Resin compositions and printed circuit boards, cured products, prepregs and high-frequency electronic components using them.

Abstract

This invention provides a resin composition that, although having low dielectric properties, exhibits good embedding properties into substrates and excellent heat resistance. It comprises: (A) a polyphenylene ether resin having a functional group at the end containing a carbon-carbon double bond; and (B) a compound having an isocyanate ring structure and two allyl groups in one molecule, and being liquid at 25°C.

Description

Technical Field

[0001] This invention relates to a resin composition and printed circuit boards, cured products, prepregs and high-frequency electronic components using the same. Prior Technology

[0002] In recent years, communication speeds in communication electronic devices (electronic substrates) such as smartphones, tablets, and communication base stations have been increasing, leading to the construction of 5G communication networks. With this increase in communication speed, stringent requirements have been placed on materials with low dielectric constants and substrates with multilayered, high-performance structures to reduce electrical signal loss in the substrates used in communication electronic devices. To achieve this, low-dielectric resin substrates, ceramic substrates, and low-dielectric interlayer adhesives are being used. Furthermore, research is also underway on communication using high-frequency signals such as 6G.

[0003] In the fabrication of electronic devices, various resin compositions are used as adhesives or sealing materials. When resin compositions are used as interlayer adhesives, they are difficult to embed into the substrate if their flowability is low. Therefore, resin compositions used as interlayer adhesives sometimes prioritize imparting low dielectric properties and suppressing flowability reduction, and resins with poor heat resistance are selected instead. For example, as a resin composition formulated with low dielectric properties and low melt viscosity, a thermoplastic resin composition containing a specific vinyl compound and a styrene / ethylene / butene / styrene block copolymer (SEBS) has been proposed (see, for example, Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] International Publication No. 2008 / 018483 Summary of the Invention

[0005] [The problem that the invention aims to solve]

[0006] As mentioned above, although the resin composition disclosed in Patent Document 1 is a resin composition with low dielectric properties and low melt viscosity, it has a high coefficient of thermal expansion, making it difficult to use directly as an interlayer bonding agent in multilayer structures. Here, as a means to reduce the coefficient of thermal expansion of the resin composition, highly packed silica filler can be cited as an example.

[0007] However, as disclosed in Patent Document 1, if a resin composition formulated with a polymer elastomer as the main component is highly filled with silica filler, the melt viscosity will increase, resulting in a decrease in the embeddability to the substrate.

[0008] This invention was made in view of the problems inherent in such prior art. The present invention provides a resin composition that, although having low dielectric properties, exhibits good embedding properties in substrates and excellent heat resistance. Furthermore, the present invention provides printed circuit boards, cured products, prepregs, and high-frequency electronic components using the said resin composition. [Methods for solving problems]

[0009] According to the present invention, resin compositions, printed circuit boards, cured products, prepregs and high-frequency electronic components as shown below can be provided.

[0010] [1] A resin composition comprising: (A) a polyphenylene ether resin having a functional group at the end containing a carbon-carbon double bond; and (B) a compound having an isocyanate ring structure and two allyl groups in one molecule and being liquid at 25°C.

[0011] [2] The resin composition as described in [1] above, wherein component (A) is a thermosetting resin.

[0012] [3] The resin composition as described in [1] or [2] above, wherein the molecular weight of component (B) is 300 to 400.

[0013] [4] The resin composition of any one of [1] to [3] above, wherein the (A) component is polyphenylene ether as shown in the following general formula (1).

[0014] [Compound 1] [Compound 2] [Compound 3]

[0015] In the above general formula (1), R1, R2, R3, R4, R5, R6, and R7 can be the same or different, and represent hydrogen atoms, halogen atoms, alkyl groups, alkyl halides, or phenyl groups. -(OXO)- is represented by the above structural formula (2), in which R8, R9, R10, R14, and R15 can be the same or different, and are halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups; R11, R12, and R13 can be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups. -(YO)- is a structure formed by randomly arranging one or more structures shown in the above structural formula (3). In this structural formula (3), R16 and R17 may be the same or different, and are halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups. R18 and R19 may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups. Z is an organic group with one or more carbon atoms, and depending on the context, it may also include oxygen, nitrogen, sulfur, or halogen atoms. a and b are at least not 0, representing integers from 0 to 300, and c and d represent integers of 0 or 1.

[0016] [5] The resin composition of any one of [1] to [4] above, wherein the (B) component is a compound represented by the following general formula (4).

[0017] [Compound 4]

[0018] In the above general formula (4), the R series are alkyl groups with 4 to 14 carbon atoms.

[0019] [6] The resin composition of any of [1] to [6] above further comprises (C) an inorganic filler.

[0020] [7] As described in [6] above, wherein the non-volatile components in the resin composition contain more than 50% by mass of component (C).

