | cured material which is a hardening reaction thing is obtained.

  The heating conditions such as the heating temperature and the heating time are not particularly limited, but are preferably in the above temperature range.

  According to the cured resin, since the cured reaction product of the resin composition of the present invention described above is included, excellent thermal characteristics can be obtained for the same reason as that of the resin composition. Other operations and effects are the same as those of the resin composition of the present invention.

  Next, the resin substrate of one embodiment of the present invention will be described. Hereinafter, the already explained resin sheet is referred to as “resin sheet of the present invention” and the cured resin product is referred to as “resin cured product of the present invention”.

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

  FIG. 4 illustrates a cross-sectional configuration of the resin substrate 40. 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 (resin cured product layer 3) of the resin composition layer 1, and more specifically, a single-layer body including one resin cured product layer 3.

  FIG. 5 illustrates a cross-sectional configuration of the resin substrate 50. 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 a plurality of cured reaction products (resin cured product layers 3) of the resin composition layer 1 are laminated. Is the 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. In FIG. 5, the case where the number of lamination | stacking of the resin cured material layer 3 is 3 layers is shown, for example.

  FIG. 6 illustrates a cross-sectional configuration of the resin substrate 60. This 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 material 2 is sandwiched between two resin cured product layers 3. ing.

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

  Note that the number of stacked three-layer structures (the number of stages) is not limited to three, but 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. For example, the metal layer is provided on the surface of the uppermost resin cured product layer 3 and also on the surface of the lowermost resin cured product layer 3.

  The metal layer includes, for example, any one or more of copper, nickel, aluminum, and the like. Further, the metal layer includes, for example, any one or more of metal foil and metal plate, and may be a single layer or a multilayer. Although the thickness of a metal layer is not specifically limited, For example, they are 3 micrometers-150 micrometers. The resin substrate 70 provided with this metal layer is a so-called metal-clad substrate.

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

  The resin substrate 70 provided with the metal layer may be subjected to any one type or two or more types of various processes such as an etching process and a drilling process as necessary. In this case, it is good also as a multilayer board | substrate by overlapping the resin substrate 70, the metal layer to which the above-mentioned various processes were performed, and any 1 type or 2 types or more of the resin sheets 10-30.

  As described above, the metal layer may be provided, or the multilayer substrate may be used as well as the resin substrates 40 to 60 described above.

  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. 4, the resin curing that is a curing reaction product of the resin composition layer 1. The physical 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, the cured reaction products of the plurality of resin composition layers 1 are used as shown in FIG. 5. A plurality of cured resin layers 3 are formed.

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

  FIG. 8 shows a cross-sectional configuration corresponding to FIG. When manufacturing this resin substrate 70, first, as shown in FIG. 8, three resin sheets 30 are laminated. Thereby, the laminated body of the three resin sheets 30 is obtained. Thereafter, 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, the resin composition is formed on both surfaces of each core material 2 as shown in FIG. A cured resin layer 3 that is a cured reaction product of the layer 1 is formed.

  Here, when using the melt of a resin composition in order to manufacture the resin sheets 10-30, as mentioned above, it avoids that a curing reaction is substantially completed at the time of the melting of a resin composition. 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.

  According to this resin substrate, since the cured resin of the present invention is included, excellent thermal characteristics can be obtained for the same reason as that of the cured resin. Other operations and effects are the same as those of the cured resin product of the present invention.

<Second Embodiment>
Next, the resin composition according to the second embodiment of the present invention will be described. The resin composition according to the present embodiment includes the same elements as those of the resin composition according to the first embodiment. For this reason, the following description will be made on portions that are different from the first embodiment. Note that the cured resin, the resin sheet, and the cured resin according to the present embodiment also include the same elements as those in the first embodiment, and hence the description thereof will be omitted.

  The resin composition according to the present embodiment is different from the first embodiment in that it includes a compound described in Formula (8) (hereinafter, Compound 3) instead of Compound 2.

  The two types of Compound 1 and Compound 3 have two different methylene groups centered on the biphenol part, and therefore, when the polymer chain is formed by reacting with hydroquinone as in the first embodiment, the biphenyl part is aggregated. Has the effect of forcibly breaking. That is, by shifting the biphenyl moiety in the direction of elongation of the polymer chain, the strong cohesive force of the mesogen moiety is adjusted, and the domain nucleation rate is suppressed.

