Multilayer body, method for manufacturing multilayer body, printed circuit board, semiconductor device, and method for manufacturing printed circuit board

Abstract

Provided are a multilayer body capable of achieving reduction in transmission loss, a multilayer body, a method for manufacturing a multilayer body, a printed circuit board, a semiconductor device, and a method for manufacturing a printed circuit board. A multilayer body has a first insulating resin layer and a second insulating resin layer in contact with the first insulating resin layer, the dielectric loss tangent of the second insulating resin layer at a frequency of 10 GHz as determined by a perturbation method cavity resonator being lower than the dielectric loss tangent of the first insulating resin layer.

Description

Technical Field

[0001] This invention relates to multilayer bodies, methods for manufacturing multilayer bodies, printed circuit boards, semiconductor devices, and methods for manufacturing printed circuit boards. Background Technology

[0002] In recent years, the miniaturization and weight reduction of various electronic devices, exemplified by smartphones, and the increase in data communication volume have been rapidly advancing. Among these advancements, the high-frequency response of printed circuit boards used in electronic devices is being further promoted.

[0003] As an example of research on such printed circuit boards, there is Patent Document 1, etc. Patent Document 1 discloses a prepreg, a metal-clad laminate, and a printed circuit board. The prepreg has a first resin layer and a second resin layer disposed on both sides of the first resin layer. The first resin layer is a semi-cured product of a first resin composition impregnated with glass cloth that does not contain hexagonal boron nitride. The second resin layer is a semi-cured product of a second resin composition containing hexagonal boron nitride. The weave density of the glass cloth in both the longitudinal and transverse directions is 54 threads or more / 25 mm. The average particle size of the hexagonal boron nitride is 10 to 30 µm. The prepreg contains 20 to 40 parts by mass of the hexagonal boron nitride, relative to 100 parts by mass of the remaining components after removing the hexagonal boron nitride from the second resin composition.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-170748 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] Patent Document 1 describes how the relative permittivity can be reduced by using the prepreg or similar materials described in Patent Document 1. However, no research was conducted on transmission loss. Reducing transmission loss is one of the most demanding performance characteristics in response to the miniaturization and weight reduction of various electronic devices and the rapid increase in data communication volume.

[0009] The object of the present invention is to provide a multilayer body capable of reducing transmission loss, as well as a multilayer body, a method for manufacturing a multilayer body, a printed circuit board, a semiconductor device, and a method for manufacturing a printed circuit board.

[0010] Solution for solving the problem

[0011] Based on the above-mentioned problems, the inventors conducted research and found that the above-mentioned problems can be solved by using a multilayer of insulating resin layer on the surface of the insulating resin layer having a dielectric loss tangent that is lower than that of the insulating resin layer.

[0012] Specifically, the above-mentioned problems were solved through the following solution.

[0013] <1> A multilayer having a first insulating resin layer and a second insulating resin layer in contact with the first insulating resin layer, wherein the dielectric loss tangent of the second insulating resin layer at a frequency of 10 GHz measured by a perturbation cavity resonator is lower than the dielectric loss tangent of the first insulating resin layer at a frequency of 10 GHz measured by a perturbation cavity resonator.

[0014] <2> according to <1> In the multilayer body, the thermal expansion coefficient of the first insulating resin layer, as determined by TMA (thermo-mechanical analysis), is below 30 ppm / ℃.

[0015] <3> according to <1> or <2> In the multilayer body, the difference between the dielectric loss tangent of the second insulating resin layer and the dielectric loss tangent of the first insulating resin layer is greater than 0.002.

[0016] <4> according to <1> ~ <3> In any one of the multilayer bodies, the thermal expansion coefficient of the first insulating resin layer, as determined by TMA (Thermo-mechanical analysis), is less than 30 ppm / °C.

[0017] The difference between the dielectric loss tangent of the second insulating resin layer and the dielectric loss tangent of the first insulating resin layer is greater than 0.002.

[0018] <5> according to <1> ~ <4> The multilayer body according to any one of the following, wherein the first insulating resin layer comprises a fiber substrate.

[0019] <6> according to <1> ~ <5> In any one of the multilayer bodies, the first insulating resin layer is a layer formed from a resin composition (1) containing a thermosetting compound and a fiber substrate.

[0020] <7> according to <1> ~ <6> The multilayer body according to any one of the following, wherein the second insulating resin layer does not contain a fiber substrate.

[0021] <8> according to <7> The multilayer body, wherein the second insulating resin layer is a layer formed from the resin composition (2),

[0022] The resin composition (2) contains a thermosetting compound, and the content of the filler material is 0 to 40% of the mass of the solid resin component contained in the resin composition (2).

[0023] <9> according to <1> ~ <8> In any one of the multilayer bodies, the second insulating resin layer is configured to contact both sides of the first insulating resin layer.

[0024] <10> according to <9> The multilayer body further includes a metal foil that contacts the surface of the second insulating resin layer opposite to the first insulating resin layer.

[0025] <11> according to <1> ~ <10> In any one of the multilayer bodies, a metal foil is further provided such that it contacts the surface of the second insulating resin layer opposite to the first insulating resin layer.

[0026] <12> according to <1> ~ <11> In any one of the multilayer bodies, the thermal expansion coefficient of the first insulating resin layer, as determined by TMA (Thermo-mechanical analysis), is less than 30 ppm / °C.

[0027] The difference between the dielectric loss tangent of the second insulating resin layer and the dielectric loss tangent of the first insulating resin layer is greater than 0.002.

[0028] The first insulating resin layer is a layer formed from a resin composition (1) containing a thermosetting compound and a fiber substrate.

[0029] The second insulating resin layer does not contain a fiber substrate.

[0030] The second insulating resin layer is a layer formed from the resin composition (2).

[0031] The resin composition (2) comprises a thermosetting compound, and the filler content is 0-40% by mass of the solid resin component contained in the resin composition (2).

[0032] The second insulating resin layer is configured to contact both sides of the first insulating resin layer.

[0033] <13> according to <12> The multilayer body further includes a metal foil that contacts the surface of the second insulating resin layer opposite to the first insulating resin layer.

[0034] <14> according to <13> The multilayer body further includes metal wiring on the surface of the second insulating resin layer.

[0035] <15> according to <14> The multilayer body has a third insulating resin layer disposed on the surface of the second insulating resin layer and covering the metal wiring.

[0036] <16> according to <1> ~ <15> In any one of the multilayer bodies, the first insulating resin layer is a layer formed of a resin composition (1) and a fiber substrate, wherein the resin composition (1) is in a cured state.

[0037] The second insulating resin layer is a layer formed of resin composition (2), wherein the resin composition (2) is in a cured state.

[0038] The resin composition (1) comprises a thermosetting compound,

[0039] The resin composition (2) contains a thermosetting compound, and the content of the filler material is 0 to 40% of the mass of the solid resin component contained in the resin composition (2).

[0040] <17> according to <1> ~ <16> The method for manufacturing a multilayer body according to any one of the following includes: bonding a second insulating resin layer side having a second insulating resin layer having a metal foil on one surface to a first insulating resin layer.

[0041] <18> according to <17> The method for manufacturing the multilayer includes: removing the protective film of a second insulating resin layer with a metal foil on one surface and a protective film on the other surface, thereby obtaining the second insulating resin layer with a metal foil on one surface.

[0042] <19> according to <17> or <18> The method for manufacturing the multilayer body includes:

[0043] The first insulating resin layer and the second insulating resin layer are bonded in a semi-cured state.

[0044] <20> A printed circuit board comprising <1> ~ <16> The multilayer body as described in any one of the following.

[0045] <21> A semiconductor device comprising <20> The printed circuit board mentioned above.

[0046] <22> A method for manufacturing a printed circuit board, comprising: <17> ~ <19> The method for manufacturing a multilayer body as described in any one of the above.

[0047] The effects of the invention

[0048] According to the present invention, it is possible to provide a multilayer body that can achieve a reduction in transmission loss, as well as a multilayer body, a method for manufacturing a multilayer body, a printed circuit board, a semiconductor device, and a method for manufacturing a printed circuit board. Attached Figure Description

[0049] Figure 1 This is a schematic diagram illustrating an example of a multilayer body (metal foil laminate) according to an embodiment.

[0050] Figure 2 This is a schematic diagram showing another example of a multilayer body in this embodiment.

[0051] Figure 3 This is a schematic diagram showing another example of a multilayer body in this embodiment.

[0052] Figure 4 This is a schematic diagram illustrating the manufacturing method of the multilayer body according to this embodiment. Detailed Implementation

[0053] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. It should be noted that the following embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0054] It should be noted that in this specification, the "~" symbol is used to encompass the numerical values ​​described before and after it as lower and upper limits. Furthermore, any combination of the upper and lower limits mentioned in this specification can be used as an example of this embodiment.

[0055] Unless otherwise specified, all physical property values ​​and characteristic values ​​in this specification are values ​​at 23°C.

[0056] In the description of groups (atomic groups) in this specification, the expressions "unsubstituted" and "unsubstituted" together include groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl) but also alkyl groups with substituents (substituted alkyl). In this specification, the expressions "unsubstituted" and "unsubstituted" are preferably unsubstituted.

[0057] Examples of substituents used in this specification are preferably halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthioalkyl, arylthioalkyl, acyl, or amino; more preferably halogen atoms, alkyl, alkoxy, aryl, aryloxy, alkenyl, or acyl; even more preferably alkyl, aryl, aryloxy, or alkenyl; and even more preferably alkyl. The formula weight of these substituents is preferably 15 or more, and preferably 200 or less. For example, in the case of methyl (-CH3), the formula weight is 15. These substituents may further have substituents, but it is preferable that they do not have substituents.

[0058] In this specification, "(meth)allyl" means either or both of allyl and methylallyl, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid.

[0059] In this specification, the term "process" is not only used for independent processes, but also for processes that cannot be clearly distinguished from other processes, as long as the desired effect of the process can be achieved.

[0060] Unless otherwise specified, the measurement methods described in the standards shown in this instruction manual may vary depending on the year, and are based on the standards as of January 1, 2023.

[0061] In the event that the measurement methods, etc., described in the standards shown in this specification become obsolete on January 1, 2023, the standards based on the obsolescence date shall apply.

[0062] Figures 1-4 Sometimes the scale and other parameters do not match reality.

[0063] A semi-cured state (semi-cured material) refers to a stage between an uncured state and a cured state (fully cured state). If the semi-cured state is heated, it will become a cured state once it melts.

[0064] Examples of uncured states include resin compositions containing solvents and varnishes.

[0065] Examples of semi-cured states include resin solids in prepregs formed from resin compositions (such as solvent-free components in the resin composition), and resin solids in metal foil laminates containing the prepregs.

[0066] Examples of cured states include resin solids in metal-clad laminates that are fully cured, and resin solids derived from resin compositions present in printed circuit boards.

[0067] Furthermore, the layer formed from the resin composition can be in any of the following states: uncured, semi-cured, or cured. The resin composition is preferably in an uncured state, and the layer formed from the resin composition is preferably in a semi-cured and / or cured state.

[0068] In this specification, the term "solid resin components" refers to components other than fillers and solvents, and mainly includes thermosetting compounds and resin additives.

[0069] In this specification, relative permittivity and permittivity are used with the same meaning.

[0070] The multilayer structure of this embodiment is characterized by having a first insulating resin layer and a second insulating resin layer in contact with the first insulating resin layer. The dielectric loss tangent of the second insulating resin layer at a frequency of 10 GHz, measured by a perturbation method cavity resonator, is lower than that of the first insulating resin layer at the same frequency. By configuring it in this way, the transmission loss of the metal wiring disposed on the surface of the second insulating resin layer can be effectively suppressed. The reason for this is presumably that by making the second insulating resin layer have a lower dielectric loss tangent, even high-frequency signals can be transmitted efficiently.

[0071] In this embodiment, the difference in dielectric loss tangent between the first insulating resin layer and the second insulating resin layer in contact with the first insulating resin layer is preferably 0.002 or more, more preferably 0.003 or more, even more preferably 0.004 or more, and preferably 0.01 or less. By setting it to the lower limit or above, there is a tendency for the dielectric loss tangent of the second insulating resin layer to be relatively lower, and the low transmission loss effect of the multilayer to be further improved. In addition, by setting it to the upper limit or below, there is a tendency for the thermal expansion characteristics of the first insulating resin layer to be relatively lower, and the low thermal expansion effect of the multilayer to be further improved.

[0072] When there are two second insulating resin layers in contact with the first insulating resin layer, the difference in dielectric loss tangent is set as the difference between the larger of the two dielectric loss tangents. Preferably, each of the second insulating resin layers in contact with the first insulating resin layer satisfies the difference in dielectric loss tangent.

[0073] In this embodiment, the dielectric loss tangent of the first insulating resin layer is preferably 0.011 or less, more preferably 0.008 or less, and typically exceeds 0.004, and may further exceed 0.005 or 0.008. In this embodiment, even if the dielectric loss tangent of the first insulating resin layer is slightly increased, the transmission loss of the multilayer as a whole can be reduced. Therefore, the first insulating resin layer can be configured to have a composition with lower thermal expansion.

[0074] In this embodiment, the dielectric loss tangent of the second insulating resin layer is preferably 0.011 or less, more preferably 0.008 or less, even more preferably 0.005 or less, and even more preferably 0.004 or less. The lower the lower limit of the dielectric loss tangent of the second insulating resin layer, the better; even a value of 0.0001 or more is sufficient to meet the required performance.

[0075] The dielectric loss tangent described above was measured according to the method described in the embodiments described later.

[0076] The thickness of the multilayer in this embodiment is not particularly limited. The total thickness of the first insulating resin layer, the second insulating resin layer, and the metal foil provided as needed is preferably 3000µm or less, more preferably 2500µm or less, and even more preferably 2000µm or less. Furthermore, it is preferably 100µm or more, more preferably 150µm or more, and even more preferably 200µm or more. By setting the thickness to be below the upper and lower limits, there is a tendency to further reduce the dielectric loss tangent of the multilayer.

[0077] In the multilayer structure of this embodiment, it is preferable that the thickness of the second insulating resin layer is thinner than the thickness of the first insulating resin layer. By making the thickness of the second insulating resin layer thinner, the second insulating resin layer achieves a skin effect, allowing electrical signals to pass through more easily.

[0078] In this embodiment, the ratio of the thickness of the first insulating resin layer and the thickness of the second insulating resin layer in contact with the first insulating resin layer of the multilayer is preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less, and even more preferably 0.6 or less. It is also preferably 0.0001 or more, more preferably 0.0005 or more, and even more preferably 0.00 or more. By setting it to the upper limit or below, there is a tendency to further reduce the dielectric loss tangent of the multilayer. Furthermore, by setting it to the lower limit or above, there is a tendency to further reduce the dielectric loss tangent of the multilayer and more effectively suppress transmission loss.

[0079] It should be noted that when the second insulating resin layer of the two layers is in contact with the first insulating resin layer, the thickness of the thinner second insulating resin layer is set as described above.

[0080] In the multilayer body of this embodiment, the thickness of the first insulating resin layer is preferably 5000µm or less, more preferably 4000µm or less, even more preferably 3000µm or less, and preferably 100µm or more, more preferably 150µm or more, and even more preferably 200µm or more.

[0081] In the multilayer of this embodiment, the thickness of the second insulating resin layer is preferably 300µm or less, more preferably 200µm or less, even more preferably 150µm or less, and even more preferably 100µm or less. It is also preferably 1µm or more, more preferably 3µm or more, even more preferably 5µm or more, and even more preferably 10µm or more. By setting it to the upper limit or below, there is a tendency to further reduce the thermal expansion coefficient of the multilayer. Furthermore, by setting it to the lower limit or above, there is a tendency to further reduce the transmission loss of the multilayer.

[0082] Next, the layer structure of the multilayer body of this embodiment will be shown in the accompanying drawings.

[0083] Figure 1 This diagram illustrates an example of a multilayer body (metal foil laminate) according to this embodiment. 1 represents the multilayer body, 2 represents the first insulating resin layer, 3 represents the second insulating resin layer in contact with the first insulating resin layer, and 4 represents the metal foil. In this embodiment, the metal foil 4 is not mandatory; it can also be a multilayer body composed of the first insulating resin layer 2 and the second insulating resin layer 3, or a multilayer body composed of three layers stacked in the order of second insulating resin layer 3 / first insulating resin layer 2 / second insulating resin layer 3. Furthermore, other layers may be included without departing from the spirit of the invention.

[0084] exist Figure 1 In this configuration, the second insulating resin layer 3.3 is arranged to contact both sides of the first insulating resin layer 2.

[0085] In addition, Figure 1 In this process, metal foils 4 and 4 are respectively arranged in contact with the surface opposite to the first insulating resin layer 2 of the second insulating resin layer 3 and 3.

[0086] Figure 1 Its shape is suitable for use as a material handling stage before processing for printed circuit boards (especially circuit boards).

[0087] Furthermore, the multilayer structure in this embodiment is not necessarily as described. Figure 1 A second insulating resin layer 3 and a metal foil 4 are respectively provided on both sides of the first insulating resin layer. For example, the second insulating resin layer can be provided on only one side of the first insulating resin layer, or the second insulating resin layer can be provided on only one side of the first insulating resin layer, with the metal foil further disposed in contact with the side opposite to the first insulating resin layer of the second insulating resin layer. Furthermore, in Figure 1 In this process, the two second insulating resin layers 3 can be the same layer, or they can be second insulating resin layers with different thicknesses and / or compositions. The same applies to metal foils.

[0088] Figure 2 This is another example of a multilayer body in this embodiment, in which a second insulating resin layer 3 is provided on the surface of the first insulating resin layer 2, but no metal foil is provided.

[0089] In addition, Figure 2 In this structure, metal wiring 5 is provided on the surface of the second insulating resin layer 3. The metal wiring is preferably copper wiring, and is fabricated using known methods such as subtractive methods (etching a metal foil to form a circuit) and (semi-)additive methods (plating a conductor layer onto an insulating layer). Such a multilayer structure is preferably used as a circuit board.

[0090] Figure 3 This is another example of a multilayer body of the present invention, in which a metal wiring 5 is provided on the surface of the second insulating resin layer 3, and a third insulating resin layer 6 is provided to cover the metal wiring 5.

[0091] That is, such as Figure 2 As shown, the third insulating resin layer 6 can be formed by providing metal wiring 5 on the surface of the second insulating resin layer 3 and then covering it with the third insulating resin layer 6. The third insulating resin layer 6 is generally preferably made of the same raw material as the second insulating resin layer 3, which will be described later.

[0092] In addition, as another example of the multilayer body of the present invention, a multilayer body can be illustrated as follows: having a first insulating resin layer, a metal wiring disposed on the surface of the first insulating resin layer, and a second insulating resin layer disposed on the surface of the first insulating resin layer and covering the metal wiring, wherein the dielectric loss tangent of the second insulating resin layer at a frequency of 10 GHz measured by a perturbation cavity resonator is lower than the dielectric loss tangent of the first insulating resin layer at a frequency of 10 GHz measured by a perturbation cavity resonator.

[0093] The details of the first insulating resin layer and the second insulating resin layer are the same as those described above, and the preferred scope is also the same.

[0094] One example of the implementation of the multilayer in this embodiment is the use of the multilayer for applications requiring a low coefficient of thermal expansion.

[0095] One of the performance requirements for printed circuit boards is sometimes a low coefficient of thermal expansion. Additionally, suppression of warpage during heating is sometimes required. When the multilayer of this embodiment is used for applications requiring these properties, the coefficient of thermal expansion of the first insulating resin layer, as measured by the TMA (Thermo-mechanical analysis) method, is preferably 30 ppm / °C or less. In this way, because the first insulating resin layer has a low coefficient of thermal expansion, even if the second insulating resin layer has a high coefficient of thermal expansion, the increase in the coefficient of thermal expansion of the multilayer can be suppressed, and warpage of the multilayer can also be suppressed. As a result, the second insulating resin layer can also possess other functions besides low thermal expansion and low warpage (further low dielectric properties (Dk and / or Df)). It should be noted that the thermal expansion coefficient mentioned here is determined according to the TMA (Thermo-Mechanical Analysis) method specified in JLS C 6481 5.19, which is the coefficient of thermal expansion in the plane direction from 50°C to 280°C when the temperature rises from 30°C to 320°C at a rate of 10°C per minute. More specifically, it is determined by the method described in the examples.

[0096] Therefore, the thermal expansion coefficient of the first insulating resin layer is preferably 30 ppm / ℃ or less, more preferably 25 ppm / ℃ or less, even more preferably 20 ppm / ℃ or less, even more preferably 15 ppm / ℃ or less, and even more preferably 10 ppm / ℃ or less. The lower limit of the thermal expansion coefficient of the first insulating resin layer is preferably 0 ppm / ℃, but even 1 ppm / ℃ or more is sufficient to meet the required performance.

