WO2024004663A1

WO2024004663A1 - Composite material, articles made using same, and method for producing composite material

Info

Publication number: WO2024004663A1
Application number: PCT/JP2023/022181
Authority: WO
Inventors: 勇輝小原; 輝彦齊藤; 貴裕濱田; 泰礼西口
Original assignee: パナソニックＩｐマネジメント株式会社
Priority date: 2022-06-30
Filing date: 2023-06-15
Publication date: 2024-01-04

Abstract

A composite material according to the present disclosure comprises a metal-organic framework and a silicon-containing polymer. The silicon-containing polymer contains a main chain including at least one unit selected from the group consisting of a styrene unit, a butadiene unit, an ethylene unit, a cyclo-olefin unit, and a silicon-containing olefin unit. Furthermore, the silicon-containing polymer contains a functional group represented by, for example, -SiR_3-n(OX)_n, wherein n is an integer from 1 to 3, X represents an hydrogen atom, a hydrocarbon group having a carbon number from 1 to 10, a moiety bound to a metal-organic framework, or a moiety bound to a silicon atom other than the silicon atom of the functional group, at least one of the X being a moiety bound to a metal-organic framework, and R represents a hydrocarbon group having a carbon number from 1 to 10.

Description

Composite materials, their applied products, and composite material manufacturing methods

The present disclosure relates to a composite material, an applied product thereof, and a method for manufacturing the composite material.

Patent Document 1 describes a resin composition for forming an insulating film containing a metal-organic structure and a curable resin. Patent Document 2 describes organosilicon compounds used in rubber compositions. Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3 disclose methods for chemically modifying the surface of a metal-organic structure.

Japanese Patent Application Publication No. 2018-80327 Japanese Patent Application Publication No. 2016-191040

The present disclosure aims to improve the chemical stability of materials containing metal-organic frameworks.

The composite material of the present disclosure includes:
a metal-organic structure;
A silicon-containing polymer.
The silicon-containing polymer includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units.

According to the present disclosure, the chemical stability of a material containing a metal-organic framework can be improved.

FIG. 1 is a diagram showing a schematic configuration of a composite material in Embodiment 1. FIG. 2 is a flowchart illustrating an example of a method for manufacturing a composite material according to the first embodiment. FIG. 3 is a diagram showing a schematic structure of a resin composition in Embodiment 3. FIG. 4 is a cross-sectional view of a resin-coated film in Embodiment 5. FIG. 5 is a cross-sectional view of the resin-coated metal foil in Embodiment 6. FIG. 6 is a cross-sectional view of a metal-clad laminate in Embodiment 7. FIG. 7 is a cross-sectional view of a wiring board in Embodiment 8. FIG. 8 is a diagram showing the infrared absorption spectrum of the composite material of Example 1 and the infrared absorption spectrum of ZIF-8. FIG. 9 is a diagram showing an O1sXPS spectrum of the composite material of Example 1. FIG. 10 is a diagram showing the O1sXPS spectrum of ZIF-8. FIG. 11 is a diagram showing an X-ray diffraction pattern of particles synthesized in Example 2 and an X-ray diffraction simulation pattern of UiO-67.

(Findings that formed the basis of this disclosure)
In recent years, in the electronics field, the level of performance required of electronic devices has been rising as the use of fifth-generation mobile communication systems (5G) expands. For example, 5G uses higher frequency bands to provide faster communication speeds than previous generations. Therefore, electronic devices are required to have electronic components that can handle high frequencies.

Transmission loss in a transmission path depends on frequency, and increases as the signal frequency increases. Transmission loss depends on the dielectric constant and dielectric loss tangent of the insulating layer. Therefore, in order to reduce the transmission loss of high-frequency signals, materials including the substrate material and the sealing material constituting the insulating layer are required to have a low dielectric constant and a low dielectric loss tangent.

Furthermore, in large-capacity communications such as 5G, the transmission distance of radio waves is short because high frequency bands are used. Therefore, it is necessary to increase the output of electronic devices. In addition, with the realization of high integration and miniaturization, the packaging density of circuits will also increase. Attempting to satisfy these needs increases the amount of heat generated per unit area of the wiring board. Therefore, wiring boards are required to have high heat dissipation properties. In order to improve the heat dissipation of wiring boards, the substrate material that makes up the insulating layer of wiring boards contains fillers with excellent thermal conductivity to increase the thermal conductivity of wiring boards. There is.

In recent years, metal organic frameworks (MOFs) have attracted attention as fillers for insulating layers. MOF is an insulating material, also called porous coordination polymer (PCP) or nanoporous metal complex. MOF is a crystalline porous material composed of metal ions or metal clusters and crosslinkable ligands. MOF is a material with a particularly low dielectric constant. MOF has a low dielectric constant required for antenna substrates for communication base stations, etc., and can satisfy a dielectric constant of 2.0 or less in high frequency bands ranging from GHz to THz, for example. It is. Additionally, MOFs can also have lower dielectric loss tangents through appropriate selection of crystal structure. Therefore, MOF is attracting attention as a filler for insulating layers of wiring boards for various communications applications. For example, Patent Document 1 describes a resin composition for forming an insulating film containing an MOF and a curable resin. MOF has a negative coefficient of thermal expansion, similar to inorganic fillers such as silica particles that are commonly used as fillers for insulating layers. Additionally, MOF has a high porosity compared to other porous materials, so it has a low dielectric constant. Furthermore, MOFs can also have lower dielectric loss tangents by appropriate selection of the crystal structure.

By the way, a wiring board is exposed to an alkaline solution and an etching solution during the process of mounting electronic components on the wiring board. When the material of the insulating layer changes in quality due to exposure to these chemical solutions, the dielectric constant and dielectric loss tangent of the insulating layer change. In wiring boards, changes in relative dielectric constant and dielectric loss tangent during the mounting process cause problems such as worsening of transmission loss and generation of signal noise due to mismatch in impedance matching. In addition, deterioration of the material of the insulating layer causes a decrease in the mechanical strength of the insulating layer, volatilization of generated by-products, etc., leading to dimensional changes in the wiring board. Furthermore, the molded product containing the sealant must not change in quality under high temperature and high humidity conditions. Therefore, the filler of the insulating layer is required to have resistance to chemical solutions and water vapor, that is, chemical stability. Chemical stability specifically refers to base resistance, acid resistance and moisture resistance.

However, since MOF has a three-dimensional porous structure constructed by self-assembly of metal ions or metal clusters and crosslinking ligands, the structure is easily altered by bases or acids. When the structure of the MOF changes and voids disappear, the chemical stability decreases. The decrease in chemical stability is particularly noticeable in MOFs with structures with high porosity.

In order to improve the chemical stability of MOF, methods of chemically modifying the surface of MOF have been proposed. For example, in Non-Patent Document 1, a dense polydopamine layer is formed on the surface of the MOF by polymerizing dopamine molecules on the surface of the MOF, and fluorinated alkylthiol molecules are further bonded to the polydopamine layer by a Michael addition reaction. It is stated that Non-Patent Document 1 states that this improves the acid resistance and base resistance of MOF. Furthermore, in Non-Patent Document 2, various two-layer polymers were formed on the surface of MOF by coating the surface of MOF with a polyacrylate polymer having a polymerization initiation point and further polymerizing in the presence of the polyacrylate polymer. It is stated that. Non-Patent Document 2 states that this improves the acid resistance and base resistance of MOF.

However, since polydopamine and polyacrylate polymers have many polar functional groups, the chemical modification methods described in Non-Patent Document 1 and Non-Patent Document 2 may result in an increase in relative dielectric constant and dielectric loss tangent. Furthermore, in the chemical modification methods described in Non-Patent Document 1 and Non-Patent Document 2, monomer components or oligomer components easily enter the voids of the MOF during the polymerization reaction. When the polymerization reaction progresses inside the voids of the MOF, the voids are closed and the relative dielectric constant and dielectric loss tangent increase. Intrusion of monomer components or oligomer components into the voids is particularly noticeable in MOFs having a structure with a high porosity.

A method of chemically modifying the surface of MOF at the molecular level has also been proposed. For example, Non-Patent Document 3 discloses that by reacting a molecule having a phosphate site at the end of an alkyl chain with MOF and bonding the metal site on the surface of the MOF with the phosphate site of the alkyl chain, the outside of the MOF is It is described that the surface was coated with alkyl chains. Non-Patent Document 3 states that as a result, the MOF achieved high water repellency while maintaining porosity. It is also stated that high resistance to acidic and basic aqueous solutions was obtained. However, according to studies conducted by the present inventors, it was found that the chemical modification method described in Non-Patent Document 3 has insufficient chemical stability.

Here, Patent Document 2 discloses an organosilicon compound having a specific configuration. Patent Document 2 describes that when the organosilicon compound is added to a rubber composition, the hysteresis loss of the cured product is significantly reduced. However, Patent Document 2 does not describe or suggest that the surface of the filler is modified with the organosilicon compound and that the chemical stability of the filler is thereby increased.

The present inventors have conducted extensive research into improving the chemical stability of materials containing metal-organic frameworks (MOFs). As a result, we came up with the composite material of the present disclosure.