  When only the compound 3 is used as the epoxy resin, or when the ratio of the compound 3 is too large, it causes a decrease in the thermal conductivity of the cured product, which is not desirable. On the other hand, when the compound 3 is not included, the nucleation rate of the domain is too high, so that the thermal conductivity of the cured product is lowered. Therefore, the molar ratio of compound 3 / compound 1 is preferably 0.05 or more and less than 2.34, more preferably 0.11 to 1.00, and preferably 0.25 to 0.67. Most preferred.

  According to the resin composition which concerns on this embodiment, as above-mentioned, the resin cured material which has the outstanding heat conductivity can be obtained.

<Third Embodiment>
Next, the resin composition according to the third embodiment of the present invention will be described. Since the resin composition according to the present embodiment also includes the same elements as those of the resin composition according to the first embodiment as in the second embodiment, parts different from the first embodiment will be described.

  The resin composition according to the present embodiment is different from the first embodiment in that the resin composition includes a compound 2 instead of the compound 1 and includes a compound 3 instead of the compound 2.

  The two types of compound 2 and compound 3 have three different numbers of methylene groups centering on the biphenol moiety, so that when the polymer chain is formed by reacting with hydroquinone as in the first embodiment, the aggregation of the biphenyl moiety Has the effect of forcibly breaking. That is, by shifting the biphenyl moiety in the direction of elongation of the polymer chain, the strong cohesive force of the mesogen moiety is adjusted, and the domain nucleation rate is suppressed.

  When only the compound 2 or 3 is used as the epoxy resin, or when the ratio of the compound 2 or 3 is too large, the thermal conductivity of the cured product is lowered, which is not desirable. On the other hand, when either compound 2 or 3 is not included, the nucleation rate of the domain is too high, so that the thermal conductivity of the cured product is lowered. Therefore, the molar ratio of compound 3 / compound 2 is preferably 0.05 or more and less than 2.34, more preferably 0.11 to 1.00, and 0.25 to 0.67. Most preferred.

  According to the resin composition which concerns on this embodiment, as above-mentioned, the resin cured material which has the outstanding heat conductivity can be obtained.

<Fourth Embodiment>
Next, the resin composition according to the fourth embodiment of the present invention will be described. Since the resin composition according to the present embodiment also includes the same elements as those of the resin composition according to the first embodiment as in the second and third embodiments, the difference from the first embodiment. explain.

  The resin composition according to this embodiment differs from the first embodiment in that it includes all of Compound 1, Compound 2, and Compound 3.

  The three types of Compound 1, Compound 2, and Compound 3 differ in the number of methylene groups by 1 to 3 centering on the biphenol part, so that when the polymer chain is formed by reacting with hydroquinone, the biphenyl part is aggregated. It has the effect of forcibly breaking. That is, when the polymer chain is oriented, the strong cohesive force of the mesogenic part is adjusted by shifting the biphenyl part in the direction of elongation of the polymer chain as shown in the formula (7), and the effect of suppressing the nucleation rate of the domain is obtained. .

  When the molar ratio of Compound 1, Compound 2, and Compound 3 is a: b: c (Compound 1: Compound 2: Compound 3), the resin composition of this embodiment is a composition diagram of these three components ( In FIG. 9), the composition ranges of (a, b, c) are A (0.30, 0, 0.70), B (0.95, 0, 0.05), C (0.95, 0.05, 0), D (0.30, 0.70, 0), E (0, 0.70, 0.30), F (0, 0.30, 0.70) It is characterized by being in an enclosed area. If it deviates from the above region, the thermal conductivity of the cured product will decrease.

  According to the resin composition which concerns on this embodiment, as above-mentioned, the resin cured material which has the outstanding heat conductivity can be obtained.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention.

  Embodiments of the present invention will be described in detail.

(Examples 1-10, Comparative Examples 1-5)
A resin composition was produced by the procedure described below, and the resulting resin composition was heated to prepare a cured resin product.

  First, an epoxy resin, a curing agent, and an additive (curing catalyst) were mixed. In this case, the mixing ratio of the epoxy resin and the curing agent is such that the ratio between the number of epoxy groups contained in the epoxy resin and the number of active hydrogens contained in the curing agent is 1: 1. Was adjusted to prepare a resin composition. The obtained resin composition was melt-mixed on a 150 ° C. hot plate and then heated for 3 hours in a dryer at 120 ° C. to be cured.