[0097] The low thermal expansion rate of the first insulating resin layer is achieved, for example, by increasing the proportion of filler material in the first insulating resin layer (e.g., more than the proportion of filler material in the second insulating resin layer). That is, by reducing the proportion of easily thermally expanding resin components in the first insulating resin layer, the thermal expansion of the first insulating resin layer can be effectively suppressed. The first insulating resin layer preferably comprises a fiber substrate. Details of the composition of the first insulating resin layer will be described later.

[0098] On the other hand, the surface of the insulating resin layer containing filler material, especially a fiber substrate, is uneven, which tends to cause deviations in electronic signals. Therefore, when the first insulating resin layer contains filler material, especially a fiber substrate, the second insulating resin layer is preferably configured to be free of filler material (especially a fiber substrate). By configuring it in this way, the surface becomes smooth, and the transmission loss of the resulting multilayer can be reduced more effectively. Details of the composition of the second insulating resin layer will be described later.

[0099] In this case, the second insulating resin layer tends to have a smaller amount of filler material compared to the first insulating resin layer, therefore it is particularly preferable to have a fiber-free substrate. Consequently, the thermal expansion coefficient of the second insulating resin layer typically tends to be higher than that of the first insulating resin layer. The thermal expansion coefficient of the second insulating resin layer can, for example, exceed 10 ppm / °C, further exceed 15 ppm / °C, and is preferably below 30 ppm / °C.

[0100] <First insulating resin layer>

[0101] In this embodiment, the first insulating resin layer is not particularly limited as long as it has a dielectric loss tangent greater than or equal to that of the second insulating resin layer at a frequency of 10 GHz as measured by the perturbation method cavity resonator of the second insulating resin layer.

[0102] The first insulating resin layer is typically a layer formed from a resin composition (1) containing a thermosetting compound and a fiber substrate, or a layer formed from a resin composition (1) containing a thermosetting compound, preferably a layer formed from a resin composition (1) containing a thermosetting compound and a fiber substrate.

[0103] In the layer formed by the resin composition (1), the resin solid component contained in the resin composition (1) may be in an uncured state, a semi-cured state, or a cured state. Preferably, the resin solid component contained in the resin composition (1) is in a semi-cured state or a cured state.

[0104] The thermosetting compound contained in the resin composition (1) is preferably a thermosetting compound containing at least one group selected from the group consisting of (methyl)allyl compounds, maleimide compounds, epoxy compounds, cyanate ester compounds, phenolic compounds, oxetane compounds, benzoxazine compounds, compounds having polymerizable unsaturated groups other than said compounds, organosilicon-modified thermosetting compounds and BT resins.

[0105] BT resin refers to a polymer formed by polymerizing cyanate ester compounds and maleimide compounds.

[0106] It should be noted that, for example, epoxy compounds containing (methyl)allyl groups may also be present in the aforementioned thermosetting compounds. Regarding such compounds, those explicitly stated in any of the categories such as "(methyl)allyl compounds" described later are classified as those explicitly stated categories (e.g., (methyl)allyl compounds). Compounds not explicitly stated are classified in this specification as those described in the preceding paragraphs.

[0107] The total amount of thermosetting compound in the resin composition (1) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, and preferably 99 parts by mass or less, more preferably 95 parts by mass or less, and even more preferably 90 parts by mass or less.

[0108] The resin composition (1) may contain only one thermosetting compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0109] The first example of a blend of thermosetting compounds in the resin composition (1) is a form comprising at least one selected from (methyl)allyl compounds, maleimide compounds, epoxy compounds, cyanate compounds, phenolic compounds, benzoxazine compounds and compounds having polymerizable unsaturated groups other than said compounds, and comprising at least one of organosilicon-modified thermosetting compounds.

[0110] The first example of a blend of thermosetting compounds in the resin composition (1) more preferably includes at least one selected from (methyl)allyl compounds, maleimide compounds, epoxy compounds and cyanate ester compounds, and includes at least one of organosilicon-modified thermosetting compounds.

[0111] In the first example of the blended form of the thermosetting compound in the resin composition (1), the content of the organosilicon-modified thermosetting compound is preferably 1 part by mass or more, and preferably 50 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the resin solids.

[0112] In the first example of a blend of thermosetting compounds in the resin composition (1), the content of thermosetting compounds other than the organosilicon-modified thermosetting compound is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, further preferably 70 parts by mass or more, and preferably 99 parts by mass or less, more preferably 95 parts by mass or less, relative to 100 parts by mass of the resin solids. The thermosetting compounds other than the organosilicon-modified thermosetting compounds are preferably selected from at least one of (methyl)allyl compounds, maleimide compounds, epoxy compounds, cyanate ester compounds, phenolic compounds, benzoxazine compounds, and compounds having polymerizable unsaturated groups other than those compounds.

[0113] A second example of the blended form of the thermosetting compound in the resin composition (1) is a form comprising one or more compounds selected from the group consisting of (methyl)allyl compounds, maleimide compounds, epoxy compounds, cyanate ester compounds, phenolic compounds, benzoxazine compounds, compounds having polymerizable unsaturated groups other than said compounds, and BT resin. In the second example, in terms of total amount, it is preferable to include one or more compounds selected from the group consisting of maleimide compounds, epoxy compounds, cyanate ester compounds, phenolic compounds, and BT resin in a proportion of 90 parts by mass or more relative to 100 parts by mass of the resin solids.

[0114] In a second example of a blend of thermosetting compounds in the resin composition (1), 3 to 50 parts by mass of maleimide compound are preferably included relative to 100 parts by mass of the total amount of thermosetting compounds.

[0115] In a second example of the blended form of the thermosetting compound in the resin composition (1), it is preferable to include 10 to 80 parts by mass of an epoxy compound relative to 100 parts by mass of the total amount of the thermosetting compound.

[0116] In a second example of a blend of thermosetting compounds in the resin composition (1), 10 to 60 parts by mass of a cyanate compound are preferably included relative to 100 parts by mass of the total amount of thermosetting compounds.

[0117] In a second example of a blend of thermosetting compounds in the resin composition (1), 10 to 60 parts by mass of a phenolic compound are preferably included relative to 100 parts by mass of the total amount of thermosetting compounds.

[0118] In a second example of a blend of thermosetting compounds in the resin composition (1), 20 to 80 parts by mass of BT resin are preferably included relative to 100 parts by mass of the total amount of thermosetting compounds.

[0119] In a second example of the blended form of the thermosetting compound in the resin composition (1), it is preferable that the compound is substantially free of silicone-modified thermosetting compounds. "Substantially free" means that the content of the silicone-modified thermosetting compound in the resin composition (1) is less than 3 parts by weight relative to 100 parts by weight of the resin solids, preferably less than 1 part by weight, and may also be less than 0.1 parts by weight.

[0120] The following provides a detailed description of these thermosetting compounds.

[0121] <<(Methyl)allyl compounds>>

[0122] (Methyl)allyl compounds are not particularly limited as long as they are compounds having one or more (methyl)allyl groups in one molecule (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2). They can be widely used in the field of printed circuit boards.

[0123] In this embodiment, the (methyl)allyl compound is preferably an allyl compound.

[0124] An example of a (methyl)allyl compound is a (methyl)allylphenol compound.

[0125] (Methyl)allylphenol compounds preferably have one or more structures in which one or more (methyl)allyl groups are directly bonded to a phenolic aromatic ring. (Methyl)allylphenol compounds preferably have one or two structures in which one or more (methyl)allyl groups are directly bonded to a phenolic aromatic ring, and preferably have two.

[0126] (Methyl)allylphenol compounds can be, for example, compounds represented by formula (1A) or formula (1B).

[0127]

[0128] (In formula (1A), Rxa independently represents (methyl)allyl, Rxb independently represents alkyl or hydrogen atom with 1 to 10 carbon atoms, Rxc independently represents aromatic ring with 4 to 12 carbon atoms, Rxc can form a fused structure with benzene ring, Rxc may or may not be present, A represents alkylene with 1 to 6 carbon atoms, arylene with 7 to 16 carbon atoms, arylene with 6 to 10 carbon atoms, fluorene, sulfonyl, oxygen atom, sulfur atom or direct bond (single bond), in the absence of Rxc, there may be more than 2 Rxa and / or Rxb groups on one benzene ring.)

[0129]

[0130] (In formula (1B), Rxd independently represents (methyl)allyl, Rxe independently represents an alkyl group or hydrogen atom with 1 to 10 carbon atoms, Rxf represents an aromatic ring with 4 to 12 carbon atoms, Rxf can form a fused structure with the benzene ring, Rxf may or may not be present, and in the absence of Rxf, there may be more than 2 Rxd and / or Rxe groups on one benzene ring.)

[0131] In formulas (1A) and (1B), compounds in which the groups represented by Rxc and Rxf form a fused structure with the benzene ring can be cited as examples. Conversely, compounds in formulas (1A) and (1B) in which the groups represented by Rxc and Rxf are absent can be cited as examples.

[0132] In formulas (1A) and (1B), there are no particular restrictions on the number of carbon atoms of 1 to 10 represented by Rxb and Rxe. Examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0133] In formula (1A), there is no particular limitation on the alkylene group with 1 to 6 carbon atoms represented by A, and examples include methylene, ethylene, trimethylene, and propylene. There is no particular limitation on the arylene group with 7 to 16 carbon atoms represented by A, and examples include groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (where Ar represents phenylene, naphthylene, or biphenylene). There is no particular limitation on the arylene group with 6 to 10 carbon atoms represented by A, and examples include phenylene rings.

[0134] The compound represented by formula (1B) preferably has Rxf as a benzene ring (a compound containing a dihydroxynaphthalene skeleton).

[0135] From the viewpoint of further improving compatibility, (methyl)allylphenol compounds are preferably (methyl)allyl bisphenols in which one (methyl)allyl group is bonded to each of the two phenolic aromatic rings of a bisphenol. Similarly, (methyl)allyl bisphenols are preferably diallyl bisphenols in which one (methyl)allyl group is bonded to each of the two phenolic aromatic rings of a bisphenol and / or diallyl bisphenols in which one propenyl group is bonded to each of the two phenolic aromatic rings of a bisphenol.

[0136] There are no particular limitations on diallyl bisphenols; examples include o,o'-diallyl bisphenol A ("DABPA" from Daiwa Chemical Industries, Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, and o,o'-diallyl bisphenol fluorene. There are also no particular limitations on diallyl bisphenols; examples include o,o'-diallyl bisphenol A ("PBA01" from Gunei Chemical Industries, Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, and o,o'-diallyl bisphenol fluorene.

[0137] The average number of phenolic groups per molecule of (methyl)allylphenol compounds is preferably 1 or more and less than 3, more preferably 1.5 or more and less than 2.5. The average number of phenolic groups is calculated by the following formula.

[0138]

[0139] In the formula, Ai represents the number of alkenylphenols with i phenol groups in the molecule, Xi represents the proportion of alkenylphenols with i phenol groups in the total alkenylphenols, and X1+X2+…Xn=1.

[0140] Another example of (methyl)allyl compounds is (methyl)allyl-substituted nadicimide compounds.

[0141] (Methyl)allyl-substituted nadicimide compounds are not particularly limited as long as they have one or more (methyl)allyl-substituted nadicimide groups in one molecule, for example, the compounds shown in formula (2d) can be cited.

[0142]

[0143] In formula (2d), R1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl or ethyl), and R2 represents an alkylene group, phenylene group, biphenylene group, naphthylene group, or a group represented by formula (7) or formula (8) below having 1 to 6 carbon atoms.

[0144]

[0145] In formula (7), R3 represents methylene, isopropylidene, -C(=O)-, -O-, -S- or -SO2-.

[0146]

[0147] In formula (8), R4 independently represents an alkylene group with 1 to 4 carbon atoms or a cycloalkylene group with 5 to 8 carbon atoms.

[0148] The (methyl)allyl-substituted nadicimide compound shown in formula (2d) can be a commercially available product or a manufactured product prepared according to known methods. Examples of commercially available products include "BANI-M" and "BANI-X" from Maruzen Petrochemical Co., Ltd.

[0149] In addition to the above, detailed information on (methyl)allyl compounds can be found in paragraphs 0016 to 0030 of International Publication No. 2020 / 022084 and paragraphs 0141 to 0160 of International Publication No. 2023 / 013709, the contents of which are incorporated herein by reference.

[0150] When the resin composition (1) contains a (methyl)allyl compound, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin solids. In addition, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.

[0151] The resin composition (1) may contain only one (methyl)allyl compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0152] <<Maleimide Compounds>>

[0153] Maleimide compounds are not particularly limited as long as they are compounds having one or more maleimide groups in one molecule (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2). Maleimide compounds commonly used in the field of printed circuit boards can be widely used.

[0154] Maleimide compounds may be exemplified as maleimide compounds that can be compounded in the resin composition (2) described below, preferably including one or more compounds selected from the group consisting of compounds of formula (M0), formula (M1), formula (M2), formula (M3), formula (M4), formula (M5), maleimide compound (M6), maleimide compound (M7) and maleimide compound (M8) as described in the resin composition (2) described below, more preferably including one or more compounds selected from the group consisting of compounds of formula (M0), formula (M2), formula (M3), formula (M4) and formula (M5), more preferably including compounds of formula (M2) and / or formula (M3).

[0155] In addition to the above, detailed information on maleimide compounds can be found in paragraphs 0092 to 0095 of International Publication No. 2020 / 022084, paragraphs 0103 to 0110 of International Publication No. 2023 / 013709, and paragraphs 0044 to 0045 of Japanese Patent No. 6414799, the contents of which are incorporated herein by reference.

[0156] When the resin composition (1) contains a maleimide compound, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin solids. In addition, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.

[0157] The resin composition (1) may contain only one maleimide compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0158] <<Epoxy Compounds>>

[0159] There are no particular limitations on epoxy compounds as long as they are compounds having one or more epoxy groups in one molecule (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2). Epoxy compounds commonly used in the field of printed circuit boards can be widely used.

[0160] It should be noted that the epoxy-modified organosilicones described later are not included in the epoxy compounds in this section.

[0161] Examples of epoxy compounds include bisphenol type epoxy resins (e.g., bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin), diallyl bisphenol type epoxy resins (e.g., diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.), and phenolic varnish type epoxy resins (e.g., phenolic varnish type epoxy resin). Epoxy resins, including bisphenol A phenolic varnish-type epoxy resins, cresol phenolic varnish-type epoxy resins, aralkyl-type epoxy resins, biphenyl-type epoxy resins containing a biphenyl skeleton, naphthalene-type epoxy resins containing a naphthalene skeleton, anthracene-type epoxy resins containing a dihydroanthracene skeleton, glycidyl esters, polyol-type epoxy resins, epoxy resins containing isocyanurate rings, dicyclopentadiene-type epoxy resins, epoxy resins containing bisphenol A type structural units and hydrocarbon structural units, and halogenated compounds thereof. These epoxy compounds can be used alone or in combination of two or more.

[0162] From the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability, the epoxy compound is preferably selected from one or more of the group consisting of aryl alkyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin and epoxy resin containing bisphenol A structural unit and hydrocarbon structural unit, and more preferably contains naphthalene epoxy resin.

[0163] <<<Aryl Alkyl Type Epoxy Resins>>>

[0164] There are no particular limitations on aralkyl-type epoxy resins, for example, compounds shown in formula (3a) can be cited.

[0165]

[0166] (In equation (3a), Ar) 3 Each independently represents a benzene ring or a naphthalene ring, Ar 4 R represents a benzene ring, naphthalene ring, or biphenyl ring. 3a Each ring can independently represent a hydrogen atom or a methyl group, k represents an integer from 1 to 50, and each ring can have substituents other than glycidoxy groups (e.g., alkyl or phenyl groups with 1 to 5 carbon atoms).

[0167] The compound shown in formula (3a) is preferably Ar 3 It is a naphthalene ring and Ar 4 Compounds consisting of benzene rings (also known as "naphthalene alkyl-type epoxy resins") and Ar 3 It is a benzene ring and Ar 4 It is a compound of biphenyl ring (also known as "biphenyl aralkyl type epoxy resin"), more preferably a biphenyl aralkyl type epoxy resin.

[0168] The preferred biphenyl aryl epoxy resin is the compound shown in formula (3b).

[0169]

[0170] (In formula (3b), ka represents an integer greater than or equal to 1, preferably 1 to 20, and more preferably 1 to 6.)

[0171] In addition, aralkyl epoxy resins can be compounds represented by formula (3c).

[0172]

[0173] (In equation (3c), ky represents an integer from 1 to 10.)

[0174] Aryl alkyl type epoxy resins can be commercially available products or products prepared by known methods. Examples of commercially available naphthalene alkyl type epoxy resins include Nippon Steel & Sumitomo Chemical Co., Ltd.'s "EPOTOHTO (registered trademark) ESN-155", "EPOTOHTO (registered trademark) ESN-355", "EPOTOHTO (registered trademark) ESN-375", "EPOTOHTO (registered trademark) ESN-475V", "EPOTOHTO (registered trademark) ESN-485", and "EPOTOHTO (registered trademark) ESN-175", Nippon Kayaku Co., Ltd.'s "NC-7000", "NC-7300", and "NC-7300L", and DIC Co., Ltd.'s "HP-5000" and "HP-9900". Commercially available products of biphenyl aralkyl type epoxy resins include, for example, "NC-3000", "NC-3000L", and "NC-3000FH" produced by Nippon Kayaku Co., Ltd.

[0175] <<<Naphthalene-type epoxy resin>>>

[0176] There is no particular limitation on the naphthalene-type epoxy resin. For example, epoxy resins other than the naphthalene aralkyl-type epoxy resins mentioned above can be cited, such as multifunctional epoxy resins containing a naphthalene skeleton and epoxy resins having a naphthalene skeleton as shown in formula (3-1). As a specific example of a naphthalene-type epoxy resin, for example, a naphthylene ether-type epoxy resin can be cited. From the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, a naphthylene ether-type epoxy resin is preferred.

[0177]

[0178] (In equation (3-1), Ar) 31 Each independently represents a benzene ring or a naphthalene ring, Ar 41 R represents a benzene ring, naphthalene ring, or biphenyl ring.31a Each ring independently represents a hydrogen atom or a methyl group, p is an integer from 0 to 2, preferably 0 or 1, kz is an integer from 1 to 50, and each ring may have substituents other than glycidoxy groups (e.g., alkyl groups with 1 to 5 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, or phenyl groups), Ar 31 and Ar 41 (At least one of them represents a naphthalene ring.)

[0179] As a compound represented by formula (3-1), a compound represented by formula (3-2) can be cited.

[0180]

[0181] (In formula (3-1), R represents methyl, and kz has the same meaning as kz in formula (3-1) above.)

[0182] Multifunctional epoxy resins containing a naphthalene skeleton can be commercially available products or products prepared by known methods. Examples of commercially available multifunctional epoxy resins containing a naphthalene skeleton include products such as "HP-9540" and "HP-9500" from DIC Corporation.

[0183] From the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability, the naphthyl ether type epoxy resin is preferably a compound shown in formula (3-3) or a compound shown in formula (3-4).

[0184]

[0185] (where R is in the formula) 13 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0186]

[0187] (In equation (3-3), R) 14 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0188] Naphthylene ether type epoxy resins can be commercially available products or products prepared by known methods. Examples of commercially available naphthylene ether type epoxy resins include products from DIC Corporation such as "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", and "EXA-7311G5".

[0189] <<<Dicyclopentadiene-type epoxy resin>>>

[0190] There are no particular limitations on dicyclopentadiene-type epoxy resins, for example, compounds shown in formulas (3-5) can be cited.

[0191]

[0192] (where R is in the formula) 3c Each can independently represent an alkyl group with 1 to 5 hydrogen atoms, and k2 represents an integer from 0 to 10.

[0193] Dicyclopentadiene-type epoxy resins can be commercially available or prepared using known methods. Examples of commercially available dicyclopentadiene-type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", and "EPICRON HP-7000HH" produced by Dai Nippon Ink & Chemical Co., Ltd.

[0194] <<<Epoxy resins containing bisphenol A structural units and hydrocarbon structural units>>>

[0195] An epoxy resin containing bisphenol A type structural unit and a hydrocarbon structural unit (also referred to as "specific epoxy resin") has one or more bisphenol A type structural units and one or more hydrocarbon structural units in its molecule. Examples of such specific epoxy resins include compounds represented by the following formula (3e).

[0196]

[0197] (where R is in the formula) 1x and R 2x Each can independently represent a hydrogen atom or a methyl group, R 3x ~R 6x Each atom independently represents a hydrogen atom, a methyl atom, a chlorine atom, or a bromine atom; X represents ethoxyethyl, di(ethoxy)ethyl, tri(ethoxy)ethyl, propyleneoxypropyl, di(propyleneoxy)propyl, tri(propyleneoxy)propyl, or an alkylene group having 2 to 15 carbon atoms; and k3 represents a natural number.

[0198] k3 represents a natural number, preferably 1 to 100, and more preferably 1 to 10.

[0199] Specific epoxy resins may be commercially available products or products prepared by known methods. Examples of commercially available specific epoxy resins include "EPICLON EXA-4850-150" and "EPICLONEXA-4816" from DIC Corporation.