[0021] [8] The resin composition of any one of [1] to [7] above further includes a polymerization initiator (D) that initiates the polymerization of the (A) component and the (B) component.

[0022] [9] The resin composition of any one of [1] to [8] above further comprises (E) a thermoplastic resin with an average molecular weight of 30,000 or more.

[0023]

[10] As described in [9] above, wherein 1 to 50% by mass of the (E) component is included in 100 parts by mass of the non-volatile components in the resin composition.

[0024]

[11] The resin composition of any of [1] to

[10] above further comprises (F) polybutadiene.

[0025]

[12] The resin composition of any one of [1] to

[11] above, wherein 100% by mass of the non-volatile components in the resin composition contains 15 to 90% by mass of component (A).

[0026]

[13] A resin composition as described in any of [1] to

[12] above, wherein 10 to 70 parts by mass of component (B) are included relative to 100 parts by mass of component (A).

[0027]

[14] A printed circuit board having a cured layer composed of a resin composition as described in any one of [1] to

[13] above.

[0028]

[15] A cured product is a cured product of a resin composition as described in any one of [1] to

[13] above.

[0029]

[16] A prepreg is made using a resin composition as described in any one of [1] to

[13] above.

[0030]

[17] A high-frequency electronic component having a cured material as described in

[15] above. [Effects of the Invention]

[0031] The resin composition of this invention exhibits excellent dielectric properties and heat resistance. Furthermore, the resin composition of this invention also has high flowability, resulting in good embedding properties in substrates and excellent film-forming properties. Therefore, the resin composition of this invention is suitable for use in printed circuit boards, cured products, prepregs, and high-frequency electronic components.

[0032] Furthermore, the printed circuit boards, cured materials, prepregs, and high-frequency electronic components of the present invention utilize the resin composition of the present invention to achieve excellent dielectric properties, as well as excellent heat resistance and embeddability. Simple Explanation of the Diagram

[0033] Figure 1 is a cross-sectional view of a multilayer wiring board, which is used to illustrate the process of conductor layer fracture due to thermal cycling. Implementation

[0034] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. Therefore, it should be understood that any appropriate modifications or improvements to the following embodiments based on the common knowledge of those skilled in the art, without departing from the spirit of the present invention, are also included within the scope of the present invention.

[0035] [Resin Composition] One embodiment of the resin composition of the present invention comprises (A) a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at its terminal and (B) a compound having an isocyanate ring structure and two allyl groups in one molecule, and being liquid at 25°C. Hereinafter, the polyphenylene ether resin having a functional group containing a carbon-carbon double bond at its terminal is sometimes referred to as component (A). Similarly, the compound having an isocyanate ring structure and two allyl groups in one molecule, and being liquid at 25°C, is sometimes referred to as component (B).

[0036] The resin composition of this embodiment exhibits excellent dielectric properties and heat resistance. Furthermore, the resin composition of this embodiment also has high fluidity, resulting in good substrate embedding and excellent film-forming properties. The polyphenylene ether resin, component (A), has functional groups containing carbon-carbon double bonds at its ends, which imparts low dielectric properties to the resin composition and improves fluidity during heating. The compound, component (B), as described above, is a compound having an isocyanate ring structure and two allyl groups per molecule, which reduces the melt viscosity of the resin composition and improves embedding properties for wiring. Furthermore, the compound, component (B), has two allyl groups, thereby achieving excellent low dielectric properties. Finally, by crosslinking and curing components (A) and (B), the resin composition of this embodiment achieves high heat resistance.

[0037] Furthermore, the resin composition of this embodiment can reduce the coefficient of thermal expansion in the thickness direction of the cured resin composition or cured layer. Hereinafter, the thickness direction of the cured resin composition or cured layer is sometimes referred to as the "Z direction".

[0038] For example, when a resin composition is used as the adhesive layer of a multilayer wiring board, if the cured resin composition or cured layer that serves as the adhesive layer has a large coefficient of thermal expansion in the thickness direction (Z direction), it may easily cause breakage around the through-holes of the multilayer wiring board. For example, Figure 1 is a cross-sectional view of a multilayer wiring board, which is used to illustrate the process of conductor layer breakage due to thermal cycling. Figure 1(a) shows the state before conductor layer breakage, and Figure 1(b) shows the state after conductor layer breakage due to thermal cycling. In Figures 1(a) and (b), the direction of the arrow indicated by the symbol Z indicates the "thickness direction (i.e., Z direction)" of the cured resin composition or cured layer that serves as the adhesive layer 16.

[0039] The multilayer wiring board 10 shown in Figure 1(a) is formed by bonding five substrates 12 (12a~12e) together with conductor layers 14 and adhesive layers 16 (16a~16d) in between. The adhesive layers 16 (16a~16d) are, for example, cured layers formed by curing a resin composition. The conductor layers 14 are configured to cover the space between each substrate 12 and each adhesive layer 16 and the entire surface of the multilayer wiring board 10.

