JP2019176146A - Method for manufacturing component built-in board, component built-in board, adhesive sheet, and resin composition - Google Patents

Abstract

SOLUTION: A method for manufacturing a component built-in board having at least an interlayer insulator layer, and electronic components 13a, 13b disposed on one face of the interlayer insulator layer, the method comprising at least: an adhesive sheet preparation step of preparing an adhesive sheet 1 having at least an adhesive layer 3a; a temporarily fixing step of tentatively fixing the electronic components to the adhesive layer of the adhesive sheet; and a hardening step of hardening the adhesive layer into an interlayer insulator layer 3b, where the adhesive layer contains a resin composition, the resin composition has a resin flow rate of 80% or more and a hardened product after hardening has a glass transition temperature of 175°C or higher.EFFECT: It is possible to reduce void generation when mounting electronic components on an adhesive sheet.SELECTED DRAWING: Figure 3

Description

  Embodiments of the present disclosure relate to a method for manufacturing a component-embedded substrate, a component-embedded substrate, for example, an adhesive sheet used for fixing an electronic component of the component-embedded substrate and an interlayer insulating layer, and a resin composition.

  In recent years, electronic devices have been required to have higher density in the trend of downsizing and multifunctionalization of electronic devices. From this point of view, the wiring board is also required to cope with high density. In order to meet such demands, a component-embedded substrate in which electronic components are embedded in a wiring substrate has been actively developed.

  Various methods are known as a method for manufacturing a component-embedded substrate. For example, methods for temporarily fixing an electronic component using an adhesive sheet are disclosed (for example, Patent Documents 1 and 2). In this method, the adhesive sheet is used for temporarily fixing an electronic component and is used as an insulating layer after curing.

  For example, Patent Document 2 discloses a thermosetting resin composition used for component fixing and insulating layer formation of a component-embedded substrate, specifically, an epoxy resin that is liquid at 25 ° C., an epoxy group, It contains an acrylic resin containing one or more groups selected from a hydroxyl group and a carboxyl group, a phenolic curing agent, and an inorganic filler, and the content of the inorganic filler is the non-volatile content of the thermosetting resin composition. A thermosetting resin composition of 20 to 70% by weight when disclosed as 100% by weight is disclosed.

  In the component-embedded substrate, a heat load is applied to the built-in electronic component and the circuit around the electronic component. In addition, the component-embedded substrate is also required to have excellent high-frequency transmission characteristics. When a high-frequency signal is transmitted to a circuit, transmission loss due to a conductor or a dielectric increases and a thermal load is applied. Therefore, the adhesive sheet is required to have high heat resistance after curing.

  For example, Patent Document 3 discloses a resin composition used for a semiconductor sealing material and an insulating layer of a circuit board. Specifically, for the purpose of improving heat resistance, an epoxy resin and a curing agent are disclosed. And an inorganic filler, wherein the epoxy resin is a polycyclic aromatic epoxy resin containing a biphenyl structure, an anthracene structure or a naphthalene structure, the curing agent is an aromatic amine, and contains an inorganic filler A resin composition having an amount of 30 to 85% by volume is disclosed.

Japanese Patent No. 4551468 Japanese Patent No. 57771988 Japanese Patent No. 5558885

  In the method of temporarily fixing an electronic component using the adhesive sheet as described above, the electronic component is temporarily fixed using the adhesiveness of the adhesive sheet by pressing the electronic component against the adhesive sheet. However, as described in Patent Documents 2 and 3, when an inorganic filler is contained in the resin composition, the adhesiveness may be lowered and it may be difficult to fix the electronic component.

  In addition, in the method of temporarily fixing an electronic component using the above adhesive sheet, voids (voids) are generated in the adhesive sheet, between the adhesive sheet and the substrate, or between the adhesive sheet and the electronic component. There's a problem. In particular, when unevenness exists on the surface of the electronic component in contact with the adhesive sheet, generation of voids between the adhesive sheet and the electronic component becomes significant. Voids may swell in subsequent processes, causing peeling and short-circuiting, reducing reliability of interlayer connection, adhesiveness of adhesive sheet after curing, and insulating property of adhesive sheet (insulating layer) after curing . Therefore, reduction of voids is desired.

  However, as described in Patent Documents 2 and 3, when an inorganic filler is contained in the resin composition, the adhesiveness decreases, so the adhesion between the adhesive sheet and the substrate or electronic component decreases, Voids may occur. Also, if a large amount of inorganic filler is added to the resin composition, the melt viscosity will increase and the fluidity during heating will decrease, making it difficult for the adhesive sheet to follow the surface of the substrate or electronic component, resulting in voids. It becomes easy to do.

Patent Document 2 exemplifies phenol novolac resins and cresol novolac resins as phenolic curing agents, but in phenol novolac resins and cresol novolac resins, the melt viscosity increases as the number of repeating units increases. Since the fluidity at the time of heating is lowered, it becomes difficult for the adhesive sheet to follow the adherend surface of the substrate or electronic component, and voids are likely to occur. Moreover, since a phenol type hardening | curing agent will advance reaction gradually also at normal temperature, it lacks storage stability.
Therefore, there has been a demand for a manufacturing method that can reduce the generation of voids when temporarily fixing an electronic component on an adhesive sheet when manufacturing a component-embedded substrate.

  The present disclosure has been made in view of the above-described problems, and can reduce the generation of voids, and can provide a highly reliable component-embedded substrate manufacturing method and component-embedded substrate. The main object is to provide a substrate and an adhesive sheet and a resin composition that have high heat resistance and can be used for such a component-embedded substrate.

  In order to solve the above-described problems, the present disclosure is a method for manufacturing a component-embedded substrate that manufactures a component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer. An adhesive sheet preparing step of preparing an adhesive sheet having at least an adhesive layer, a temporary fixing step of temporarily fixing an electronic component to the adhesive layer of the adhesive sheet, and a curing step of curing the adhesive layer to form an interlayer insulating layer The adhesive layer contains a resin composition, the resin composition has a resin flow rate of 80% or more, and the cured product has a glass transition temperature of 175 ° C. or more. A method for manufacturing a component-embedded substrate is provided.

  Further, the present disclosure is a method for manufacturing a component-embedded substrate that includes at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer, and includes at least an adhesive layer. There are at least an adhesive sheet preparing step for preparing an adhesive sheet, a temporary fixing step for temporarily fixing an electronic component to the adhesive layer of the adhesive sheet, and a curing step for curing the adhesive layer to form an interlayer insulating layer. The adhesive layer contains a resin composition, and the resin composition includes an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, and the epoxy resin Includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolak skeleton, and the curing accelerator is at 23 ° C. Body is a imidazole compound, to provide a method for manufacturing a component-embedded substrate.

  Furthermore, the present disclosure is a component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer, wherein the interlayer insulating layer contains a cured product of the resin composition And the said resin composition provides the component built-in board whose resin flow rate is 80% or more and whose glass transition temperature of the said hardened | cured material is 175 degreeC or more.

  Further, the present disclosure provides a component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer, wherein the interlayer insulating layer includes an epoxy resin and an epoxy-modified silicone resin. And a cured product of a resin composition comprising an acrylic resin, a latent curing agent, and a curing accelerator, wherein the epoxy resin is at least selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton The epoxy resin (A) which has one, and the said hardening accelerator is a solid imidazole compound at 23 degreeC, and provides the component built-in board | substrate.

  Furthermore, the present disclosure is an adhesive sheet used for fixing an electronic component of a component-embedded substrate and an interlayer insulating layer, having at least an adhesive layer, the adhesive layer containing a resin composition, and the resin composition The product provides an adhesive sheet having a resin flow rate of 80% or more and a glass transition temperature of a cured product of the resin composition of 175 ° C. or more.

  Furthermore, the present disclosure is an adhesive sheet having at least an adhesive layer, and the adhesive layer includes an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, The epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton, and the curing accelerator is an imidazole compound that is solid at 23 ° C. Provide a sheet.

  Further, the present disclosure is a resin composition used for fixing electronic components and interlayer insulating layers of a component-embedded substrate, wherein the resin flow rate is 80% or more, and the glass transition temperature of the cured product is 175 ° C. or more. A resin composition is provided.

  Furthermore, the present disclosure provides a resin composition including an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, wherein the epoxy resin includes a naphthalene skeleton, an anthracene A resin composition comprising an epoxy resin (A) having at least one selected from the group consisting of a skeleton and a novolak skeleton, wherein the curing accelerator is an imidazole compound that is solid at 23 ° C.

  According to the present disclosure, when used as an adhesive layer before curing, the tackiness and fluidity are high, and when functioning as an interlayer insulating layer after curing, a resin composition having high heat resistance is used as an adhesive sheet. It is possible to reduce the generation of voids, and it is possible to produce a highly reliable component-embedded substrate.

It is a schematic sectional drawing which shows an example of the adhesive sheet of this indication. It is a schematic sectional view showing an example of a component built-in substrate of this indication. It is process drawing which shows an example of the manufacturing method of the component built-in board | substrate of this indication. It is process drawing which shows an example of the manufacturing method of the component built-in board | substrate of this indication. It is a schematic sectional drawing which shows another example of the component built-in board | substrate of this indication. It is process drawing which shows the other example of the manufacturing method of the component built-in board | substrate of this indication. It is process drawing which shows the other example of the manufacturing method of the component built-in board | substrate of this indication. It is explanatory drawing for demonstrating the measuring method of a resin flow rate.

  Hereinafter, the resin composition, the adhesive sheet, the component built-in substrate, and the method for producing the component built-in substrate of the present disclosure will be described in detail.

A. Resin Composition There are two embodiments of the resin composition of the present disclosure. Each will be described below.

A-1. 1st embodiment The resin composition of this aspect is a resin composition containing an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, , An epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolak skeleton, and the curing accelerator is an imidazole compound that is solid at 23 ° C.

  In this embodiment, the epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton, and the epoxy resin (A) has a rigid skeleton. Therefore, the heat resistance after curing of the resin composition can be improved. In this embodiment, since the latent curing agent and the curing accelerator are used in combination, the curing reaction of the epoxy resin can be promoted, and the heat resistance after curing of the resin composition can be further improved. When a component-embedded substrate is produced using the resin composition of this embodiment, the resin composition of this embodiment is used as an interlayer insulating layer of the component-embedded substrate after curing. Therefore, since the resin composition of this embodiment can improve the heat resistance after curing, an interlayer insulating layer having excellent heat resistance can be obtained.

  In this embodiment, an imidazole compound that is solid at 23 ° C. is included as a curing accelerator. Here, the imidazole compound acts as a catalyst in the curing reaction of the epoxy resin. Since the imidazole compound used in this embodiment is solid at 23 ° C., it is less likely to come into contact with an epoxy resin or a latent curing agent at room temperature than a liquid imidazole compound at 23 ° C., and changes to a liquid state upon heating. By doing so, since the curing reaction occurs actively, the start of the reaction can be delayed. Therefore, the time until the reaction starts can be lengthened, and the flexibility and fluidity during heating can be improved.

  Therefore, when the epoxy resin has a rigid structure, the softening point of the resin composition is high, and the melt viscosity tends to be high. In this embodiment, the flexibility and fluidity during heating can be ensured despite the fact that the epoxy resin (A) having a rigid structure is included. Therefore, when producing a component-embedded substrate using an adhesive sheet having an adhesive layer containing the resin composition of this aspect, it is possible to suppress the generation of voids between the adhesive layer and the electronic component. is there. In addition, for example, even when unevenness is present on the surface of the electronic component that contacts the adhesive layer, it is possible to suppress the generation of voids between the adhesive layer and the electronic component. Furthermore, in the case of manufacturing a component-embedded substrate using an adhesive sheet having an adhesive layer containing the resin composition of this aspect, when the adhesive layer is disposed on one surface of the substrate, the adhesive layer is attached to the substrate. Since it becomes easy to adhere | attach on a surface, it can suppress that a void generate | occur | produces between an adhesion layer and a board | substrate. Therefore, peeling and short-circuit due to voids can be suppressed, and reliability of interlayer connection, adhesiveness of the adhesive layer after curing, and insulating property of the adhesive layer (interlayer insulating layer) after curing can be improved.

  Thus, in this embodiment, since the curing accelerator is an imidazole compound that is solid at 23 ° C., it has a high potential at normal temperature and does not accelerate the curing reaction, but promotes the curing reaction at a high temperature. It is possible to suppress the generation of voids while increasing the.

Moreover, in this aspect, water resistance can be improved by including an epoxy-modified silicone resin.
Furthermore, in this aspect, when an acrylic resin is contained, when the resin composition of this aspect is used for an adhesive sheet, applicability and film-forming property can be improved.

  In general, since the epoxy-modified silicone resin is liquid at room temperature, the flexibility of the resin composition can be increased by including the epoxy-modified silicone resin in this embodiment. Therefore, when the epoxy resin has a rigid skeleton, the glass transition temperature tends to be high and the tackiness tends to be reduced. However, the resin composition contains an epoxy-modified silicone resin that is liquid at room temperature. Can improve the tackiness. Therefore, when manufacturing a component-embedded substrate using an adhesive sheet having an adhesive layer containing the resin composition of this embodiment, an electronic component can be attached to the surface of the adhesive layer at room temperature.

  Here, in the component-embedded substrate, high positional accuracy is required with the increase in the density of electronic components. As a method for manufacturing a component-embedded substrate, for example, a method of temporarily fixing an electronic component using an adhesive sheet or an adhesive sheet is known, but in a method of temporarily fixing an electronic component using an adhesive sheet, the electronic component is When sealing with resin after temporary fixing, the position of the electronic component may be shifted or tilted by the flow of the resin. Moreover, in the method of temporarily fixing an electronic component using an adhesive sheet, the adhesive sheet is melted when temporarily fixing the electronic component while heating the adhesive sheet, or when the adhesive sheet is cured after temporarily fixing the electronic component. There is a possibility that the position of the electronic component is shifted or tilted due to curing shrinkage of the adhesive sheet.