[0200] In addition to the above, detailed information about the epoxy compounds can be found in paragraphs 0117 to 0133 of International Publication No. 2020 / 022084, paragraphs 0189 to 0214 of International Publication No. 2023 / 013709, and paragraphs 0047 to 0053 of Japanese Patent No. 6414799, the contents of which are incorporated herein by reference.

[0201] When the resin composition (1) contains an epoxy compound, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin solids. In addition, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.

[0202] The resin composition (1) may contain only one epoxy compound or two or more. When it contains two or more, the total amount is preferably within the range described above.

[0203] <<Cyanate Compounds>>

[0204] As a cyanate compound, there is no particular limitation as long as it is a compound having two or more cyanate groups in one molecule. Examples include naphthol aralkyl cyanate compounds such as those shown in formula (5), phenolic varnish cyanate compounds such as those shown in formula (6) other than those shown in formula (5), biphenyl aralkyl cyanate compounds, diallyl bisphenol cyanate compounds, bis(3,3-dimethyl-4-cyanate-phenyl)methane, bis(4-cyanate-phenyl)methane, 1,3-dicyanate-phenyl, and 1,4-dicyanate-phenyl. Benzene, 1,3,5-tricyanate-based benzene, 1,3-dicyanate-based naphthalene, 1,4-dicyanate-based naphthalene, 1,6-dicyanate-based naphthalene, 1,8-dicyanate-based naphthalene, 2,6-dicyanate-based naphthalene, 2,7-dicyanate-based naphthalene, 1,3,6-tricyanate-based naphthalene, 4,4'-dicyanate-based biphenyl, bis(4-cyanate-based phenyl) ether, bis(4-cyanate-based phenyl) sulfide, bis(4-cyanate-based phenyl) sulfone, 2,2-bis(4-cyanate-based phenyl) propane. These cyanate compounds can be used alone or in combination of two or more. Among these, from the viewpoint of further improving the low thermal expansion and chemical resistance of the first insulating resin layer, the cyanate compounds preferably include naphthol aralkyl-type cyanate compounds and / or phenolic varnish-type cyanate compounds, more preferably including compounds shown in formula (5).

[0205]

[0206] (In equation (5), R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer greater than or equal to 1.)

[0207] n2 is preferably an integer from 1 to 20, more preferably an integer from 1 to 10, and even more preferably an integer from 1 to 6.

[0208]

[0209] (In equation (6), R) ya Each independently represents a (methyl)allyl group or hydrogen atom with 2 to 8 carbon atoms, R yb Each independently represents an alkyl group or hydrogen atom with 1 to 10 carbon atoms, R yc Each independently represents an aromatic ring with 4 to 12 carbon atoms, R yc It can form a fused structure with the benzene ring, R yc It may exist or it may not exist, A 1a Each independently represents an alkylene group with 1-6 carbon atoms, an arylene group with 7-16 carbon atoms, an aryl group with 6-10 carbon atoms, a fluorene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a single bond (direct bonding), in R ycIn the absence of R, a benzene ring can have more than two R atoms. ya and / or R yb (The radical group. n represents an integer from 1 to 20.)

[0210] In equation (6), R is used as ya Examples of (methyl)allyl groups with 2 to 8 carbon atoms include vinyl, allyl, propenyl, butenyl, and hexenyl.

[0211] In equation (6), R is used as yb The alkyl groups represented by carbon atoms numbering 1 to 10 include, for example, straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0212] In equation (6), A is used as 1a Examples of alkylene groups with 1 to 6 carbon atoms include methylene, ethylene, trimethylene, and propylene. Additionally, in formula (6), A... 1a The arylene alkyl group representing 7 to 16 carbon atoms can be exemplified by groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (where Ar represents phenylene, naphthylene, or biphenylene). Furthermore, as A... 1a The arylene group represented by carbon atoms is, for example, a phenylene ring.

[0213] In equation (6), n represents an integer from 1 to 20, preferably an integer from 1 to 15, and more preferably an integer from 1 to 10.

[0214] From the perspective of further improving the low thermal expansion and chemical resistance of the first insulating resin layer and having a higher glass transition temperature, the compound represented by formula (6) is preferably a phenolic varnish-type cyanate compound, and more preferably the compound represented by formula (c1).

[0215]

[0216] In formula (c1), Rx independently represents a hydrogen atom or a methyl group, R independently represents an alkenyl group with 2 to 8 carbon atoms, an alkyl group with 1 to 10 carbon atoms, or a hydrogen atom, and n represents an integer from 1 to 10.

[0217] These cyanate compounds can also be manufactured using known methods. Specific manufacturing methods include, for example, those described in Japanese Patent Application Publication No. 2017-195334 (particularly paragraphs 0052-0057).

[0218] In addition to the above, in this embodiment, cyanate compounds described in International Publication No. 2021 / 172317, which is incorporated herein by reference, can be used.

[0219] In this embodiment, the relative permittivity of the cured cyanate ester compound at a frequency of 10 GHz, as measured by the cavity resonance perturbation method, is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably less than 2.9. In addition, the lower limit is actually 2.4 or more.

[0220] When the resin composition (1) contains a cyanate ester compound, the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition (1) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. By making the content of the cyanate ester compound 0.1 parts by mass or more, there is a tendency for excellent adhesion to the metal foil (plating and / or wiring pattern) of the first insulating resin layer, excellent micro-wiring formation, heat resistance, flame resistance, chemical resistance, low dielectric properties (relative permittivity and / or dielectric loss tangent), and excellent insulation. The upper limit of the content of the cyanate ester compound relative to 100 parts by mass of the resin solids in the resin composition (1) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. Depending on the application, it can be 8 parts by mass or less or 6 parts by mass or less.

[0221] The resin composition (1) in this embodiment may contain only one cyanate ester compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0222] <<Phenolic Compounds>>

[0223] As for phenolic compounds, there are no particular limitations as long as a molecule contains two or more phenolic hydroxyl groups. Examples include phenols, bisphenols (such as bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (such as diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diallyl bisphenol S, etc.), phenolic varnish resins (such as phenolic varnish resin, naphthol varnish resin, cresol varnish resin, etc.), naphthyl-type phenolic resins, dihydroanthracene-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, and aralkyl-type phenolic resins. These phenolic compounds can be used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion of copper foil, phenolic compounds containing aralkyl-type phenolic resins are preferred.

[0224] <<<Aryl Alkyl Phenolic Resins>>>

[0225] Examples of aralkyl-type phenolic resins include compounds represented by formula (c2).

[0226]

[0227] (In formula (c2), Ar) 1 Each independently represents a benzene ring or a naphthalene ring, Ar 2 R represents a benzene ring, naphthalene ring, or biphenyl ring. 2a Each ring can independently represent a hydrogen atom or a methyl group, where m represents an integer from 1 to 50, and each ring may have substituents other than hydroxyl groups.

[0228] The substituent is, for example, an alkyl or phenyl group having 1 to 5 carbon atoms.

[0229] From the viewpoint of further improving the adhesion of the metal foil in the first insulating resin layer, the compound represented by formula (c2) is preferably Ar from formula (c2). 1 It is a naphthalene ring and Ar 2 Compounds containing a benzene ring (hereinafter also referred to as "naphthol aralkyl phenolic resins") and Ar in formula (c2) 1 It is a benzene ring and Ar 2 It is a compound of biphenyl ring (hereinafter also referred to as "biphenyl aryl phenolic resin").

[0230] Naphthol aralkyl phenolic resin is preferably a compound represented by formula (2b).

[0231]

[0232] (In equation (2b), R) 2a Each atom can be independently represented by a hydrogen atom or a methyl group, and m represents an integer from 1 to 10.

[0233] In equation (2b), R 2a Preferably, m represents a hydrogen atom, and m preferably represents an integer from 1 to 6.

[0234] The preferred phenolic resin is the compound shown in formula (2c).

[0235]

[0236] (In equation (2c), R) 2b Each of the following can be independently represented as a hydrogen atom, an alkyl group or a phenyl group with 1 to 5 carbon atoms, and m1 represents an integer from 1 to 20.

[0237] In equation (2c), R 2b The preferred symbol is a hydrogen atom, and m1 is preferably an integer from 1 to 6.

[0238] Aryl alkyl phenolic resins can be commercially available or manufactured using known methods. Examples of commercially available aryl alkyl phenolic resins include "KAYAHARD GPH-65", "KAYAHARD GPH-78", and "KAYAHARD GPH-103" (biphenyl aryl phenolic resin) from Nippon Chemical Co., Ltd., and "SN-495" (naphthol aryl phenolic resin) from Nippon Steel Chemical Co., Ltd.

[0239] When the resin composition (1) contains a phenolic compound, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin solids. In addition, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.

[0240] The resin composition (1) may contain only one phenolic compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0241] <<Other Thermosetting Compounds>>

[0242] Oxycyclic butane compounds, benzoxazine compounds, and compounds with polymerizable unsaturated groups, etc.

[0243] Details of these resins can be found in paragraphs 0135 to 0138 of International Publication No. 2020 / 022084, paragraphs 0036 to 0039 of International Publication No. 2023 / 013709, and paragraphs 0066 to 0069 and 0094 to 0106 of International Publication No. 2023 / 171553, the contents of which are incorporated herein by reference.

[0244] <<Organosilicon-modified thermosetting compounds>>

[0245] The resin composition (1) may contain an organosilicon-modified thermosetting compound comprising at least one group selected from the group consisting of maleimide, amino, epoxy, carboxyl, vinyl, hydroxyl and (meth)acryloyl groups and a polysiloxane structure.

[0246] The organosilicon-modified thermosetting compound preferably has a polysiloxane skeleton in the molecule in which siloxane bonds are repeatedly formed, and contains at least one group selected from the group consisting of maleimide, amino, epoxy, carboxyl, vinyl, hydroxy and (meth)acryloyl.

[0247] <<<Epoxy-Modified Organosilicon>>>

[0248] The first embodiment of organosilicon-modified thermosetting compounds is an organosilicon compound having an epoxy group (hereinafter, sometimes referred to as "epoxy-modified organosilicon").

[0249] There are no particular limitations on epoxy-modified organosilicon compounds or resins that are modified by groups containing epoxy groups. The resin composition (1), by containing epoxy-modified organosilicon, exhibits excellent low thermal expansion and chemical resistance for the first insulating resin layer.

[0250] The polysiloxane structure can be a linear organosilicon structure, a cyclic organosilicon structure, or a mesh-like organosilicon structure. In this embodiment, a linear organosilicon structure is preferred.

[0251] There are no particular limitations on the groups containing epoxy groups, for example, the groups shown in the following formula (a1) can be cited.

[0252]

[0253] (In formula (a1), R) 0 The symbol represents an alkylene group (e.g., methylene, ethylene, propylene, etc., with 1 to 5 carbon atoms), and X represents a monovalent group as shown in formula (a2) or formula (a3) ​​below.

[0254]

[0255]

[0256] In formula (a1), the alkylene group is preferably an alkylene group with 1 to 5 carbon atoms, such as methylene, ethylene, or propylene.

[0257] As a preferred example of the epoxy compound used in epoxy-modified organosilicon, the epoxy compound described in the above-mentioned <<Epoxy Compounds>> section can be cited.

[0258] The epoxy-modified organosilicon preferably comprises an epoxy-modified organosilicon having an epoxy equivalent of 140 to 250 g / mol. By comprising an epoxy-modified organosilicon having an epoxy equivalent within the aforementioned range, the epoxy-modified organosilicon tends to further improve compatibility with thermosetting compounds, low thermal expansion, and chemical resistance in a balanced manner. From the same viewpoint, the aforementioned epoxy equivalent is more preferably 145 to 245 g / mol, and even more preferably 150 to 240 g / mol.

[0259] From the viewpoint of achieving a good balance in further improving compatibility with thermosetting compounds, low thermal expansion, and chemical resistance, epoxy-modified organosilicones preferably contain two or more types of epoxy-modified organosilicones. In this case, the two or more epoxy-modified organosilicones preferably each have different epoxy equivalents; more preferably, they include epoxy-modified organosilicones with an epoxy equivalent of 50-350 g / mol and epoxy-modified organosilicones with an epoxy equivalent of 400-4000 g / mol; even more preferably, they include epoxy-modified organosilicones with an epoxy equivalent of 140-250 g / mol and epoxy-modified organosilicones with an epoxy equivalent of 450-3000 g / mol.

[0260] When the epoxy-modified organosilicon contains two or more types of epoxy-modified organosilicon, the average epoxy equivalent of the epoxy-modified organosilicon is preferably 140~3000 g / mol, more preferably 250~2000 g / mol, and even more preferably 300~1000 g / mol. The average epoxy equivalent is calculated by the following formula.

[0261]

[0262] (In the formula, Ei represents the epoxy equivalent of one of the epoxy-modified organosilicones among two or more epoxy-modified organosilicones, Wi represents the proportion of the above epoxy-modified organosilicones in the epoxy-modified organosilicones, and W1+W2+…Wn=1.)

[0263] From the viewpoint of being able to further improve compatibility with thermosetting compounds, low thermal expansion and chemical resistance in a good balance, epoxy-modified organosilicon preferably contains epoxy-modified organosilicon as shown in formula (1).

[0264]

[0265] (In equation (1), R) 1 Each can independently represent an alkylene, phenylene, or arylene group, R 2 Each can independently represent an alkyl or phenyl group with 1 to 10 carbon atoms, where n represents an integer greater than 1.

[0266] In equation (1), R 1 Each can independently represent an alkylene, phenylene, or arylene. In formula (1), R 1 The alkylene group shown can be any type of linear, branched, or cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 4. There are no particular limitations on the alkylene group; for example, methylene, ethylene, or propylene are examples.

[0267] In equation (1), R 1The number of carbon atoms in the arylene alkyl group shown is preferably 7 to 30, more preferably 7 to 13. There are no particular limitations on the arylene alkyl group, for example, the group shown in formula (XI) can be cited.

[0268] Formula (XI)

[0269]

[0270] (In formula (XI), * represents a connecting key.)

[0271] In equation (1), R 1 The indicated group may further have substituents. Examples of substituents include straight-chain alkyl groups with 1 to 10 carbon atoms, branched alkyl groups with 3 to 10 carbon atoms, cyclic alkyl groups with 3 to 10 carbon atoms, straight-chain alkoxy groups with 1 to 10 carbon atoms, branched alkoxy groups with 3 to 10 carbon atoms, and cyclic alkoxy groups with 3 to 10 carbon atoms. Wherein, R 1 Propylene is particularly preferred.

[0272] In equation (1), R 2 Each of these groups independently represents an alkyl or phenyl group having 1 to 10 carbon atoms. The alkyl and phenyl groups may have substituents. The alkyl groups having 1 to 10 carbon atoms can be any type of straight-chain, branched, or cyclic. There are no particular limitations on the type of alkyl group; examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Wherein, R... 2 Preferably methyl or phenyl.

[0273] In formula (1), n ​​represents an integer greater than or equal to 1, for example, 1 to 100. From the viewpoint of being able to further improve compatibility with thermosetting compounds, low thermal expansion and chemical resistance in a good balance, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

[0274] From the viewpoint of achieving a good balance in further improving compatibility with thermosetting compounds, low thermal expansion, and chemical resistance, epoxy-modified organosilicon preferably contains two or more epoxy-modified organosilicones represented by formula (1). In this case, the epoxy-modified organosilicones containing two or more types preferably have different n values, and more preferably contain epoxy-modified organosilicones with n of 1 to 2 in formula (1) and epoxy-modified organosilicones with n of 5 to 20 in formula (1).

[0275] The average number of epoxy groups per molecule of epoxy-modified organosilicon is preferably 1 or more and less than 3, more preferably 1.5 or more and less than 2.5. The average number of epoxy groups is calculated by the following formula.

[0276]

[0277] (In the formula, Bi represents the number of epoxy groups in the epoxy-modified organosilicon with i epoxy groups in the molecule, Yi represents the proportion of the epoxy-modified organosilicon with i epoxy groups in the total epoxy-modified organosilicon, and Y1+Y2+…Yn=1.)

[0278] Epoxy-modified organosilicon can be an epoxy-modified organosilicon comprising structural units derived from alkenylphenol, structural units derived from epoxy-modified organosilicon, and structural units derived from epoxy compounds other than epoxy-modified organosilicon (hereinafter, sometimes referred to as "epoxy-modified organosilicon (X1)").

[0279] Epoxy-modified organosilicon (X1) may, as needed, further include structural units derived from phenolic compounds other than alkenylphenols.

[0280] As a preferred example of an alkenylphenol, which constitutes a structural unit derived from alkenylphenol, is the (methyl)allylphenol compound described in the above-mentioned <<(methyl)allyl compounds>> section.

[0281] As a preferred example of a phenolic compound constituting a structural unit derived from a phenolic compound other than a structural unit derived from an enylphenol, the phenolic compounds described in the above-mentioned section on "phenolic compounds" can be cited.

[0282] The content of the structural unit derived from alkenylphenol relative to the total mass of epoxy-modified organosilicon (X1) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 10 to 40% by mass. By keeping the content of this structural unit within the above range, there is a tendency to exhibit better compatibility with other thermosetting compounds.

[0283] The content of the structural unit derived from epoxy-modified organosilicon is preferably 20 to 60% by mass relative to the total mass of epoxy-modified organosilicon (X1), more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass. By keeping the content of this structural unit within the above range, the first insulating resin layer tends to exhibit better low thermal expansion and chemical resistance in a balanced manner.

[0284] The structural units derived from epoxy-modified organosilicon are preferably derived from epoxy-modified organosilicon having an epoxy equivalent of 50 to 350 g / mol (hereinafter also referred to as "low-equivalent epoxy-modified organosilicon") and epoxy-modified organosilicon having an epoxy equivalent of 400 to 4000 g / mol (hereinafter also referred to as "high-equivalent epoxy-modified organosilicon").

[0285] The content of structural units derived from low-equivalent epoxy-modified organosilicon is preferably 5 to 25% by mass relative to the total mass of epoxy-modified organosilicon (X1), more preferably 7.5 to 20% by mass, and even more preferably 10 to 17% by mass.

[0286] The content of structural units derived from high-equivalent epoxy-modified organosilicon is preferably 15 to 55% by mass relative to the total mass of epoxy-modified organosilicon (X1), more preferably 20 to 52.5% by mass, and even more preferably 25 to 50% by mass.

[0287] Regarding epoxy-modified organosilicon, in addition to the above, reference can be made to paragraphs 0031 to 0044, 0069 to 0088 of International Publication No. 2020 / 022084 and paragraphs 0128 to 0232 of International Publication No. 2023 / 013709, the contents of which are incorporated into this specification.

[0288] <<<Amino-modified organosilicon>>>

[0289] A second embodiment of the organosilicon-modified thermosetting compound is a compound having structural units derived from amino-modified organosilicon and structural units derived from maleimide compounds (hereinafter, sometimes referred to as "amino-modified organosilicon").

[0290] The amino-modified organosilicon is preferably a polymer obtained by polymerizing amino-modified organosilicon with maleimide compounds and with carboxylic acids and / or carboxylic anhydrides.

[0291] The following is an explanation of amino-modified organosilicon.

[0292] It should be noted that, in this specification, "structural units derived from amino-modified organosilicon" and "structural units derived from maleimide compounds" refer not only to structural units formed by polymerizing the components of amino-modified organosilicon and maleimide compounds in amino-modified organosilicon, but also to structural units formed through reactions that provide the same structural units. Hereinafter, the term "structural units derived from..." will be explained similarly in this specification.

[0293] The content of structural units derived from amino-modified organosilicon is preferably 5 to 70% by mass relative to 100% by mass of all structural units in the amino-modified organosilicon, more preferably 10 to 50% by mass, and even more preferably 15 to 45% by mass.

[0294] The content of structural units derived from maleimide compounds is preferably 30 to 95% by mass relative to 100% by mass of all structural units in amino-modified organosilicon, more preferably 50 to 90% by mass, and even more preferably 55 to 85% by mass.

[0295] The amine value of the amino-modified organosilicon is preferably 2.0 mg KOH / g or less, more preferably 1.0 mg KOH / g or less, and even more preferably 0.5 mg KOH / g or less. It should be noted that the amine value is the sum of the primary and secondary amines. When the amine value is 2.0 mg KOH / g or less, there is a tendency to suppress the increase in viscosity of the resin composition (1), the increase in molecular weight, the gelation of the varnish, and the increase in the viscosity of the prepreg. Furthermore, the lower the amine value, the more likely it is to suppress the increase in viscosity and molecular weight of the resin composition (1). The lower limit of the amine value is preferably 0 mg KOH / g. The amine value is determined according to the method of JIS K 7237:1995.