  As the epoxy resin, Compound 1 and Compound 2 were used. As the curing agent, hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and methylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were used. The types of epoxy resin and curing agent and the content (parts by mass) in the mixture are as shown in Table 1. As the curing catalyst, N, N-dimethyl-m-anisidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and the amount added was 0.5 mol% with respect to the total number of epoxy groups contained in the epoxy resin.

  Compound 1 represented by the above formula (1) was synthesized according to a conventional method. 4,4′-biphenol (25.0 g, 0.134 mol) was dissolved in acetone (1 L) and 1-bromo-3-butene (52.3 g, 0.402 mol) and potassium hydroxide (22.5 g, 0.24 mol) were dissolved. 402 mol) was added and refluxed for 14 hours. The solvent was removed from the reaction mixture, and the resulting solid was washed with methanol to obtain 34.3 g of the target olefin represented by the following formula (6).

  The obtained olefin (34.3 g, 0.117 mol) was dissolved in dichloromethane (1 L) and cooled to 0 ° C. MCPBA (containing about 30% water, 86.6 g) was added thereto, and the temperature was raised to room temperature while stirring. Thereafter, stirring was continued for 6 hours. The obtained reaction mixture was diluted with methanol, and the dichloromethane content was distilled off. The produced precipitate was collected by filtration and washed repeatedly with methanol. The yield of compound 1 described in the above formula (1) as a white powder was 34.0 g, and the yield was 89%.

  Compound 2 represented by the above formula (2) was synthesized according to a conventional method. 4,4'-biphenol (25.0 g, 0.134 mol) was dissolved in epichlorohydrin (200 mL), and potassium hydroxide (16 g) was added to reflux for 14 hours. Epichlorohydrin was distilled off from the reaction mixture. Water was poured into the reaction mixture to make a slurry, and then the solid was collected by filtration. The obtained solid was washed with methanol and dried. The obtained crude was recrystallized from hot acetone to obtain the desired product. The yield was 34.8 g, and the yield was 87%.

  The thermal conductivity of the cured product was calculated by multiplying the thermal diffusivity, specific heat, and density. For the measurement of the thermal diffusivity, a xenon flash method thermal diffusivity measuring device TD-1 HTV (manufactured by Advance Riko Co., Ltd.) was used. Specific heat (25 degreeC) was calculated | required using MDSC Q2000 (made by TA Instrumental). The density was determined by the Archimedes method. Table 1 shows the measurement results of thermal conductivity.

  By using the resin composition of the present invention, a cured resin product having a high thermal conductivity of 0.4 W / (m · K) or more was obtained.

  Among them, a cured product having a particularly high thermal conductivity is obtained when a mixture of compound 2 / compound 1 having a molar ratio of 0.43 and 1.00 as an epoxy resin and hydroquinone are used as curing agents (Examples 2 and 3). Obtained.

  Further, when an epoxy resin is used, a mixture having a molar ratio of Compound 2 / Compound 1 of 1.00 and a curing agent in which the molar ratio of hydroquinone / methylhydroquinone is 19.0 and 1.00 are used (Example 5, Similarly, in 6), a cured product having high thermal conductivity was obtained.

  When the compound 1 or the compound 2 was used as the epoxy resin, the thermal conductivity was low (Comparative Examples 1 and 2).

  Further, when the molar ratio of Compound 2 / Compound 1 was 2.34 or more, the thermal conductivity was low (Comparative Example 3).

  When aluminum oxide (76 wt%, 50 vol%) is added as inorganic particles to the resin composition of the present invention (Example 8), or when magnesium oxide (74.1 wt%, 50 vol%) is added (Example 9) ), Magnesium oxide (52.8 wt%, 40 vol%) and boron nitride (15.7 wt%, 10 vol%) were mixed and added (Example 10), and all showed high thermal conductivity.

  Even when aluminum oxide (76 wt%, 50 vol%) was added to the resin composition having a compound 2 / compound 1 molar ratio of 2.34 or more, a composite exhibiting high thermal conductivity was not obtained (Comparative Example 4). .

(Comparative Example 5)
After using methylhydroquinone instead of hydroquinone as a curing agent, the resin composition was cured under the same conditions as in Examples 1 to 10 at the contents shown in Table 1. As a result of measuring the thermal conductivity by the same method, it was a low value of 0.32 W / (m · K).