  On the other hand, in this embodiment, since the epoxy resin (A) has a rigid structure, molecular motion is suppressed, so that curing shrinkage can be suppressed. Therefore, an adhesive layer containing the resin composition of this embodiment When a component-embedded substrate is manufactured using an adhesive sheet having the above, position displacement of an electronic component due to curing shrinkage of the adhesive layer can be suppressed. In addition, as described above, since the electronic component can be attached to the surface of the adhesive layer at room temperature, it is not necessary to heat the adhesive layer when placing the electronic component on the surface of the adhesive layer. It is possible to avoid displacement of the electronic component due to melting. In addition, since the resin composition of this embodiment is thermosetting, the adhesive layer is thermally cured before sealing the electronic component with the resin, thereby improving the adhesion between the cured adhesive layer and the electronic component. Therefore, unlike the pressure-sensitive adhesive sheet, when the electronic component is sealed with a resin, it is possible to suppress the displacement of the electronic component due to the flow of the resin. For this reason, it is possible to suppress displacement of the electronic component. Therefore, by using the resin composition of this aspect, it is possible to obtain a component-embedded substrate with high reliability.

  Therefore, by using the resin composition of this embodiment, it is possible to obtain a component-embedded substrate that is excellent in heat resistance, and further excellent in positional accuracy of electronic components and has high reliability.

  Hereinafter, each component of the resin composition of this embodiment will be described.

1. Epoxy resin The epoxy resin contained in the resin composition of the present embodiment includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton.

  The epoxy resin (A) only needs to have at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton. For example, the epoxy resin (A) may have only a naphthalene skeleton, May have only a novolak skeleton, may have a naphthalene skeleton and a novolak skeleton, or may have an anthracene skeleton and a novolak skeleton.

  The epoxy resin (A) having a naphthalene skeleton is one having one or more naphthalene skeletons and one or more epoxy groups or glycidyl groups in one molecule, and a latent curing agent and a curing accelerator; Any combination may be used as long as it causes a crosslinking polymerization reaction and cures. The epoxy resin (A) having a naphthalene skeleton includes not only a prepolymer but also a monomer type epoxy compound. Examples of the epoxy resin (A) having a naphthalene skeleton include naphthol type epoxy resins, naphthalene diol type epoxy resins, bisnaphthol type epoxy resins, and naphthol aralkyl type epoxy resins.

  Among them, the epoxy resin (A) having a naphthalene skeleton is a dimer and preferably has four epoxy groups or glycidyl groups in one molecule, that is, is tetrafunctional. It is considered that the epoxy resin (A) having such a naphthalene skeleton can increase the crosslinking density and improve the heat resistance after curing.

  As an epoxy resin (A) having an anthracene skeleton, one molecule having one or more anthracene skeletons and one or more epoxy groups or glycidyl groups, a latent curing agent and a curing accelerator, Any combination may be used as long as it causes a crosslinking polymerization reaction and cures. Examples of the epoxy resin (A) having an anthracene skeleton include monomeric epoxy compounds.

  The epoxy resin (A) having a novolak skeleton is one having one or more novolak skeletons and one or more epoxy groups or glycidyl groups in one molecule, and a latent curing agent and a curing accelerator, Any combination may be used as long as it causes a crosslinking polymerization reaction and cures. Examples of the epoxy resin (A) having a novolak skeleton include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a bisphenol F novolak type epoxy resin, a naphthalene-containing novolak type epoxy resin, and an anthracene containing novolak. Type resin, brominated phenol novolac type epoxy resin, alkylphenol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, biphenyl novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin , Triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, phenol aralkyl type epoxy resin, Off tall aralkyl type epoxy resins.

  Especially, it is preferable that the epoxy resin (A) which has a novolak skeleton is a triphenylmethane type epoxy resin. The triphenylmethane type epoxy resin can increase the crosslink density because of its high rigidity and the large number of functional groups per molecule among the epoxy resins (A) having the novolak skeleton. The heat resistance after curing of the resin composition can be improved. Thereby, when the resin composition of this aspect is used for the interlayer insulation layer of a component built-in board, the component built-in board excellent in heat resistance can be obtained.

Among examples of the epoxy resin (A) having the novolak skeleton, a naphthalene-containing novolak epoxy resin, a naphthol aralkyl epoxy resin, a naphthol-phenol co-condensed novolac epoxy resin, a naphthol-cresol co-condensed novolac epoxy resin, and the like An epoxy resin having a naphthalene skeleton and a novolak skeleton.
In addition, among the examples of the epoxy resin (A) having the novolac skeleton, the anthracene-containing novolac epoxy resin is an epoxy resin having an anthracene skeleton and a novolac skeleton.

  An epoxy resin (A) may be used independently and may be used 2 or more types.

The epoxy resin (A) may have one or more epoxy groups or glycidyl groups in one molecule, but usually has two or more epoxy groups or glycidyl groups in one molecule. That is, it is a bifunctional or higher functional epoxy resin.
Among these, when the epoxy resin (A) has at least one of a naphthalene skeleton and a novolak skeleton, it is preferably a trifunctional or higher functional epoxy resin. The trifunctional or higher functional epoxy resin (A) can increase the crosslink density and can further improve the heat resistance after curing. Moreover, it is thought that the epoxy resin (A) more than trifunctional functions as a tackifier, and can improve the adhesiveness before hardening of a resin composition. That is, by including the trifunctional or higher functional epoxy resin (A), both adhesiveness and heat resistance can be enhanced.

  The epoxy resin (A) may be an epoxy resin that is liquid at normal temperature, or may be an epoxy resin that is solid at normal temperature. In addition, normal temperature means 23 degreeC.

  The content of the epoxy resin (A) in the resin composition can be, for example, 5% by mass or more, especially 7% by mass or more when the nonvolatile content of the resin composition is 100% by mass. Is preferred. Moreover, the said content can be 17 mass% or less, for example, and it is preferable that it is 10 mass% or less especially. When there is too little content of an epoxy resin (A), there exists a possibility that the heat resistance after hardening of a resin composition may fall. Moreover, when there is too much content of an epoxy resin (A), there exists a possibility that the adhesiveness of a resin composition may fall.

  Moreover, the epoxy resin may contain epoxy resins other than the said epoxy resin (A).

  As an epoxy resin other than the above epoxy resin (A), it has one or more epoxy groups or glycidyl groups in one molecule, does not have a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton, and is a latent curing agent and curing accelerator. If it hardens | cures by raise | generating a crosslinking polymerization reaction by combined use with an agent, it will not specifically limit, The epoxy resin generally used for an epoxy resin adhesive can be used. For example, aromatic epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and the like can be given. Specifically, modified epoxy such as bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triazine nucleus-containing epoxy resin, glycol type epoxy resin, pentaerythritol type epoxy resin, urethane modified epoxy resin or rubber modified epoxy resin Examples thereof include resins. These epoxy resins may be used alone or in combination of two or more.

  Especially, an epoxy resin can contain a bisphenol type epoxy resin (B) other than the said epoxy resin (A). The bisphenol type epoxy resin (B) is inexpensive and can improve dimensional stability, water resistance, chemical resistance, electrical insulation, and the like.

  Examples of the bisphenol type epoxy resin (B) include bisphenol A type epoxy resin and bisphenol F type epoxy resin. Among these, bisphenol A type epoxy resin is preferable. Bisphenol type epoxy resin (B) may be used independently and may be used 2 or more types.

  The bisphenol type epoxy resin (B) may be an epoxy resin that is liquid at normal temperature, or may be an epoxy resin that is solid at normal temperature. In addition, normal temperature means 23 degreeC.

  The bisphenol A type epoxy resin can exist in a liquid state at room temperature or a solid state at room temperature, depending on the number of repeating units of the bisphenol skeleton in one molecule. A bisphenol A type epoxy resin having a main chain bisphenol skeleton of 1 or more and 3 or less is liquid at room temperature. A bisphenol A type epoxy resin having a main chain bisphenol skeleton of 2 or more and 10 or less is solid at room temperature. Such a relatively low molecular weight bisphenol A type epoxy resin has crystallinity, and even a solid one that is crystallized at room temperature rapidly melts and changes to a low-viscosity liquid when the temperature reaches the melting point or higher. Therefore, when bisphenol A type epoxy resin is used, the adhesive strength of the adhesive layer after curing can be increased. In addition, such a relatively low molecular weight bisphenol A type epoxy resin has a high crosslink density, and therefore has high mechanical strength, good chemical resistance, high curability, and low free volume, resulting in low hygroscopicity. It has the feature of becoming smaller.

  The resin composition only needs to contain at least one of a bisphenol type epoxy resin that is liquid at normal temperature and a bisphenol type epoxy resin that is solid at normal temperature as the bisphenol type epoxy resin (B). It may contain only resin, may contain only bisphenol type epoxy resin that is solid at normal temperature, and may contain both bisphenol type epoxy resin that is liquid at normal temperature and bisphenol type epoxy resin that is solid at normal temperature .

  When the resin composition contains a bisphenol-type epoxy resin that is liquid at normal temperature, the adhesiveness of the resin composition before curing can be increased. For this reason, when the epoxy resin has a rigid skeleton, the glass transition temperature tends to be high and the tackiness tends to be reduced. However, by including a bisphenol-type epoxy resin that is liquid at room temperature, the tackiness of the resin composition can be improved. Can increase the sex.

  On the other hand, a bisphenol-type epoxy resin that is solid at room temperature rapidly melts and changes to a low-viscosity liquid when it reaches a temperature equal to or higher than the melting point. Therefore, a part using an adhesive sheet having an adhesive layer containing the resin composition of this embodiment is used. In the case of manufacturing a built-in substrate, the adhesive layer is brought into close contact with the electronic component by heating, and the adhesive layer and the electronic component are firmly bonded to each other by being heated and cured, so that the adhesive strength can be increased. Therefore, when the resin composition contains a bisphenol-type epoxy resin that is solid at room temperature, the adhesiveness of the resin composition after curing can be improved.

  When the resin composition contains both a bisphenol type epoxy resin that is liquid at normal temperature and a bisphenol type epoxy resin that is solid at normal temperature, flexibility can be obtained while maintaining mechanical strength. As a result, the adhesive strength after curing of the resin composition can be improved while improving tackiness.

  The softening point of the bisphenol A type epoxy resin that is solid at room temperature is preferably 50 ° C. or higher and 130 ° C. or lower, for example. When the softening point is within the above range and is relatively high, the start of the reaction can be delayed, and the flexibility during heating can be increased. Therefore, when manufacturing a component built-in board | substrate using the adhesive sheet which has an adhesive layer containing the resin composition of this aspect, it is thought that generation | occurrence | production of a void can further be reduced.

  Specifically, as a bisphenol A type epoxy resin that is liquid at room temperature and has a bisphenol skeleton of the main chain of 1 or more and 3 or less, jER828 manufactured by Mitsubishi Chemical Corporation may be mentioned. Examples of the bisphenol A type epoxy resin that is solid at normal temperature and has a main chain bisphenol skeleton of 2 or more and 10 or less include jER1001 and jER1009 manufactured by Mitsubishi Chemical Corporation.

  The content of the bisphenol-type epoxy resin (B) in the resin composition can be, for example, 45% by mass or less when the nonvolatile content of the resin composition is 100% by mass. When there is too much content of a bisphenol-type epoxy resin (B), content of the said epoxy resin (A) will decrease relatively, and there exists a possibility that the heat resistance after hardening of a resin composition may fall. Moreover, the said content can be 25 mass% or more, for example.

  Moreover, an epoxy resin can contain the epoxy resin (C) more than trifunctional other than the said epoxy resin (A) and an epoxy resin (B). When the trifunctional or higher functional epoxy resin (C) forms a crosslinked structure, the heat resistance of the resin composition after curing can be improved. Moreover, it is thought that the epoxy resin (C) more than trifunctional functions as a tackifier, and can improve the adhesiveness before hardening of a resin composition. That is, when the resin composition contains a trifunctional or higher functional epoxy resin (C), both adhesiveness and heat resistance can be improved.

  Examples of the tri- or higher functional epoxy resin (C) include an epoxy resin having an aminophenol structure, an epoxy resin having a bis (aminophenyl) methane structure, and an epoxy resin having an oxiranylcyclohexane structure. Among these, an epoxy resin having a bis (aminophenyl) methane structure is preferable. Specific examples include N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane. The trifunctional or higher functional epoxy resin (C) may be used alone or in combination of two or more.

  Examples of the epoxy group or glycidyl group contained in the tri- or higher functional epoxy resin (C) include a glycidylamine group and a glycidyl ether group. Among them, from the viewpoint of the storage stability of the resin composition, 1 Epoxy resins having 3 or more glycidyl groups in the molecule are preferred.

  A commercially available product may be used as the trifunctional or higher functional epoxy resin (C). For example, jER630 (an epoxy resin having an aminophenol structure) manufactured by Mitsubishi Chemical Corporation, jER604 (an epoxy resin having a diaminodiphenylmethane structure) manufactured by Mitsubishi Chemical Corporation, EHPE3150 (an epoxy resin having an oxiranylcyclohexane structure) manufactured by Daicel Corporation Etc.

  The content of the trifunctional or higher functional epoxy resin (C) in the resin composition can be, for example, 15% by mass or more and 35% by mass or less when the nonvolatile content of the resin composition is 100% by mass. . When the content of the trifunctional or higher functional epoxy resin (C) is within the above range, both the tackiness before curing of the resin composition and the heat resistance after curing of the resin composition can be enhanced.

  The content of the epoxy resin in the resin composition can be, for example, 50% by mass or more and 90% by mass or less when the nonvolatile content of the resin composition is 100% by mass.