[0296] The weight-average molecular weight (Mw) of the amino-modified organosilicon is preferably 5,000 to 20,000, more preferably 10,000 to 15,000. By setting the weight-average molecular weight to 5,000 or higher, there is a tendency to decrease the thermal expansion coefficient of the prepreg; by setting the weight-average molecular weight to 20,000 or lower, there is a tendency to suppress the increase in viscosity of the resin composition (1), the increase in molecular weight, the gelation of the varnish, and the increase in the viscosity of the prepreg. To achieve a weight-average molecular weight of 5,000 to 20,000 for the amino-modified organosilicon, it is only necessary to control the reaction conditions such as temperature and time during the preparation of the amino-modified organosilicon. In this embodiment, the weight-average molecular weight can be determined by gel permeation chromatography (GPC) and calculated using a standard polystyrene calibration curve.

[0297] From the viewpoint of improving the reactivity between the components constituting amino-modified organosilicon and its compatibility with other thermosetting compounds, amino-modified organosilicon is preferably a polymer (hereinafter sometimes referred to as "polymer (B1)") obtained by polymerizing at least amino-modified organosilicon, a maleimide compound, and a carboxylic acid and / or carboxylic anhydride. Polymer (B1) contains at least structural units derived from amino-modified organosilicon and structural units derived from maleimide compounds.

[0298] Regarding maleimide compounds, refer to the matters described in the <<Maleimide Compounds>> which may be included in the resin composition (1), and the preferred range is also the same.

[0299] Amino-modified organosilicones are not particularly limited to any organosilicon having one or more amino groups in the molecule, but are preferably organosilicones having two or more amino groups in the molecule, and more preferably include amino-modified organosilicones of formula (1). Amino-modified organosilicones or polymers (B1) can exhibit excellent compatibility with other thermosetting compounds by containing structural units derived from amino-modified organosilicones. Amino-modified organosilicones can be used alone or in appropriate combinations of two or more.

[0300]

[0301] In equation (1), R a Each can independently represent a hydrogen atom, alkyl group, or phenyl group. R b Each can independently represent a single bond, alkylene group, or arylene group. n represents an integer from 1 to 100.

[0302] Examples of alkyl groups include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched-chain alkyl groups such as isopropyl, isobutyl, and tert-butyl. Among these, methyl is preferred.

[0303] As R b Alkylene is preferred. Examples of alkylene compounds include methylene, ethylene, trimethylene, and tetramethylene. Furthermore, as an alkylene compound, it is more preferable to have 1 to 4 carbon atoms in its main chain, and even more preferably trimethylene.

[0304] Examples of aryl groups include phenyl, naphthyl, indene, biphenyl, and anthracene.

[0305] The amino equivalent of the amino-modified organosilicon is preferably 130~6000 g / mol, more preferably 500~3000 g / mol, and even more preferably 600~2500 g / mol. The amino equivalent is determined according to the method in JIS K 7237:1995.

[0306] Amino-modified organosilicones can be commercially available products or products manufactured using known methods. Examples of commercially available amino-modified organosilicones include "X-22-161A" (amino equivalent: 800 g / mol), "X-22-161B" (amino equivalent: 1500 g / mol), and "KF-8010" (amino equivalent: 430 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd.

[0307] The carboxylic acid used in the manufacture of the polymer (B1) is not particularly limited, but is preferably selected from at least one of the group consisting of maleic acid, phthalic acid, succinic acid, acetic acid and propionic acid, more preferably selected from at least one of the group consisting of maleic acid, phthalic acid, succinic acid and acetic acid, and even more preferably selected from at least one of the group consisting of maleic acid, phthalic acid and succinic acid.

[0308] The carboxylic anhydride is not particularly limited, but is preferably selected from at least one of the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, acetic anhydride and propionic anhydride, more preferably selected from at least one of the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride and acetic anhydride, and even more preferably selected from at least one of the group consisting of maleic anhydride, phthalic anhydride and succinic anhydride.

[0309] Among them, monocarboxylic acid and / or monocarboxylic anhydride, or dicarboxylic acid and / or dicarboxylic anhydride are preferred, and dicarboxylic acid and / or dicarboxylic anhydride are more preferred. By making the carboxylic acid and / or carboxylic anhydride each be a dicarboxylic acid and / or dicarboxylic anhydride, there is a tendency that the effect of the present embodiment can be more effectively enhanced as compared with the case where a monocarboxylic acid and / or monocarboxylic anhydride is used.

[0310] Each of the carboxylic acids and the carboxylic anhydrides may be used alone, or in an appropriate combination of two or more. In addition, the carboxylic acid and the carboxylic anhydride may be used alone or in combination.

[0311] In the present embodiment, it is preferable to use only the carboxylic anhydride as compared with the case of using only the carboxylic acid. Since the carboxylic anhydride has more excellent reactivity, there is a tendency that the reactivity of the polymer (B1) can be appropriately suppressed by reacting with the amino group in the polymer (B1). As a result, there is a tendency that the storage stability of the resin composition (1) and the prepreg containing the polymer (B1) (for example, suppression of increase in viscosity of the resin composition (1), increase in molecular weight, gelation of the varnish, increase in viscosity of the prepreg, and the like) is excellent, and the moldability when mixed with other thermosetting compounds is also excellent.

[0312] With respect to 100% by mass of all the structural units in the polymer (B1), the content of the structural unit derived from the amino-modified organosilicon in the polymer (B1) is preferably 15 to 60% by mass, more preferably 20 to 55% by mass, and further preferably 30 to 50% by mass.

[0313] With respect to 100% by mass of all the structural units in the polymer (B1), the content of the structural unit derived from the maleimide compound in the polymer (B1) is preferably 35 to 75% by mass, more preferably 40 to 70% by mass, and further preferably 44 to 65% by mass.

[0314] With respect to 100% by mass of all the structural units in the polymer (B1), the content (total content) of the structural units derived from the carboxylic acid and / or the carboxylic anhydride in the polymer (B1) is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and further preferably 1 to 6% by mass.

[0315] Regarding the epoxy-modified organosilicon, in addition to the above, reference can be made to the descriptions in paragraphs 0075 to 0127 of International Publication No. 2023 / 013709, the contents of which are incorporated into the present specification.

[0316] <<BT Resin>>

[0317] BT resin refers to a resin produced by polymerizing cyanate ester compounds and maleimide compounds. Polymerization can be carried out in a solvent-free environment or by heating and mixing the polymers in solvents (such as methyl ethyl ketone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, toluene, and xylene).

[0318] The cyanate ester compound used in the synthesis of BT resin is not particularly limited, but is preferably the cyanate ester compound described in the above-mentioned <<cyanate ester compound>> section.

[0319] The maleimide compound used in the synthesis of BT resin is not particularly limited, but is preferably the maleimide compound described in the above-mentioned section on maleimide compounds.

[0320] The proportion of cyanate compounds in BT resin is not particularly limited, but is preferably in the range of 25 to 95% by mass relative to the total amount of BT resin, and more preferably in the range of 30 to 90% by mass.

[0321] The proportion of maleimide compounds in BT resin is not particularly limited. From the viewpoint of the glass transition temperature, flame retardancy and curability of the first insulating resin layer, it is preferably in the range of 5 to 75% by mass relative to the total amount of BT resin, and more preferably in the range of 10 to 70% by mass.

[0322] In addition, BT resin is usually a prepolymer, and its number average molecular weight is preferably in the range of 100 to 100,000.

[0323] Regarding resins, in addition to the above, reference can be made to paragraphs 0055-0057 of Japanese Patent No. 6414799, the contents of which are incorporated herein by reference.

[0324] When the resin composition (1) contains BT resin, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin solids. In addition, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less.

[0325] The resin composition (1) may contain only one type of BT resin or two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0326] <<Filling Material>>

[0327] The resin composition (1) preferably includes a filler material. By including a filler material, the physical properties of the resin composition (1), its cured product, such as dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame retardancy, and low thermal expansion, can be further improved.

[0328] Furthermore, the filling material used in this embodiment preferably exhibits excellent low dielectric properties. For example, the relative permittivity (Dk) of the filling material used in this embodiment at a frequency of 10 GHz, measured according to the cavity resonator perturbation method, is preferably 8.0 or less, more preferably 6.0 or less, and even more preferably 4.0 or less. Additionally, the lower limit of the relative permittivity is, for example, 2.0 or more. Furthermore, the dielectric loss tangent (Df) of the filling material used in this embodiment at a frequency of 10 GHz, measured according to the cavity resonator perturbation method, is preferably 0.05 or less, more preferably 0.01 or less. Additionally, the lower limit of the dielectric loss tangent is, for example, 0.0001 or more.

[0329] The type of filler material used in this embodiment is not particularly limited, and filler materials commonly used by those skilled in the art can be used. Specifically, examples include natural silica, fused silica, synthetic silica, amorphous silica, fumed silica (AEROSIL), hollow silica, and other silica; metal oxides such as alumina, white carbon, titanium dioxide, titanium oxide, zinc oxide, magnesium oxide, and zirconium oxide; composite oxides such as zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, and calcium titanate; nitrides such as boron nitride, condensed boron nitride, silicon nitride, and aluminum nitride; metal hydroxides (including hydrates) such as aluminum hydroxide, heat-treated aluminum hydroxide (aluminum hydroxide that has undergone heat treatment to remove part of its water of crystallization), boehmite, and magnesium hydroxide; molybdenum oxide, Inorganic filler materials include zinc molybdate and other molybdenum compounds; barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, NER-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including E-glass, T-glass, D-glass, S-glass, Q-glass, and other glass micropowders), insulating glass, spherical glass, etc. Examples of organic filler materials include styrene-type, butadiene-type, acrylic-type rubber powders, core-shell rubber powders, silicone resin powders, silicone rubber powders, silicone composite powders, etc.

[0330] In this embodiment, the filler material preferably comprises an inorganic filler material, more preferably one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, magnesium olivine, titanium oxide, barium titanate, strontium titanate, and calcium titanate. From the viewpoint of low dielectric properties, it is more preferably one or more selected from the group consisting of silica and aluminum hydroxide, and even more preferably silica. By including these inorganic filler materials, the heat resistance, dielectric properties, thermal expansion properties, dimensional stability, flame retardancy, and other properties of the cured first insulating resin layer are further improved.

[0331] The content of filler material in the resin composition (1) can be appropriately set according to the desired characteristics and is not particularly limited. It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 80 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition (1). By setting the content of filler material to the lower limit value or above, there is a tendency to further improve the heat resistance, low thermal expansion, and dielectric loss tangent of the first insulating resin layer. Furthermore, the upper limit value of the content of filler material relative to 100 parts by mass of the resin solids in the resin composition (1) is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, further preferably 300 parts by mass or less, and even more preferably 250 parts by mass or less, and can be 200 parts by mass or less, or 120 parts by mass or less. By setting the content of filler material to the upper limit value or less, there is a tendency to further improve the formability of the first insulating resin layer.

[0332] In the resin composition (1), as an example of a preferred embodiment, the content of the filler material is 30% to 90% by mass of the components other than the solvent.

[0333] The resin composition (1) may contain only one type of filler or two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0334] When a filler, particularly an inorganic filler, is used in the resin composition (1), a silane coupling agent may be further included. By including a silane coupling agent, there is a tendency to further improve the dispersibility of the filler and the adhesion strength between the resin components and the filler and the substrate described later.

[0335] As a silane coupling agent, there are no particular limitations. Examples of silane coupling agents commonly used in the surface treatment of inorganic materials include aminosilane compounds (such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (such as γ-epoxypropoxypropyltrimethoxysilane, etc.), vinylsilane compounds (such as vinyltrimethoxysilane, etc.), styrylsilane compounds (such as p-styryltrimethoxysilane, etc.), acrylic silane compounds (such as γ-acryloyloxypropyltrimethoxysilane, etc.), cationic silane compounds (such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), and phenylsilane compounds (such as phenyltrimethoxysilane, etc.). Silane coupling agents can be used alone or in combination of two or more.

[0336] The content of the silane coupling agent is not particularly limited, but is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solids in the resin composition (1).

[0337] Flame retardants

[0338] The resin composition (1) may contain a flame retardant. Examples of flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and organosilicon-based flame retardants, with phosphorus-based flame retardants being preferred.

[0339] As flame retardants, known alternatives can be used, such as brominated epoxy resins, brominated polycarbonates, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl methacrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, and other halogenated flame retardants; red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tri(xyl) phosphate, trialkyl phosphate, etc. Phosphorus-based flame retardants include esters, dialkyl phosphates, trichloroethyl phosphates, phosphazenes, 1,3-phenylenebis(phenyl phosphate), 1,3-phenylenebis(2,6-di(xylyl) phosphate), and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, some boehmite, zinc borate, and antimony trioxide; and silicone-based flame retardants include silicone rubber and silicone resin.

[0340] In this embodiment, among these, 1,3-phenylene bis(2,6-bis(di(xylyl)phosphate) does not impair the low dielectric properties (Dk and / or Df), and is therefore preferred.

[0341] When the resin composition (1) contains a flame retardant, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, depending on the application, etc., it can be 12 parts by mass or more. In addition, the lower limit of the flame retardant content is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, depending on the application, etc., it can be 20 parts by mass or less or 15 parts by mass or less.

[0342] Flame retardants can be used alone or in combination of two or more. When using two or more, the total amount shall be within the range mentioned above.

[0343] <<Active Ester Compounds>>

[0344] The resin composition (1) may contain an active ester compound. There are no particular limitations on the active ester compound, for example, reference can be made to paragraphs 0064 to 0066 of International Publication No. 2021 / 172317, the contents of which are incorporated herein by reference.

[0345] When the resin composition (1) contains an active ester compound, it is preferably 1 part by mass or more, and more preferably 50 parts by mass or less, relative to 100 parts by mass of the resin solids in the resin composition (1).

[0346] The resin composition (1) in this embodiment may contain only one active ester compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0347] Alternatively, the resin composition (1) of this embodiment may also be substantially free of active ester compounds. "Substantially free" means that the content of active ester compounds is less than 1 part by mass relative to 100 parts by mass of the resin solids in the resin composition (1), preferably less than 0.1 parts by mass, and more preferably less than 0.01 parts by mass.

[0348] <<Dispersant>>

[0349] The resin composition (1) may contain a dispersant. As a dispersant, it is preferable to use a dispersant commonly used in coatings, and there is no particular limitation on its type. The dispersant is preferably a wetting dispersant of the copolymer matrix; specific examples include DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark)-W996, W9010, W903, W940, etc., manufactured by BYK Japan Co., Ltd.

[0350] When the resin composition (1) contains a dispersant, the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition (1) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and may also be 0.3 parts by mass or more. Furthermore, the upper limit of the dispersant content relative to 100 parts by mass of the resin solids in the resin composition (1) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

[0351] One type of dispersant may be used alone or in combination of two or more. When two or more types are used, the total dosage shall be within the range mentioned above.

[0352] <<Cure Accelerator>>

[0353] The resin composition (1) may further comprise a curing accelerator. There are no particular limitations on the curing accelerator, but examples include imidazoles such as 2-ethyl-4-methylimidazolium and triphenylimidazolium; organic peroxides such as benzoyl peroxide, bis(1-methyl-1-phenylethyl) peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyldisperoxyphthalate, α,α'-di(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3; azo compounds such as azobisnitrile (e.g., azobisisobutyronitrile); N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, and 2- Tertiary amines such as N-ethylaniline ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutyldiamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; high-temperature decomposition free radical generators such as 2,3-dimethyl-2,3-diphenylbutane; organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octanoate, manganese octanoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; substances formed by dissolving these organometallic salts in phenol, bisphenol, and other hydroxyl-containing compounds; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organotin compounds such as dioctyltin oxide, other alkyltin compounds, and alkyltin oxides.

[0354] The preferred curing accelerator is one or more selected from the group consisting of imidazoles, organic peroxides and organometallic salts, and more preferably, a combination of imidazoles and organometallic salts, or imidazoles and organic peroxides.

[0355] When the resin composition (1) contains a curing accelerator, the lower limit of its content relative to 100 parts by weight of the resin solids in the resin composition (1) is preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, and even more preferably 0.1 parts by weight or more. Furthermore, the upper limit of the content of the curing accelerator relative to 100 parts by weight of the resin solids in the resin composition (1) is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, even more preferably 3 parts by weight or less, even more preferably 2 parts by weight or less, even more preferably 1.5 parts by weight or less, and can be 1.0 parts by weight or less, 0.8 parts by weight or less, or 0.7 parts by weight or less.

[0356] Curing accelerators can be used alone or in combination of two or more. When using two or more, the total dosage should be within the range mentioned above.

[0357] <<Solvent>>

[0358] The resin composition (1) may contain a solvent, preferably an organic solvent. When containing a solvent, the resin composition (1) is in the form of a solution or varnish in which at least a portion, preferably all, of the above-mentioned solid resin components are dissolved or compatible with the solvent. As a solvent, there are no particular limitations as long as it is a polar or non-polar organic solvent capable of dissolving or compatibility with at least a portion, preferably all, of the above-mentioned solid resin components. Examples of polar organic solvents include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexanone, etc.), cellosols (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), and amides (e.g., dimethoxyacetamide, dimethylformamide, etc.). Examples of non-polar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.).

[0359] Solvents can be used alone or in combination of two or more.

[0360] <<Other Resin Additives>>

[0361] In addition to the above-mentioned components, the resin composition (1) may also contain various polymeric compounds such as elastomers, styrene oligomers, and thermoplastic resin oligomers, as well as various additives. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, pigments (dyes, pigments), thickeners, flow modifiers, lubricants, defoamers, leveling agents, gloss agents, quinones, phenols, nitrosamines, hydroxylamines, and other polymerization inhibitors. These additives may be used individually or in combination of two or more.

[0362] <Fiber substrate>

[0363] The first insulating resin layer preferably comprises a fiber substrate.

[0364] Fiber substrate is a substrate formed of fibers, suitable as a substrate for the first insulating resin layer (prepreg substrate), preferably glass cloth.

[0365] The glass cloth is preferably a substrate formed of glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, NER-glass).

[0366] There are no particular limitations on the form of the fiber substrate, and examples include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, and surface-finished mats. These fiber substrates can be used alone or in combination of two or more. Among these fiber substrates, from the viewpoint of dimensional stability, woven fabrics that have undergone super-opening treatment and mesh blocking treatment are preferred. From the viewpoint of strength and low water absorption, fiber substrates with a thickness of less than 200µm and a mass of 250g / m² are preferred. 2 From the viewpoint of moisture absorption and heat resistance, the following glass fabrics are preferably surface-treated with epoxy silanes, amino silanes, etc. From the viewpoint of electrical properties, low-dielectric glass cloths formed of glass fibers exhibiting low relative permittivity and low dielectric loss tangent, such as L-glass, NE-glass, NER-glass, and Q-glass, are more preferred.

[0367] Examples of fiber substrates with low relative permittivity include those with a relative permittivity of 5.0 or less (preferably 3.0 to 4.9). Examples of fiber substrates with low dielectric loss tangent include those with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative permittivity and dielectric loss tangent are values ​​measured using a perturbation method cavity resonator at a frequency of 10 GHz.

[0368] In addition, in this embodiment, inorganic fibers other than glass (such as quartz) and organic fibers (such as polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.) may also be used as fiber substrates depending on the application.

[0369] <Second insulating resin layer>

[0370] In this embodiment, the second insulating resin layer is not particularly limited as long as the dielectric loss tangent of the second insulating resin layer at the frequency measured by the perturbation method cavity resonator at 10 GHz is lower than the dielectric loss tangent of the first insulating resin layer at the frequency measured by the perturbation method cavity resonator at 10 GHz.

[0371] The second insulating resin layer is typically a layer formed from a resin composition (2) containing a thermosetting compound. Furthermore, the second insulating resin layer is generally preferably free of a fiber substrate (especially glass cloth).

[0372] In the layer formed by the resin composition (2), the resin solid components contained in the resin composition (2) may be in an uncured state, a semi-cured state, or a cured state. Preferably, the resin solid components contained in the resin composition (2) are in a semi-cured state or a cured state.

[0373] The type of thermosetting compound contained in the resin composition (2) is not particularly limited, but preferably includes at least one selected from the group consisting of maleimide compounds, cyanate compounds, polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends, polymers having structural units shown in formula (V), (meth)allyl compounds, (meth)acrylate compounds, compounds having indane skeletons with carbon-carbon unsaturated double bonds at the ends, epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, arylcyclobutene compounds, perfluorovinyl ether resins, polyamide compounds, polyimide compounds, and compounds having vinylidene compounds.

[0374]

[0375] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * indicates a bonding position.)

[0376] <<Maleimide Compounds>>

[0377] The resin composition (2) may contain a maleimide compound. The resin composition (2) is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2), and can be a widely used compound in the field of printed circuit boards.