(Summary of one aspect of the present disclosure)
A composite material according to a first aspect of the present disclosure includes a metal-organic framework and a silicon-containing polymer. The silicon-containing polymer includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units. According to the above configuration, the chemical stability of the material containing the metal-organic structure can be improved.

In the second aspect of the present disclosure, for example, in the composite material according to the first aspect, the silicon-containing polymer may be attached to the surface of the metal-organic structure. According to the above configuration, the chemical stability of the material containing the metal-organic structure can be further improved.

In the third aspect of the present disclosure, for example, in the composite material according to the first or second aspect, the metal-organic structure may include a metal oxide cluster. According to the above configuration, the chemical stability of the material containing the metal-organic structure can be improved.

In the fourth aspect of the present disclosure, for example, in the composite material according to any one of the first to third aspects, the metal oxide cluster may include a Zr oxide cluster. According to the above configuration, the chemical stability of the material containing the metal-organic structure can be improved.

In a fifth aspect of the present disclosure, for example, in the composite material according to any one of the first to fourth aspects, the silicon-containing polymer may include a first side chain containing a silicon atom and an oxygen atom. Often, it may be bonded to the metal-organic framework via the silicon atom and the oxygen atom. According to the above configuration, the chemical stability of the material containing the metal-organic structure can be further improved. Furthermore, it becomes possible to form a composite of a material containing a metal-organic structure with another compound without impairing the chemical stability of the material containing the metal-organic structure.

In a sixth aspect of the present disclosure, for example, in the composite material according to any one of the first to fifth aspects, the silicon-containing polymer contains a functional group represented by -SiR _3-n (OX) _n . You can stay there. Here, n is an integer of 1 to 3, and Represents a part that is bonded to a silicon atom. At least one of X is a moiety bonded to the metal-organic structure. R represents a hydrocarbon group having 1 to 10 carbon atoms. According to the above configuration, the chemical stability of the material containing the metal-organic structure is further improved.

In a seventh aspect of the present disclosure, for example, in the composite material according to any one of the first to sixth aspects, the silicon-containing polymer is selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds. The second side chain may include at least one side chain. According to the above configuration, when a composite material is used as a filler, the heat dissipation properties of the filler are improved.

In the eighth aspect of the present disclosure, for example, in the composite material according to the seventh aspect, the second side chain may consist only of a chain structure. According to the above configuration, when a composite material is used as a filler, the heat dissipation properties of the filler are improved.

In the ninth aspect of the present disclosure, for example, in the composite material according to any one of the first to eighth aspects, the main chain may include the butadiene unit. According to the above configuration, the chemical stability of the material containing the metal-organic structure is further improved.

In the tenth aspect of the present disclosure, for example, in the composite material according to the ninth aspect, the main chain may include a copolymer containing the styrene unit and the butadiene unit. According to the above configuration, the chemical stability of the material containing the metal-organic structure is further improved.

In the eleventh aspect of the present disclosure, for example, in the composite material according to the sixth aspect, the silicon-containing polymer may be represented by the following formula (1) containing a plurality of repeating units.
In the formula (1), a and d represent a number greater than or equal to 0, b and c represent a number greater than 0, and R ¹ to R ⁵ independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, It represents an atom or -CH ₃ , and the order of the plurality of repeating units is arbitrary. According to the above configuration, the chemical stability of the material containing the metal-organic structure is further improved.

In the twelfth aspect of the present disclosure, for example, in the composite material according to the eleventh aspect, 0.15≦c/(b+c+d) may be satisfied in the formula (1). According to the above configuration, the chemical stability of the material containing the metal-organic structure is further improved.

In a thirteenth aspect of the present disclosure, for example, in the composite material according to any one of the first to twelfth aspects, the metal organic framework may include UiO-67. According to the above configuration, excellent dielectric properties are achieved.

The filler according to the fourteenth aspect of the present disclosure includes the composite material according to any one of the first to thirteenth aspects. According to the above configuration, a filler with improved chemical stability can be provided.

The resin composition according to the fifteenth aspect of the present disclosure includes the filler according to the fourteenth aspect. According to the fifteenth aspect, it is possible to provide a resin composition that exhibits a low dielectric loss tangent and has excellent heat resistance.

The prepreg according to the 16th aspect of the present disclosure includes the resin composition of the 15th aspect or a semi-cured product of the resin composition.

The resin-coated film according to the seventeenth aspect of the present disclosure is
A resin layer comprising the resin composition of the fifteenth aspect or a semi-cured product of the resin composition;
a support film;
It is equipped with

The resin-coated metal foil according to the eighteenth aspect of the present disclosure includes:
A resin layer comprising the resin composition of the fifteenth aspect or a semi-cured product of the resin composition;
metal foil and
It is equipped with

The metal clad laminate according to the nineteenth aspect of the present disclosure includes:
An insulating layer comprising a cured product of the resin composition of the fifteenth aspect or a cured product of the prepreg of the sixteenth aspect;
metal foil and
It is equipped with

The wiring board according to the 20th aspect of the present disclosure,
An insulating layer comprising a cured product of the resin composition of the fifteenth aspect or a cured product of the prepreg of the sixteenth aspect;
wiring and
We are prepared.

According to the 16th to 20th aspects, various applied products suitable for high frequencies can be provided.

A method for manufacturing a composite material according to a twenty-first aspect of the present disclosure includes attaching a silicon-containing polymer to a metal-organic framework. The silicon-containing polymer includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units. According to the above configuration, a material containing a metal-organic structure with improved chemical stability can be manufactured.

In the twenty-second aspect of the present disclosure, for example, in the method for manufacturing a composite material according to the twenty-first aspect, the metal-organic structure may include a metal oxide cluster. According to the above configuration, the chemical stability of the material containing the metal-organic structure is improved.

In the twenty-third aspect of the present disclosure, for example, in the method for manufacturing a composite material according to the twenty-first or twenty-second aspect, the number average molecular weight of the silicon-containing polymer may be 1200 or more. According to the above configuration, the chemical stability of the material containing the metal-organic structure is improved.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.

(Embodiment 1)
Embodiment 1 will be described below with reference to FIGS. 1 and 2.

[Composite material]
FIG. 1 is a diagram showing a schematic configuration of a composite material 10 in the first embodiment. The composite material 10 includes a metal organic framework 1 (hereinafter referred to as "MOF 1") and a silicon-containing polymer 2. Silicon-containing polymer 2 contains silicon atoms. The silicon-containing polymer 2 includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units.

The silicon-containing polymer 2 may be attached to the surface of the MOF 1. The silicon-containing polymer 2 may cover at least a portion of the surface of the MOF 1. The silicon-containing polymer 2 may cover the entire surface of the MOF 1, or may cover only a portion of the surface of the MOF 1.

The silicon-containing polymer 2 is a low polar polymer. The silicon-containing polymer 2 can suppress water molecules, acids, and bases from reaching the MOF 1 better than silicon-containing low-molecular-weight compounds such as alkylsilanes. Acids are, for example, protons or oxonium ions. The base is, for example, a hydroxide ion. Therefore, the composite material 10 has particularly excellent base resistance and acid resistance when the silicon-containing polymer 2 is attached to the surface of the MOF 1. That is, the composite material 10 has high chemical stability. In addition, in this disclosure, "silicon-containing low molecular compound" means an organosilicon compound with a molecular weight of less than 1,200.

The silicon-containing polymer 2 hardly penetrates into the pores of the MOF 1. In addition, the main skeleton of the main chain of silicon-containing polymer 2 is a hydrocarbon group, and like the polydopamine and polyacrylate polymers used in Non-patent Document 1 and Non-patent Document 2, it has many polar functional groups. do not have. Therefore, according to the composite material 10, increases in relative dielectric constant and dielectric loss tangent are also suppressed. In this way, in the composite material 10, an increase in relative dielectric constant and dielectric loss tangent is suppressed, and an improvement in chemical stability is realized.

[Metal-organic framework (MOF)]
MOF 1 may include one selected from the group consisting of metal oxide clusters and zeolite-like imidazolate structures (hereinafter referred to as "ZIF").

MOF1 may include metal oxide clusters. Examples of the metal oxide cluster include a metal oxide cluster containing a structural unit represented by the composition formula M ₆ O _x (OH) _8-x . M is a tetravalent group 4 element. M is, for example, Zr, Hf or Ce. The saturated coordination number is 12. M may be Zr. That is, the metal oxide cluster may be a Zr oxide cluster. Such crosslinking ligands of metal oxide clusters include, for example, carboxylate groups (-COO) and hydroxyl groups (-OH).

MOF1 may have a Zr oxide cluster and a crosslinkable ligand containing a carboxylate group. Such zirconium-based MOFs are also called Zr-MOFs. In Zr-MOF, the Zr oxide cluster includes a structural unit represented by the composition formula Zr ₆ O _x (OH) _8-x (0≦x≦8). Two or more and twelve or more crosslinkable ligands containing at least two or more carboxylate groups may be bonded to such a Zr oxide cluster. Zr-MOF having the above structure is derived from the strong bond of Zr(IV)-O, has high chemical stability and high thermal stability, and has high porosity. Therefore, Zr-MOF is particularly useful. Examples of Zr-MOF include UiO-66, UiO-67, UiO-68, NU-1000, NU-1103, MOF-808, PCN-224, DUT-52, BUT-30, MIL-140, etc. .