2. Curing accelerator The curing accelerator used in this embodiment is an imidazole compound that is solid at 23 ° C.

For example, the reaction start temperature of the imidazole compound is preferably 110 ° C. or higher, and more preferably 130 ° C. or higher. When the reaction start temperature of the imidazole compound is in the above range, the reaction start can be delayed. Therefore, the time until the reaction starts can be lengthened, and the flexibility and fluidity during heating can be improved. Therefore, when manufacturing a component built-in board | substrate using the adhesive sheet which has the contact bonding layer containing the resin composition of this aspect, generation | occurrence | production of a void can be suppressed.
On the other hand, the reaction start temperature of the imidazole compound is preferably, for example, 200 ° C. or lower. When the said reaction start temperature is too high, it is necessary to make it high temperature at the time of hardening of the resin composition of this aspect, and there exists a possibility that a resin composition may deteriorate.

  Here, the reaction start temperature of the imidazole compound can be determined by differential scanning calorimetry (DSC). Specifically, it can be determined by the following procedure. First, a resin composition in which 5 parts by weight of an imidazole compound is blended with 100 parts by weight of a liquid bisphenol A type epoxy resin (molecular weight 380, epoxy equivalent 190 g / eq) is prepared. Next, 20 mg of the resin composition is measured using a DSC apparatus (differential scanning calorimeter, manufactured by Netch Co., Ltd.) under conditions of a temperature rising rate of 10 ° C./min and a measurement range of 30 ° C. to 250 ° C. In the relationship between the calorific value (W / g) on the vertical axis and the temperature (° C) on the horizontal axis obtained by DSC, the intersection of the tangent and the temperature axis where the peak has the steepest peak in the rising curve of the lowest temperature exothermic peak The temperature at is the reaction initiation temperature.

  The imidazole compound only needs to be solid at 23 ° C., and can be appropriately selected from imidazole curing accelerators generally used in one-component heat-curable epoxy resin adhesives. For example, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 -Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]- Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4 Methyl-5-hydroxymethyl imidazole, and the like.

  Moreover, as an imidazole compound, you may use a commercially available thing. Specifically, Cure Sole C11Z-CN (1-cyanoethyl-2-undecylimidazole), 2E4MZ-CN (1-cyanoethyl-2-ethyl-4-methylimidazole), 2PZ-CN (1) manufactured by Shikoku Chemical Industry Co., Ltd. -Cyanoethyl-2-phenylimidazole), 2PZCNS-PW (1-cyanoethyl-2-phenylimidazolium trimellitate), 2MZ-A and 2MZA-PW (2,4-diamino-6- [2'-methylimidazole) Ryl- (1 ′)]-ethyl-s-triazine), C11Z-A (2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine), 2E4MZ-A (2,4-Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazi 2MA-OK and 2MAOK-PW (2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct), 2PHZ-PW (2 -Phenyl-4,5-dihydroxymethylimidazole), 2P4MHZ-PW (2-phenyl-4-methyl-5-hydroxymethylimidazole) and the like.

  Among them, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenyl- 4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole can be preferably used. In particular, 2-phenyl-4,5-dihydroxymethylimidazole is preferable. These imidazole compounds have a high reaction start temperature of 130 ° C. or higher, and can further reduce the generation of voids.

  The imidazole compound preferably has a hydroxy group. Since the imidazole compound having a hydroxy group is crystallized by a hydrogen bond between hydroxy groups, it is considered that the reaction start temperature tends to increase.

  An imidazole compound may be used independently and may be used 2 or more types.

  The content of the imidazole compound is not particularly limited as long as it does not greatly deviate from the general distribution in general-purpose one-pack epoxy resin adhesives. For example, the content of the imidazole compound can be an amount that allows the epoxy resin and the latent curing agent to sufficiently react with each other. It is set as appropriate according to the combination and type. Specifically, the content of the imidazole compound can be 0.5 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the epoxy resin and the epoxy-modified silicone resin. When there is too little content of an imidazole compound, there exists a possibility of becoming a factor of poor curing. Moreover, when there is too much content of an imidazole compound, the adhesiveness of a resin composition will fall, or the adhesiveness after hardening of a resin composition will fall, and components are built in using the resin composition of this aspect. When a board | substrate is manufactured, there exists a possibility that the adhesiveness of the interlayer insulation layer containing the hardened | cured material of the resin composition of this aspect and an electronic component may become weak.

3. Latent Curing Agent The latent curing agent used in this embodiment is not particularly limited as long as it can use an imidazole compound as a curing accelerator, and is generally used in a one-component heat-curable epoxy resin adhesive. It can be used by appropriately selecting from among the curing agents.

  Among these, the latent curing agent preferably has thermal latency. That is, a heat latent curing agent is preferable. Further, the heat latent curing agent may be microencapsulated.

  The latent curing agent is preferably solid at 23 ° C. Although the latent curing agent that is solid at 23 ° C. has a high potential at normal temperature and does not cause a curing reaction, it causes a curing reaction at a high temperature, so that generation of voids can be suppressed.

  The melting point of the latent curing agent is preferably 150 ° C. or higher and 220 ° C. or lower, for example. When the melting point of the latent curing agent is in the above range, it is possible to lengthen the time until the reaction starts and to improve the flexibility and fluidity during heating. Therefore, when manufacturing a component built-in board | substrate using the adhesive sheet which has the contact bonding layer containing the resin composition of this aspect, generation | occurrence | production of a void can be suppressed. On the other hand, if the melting point is too high, the resin composition of this embodiment needs to be heated at the time of curing, and the resin composition may be deteriorated.

  Here, the melting point of the latent curing agent can be determined by differential scanning calorimetry (DSC).

  Moreover, it is preferable that the reaction start temperature of a latent hardening agent is 110 degreeC or more and 200 degrees C or less, for example. When the reaction start temperature of the latent curing agent is in the above range, the time until the reaction starts can be lengthened, and the flexibility and fluidity during heating can be improved. Therefore, when manufacturing a component built-in board | substrate using the adhesive sheet which has the contact bonding layer containing the resin composition of this aspect, generation | occurrence | production of a void can be suppressed. On the other hand, when the said reaction start temperature is too high, it is necessary to make it high temperature at the time of hardening of the resin composition of this aspect, and there exists a possibility that a resin composition may deteriorate.

  Here, the reaction start temperature of the latent curing agent can be determined by differential scanning calorimetry (DSC). Specifically, it can be determined by the following procedure. First, a resin composition in which 5 parts by weight of a latent curing agent is blended with 100 parts by weight of a liquid bisphenol A type epoxy resin (molecular weight 380, epoxy equivalent 190 g / eq) is prepared. Next, 20 mg of the resin composition is measured using a DSC apparatus (differential scanning calorimeter, manufactured by Netch Co., Ltd.) under conditions of a temperature rising rate of 10 ° C./min and a measurement range of 30 ° C. to 250 ° C. In the relationship between the calorific value (W / g) on the vertical axis and the temperature on the horizontal axis (° C.) obtained by DSC measurement, the tangent line of the portion where the slope of the peak is steepest in the rising curve of the exothermic peak at the lowest temperature and the temperature axis The temperature at the intersection is taken as the reaction start temperature.

  Examples of the heat latent curing agent include dicyandiamide curing agents such as dicyandiamide (DICY), organic acid dihydrazide curing agents, amine adduct curing agents, and organic phosphorus curing agents.

  In particular, the latent curing agent is preferably a dicyandiamide-based curing agent, and more preferably dicyandiamide. Since the dicyandiamide-based curing agent has a high melting point and tends to have a high curing temperature, it is possible to lengthen the time until the reaction starts. Thereby, it is presumed that rapid viscosity increase during heating can be suppressed, and fluidity and flexibility during heating can be secured. Therefore, when a component-embedded substrate is manufactured using the resin composition of this embodiment by using a dicyandiamide curing agent and an imidazole compound, an interlayer insulating layer containing a cured product of the resin composition of this embodiment; It is possible to reduce voids between the electronic components, that is, voids under the electronic components. In addition, dicyandiamide can increase the crosslinking density and further improve the heat resistance because hydrogen of all amino groups and imino groups reacts with the epoxy resin.

The content of the latent curing agent can be appropriately determined depending on the amine value of the latent curing agent. For example, when dicyandiamide is used as the latent curing agent, the content of dicyandiamide can be 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the epoxy resin and the epoxy-modified silicone resin. If the content of dicyandiamide is in the above range, the heat resistance after curing of the resin composition can be increased, the adhesive strength can be prevented from deteriorating due to a temperature change, and the storage stability can be maintained. If the storage stability is low, the curing reaction may proceed during storage of the resin composition or the adhesive sheet using the resin composition. Moreover, when there is too much content of dicyandiamide, after the resin composition hardens | cures, an unreacted latent hardening | curing agent may remain and adhesive force may fall.
In addition, when the latent curing agent is other than dicyandiamide, there is no particular problem unless the content of the latent curing agent greatly deviates from the general distribution in a general-purpose one-pack epoxy resin adhesive. .

4). Epoxy-modified silicone resin The epoxy-modified silicone resin contained in the resin composition of the present embodiment refers to an epoxy group or an epoxy compound introduced into a part of the silicone resin. The silicone resin is a compound having a polyorganosiloxane skeleton, and is usually a compound having a main skeleton (main chain) portion mainly composed of repeating organosiloxane units, and the main skeleton having at least one silanol group. An epoxy-modified silicone resin can be obtained by an addition reaction between a group and an epoxy compound. The main skeleton of the silicone resin may have a branched structure as long as it has at least one silanol group. The epoxy-modified silicone resin may be a reaction product of an epoxy resin and a silicone resin. For example, the epoxy-modified silicone resin may be a reaction product of an OH group in the epoxy resin skeleton and silanol. In the above reaction product, the amount of epoxy resin is larger, and even if the silicone is apparently hanging from the epoxy resin, the epoxy-modified silicone resin is used. Epoxy-modified silicone resins may be used alone or in appropriate combination of two or more.

  A commercially available epoxy-modified silicone resin may be used. Examples thereof include ES1001N, ES1002T, ES1023 (manufactured by Shin-Etsu Silicone Co., Ltd.); methyl silicate MSEP2 (manufactured by Mitsubishi Chemical Corporation), and the like.

  The content of the epoxy-modified silicone resin in the resin composition can be, for example, 5% by mass or more and 20% by mass or less when the nonvolatile content of the resin composition is 100% by mass.

5. Acrylic resin The acrylic resin contained in the resin composition of this embodiment preferably has compatibility with the epoxy resin. When the resin composition of this embodiment contains an acrylic resin that is compatible with the epoxy resin, the film-forming property can be improved. When the resin composition of this embodiment is used for an adhesive sheet, it is long. The sheet shape can be maintained for a period. In addition, in the resin composition, since the epoxy resin functions as a plasticizer, the addition of an acrylic resin having compatibility with the epoxy resin plasticizes the entire resin composition. Sex is demonstrated. As a result, it becomes possible to improve the adhesiveness before curing of the resin composition and the adhesion to electronic components, and the toughness after curing of the resin composition is improved and the adhesive strength is further increased. Can do.

  Here, the fact that the acrylic resin has compatibility with the epoxy resin means that it has good affinity with the epoxy resin and does not undergo phase separation when mixed with the epoxy resin at an arbitrary ratio. In the resin composition, the acrylic resin is compatible with the epoxy resin, for example, when the resin composition is used for an adhesive sheet, the adhesive layer containing the resin composition has high transparency, adhesion The haze value of the layer is low, and when the surface or cross section of the adhesive layer is observed with a scanning electron microscope (SEM) or transmission electron microscope (TEM), there are no micron-sized islands in the layer, Etc. can be confirmed.

  The acrylic resin is not particularly limited as long as it has good compatibility with the epoxy resin. The acrylic resin may have a polar group. Examples of the polar group include an epoxy group, a hydroxyl group, a carboxyl group, a nitrile group, and an amide group.

  The acrylic resin is a homopolymer of an acrylate monomer, may be a mixed component containing two or more of the above homopolymers, and is a copolymer of two or more acrylate monomers. A component containing one or more copolymers may be used. The acrylic resin may be a mixed component of the homopolymer and the copolymer. The concept of methacrylic acid is also included in the “acrylic acid” of the acrylate monomer. Specifically, the acrylic resin may be a mixture of a methacrylate polymer and an acrylate polymer, or may be an acrylate polymer such as acrylate-acrylate, methacrylate-methacrylate, methacrylate-acrylate. . Especially, it is preferable that an acrylic resin contains the copolymer ((meth) acrylic acid ester copolymer) of 2 or more types of acrylic acid ester monomers.

  As a monomer component which comprises a (meth) acrylic acid ester copolymer, the monomer component of Unexamined-Japanese-Patent No. 2014-0665889 is mentioned, for example. The monomer component may have the polar group described above. This is because in the resin composition before curing, the compatibility with the epoxy resin is improved, and the adhesive force before curing and the adhesive force after curing can be increased. Examples of the (meth) acrylic acid ester copolymer include ethyl acrylate-butyl acrylate-acrylonitrile copolymer, ethyl acrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, and the like. “Acrylic acid” such as methyl acrylate and ethyl acrylate includes “methacrylic acid” such as methyl methacrylate and ethyl methacrylate.

  The (meth) acrylic acid ester copolymer is preferably a block copolymer, and more preferably an acrylic block copolymer such as a methacrylate-acrylate copolymer. The acrylate and methacrylate constituting the acrylic block copolymer are, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzylid acrylate, etc. Is mentioned. These “acrylic acids” include methacrylic acid.

  Specific examples of the methacrylate-acrylate copolymer include acrylic copolymers such as methyl methacrylate-butyl acrylate-methyl methacrylate (MMA-BA-MMA) copolymer. The MMA-BA-MMA copolymer also includes a block copolymer of polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate (PMMA-BA-MMA). Such an acrylic copolymer has improved film forming properties and can exhibit sufficient adhesion to the adherend surface.