[0378] In this embodiment, the maleimide compound preferably includes one or more compounds selected from the group consisting of compounds represented by formula (M0), formula (M1), formula (M2), formula (M3), formula (M4), formula (M5), maleimide compound (M6), maleimide compound (M7), and maleimide compound (M8), and more preferably includes compounds selected from the group consisting of compounds represented by formula (M0), formula (M1), formula (M2), formula (M3), formula (M4), and formula (M5). The compound is selected from the group consisting of the compound shown in formula (4) and the compound shown in formula (5). More preferably, it includes one or more compounds selected from the group consisting of the compound shown in formula (M0), the compound shown in formula (M1), the compound shown in formula (M3), the compound shown in formula (M4), and the compound shown in formula (M5). Even more preferably, it includes one or more compounds selected from the group consisting of the compound shown in formula (M1), the compound shown in formula (M3), and the compound shown in formula (M5). Even more preferably, it includes the compound shown in formula (M1) and / or the compound shown in formula (M3). When these maleimide compounds are used in materials for printed circuit boards (e.g., metal-clad laminates), they can impart excellent heat resistance.

[0379]

[0380] (In formula (M0), R) 51 Each independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, R 52 Each atom can be independently represented by a hydrogen atom or a methyl group, and n1 represents an integer greater than or equal to 1.

[0381] R 51 Each is preferably selected independently from the group consisting of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and phenyl, more preferably hydrogen atom and / or methyl, and even more preferably hydrogen atom.

[0382] R 52 Methyl is preferred.

[0383] n1 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably an integer from 1 to 3, even more preferably 1 or 2, and even more preferably 1.

[0384] Specifically, the following compounds can be cited as preferred examples of formula (M0).

[0385]

[0386] In the above formula, R 8 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group, with methyl being preferred.

[0387] The compound represented by formula (M0) can be a single compound or a mixture of two or more compounds. Examples of mixtures include mixtures of compounds with n1 different values, and R... 51 and / or R 52 This includes mixtures of compounds with different types of substituents, mixtures of compounds with different bonding positions (meta, para, or ortho) of the maleimide group and oxygen atom relative to the benzene ring, and mixtures of compounds formed by combining two or more of these different positions. The same applies to formulas (M1) to (M7) below.

[0388]

[0389] (In formula (M1), R) M1 R M2 R M3 and R M4 Each can independently represent a hydrogen atom or an organic group. R M5 and R M6 Each can independently represent a hydrogen atom or an alkyl group. Ar MThis indicates a divalent aromatic group. A is an alicyclic group with a 4- to 6-membered ring. R M7 and R M8 Each is an alkyl group independently. mx is 1 or 2, lx is 0 or 1. R M9 and R M10 Each can independently represent a hydrogen atom or an alkyl group. R M11 R M12 R M13 and R M14 Each can independently represent a hydrogen atom or an organic group. R M15 Each of these groups independently represents an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, an alkylthio group with 1-10 carbon atoms, a cycloalkyl group with 3-10 carbon atoms, an aryl group with 6-10 carbon atoms, an aryloxy group with 6-10 carbon atoms, an arylthio group with 6-10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.

[0390] R in the formula M1 R M2 R M3 and R M4 Each can independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. R M1 and R M3 Each is preferably an alkyl group, R M2 and R M4 Hydrogen atoms are preferred.

[0391] R M5 and R M6 Each of the terms independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0392] Ar M The aromatic group representing the divalent group is preferably phenylene, naphthyl, phenanthrene, or anthracene, more preferably phenylene, and even more preferably m-phenylene. Ar M It may have substituents, with alkyl groups being preferred, more preferably alkyl groups having 1 to 12 carbon atoms, further preferably alkyl groups having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. However, Ar M Preferably unsubstituted.

[0393] A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group that forms an inden ring together with the benzene ring). RM7 and R M8 Each of the components is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0394] mx is 1 or 2, preferably 2.

[0395] lx is 0 or 1, preferably 1.

[0396] R M9 and R M10 Each can be independently represented by a hydrogen atom or an alkyl group, more preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0397] R M11 R M12 R M13 and R M14 Each can independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. R M12 and R M13 Each is preferably an alkyl group, R M11 and R M14 Hydrogen atoms are preferred.

[0398] R M15 Each of the following can be independently represented as an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0399] px represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0400] nx represents an integer from 1 to 20. nx can also be an integer less than 10.

[0401] It should be noted that the resin composition (2) may contain only one compound represented by formula (M1) and at least two compounds with different nx values, or it may contain two or more compounds. When containing two or more compounds, in order to produce a low melting point (low softening point), low melt viscosity, and excellent workability, the average value (average number of repeating units) n of nx in the compound represented by formula (M1) in the resin composition (2) is preferably 0.92 or more, more preferably 0.95 or more, further preferably 1.0 or more, and even more preferably 1.1 or more. In addition, n is preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, even more preferably 6.0 or less, and may also be 5.0 or less. The same applies to formulas (M1-1) and the like described later.

[0402] The compound represented by formula (M1) is preferably the compound represented by formula (M1-1) below.

[0403]

[0404] (In formula (M1-1), R) M21 R M22 R M23 and R M24 Each can independently represent a hydrogen atom or an organic group. R M25 and R M26 Each can independently represent a hydrogen atom or an alkyl group. R M27 R M28 R M29 and R M30 Each can independently represent a hydrogen atom or an organic group. R M31 and R M32 Each can independently represent a hydrogen atom or an alkyl group. R M33 R M34 R M35 and R M36 Each can independently represent a hydrogen atom or an organic group. R M37 R M38 and R M39 Each can independently represent a hydrogen atom or an alkyl group. nx represents an integer greater than 1 and less than 20.

[0405] R in the formula M21 R M22 R M23 and R M24 Each can independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. R M21 and R M23 Preferably alkyl, R M22 and RM24 Hydrogen atoms are preferred.

[0406] R M25 and R M26 Each of the terms independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0407] R M27 R M28 R M29 and R M30 Each can be independently represented by a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0408] R M31 and R M32 Each of the terms independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0409] R M33 R M34 R M35 and R M36 Each can be independently represented by a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0410] R M33 and R M36 Preferably, hydrogen atoms, R M34 and R M35 Alkyl groups are preferred.

[0411] R M37 R M38 and R M39 Each of the terms independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0412] nx represents an integer greater than 1 and less than 20. nx can also be an integer less than 10.

[0413] The compound represented by formula (M1-1) is preferably the compound represented by formula (M1-2) below.

[0414]

[0415] (In formula (M1-2), R) M21 R M22 R M23 and R M24 Each can independently represent a hydrogen atom or an organic group. R M25 and R M26 Each can independently represent a hydrogen atom or an alkyl group. R M27 R M28 R M29 and R M30 Each can independently represent a hydrogen atom or an organic group. R M31 and R M32 Each can independently represent a hydrogen atom or an alkyl group. R M33 R M34 R M35 and R M36 Each can independently represent a hydrogen atom or an organic group. R M37 R M38 and R M39 Each can independently represent a hydrogen atom or an alkyl group. nx represents an integer greater than 1 and less than 20.

[0416] In formula (M1-2), R M21 R M22 R M23 R M24 R M25 R M26 R M27 R M28 R M29 R M30 R M31 R M32 R M33 R M34 R M35 R M36 R M37 R M38 R M39 And nx and R in equation (M1-1) M21 R M22 R M23 R M24 R M25 R M26 R M27 R M28 R M29 R M30 R M31 R M32 R M33 R M34R M35 R M36 R M37 R M38 R M39 It has the same meaning as nx, and the preferred range is also the same.

[0417] The compound represented by formula (M1-1) is preferably the compound represented by formula (M1-3) below, and more preferably the compound represented by formula (M1-4) below.

[0418]

[0419] (In formula (M1-3), nx represents an integer greater than 1 and less than 20.)

[0420] nx can be an integer less than 10.

[0421]

[0422] (In formula (M1-4), nx represents an integer greater than 1 and less than 20.)

[0423] nx can be an integer less than 10.

[0424] The molecular weight of the compound represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. By setting it to the lower limit or above, there is a tendency to further improve the low dielectric properties and low water absorption of the obtained cured product (insulating resin layer). Furthermore, the molecular weight of the compound represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. By setting it to the upper limit or below, there is a tendency to further improve the heat resistance and workability of the obtained cured product (insulating resin layer).

[0425] The maleimide equivalent of the compound represented by formula (M1) is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, and even more preferably 200 g / eq. or more. The upper limit of the maleimide equivalent is preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, and even more preferably 800 g / eq. or less. Here, the maleimide equivalent represents the mass of the maleimide compound per 1 equivalent of maleimide groups. When the maleimide equivalent of the compound represented by formula (M1) is within the above range, there is a tendency for the resulting cured product (insulating resin layer) to have further improved low dielectric properties, low water absorption, heat resistance, and workability.

[0426] The molecular weight distribution (Mw / Mn) of the compound represented by formula (M1), as determined by gel permeation chromatography (GPC), is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and still more preferably 1.3 to 3.4. When the Mw / Mn of the compound represented by formula (M1) is within the above range, there is a tendency for the resulting cured product (insulating resin layer) to have further improved low dielectric properties, low water absorption, heat resistance, and workability.

[0427] Furthermore, detailed information about the compound represented by formula (M1) can be found in International Publication No. 2020-217679, the contents of which are incorporated herein by reference.

[0428]

[0429] (In formula (M2), R) 54 Each can independently represent a hydrogen atom or a methyl group, and n4 represents an integer greater than or equal to 1.

[0430] n4 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably an integer from 1 to 3, and even more preferably 1 or 2, but can also be 1.

[0431] The compound represented by formula (M2) can be a mixture of n4 different compounds, preferably a mixture. Additionally, as described in part of the compound represented by formula (M0), it can also be a mixture of other compounds with different components.

[0432]

[0433] (In formula (M3), R) 55 Each can independently represent an alkyl or phenyl group with 1 to 8 hydrogen atoms or carbon atoms, and n5 represents an integer greater than 1 and less than 10.

[0434] R 55 Each is preferably selected independently from the group consisting of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and phenyl, more preferably hydrogen atom and / or methyl, and even more preferably hydrogen atom.

[0435] n5 is preferably an integer greater than or equal to 1 and less than or equal to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2.

[0436] The compound represented by formula (M3) can be a mixture of n5 different compounds, preferably a mixture. Additionally, as described in part of the compound represented by formula (M0), it can also be a mixture of other compounds with different components.

[0437]

[0438] (In formula (M4), R) 56 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group; R 57 Each can independently represent a hydrogen atom or a methyl group.

[0439] R 56 Preferably, each benzene ring is independently methyl or ethyl, more preferably, each of the two benzene rings is methyl and ethyl. 57 Methyl is preferred.

[0440]

[0441] (In formula (M5), R) 58 Each independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, R 59 Each can independently represent a hydrogen atom or a methyl group, and n6 represents an integer greater than or equal to 1.

[0442] R 58 Each is preferably selected independently from the group consisting of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and phenyl, more preferably hydrogen atom and / or methyl, and even more preferably hydrogen atom.

[0443] R 59 Methyl is preferred.

[0444] n6 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably an integer from 1 to 3, and even more preferably 1 or 2, or it can be 1.

[0445] The compound represented by formula (M5) can be a mixture of n6 different compounds, preferably a mixture. Additionally, as described in part of the compound represented by formula (M0), it can also be a mixture of other compounds with different components.

[0446] Maleimide compound (M6) is a compound having the structural unit shown in formula (M6) and maleimide groups at both ends of the molecular chain.

[0447]

[0448] (In formula (M6), R) 61 R represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 16 carbon atoms. 62 R represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 16 carbon atoms. 63Each group independently represents a straight-chain or branched alkyl group with 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group with 2 to 16 carbon atoms. Each group independently represents an integer from 0 to 10.

[0449] Details of the maleimide compound (M6) and its manufacturing method can be found in paragraphs 0061 to 0066 of International Publication No. 2020 / 262577, the contents of which are incorporated herein by reference.

[0450] Maleimide compound (M7) is a maleimide compound that uses an aromatic amine compound (a1) having one or more but three or fewer alkyl groups on an aromatic ring, an aromatic divinyl compound (a2) having two vinyl groups, and maleic anhydride as reactants (1).

[0451] The maleimide compound (M7) is preferably a compound represented by formula (M7).

[0452]

[0453] (In the above formula (M7), R) 1 Each independently represents an alkyl group having 1 to 10 carbon atoms, R 2 Each of these groups independently represents an alkyl, alkoxy, or alkylthio group having 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group.

[0454] R 3 R 4 R 5 and R 6 Each can independently represent a hydrogen atom or a methyl group, and R 3 and R 4 One of them is a hydrogen atom, and the other is a methyl group, R 5 and R 6 One of them is a hydrogen atom, and the other is a methyl group.

[0455] X 1 Each of the substituents is independently represented by the following formula (x):

[0456]

[0457] (In equation (x), R) 7 and R 8 Each can independently represent a hydrogen atom or a methyl group, and R 7 and R 8 One of them is a hydrogen atom, and the other is a methyl group, R 9Each of these groups independently represents an alkyl, alkoxy, or alkylthio group with 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group with 6 to 10 carbon atoms; a cycloalkyl group with 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, where t represents an integer from 0 to 4.

[0458] r represents the number of combinations with X. 1 X of the benzene ring 1 The average of the substitution numbers, where p represents an integer from 1 to 3, q ​​represents an integer from 0 to 4, and k represents an integer from 1 to 100.

[0459] Details of the maleimide compound (M7) used in this embodiment can be found in Japanese Patent No. 7160151, the contents of which are incorporated herein by reference.

[0460] Maleimide compound (M8) is a maleimide compound having eight or more hydrocarbon groups linked in a straight chain, preferably a compound represented by formula (M8). Such bismaleimide compounds (M8) tend to have higher stress relief capabilities, and as a result, tend to have a further reduced coefficient of thermal expansion of the cured product, and tend to have better dielectric constant and dielectric loss tangent isoelectric properties.

[0461]

[0462] (In formula (M8), R) 1 and R 3 Each can independently represent a hydrocarbon group consisting of eight or more atoms linked in a straight chain, R 2 Each group independently represents a cyclic hydrocarbon group, whether substituted or unsubstituted, consisting of 4 or more but less than 10 atoms forming the ring, and may contain heteroatoms; n represents a number from 0 to 10.

[0463] In formula (M8), R is preferred. 1 and R 3 For Yasinki, R 2 Cycloalkylene groups with alkyl groups having 6 to 8 carbon atoms as substituents.

[0464] As for the maleimide compound (M8), reference can be made to paragraphs 0013 to 0022 of Japanese Patent Application Publication No. 2018-083893 and paragraphs 0011 to 0022 of Japanese Patent Application Publication No. 2018-090728, the contents of which are incorporated into this specification.

[0465] Maleimide compounds can be manufactured using known methods or commercially available products. Examples of commercially available products include "BMI-80" manufactured by K·I Chemical Industry Co., Ltd. (M0), "NE-X-9470S" and "NE-X-9480S" manufactured by DIC Corporation (M1), "BMI-2300" manufactured by Yamato Chemical Industry Co., Ltd. (M2), "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. (M3), and "M4" manufactured by K·I Chemical Industry Co., Ltd. BMI-70 manufactured by Co., Ltd., BMI-5100 manufactured by Daiwa Chemical Industry Co., Ltd., MIR-5000 manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M5), MIZ-001 manufactured by Nippon Kayaku Co., Ltd. as a maleimide compound (M6), NE-X-9500 manufactured by DIC Co., Ltd. as a maleimide compound (M7), SFR manufactured by Resonac Co., Ltd. as a maleimide compound (M8), BMI-689, BMI-3000, and BMI-5000 manufactured by DESIGNER MOLECULES INC.

[0466] In addition, examples of maleimide compounds other than those mentioned above include oligomers of N-phenylmaleimide, N-cyclohexylmaleimide, phenylmethane maleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimide-phenoxy)benzene, 1,3-bis(4-maleimide-phenoxy)benzene and their prepolymers, as well as prepolymers of these maleimides with amines.

[0467] Furthermore, in addition to the above, the contents of the compounds described in paragraphs 0051 to 0068 of International Publication No. 2020 / 262577 can be incorporated into this specification.

[0468] When the resin composition (2) contains a maleimide compound, the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, or 60 parts by mass or more. By setting the content of the maleimide compound to the above-mentioned lower limit or above, there is a tendency to improve the heat resistance of the second insulating resin layer. In addition, the upper limit of the content of the maleimide compound relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less. By setting the content of the maleimide compound to the above-mentioned upper limit or less, there is a tendency to improve the metal foil peel strength and low water absorption of the second insulating resin layer.

[0469] The resin composition (2) in this embodiment may contain only one maleimide compound or two or more. When it contains two or more, the total amount is preferably within the range described above.

[0470] <<Cyanate Compounds>>

[0471] The resin composition (2) preferably contains a cyanate ester compound. By including a cyanate ester compound in the resin composition (2), the adhesion between the insulating resin layer and the metal foil (plating and / or wiring pattern) and the formation of fine wiring are further improved.

[0472] Cyanate ester compounds are not particularly limited as long as they contain one or more cyanate groups (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2) per molecule, and can be widely used in the field of printed circuit boards. Furthermore, cyanate ester compounds are preferably compounds in which the cyanate groups are directly bonded to an aromatic skeleton (aromatic ring).

[0473] As the cyanate compound, the cyanate compound described in the resin composition (1) is preferred, more preferably a naphthol aralkyl type cyanate compound, and even more preferably a cyanate compound represented by formula (5).

[0474] When the resin composition (2) contains a cyanate ester compound, the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. By making the content of the cyanate ester compound 0.1 parts by mass or more, there is a tendency for excellent adhesion to the metal foil (plating and / or wiring pattern) of the second insulating resin layer, excellent micro-wiring formation, heat resistance, flame resistance, chemical resistance, low dielectric properties (relative permittivity and / or dielectric loss tangent), and excellent insulation. The upper limit of the content of the cyanate ester compound relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. Depending on the application, it can be 8 parts by mass or less or 6 parts by mass or less.

[0475] The resin composition (2) in this embodiment may contain only one cyanate ester compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0476] <<Polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends>>

[0477] The resin composition (2) preferably contains a polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends. By including the resin composition (2) in a polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends, the adhesion of the insulating resin layer to the metal foil (plating and / or wiring pattern) and the ability to form microwires are further improved.

[0478] Polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends are preferably polyphenylene ether compounds having two or more carbon-carbon unsaturated double bonds at the ends, more preferably polyphenylene ether compounds having two or more groups selected from the group consisting of (meth)acryloyl, (meth)allyl, and vinylbenzyl at the ends, and even more preferably polyphenylene ether compounds having two or more groups selected from the group consisting of (meth)acryloyl and vinylbenzyl at the ends. By using these polyphenylene ether compounds, in addition to further improving the adhesion between the insulating resin layer and the metal foil (plating and / or wiring pattern) and the ability to form fine wiring, there is also a tendency to more effectively improve the low dielectric properties and low water absorption of printed circuit boards, etc.

[0479] The following is a detailed explanation of their features.

[0480] Polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends can be exemplified by compounds having the phenylene ether skeleton shown in the following formula (X1).

[0481]

[0482] (In formula (X1), R) 24 R 25 R 26 and R 27 (The same or different can be selected to represent alkyl, aryl, halogen, or hydrogen atoms with 6 or fewer carbon atoms.)

[0483] Polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends may further include structural units shown in formula (X2) and / or formula (X3).

[0484]

[0485] (In formula (X2), R) 28 R 29 R 30 R 34 and R 35 The same or different can be used to indicate alkyl or phenyl groups with 6 or fewer carbon atoms. R 31 R 32 and R 33 (Optional, either the same or different, consisting of alkyl or phenyl groups with 6 or fewer hydrogen atoms.)

[0486]

[0487] (In formula (X3), R) 36 R 37 R 38 R 39 R 40 R 41 R 42 and R 43 The following can be chosen to be the same or different: an alkyl or phenyl group with 6 or fewer carbon atoms, and a hydrogen atom. -A- can be a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0488] The polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends is preferably a modified polyphenylene ether compound whose ends are partially or completely functionalized with olefinic unsaturated groups (hereinafter sometimes referred to as "modified polyphenylene ether compound (g)"). More preferably, it is a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acryloyl, (meth)allyl, and vinylbenzyl at the ends. Using such a modified polyphenylene ether compound (g) further improves the adhesion between the insulating resin layer and the metal foil (plating and / or wiring pattern) and the formation of fine wiring, further reduces the dielectric loss tangent (Df) of the cured resin composition (2), and improves low water absorption. One or more modified polyphenylene ether compounds (g) can be used.

[0489] Examples of modified polyphenylene ether compounds (g) include polyphenylene ether compounds represented by formula (OP).

[0490]

[0491] (In formula (OP), X represents an aromatic group, -(YO) n1 - indicates a polyphenylene ether structure, n1 represents an integer from 1 to 100, and n2 represents an integer from 1 to 4. Rx is the group shown in formula (Rx-1) or formula (Rx-2).

[0492]

[0493] In equations (Rx-1) and (Rx-2), R 1 R 2 and R 3 Each group independently represents a hydrogen atom, alkyl, alkenyl, or alkynyl group. * indicates the bonding site with an oxygen atom. Mc independently represents a hydrocarbon group with 1 to 12 carbon atoms. z represents an integer from 0 to 4. r represents an integer from 1 to 6.