  From the results shown in Table 1, an epoxy resin cured product having high thermal conductivity is obtained by using Compound 1 and Compound 2 as epoxy resins and hydroquinone and methylhydroquinone as curing agents in combination within an appropriate composition range. Obtained.

(Example 11)
For the resin substrate 50 shown in FIG. 5, a resin composition was prepared under the same conditions as in Example 2, and then a solvent (methyl ethyl ketone) was added and the solvent was stirred. Thereby, since the epoxy resin and the curing agent were dissolved in the solvent, a liquid resin composition was obtained. In this case, the concentration of the solid content (curing agent) was 65% by mass.

  Subsequently, after applying a liquid resin composition to the surface of the support (PET film, thickness = 0.05 mm), the liquid resin composition was dried (temperature = 80 ° 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 was a single layer body shown in FIG. 1 was obtained. After that, the resin sheet 10 was peeled from the support.

  Subsequently, ten resin sheets 10 were stacked to produce a resin sheet 20 (the number of laminated resin composition layers 1 = 10 layers), which is the laminate shown in FIG. Finally, the laminate is heated (temperature = 110 ° C.) and pressurized (pressure = 1 MPa, time = 20 minutes) using a flat plate press, and then the laminate is further heated (temperature = 130 ° C.) and pressurized (temperature = 130 ° C.). Pressure = 4 MPa, time = 1 hour). In this heating process, since the reaction of the resin composition was substantially completed in each resin composition layer 1, a cured resin layer 3 containing a cured reaction product of the resin composition was formed. Thus, the resin substrate 50 (the number of laminated resin cured product layers 3 = 10 layers, thickness = 0.9 mm) was completed.

  The produced resin substrate had a thermal conductivity of 0.49 W / m · K, and a resin substrate having a high thermal conductivity was obtained.

Example 12
A resin substrate was produced from the resin composition described in Example 8 under the same conditions as in Example 11. The produced aluminum oxide-containing resin substrate had a thermal conductivity of 3.04 W / m · K, and a resin substrate having a high thermal conductivity was obtained.

(Examples 13 to 19)
Next, Examples and Comparative Examples using Compound 1 and Compound 3 as epoxy resins will be described in detail only for parts different from Example 1. The types of epoxy resin and curing agent and the content (parts by mass) in the mixture are as shown in Table 2.

  Compound 3 represented by the above formula (8) was synthesized as follows. 4,4′-Biphenol (10.0 g, 0.054 mol) was dissolved in acetone (200 mL) and 1-bromo-6-chloromethane (43.0 g, 0.216 mol) and potassium carbonate (16.3 g, 0. 118 mol) 18-crown 6-ether was added in a catalytic amount and refluxed for 24 hours. The solvent was removed from the reaction mixture, and the obtained solid was washed with methanol to obtain 21.7 g of the desired halide represented by the following formula (9).

  The obtained halide (18.6 g, 0.044 mol) was dissolved in anhydrous toluene (500 ml), and potassium t-butoxide (15.1 g, 0.135 mol) and a catalytic amount of 18-crown 6-ether were added for 2 hours. Refluxed. Thereafter, a small amount of water was added at room temperature and refluxed for 1 hour to convert unreacted halide into alcohol. The solvent was removed from the reaction mixture, and the obtained solid was purified by silica gel column chromatography (hexane: chloroform = 1: 1) to obtain 15.4 g of the target olefin represented by the following formula (10).

  The obtained olefin (15.4 g, 0.044 mol) was dissolved in dichloromethane (400 mL) and cooled to 0 ° C. MCPBA (containing about 30% water, 43.3 g) was added thereto, and the temperature was raised to room temperature while stirring. Thereafter, stirring was continued for 6 hours. The obtained reaction mixture was diluted with methanol, and the dichloromethane content was distilled off. The produced precipitate was collected by filtration and washed repeatedly with methanol. The yield of the compound described in the above formula (8) as a white powder was 13.8 g, and the yield was 91.4%.

  As shown in Table 2, also in Examples 13 to 19, a cured resin product having a high thermal conductivity of 0.4 W / (m · K) or more was obtained by using the resin composition of the present invention.

(Comparative Example 6)
On the other hand, when a resin composition containing compound 3 excessively more than compound 1 was used, a cured resin product having a high thermal conductivity of 0.4 W / (m · K) or more was not obtained.