  The acrylic copolymer may not have a polar group, and may be a modified product in which the polar group described above is partially introduced. Since the modified product further improves the compatibility with the epoxy resin in the resin composition before curing, the adhesive strength is further improved.

  Among them, the acrylic resin has (meth) acrylic acid having a first polymer portion having a glass transition temperature (Tg) of 10 ° C. or lower and a second polymer portion having a glass transition temperature (Tg) of 20 ° C. or higher. An ester copolymer is preferred. Such a (meth) acrylic acid ester copolymer has a first polymer portion that becomes a soft segment and a second polymer portion that becomes a hard segment. By adding such a copolymer, when the resin composition is used for an adhesive sheet, it is possible to effectively suppress floating and peeling on the adherend surface, and toughness after curing is improved. This is because the adhesive strength can be further increased.

  The manifestation of the above effect can be estimated as follows. In conventional epoxy resin adhesives, acrylic resin is added in addition to epoxy resin in order to impart toughness and flexibility, but the addition of acrylic resin reduces the heat resistance of the adhesive itself. There was a case of decline. On the other hand, by using an acrylic resin having both a soft segment and a hard segment, such as the (meth) acrylic acid ester copolymer, the hard segment contributes to heat resistance, and the soft segment is tough or flexible. Therefore, it is considered that the cured resin composition has toughness and can maintain excellent adhesiveness.

  At least one of the first polymer portion and the second polymer portion contained in the (meth) acrylic acid ester copolymer has compatibility with the epoxy resin. When the first polymer portion is compatible with the epoxy resin, flexibility can be increased. Moreover, when a 2nd polymer part has compatibility with an epoxy resin, cohesion and toughness can be improved.

  When one of the first polymer part or the second polymer part is not compatible with the epoxy resin, the (meth) acrylate copolymer is a polymer part compatible with the epoxy resin. And a compatible part that is a polymer part that is not compatible with the epoxy resin. In this case, when the (meth) acrylic acid ester copolymer is added to the resin composition, the compatible site is compatible with the epoxy resin, and the incompatible site is not compatible with the epoxy resin, so that phase separation occurs. As a result, a sea-island structure appears in the cured resin composition. As for the sea-island structure, the type of (meth) acrylic acid ester copolymer, the compatibility of the first polymer part and the second polymer part contained in the (meth) acrylic acid ester copolymer, and the modification by introducing a polar group Depending on the presence or absence, for example, a sea-island structure in which the compatible part of the cured epoxy resin and the (meth) acrylic acid ester copolymer is the sea, and the incompatible part of the (meth) acrylic acid ester copolymer is the island Or a sea-island structure in which the incompatible part of the (meth) acrylic acid ester copolymer is the sea, and the cured part of the epoxy resin and the compatible part of the (meth) acrylic acid ester copolymer are islands, (meta) A sea-island structure in which an acrylic ester copolymer is the sea and a cured product of the epoxy resin is an island is exemplified. Since the cured resin composition has such a sea-island structure, stress can be easily dispersed, so that interface fracture can be avoided and excellent adhesive strength can be maintained.

  The (meth) acrylic acid ester copolymer is preferably a block copolymer, and in particular, A-B-A having a compatible site as the polymer block A and an incompatible site as the polymer block B. A block copolymer is preferred. Furthermore, the first polymer part is an incompatible part, the second polymer part is a compatible part, the first polymer part is a polymer block B, and the second polymer part is a polymer block A. -B-A block copolymers are preferred. By using such an ABA block copolymer as the acrylic resin, the cured resin composition and the (meth) acrylic acid ester copolymer compatible site in the cured resin composition are the sea, In the case of a sea-island structure in which the incompatible part of the (meth) acrylic acid ester copolymer is an island, the island part can be made small. In addition, in the case of a sea-island structure in which the incompatible part of the (meth) acrylic acid ester copolymer is the sea, the cured part of the epoxy resin and the compatible part of the (meth) acrylic acid ester copolymer are islands, In the case of a sea-island structure in which the (meth) acrylic acid ester copolymer is the sea and the cured product of the epoxy resin is an island, the sea portion can be reduced. Therefore, in the cured resin composition, the epoxy resin and the acrylic resin are apparently in a compatible state. By developing such an apparent compatibility state, the cured resin composition can further disperse stress, so that interface fracture can be avoided and excellent adhesive strength is maintained. can do.

  The (meth) acrylic acid ester copolymer may be a modified product in which the above-mentioned polar group is introduced into a part of the first polymer part or the second polymer part. While the heat resistance after hardening of a resin composition improves more, compatibility with an epoxy resin also improves, Therefore Adhesion improves.

  Tg of the 1st polymer part contained in the said (meth) acrylic acid ester copolymer is 10 degrees C or less, in the range of -150 degreeC or more and 10 degrees C or less, Especially -130 degrees C or more and 0 degrees C or less. Within the range, in particular, within the range of −110 ° C. or more and −10 ° C. or less.

The Tg of the first polymer portion is calculated by the following formula based on the Tg (K) of each homopolymer described in “POLYMERHANDBOOK 3rd edition” (published by John Wiley & Sons, Ink.). Can be sought.
1 / Tg (K) = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n
W _n ; mass fraction of each monomer Tg _n ; Tg (K) of homopolymer of each monomer, polymer handbook (3rd Ed., J. Brandrup and EH Immergut, WILEY INTERSCIENCE) Publicly available published values such as medium values may be used. The same applies to Tg of the second polymer portion described later.

  The first polymer portion contained in the (meth) acrylic acid ester copolymer may be a homopolymer or a copolymer, but is preferably a homopolymer. The monomer component and the polymer component constituting the first polymer portion may be any monomer component and polymer component that can obtain the first polymer portion having a Tg in a predetermined range. Acrylic acid ester monomers such as butyl acid, 2-ethylhexyl acrylate, isononyl acrylate and methyl acrylate, other monomers such as vinyl acetate, acetal and urethane Copolymers such as a monomer and EVA are listed.

  The Tg of the second polymer portion contained in the (meth) acrylic acid ester copolymer is 20 ° C. or higher, and within the range of 20 ° C. or higher and 150 ° C. or lower, particularly within the range of 30 ° C. or higher and 150 ° C. or lower. In particular, it can be in the range of 40 ° C. or more and 150 ° C. or less.

  Further, the second polymer portion contained in the (meth) acrylic acid ester copolymer may be a homopolymer or a copolymer, but is preferably a homopolymer. . The monomer component constituting the second polymer portion may be any monomer component capable of obtaining the second polymer portion having a Tg within a predetermined range. For example, an acrylic ester unit such as methyl methacrylate is used. Other monomers such as isomers, acrylamide, styrene, vinyl chloride, amide, acrylonitrile, cellulose acetate, phenol, urethane, vinylidene chloride, methylene chloride, methacrylonitrile, and polar groups containing the above polar groups The body is mentioned.

  Specific examples of the (meth) acrylic acid ester copolymer having the first polymer portion and the second polymer portion include the MMA-BA-MMA copolymer described above.

  The weight average molecular weight of the acrylic resin can be appropriately set according to the tackiness and cohesive force required for the resin composition, and among these, the weight average molecular weight of the epoxy resin and the epoxy-modified silicone resin is preferably larger. This is because it is necessary to leave the film forming property to the acrylic resin, and the epoxy resin needs to work as a plastic component. Specifically, the weight average molecular weight of the acrylic resin can be in the range of 10,000 or more and 900,000 or less, particularly 30,000 or more and 500,000 or less. If the weight average molecular weight of the acrylic resin is too small, the three-dimensional crosslinking becomes dominant and the toughness may be lowered. On the other hand, if the weight is too large, the compatibility is deteriorated and the strength is lowered. The weight average molecular weight of the acrylic resin can be measured by GPC (eluent: THF, standard substance: PS, sample: 20 μL, flow rate: 1 mL / min, column temperature: 40 ° C.).

  The content of the acrylic resin in the resin composition can be appropriately adjusted according to the types of the acrylic resin and the epoxy resin, the tackiness, cohesiveness, viscosity, and the like required for the resin composition. For example, when the resin composition contains the (meth) acrylic acid ester copolymer as an acrylic resin, the content of the (meth) acrylic acid ester copolymer is 4 parts by mass with respect to 100 parts by mass of the epoxy resin. The amount can be 100 parts by mass or less. When both are blended at this ratio, the resin composition has a structure in which acrylic resin is dispersed in the form of fine particles of nano-order level in the epoxy resin before curing, and an apparent compatibility state is expressed. The And the resin composition can exhibit the outstanding adhesive strength by hardening | curing, maintaining an apparent compatibility state. Moreover, since the cured resin composition has the above-described structure, water can be prevented from entering from the interface with the adherend, and further excellent adhesion retention characteristics can be obtained.

6). Particles The resin composition of this embodiment may contain particles. By including particles, when manufacturing a component-embedded substrate using the resin composition of this aspect, the shrinkage of the adhesive layer containing the resin composition can be reduced and the adhesive layer can be cured. The electronic parts can be made difficult to move. Therefore, the position shift at the time of fixing an electronic component using the resin composition of this aspect can be suppressed. Furthermore, the heat resistance and intensity | strength after hardening of a resin composition can be improved by containing particle | grains.

  The particles contained in the resin composition of the present embodiment may have any insulating property, and for example, any of inorganic particles and organic particles can be used. Of these, organic particles are preferable, and resin particles are particularly preferable. This is because the resin particles can improve the dispersibility in the epoxy resin. Thereby, the fall of the adhesiveness by particle | grains can be suppressed. In addition, when manufacturing a component-embedded substrate using the resin composition of this aspect, it is possible to suppress curing shrinkage of the adhesive layer containing the resin composition and to move the electronic component when the adhesive layer is cured. It is possible to suppress the displacement of the electronic component.

  As the inorganic particles, inorganic fillers generally used for adhesives can be used. For example, silica, alumina, titanium oxide, zirconium oxide, magnesium oxide, aluminum nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, magnesium hydroxide, aluminum borate, barium titanate, strontium titanate, Examples thereof include particles of calcium titanate, magnesium titanate, bismuth titanate, barium zirconate, calcium zirconate, glass, talc, clay, mica and the like.

As the resin particles, organic fillers generally used for adhesives can be used. Examples include acrylic particles, polystyrene particles, urethane particles, polyamide particles, polyimide particles, polyester particles, and polyethylene particles.
Among these, acrylic particles are preferable. Acrylic particles are less likely to aggregate even when added to an epoxy resin, and can improve dispersibility in the epoxy resin. Thereby, the fall of the adhesiveness by particle | grains can be suppressed. In addition, when manufacturing a component-embedded substrate using the resin composition of this aspect, it is possible to suppress curing shrinkage of the adhesive layer containing the resin composition and to move the electronic component when the adhesive layer is cured. It is possible to suppress the displacement of the electronic component.

The particles may have a core-shell structure.
Although it does not specifically limit as a shell part of a core-shell structure, It is preferable that it is resin. This is because the particles covered with the resin can increase the affinity with the epoxy resin and improve the dispersibility in the epoxy resin.
Moreover, it does not specifically limit as resin which comprises a shell part, However, It is preferable that it is an acrylic resin. Particles covered with an acrylic resin are less likely to aggregate even when added to an epoxy resin and can increase dispersibility in the epoxy resin. That is, the acrylic particles may have a single structure or a core-shell structure.

  In addition, the core part of the core-shell structure is not particularly limited, and may be, for example, an inorganic material or an organic material. In the case of an organic material, for example, it may be rubber or resin. When the core part is rubber, toughness can be imparted to the adhesive layer. Examples of the rubber include butadiene rubber.

Moreover, the particle | grains may have a reactive functional group on the surface. This is because the affinity with the epoxy resin can be increased.
Examples of the reactive functional group include an epoxy group, an amino group, and an acrylic group. Among these, an epoxy group is preferable. This is because the affinity with the epoxy resin can be improved.

In the case of inorganic particles, inorganic particles having a reactive functional group on the surface can be obtained by surface modification with a silane coupling agent. As the silane coupling agent, for example, a general silane coupling agent having an alkoxy group, amino group, vinyl group, epoxy group, mercapto group, chloro group or the like can be used.
The method of decorating the surface of the inorganic particles with the silane coupling agent is not particularly limited, and a general method can be applied.

  In the case of resin particles, a resin having a reactive functional group may be used in advance, or the reactive functional group may be introduced by reacting the resin particles.

  The particles may be used alone or in combination of two or more.

  The shape of the particles is not particularly limited, and may be any shape such as a sphere, an ellipsoid, a polyhedron, and a scale shape.

  The average particle diameter of the particles can be, for example, 0.01 μm or more and 20 μm or less. Particles having an average particle size that is too small are difficult to produce and may reaggregate. Further, if the average particle size is too large, when the component-embedded substrate is produced using the resin composition of this aspect, it becomes larger than the thickness of the adhesive layer containing the resin composition, and the adhesive layer and the electronic component or substrate There is a possibility that the adhesiveness of the material will be lowered.

  Here, the average particle diameter of the particles is an average of 20 particles observed in a transmission electron microscope (TEM) photograph of a cross section of the adhesive layer containing the resin composition in the adhesive sheet using the resin composition of this embodiment. Can be a value. The average particle diameter of the particles can also be measured by a dynamic light scattering method (DLS).

  Content of the particle | grains in a resin composition can be 5 mass% or more and 20 mass% or less, for example, when the non volatile matter of a resin composition is 100 mass%. If the content of the particles is too small, the effect of suppressing the displacement of the electronic component may not be sufficiently obtained when the component-embedded substrate is manufactured using the resin composition of this aspect. Moreover, when there is too much content of particle | grains, the adhesiveness of a resin composition will fall and sufficient tack force may not be obtained, but there exists a possibility that it may become easy to generate | occur | produce a void.