The Zr-MOF may be, for example, UiO-67. UiO-67 is constructed from a Zr oxide cluster containing a structural unit represented by the composition formula Zr ₆ O ₄ (OH) ₄ and 4,4'-biphenyldicarboxylate, which is a crosslinking ligand. . UiO-67 is represented by the composition formula Zr ₆ O ₄ (OH) ₄ (bpdc) ₆ . Here, bpdc represents 4,4'-biphenyldicarboxylate. UiO-67 has a helium-equivalent porosity of 68% calculated using the RASPA package (https://iraspa.org/) (see Non-Patent Document 4), and has a low dielectric constant and a low dielectric loss tangent. There is expected.

Zr-MOF particles may be used as the MOF1. The shape of the Zr-MOF particles is not particularly limited. The shape of the Zr-MOF particles may be, for example, scaly, spherical, ellipsoidal, rod-like, or amorphous. The average particle size of the Zr-MOF particles is not particularly limited. The average particle diameter of the Zr-MOF particles may be, for example, 0.01 μm or more and 100 μm or less, or 0.05 μm or more and 50 μm or less. In the present disclosure, the average particle size of Zr-MOF particles means the median diameter. The median diameter means the particle diameter (d50) when the cumulative volume in the volume-based particle size distribution is equal to 50%. The volume-based particle size distribution is measured using, for example, a laser diffraction measuring device.

MOF1 may include ZIF. MOF1 may be a ZIF. ZIF is a general term for MOFs having a three-dimensional crystal structure similar to zeolites. ZIF has a tetrahedral four-coordinate (tetrahedral: Td) central metal ion and a crosslinking ligand containing an imidazolate, and is constructed by a metal-imidazolate-metal coordination bond. Examples of the central metal ion include Zn ²⁺ and Co ²⁺ . ZIF is useful because it has high thermal stability and high porosity. Examples of ZIF include ZIF-4, ZIF-7, ZIF-8, ZIF-12, ZIF-67, ZIF-90, ZIF-412, and the like. ZIF may include Zn ²⁺ and a crosslinkable ligand including imidazolate.

ZIF may be, for example, ZIF-8. ZIF-8 is represented by the composition formula Zn ^II (2-MeIm) ₂ . Here, 2-MeIm represents 2-methylimidazolate. ZIF-8 has a sodalite crystal structure in which Zn ²⁺ is crosslinked with 2-methylimidazolate, which is a ligand, and has high thermal stability and high chemical stability. ZIF-8 has a helium-equivalent porosity of 48% calculated using the RASPA package (https://iraspa.org/) (see Non-Patent Document 5), and has a low dielectric constant and a low dielectric loss tangent. There is expected.

ZIF particles may be used as the MOF1. The shape of the ZIF particles is not particularly limited. The shape of the ZIF particles may be, for example, scaly, spherical, ellipsoidal, rod-like, or amorphous. The average particle size of ZIF particles is not particularly limited. The average particle size of the ZIF particles may be, for example, 0.01 μm or more and 100 μm or less, or 0.05 μm or more and 50 μm or less. In this disclosure, the average particle size of ZIF particles means the median size.

[Silicon-containing polymer]
Silicon-containing polymer 2 contains silicon atoms. The silicon-containing polymer 2 further includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units. The silicon-containing polymer 2 can suppress the access of water molecules, acids, and bases compared to silicon-containing low-molecular compounds such as alkylsilanes. Acids are, for example, protons and oxonium ions. The base is, for example, a hydroxide ion. Further, due to its structural characteristics, the silicon-containing polymer 2 can suppress the adsorption of moisture in the atmosphere. In addition, the silicon-containing polymer 2 itself is less likely to evaporate by heating than silicon-containing low-molecular compounds such as alkylsilanes. Therefore, the silicon-containing polymer 2 is also useful from the viewpoint of heat resistance.

In addition to the main chain, the silicon-containing polymer 2 may include side chains branching from the main chain. Silicon-containing polymer 2 may include multiple side chains. The main chain may include a first main chain made up of carbon atoms bonded to each other. The silicon-containing polymer 2 may include a side chain containing a silicon atom together with the first main chain.

The silicon-containing polymer 2 may include a first side chain containing a silicon atom and an oxygen atom. Silicon-containing polymer 2 may be bonded to MOF 1 via silicon atoms and oxygen atoms. More specifically, silicon-containing polymer 2 may include oxygen atoms bonded to silicon atoms and MOF 1.

The manner in which the silicon-containing polymer 2 is bonded to the MOF 1 via silicon atoms and oxygen atoms is assumed as follows. Usually, inside the MOF 1, a metal ion or a metal cluster has a predetermined number of sites capable of coordination, and a crosslinking ligand is bonded to each of these sites capable of coordination. On the other hand, on the surface of MOF 1, at least one site to which a crosslinking ligand is not bonded remains among the coordination possible sites possessed by the metal ion or metal cluster. The coordination possible sites exposed on the surface of MOF1 are Lewis acidic, and bond with, for example, Lewis basic oxygen atoms. That is, it is expected that an MO bond exists between the surface of MOF1 and the oxygen atom. M represents a metal atom. Therefore, in the composite material 10, at least one MO bond is expected to be formed between the silicon-containing polymer 2 and the MOF1. Furthermore, it is known that some of the remaining coordination sites have a hydroxyl group (-OH) bonded to them (see, for example, Non-Patent Document 6 and Non-Patent Document 7). That is, it is expected that M--OH bonds exist on the surface of MOF1. It is known that the M--OH bond forms a M--O--Si bond by, for example, a silane coupling reaction. From the above, it is predicted that in the composite material 10, the silicon-containing polymer 2 is bonded to the MOF 1 due to the formation of at least one MOF-Si bond between the silicon-containing polymer 2 and the MOF 1. Ru. It is also expected that the M-OH bond on the surface of MOF1 forms an M-OH-O hydrogen bond with the oxygen atom of the silicon-containing polymer. Therefore, in the composite material 10, it is expected that the silicon-containing polymer 2 is bonded to the MOF 1 by forming at least one or more M-OH-O bond between the silicon-containing polymer 2 and the MOF 1. .

For example, when MOF1 is a Zr-MOF, it is expected that a Zr coordination site or a Zr-OH bond exists on the surface of MOF1. Therefore, in this case, at least one Zr-O bond, Zr-O-Si bond, or Zr-OH-O bond is formed between the silicon-containing polymer 2 and the Zr-MOF. It is expected that polymer 2 is attached to the Zr-MOF.

Note that when the Zr-MOF is UiO-67, bpdc ligands are bonded to all (for example, 12) coordination possible sites of the Zr oxide cluster on the surface of UiO-67. Therefore, there are the least number of coordination possible sites to which no crosslinking ligand is bonded, or Zr--OH sites to which a hydroxyl group is bonded. However, since the silicon-containing polymer 2 is bonded to the surface of the MOF 1, if the Zr-MOF is UiO-67, there are also Zr coordination sites or Zr-OH sites on the surface of UiO-67. silicon-containing polymer 2 on the surface, and can form a Zr-O bond, Zr-O-Si bond, or Zr-OH-O bond with the silicon-containing polymer 2 through these sites. It is considered possible to obtain immobilized UiO-67.

For example, when MOF1 is ZIF-8, it is expected that Zn coordination sites or Zn--OH bonds are present on the surface of ZIF-8. Therefore, in this case, at least one Zn-O bond, Zn-O-Si bond, or Zn-OH-O bond is formed between the silicon-containing polymer 2 and ZIF-8, so that the silicon-containing Polymer 2 is expected to be attached to ZIF-8.

In the composite material 10, when the silicon-containing polymer 2 is immobilized on the surface of the MOF 1 by bonding, it becomes possible to form a composite with other compounds without impairing chemical stability. For example, in order to obtain a resin composition containing the composite material 10 and other compounds, a process of dissolving it in a predetermined solvent for kneading or a process of mechanical dispersion treatment is required. When the silicon-containing polymer 2 is immobilized on the MOF 1 by bonding, a state in which the silicon-containing polymer 2 is not present on the surface of the MOF 1 in the obtained resin composition can be avoided even after such a step. Even when forming a resin composition containing MOF 1, silicon-containing polymer 2, and other compounds in a one-step process, a state in which silicon-containing polymer 2 is not present on the surface of MOF 1 in the resulting resin composition can be avoided. Ru. In this way, when the silicon-containing polymer 2 is immobilized on the surface of the MOF 1 by bonding, the expected chemical stability is exhibited even in the state of the resin composition.

In addition, in the composite material 10, when the silicon-containing polymer 2 is immobilized on the surface of the MOF 1 by bonding, the surface of the MOF 1 is always covered with a low polarity polymer, which increases the dispersibility in a predetermined solvent. We can also expect an improvement in In particular, dispersibility is improved in nonpolar solvents. A non-polar solvent is, for example, toluene. This improves the dispersibility of the composite material 10 in the resin composition, so that effects such as, for example, improvement in the mechanical properties of the resin composition and suppression of variations in dielectric properties in the resin composition can be expected.