(Examples 20 to 24)
Next, Examples and Comparative Examples using Compound 2 and Compound 3 as the epoxy resin will be described in detail only for parts different from Example 1. Compound 3 was prepared in the same manner as Compound 3 used in Examples 13-19. The types of epoxy resin and curing agent and the content (parts by mass) in the mixture are as shown in Table 2.

  As shown in Table 2, also in Examples 20 to 24, a cured resin product having a high thermal conductivity of 0.4 W / (m · K) or more was obtained by using the resin composition of the present invention.

(Comparative Examples 7 and 8)
On the other hand, when a resin composition containing too much compound 3 than compound 2 or a resin composition containing too much compound 2 relative to compound 3 is used, it is as high as 0.4 W / (m · K) or more. A cured resin product showing thermal conductivity was not obtained.

(Comparative Example 9)
In addition, also when using only the compound 3 and using the resin composition which does not contain both the compound 1 and the compound 2, a resin cured product showing a high thermal conductivity of 0.4 W / (m · K) or more is obtained. There wasn't.

(Examples 25-30)
Next, Examples and Comparative Examples using all of Compound 1, Compound 2, and Compound 3 as epoxy resins will be described in detail only for parts different from Example 1. The types of epoxy resin and curing agent and the content (parts by mass) in the mixture are as shown in Table 3.

  In FIG. 9, Examples 25 to 30 are plotted as ●, and Comparative Examples 10 and 11 as ◯. When the molar ratio of the three components of Compound 1, Compound 2, and Compound 3 is a: b: c (a + b + c = 100), respectively, (a, b, c) on the composition diagram (FIG. 9) of these three components ) Have a composition range of A (0.30, 0, 0.70), B (0.95, 0, 0.05), C (0.95, 0.05, 0), D (0. 30, 0.70, 0), E (0, 0.70, 0.30), and F (0, 0.30, 0.70). The region surrounded by is not including the hexagonal line determined by the point ABCDEF.), And a cured resin product having a high thermal conductivity of 0.4 W / (m · K) or more was obtained.

(Comparative Examples 10 and 11)
When a resin composition in which the molar ratio of the three components of Compound 1, Compound 2, and Compound 3 is outside the region surrounded by the point ABCDEF is used, a high thermal conductivity of 0.4 W / (m · K) or more. The cured resin product showing the rate was not obtained.

  While the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the modes described in the embodiments and examples, and various modifications can be made.

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

Claims (7)

An epoxy compound represented by the formula (1), another epoxy compound represented by the formula (2) or (8), and a curing agent containing hydroquinone, the epoxy compound and the other epoxy compound, The resin composition whose molar ratio (other epoxy / epoxy) is 0.05 or more and less than 2.34.

A first epoxy compound represented by the formula (1);
A second epoxy compound represented by the formula (2);
A third epoxy compound represented by formula (8);
A curing agent containing hydroquinone, and
When the molar ratio of the first epoxy compound, the second epoxy compound, and the third epoxy compound is a: b: c (first epoxy: second epoxy: third epoxy) In addition,
The composition range of (a, b, c) on the three component composition diagram is
A (0.30, 0, 0.70),
B (0.95, 0, 0.05);
C (0.95, 0.05, 0),
D (0.30, 0.70, 0),
E (0, 0.70, 0.30),
A resin composition which is a region surrounded by F (0, 0.30, 0.70).
(However, the region surrounded by the point ABCDEF does not include the hexagonal line determined by the point ABCDEF.)

The epoxy compound represented by Formula (2), the other epoxy compound represented by Formula (8), and the hardening | curing agent containing hydroquinone, The molar ratio of the said epoxy compound and the said other epoxy compound ( Resin composition whose other epoxy / epoxy) is 0.4 or more and less than 2.34.

  The resin according to any one of claims 1 to 3, wherein the curing agent includes methylhydroquinone, and a molar ratio of the hydroquinone to the methylhydroquinone (hydroquinone / methylhydroquinone) is 0.4 to 19.0. Composition.   A cured resin obtained by curing the resin composition according to any one of claims 1 to 4.   The resin sheet containing the resin composition as described in any one of Claims 1-4.   A resin substrate obtained by laminating one or more of the resin sheets according to claim 6 and molding and curing them.

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