  Moreover, when preparing the resin composition of this aspect, as a particle, you may use the composition disperse | distributed to particle | grains in resin. That is, you may mix an epoxy resin and the composition which disperse | distributed particle | grains in resin. In the composition dispersed in particles in the resin, an epoxy resin is preferably used as the resin. By using a composition in which particles are dispersed in advance in the resin, the dispersibility of the particles in the epoxy resin can be improved.

7. Other components The resin composition of the present embodiment is, for example, a lubricant, a plasticizer, an antistatic agent, an antiblocking agent, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a dye, a pigment, etc. It may contain a coloring agent.

  Moreover, the resin composition of this aspect can contain coupling agents, such as a silane type, a titanium type, and an aluminum type, as needed. Thereby, when manufacturing a component built-in board | substrate using the resin composition of this aspect, the adhesiveness of the contact bonding layer containing a resin composition and an electronic component can be improved. Moreover, when using the resin composition of this aspect for an adhesive sheet, as mentioned later, when an adhesive layer contains a core material, adhesiveness with a core material can be improved.

  Moreover, as a silane coupling agent, an epoxy-type silane coupling agent is used preferably especially. By using an epoxy-modified silicone resin and an epoxy-based silane coupling agent in combination, water resistance and adhesive strength can be further improved.

  Examples of the epoxy silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) Diethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl ] (Ethyl) dimethoxysilane, [2- (3,4-epoxycyclo Xyl) ethyl] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycid (Xypropyl) (methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (Methoxy) dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3 4-epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, or a partial condensate thereof. Can be mentioned. An epoxy-type silane coupling agent may be used independently and may be used in combination of 2 or more types as appropriate.

  The resin composition of this embodiment may contain a solvent. When the resin composition of this embodiment is used for an adhesive sheet, the solvent contained in the resin composition is volatilized and removed when the resin composition is applied and dried to form an adhesive layer.

8). Resin Composition The glass transition temperature after curing of the resin composition of the present embodiment can be, for example, 150 ° C. or higher, and is preferably 175 ° C. or higher. When the glass transition temperature after curing of the resin composition is in the above range, when producing a component-embedded substrate using the resin composition of this embodiment, an interlayer insulating layer having excellent heat resistance can be obtained. it can. In addition, although the upper limit of the glass transition temperature after hardening of a resin composition is not specifically limited, It can be set as about 350 degreeC.

Here, when measuring the glass transition temperature after curing of the resin composition, the resin composition is first heated and cured. The heating temperature at the time of curing is 150 ° C. or higher and 180 ° C. or lower. The heating time is 30 minutes or more and 60 minutes or less.
The glass transition temperature (Tg) means a value measured by a method (DMA method) based on the peak top value of loss tangent (tan δ). The loss tangent is determined by the value of loss elastic modulus / storage elastic modulus. These elastic moduli are measured using a dynamic viscoelasticity measuring device for stress when a force is applied to the cured resin composition at a constant frequency. Specifically, using a dynamic viscoelasticity measuring device RSA-III manufactured by TA Instruments, the dynamic viscosity conforming to JIS K7244-1 (Plastics-Test method for dynamic mechanical properties-Part 1: General rules). It can be measured by the elastic measurement method under the following conditions.
・ Attachment mode: Compression mode ・ Frequency: 1.0 Hz
・ Temperature range: -50 ℃ to 250 ℃ ・ Temperature increase rate: 5 ℃ / min

  The resin composition of this embodiment can be prepared by mixing the above-described components and kneading and dispersing as necessary. The mixing and dispersing method is not particularly limited, and a general kneading and dispersing machine such as a two-roll mill, a three-roll mill, a pebble mill, a tron mill, a Segvari attritor, a high-speed impeller disperser, and a high-speed stone mill A high speed impact mill, a desper, a high speed mixer, a ribbon blender, a kneader, an intensive mixer, a tumbler, a blender, a desperser, a homogenizer, an ultrasonic disperser, and the like can be applied. When using multiple types of epoxy resins, first stir the hard epoxy resin, then mix and stir the latent curing agent, dilute with a solvent, mix and stir the soft epoxy resin, and then add the acrylic resin. It is preferable to mix and stir.

9. Applications The resin composition of this embodiment can be used as a one-component heat-curable epoxy resin adhesive. In general, an epoxy resin adhesive is excellent in adhesiveness, durability, and insulation, and can be made solvent-free. Therefore, the resin composition of this aspect is suitable for an adhesive layer of an adhesive sheet that is used for fixing an electronic component in the method for manufacturing a component-embedded substrate and that is used for an interlayer insulating layer of the component-embedded substrate.

  In addition, the adhesive sheet using the resin composition of this embodiment, the component-embedded substrate, and the manufacturing method thereof will be described later.

A-2. Second Embodiment A second embodiment of the resin composition of the present disclosure is a resin composition used for fixing an electronic component of a component-embedded substrate and an interlayer insulating layer, and having a resin flow rate of 80% or more and curing. The glass transition temperature of an object is 175 degreeC or more.

  Since the resin composition of this embodiment has a value of the resin flow rate as described above, when it is used as an adhesive layer for temporarily fixing an electronic component in the production of a component-embedded substrate, it has fluidity. Since it is excellent, it becomes possible to reduce the generation of voids between the electronic component and the adhesive layer during temporary fixing. In addition, since the glass transition temperature of the cured product obtained by curing the adhesive layer has the value as described above, it can have excellent heat resistance when functioning as an interlayer insulating layer after curing. And

1. Resin flow rate The resin flow rate in this embodiment is used as an index of fluidity when temporarily fixing an electronic component. If the resin flow rate is high, the resin flow rate is applied to the adhesive layer containing the resin composition. When the electronic component is temporarily fixed, the resin composition can flow along the electronic component. This makes it possible to suppress the generation of voids.
In this embodiment, the resin flow rate of the resin composition is 80% or more, preferably 85% or more, particularly preferably 90% or more. This is because generation of voids can be further suppressed.

The method for measuring the resin flow rate in this embodiment is as follows.
1. The resin composition is made into a 35 μm thick sheet (a in FIG. 8A), and a polyimide film (“Kapton 500H” manufactured by Toray DuPont Co., Ltd., thickness 125 μm, b in FIG. 8A) is formed on one surface of the sheet. Bond at 25 ° C.
The obtained laminate is cut into a size of 5 cm × 5 cm, and then a circular hole is formed in a plan view so that the diameter is 6 mm at the center.
Next, the laminated body with holes was bonded to copper foil (“RCF-T5B-35μ”, Fukuda Metal Foil Powder Co., Ltd., thickness 35 μm, c in FIG. 8A) at a temperature of 25 ° C., and the copper foil was laminated to the laminated body. Are cut into 5 cm × 5 cm, which is the same size as the above, to obtain a laminate with copper foil (FIG. 8A).

2. On the lower surface of a hot press machine (SA-901 manufactured by Tester Sangyo Co., Ltd.) having a heating stage (d in FIG. 8B) in which the obtained laminate with copper foil was heated to 150 ° C. on the upper and lower surfaces. The laminate with copper foil is arranged so that the foil side is in contact. Immediately after the placement, heating press is performed under the condition of pressurization condition 60.3 kgf / cm ² × 150 ° C. × 100 seconds (FIG. 8B).

3. Take out the heat-pressed laminate with copper foil, and from the opposite side of the copper foil, observe the circular hole with an optical microscope, the area where the resin composition flowed on the copper foil, that is, the copper foil becomes invisible The measured area is measured (FIG. 8C).
The resin flow rate is calculated by the following formula.
Resin flow rate (%) = resin flow area / hole area × 100

2. Glass transition temperature of hardened | cured material In this aspect, although the glass transition temperature of hardened | cured material is 175 degreeC or more, it is especially preferable that it is 180 degreeC or more, especially 185 degreeC or more.

The glass transition temperature of the cured product in this embodiment is a glass transition temperature after curing the resin composition, and after the resin composition was used as an adhesive layer, it was cured to form an interlayer insulating layer. The heat resistance at the time is shown. In this embodiment, since the glass transition temperature is not less than the value described above, it can be used as an interlayer insulating layer having high heat resistance. In addition, although the upper limit of the glass transition temperature after hardening of a resin composition is not specifically limited, It can be set as about 350 degreeC.
About the measuring method of the glass transition temperature of the hardened | cured material in this aspect, the method same as the method described in "8. Resin composition" of "A-1. 1st Embodiment" can be used.

3. Applications The resin composition of this embodiment is used for fixing electronic components on a component-embedded substrate and for an interlayer insulating layer. Further, in the method for manufacturing a component-embedded substrate, the component-embedded substrate is used for temporarily fixing an electronic component, and is then cured and used as an interlayer insulating layer of the component-embedded substrate.
The details of these component-embedded substrate and the method of manufacturing the component-embedded substrate are as described later, and thus the description thereof is omitted here.

4). Composition The composition of the material used for the resin composition of the present embodiment is not particularly limited as long as it has the resin flow rate and the glass transition temperature after curing falls within the above range. The material described in the above “first embodiment” can be preferably used.

B. Adhesive Sheet The adhesive sheet of the present disclosure has two embodiments. Each will be described below.
B-1. 1st embodiment The adhesive sheet of this aspect is an adhesive sheet having at least an adhesive layer, and the adhesive layer comprises an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator. And the epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton and a novolac skeleton, and the curing accelerator is an imidazole solid at 23 ° C. A compound.

  In the present specification, the “sheet” includes a member called “film” or the like. Further, the “film” includes a member called “sheet” or the like.

  FIG. 1 is a schematic cross-sectional view showing an example of the adhesive sheet of this embodiment. The adhesive sheet 1 has at least an adhesive layer 3. The adhesive sheet may have a release layer on at least one surface of the adhesive layer. In the example shown in FIG. 1, release layers 2 a and 2 b are disposed on both surfaces of the adhesive layer 3, respectively.

  The adhesive layer in this embodiment includes the above-described resin composition. Therefore, as described in the above section “A-1. First embodiment”, by using the adhesive sheet of this embodiment, the heat resistance is excellent, the electronic component is excellent in positional accuracy, and the reliability is high. It is possible to obtain a high component built-in substrate.

  Hereinafter, each structure of the adhesive sheet of this aspect is demonstrated.

1. Adhesive layer The adhesive sheet of this aspect has an adhesive layer at least.

  The adhesive layer includes an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, and the epoxy resin is selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton. And the curing accelerator is an imidazole compound that is solid at 23 ° C. That is, an adhesive layer contains the above-mentioned resin composition.

  The resin composition has been described in detail in the above-mentioned section “A-1. First embodiment”, and thus the description thereof is omitted here.

  The glass transition temperature after curing of the adhesive layer can be, for example, 150 ° C. or higher, and is preferably 175 ° C. or higher. In addition, about the glass transition temperature after hardening of a contact bonding layer, it can be made to be the same as that of the glass transition temperature after hardening of the above-mentioned resin composition.

  The relative dielectric constant of the adhesive layer at 23 ° C. and a frequency of 1 GHz is preferably 3.2 or less, and more preferably 3.1 or less. The relative dielectric constant of the adhesive layer at 23 ° C. and a frequency of 10 GHz is preferably 3.2 or less, and more preferably 3.1 or less. When the relative dielectric constant of the adhesive layer is in the above range, transmission loss can be reduced when the adhesive layer in this aspect is used as an interlayer insulating layer of a component-embedded substrate. The lower limit of the relative dielectric constant of the adhesive layer is not particularly limited.

  The dielectric loss tangent of the adhesive layer at 23 ° C. and a frequency of 1 GHz is preferably 0.035 or less, and more preferably 0.030 or less. The dielectric loss tangent of the adhesive layer at 23 ° C. and a frequency of 10 GHz is preferably 0.035 or less, and more preferably 0.030 or less. Since the dielectric loss tangent of the adhesive layer is within the above range, transmission loss can be reduced when the adhesive layer in this embodiment is used as an interlayer insulating layer of a component-embedded substrate. In addition, the minimum of the said dielectric loss tangent of an contact bonding layer is not specifically limited.

Here, the relative dielectric constant and the dielectric loss tangent at a frequency of 1 GHz are values measured according to IEC 62810. Specifically, it can be measured by the following method. First, when the adhesive sheet has a release layer, the release layer is peeled off to form a single adhesive layer, and a test piece is prepared. The dimension of a test piece shall be 16 mm x 92 mm. Next, in accordance with IEC 62810, the relative dielectric constant and dielectric loss tangent are measured with the following apparatus and conditions. The values of relative dielectric constant and dielectric loss tangent are measured values of one sample.
・ Measuring method: Cavity resonator method ・ Device: Vector network analyzer HP8510 (manufactured by Agilent Technologies)
Synthesizer sweeper HP83651A (same as above)
Test set HP8517B (same as above)
-Resonator dimensions: Diameter 229mm, Height 40mm
Test environment: 22 ° C, 60% RH

The relative dielectric constant and dielectric loss tangent at a frequency of 10 GHz are values measured according to JIS R1641. Specifically, it can be measured by the following method. First, when the adhesive sheet has a release layer, the release layer is peeled off to form a single adhesive layer, and a test piece is prepared. The dimension of a test piece shall be 60 mm x 100 mm. Next, in accordance with JIS R1641, the dielectric constant and dielectric loss tangent are measured with the following apparatus and conditions. The values of relative dielectric constant and dielectric loss tangent are measured values of one sample.
・ Measuring method: Cavity resonator method ・ Device: Vector network analyzer HP8510 (manufactured by Agilent Technologies)
Synthesizer sweeper HP83651A (same as above)
Test set HP8517B (same as above)
・ Resonator dimensions: Diameter 42mm, Height 30mm
Test environment: 22 ° C, 60% RH

  The dielectric breakdown voltage of the adhesive layer is preferably 130 kV / mm or more, for example. If the dielectric breakdown voltage of the adhesive layer is in the above range, the adhesive layer in this embodiment can be suitably used as the interlayer insulating layer of the component built-in substrate. The upper limit of the dielectric breakdown voltage of the adhesive layer is not particularly limited.