The silicon-containing polymer 2 may contain a functional group represented by -SiR _3-n (OX) _n . Here, n is an integer from 1 to 3, and X is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a bond bonded to MOF1, or a bond to a silicon atom other than the silicon atom of the above functional group. represents a joint that is The bonding portion X can also be represented by a single bond (-). A hydrocarbon group having 1 to 10 carbon atoms is, for example, an alkyl group having 1 to 10 carbon atoms, especially 1 to 3 carbon atoms. At least one of X is a bonding portion that is bonded to MOF1. R represents a hydrocarbon group having 1 to 10 carbon atoms. The silicon-containing polymer 2 having such a configuration is immobilized on the surface of the MOF 1 via MO--O--Si bonds. Therefore, the surface of MOF 1 is more densely covered with silicon-containing polymer 2, so that the chemical stability of composite material 10 is further improved.

In the functional group represented by -SiR _3-n (OX) _n , R may be an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms may have a linear, cyclic, or branched structure. Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group. group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, α-naphthyl group, β-naphthyl group, and the like.

When the silicon-containing polymer 2 contains a functional group represented by -SiR _3-n (OX) _n , and X contains a bond bonding to another silicon atom, the silicon-containing polymer 2 contains a functional group represented by -SiR 3-n (OX) n. Contains siloxane units represented by O-Si. The silicon-containing polymer 2 may include a second main chain composed of siloxane units. The silicon-containing polymer 2 having such a structure may have a network structure in which siloxane units (Si--O--Si) are spread out in a network.

The silicon-containing polymer 2 may include a second side chain containing at least one selected from the group consisting of a carbon-carbon double bond and a carbon-carbon triple bond. According to such a structure, the carbon-carbon double bond or the carbon-carbon triple bond reacts with the reactive residue of the resin contained in the insulating layer to form a bond, so that the adhesiveness between the composite material 10 and the resin is improved. Improves sex. This reduces the thermal resistance at the interface between the composite material 10 and the resin, and improves the thermal conductivity of the insulating layer. As a result, the heat dissipation of the wiring board is improved. Examples of the group containing a carbon-carbon double bond include a vinyl group, a methallyl group, an acryloyl group, and the like. The silicon-containing polymer 2 may have one type selected from these, or may have two or more types. From the viewpoint of easy reactivity, the group containing a carbon-carbon double bond is preferably a vinyl group. Examples of the reactive residue of the resin contained in the insulating layer include a vinyl group, a methallyl group, an acryloyl group, and the like. Examples of the group containing a carbon-carbon triple bond include an ethynyl group and a propargyl group. The silicon-containing polymer 2 may have one type selected from these, or may have two or more types. Examples of the reactive residue of the resin contained in the insulating layer include an ethynyl group and a propargyl group. At least one selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds may be located at the end of the second side chain. The second side chain may consist only of a chain structure.

Note that from the viewpoint of avoiding deterioration due to oxidation, it is desirable that the content of carbon-carbon double bonds and carbon-carbon triple bonds present inside the silicon-containing polymer 2 is small.

The silicon-containing polymer 2 may further include side chains other than the first side chain and the second side chain. The side chains other than the first side chain and the second side chain may have, for example, a cyclic structure. The cyclic structure of the side chain is, for example, an aryl group.

The main chain of the silicon-containing polymer 2 may include a butadiene unit. According to the above configuration, the chemical stability of the composite material 10 is further improved.

The main chain of the silicon-containing polymer 2 may include a copolymer containing styrene units and butadiene units. According to the above configuration, the chemical stability of the composite material 10 is further improved.

The silicon-containing polymer 2 may be represented by the following formula (1) containing multiple repeating units. According to such a configuration, the chemical stability of the composite material 10 is further improved.

In the above formula (1), a and d represent a number greater than or equal to 0, b and c represent a number greater than 0, and R ¹ to R ⁵ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a bromine atom. Represents an atom or -CH ₃ . However, the order of the plurality of repeating units is arbitrary. The functional group represented by -SiR _3-n (OX) _n is as explained above. In addition, in the d part of the above formula (1), the bond shown by the wavy line means either trans or cis, or a mixture of both.

In the above formula (1), the silicon-containing polymer 2 may satisfy 0≦a≦500, 1≦b≦500, 1≦c≦500, 0≦d≦500, and 5≦a≦300, 5 The following may be satisfied: ≦b≦300, 1≦c≦100, and 5≦d≦300.

In the above formula (1), the silicon-containing polymer 2 may satisfy 5≦a≦100, 5≦b≦100, 1≦c≦80, 5≦d≦100, and 5≦a≦20, 5 ≦b≦50, 1≦c≦60, and 5≦d≦40.

In the above formula (1), c represents the repeating number of butadiene units having silicon and oxygen in their side chains. (b+c+d) represents the total of a butadiene unit having a repeating number b, a butadiene unit having a repeating number c, and a butadiene unit having a repeating number d. The silicon-containing polymer 2 may satisfy 0.15≦c/(b+c+d) in the above formula (1). In other words, in the above formula (1), the value calculated by 100×{c/(b+c+d)} may be 15% or more. According to the above configuration, the chemical stability of the composite material 10 is further improved. In the above formula (1), the value calculated by 100×{c/(b+c+d)} may be 17% or more. The upper limit of the value calculated by 100×{c/(b+c+d)} is, for example, 80%. However, the value calculated by 100×{c/(b+c+d)} is not particularly limited as long as it is within a range that can exhibit desired chemical stability and dielectric properties.

[Method for manufacturing composite material]
Next, a method for manufacturing the above-mentioned composite material will be explained.

FIG. 2 is a flowchart illustrating an example of a method for manufacturing the composite material 10 in the first embodiment. The method for manufacturing composite material 10 includes attaching silicon-containing polymer 2 to the surface of MOF 1 (step S1). The silicon-containing polymer 2 includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units.

In step S1, the silicon-containing polymer 2 may be bonded to the surface of the MOF 1 via silicon atoms and oxygen atoms.

MOF 1 may include one selected from the group consisting of metal oxide clusters and ZIF. MOF1 may include metal oxide clusters.

Here, the silicon-containing polymer 2 represented by the above formula (1) is represented by the following formula (2) before being bonded to the MOF 1.

In the above formula (2), R ⁶ and R ⁷ independently represent a hydrocarbon group having 1 to 10 carbon atoms. m represents an integer from 1 to 3. a and d represent a number greater than or equal to 0, and b and c represent a number greater than 0.

In the above formula (2), R ⁶ and R ⁷ may independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms are as described for the functional group represented by -SiR _3-n (OX) _n . However, in the above formula (2), the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. R ⁶ and R ⁷ are preferably linear alkyl groups, more preferably methyl or ethyl groups, independently of each other.

In a high frequency band ranging from GHz to THz, the dielectric loss tangent largely depends on the orientational polarization of organic molecules contained in the material of the wiring board. Therefore, the hydroxyl groups present on the surface of MOF 1 can increase the dielectric loss tangent. However, in the silicon-containing polymer represented by the above formula (2), the silicon-containing polymer acts on the hydroxyl groups present on the surface of the MOF 1, thereby bonding to the surface of the MOF 1. The silicon-containing polymer 2 after bonding is represented by the above formula (1). In the composite material 10, the number of hydroxyl groups present on the surface of the MOF 1 is reduced due to the bonding of the silicon-containing polymer 2, so that an effect of suppressing an increase in the dielectric loss tangent can be expected.

The silicon-containing polymer represented by the above formula (2) can be obtained through the reaction shown in the scheme below. Specifically, a styrene-butadiene copolymer represented by the following formula (3) and an organosilicon compound represented by the following formula (4) are combined in the presence of a platinum compound-containing catalyst, preferably a platinum compound-containing catalyst and an assistant. Hydrosilylation occurs in the presence of a catalyst. Thereby, a silicon-containing polymer represented by the above formula (2) can be obtained.

The styrene-butadiene copolymer represented by the above formula (3) can be synthesized by a known method such as emulsion polymerization or solution polymerization using butadiene and styrene as raw material monomers. The styrene-butadiene copolymer represented by the above formula (3) can also be obtained as a commercial product. Commercially available products include, for example, Ricon 100, Ricon 181, Ricon 184 (all manufactured by Clay Valley), L-SBR-820, L-SBR-841 (all manufactured by Kuraray), 1,2-SBS (all manufactured by Nippon Soda). (manufactured by), etc.

Examples of the organosilicon compound represented by the above formula (4) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane.

Note that the value of c is maintained before and after the silicon-containing polymer is bonded to the surface of MOF1. That is, the value of c in the above equation (2) and the value of c in the above equation (1) are equal. Therefore, in the above equation (2), the silylation rate calculated by 100 x {c/(b+c+d)} is the same as the silylation rate calculated by 100 x {c/(b+c+d)} in the above equation (1). It can be considered as

In the state before bonding to the surface of MOF 1, the number average molecular weight of the silicon-containing polymer may be 1200 or more, or 5000 or more. According to the above configuration, the density of the coating with the silicon-containing polymer 2 is improved, so that the chemical stability of the composite material 10 is improved. The upper limit of the number average molecular weight of the silicon-containing polymer before bonding to the surface of MOF 1 is not particularly limited. The upper limit of the number average molecular weight of the silicon-containing polymer before bonding to the surface of MOF 1 is, for example, 10,000 or less. Note that in the present disclosure, the number average molecular weight is a polystyrene-equivalent number average molecular weight calculated using gel permeation chromatography (GPC).