[0494] When n1 and / or n2 are integers of 2 or more, the n1 structural units (YO) and / or n2 structural units may each be chosen to be the same or different. n2 is preferably 2 or more, and more preferably 2.

[0495] In equations (Rx-1) and (Rx-2), R 1 R 2 and R 3 Each can independently represent a hydrogen atom, alkyl group, alkenyl group, or alkynyl group.

[0496] R 1 Preferably, it is a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0497] R 2 and R 3 Each is independently preferred to have a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0498] As R 1 R 2 and R 3 The number of carbon atoms in each of the alkyl, alkenyl, or alkynyl groups is preferably 5 or less, more preferably 3 or less.

[0499] In formula (Rx-1), r represents an integer from 1 to 6, preferably an integer from 1 to 5, more preferably an integer from 1 to 4, even more preferably an integer from 1 to 3, even more preferably 1 or 2, and even more preferably 1.

[0500] In formula (Rx-1), Mc independently represents a hydrocarbon group with 1 to 12 carbon atoms, preferably a hydrocarbon group with 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms, further preferably methyl, ethyl, isopropyl, isobutyl, tert-butyl, pentyl, octyl or nonyl, and even more preferably methyl, ethyl, isopropyl, isobutyl or tert-butyl.

[0501] In formula (Rx-1), z represents an integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, even more preferably 0 or 1, and even more preferably 0.

[0502] Specific examples of the group represented by formula (Rx-1) are vinylbenzyl and specific examples of the group represented by formula (Rx-2) are (meth)acryloyl.

[0503] The preferred compound is the compound shown in formula (OP-1) as the modified polyphenylene ether compound (g).

[0504]

[0505] In formula (OP-1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 R 2 and R 3 Each group independently represents a hydrogen atom, alkyl, alkenyl, or alkynyl group; n1 represents an integer from 1 to 6; n2 represents an integer from 1 to 100; and n3 represents an integer from 1 to 4.

[0506] When n2 and / or n3 are integers of 2 or more, the n2 structural units (YO) and / or n3 structural units may each be chosen to be the same or different. n3 is preferably 2 or more, and more preferably 2.

[0507] The modified polyphenylene ether compound (g) in this embodiment is preferably the compound shown in formula (OP-2).

[0508]

[0509] Here, -(OXO)- is preferably represented by formula (OP-3) and / or formula (OP-4):

[0510]

[0511] (In formula (OP-3), R) 4 R 5 R 6 R 10 and R 11 Choose either the same or different, which are alkyl or phenyl groups having 6 or fewer carbon atoms. R 7 R 8 and R 9 (Optional, either the same or different, consisting of alkyl or phenyl groups with 6 or fewer hydrogen atoms.)

[0512]

[0513] (In formula (OP-4), R) 12 R 13 R 14 R 15 R 16 R 17 R 18 and R 19 (The following can be selected, either the same or different, and can be an alkyl or phenyl group with 6 or fewer carbon atoms, containing hydrogen atoms. -A- can be a divalent hydrocarbon group that is straight-chain, branched, or cyclic with 20 or fewer carbon atoms.)

[0514] Furthermore, -(YO)- is preferably represented by formula (OP-5):

[0515]

[0516] (In formula (OP-5), R) 20 R 21 Choose either the same or different, which are alkyl or phenyl groups having 6 or fewer carbon atoms. R 22 R 23 Choose either the same or different, which are alkyl or phenyl groups having 6 or fewer hydrogen atoms or carbon atoms. Specifically, via R... 20 and R 21 Each of the groups has one or more methyl and / or cyclohexyl groups, resulting in a resin molecule with higher rigidity. Molecules with higher rigidity have lower mobility compared to molecules with lower rigidity, thus the relaxation time during dielectric relaxation is longer, and the low dielectric properties (Dk and / or Df) are excellent, making them preferred.

[0517] An example of Formula (OP-5) is the following structure.

[0518]

[0519] Regarding the polyphenylene compound having the above structure, reference can be made to the description in Japanese Patent Laid-Open No. 2019-194312, the content of which is incorporated into the present specification.

[0520] In Formula (OP-2), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100. Each of a and b is independently preferably an integer of 0 to 50, more preferably an integer of 1 to 30, and still more preferably an integer of 1 to 10. When a and / or b is an integer of 2 or more, two or more of -(Y-O)- may each independently be arranged in a single structure, or two or more structures may be arranged in a block or random manner.

[0521] In addition, when a plurality of compounds represented by Formula (OP-2) are contained, the average value of a is preferably 1 < a < 10, and the average value of b is preferably 1 < b < 10.

[0522] Examples of -A- in Formula (OP-4) include divalent organic groups such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene, but are not limited thereto.

[0523] In the compound represented by the above Formula (OP-2), R is preferred 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 are alkyl groups having 3 or less carbon atoms, and R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23The polyphenylene ether compound is an alkyl group having 3 or fewer hydrogen atoms or carbon atoms. Particularly preferred are the -(OXO)- shown in formula (OP-3) or formula (OP-4) as formula (OP-9), formula (OP-10) and / or formula (OP-11), and the -(YO)- shown in formula (OP-5) as formula (OP-12) or formula (OP-13). When a and / or b are integers of 2 or more, the two or more -(YO)- are each independently arranged in a structure consisting of two or more formulas (OP-12) and / or formula (OP-13), or they may be arranged in a block or random arrangement of formulas (OP-12) and (OP-13).

[0524]

[0525]

[0526] (In formula (OP-10), R) 44 R 45 R 46 and R 47 The atom can be either the same or different, and can be either hydrogen or methyl. -B- is a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0527] -B- can be given as a specific example that is the same as the specific example of -A- in equation (OP-4).

[0528]

[0529] In formula (OP-11), -B- is a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0530] -B- can be given as a specific example that is the same as the specific example of -A- in equation (OP-4).

[0531]

[0532]

[0533] The polyphenylene ether compound used in this embodiment is further preferably the compound shown in formula (OP-14) and / or the compound shown in formula (OP-15), and is further preferably the compound shown in formula (OP-15).

[0534]

[0535] (In equation (OP-14), a and b each independently represent integers from 0 to 100, and at least one of a and b is an integer from 1 to 100.)

[0536] In equation (OP-14), a and b have the same meaning as a and b in equation (OP-2), and the preferred range is also the same.

[0537]

[0538] (In equation (OP-15), a and b each independently represent integers from 0 to 100, and at least one of a and b is an integer from 1 to 100.)

[0539] In equation (OP-15), a and b have the same meaning as a and b in equation (OP-2), and the preferred range is also the same.

[0540] Alternatively, the polyphenylene ether compound used in this embodiment can also be a compound represented by formula (OP-16).

[0541]

[0542] (In equation (OP-16), a and b each independently represent integers from 0 to 100, and at least one of a and b is an integer from 1 to 100.)

[0543] Polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends can be manufactured by known methods or commercially available products can be used. Examples of commercially available products include "SA9000" manufactured by SABIC Innovative Plastics, a modified polyphenylene ether compound with a methacryloyl group at the end. Examples of modified polyphenylene ether compounds with a vinyl benzyl group at the end include "OPE-2St1200" and "OPE-2st2200" manufactured by Mitsubishi Gas Chemical Co., Ltd. Alternatively, a modified polyphenylene ether compound with a vinyl benzyl group at the end can be obtained by modifying a hydroxyl-terminated polyphenylene ether compound such as "SA90" manufactured by SABIC Innovative Plastics to a vinyl benzyl group using a vinyl benzyl chloride or similar substance.

[0544] Furthermore, details of polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends can be found in Japanese Patent Application Publication No. 2006-028111, Japanese Patent Application Publication No. 2018-131519, International Publication No. 02019-138992, and International Publication No. 2022-054303, which are incorporated herein by reference.

[0545] The number-average molecular weight (details as described in the examples below) of polyphenylene ether compounds (preferably modified polyphenylene ether compounds (g)) with carbon-carbon unsaturated double bonds at the ends, converted to polystyrene by GPC (gel permeation chromatography), is preferably 500 or more and 3,000 or less. By setting the number-average molecular weight to 500 or more, there is a tendency to further suppress tackiness when the resin composition (2) is formed into a coating film. By setting the number-average molecular weight to 3,000 or less, there is a tendency to further improve solubility in solvents.

[0546] Furthermore, the weight-average molecular weight (according to the method described in the examples below) of the polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) having carbon-carbon unsaturated double bonds at the ends is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. By setting the value above the lower limit, there is a tendency for the relative permittivity (Dk) and / or dielectric loss tangent (Df) of the cured resin composition (2) to become lower, and by setting the value below the upper limit, there is a tendency for the solubility, low viscosity and formability of the resin composition (2) in solvents when making varnishes, etc., as described below, to be further improved.

[0547] Furthermore, in the case of the modified polyphenylene ether compound (g), the equivalent amount of the terminal carbon-carbon unsaturated double bonds relative to each carbon-carbon unsaturated double bond is preferably 400 to 5000 g, more preferably 400 to 2500 g. By setting the value above the lower limit, there is a tendency for the relative permittivity (Dk) and / or dielectric loss tangent (Df) of the cured resin composition (2) to become lower. By setting the value below the upper limit, there is a tendency for the solubility, low viscosity, and moldability of the resin composition (2) to be further improved.

[0548] When the resin composition (2) contains a polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends, the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 13 parts by mass or more. By setting it to the lower limit or above, in addition to further improving the adhesion between the second insulating resin layer and the metal foil (plating and / or wiring pattern) and the ability to form fine wiring, there is also a tendency for better low dielectric properties (Dk and / or Df) and moisture absorption and heat resistance. In addition, the upper limit of the content of the polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, further preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less. By setting it below the aforementioned upper limit value, there is a tendency for the second insulating resin layer to exhibit superior adhesion, heat resistance, and chemical resistance to the metal layer (plating and / or wiring pattern).

[0549] The resin composition (2) in this embodiment may contain only one type of polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end, or it may contain two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0550] <<Compounds with an indene skeleton and a carbon-carbon unsaturated double bond at the end>>

[0551] The resin composition (2) may include a compound having an indane skeleton with carbon-carbon unsaturated double bonds at the ends.

[0552] An example of a compound with an indene skeleton having carbon-carbon unsaturated double bonds at the ends is the resin shown in formula (T).

[0553]

[0554] In formula (T), R is a group that contains the structural unit shown in formula (Tx). x It is a group containing a carbon-carbon unsaturated double bond. R y y represents a hydrogen atom, a -O- group containing a carbon-carbon unsaturated double bond, or other groups. y1 is an integer from 1 to 4. Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group with 1 to 20 carbon atoms optionally substituted by a hydroxyl or halogen atom. y represents an integer from 0 to 4.

[0555]

[0556] (In equation (Tx), n, o, and p are the average number of structural units. n represents a number greater than 0 and less than 20, and o and p independently represent numbers from 0 to 20, satisfying 1.0 ≤ n + o + p ≤ 20.0. Ma independently represents a hydrocarbon group with 1 to 12 carbon atoms arbitrarily substituted by halogen atoms. x independently represents an integer from 0 to 4. Structural units (a), (b), and (c) are bonded to structural units (a) to (c) at *, and the structural units can be bonded randomly.)

[0557] In addition, compounds with an indane skeleton having carbon-carbon unsaturated double bonds at the ends can be resins with structural units derived from compounds represented by formula (DIP) as the main components and having structures represented by formula (In-1) and / or formula (In-2).

[0558]

[0559] (In formula (DIP), Ma independently represents 1 to 12 hydrocarbon groups that are optionally substituted with halogen atoms. x represents an integer from 0 to 4.)

[0560]

[0561] In formula (In-1), Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group with 1 to 20 carbon atoms optionally substituted by a hydroxyl or halogen atom. y represents an integer from 0 to 3. R x Groups containing carbon-carbon unsaturated double bonds. * indicates bonding sites with other sites.

[0562]

[0563] In formula (In-2), Ma independently represents a hydrocarbon group with 1 to 12 carbon atoms optionally substituted by a halogen atom. x represents an integer from 0 to 3. Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group with 1 to 20 carbon atoms optionally substituted by a hydroxyl or halogen atom. y represents an integer from 0 to 4. R x This refers to a group containing a carbon-carbon unsaturated double bond. xp is the number of linking bonds to the benzene ring, an integer of 1 or 2. * indicates a bonding site with other sites.

[0564] Compounds with an indene skeleton having a carbon-carbon unsaturated double bond at the end can be described in this specification with reference to paragraphs 0011-0025 of International Publication No. 2023 / 176766, paragraphs 0012-0033 of International Publication No. 2023 / 176764, paragraphs 0012-0033 of International Publication No. 2023 / 176763, and paragraphs 0026-0043 of International Publication No. 2023 / 176765, the contents of which are incorporated herein by reference.

[0565] <<Compounds containing vinylidene>>

[0566] The resin composition (2) may contain compounds having vinylidene content.

[0567] Examples of compounds containing vinylidene molecules include compounds containing one or more -CH=CH- groups, with compounds containing one -CH=CH- group being preferred. Furthermore, compounds that are both vinylidene compounds and maleimide compounds are defined as maleimide compounds.

[0568] Specific examples of compounds having vinylidene content include acenaphthene and pyracylene, with acenaphthene being more preferred.

[0569] In this specification, as with the imidazole compounds described later, compounds that are also compounds having vinylidene content and are explicitly stated as components other than compounds having vinylidene content (e.g., curing accelerators) are defined as compounds that do not have vinylidene content.

[0570] Details of polymers, (meth)allyl compounds, (meth)acrylate compounds, epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, arylcyclobutene compounds, perfluorovinyl ether resins, polyamide compounds, and polyimide compounds having the structural units shown in formula (V) can be found in paragraphs 0075 to 0105 of International Publication No. 2023 / 171554 and paragraphs 0198 to 0200 of International Publication No. 2023 / 176765, the contents of which are incorporated herein by reference.

[0571] Relative to 100 parts by mass of the resin solids in the resin composition (2), the content of the polymer having the structural unit shown in formula (V) in the resin composition (2) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. Depending on the application, it can be 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more. By setting the content of the polymer having the structural unit shown in formula (V) to the lower limit value or above, there is a tendency to further improve the low dielectric properties and low water absorption of the second insulating resin layer. In addition, relative to 100 parts by mass of the resin solids in the resin composition (2), the upper limit value of the content of the polymer having the structural unit shown in formula (V) is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. Depending on the application, it can be 30 parts by mass or less or 20 parts by mass or less. By setting the content of the thermosetting compound to the upper limit value or less, there is a tendency to further improve the heat resistance, plating adhesion, and low thermal expansion of the insulating resin layer of the second insulating resin layer.

[0572] The resin composition (2) may contain only one polymer having the structural unit shown in formula (V), or it may contain two or more polymers. When it contains two or more polymers, the total amount is preferably within the range described above.

[0573] Relative to 100 parts by mass of the resin solids in the resin composition (2), the total amount of the thermosetting compound in the resin composition (2) is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 55 parts by mass or more. By setting the content of the thermosetting compound to the lower limit value or above, there is a tendency to further improve the heat resistance and coating adhesion of the second insulating resin layer. In addition, relative to 100 parts by mass of the resin solids in the resin composition (2), the upper limit value of the content of the thermosetting compound is preferably 99 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less. Depending on the application, it can be 80 parts by mass or less, or 70 parts by mass or less. By setting the content of the thermosetting compound to the upper limit value or less, there is a tendency to further improve the low dielectric properties and low water absorption of the second insulating resin layer.

[0574] The resin composition (2) may contain only one thermosetting compound or two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0575] <<Elastomers>>

[0576] The resin composition (2) may contain an elastomer. In this embodiment, the elastomer is preferably a thermoplastic elastomer.

[0577] The thermoplastic elastomer in this embodiment is not particularly limited, and examples include at least one selected from the group consisting of polyisoprene, polybutadiene, styrene-butadiene, butyl rubber, ethylene-propylene rubber, styrene-butadiene-ethylene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butene-styrene, styrene-propylene-styrene, styrene-ethylene-propylene-styrene, fluororubber, silicone rubber, their hydrides, their alkyl compounds, and their copolymers.

[0578] In addition, examples of elastomers include oligomers or polymers with curable vinyl functional groups described in paragraphs 0044 and 0045 of Japanese Patent Application Publication No. 2019-194312, and polybutadiene resins are also included in this specification.

[0579] The number-average molecular weight of the elastomer (preferably a thermoplastic elastomer) in this embodiment is preferably 1,000 or more. By having a number-average molecular weight of 1,000 or more, the resulting cured product (insulating resin layer) tends to have superior low dielectric properties (Dk and / or Df, especially low dielectric loss tangent). The number-average molecular weight is preferably 1,500 or more, more preferably 2,000 or more, and can be 60,000 or more, 70,000 or more, or 80,000 or more, depending on the application, etc. The upper limit of the number-average molecular weight of the elastomer (preferably a thermoplastic elastomer) is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. By setting it to the upper limit value or below, there is a tendency for the solubility of the elastomer component in the resin composition (2) to increase.

[0580] When the resin composition (2) contains two or more elastomers, it is preferable that the number average molecular weight of their mixture satisfies the above-mentioned range.

[0581] The elastomer used in this embodiment may include resins containing a polybutadiene structure. Optionally, some or all of the polybutadiene structure may be hydrogenated. Specific examples include Nippon Soda Corporation's B-1000, B-2000, B-3000, BI-2000, BI-3000, CRAY VALLEY Corporation's Ricon100, Ricon130, Ricon131, Ricon142, Ricon150, Ricon181, Ricon184, etc.

[0582] The elastomers used in this embodiment can be resins containing a poly(meth)acrylate structure. Specific examples include Teisan Resin manufactured by Nagase ChemteX, and ME-2000, W-197C, KG-15, and KG-3000 manufactured by Negami Kogyo Co., Ltd.

[0583] The elastomer used in this embodiment can be a resin containing a polycarbonate structure. Sometimes, a resin containing a polycarbonate structure is referred to as a "polycarbonate resin." Examples of such resins include carbonate resins without reactive groups, hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, acid anhydride-containing carbonate resins, isocyanate-containing carbonate resins, urethane-containing carbonate resins, and epoxy-containing carbonate resins. Here, a reactive group refers to a functional group such as hydroxyl, phenolic hydroxyl, carboxyl, acid anhydride, isocyanate, urethane, and epoxy groups that can react with other components.

[0584] Specific examples of polycarbonate resins include FPC0220 and FPC2136 manufactured by Mitsubishi Gas Chemical Co., Ltd., and T6002 and T6001 (polycarbonate diol) manufactured by Asahi Kasei Corporation.

[0585] The elastomers used in this embodiment can be resins containing a polysiloxane structure. Specific examples include SMP-2006, SMP-2003PGMEA, SMP-5005PGMEA, KR-510, and SMP-7014-3S manufactured by Shin-Etsu Silicones Co., Ltd.

[0586] Examples of elastomers used in this embodiment include resins containing polyalkylene structures and / or polyalkylene oxide structures. The polyalkylene oxide structure is preferably a polyalkylene oxide structure with 2 to 15 carbon atoms, more preferably a polyalkylene oxide structure with 3 to 10 carbon atoms, and particularly preferably a polyalkylene oxide structure with 5 to 6 carbon atoms. Specific examples of resins containing polyalkylene structures and / or polyalkylene oxide structures include PTXG-1000 and PTXG-1800 manufactured by Asahi Kasei Corporation.

[0587] The elastomer used in this embodiment can be a resin containing a polyisoprene structure. Specific examples include KL-610 and KL613 manufactured by Kuraray.

[0588] The elastomer used in this embodiment can be a resin containing a polyisobutylene structure. Specific examples include SIBSTAR-073T (styrene-isobutylene-styrene triblock copolymer) and SIBSTAR-042D (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0589] In this embodiment, the thermoplastic elastomer is preferably a thermoplastic elastomer comprising styrene monomer units and conjugated diene monomer units (hereinafter referred to as "thermoplastic elastomer (E)"). By using such a thermoplastic elastomer (E), the resulting cured product (insulating resin layer) exhibits superior low dielectric properties (Dk and / or Df, especially low dielectric loss tangent).

[0590] The thermoplastic elastomer (E) in this embodiment comprises styrene monomer units. By including styrene monomer units, the solubility of the thermoplastic elastomer (E) in the resin composition (2) is improved. Examples of styrene monomers include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc., among which styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Styrene is particularly preferred.

[0591] The content of styrene monomer units in the aforementioned thermoplastic elastomer (E) is preferably in the range of 10 to 50% by mass of all monomer units, more preferably in the range of 13 to 45% by mass, and even more preferably in the range of 15 to 40% by mass. When the content of styrene monomer units is 50% by mass or less, the adhesion and bonding properties with fiber substrates, etc., become better. In addition, if it is 10% by mass or more, adhesion enhancement can be suppressed, residue and stop marks are less likely to occur, and there is a tendency for the adhesive surfaces to peel off easily, which is therefore preferred.