Here, the dielectric breakdown voltage is a value measured in accordance with ASTM D149. Specifically, it can be measured by the following method. First, when the adhesive sheet has a release layer, the release layer is peeled off to form a single adhesive layer, and a test piece is prepared. Next, in accordance with ASTM D149, the dielectric breakdown voltage is measured with the following apparatus and conditions.
・ Test equipment: Dielectric breakdown tester HAT-300-100RHO (manufactured by Yamazaki Sangyo Co., Ltd.)
-Test piece dimensions: 50 mm x 50 mm
・ Electrode size: Vertical 25mmφ cylindrical shape ・ Ambient medium: Insulating oil ・ For test ventilation: Room temperature (23 ± 2 ℃)
-Boosting speed: 0.2 kV / sec

  The thickness of the adhesive layer may be any thickness as long as the adhesive layer can be used for fixing the electronic component of the component-embedded substrate and the interlayer insulating layer, and can be, for example, 5 μm or more and 100 μm or less.

The adhesive layer can be formed, for example, by applying a resin composition to one surface of a release layer described later and removing the solvent. The specific application method is not particularly limited as long as it is a method capable of applying the resin composition. For example, roll coat, reverse roll coat, transfer roll coat, gravure coat, gravure reverse coat, comma coat , Rod coat, blade coat, bar coat, wire bar coat, die coat, lip coat, dip coat and the like.
Moreover, the adhesive sheet which has a peeling layer on both surfaces of an adhesive layer can be obtained by arrange | positioning another peeling layer on the coating film of a resin composition.

  Moreover, the adhesive layer may further include a core material, and the core material may be impregnated with the resin composition. As a core material, the core material generally used for an adhesive sheet can be used. For example, a woven fabric or a non-woven fabric is preferably used. Examples of the woven or non-woven fabric include heat-resistant plastic fibers such as liquid crystal polymers, glass fibers, aramid fibers, carbon fibers, polyester non-woven fabrics, vinylon fibers, and urethane foam, and woven fabrics composed of these. Nonwoven fabric can be used.

The adhesive layer including the core material can be formed by the following method.
First, the release layer and the core material are run using a coating machine, the resin composition is applied to the surface having the core material, the core material is impregnated, and then the resin impregnated in the core material An adhesive layer containing a core material can be obtained by drying the composition and removing the solvent. Moreover, the adhesive sheet which has a peeling layer on both surfaces of an adhesive layer can be obtained by arrange | positioning another peeling layer in the application surface of a resin composition.

  First, the resin composition is applied to the first release layer and dried, the first release layer is laminated with the core material sheet via the resin composition, and the resin composition is applied to the second release layer. And then laminating the second release layer so as to face the first release layer through the core sheet, thereby obtaining an adhesive layer in which the core is impregnated with the resin composition. it can. The temperature of the drum at the time of the lamination can be, for example, 70 ° C. or higher and 90 ° C. or lower.

2. Peeling layer The adhesive sheet of this aspect can have a peeling layer and an adhesive layer. The release layer may be disposed on one side of the adhesive layer or may be disposed on both sides of the adhesive layer.

  As the release layer, a release layer generally used for an adhesive sheet can be used. For example, a release film, a release paper, etc. are mentioned. Moreover, you may use what has a release layer in the single side | surface or both surfaces of base materials, such as quality paper, a coated paper, an impregnation paper, and a plastic film. The release layer is not particularly limited as long as it is a material having releasability. For example, silicone resin, organic resin-modified silicone resin, fluororesin, aminoalkyd resin, melamine resin, acrylic resin, polyester There are resins. These resins can be used in any of emulsion type, solvent type and solventless type.

The release layer preferably has a predetermined release force with respect to the adhesive layer. Specifically, the peel force can be set to 1 mN / cm or more and 2000 mN / cm or less, preferably 100 mN / cm or more and 1000 mN / cm or less. When the peeling force of the peeling layer is within the above range, the peeling layer and the adhesive layer can be sufficiently bonded, and peeling can be performed well.
In addition, as a measuring method of peeling force, the adhesive sheet which has a peeling layer on both surfaces of an adhesive layer is cut, and it is set as a test body with a width of 25 mm, according to JIS Z0237: 2009 (adhesive tape * adhesive sheet test method), A method of measuring peel strength at a peel rate of 0.3 m / min and a peel angle of 180 ° can be employed.

When the release layers are disposed on both surfaces of the adhesive layer, the two release layers may be the same or different.
Moreover, when the peeling layer is arrange | positioned at both surfaces of the contact bonding layer, it is preferable that one has light peelability and the other has heavy peelability.

3. Applications The adhesive sheet of this aspect is preferably used for fixing electronic components in a method for producing a component-embedded substrate, and is preferably used for an interlayer insulating layer of the component-embedded substrate.

  In addition, the component built-in substrate using the adhesive sheet of this aspect and the manufacturing method thereof will be described later.

B-2. Second Embodiment A second embodiment of the adhesive sheet of the present disclosure is an adhesive sheet used for fixing an electronic component of a component-embedded substrate and an interlayer insulating layer, and has at least an adhesive layer, and the adhesive layer is a resin The resin composition is an adhesive sheet having a resin flow rate of 80% or more and a glass transition temperature of a cured product of the resin composition of 175 ° C. or more.

Since the resin composition used for the adhesive sheet of this embodiment is the same as the resin composition described in the above “A-2. Second embodiment”, the description thereof is omitted here.
In addition, since it is the same as that described in “3. Application” of “A-2. Second embodiment”, the “used to fix electronic components of the component-embedded substrate and the interlayer insulating layer” The description here is omitted.

  Furthermore, other characteristics such as the relative dielectric constant, dielectric loss tangent, dielectric breakdown voltage, and thickness of the adhesive layer, the description of the release layer, and the like are the same as in the description of “B-1. First Embodiment” above. Explanation here is omitted.

C. Component-embedded substrate The component-embedded substrate of the present disclosure has two embodiments. Each will be described below.

C-1. First Embodiment A component-embedded substrate according to this aspect is a component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer, and the interlayer insulating layer includes an epoxy resin. And a cured product of a resin composition comprising an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, the epoxy resin comprising a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton An epoxy resin (A) having at least one selected from the group is included, and the curing accelerator is an imidazole compound that is solid at 23 ° C.

  In addition, the interlayer insulation layer containing the hardened | cured material of the said resin composition may be called a 1st interlayer insulation layer.

  The component-embedded substrate of this aspect is not particularly limited as long as it has at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer. Hereinafter, the component-embedded substrate of this aspect will be described with specific examples.

  FIG. 2 is a schematic cross-sectional view showing an example of the component-embedded substrate of this aspect. As shown in FIG. 2, the component-embedded substrate 10 includes a substrate 11 having an opening 12, a first interlayer insulating layer 3 b disposed on one surface of the substrate 11, and a first in the opening 12 of the substrate 11. Electronic components 13a and 13b disposed on the surface of the interlayer insulating layer 3b, a second interlayer insulating layer 14 disposed so as to cover the opening 12 of the substrate 11 and the electronic components 13a and 13b, and a second interlayer insulating layer 14 The conductive portion 16 disposed in the opening 15 of the first interlayer insulating layer 3b and the wiring 17 disposed on the surface opposite to the surface on the substrate 11 side of the first interlayer insulating layer 3b and connected to the conductive portion 16, and the first interlayer insulating layer A third interlayer insulating layer 19 disposed on the surface of the layer 3b on the wiring 17 side, a conductive portion 21 disposed in an opening of the third interlayer insulating layer 19, and a first interlayer insulating layer of the third interlayer insulating layer 19 A wiring 23 disposed on the surface opposite to the surface on the 3b side and connected to the conductive portion 21 The second interlayer insulating layer 14 is disposed on the surface opposite to the surface on the substrate 11 side, and is disposed on the wiring 18 connected to the conductive portion 16 and on the surface of the second interlayer insulating layer 14 on the wiring 18 side. The fourth interlayer insulating layer 20, the conductive portion 22 disposed in the opening of the fourth interlayer insulating layer 20, and the surface opposite to the surface of the fourth interlayer insulating layer 20 on the second interlayer insulating layer 14 side And a wiring 24 connected to the conductive portion 22. The first interlayer insulating layer 3b contains a cured product of a resin composition containing an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, and the epoxy resin Includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolak skeleton, and the curing accelerator is an imidazole compound that is solid at 23 ° C. That is, the 1st interlayer insulation layer 3b contains the hardened | cured material of the above-mentioned resin composition.

  FIG. 5 is a schematic cross-sectional view showing another example of the component-embedded substrate of this aspect. As shown in FIG. 5, the component-embedded substrate 30 includes the first interlayer insulating layer 3b, the electronic components 13a and 13b disposed on one surface of the first interlayer insulating layer 3b, and the electrons of the first interlayer insulating layer 3b. A second interlayer insulating layer 32 disposed so as to cover the electronic components 13a and 13b, a conductive portion 34 disposed in an opening of the second interlayer insulating layer 32, and a first interlayer on the surface on the component 13a and 13b side The metal foil wiring 31 disposed on the surface opposite to the surface on the second interlayer insulating layer 32 side of the insulating layer 3b and connected to the conductive portion 34, and the surface on the metal foil wiring 31 side of the first interlayer insulating layer 3b The third interlayer insulating layer 36 disposed on the side, the conductive portion 38 disposed in the opening of the third interlayer insulating layer 36, and the opposite side of the surface of the third interlayer insulating layer 36 on the first interlayer insulating layer 3b side Wiring 40 connected to the conductive portion 38 and the first interlayer insulating layer 32 of the second interlayer insulating layer 32. A wiring 35 disposed on a surface opposite to the surface on the layer 3b side and connected to the conductive portion 34; a fourth interlayer insulating layer 37 disposed on a surface of the second interlayer insulating layer 32 on the wiring 35 side; The conductive portion 39 disposed in the opening of the fourth interlayer insulating layer 37 and the surface of the fourth interlayer insulating layer 37 opposite to the surface on the second interlayer insulating layer 32 side are connected to the conductive portion 39. Wiring 41. The first interlayer insulating layer 3b contains a cured product of a resin composition containing an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator, and the epoxy resin Includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolak skeleton, and the curing accelerator is an imidazole compound that is solid at 23 ° C. That is, the 1st interlayer insulation layer 3b contains the hardened | cured material of the above-mentioned resin composition.

  The first interlayer insulating layer in this embodiment contains the resin composition described in the section “A-1. First embodiment”. Therefore, as described in the above section “A-1. First Embodiment”, in this embodiment, the component-embedded substrate having excellent heat resistance, excellent position accuracy of electronic components, and high reliability. Is possible.

  Hereinafter, each configuration of the component-embedded substrate of this aspect will be described.

1. 1st interlayer insulation layer The 1st interlayer insulation layer in this aspect contains the hardened | cured material of the resin composition containing an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent hardening agent, and a hardening accelerator. The epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton, and the curing accelerator is an imidazole compound that is solid at 23 ° C. . That is, a 1st interlayer insulation layer contains the hardened | cured material of the above-mentioned resin composition.

  The resin composition has been described in detail in the above-mentioned section “A-1. First embodiment”, and thus the description thereof is omitted here.

  The glass transition temperature of the first interlayer insulating layer can be, for example, 150 ° C. or higher, and is preferably 175 ° C. or higher. In addition, about the glass transition temperature after hardening of a contact bonding layer, it can be made to be the same as that of the glass transition temperature after hardening of the above-mentioned resin composition.

  In addition, the insulating properties such as the relative dielectric constant, dielectric loss tangent, dielectric breakdown voltage, etc. of the first interlayer insulating layer can be the same as the insulating properties of the adhesive layer of the adhesive sheet described above.

  The thickness of a 1st interlayer insulation layer should just be the thickness of the interlayer insulation layer of a common component built-in board, and can be made to be the same as the thickness of the adhesion layer of the above-mentioned adhesion sheet.

  In the manufacturing method of the component-embedded substrate of this aspect, after the electronic component is disposed on one surface of the adhesive layer, the adhesive layer is cured to form the first interlayer insulating layer.

2. Electronic component The electronic component used in this aspect may be, for example, an active component such as a semiconductor or a passive component such as a resistor, an inductance, or a capacitor.

3. Substrate In the component-embedded substrate of this aspect, for example, the first interlayer insulating layer is disposed on one surface of the substrate having the opening, and the electronic component is disposed on the surface of the first interlayer insulating layer in the opening of the substrate. May be.

  The substrate is not particularly limited, and examples thereof include metal base substrates, metal core substrates, copper-clad laminates, metal base materials such as metal foils and metal plates, and the like. As a metal which comprises said board | substrate, copper, aluminum, iron etc. are mentioned, for example.

  As a method for forming a through hole in a substrate, a method for forming a through hole that is generally applied to manufacture of a component built-in substrate can be employed.

4). Second Interlayer Insulating Layer In the component-embedded substrate of this aspect, for example, the first interlayer insulating layer is disposed on one surface of the substrate having the opening, and the electronic component is disposed on the surface of the first interlayer insulating layer in the opening of the substrate. Is disposed, the second interlayer insulating layer may be disposed so as to cover the opening of the substrate and the electronic component. Further, for example, as described later, when the wiring is arranged on the surface of the first interlayer insulating layer opposite to the surface on the electronic component side, the electronic component on the surface of the first interlayer insulating layer on the electronic component side A second interlayer insulating layer may be disposed so as to cover the surface. The electronic component is fixed and sealed by the second interlayer insulating layer.

As a material for the second interlayer insulating layer, for example, a sealing resin composition, an interlayer insulating film, a prepreg, or the like can be used.
As the encapsulating resin composition, the interlayer insulating film, and the prepreg, those generally used for manufacturing a component-embedded substrate can be used.