In step S1, silicon-containing polymer 2 may be bonded to the surface of MOF 1. For example, when the silicon-containing polymer before bonding to the surface of MOF 1 is represented by the above formula (2), silicon-containing polymer 2 can be bonded to the surface of MOF 1 by the following reaction. When the surface of MOF 1 and the silicon-containing polymer 2 are bonded via an M-O bond or a M-OH-O bond, O in -SiR _3-n (OX) _n is bonded to M or M-OH. do. When the surface of MOF 1 and the silicon-containing polymer 2 are bonded via an M-O-Si bond, first, the silicon-containing polymer represented by the above formula (2) is hydrolyzed to form a silanol group (Si-OH). is generated. Next, the silanol groups are partially bonded by dehydration condensation with the hydroxyl groups present on the surface of MOF1. At this time, a metal-oxygen-silicon bond (MO-Si bond) formed by dehydration condensation is formed between the silicon-containing polymer and the surface of MOF1. As a result, the silicon-containing polymer 2 is immobilized on the surface of the MOF 1 by bonding. Furthermore, dehydration condensation between the silicon-containing polymers 2 can be promoted by heat treatment or addition of an acid or a base. As a result, the silicon-containing polymers 2 are continuously bonded to each other via siloxane bonds (Si--O--Si). By doing so, the thickness of the layer of silicon-containing polymer 2 can also be controlled. The thickness of the layer of the silicon-containing polymer 2 should be selected under appropriate conditions depending on the properties of the MOF 1, the required dielectric properties and chemical stability, and further depending on the properties of the resin of the insulating layer. Bye.

(Embodiment 2)
The filler according to the present embodiment contains the composite material 10 according to the first embodiment.

The filler according to this embodiment may be a filler for forming an insulating layer. In the present disclosure, the filler for forming an insulating layer is a filler that is mixed with a resin component and used as an insulating material for a wiring board, a sealing material in an IC chip, or the like. When the filler according to this embodiment is used as a filler for forming an insulating layer, it is possible to improve chemical stability while suppressing increases in relative dielectric constant and dielectric loss tangent.

The filler according to this embodiment is manufactured by, for example, kneading the composite material 10 according to Embodiment 1 with an epoxy resin, a silicone resin, or a non-silicone acrylic resin or ceramic resin. sell.

(Embodiment 3)
FIG. 3 is a diagram showing a schematic configuration of a resin composition 20 in Embodiment 3. The resin composition 20 includes, for example, a filler 22 and a curable resin 24.

The filler 22 includes the composite material 10 described in Embodiment 1. According to this embodiment, it is possible to provide a resin composition 20 that exhibits a low dielectric loss tangent and has excellent heat resistance. As the filler 22, only the composite material 10 may be used, or other filler materials such as silica particles may be used in combination with the composite material 10.

Examples of the curable resin 24 include epoxy resins, cyanate ester compounds, maleimide compounds, phenol resins, acrylic resins, polyamide resins, polyamideimide resins, thermosetting polyimide resins, and polyphenylene ether resins. As the curable resin 24, one kind or a combination of two or more kinds selected from these can be used.

The resin composition 20 may contain other components. Other ingredients include curing agents, flame retardants, ultraviolet absorbers, antioxidants, reaction initiators, silane coupling agents, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, and erasers. Examples include foaming agents, dispersants, leveling agents, brighteners, antistatic agents, polymerization inhibitors, and organic solvents. As other components, one type or a combination of two or more types selected from these can be used as necessary.

(Embodiment 4)
The prepreg according to Embodiment 4 includes the resin composition 20 of Embodiment 3 shown in FIG. 3 or a semi-cured product thereof, and a fibrous base material. The fibrous base material is present in the matrix of the resin composition 20 or semi-cured material. Prepreg is a composite material of the resin composition 20 and a fibrous base material. According to this embodiment, it is possible to provide a prepreg suitable for high-frequency wiring boards.

In this embodiment, the semi-cured material refers to a material that is partially cured to the extent that the resin composition 20 can be further cured. That is, the semi-cured material is a material obtained by semi-curing the resin composition 20. For example, when the resin composition 20 is heated, its viscosity gradually decreases. If heating is continued, curing will then begin and its viscosity will gradually increase. In such a case, the semi-cured state includes the state of the resin composition 20 during the period from the time when the viscosity starts to increase until the time when it is completely cured.

As the fibrous base material, known materials used in various electrically insulating material laminates can be used. Examples of the fibrous base material include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper.

The resin composition 20 is impregnated into the fibrous base material through treatments such as dipping and coating. By heating the fibrous base material impregnated with the resin composition 20 under predetermined heating conditions, a pre-cured or semi-cured prepreg according to the present embodiment can be obtained.

(Embodiment 5)
FIG. 4 is a cross-sectional view of a resin-coated film 30 in Embodiment 5. The resin-coated film 30 includes a resin layer 32 containing the resin composition 20 or a semi-cured product thereof, and a support film 34. According to this embodiment, a resin-coated film 30 suitable for an insulating layer can be provided. The resin layer 32 is supported by a support film 34. In the example of FIG. 4, a support film 34 is placed on the surface of the resin layer 32. However, another layer such as an adhesive layer may be provided between the resin layer 32 and the support film 34.

The resin layer 32 contains the resin composition 20 of Embodiment 3 shown in FIG. 3 or a semi-cured product thereof, and may or may not contain a fibrous base material. As the fibrous base material, the same material as the fibrous base material of the prepreg can be used. The resin layer 32 hardens and changes into an insulating layer. An example of such an insulating layer is an insulating layer of a wiring board.

As the support film 34, any support film used for resin-coated films can be used without limitation. Examples of the support film 34 include resin films such as polyester films and polyethylene terephthalate films.

(Embodiment 6)
FIG. 5 is a cross-sectional view of resin-coated metal foil 40 in Embodiment 6. The resin-coated metal foil 40 includes a resin layer 42 containing the resin composition 20 or a semi-cured product thereof, and a metal foil 44. A resin layer 42 is supported by a metal foil 44. According to this embodiment, a resin-coated metal foil 40 suitable for electronic circuit components such as wiring boards can be provided. In the example of FIG. 5, a metal foil 44 is placed on the surface of the resin layer 42. However, another layer such as an adhesive layer may be provided between the resin layer 42 and the metal foil 44.

The resin layer 42 contains the resin composition of Embodiment 3 shown in FIG. 3 or a semi-cured product thereof, and may or may not contain a fibrous base material. As the fibrous base material, the same material as the fibrous base material of the prepreg can be used. The resin layer 42 hardens and changes into an insulating layer. An example of such an insulating layer is an insulating layer of a wiring board.

As the metal foil 44, resin-coated metal foil and metal foil used for metal-clad laminates can be used without limitation. Examples of the metal foil include copper foil and aluminum foil.

(Embodiment 7)
FIG. 6 is a cross-sectional view of a metal-clad laminate 50 in Embodiment 7. Metal-clad laminate 50 includes an insulating layer 52 and at least one metal foil 54 . According to this embodiment, a metal-clad laminate 50 suitable for a wiring board can be provided. The insulating layer 52 includes a cured product of the resin composition 20 of the third embodiment shown in FIG. 3 or a cured product of the prepreg of the fourth embodiment. Metal foil 54 is placed on the surface of insulating layer 52. In this embodiment, metal foils 54 are placed on each of the front and back surfaces of the insulating layer 52.

The metal-clad laminate 50 is typically manufactured using the prepreg of Embodiment 4. For example, a laminate is formed by stacking 1 to 20 sheets of prepreg. A metal-clad laminate 50 is obtained by placing metal foil on one or both sides of the prepreg laminate and heating and pressurizing the prepreg laminate. Examples of the metal foil 54 include copper foil, aluminum foil, and the like.

For example, the molding conditions for manufacturing a laminate for electrically insulating materials and a multilayer board can be applied to the molding conditions for manufacturing the metal-clad laminate 50.

(Embodiment 8)
FIG. 7 is a cross-sectional view of wiring board 60 in Embodiment 8. Wiring board 60 includes an insulating layer 62 and wiring 64. According to this embodiment, a wiring board 60 suitable for high frequencies can be provided. The insulating layer 62 includes a cured product of the resin composition 20 of the third embodiment shown in FIG. 3 or a cured product of the prepreg of the fourth embodiment. The wiring 64 is supported by the insulating layer 62. Specifically, the wiring 64 is arranged on the insulating layer 62. Wiring 64 may be formed by partially removing the metal foil.

By patterning the metal foil 54 on the surface of the metal-clad laminate 50 shown in FIG. 6 by a method such as etching, a wiring board 60 in which wiring 64 forming a circuit is provided on the surface of the insulating layer 62 is obtained. That is, the wiring board 60 is obtained by partially removing the metal foil 54 on the surface of the metal-clad laminate 50 so that a circuit is formed.