[0592] The thermoplastic elastomer (E) may contain only one type of styrene monomer unit or two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0593] The method for determining the styrene monomer unit content in the thermoplastic elastomer (E) of this embodiment can be found in International Publication No. 2017 / 126469, which is incorporated herein by reference. The same applies to conjugated diene monomer units, etc., which will be described later.

[0594] The aforementioned thermoplastic elastomer (E) comprises a conjugated diene monomer unit. By comprising a conjugated diene monomer unit, the solubility of the thermoplastic elastomer (E) in the resin composition (2) is improved. As a conjugated diene monomer, there is no particular limitation as long as it is a diene having a pair of conjugated double bonds. Examples of conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and isoprene being preferred, and 1,3-butadiene being more preferred.

[0595] Thermoplastic elastomers (E) may contain only one type of conjugated diene monomer unit or more than two types.

[0596] In the aforementioned thermoplastic elastomer (E), the mass ratio of styrene monomer units to conjugated diene monomer units is preferably in the range of 5 / 95 to 80 / 20, more preferably in the range of 7 / 93 to 77 / 23, and even more preferably in the range of 10 / 90 to 70 / 30. When the mass ratio of styrene polymer units to conjugated diene monomer units is in the range of 5 / 95 to 80 / 20, adhesion enhancement can be suppressed and high adhesive strength can be maintained, resulting in good peelability between the bonded surfaces.

[0597] The aforementioned thermoplastic elastomer (E) can be hydrogenated completely, partially, or not at all.

[0598] The aforementioned thermoplastic elastomer (E) may contain other monomer units besides styrene monomer units and conjugated diene monomer units, or it may not contain other monomer units. Examples of other monomer units include aromatic vinyl compound units other than styrene monomer units.

[0599] The thermoplastic elastomer (E) preferably has a total of styrene monomer units and conjugated diene monomer units of 90% or more by mass of all monomer units, more preferably 95% or more by mass, even more preferably 97% or more by mass, and even more preferably 99% or more by mass.

[0600] As described above, the thermoplastic elastomer (E) may contain only one type of styrene monomer unit and one type of conjugated diene monomer unit, or it may contain two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0601] The thermoplastic elastomer (E) used in this embodiment can be a block polymer or a random polymer. Alternatively, it can be a hydrogenated elastomer with hydrogenated conjugated diene monomer units, an unhydrogenated elastomer, or a partially hydrogenated elastomer, preferably an unhydrogenated or partially hydrogenated elastomer.

[0602] In one embodiment of this invention, the thermoplastic elastomer (E) is a hydrogenated elastomer. Here, a hydrogenated elastomer refers to, for example, a thermoplastic elastomer in which the double bonds based on conjugated diene monomer units are hydrogenated, including substances with a hydrogenation rate of 80% or more, in addition to substances with a hydrogenation rate of 100%. The hydrogenation rate of the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. In this embodiment, the hydrogenation rate is determined by… 1The results of H-NMR spectroscopy were calculated.

[0603] In one embodiment of this invention, the thermoplastic elastomer (E) is an unhydrogenated elastomer. Here, an unhydrogenated elastomer refers to one in which the proportion of hydrogenated double bonds in the double bonds based on conjugated diene monomer units, i.e., the hydrogenation rate, is 20% or less. The hydrogenation rate is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.

[0604] On the other hand, partially hydrogenated elastomers refer to thermoplastic elastomers in which a portion of the double bond based on the conjugated diene monomer unit is hydrogenated, typically referring to elastomers with a hydrogenation rate of less than 80% and greater than 20%.

[0605] Commercially available thermoplastic elastomers (E) used in this embodiment include SEPTON (registered trademark) 2104, V9461, S8104 manufactured by Kuraray Co., Ltd.; SOE (registered trademark) S1606, S1613, S1609, S1605 manufactured by Asahi Kasei Corporation; H1041, H1043, P2000, MP10 manufactured by Tuftec (registered trademark) manufactured by Asahi Kasei Corporation; and DYNARON (registered trademark) 9901P, TR2250 manufactured by JSR Co., Ltd.

[0606] The elastomer used in this embodiment can also be a liquid diene. A liquid diene refers to a liquid elastomer containing conjugated diene monomer units. Examples of conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and isoprene being preferred, and 1,3-butadiene being more preferred.

[0607] Examples of liquid dienes used in this embodiment include liquid polybutadiene, liquid polyisoprene, modified liquid polybutadiene, modified liquid polyisoprene, a copolymer of liquid acrylonitrile-butadiene, and a copolymer of liquid styrene-butadiene.

[0608] Furthermore, there are no particular limitations on the number-average molecular weight of the liquid diene, as long as it is liquid at 20°C, but it is preferably 500 or more and 10,000 or less.

[0609] When the resin composition (2) contains a thermoplastic elastomer (preferably thermoplastic elastomer (E)), its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, and can be 12 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition (2). By setting it to the lower limit or above, there is a tendency for the dielectric properties (low dielectric loss tangent) of the second insulating resin layer to be further improved. In addition, the upper limit of the content of thermoplastic elastomer relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less. By setting it to the upper limit or below, there is a tendency for the heat resistance of the second insulating resin layer to be further improved.

[0610] The resin composition (2) may contain only one thermoplastic elastomer or two or more. When it contains two or more, the total amount is preferably within the range described above.

[0611] <<Styrene-based oligomers>>

[0612] In the resin composition (2), styrene-based oligomers may also be used in combination to improve the low dielectric constant and low dielectric loss tangent. However, components that are other components specified in this specification and are styrene-based oligomers are classified as other components.

[0613] The styrene-based oligomers of this embodiment refer to the following substances: compounds formed by polymerizing at least one selected from the group consisting of styrene and styrene derivatives (α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, etc.) and vinyltoluene, having a number-average molecular weight of 178 to 1600, an average number of aromatic rings of 2 to 14, a total amount of aromatic rings of 2 to 14 of 50% by mass or more, and a boiling point of 300°C or more, preferably without a branched structure.

[0614] Styrene oligomers are typically thermoplastic. Furthermore, styrene oligomers do not possess carbon-carbon unsaturated double bonds capable of polymerization. However, compounds that are both styrene oligomers and thermosetting compounds are classified as thermosetting compounds.

[0615] In addition, for details of styrene oligomers, please refer to paragraphs 0065 to 0067 of International Publication No. 2019 / 230945 and paragraphs 0253 to 0245 of International Publication No. 2023 / 176765, the contents of which are incorporated into this specification.

[0616] When the resin composition (2) contains styrene-based oligomers, the content of these oligomers relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. By setting this lower limit or above, the low dielectric properties (Dk and / or Df) of the resulting cured product (insulating resin layer) tend to be further improved. In addition, the upper limit of the content of styrene-based oligomers relative to 100 parts by mass of the resin solids in the resin composition (2) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. By setting this upper limit or below, the heat resistance tends to be further improved. In addition, the low dielectric properties (Dk and / or Df) and chemical resistance of the resulting cured product (insulating resin layer) tend to be further improved.

[0617] The resin composition (2) may contain only one type of styrene oligomer or two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0618] <<Filling Material>>

[0619] The resin composition (2) may contain filler materials. By including filler materials, the dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame retardancy, low thermal expansion, and other physical properties of the resin composition (2) and its cured product can be further improved.

[0620] The filler materials that may be included in the resin composition (2) have the same meaning as those that may be included in the resin composition (1), and the preferred range is also the same.

[0621] The content of filler material in the resin composition (2) can be appropriately set according to the desired characteristics and is not particularly limited. It is 0 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 80 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition (1). By setting the content of filler material to the lower limit value or above, there is a tendency to further improve the heat resistance, low thermal expansion, and dielectric loss tangent of the first insulating resin layer. Furthermore, the upper limit value of the content of filler material relative to 100 parts by mass of the resin solids in the resin composition (1) is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 150 parts by mass or less, and even more preferably 120 parts by mass or less, and can be 50 parts by mass or less, or 20 parts by mass or less. By setting the content of filler material to the upper limit value or less, there is a tendency to further improve the formability of the first insulating resin layer.

[0622] In the resin composition (2), as an example of a preferred embodiment, the content of the filler material is 30% to 90% by mass of the components other than the solvent.

[0623] In the resin composition (2), as another example of a preferred embodiment, the content of the filler material is 0 to 50% by mass (preferably 0 to 45% by mass, more preferably 0 to 40% by mass) of the resin solids.

[0624] The resin composition (2) may contain only one type of filler or two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0625] Flame retardants

[0626] The resin composition (2) may contain a flame retardant. Examples of flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and organosilicon-based flame retardants, with phosphorus-based flame retardants being preferred.

[0627] The flame retardants that may be included in the resin composition (2) have the same meaning as those that may be included in the resin composition (1), and the preferred range (including the preferred content) is also the same.

[0628] <<Active Ester Compounds>>

[0629] The resin composition (2) may contain an active ester compound.

[0630] The active ester compounds that may be included in the resin composition (2) have the same meaning as those that may be included in the resin composition (1), and the preferred range (including the preferred content) is also the same.

[0631] <<Dispersant>>

[0632] The resin composition (2) may contain a dispersant.

[0633] The dispersants that may be included in the resin composition (2) have the same meaning as the dispersants that may be included in the resin composition (1), and the preferred range (including the preferred content) is also the same.

[0634] <<Cure Accelerator>>

[0635] The resin composition (2) may further include a curing accelerator.

[0636] The curing accelerators that may be included in the resin composition (2) have the same meaning as those that may be included in the resin composition (1), and the preferred range (including the preferred content) is also the same.

[0637] <<Solvent>>

[0638] The resin composition (2) may contain a solvent, preferably an organic solvent.

[0639] The solvents that may be included in the resin composition (2) have the same meaning as those that may be included in the resin composition (1), and the preferred range (including the preferred content) is also the same.

[0640] <<Other Resin Additives>>

[0641] In addition to the above-mentioned components, the resin composition (2) may also contain various polymeric compounds such as oligomers of thermoplastic resins and various additives. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, pigments (dyes, pigments), thickeners, flow regulators, lubricants, defoamers, leveling agents, gloss agents, polymerization inhibitors such as quinones, phenols, nitrosamines, and hydroxylamines. These additives may be used alone or in combination of two or more.

[0642] <Metal Foil>

[0643] The multilayer body of this embodiment may have a metal foil. That is, the multilayer body of this embodiment may be a metal foil-clad laminate (sometimes also called a metal foil-clad laminate).

[0644] That is, an example is provided on the surface of the first insulating resin layer and / or the second insulating resin layer with a metal foil.

[0645] More specifically, an example is a multilayer body in which a metal foil is further disposed in such a way that it is in contact with the surface opposite to the first insulating resin layer of the second insulating resin layer.

[0646] Another example is a multilayer body in which a metal foil is further disposed in contact with the surface opposite to the first insulating resin layer of the second insulating resin layer.

[0647] As the metal foil, metal foil used for printed circuit board materials is preferred, such as rolled copper foil, electrolytic copper foil, etc. The thickness of the metal foil (preferably copper foil) is not particularly limited and can be approximately 1.5 to 70 µm. Furthermore, the surface roughness Rz of the metal foil (preferably copper foil) is preferably adjusted to 0.2 to 4.0 µm, as measured according to JIS B0601:2013. By setting the surface roughness Rz of the metal foil (preferably copper foil) to 0.2 µm or more, the surface roughness of the metal foil (preferably copper foil) becomes an appropriate value, and there is a tendency to further improve the peel strength of the metal foil (preferably copper foil). On the other hand, by setting the surface roughness Rz of the metal foil (preferably copper foil) to 4.0 µm or less, the surface roughness of the metal foil (preferably copper foil) becomes an appropriate value, and there is a tendency to further improve the dielectric loss tangent characteristics of the resulting cured product. From the viewpoint of dielectric loss tangent characteristics of the obtained cured product and copper foil peel strength, the surface roughness Rz of the metal foil (preferably copper foil) is more preferably 0.5µm or more, further preferably 0.6µm or more, particularly preferably 0.7µm or more, and even more preferably 3.5µm or less, further preferably 3.0µm or less, and particularly preferably 2.0µm or less.

[0648] The metal foil (preferably copper foil) disposed on the surface of the second insulating resin layer is particularly preferred to satisfy the above-mentioned Rz.

[0649] The multilayer material of this embodiment is suitable for use as a resin composition for electronic materials such as low relative permittivity materials and / or low dielectric loss tangent materials, insulating resin layers for printed circuit boards, and semiconductor packaging materials. The multilayer material of this embodiment is also suitable for use as a material for metal-clad laminates, resin composites, and printed circuit boards.

[0650] Therefore, this embodiment discloses a printed circuit board incorporating the multilayer structure of this embodiment. Additionally, a semiconductor device incorporating the printed circuit board of this embodiment is disclosed.

[0651] <Manufacturing Methods of Multilayer Materials>

[0652] Next, the manufacturing method of the multilayer body in this embodiment will be described.

[0653] The method for manufacturing a multilayer in this embodiment includes bonding a second insulating resin layer to a first insulating resin layer.

[0654] In the manufacturing method of the multilayer body of this embodiment, it is preferable to bond the first insulating resin layer in a cured state to the second insulating resin layer in a semi-cured state. This bonding method makes it difficult for the two layers (the materials of both layers) to mix, thus more effectively reducing transmission losses. Alternatively, it is also preferable to bond the first and second insulating resin layers in a semi-cured state. This bonding method simplifies the process.

[0655] One example of the manufacturing method of the multilayer body in this embodiment includes bonding a second insulating resin layer side having a second insulating resin layer having a metal foil on one surface to a first insulating resin layer.

[0656] The second insulating resin layer having a metal foil on one surface is preferably obtained by removing one metal foil from a second insulating resin layer having metal foil on both surfaces. Alternatively, the second insulating resin layer having a metal foil on one surface is also preferably obtained by removing the protective film from a second insulating resin layer having a metal foil on one surface and a protective film on the other surface. The protective film is preferably a thermoplastic resin film, more preferably a polyethylene terephthalate resin film.

[0657] Furthermore, the first insulating resin layer is preferably obtained by removing at least one metal foil from the first insulating resin layer with metal foil on both surfaces.

[0658] Alternatively, the first insulating resin layer may also be a prepreg, with at least one (or both) side of the prepreg bonded to a second insulating resin layer side having a metal foil on one surface.

[0659] The following is based on Figure 4 The manufacturing method of the multilayer body according to this embodiment will be described. The multilayer body of this embodiment is not limited to... Figure 4 As shown. In Figure 4 In China, for the sake of Figures 1-3 Identical components are represented by the same reference numerals. It should be noted that in... Figure 4 For convenience, the metal foil in the insulating resin layer with metal foil that is peeled off during the manufacturing process of the multilayer is indicated by reference numeral 41. However, depending on the application of the multilayer, there may also be cases where the metal foil shown by reference numeral 4 is peeled off.

[0660] In the multilayer body of this embodiment, the metal foil 41 on both surfaces of the first insulating resin layer 7 with metal foil 41 on both surfaces of the first insulating resin layer 2 is usually removed. Figure 4(a)). Additionally, the metal foil 41 (not shown) of one side of the second insulating resin layer 3, which has metal foil 4·41 on both surfaces, is typically removed. Next, the second insulating resin layer side of the second insulating resin layer 3, having metal foil 4 on one surface, is bonded to the first insulating resin layer 2 from which the metal foil 41 has been removed. Figure 4 (b) Preferably, the first insulating resin layer 2 is manufactured as a metal foil laminate, the metal foil 41.41 of the first insulating resin layer 2 is removed, and the second insulating resin layer 3 is bonded to the first insulating resin layer 2. With this configuration, the second insulating resin layer 3 is bonded in a semi-cured state, so the materials of the two are difficult to mix, and transmission loss can be reduced more effectively.

[0661] exist Figure 4 In the process shown in (b), the second insulating resin layer 3 is bonded to both surfaces of the first insulating resin layer 2, but it is also possible to bond the second insulating resin layer 3 to only one surface of the first insulating resin layer 2. In addition, if the second insulating resin layer 3 is bonded to only one surface of the first insulating resin layer 2, the metal foil 41 on only one surface of the first insulating resin layer 2 may be removed.

[0662] In the multilayer body of this embodiment, the process of removing the metal foil 41.41 of the first insulating resin layer 7 with metal foil 41.41 on both surfaces of the first insulating resin layer 2 and the process of removing the metal foil of the second insulating resin layer (not shown) with metal foil 4.41 on both surfaces of the second insulating resin layer 3 can be performed simultaneously, or either process can be performed first.

[0663] The removal of the metal foil is preferably carried out by etching.

[0664] Alternatively, instead of the second insulating resin layer 3 with metal foil 4.41 on both surfaces, a second insulating resin layer with metal foil on one surface and a protective film on the other surface can be used. In this case, it is preferable to peel off the protective film to bond it to the first insulating resin layer.

[0665] Furthermore, the process of bonding the first insulating resin layer 2 and the second insulating resin layer 3 is preferably carried out in such a way that the two are in surface contact. As a bonding method, examples include using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., to perform lamination molding at a temperature of about 180~350°C, a heating time of about 100~300 minutes, and a surface pressure of about 1~10 MPa.

[0666] Of course, the multilayer body of this embodiment can also be obtained by methods other than those described above.

[0667] For example, another example of the manufacturing method of the multilayer body in this embodiment preferably involves bonding the second insulating resin layer, which is a prepreg, to the first insulating resin layer, which is also a prepreg. In this case, the bonding method can also include a method of lamination molding using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of about 1 to 10 MPa.

[0668] In the manufacturing method of the multilayer body in this embodiment, as described above... Figure 2 As shown, it is also preferable to form metal wiring 5 on the surface of the second insulating resin layer 3. In this way, by forming metal wiring 5 on the surface of the second insulating resin layer 3, it is preferably used as a printed circuit board. That is, in this embodiment, the multilayer preferably forms circuits or mounts components on the side of the second insulating resin layer 3.

[0669] That is, the multilayer body of this embodiment preferably has an outer layer circuit and / or components disposed on the surface of the second insulating resin layer.

[0670] In addition, as mentioned above Figure 3 As shown, a third insulating resin layer 6 is preferably formed on the surface of the metal wiring 5. With this configuration, a printed circuit board in which metal circuitry is embedded within the insulating resin layer can be obtained. The metal wiring is preferably copper wiring, and is drawn according to known methods.

[0671] The third insulating resin layer is identical to the one described in the section on the second insulating resin layer, and the preferred scope is also the same. The second and third insulating resin layers may be the same or different. In either case, the third insulating resin layer is preferably a layer formed of resin composition (2).

[0672] More specifically, in this embodiment, an inner layer circuit is formed on the surface of the multilayer body. This circuit is then blackened to form the inner layer circuit. The inner layer circuit is then alternately arranged with the multilayer body of this embodiment, one sheet at a time. Finally, copper foil is placed on the outermost layer. Under the above conditions, lamination is preferably performed under vacuum, thereby fabricating a multilayer body. The manufacturing method of the multilayer body in this embodiment is suitable for use as a method for manufacturing printed circuit boards.

[0673] Furthermore, this embodiment also relates to a semiconductor device including the printed circuit board. Details of the semiconductor device can be found in paragraphs 0200-0202 of Japanese Patent Application Publication No. 2021-021027, and these contents are incorporated herein by reference.

[0674] Example

[0675] The following examples illustrate the present invention in more detail. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of protection of the present invention is not limited to the specific examples shown below.

[0676] If the measuring instruments used in the embodiments are difficult to obtain due to production stoppages or other reasons, other instruments with equivalent performance can be used for measurement.

[0677] <Synthetic Example 1: Synthesis of α-Naphthol Aryl Acrylate Cyanate Compound (SNCN)>

[0678] 0.47 mol (OH group equivalent) of α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., manufactured by Nippon Steel Chemical Co., Ltd.: the number of repeating units of naphthol aralkyl is 1~5) was dissolved in 500 mL of chloroform. 0.7 mol of triethylamine was added to this solution to prepare solution 1. While maintaining the temperature at -10°C, solution 1 was added dropwise over 1.5 hours to 300 g of a chloroform solution of 0.93 mol of cyanogen chloride. After the addition was complete, the mixture was stirred for 30 minutes. Then, a mixture of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise to the reactor, and the reaction was stirred for 30 minutes to complete the reaction. The byproduct triethylamine hydrochloride was separated from the reaction solution by filtration. The resulting filtrate was washed with 500 mL of 0.1N hydrochloric acid and then repeatedly washed four times with 500 mL of water. After drying with sodium sulfate, it was evaporated at 75°C and then degassed under reduced pressure at 90°C to obtain a brown solid α-naphthol aralkyl cyanate compound of formula (S1) (where R is a cyanate compound of formula (S1)). C1 ~R C4 All are hydrogen atoms, n c (A mixture of 1-5) (cyanate equivalent: 261 g / eq.). The α-naphthol aralkyl cyanate compound was obtained by infrared absorption spectroscopy analysis, with results at 2264 cm⁻¹. -1 Absorption of cyanate groups was confirmed in the vicinity.