  The method of filling the resin into the through hole of the substrate and thermosetting it is not particularly limited. For example, a method of injecting and heating a sealing resin composition, laminating an interlayer insulating film A method of heating, a method of laminating and heating a prepreg, a method of injecting a sealing resin composition, a method of laminating and heating an interlayer insulating film, a method of injecting a resin composition for sealing, and a prepreg The method of laminating and heating is used.

  Moreover, as the above-described method, a known method can be appropriately employed. When using an interlayer insulation film, the method of laminating | stacking an interlayer insulation film by vacuum lamination etc., for example, and heating can be used. Moreover, in the case of the method using a prepreg, the method etc. which heat-press in a vacuum can be used, for example.

  In the case of laminating an interlayer insulating film or prepreg after injecting the sealing resin composition, the sealing resin composition injected into the through hole is thermally cured before laminating the interlayer insulating film or prepreg. Alternatively, after the interlayer insulating film or prepreg is laminated, it may be thermally cured all at once.

  Curing conditions such as heating temperature and heating time can be general conditions in the production of the component-embedded substrate.

5. Metal Foil Wiring In the component-embedded substrate of this aspect, for example, a metal foil wiring may be arranged on the surface of the first interlayer insulating layer opposite to the surface on the electronic component side.

As a material for the metal foil wiring, a metal foil can be used.
As metal foil, what is generally used for manufacture of a component built-in board can be used.

  As a patterning method of the metal foil, for example, a photolithography method can be used.

6). Other members The component-embedded substrate of this aspect may have other members as needed in addition to the above-described members. The other member can generally be any member that constitutes the component-embedded substrate, for example, an interlayer insulating layer other than the first interlayer insulating layer and the second interlayer insulating layer, or other than the metal foil wiring. Examples thereof include a wiring and a conductive portion that is disposed in the opening of each interlayer insulating layer and connected to the wiring.

C-2. Second Embodiment A component-embedded substrate according to this aspect is a component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer, wherein the interlayer insulating layer has a resin composition. The resin composition has a resin flow rate of 80% or higher, and the cured product has a glass transition temperature of 175 ° C. or higher.

According to the component-embedded substrate of this aspect, since the cured product of the resin composition described above is used as the interlayer insulating layer, there is less void around the electronic component, and the component insulating layer has good heat resistance. It can be a substrate.
The component-embedded substrate of this aspect is the above-mentioned “C-1. First embodiment” except that the interlayer insulating layer is a cured product of the resin composition described in “A-2. Second embodiment” described above. Since this is the same as the “mode”, the description here is omitted.

D. Method for Producing Component-Incorporated Substrate The method for producing a component-embedded substrate of the present disclosure can be divided into two embodiments. Each will be described below.

D-1. First Embodiment A first aspect of a method of manufacturing a component-embedded substrate according to this aspect is a component-embedded device that manufactures a component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer. A method for manufacturing a substrate, comprising: an adhesive sheet preparation step for preparing an adhesive sheet having at least an adhesive layer; a temporary fixing step for temporarily fixing an electronic component to the adhesive layer of the adhesive sheet; and the adhesive layer being cured. A curing step as an interlayer insulating layer, wherein the adhesive layer contains a resin composition, and the resin composition includes an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, and a latent curing agent. An epoxy resin having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolak skeleton The curing accelerator containing (A) is an imidazole compound that is solid at 23 ° C.

  According to the manufacturing method of the component built-in substrate of this aspect, since the adhesive layer is the resin composition as described above, in the temporary fixing step, it is possible to ensure the fluidity of the adhesive layer, and It is possible to prevent the occurrence of voids when temporarily fixing the electronic component. Moreover, in the said hardening process, there exists an effect that it can be set as an interlayer insulation layer with high heat resistance by hardening | curing the said resin composition and setting it as an interlayer insulation layer.

  In this aspect, as above-mentioned, it has an adhesive sheet preparation process, a temporary fixing process, and a hardening process. Hereinafter, each process will be described.

1. Adhesive sheet preparation process Since the adhesive sheet prepared in the adhesive sheet preparation process in this aspect is the same as the adhesive sheet described in the above "B-1. First embodiment", description thereof is omitted here.

2. Temporary Fixing Step The temporary fixing step in this aspect is a step of temporarily fixing an electronic component to the adhesive layer included in the adhesive sheet.

In this step, when the electronic component is disposed on one surface of the adhesive layer, the electronic component may be heated, but it may not be heated because the electronic component can be attached at room temperature.
In this step, the temporarily fixed electronic component is the same as that described in “2. Electronic component” in “C-1. First embodiment”, and thus description thereof is omitted here.

3. Curing Step The curing step in this embodiment is a step in which the adhesive layer on which the electronic component is temporarily fixed is cured to form an interlayer insulating layer.

The heating temperature at the time of curing the adhesive layer can be, for example, 60 ° C. or more and 250 ° C. or less, more preferably 100 ° C. or more and 180 ° C. or less, and particularly preferably 150 ° C. or more and 180 ° C. or less. .
The heating time can be, for example, 1 minute or more and 240 minutes or less, more preferably 10 minutes or more and 120 minutes or less, and particularly preferably 30 minutes or more and 60 minutes or less.

4). Others The manufacturing method of the component-embedded substrate of this aspect is not particularly limited as long as it has the above-described adhesive sheet preparation step, temporary fixing step, and curing step.
A specific aspect of the method for manufacturing a component-embedded substrate including such other steps will be described with reference to the drawings. In addition, regarding the members such as the substrate, the second interlayer insulating layer, and the metal foil wiring in the following specific modes, “3. Substrate” and “4. Second interlayer” in “C-1. First embodiment” above. Since it is the same as that described in “Insulating layer”, “5. Metal foil wiring”, and “6. Other members”, description thereof is omitted here.

  3 (a) to 3 (h) and FIGS. 4 (a) to 4 (c) are process diagrams showing an example of a method for manufacturing a component built-in substrate according to this aspect, and a method for manufacturing the component built-in substrate shown in FIG. It is an example. First, a substrate 11 is prepared as shown in FIG. 3A, and a plurality of through holes 12a are formed in the substrate 11 as shown in FIG. Moreover, as shown in FIG.3 (c), the adhesive sheet 1 which has the contact bonding layer 3a at least is prepared. The adhesive sheet 1 shown in FIG. 3C has release layers 2a and 2b on both surfaces of the adhesive layer 3a. Next, as shown in FIG.3 (d), the surface by the side of the adhesive layer 3a of the adhesive sheet 1 is bonded to one surface of the board | substrate 11 which has the through-hole 12a. At this time, when the release layers 2a and 2b are disposed on both surfaces of the adhesive layer 3a, one of the release layers 2b is peeled off to expose the surface of the adhesive layer 3a before bonding. Next, as illustrated in FIG. 3E, electronic components 13 a and 13 b are disposed on the surface of the adhesive sheet 1 on the adhesive layer 3 a side in the through hole 12 a of the substrate 11. At this time, the electronic components 13a and 13b are temporarily fixed by the adhesiveness of the adhesive layer 3a. Next, as shown in FIG. 3F, the adhesive layer 3a is thermally cured. Thereby, the first interlayer insulating layer 3b is formed.

  Next, as shown in FIGS. 3G to 3H, the interlayer insulating film 14a is disposed on the surface of the substrate 11 opposite to the surface of the first interlayer insulating layer 3b (adhesive layer after curing). Thereafter, for example, vacuum lamination is performed and heating is performed. At this time, since the resin constituting the interlayer insulating film 14a is melted, the inside of the through hole 12a is filled with the resin, and then the resin is thermally cured. Thereby, the second interlayer insulating layer 14b is formed.

  Next, as shown in FIG. 4A, a hole 15a is formed in the first interlayer insulating layer 3b and the second interlayer insulating layer 14b. At this time, in the case where the release layer 2a is disposed on the surface of the first interlayer insulating layer 3b opposite to the surface on the substrate 11, the release layer 2a is released before the formation of the hole. Next, as shown in FIG. 4B, for example, electroless plating and electrolytic plating are performed to form the conductive portion 16 in the hole 15a, and the surfaces of the first interlayer insulating layer 3b and the second interlayer insulating layer 14b. Conductive layers 17a and 18a are formed. Next, as shown in FIG. 3C, the conductive layers 17a and 18a are patterned by, for example, photolithography to form wirings 17b and 18b.

  Thereafter, although not shown, a general multilayering process is performed. Thereby, the component built-in substrate 10 as shown in FIG. 2 can be obtained.

  6 (a) to 6 (h) and FIG. 7 (a) are process diagrams showing another example of the method for manufacturing the component-embedded substrate of this aspect, and an example of the method for manufacturing the component-embedded substrate shown in FIG. It is. First, as shown in FIG. 6A, a metal foil 31a is prepared, and an adhesive sheet 1 having at least an adhesive layer 3a is prepared. The adhesive sheet 1 shown in FIG. 6A has release layers 2a and 2b on both surfaces of the adhesive layer 3a. Next, as shown in FIG.6 (b), the surface at the side of the adhesive layer 3a of the adhesive sheet 1 is bonded to one surface of the metal foil 31a. At this time, when the release layers 2a and 2b are disposed on both surfaces of the adhesive layer 3a, one of the release layers is peeled off before the bonding to expose the surface of the adhesive layer 3a. Next, as shown in FIG.6 (c), electronic components 13a and 13b are arrange | positioned in the surface on the opposite side to the surface at the side of the metal foil 31a of the contact bonding layer 3a. At this time, the electronic components 13a and 13b are temporarily fixed by the adhesiveness of the adhesive layer 3a. At this time, if the release layer is disposed on the surface of the first interlayer insulating layer 3b opposite to the surface on the metal foil 31a side, the release layer is removed before the electronic component is disposed. Next, as shown in FIG. 6D, the adhesive layer 3a is thermally cured. Thereby, the first interlayer insulating layer 3b is formed.

  Next, as shown in FIGS. 6E to 6F, an interlayer insulating film 32a is formed on the surface of the first interlayer insulating layer 3b (adhesive layer after curing) opposite to the surface on the metal foil 31a side. After placement, for example, vacuum laminate and heat. At this time, since the resin constituting the interlayer insulating film 32a is melted, the electronic components 13a and 13b are covered with the resin, and then the resin is thermally cured. Thereby, the second interlayer insulating layer 32b is formed.

  Next, as shown in FIG. 6G, a hole 33a is formed in the first interlayer insulating layer 3b and the second interlayer insulating layer 32b. Next, as shown in FIG. 6 (h), for example, electroless plating and electrolytic plating are performed to form the conductive portion 34 in the hole 33a, and the conductive layer 35a is formed on the surface of the second interlayer insulating layer 32b. . Next, as shown in FIG. 7A, the metal foil 31a and the conductive layer 35a are patterned by, for example, photolithography to form the metal foil wiring 31b and the wiring 35b.

  Thereafter, although not shown, a general multilayering process is performed. Thereby, the component built-in substrate 10 as shown in FIG. 5 can be obtained.

D-2. Second Embodiment A second embodiment of the method for manufacturing a component-embedded substrate according to this aspect is to manufacture a component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer. A method for manufacturing a component-embedded substrate, comprising: an adhesive sheet preparation step for preparing an adhesive sheet having at least an adhesive layer; a temporary fixing step for temporarily fixing an electronic component to the adhesive layer of the adhesive sheet; and curing the adhesive layer Curing step to form an interlayer insulating layer, wherein the adhesive layer contains a resin composition, and the resin composition has a resin flow rate of 80% or more, and is a cured product after curing. The glass transition temperature is 175 ° C. or higher.

  According to the method for manufacturing a component-embedded substrate of this aspect, since the adhesive layer is the resin composition as described above, fluidity can be secured in the temporary fixing step, and the adhesive layer and the electronic component can be secured. It is possible to prevent voids from occurring between them. Moreover, in the said hardening process, there exists an effect that it can be set as an interlayer insulation layer with high heat resistance by hardening | curing the said resin composition and setting it as an interlayer insulation layer.

  The method for manufacturing a component-embedded substrate according to this aspect is the same as that described in “D-1. First Embodiment” except that the resin composition is the resin composition described in “A-2. Second Embodiment”. Since this is the same as the “mode”, the description here is omitted.

  The present disclosure is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has the same configuration as the technical idea described in the claims of the present disclosure and has the same function and effect regardless of the present embodiment. It is included in the technical scope of the disclosure.

  The present disclosure will be described in more detail with reference to examples and comparative examples below. In addition, each composition is a mass part of solid content except a solvent.

  Table 1 below shows the imidazole compounds 1 to 6 used in this example.

  The reaction start temperatures of these imidazole compounds were determined by differential scanning calorimetry (DSC). That is, first, a resin composition in which 5 parts by weight of an imidazole compound was blended with 100 parts by weight of a liquid bisphenol A type epoxy resin (molecular weight 380, epoxy equivalent 190 g / eq) was prepared. Next, 20 mg of the resin composition was measured using a DSC apparatus (differential scanning calorimeter, manufactured by Netch Co., Ltd.) under the conditions of a temperature rising rate of 10 ° C./min and a measurement range of 30 ° C. to 250 ° C. In the relationship between the calorific value (W / g) on the vertical axis and the temperature (° C) on the horizontal axis obtained by DSC, the intersection of the tangent and the temperature axis where the peak has the steepest peak in the rising curve of the lowest temperature exothermic peak The temperature at was the reaction start temperature.