A new laminate may be formed by laminating the prepreg of Embodiment 4 on at least one surface of the wiring board 60 and applying heat and pressure. A multilayer wiring board can be obtained by patterning the metal foil on the surface of the obtained laminate to form wiring.

Examples are shown below to specifically explain the present disclosure. The examples are illustrative of the disclosure and are not limiting.

≪Example 1≫
[Metal-organic framework (MOF)]
As the MOF, ZIF-8 particles (manufactured by Aldrich, product name: Basolite Z1200) were used.

[Synthesis of silicon-containing polymer]
A silicon-containing polymer represented by the above formula (2) was synthesized as a silicon polymer. Specifically, a styrene-butadiene copolymer represented by the above formula (3) (manufactured by Nippon Soda Co., Ltd., product number: 1,2-SBS) and an organosilicon compound represented by the above formula (4) (manufactured by Tokyo Kasei Kogyo Co., Ltd., product number: 1,2-SBS) (product number: T0135, m=3, R ⁶ =H) was hydrosilylated in the presence of a platinum catalyst. Thereby, the silicon-containing polymer of Example 1 represented by the above formula (2) was obtained. The composition of the obtained silicon-containing polymer was determined from the ratio of the integral values of the peaks corresponding to each functional group in the profile obtained from ¹ H nuclear magnetic resonance (NMR) measurement (600 MHz). JNM ECZ600R manufactured by JEOL was used as an NMR apparatus. As a result, the silicon-containing polymer of Example 1 has a=10, b=61, c=13, d=0, m=3, R ⁶ =methyl group (-CH ₃ ) in the above formula (2). It was fulfilling. The silylation rate of the silicon-containing polymer of Example 1 was 17.6%. The silylation rate was confirmed by calculating the ratio of the end to which the functional group represented by --SiR ² _3-m (OR ¹ ) _m was introduced and the end to which the functional group was not introduced. The number average molecular weight of the silicon-containing polymer was calculated to be 5900 by GPC measurement (manufactured by Tosoh Corporation, HLC-8320GPC).

[Synthesis of composite materials]
A first solution was obtained by dissolving 2.5 g of silicon-containing polymer in 5 mL of toluene. Next, 2 g of ZIF-8 particles were added to 20 mL of toluene, and the particles were dispersed using an ultrasonic cleaner to obtain a second solution. While stirring the second solution with a magnetic stirrer, the previously prepared first solution was added, and the mixture was stirred at room temperature for 12 hours. Thereafter, a powder was obtained by filtration. After adding toluene to the obtained powder and performing ultrasonic dispersion, the supernatant liquid was removed by centrifugation. After repeating the above washing operation three times, it was dried in the air. As a result, composite material particles of Example 1 were obtained.

[Confirmation of bonding of silicon-containing polymer]
It was confirmed by the infrared absorption spectrum and O1sXPS spectrum of the composite material that the silicon-containing polymer was bonded to the surface of ZIF-8 in the composite material of Example 1. Infrared absorption spectra were obtained by the diffuse reflection method of Fourier transform infrared spectroscopy (FT-IR).

FIG. 8 shows the infrared absorption spectrum of the composite material of Example 1 and the infrared absorption spectrum of ZIF-8. In FIG. 8, the horizontal axis indicates wave number (cm ^-1 ), and the vertical axis indicates transmittance (%). Note that since FIG. 8 is a diagram for comparing trends of two infrared absorption spectra, the scale on the vertical axis is omitted. As shown in FIG. 8, in the composite material of Example 1, a peak P derived from the bending vibration of the vinyl group was observed, which confirmed the presence of silicon-containing polymer on the surface of ZIF-8. Ta.

FIG. 9 shows the O1sXPS spectrum of the composite material of Example 1. FIG. 10 shows the O1sXPS spectrum of ZIF-8. In FIGS. 9 and 10, the horizontal axis indicates binding energy (eV), and the vertical axis indicates intensity in arbitrary units. As shown in FIG. 9, peak separation of the O1sXPS spectrum of the composite material of Example 1 confirmed Si--O--Zn bonds and Si--O--Si bonds. From these results, it was confirmed that in the composite material of Example 1, the silicon-containing polymer was immobilized on the surface of ZIF-8 via bonds including Zn--O--Si bonds.

[Preparation of membrane containing composite material]
A membrane of Example 1 containing 40 vol % of the composite material particles of Example 1 was produced by the following method. Note that the density of the composite material particles was 0.921 g/cm ³ , and the density of all other constituent elements was 1 g/cm ³ . First, 0.7950 g of reactive low molecular weight (molecular weight 2400) polyphenylene ether as the main component of the resin and 0.0900 g of allyl cyanurate derivative (manufactured by Shikoku Kasei Co., Ltd., product name: L-DAIC), 0.0150 g of dicumyl peroxide as a polymerization initiator, and 0.5526 g of the composite material particles of Example 1 were added in this order to obtain a mixture. The mixture was dispersed for 3 minutes using an ultrasonic cleaner, and then stirred for 30 minutes using a magnetic stirrer to obtain a suspension. The suspension was heated at 90° C. for 1 hour, and then vacuumed at 110° C. for 3 minutes several times. As a result, a paste-like solid from which the solvent had been removed was obtained. The paste-like solid was pressed for 5 minutes at 150° C. and 10 MPa, and subsequently pressed for 5 minutes at 190° C. and 10 MPa to harden it. Thereafter, the film of Example 1 was obtained by evacuation at 200° C. for 12 hours. The thickness of the film in Example 1 was 0.273 mm. The thickness of the film was measured at five arbitrary points on the film, and was determined as the average value of the measured values.

≪Comparative example 1≫
As the MOF, the ZIF-8 particles used in Example 1 (manufactured by Aldrich, product name: Basolite Z1200) were used. In Comparative Example 1, a composite material was synthesized using polydopamine instead of the silicon-containing polymer. Dopamine has recently attracted attention as a natural adhesive that strongly binds to the surface of inorganic fillers. 4.2 g of trishydroxymethylaminomethane was dissolved in 100 mL of deionized water, and then hydrochloric acid was added to obtain a Tris buffer solution adjusted to pH 7. Next, 3 g of ZIF-8 particles were added to the Tris buffer solution, and while stirring with a magnetic stirrer, 2.25 g of dopamine hydrochloride was added and stirred at 80° C. for 20 hours. Thereafter, a powder was obtained by filtration. After adding deionized water to the obtained powder and performing ultrasonic dispersion, the supernatant liquid was removed by centrifugation. After repeating the above washing operation three times, the composite material particles of Comparative Example 1 were obtained by drying in the air. Since the color of the powder changed from white to gray, which is characteristic of a dopamine layer, it was confirmed that the surface of the ZIF-8 powder was modified with a dopamine layer.

≪Comparative example 2≫
As the MOF, the ZIF-8 particles used in Example 1 (manufactured by Aldrich, product name: Basolite Z1200) were used. In Comparative Example 2, a composite material was synthesized using 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-503) instead of the silicon-containing polymer. 3-methacryloxypropyltrimethoxysilane is one of the common silane coupling agents made of a silicon-containing low-molecular compound. Surface modification was carried out in the same manner as in Example 1, except that the silicon-containing polymer was changed to 3-methacryloxypropyltrimethoxysilane.

A membrane of Comparative Example 2 was produced in the same manner as in Example 1, except that the composite material particles of Comparative Example 2 were used as the composite material particles. The thickness of the film of Comparative Example 2 was 0.268 mm.

≪Comparative example 3≫
As the particles of Comparative Example 3, the ZIF-8 particles (manufactured by Aldrich, product name: Basolite Z1200) used in Example 1 were used as they were.

A membrane of Comparative Example 3 was produced in the same manner as in Example 1, except that ZIF-8 particles of Comparative Example 3 were used as composite material particles. The thickness of the film of Comparative Example 3 was 0.260 mm.

The dielectric properties and chemical stability of each particle obtained in Example 1 and Comparative Examples 1 to 3 described above were evaluated before and after surface modification based on the method described below.

[Evaluation of pore volume of particles before and after surface modification]
The pore volume at a relative pressure of 0.99 of the ZIF-8 particles before and after surface modification was measured by nitrogen adsorption measurement at 77K. BELSORP MINI X manufactured by Microtrac Bell was used as a nitrogen adsorption measuring device. During the measurement, the particles were pretreated under the conditions of vacuum (10 Pa or less), 200° C., and 1 hour. The results are shown in Table 1.