[0679]

[0680] <Synthetic Example 2: Synthesis of a polymer (va) having the structural unit shown in formula (V)>

[0681] 2.25 mol (292.9 g) of divinylbenzene, 1.32 mol (172.0 g) of ethylvinylbenzene, 11.43 mol (1190.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were added to a reactor. 600 mmol of a boron trifluoride diethyl ether complex was added at 70 °C, and the reaction was carried out for 4 hours. After stopping the polymerization reaction with an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water. The polymer (va) with the structural unit shown in formula (V) was recovered by devolatilization under reduced pressure at 60 °C. The obtained polymer (va) with the structural unit shown in formula (V) was weighed, confirming that 860.8 g of polymer (va) with the structural unit shown in formula (V) was obtained.

[0682] The obtained polymer (va) with the structural unit shown in formula (V) has a number-average molecular weight Mn of 2,060, a weight-average molecular weight Mw of 30,700, and a monodispersity Mw / Mn of 14.9. This was achieved through... 13 C-NMR and 1 ¹H-NMR analysis revealed resonance lines originating from the individual monomer units used as raw materials in the polymer (va) having the structural unit shown in formula (V). Based on the NMR and GC analysis results, the proportions of each monomer unit (derived from the structural units of each raw material) in the polymer (va) having the structural unit shown in formula (V) were calculated as follows.

[0683] Structural units derived from divinylbenzene: 20.9 mol% (24.3 wt%)

[0684] Structural units derived from ethyl vinylbenzene: 9.1 mol% (10.7 wt%)

[0685] Structural units derived from styrene: 70.0 mol% (65.0 mass%)

[0686] In addition, the structural units of residual vinyl groups derived from divinylbenzene are 16.7 mol% (18.5 mass%).

[0687] <Determination of weight-average molecular weight and number-average molecular weight>

[0688] The weight-average molecular weight and number-average molecular weight were determined by gel permeation chromatography (GPC). A delivery pump (Shimadzu Corporation, LC-20AD), a differential refractive index detector (Shimadzu Corporation, RID-10A), and a GPC column (Showa Denko Corporation, GPC KF-801, 802, 803, 804) were used. Tetrahydrofuran was used as the solvent, the flow rate was 1.0 mL / min, the column temperature was 40 °C, and the analysis was based on a standard curve of monodisperse polystyrene.

[0689] Example 1

[0690] <Manufacturing of Copper Clad Laminate (1-1)>

[0691] A prepreg formed from S-glass fabric (100µm thick) and resin composition (1-1) was manufactured according to Example 1 of International Publication No. 2020 / 022084. Specifically, it was manufactured as follows.

[0692] First, in a three-necked flask equipped with a thermometer and a serpentine condenser, add 5.3 parts by weight of diallyl bisphenol A (DABPA, Yamato Chemical Co., Ltd.), 5.8 parts by weight of bis(cresol)fluorene (BCF, Osaka Gas Chemical Co., Ltd.), 4.4 parts by weight of epoxy-modified organosilicon 1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / mol), 8.7 parts by weight of epoxy-modified organosilicon 2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 490 g / mol), 5.8 parts by weight of biphenyl-type epoxy compound (YL-6121H, Mitsubishi Chemical Co., Ltd.), and 30 parts by weight of propylene glycol monomethyl ether acetate (DOWANOLPMA, Dow Chemical Japan Co., Ltd.) as a solvent, and heat and stir in an oil bath to 120°C. After confirming that the raw material is dissolved in the solvent, 0.3 parts by mass of imidazole catalyst g1 (TBZ, Shikoku Chemical Industry Co., Ltd.) were added. The mixture was heated to 140°C and stirred for 5 hours. After cooling, a phenoxy polymer solution (50% by mass of solid content) was obtained (polymer generation process).

[0693] In 30 parts by mass (solids equivalent) of the phenoxy polymer solution, 26 parts by mass of the α-naphthol aralkyl cyanate compound (SNCN) obtained by Synthesis Example 1 (cyanate equivalent: 261 g / eq.), 17 parts by mass of the phenolic varnish-type maleimide compound (BMI-2300, Yamato Kasei Corporation), 27 parts by mass of the naphthyl ether-type epoxy compound (HP-6000, DIC Corporation), 100 parts by mass of spherical silica (SFP-130MC, Denka Corporation), 40 parts by mass of spherical silica (SC-4500SQ, Admatechs Corporation), and 1 part by mass of the wetting and dispersing agent (DISPERBYK-161, BYK) were mixed. 5 parts by weight of silane coupling agent (KMB-403, Shin-Etsu Chemical Industry Co., Ltd.) were used to obtain a varnish (resin composition (1-1)) (varnish production process). The varnish was impregnated and coated onto glass cloth (S glass cloth, 100µm thick), and dried at 150°C for 3 minutes to obtain an insulating resin layer (1-1) (prepreg with a solid content (including filler material) of 46% by weight) (prepreg production process).

[0694] Eight sheets of the prepreg obtained above are overlapped, and electrolytic copper foil (3EC-M2S-VLP, manufactured by Mitsui Metals & Minerals Co., Ltd.) with a thickness of 12µm is placed on top and bottom, and then subjected to a pressure of 30kgf / cm. 2 The copper-clad laminate (1-1) is laminated at 220°C for 120 minutes to obtain a copper-clad laminate (1-1) having an insulating resin layer (1-1) with a thickness of 0.8 mm formed by the resin composition (1-1).

[0695] <Determination of Dielectric Loss Tangent (Df)>

[0696] The copper foil on both sides of the copper-clad laminate (1-1) was removed by etching, and after drying at 120°C for 60 minutes, the dielectric loss tangent (Df) after drying was measured at 10 GHz using a perturbation method cavity resonator. The measurement temperature was set to 23°C.

[0697] The perturbation method cavity resonator used is the Agilent 8722ES manufactured by Agilent Technologies.

[0698] It should be noted that the relative permittivity (Dk) can also be determined using the same method.

[0699] The evaluation will be conducted according to the following criteria.

[0700] <<Dielectric Loss Tangent (Df)>>

[0701] A: Below 0.005

[0702] B: Greater than 0.005 and less than 0.008

[0703] C: Greater than 0.008 and less than 0.011

[0704] D: Exceeds 0.011

[0705] <Ratio of thermal expansion>

[0706] The coefficient of linear thermal expansion (CTE) is determined by the TMA (Thermo-Mechanical Analysis) method specified in JlS C 6481 5.19, as described below.

[0707] Specifically, by etching away the copper foil on both sides of the copper-clad laminate (1-1) obtained above, for evaluation samples cut (miniaturized) to 5.0 mm × 5.0 mm × 0.8 mm, the coefficient of thermal expansion (CTE(XY)) in the thickness direction (unit: ppm / ℃) was measured using a thermomechanical analysis apparatus (TA Instruments, TMA Q-400) at a rate of 10℃ per minute from 30℃ to 320℃, from 50℃ to 280℃. ppm is a volume ratio. For other details, refer to JIS C6481 5.19 above. The evaluation is as follows. ppm is a volume ratio. For other details, refer to JIS C 6481 5.19 above.

[0708] The evaluation is conducted as follows. The evaluation results are shown in Table 1.

[0709] A: Below 10ppm / ℃

[0710] B: Exceeding 10 ppm / ℃ but below 15 ppm / ℃

[0711] C: Exceeding 15 pm / ℃ and below 20 ppm / ℃

[0712] D: Exceeding 20ppm / ℃

[0713] <Manufacturing of copper foil (2) with insulating resin layer (2)>

[0714] Five parts by mass of a maleimide compound (manufactured by Nippon Kayaku Co., Ltd., MIR-3000, equivalent to the compound shown in formula (M3)), 29 parts by mass of a maleimide compound (ma) with the structure shown below (manufactured by DIC, "NE-X-9470S", equivalent to the compound shown in formula (M1)), 30 parts by mass of a polymer (va) having the structural unit shown in formula (V) obtained in Synthesis Example 2, and 15 parts by mass of a hydrogenated styrene-based thermoplastic elastomer (SEBS, block copolymer, SEPTON2104, Mn83000) were prepared. The following are included: 5 parts by weight of the α-naphthol aralkyl cyanate compound (SNCN) obtained in Synthesis Example 1 (cyanate equivalent: 261 g / eq.), 15 parts by weight of the phosphorus-based flame retardant (PX-200, Daihachi Chemical Industry Co., Ltd.), 1 part by weight of N-phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., product number: P0900), 0.3 parts by weight of the wetting and dispersing agent (manufactured by BYK Corporation, BYK-2009), and 0.5 parts by weight of the wetting and dispersing agent (DISPERBYK-161, BYK). 100 parts by weight of vinylsilane-treated silica methyl ethyl ketone (MEK) slurry (SC2050MNU (trade name), median particle size 0.5µm, non-volatile content 70% by weight), manufactured by Japan Co., Ltd., were dissolved, dispersed and mixed with methyl ethyl ketone to obtain a varnish (resin composition (2)). It should be noted that the above-mentioned amounts of addition represent the amount of solid components.

[0715] Maleimide compounds (ma)

[0716]

[0717] n is an integer from 1 to 20.

[0718] The obtained varnish was applied to the surface of an ultrathin copper foil with a carrier copper foil (ultrathin copper foil thickness 1.5µm, surface roughness Rz 1.3µm, carrier copper foil thickness 18µm, MT-FL, manufactured by Mitsui Metals & Mining Co., Ltd.) using a bar coater, and dried at 130°C for 3 minutes to obtain a copper foil (2) with an insulating resin layer (2) and a thickness of 20µm.

[0719] The dielectric loss tangent (Df) and thermal expansion coefficient of the cured material, which serves as the insulating resin layer (2), were measured in the same manner as described above.

[0720] The evaluation criteria are as follows.

[0721] <<Dielectric Loss Tangent (Df)>>

[0722] A: Below 0.005

[0723] B: Greater than 0.005 and less than 0.008

[0724] C: Greater than 0.008 and less than 0.011

[0725] D: Exceeds 0.011

[0726] <<Ratio of Thermal Expansion>>

[0727] A: Below 10ppm / ℃

[0728] B: Exceeding 10 ppm / ℃ but below 15 ppm / ℃

[0729] C: Exceeding 15 pm / ℃ and below 20 ppm / ℃

[0730] D: Exceeding 20ppm / ℃

[0731] <Manufacturing of Multilayers>

[0732] The copper foils on both sides of the copper-clad laminate (1-1) and one of the two copper foils (2) with insulating resin layers (2) are removed by etching. The insulating resin layers (2) of the copper foils (2) with insulating resin layers (2) are arranged opposite to each other on both sides of the insulating resin layer (1-1) of the copper-clad laminate (1-1) under a pressure of 30 kgf / cm 2 The material is hot-pressed at 220℃ for 120 minutes to obtain a multilayer body composed of copper foil / insulating resin layer (2) / insulating resin layer (1-1) / insulating resin layer (2) / copper foil.

[0733] <Dielectric loss tangent (Df)>

[0734] For the obtained multilayer, the coefficient of linear expansion was determined by the same method as described above for the determination of the dielectric loss tangent (Df).

[0735] The evaluation is conducted as follows. The evaluation results are shown in Table 1.

[0736] <<Dielectric Loss Tangent (Df)>>

[0737] A: Below 0.005

[0738] B: Greater than 0.005 and less than 0.008

[0739] C: Greater than 0.008 and less than 0.011

[0740] D: Exceeds 0.011

[0741] <Ratio of thermal expansion>

[0742] For the obtained multilayer body, the coefficient of linear expansion was determined using the same method as described above for the <thermal expansion coefficient>.

[0743] The evaluation is conducted as follows. The evaluation results are shown in Table 1.

[0744] A: Below 10ppm / ℃

[0745] B: Exceeding 10 ppm / ℃ but below 15 ppm / ℃

[0746] C: Exceeding 15 pm / ℃ and below 20 ppm / ℃

[0747] D: Exceeding 20ppm / ℃

[0748] <Determination of Deviation>

[0749] Etching was performed on only one side of the copper foil in the multilayer structure consisting of copper foil / insulating resin layer (2) / insulating resin layer (1-1) / insulating resin layer (2) / copper foil obtained above to form 15 microstrip lines with a circuit length of 10 cm. The transmission speed of the 15 conductor wirings (impedance 50Ω) from 10 GHz to 40 GHz was measured, and the difference between the maximum and minimum values ​​was calculated as the deviation (SKEW).

[0750] A: The difference between the maximum and minimum values ​​is 5.0 × 10. -12 s and below

[0751] B: The difference between the maximum and minimum values ​​exceeds 5.0 × 10 -12 s is 10.0 × 10 -12 s and below

[0752] C: The difference between the maximum and minimum values ​​is 10.0 × 10 -12 s and above

[0753] <Measurement of Transmission Loss>

[0754] Etching was performed on only one side of the copper foil in the multilayer structure consisting of copper foil / insulating resin layer (2) / insulating resin layer (1-1) / insulating resin layer (2) / copper foil obtained above to fabricate a circuit board with a microstrip line of 10 cm in length, and the transmission characteristics were evaluated. A network analyzer N5227B manufactured by Keysight Technology was used to transmit high-frequency signals, and the transmission loss at 40 GHz was measured.

[0755] A: Below 0.7dB / cm

[0756] B: Exceeding 0.7 dB / cm but below 1.0 dB / cm

[0757] C: Exceeding 1.0 dB / cm

[0758] Example 2

[0759] In Example 1, the same procedure was followed except that an insulating resin layer (1-2) was used with the prepreg used in the insulating resin layer (1-1) replaced with the prepreg shown below.

[0760] One part by weight of alumina nanoparticles (product name "NANOBYK-3610", average particle size: 20nm, BYK) surface-treated with a polysiloxane-based modifier were used. 300 parts by weight of spherical fused silica (product name "FB-3SDC", average particle size: 3.0µm, manufactured by DIC Corporation), 100 parts by weight of spherical fused silica (SFP-120MC, average particle size: 0.3µm, manufactured by DIC Corporation), 36 parts by weight of the α-naphthol aralkyl cyanate compound (SNCN) obtained in Synthesis Example 1 (cyanate equivalent: 261 g / eq.), 26 parts by weight of maleimide compound (product name "BMI-2300"), 38 parts by weight of naphthyl ether type epoxy compound (product name "HP-6000", epoxy equivalent: 250 g / eq., manufactured by DIC Corporation), and 1 part by weight of wetting and dispersing agent (product name "disperbyk-161", manufactured by BYK Corporation). A varnish (resin composition (1-2)) is obtained by mixing 2 parts by weight of a wetting and dispersing agent (product name "disperbyk-111", manufactured by BYK Japan Co., Ltd.), 5 parts by weight of a silane coupling agent (product name "Z6040", manufactured by Toray Dow Corning Co., Ltd.), and 1 part by weight of 2,4,5-triphenylimidazole (manufactured by Wako Pure Chemical Industries Co., Ltd.).

[0761] The varnish was diluted with methyl ethyl ketone and impregnated onto a 0.1 mm thick E-glass fabric. It was then heated and dried at 140°C for 3 minutes to obtain a prepreg with an insulating resin layer (1-2) (63% by mass of solid components (including filler materials)).

[0762] Comparative Example 1

[0763] For the copper-clad laminate (1-1) manufactured in Example 1, the dielectric loss tangent (Df), thermal expansion coefficient, deviation, and transmission loss were measured in the same manner as in Example 1.

[0764] [Table 1]

[0765]

[0766] In Table 1 above, ΔDf represents the difference between the Df of the first insulating resin layer and the Df of the second insulating resin layer.

[0767] Although the invention has been described in detail using specific methods, it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.

[0768] Explanation of reference numerals in the attached figures

[0769] 1. Multilayer

[0770] 2 First insulating resin layer

[0771] 3 Second insulating resin layer

[0772] 4 metal foil

[0773] 41 metal foil

[0774] 5. Metal wiring

[0775] 6 Third insulating resin layer

[0776] 7. First insulating resin layer with metal foil

Claims

1. A multilayer having a first insulating resin layer and a second insulating resin layer in contact with the first insulating resin layer, wherein the dielectric loss tangent of the second insulating resin layer at a frequency of 10 GHz measured by a perturbation cavity resonator is lower than the dielectric loss tangent of the first insulating resin layer at a frequency of 10 GHz measured by a perturbation cavity resonator.

2. The multilayer body according to claim 1, wherein, The thermal expansion coefficient of the first insulating resin layer, as determined by the TMA (thermomechanical analysis) method, is below 30 ppm / ℃.

3. The multilayer body according to claim 1, wherein, The difference between the dielectric loss tangent of the second insulating resin layer and the dielectric loss tangent of the first insulating resin layer is greater than 0.

002.

4. The multilayer body according to claim 1, wherein, The thermal expansion coefficient of the first insulating resin layer, as determined by the TMA (thermomechanical analysis) method, is below 30 ppm / ℃. The difference between the dielectric loss tangent of the second insulating resin layer and the dielectric loss tangent of the first insulating resin layer is greater than 0.

002.

5. The multilayer body according to any one of claims 1 to 4, wherein, The first insulating resin layer comprises a fiber substrate.

6. The multilayer body according to any one of claims 1 to 4, wherein, The first insulating resin layer is a layer formed from a resin composition 1 containing a thermosetting compound and a fiber substrate.

7. The multilayer body according to any one of claims 1 to 4, wherein, The second insulating resin layer does not contain a fiber substrate.

8. The multilayer body according to claim 7, wherein, The second insulating resin layer is a layer formed from resin composition 2. The resin composition 2 contains a thermosetting compound, and the content of the filler material is 0 to 40% by mass of the solid resin component contained in the resin composition 2.

9. The multilayer body according to any one of claims 1 to 4, wherein, The second insulating resin layer is configured to contact both sides of the first insulating resin layer.

10. The multilayer body according to claim 9, wherein, A metal foil is further provided, such that it contacts the surface of the second insulating resin layer opposite to the first insulating resin layer.

11. The multilayer body according to any one of claims 1 to 4, wherein, A metal foil is further provided, such that it contacts the surface of the second insulating resin layer opposite to the first insulating resin layer.

12. The multilayer body according to claim 11, wherein, The surface roughness Rz of the metal foil disposed in such a manner as to be in surface contact with the second insulating resin layer, as measured according to JIS B0601:2013, is 0.2~4.0µm.

13. The multilayer body according to claim 1, wherein, The thermal expansion coefficient of the first insulating resin layer, as determined by the TMA (thermomechanical analysis) method, is below 30 ppm / ℃. The difference between the dielectric loss tangent of the second insulating resin layer and the dielectric loss tangent of the first insulating resin layer is greater than 0.

002. The first insulating resin layer is a layer formed from a resin composition 1 containing a thermosetting compound and a fiber substrate. The second insulating resin layer does not contain a fiber substrate. The second insulating resin layer is a layer formed from resin composition 2. The resin composition 2 contains a thermosetting compound, and the filler content is 0-40% by mass of the solid resin component contained in the resin composition 2. The second insulating resin layer is configured to contact both sides of the first insulating resin layer.

14. The multilayer body according to claim 13, wherein, A metal foil is further provided, such that it contacts the surface of the second insulating resin layer opposite to the first insulating resin layer.

15. The multilayer body according to claim 13, wherein, Metal wiring is further provided on the surface of the second insulating resin layer.

16. The multilayer body according to claim 14, having a third insulating resin layer disposed on the surface of the second insulating resin layer and covering the metal wiring.

17. The multilayer body according to claim 1, 2 or 13, having an outer layer circuit and / or element disposed on the surface of the second insulating resin layer.

18. The multilayer body according to any one of claims 1-4 and 13-16, wherein, The first insulating resin layer is a layer formed of resin composition 1 and a fiber substrate, wherein the resin composition 1 is in a cured state. The second insulating resin layer is a layer formed of resin composition 2, which is in a cured state. The resin composition 1 contains a thermosetting compound. The resin composition 2 contains a thermosetting compound, and the content of the filler material is 0 to 40% by mass of the solid resin component contained in the resin composition 2.

19. A method for manufacturing a multilayer body according to any one of claims 1-4 and 13-16, comprising: The second insulating resin layer side, which has a metal foil on one surface, is bonded to the first insulating resin layer.

20. The method for manufacturing a multilayer body according to claim 19, comprising: The protective film of the second insulating resin layer with metal foil on one surface and a protective film on the other surface is removed to obtain the second insulating resin layer with metal foil on one surface.

21. The method for manufacturing a multilayer body according to claim 19, comprising: The first insulating resin layer and the second insulating resin layer are bonded in a semi-cured state.

22. A printed circuit board comprising a multilayer as described in any one of claims 1-4 and 13-16.

23. A semiconductor device comprising the printed circuit board of claim 22.

24. A method for manufacturing a printed circuit board, comprising the method for manufacturing a multilayer body as described in claim 20.

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