[Example 1]
(Preparation of resin composition)
50 parts by mass of a bisphenol A type epoxy resin (“jER1001” Mitsubishi Chemical Corporation), 65 parts by mass of a tetrafunctional epoxy resin (tetraglycidyldiaminodiphenylmethane, “jER604” Mitsubishi Chemical Corporation), and a naphthalene type epoxy resin (“HP -4710 "DIC Corporation" 15 parts by mass, acrylic resin (PMMA-PBA-PMMA copolymer, "M22N" Arkema Corporation) 30 parts by mass, epoxy-modified silicone resin ("ES1023" Shin-Etsu Chemical Co., Ltd.) 45%) 44.4 parts by mass (20 parts by mass in terms of solid content), 2 parts by mass of an epoxy-based silane coupling agent (“KBM403”, Shin-Etsu Chemical Co., Ltd.), bisphenol A type epoxy resin and core-shell type rubber Master batch with dispersed particles Formulation amount of core shell particles whose core part is butadiene rubber: 33% by mass, 65 parts by mass of “Kaneace MX153” Kaneka Co., Ltd., 15.1 parts by mass of dicyandiamide (“Dyhard100SH” Evonik Co., Ltd.), and imidazole Compound 1 (“2PHZ-PW”, Shikoku Kasei Kogyo Co., Ltd.) 1.51 parts by mass was mixed with a stirrer and diluted with ethyl acetate to prepare a resin composition.

(Formation of adhesive layer)
On the release film 1 (“E7304”, Toyobo Co., Ltd., thickness 38 μm), the above resin composition is coated with a comma coater so that the thickness after drying the organic solvent is 35 μm, and the release film 2 is applied to the coated surface. (“E7006” Toyobo Co., Ltd., thickness 38 μm) were bonded together to produce an adhesive sheet.

[Examples 2 to 4]
As shown in Table 2, a resin composition was prepared in the same manner as in Example 1 except that the blending amounts of naphthalene type epoxy resin, dicyandiamide, and imidazole compound 1 were changed, and an adhesive sheet was produced.

[Examples 5 to 6]
As shown in Table 2, in place of the naphthalene type epoxy resin, anthracene type epoxy resin (“YX-8800”, Mitsubishi Chemical Co., Ltd.) was blended, and the blending amounts of dicyandiamide and imidazole compound 1 were changed. In the same manner as in Example 1, a resin composition was prepared and an adhesive sheet was produced.

[Examples 7 to 9]
As shown in Table 2, in place of naphthalene type epoxy resin, novolak type epoxy resin ("EPPN-502H" Nippon Kayaku Co., Ltd.) was blended, and the blending amounts of dicyandiamide and imidazole compound 1 were changed. In the same manner as in Example 1, a resin composition was prepared to produce an adhesive sheet.

[Example 10]
As shown in Table 2, in place of the naphthalene type epoxy resin, a phenol novolac type epoxy resin (“N-775” DIC Corporation) was blended, and the blending amounts of dicyandiamide and imidazole compound 1 were changed, In the same manner as in Example 1, a resin composition was prepared and an adhesive sheet was produced.

[Example 11]
As shown in Table 2, in place of the naphthalene type epoxy resin, a cresol novolac type epoxy resin ("N-673" DIC Corporation) was blended, and the blending amounts of dicyandiamide and imidazole compound 1 were changed, In the same manner as in Example 1, a resin composition was prepared and an adhesive sheet was produced.

[Example 12]
As shown in Table 2, a resin composition was prepared and bonded in the same manner as in Example 2 except that imidazole compound 2 (“2P4MZ”, Shikoku Kasei Kogyo Co., Ltd.) was blended in place of imidazole compound 1. A sheet was produced.

[Example 13]
As shown in Table 2, a resin composition was prepared and bonded in the same manner as in Example 2 except that imidazole compound 3 ("1B2PZ" Shikoku Kasei Kogyo Co., Ltd.) was blended in place of imidazole compound 1. A sheet was produced.

[Example 14]
As shown in Table 2, a resin composition was prepared in the same manner as in Example 2 except that imidazole compound 4 (“2MAOK-PW”, Shikoku Kasei Kogyo Co., Ltd.) was used instead of imidazole compound 1. An adhesive sheet was prepared.

[Example 15]
As shown in Table 2, a resin composition was prepared in the same manner as in Example 2 except that imidazole compound 5 (“2P4MHZ-PW”, Shikoku Chemical Industry Co., Ltd.) was blended in place of imidazole compound 1. An adhesive sheet was prepared.

[Example 16]
As shown in Table 2, a resin composition was prepared and bonded in the same manner as in Example 1 except that the amount of tetrafunctional epoxy resin, naphthalene type epoxy resin, dicyandiamide, and imidazole compound 1 was changed. A sheet was produced.

[Comparative Example 1]
As shown in Table 2, the phthalocyanine type epoxy resin is not blended, the dicyandiamide blending amount is changed, and the imidazole compound 1 is replaced with a tertiary amine compound ("Amicure MY-HK" Ajinomoto Fine Techno Co., Ltd.). A resin composition was prepared in the same manner as in Example 1 except that an adhesive sheet was produced.

[Comparative Example 2]
As shown in Table 2, in place of dicyandiamide and imidazole compound 1, 25 parts by mass of a novolac type phenol resin (“LA-7054” DIC Corporation) was blended, and silica particles (“SO-C4”, Admatechs Corporation). ) A resin composition was prepared in the same manner as in Example 2 except that 40 parts by mass were blended to prepare an adhesive sheet.

[Comparative Example 3]
As shown in Table 2, a resin composition was prepared and an adhesive sheet was prepared in the same manner as in Example 2 except that dicyandiamide was not blended and the blending amount of imidazole compound 1 was changed.

[Comparative Example 4]
As shown in Table 2, the amount of dicyandiamide was changed, and instead of the imidazole compound 1, a tertiary amine compound (“Amicure MY-HK” Ajinomoto Fine Techno Co., Ltd.) was added, and Example 8 and Similarly, a resin composition was prepared and an adhesive sheet was produced.

[Comparative Example 5]
Example 1 except that imidazole compound 6 (“2E4MZ” Shikoku Kasei Kogyo Co., Ltd.), which is liquid at 23 ° C., was used instead of imidazole compound 1 (“2PHZ-PW” Shikoku Kasei Kogyo Co., Ltd.) of Example 1. In the same manner as in No. 1, the resin composition was adjusted to prepare an adhesive layer sheet.
However, at the stage of forming the adhesive layer sheet, it was already cured and was not tacky.

[Evaluation]
(Glass transition temperature (Tg))
First, the adhesive sheet was heated at 150 ° C. for 30 minutes to cure the adhesive layer, and then the release films on both sides were peeled off. Thereafter, Tg of the adhesive layer after curing was measured under the following conditions by a dynamic viscoelasticity measuring method based on JIS K7244-1 using a dynamic viscoelasticity measuring device “RSA-III” (manufactured by TA Instruments). did.
・ Attachment mode: Compression mode ・ Frequency: 1.0 Hz
-Temperature range: -50 ° C to 250 ° C
・ Temperature increase rate: 5 ° C / min

(Tackiness)
First, one release film of the adhesive sheet was peeled to expose the adhesive layer, and was attached to a jig dedicated to the testing machine. A stainless steel probe having a diameter of 5.05 mm was pressed on the adhesive layer surface of the adhesive sheet at a temperature of 25 ° C., a load of 1 kgf / cm ² , a contact speed of 5 mm / min, held for 10 seconds, and then pulled at a peel speed of 1 mm / min. I peeled it off. The load when peeling was measured. This measurement was performed three times, and the average value was taken as the tack force. And it evaluated by the following reference | standard.
○: 1N / φ5.0mm or more Δ: 0.5N / φ5.0mm or more, 1N / φ5.0mm or less x: 0.5N / φ5.0mm or less

(void)
After peeling off one release film of the adhesive sheet, using a laminator ("GL835PRO" manufactured by Aco Brands Japan), copper foil ("RCF-T5B-35μ") Fukuda Metal Foil Powder Co., Ltd., thickness 35 μm The surface of the adhesive layer of the adhesive sheet was bonded to one surface of (). Next, 10 electronic components (“GRM153” from Murata Manufacturing Co., Ltd.) were placed on the adhesive layer, and heated at 150 ° C. for 30 minutes to cure the adhesive layer. Then, the obtained laminated body was cut | disconnected, the cross section of the electronic component was observed, and the presence or absence of the void directly under an electronic component was confirmed about ten electronic components. And it evaluated by the following reference | standard.
A: There are no voids immediately below the electronic parts for all 10 electronic parts. O: Among 1 to 5 electronic parts, there are voids immediately below the electronic parts. Δ: 6 out of 10 parts. There are voids directly below the electronic component for not less than 9 electronic components. X: Among 10 electronic components, there are voids immediately below the electronic component.

(Specific dielectric constant and dielectric loss tangent)
The relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured according to IEC 62810, and the relative dielectric constant and dielectric loss tangent at 10 GHz were measured according to JIS R1641. First, the release films on both sides were peeled from the adhesive sheet to prepare a test piece. The dimensions of the test piece were 16 mm × 92 mm for measurement of relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz, and 60 mm × 100 mm for measurement of relative dielectric constant and dielectric loss tangent at a frequency of 10 GHz. Next, the relative dielectric constant and dielectric loss tangent were measured with the following apparatus and conditions. The values of relative permittivity and dielectric loss tangent were measured values for one sample.
・ Measuring method: Cavity resonator method ・ Device: Vector network analyzer HP8510 (manufactured by Agilent Technologies)
Synthesizer sweeper HP83651A (same as above)
Test set HP8517B (same as above)
-Resonator dimensions: 1GHz, diameter 229mm, height 40mm
In the case of 10 GHz, the diameter is 42 mm and the height is 30 mm.
Test environment: 22 ° C, 60% RH

(Dielectric breakdown voltage)
The dielectric breakdown voltage was measured according to ASTM D149. First, the release films on both sides were peeled from the adhesive sheet to prepare a test piece. Next, the breakdown voltage was measured with the following apparatus and conditions. The value of the dielectric breakdown voltage was an average value of measured values of three samples.
・ Test equipment: Dielectric breakdown tester HAT-300-100RHO (manufactured by Yamazaki Sangyo Co., Ltd.)
-Test piece dimensions: 50 mm x 50 mm
・ Electrode size: Vertical 25mmφ cylindrical shape ・ Ambient medium: Insulating oil ・ For test ventilation: Room temperature (23 ± 2 ℃)
-Boosting speed: 0.2 kV / sec

(Resin flow rate)
The resin flow rate was measured by the method described in “1. Resin flow rate” in “A-2. Second embodiment”.

DESCRIPTION OF SYMBOLS 1 ... Adhesive sheet 2a, 2b ... Release layer 3, 3a ... Adhesive layer

Claims (16)

A component built-in substrate manufacturing method for manufacturing a component built-in substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer,
An adhesive sheet preparation step of preparing an adhesive sheet having at least an adhesive layer;
A temporary fixing step of temporarily fixing an electronic component to the adhesive layer of the adhesive sheet;
A curing step of curing the adhesive layer to form an interlayer insulating layer,
The adhesive layer contains a resin composition,
The said resin composition is a manufacturing method of the component built-in board whose resin flow rate is 80% or more, and the glass transition temperature of the hardened | cured material after hardening is 175 degreeC or more. A component built-in substrate manufacturing method for manufacturing a component built-in substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer,
An adhesive sheet preparation step of preparing an adhesive sheet having at least an adhesive layer;
A temporary fixing step of temporarily fixing an electronic component to the adhesive layer of the adhesive sheet;
A curing step of curing the adhesive layer to form an interlayer insulating layer,
The adhesive layer contains a resin composition,
The resin composition includes an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator,
The epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton,
The said hardening accelerator is a manufacturing method of the component built-in board | substrate which is a solid imidazole compound at 23 degreeC. A component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer,
The interlayer insulating layer contains a cured product of the resin composition,
The resin composition has a resin flow rate of 80% or more,
A component-embedded substrate, wherein the cured product has a glass transition temperature of 175 ° C or higher. A component-embedded substrate having at least an interlayer insulating layer and an electronic component disposed on one surface of the interlayer insulating layer,
The interlayer insulating layer contains a cured product of a resin composition containing an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator,
The epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton,
The component-embedded substrate, wherein the curing accelerator is an imidazole compound that is solid at 23 ° C.   The component built-in substrate according to claim 4, wherein the cured product has a glass transition temperature of 175 ° C. or higher. An adhesive sheet used for fixing an electronic component of a component-embedded substrate and an interlayer insulating layer,
Having at least an adhesive layer,
The adhesive layer contains a resin composition;
The resin composition has a resin flow rate of 80% or more,
The adhesive sheet whose glass transition temperature of the hardened | cured material of the said resin composition is 175 degreeC or more. An adhesive sheet having at least an adhesive layer,
The adhesive layer includes an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator,
The epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton,
The said hardening accelerator is an adhesive sheet which is a solid imidazole compound at 23 degreeC. A resin composition used for fixing an electronic component of a component-embedded substrate and an interlayer insulating layer,
The resin composition whose resin flow rate is 80% or more and whose glass transition temperature of hardened | cured material is 175 degreeC or more. The resin composition includes an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator,
The epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton,
The resin composition according to claim 8, wherein the curing accelerator is an imidazole compound that is solid at 23 ° C. A resin composition comprising an epoxy resin, an epoxy-modified silicone resin, an acrylic resin, a latent curing agent, and a curing accelerator,
The epoxy resin includes an epoxy resin (A) having at least one selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, and a novolac skeleton,
The said hardening accelerator is a resin composition which is an imidazole compound solid at 23 degreeC.   The resin composition of Claim 9 or Claim 10 whose reaction start temperature of the said imidazole compound is 110 degreeC or more.   The resin composition according to claim 9, wherein the latent curing agent is dicyandiamide.   The resin composition according to any one of claims 9 to 12, wherein the epoxy resin contains a bisphenol-type epoxy resin (B).   The resin composition according to any one of claims 9 to 13, wherein the epoxy resin includes a tri- or higher functional epoxy resin (C).   The content of the said epoxy resin (A) is 5 mass% or more and 17 mass% or less when the non volatile matter of the said resin composition is 100 mass%, Any one of Claim 9 to 14 The resin composition according to claim 1.   The resin composition according to any one of claims 10 to 15, which is used for fixing an electronic component of a component-embedded substrate and for an interlayer insulating layer.