[Evaluation of dielectric properties of particles before and after surface modification]
The relative dielectric constant and dielectric loss tangent of the ZIF-8 particles before and after surface modification were measured by a cavity resonance method at a frequency of 1 GHz. MS46122B manufactured by AET was used as the cavity resonator. During the measurement, the particles were pretreated under the conditions of vacuum (10 Pa or less), 200° C., and 1 hour. Thereafter, measurements were performed in the atmosphere. The filling factor of the sample tube was calculated from the true density of ZIF-8, and the relative dielectric constant and dielectric loss tangent of the particles were calculated. The dielectric constant and dielectric loss tangent of the particles were calculated by converting the actually measured values by the filling factor of the sample tube. The filling factor of the sample tube was determined from the mass of the particles, the bulk volume occupied by the particles in the sample tube, and the true density of each particle. As the true density of ZIF-8, the density calculated from the crystal structure (0.921 g/cm ³ ) was used. The true density of the particles after surface modification was determined from the following formulas (X1) and (Y1). The porosity of ZIF-8 was 50%. The results are shown in Table 1. If the dielectric constant after surface modification was 2.00 or less and the dielectric loss tangent was 0.003 or less, it was determined that the dielectric properties were not deteriorated by surface modification.
True density of particles after surface modification = (density calculated from the crystal structure of ZIF-8) ÷ ((porosity of ZIF-8 x 0.01) x (porosity maintenance rate) x 0.01)... Formula (X1)
Void maintenance rate = (pore volume of particles after surface modification) ÷ (pore volume of particles before surface modification)...Equation (Y1)

[Evaluation of chemical stability of film before and after etching treatment]
The dielectric constant of the film containing composite material particles before and after etching was measured by cavity resonance method at a frequency of 40 GHz. MS46122B manufactured by AET was used as the cavity resonator. The results are shown in Table 1. If the absolute value of the change in relative dielectric constant before and after etching treatment is 0.02 or less, the film is chemically stable enough to not cause design problems when applied as an insulating layer of a wiring board. It was determined that the person has sex. Note that 0.02 or less is also within the error range of the measuring device (±0.02). The etching process was performed under the following conditions. As the etching solution, a cupric chloride solution (HCl concentration: 2.5 mol/liter: containing CuCl ₂ , H ₂ O ₂ , and H ₂ O), which is commonly used in the patterning process of copper plates, was used. A film cut into 4 cm x 4 cm was soaked in the etching solution for 80 hours at room temperature. Thereafter, the membrane was washed several times with water and vacuumed at 40° C. for 30 minutes. Thereby, a film after etching treatment was obtained.

≪Consideration≫
As shown in Table 1, in Example 1, no deterioration of the dielectric constant and dielectric loss tangent was observed after surface modification, and excellent dielectric properties were exhibited.

As shown in Table 1, in Example 1, there was almost no change in the dielectric constant before and after the etching treatment, and excellent chemical stability was exhibited. This is believed to be because in Example 1, the etching treatment caused almost no change in the structure of ZIF-8.

On the other hand, in Comparative Example 1, the relative dielectric constant and dielectric loss tangent increased due to surface modification, and the dielectric properties deteriorated. This is thought to be because a polymerization reaction progressed inside the pores of ZIF-8 during surface modification, resulting in occlusion of the pores, and also because hydroxyl groups (-OH) present in large amounts in the dopamine skeleton were exposed on the surface. . In Comparative Example 2, although the deterioration of dielectric properties due to surface modification was somewhat alleviated compared to Comparative Example 1, the relative dielectric constant changed due to the etching treatment, similar to Comparative Example 3 without a surface modification layer. This is considered to be because, in Comparative Example 2, the structure of ZIF-8 collapsed due to the etching process, particles were eluted into the etching solution, and voids increased.

≪Example 2≫
[Synthesis of metal-organic framework (MOF)]
UiO-67 was used as the MOF. UiO-67 particles were synthesized by the same synthesis method as UiO-67 of sample C-3BA described in Non-Patent Document 8. It was confirmed by powder X-ray diffraction measurement that the synthesized particles had the structure of UiO-67. RINT2000 manufactured by Rigaku Co., Ltd. was used as a powder X-ray diffraction measuring device. Cu-Kα radiation (λ=1.541 Å) was used as an X-ray source in powder X-ray diffraction. FIG. 11 shows an example of the X-ray diffraction pattern of the particles synthesized in Example 2 and an X-ray diffraction simulation pattern of UiO-67 predicted from the crystal structure. In FIG. 11, the horizontal axis shows the diffraction angle (2θ), and the vertical axis shows the X-ray intensity. Note that since FIG. 11 is a diagram for comparing trends of two X-ray diffraction patterns, the scale on the vertical axis is omitted. Since the trends of the X-ray diffraction patterns of both particles were similar, it was determined that the crystal structure of the particles synthesized in Example 2 was UiO-67.

[Silicon-containing polymer]
The silicon-containing polymer synthesized in Example 1 was used as the silicon-containing polymer.

[Synthesis of composite materials]
A first solution was obtained by dissolving 1 g of silicon-containing polymer in 5 mL of toluene. Next, 3 g of UiO-67 particles were added to 30 mL of toluene, and the particles were dispersed using an ultrasonic cleaner to obtain a second solution. While stirring the second solution with a magnetic stirrer, the previously prepared first solution was added, and the mixture was stirred at room temperature for 12 hours. Thereafter, a powder was obtained by filtration. After adding toluene to the obtained powder and performing ultrasonic dispersion, the supernatant liquid was removed by centrifugation. After repeating the above washing operation three times, it was dried in the air. As a result, composite material particles of Example 2 were obtained.

[Confirmation of bonding of silicon-containing polymer]
Since it was confirmed that the silicon-containing polymer was bonded to the surface of MOF (ZIF-8) in the composite material of Example 1, the silicon-containing polymer was bonded to the surface of the MOF (ZIF-8) in the composite material of Example 2 as well. It was speculated that this bonded to the surface of MOF (UiO-67).

≪Comparative example 4≫
UiO-67 synthesized in Example 2 was used as the MOF. In Comparative Example 4, a composite material was synthesized using polydopamine instead of the silicon-containing polymer. Dopamine has recently attracted attention as a natural adhesive that strongly binds to the surface of inorganic fillers. It is known that a polydopamine film is formed by self-oxidative polymerization of dopamine on the surface of a MOF. 4.2 g of trishydroxymethylaminomethane was dissolved in 100 mL of deionized water, and then hydrochloric acid was added to obtain a Tris buffer solution adjusted to pH=7. Next, 3 g of UiO-67 particles were added to the Tris buffer, and while stirring with a magnetic stirrer, 2.25 g of dopamine hydrochloride was added and stirred at 80° C. for 20 hours. Thereafter, a powder was obtained by filtration. After adding deionized water to the obtained powder and performing ultrasonic dispersion, the supernatant liquid was removed by centrifugation. After repeating the above washing operation three times, the composite material particles of Comparative Example 1 were obtained by drying in the air. Since the color of the powder changed from white to gray, which is characteristic of a dopamine layer, it was confirmed that the surface of the UiO-67 powder was modified with a dopamine layer.

≪Comparative example 5≫
UiO-67 synthesized in Example 1 was used as the MOF. In Comparative Example 5, a composite material was synthesized using 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-503) instead of the silicon-containing polymer. 3-methacryloxypropyltrimethoxysilane is one of the common silane coupling agents made of a silicon-containing low-molecular compound. Surface modification was carried out in the same manner as in Example 2, except that the silicon-containing polymer was changed to 3-methacryloxypropyltrimethoxysilane.

≪Comparative example 6≫
As the particles of Comparative Example 6, UiO-67 synthesized in Example 2 was used as it was.

The dielectric properties and chemical stability of each particle obtained in Example 2 and Comparative Examples 4 to 6 described above were evaluated before and after surface modification based on the method described below.

[Evaluation of dielectric properties of particles before and after surface modification]
The dielectric properties of UiO-67 particles before and after surface modification were evaluated for Examples and Comparative Examples using the following three methods.

[Evaluation of pore volume of particles before and after surface modification]
The pore volume of the UiO-67 particles before and after surface modification at a relative pressure of 0.99 was measured by nitrogen adsorption measurement at 77K. BELSORP MINI X manufactured by Microtrac Bell was used as a nitrogen adsorption measuring device. During the measurement, the particles were pretreated under vacuum (10 Pa or less) at 150° C. for 5 hours. The results are shown in Table 2.

[Evaluation of dielectric properties of particles before and after surface modification]
The relative dielectric constant and dielectric loss tangent of the UiO-67 particles before and after surface modification were measured by a cavity resonance method at a frequency of 1 GHz. Considering the possibility that UiO-67 particles adsorb moisture in the atmosphere, which may affect the values of the dielectric constant and dielectric loss tangent, measurements of the dielectric constant and dielectric loss tangent were carried out in powder form under an _N2 atmosphere. I went there. MS46122B manufactured by AET was used as the cavity resonator. During the measurement, the particles were pretreated under vacuum (10 Pa or less) at 150° C. for 5 hours. Thereafter, the sample tube was filled with particles under an N ₂ atmosphere without being exposed to the atmosphere, and measurements were performed. The filling factor of the sample tube was calculated from the true density of UiO-67, and the relative dielectric constant and dielectric loss tangent of the particles were calculated. The dielectric constant and dielectric loss tangent of the particles were calculated by converting the actually measured values by the filling factor of the sample tube. The filling factor of the sample tube was determined from the mass of the particles, the bulk volume occupied by the particles in the sample tube, and the true density of each particle. The density calculated from the crystal structure (0.708 g/cm ³ ) was used as the true density of UiO-67. The true density of the particles after surface modification was determined from the following formulas (X2) and (Y1). The porosity of UiO-67 was 68%. The results are shown in Table 2. If the dielectric constant after surface modification was 2.00 or less and the dielectric loss tangent was 0.002 or less, it was determined that the dielectric properties were not deteriorated by the surface modification.
True density of particles after surface modification = (density calculated from the crystal structure of UiO-67) ÷ ((porosity of UiO-67 x 0.01) x (porosity maintenance rate) x 0.01)... Formula (X2)
Void maintenance rate = (pore volume of particles after surface modification) ÷ (pore volume of particles before surface modification)...Equation (Y1)

[Evaluation of chemical stability of particles after etching treatment]
The chemical stability of the composite material particles after the etching process was evaluated for Example 2 and Comparative Examples 4 to 6 using the following three methods.

[Evaluation of pore volume of particles after etching treatment]
The pore volume of the composite material particles after the etching treatment was measured by nitrogen adsorption measurement at 77K as described above. The results are shown in Table 1. The etching process was performed under the following conditions. As the etching solution, a cupric chloride solution (HCl concentration: 2.5M: containing CuCl ₂ , H ₂ O ₂ , and H ₂ O), which is commonly used in patterning processing of copper plates, was used. 5 mL of etching solution was impregnated with 1 g of particles for 1 minute and stirred. Thereafter, the particles were washed with water and filtered to obtain etched particles.

[Evaluation of dielectric properties of particles after etching treatment]
The dielectric constant and dielectric loss tangent of the composite material particles after the etching treatment were measured by the cavity resonance method at a frequency of 1 GHz as described above. The relative permittivity and dielectric loss tangent of the particles were calculated by converting the actually measured values by the filling factor of the sample tube. The filling factor of the sample tube was determined from the mass of the particles, the bulk volume occupied by the particles in the sample tube, and the true density of each particle. The true density of the particles after the etching process was determined from the following equations (X3) and (Y2). The results are shown in Table 2. If the dielectric constant after etching treatment was 2.00 or less and the dielectric loss tangent was 0.002 or less, it was determined that the dielectric constant was maintained low enough to be applicable as a low dielectric filler for an insulating layer.
True density of particles after etching treatment = (true density of particles after surface modification) ÷ ((porosity of UiO-67 x 0.01) x (porosity maintenance rate) x 0.01)...Equation (X3 )
Void maintenance rate = (pore volume of particles after surface modification) ÷ (pore volume of particles after etching treatment)...Equation (Y2)

The etching process was performed under the following conditions. As the etching solution, a cupric chloride solution (HCl concentration 2.5 mol/liter: containing CuCl ₂ , H ₂ O ₂ , and H ₂ O) was used. 5 mL of etching solution was impregnated with 1 g of particles for 1 minute and stirred. Thereafter, the particles were washed with water and filtered to obtain etched particles.

≪Consideration≫
As shown in Table 2, in Example 2, the voids were relatively maintained, and increases in the relative dielectric constant and dielectric loss tangent after surface modification were suppressed.

As shown in Table 2, in Example 2, the voids were relatively maintained even after the etching treatment, and increases in the relative permittivity and dielectric loss tangent were suppressed. That is, the composite material of Example 2 had improved chemical stability.

On the other hand, in Comparative Example 4, the relative dielectric constant and dielectric loss tangent increased due to surface modification. This is thought to be because a polymerization reaction progressed inside the pores of UiO-67 during surface modification, resulting in occlusion of the pores, and also because hydroxyl groups (-OH) present in large amounts in the dopamine skeleton were exposed on the surface. . In Comparative Example 5, although the increase in relative permittivity and dielectric loss tangent due to surface modification is suppressed compared to Comparative Example 4, the increase in relative permittivity and dielectric loss tangent due to the etching treatment is suppressed as compared to Comparative Example 6 without a surface modification layer. has increased significantly. This is considered to be because in Comparative Example 5, the three-dimensional porous structure of UiO-67 progressed to collapse due to the etching process.

As described above, in the composite materials of Examples 1 and 2, chemical stability was improved while suppressing increases in relative permittivity and dielectric loss tangent. Therefore, by using such a composite material as a filler, it is expected that the resin composition will have a low dielectric constant and dielectric loss tangent, and that the alteration of the three-dimensional porous structure of the MOF due to etching treatment will be suppressed. . As a result, it is possible to provide a product that can be mounted as an insulating layer on a wiring board.

In Example 1, ZIF-8 is used as the MOF, but instead of ZIF-8, for example, ZIF-4, ZIF-7, ZIF-12, ZIF-67, ZIF-90, or ZIF- Even when ZIF such as No. 412 is used, it is presumed that chemical stability is improved while suppressing increases in relative dielectric constant and dielectric loss tangent. Further, in Example 2, UiO-67 is used as the MOF, but instead of UiO-67, for example, UiO-66, UiO-68, NU-1000, NU-1103, MOF-808, PCN-224 Even when Zr-MOF such as , DUT-52, BUT-30, or MIL-140 is used, it is presumed that chemical stability is improved while suppressing increases in relative dielectric constant and dielectric loss tangent. . This is because the composite material of the present disclosure achieves improved chemical stability while suppressing increases in relative dielectric constant and dielectric loss tangent by including MOF and silicon-containing polymer.

Although the present disclosure has been adequately and fully described through the embodiments above to express the present disclosure, those skilled in the art will readily be able to modify and/or improve the above-described embodiments. should be recognized as such. Therefore, unless the modification or improvement made by a person skilled in the art does not go beyond the scope of the claims stated in the claims, the modifications or improvements are within the scope of the claims. It is interpreted as encompassing.

The composite material of the present disclosure can realize a filler with excellent dielectric properties and chemical stability, so it is suitable for applications such as wiring boards of electronic devices used for large-capacity communications.

1 Metal-organic structure 2 Silicon-containing polymer 10 Composite material 20 Resin composition 22 Filler 24 Curable resin 30 Resin-coated film 32 Resin layer 34 Support film 40 Resin-coated metal foil 42 Resin layer 44 Metal foil 50 Metal-clad laminate 52 Insulation Layer 54 Metal foil 60 Wiring board 62 Insulating layer 64 Wiring

Claims

a metal-organic structure;
a silicon-containing polymer;
The silicon-containing polymer includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units.
Composite material.
the silicon-containing polymer is attached to the surface of the metal-organic structure;
Composite material according to claim 1.
The metal-organic framework includes metal oxide clusters.
Composite material according to claim 1.
The metal oxide cluster includes a Zr oxide cluster.
Composite material according to claim 3.
The silicon-containing polymer includes a first side chain containing a silicon atom and an oxygen atom, and is bonded to the metal-organic framework via the silicon atom and the oxygen atom.
Composite material according to claim 1.
The silicon-containing polymer contains a functional group represented by -SiR 3-n (OX) n ,
n is an integer from 1 to 3,
X represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a moiety bonded to the metal-organic structure, or a moiety bonded to a silicon atom other than the silicon atom of the functional group,
At least one of X is a moiety bonded to the metal organic structure,
R represents a hydrocarbon group having 1 to 10 carbon atoms,
Composite material according to claim 1.
The silicon-containing polymer includes a second side chain containing at least one selected from the group consisting of a carbon-carbon double bond and a carbon-carbon triple bond.
Composite material according to claim 1.
The second side chain consists of only a chain structure,
Composite material according to claim 7.
the main chain includes the butadiene unit,
Composite material according to claim 1.
the main chain comprises a copolymer comprising the styrene units and the butadiene units;
Composite material according to claim 9.
The silicon-containing polymer is represented by the following formula (1) containing a plurality of repeating units,
Composite material according to claim 6.
In the above formula (1),
a and d represent a number of 0 or more,
b and c represent numbers greater than 0,
R 1 to R 5 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or -CH 3 ,
The order of the plurality of repeating units is arbitrary.
In the formula (1), 0.15≦c/(b+c+d) is satisfied,
Composite material according to claim 11.
The metal-organic framework includes UiO-67.
Composite material according to claim 1.
Comprising the composite material according to claim 1.
filler.
Comprising the filler according to claim 14,
Resin composition.
comprising the resin composition according to claim 15 or a semi-cured product of the resin composition,
prepreg.
A resin layer comprising the resin composition according to claim 15 or a semi-cured product of the resin composition,
a support film;
Film with resin.
A resin layer comprising the resin composition according to claim 15 or a semi-cured product of the resin composition,
comprising a metal foil and
Metal foil with resin.
An insulating layer comprising a cured product of the resin composition according to claim 15 or a cured product of the prepreg according to claim 16,
comprising a metal foil and
Metal-clad laminate.
An insulating layer comprising a cured product of the resin composition according to claim 15 or a cured product of the prepreg according to claim 16,
Wiring and equipped,
wiring board.
depositing a silicon-containing polymer on the metal-organic framework;
The silicon-containing polymer includes a main chain containing at least one selected from the group consisting of styrene units, butadiene units, ethylene units, cycloolefin units, and fluorine-containing olefin units.
Method of manufacturing composite materials.
The metal-organic framework includes metal oxide clusters.
A method for manufacturing a composite material according to claim 21.
The number average molecular weight of the silicon-containing polymer is 1200 or more,
A method for manufacturing a composite material according to claim 21.