[0040] The multilayer wiring board 10 shown in FIG1(a) is provided with through holes 22 for electrically connecting the island portion on the surface of the multilayer wiring board 10 with the island portion on the back side. The inner wall surface of the through holes 22 is also covered by the conductor layer 14 mentioned above.

[0041] As shown in Figure 1(a), if the multilayer wiring board 10 is used in an environment with significant temperature changes, as shown in Figure 1(b), fractures 24 may occur in the conductor layer 14. For example, if a thermal cycle of -55°C to 125°C is applied to the multilayer wiring board 10 shown in Figure 1(a) as one cycle, stress is generated due to the expansion caused by the temperature change, making it easier for fractures 24 to occur in the conductor layer 14. Furthermore, if the adhesive layer 16 has a large coefficient of thermal expansion in the Z direction, even greater stress will be generated on the conductor layer 14 covering the inner wall of the through-hole 22, resulting in more pronounced fractures 24 in the conductor layer 14.

[0042] The resin composition of this embodiment can reduce the coefficient of thermal expansion in the thickness direction (i.e., the "Z direction" in FIG1) of its cured product or cured layer, thereby effectively suppressing the occurrence of fracture 24 in the conductor layer 14 as shown in FIG1(b).

[0043] In addition to components (A) and (B) mentioned above, the resin composition of this embodiment may also include other components such as (C) inorganic filler, (D) polymerization initiator, (E) thermoplastic resin, and (F) polybutadiene. Hereinafter, the above components will sometimes be appropriately referred to as components (C) to (F).

[0044] [(A) ingredient] Component (A) is a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at its end. Examples of functional groups containing carbon-carbon double bonds include, for example, terminal vinyl groups, vinylidene groups, or vinylidene groups. Component (A) is not particularly limited as long as it has a functional group containing a carbon-carbon double bond at its end and contains polyphenylene ether in its backbone. By including component (A), the resin composition can be endowed with low dielectric properties and improved heat resistance and coefficient of thermal expansion. Component (A) is preferably a thermosetting resin. Furthermore, component (A) is particularly preferably a polyphenylene ether resin with a vinyl group at its end. Low dielectric properties are obtained due to the presence of a vinyl group at the end.

[0045] (A) The components can be exemplified by compounds with structures shown in the following general formula (1).

[0046] [Compound 5] [Compound 6] [Compound 7]

[0047] In the above general formula (1), R1, R2, R3, R4, R5, R6, and R7 may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups, alkyl halides, or phenyl groups. Also, -(OXO)- is represented by the above structural formula (2), in which R8, R9, R10, R14, and R15 may be the same or different, and are halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups; R11, R12, and R13 may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups. Furthermore, -(YO)- is a random arrangement of one structure shown in the above structural formula (3) or two or more structures shown in the above structural formula (3). In this structural formula (3), R16 and R17 may be the same or different, and are halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups. R18 and R19 may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups. Furthermore, Z is an organic group with 1 or more carbon atoms, and may sometimes include oxygen atoms, nitrogen atoms, sulfur atoms, or halogen atoms. At least one of a and b is not 0, and represents an integer from 0 to 300. c and d represent integers 0 or 1. For example, the compound shown in general formula (1) is described in Japanese Patent Application Publication No. 2004-59644.

[0048] The compound represented by general formula (1) has styrene functional groups at both ends, thus the resin composition containing component (A) becomes easily cured by heating. From the viewpoint of curability, R1 to R7 of the compound represented by general formula (1) are preferably hydrogen.

[0049] In the above structural formula (2) representing the composition of the -(OXO)- group of the compound shown in general formula (1), R8, R9, R10, R14, and R15 are preferably alkyl groups with 3 or fewer carbon atoms, and particularly preferably methyl groups. Furthermore, in the above structural formula (2), R11, R12, and R13 are preferably hydrogen atoms or alkyl groups with 3 or fewer carbon atoms, and particularly preferably methyl groups. Specifically, the following structural formula (5) can be listed.

[0050] [Compound 8]

[0051] In the above structural formula (3) representing the composition of the -(YO)- of the compound shown in general formula (1), R16 and R17 are preferably alkyl groups with 3 or fewer carbon atoms, and particularly preferably methyl groups. Furthermore, in the above structural formula (3), R18 and R19 are preferably hydrogen atoms or alkyl groups with 3 or fewer carbon atoms, and particularly preferably methyl groups. Specifically, the following structural formulas (6) or (7) can be listed.

[0052] [Compound 9]

[0053] Z can be exemplified by alkyl groups having 3 or fewer carbon atoms, specifically methylene.

[0054] At least one of a and b is not 0, and it represents an integer from 0 to 300, preferably an integer from 0 to 30.

[0055] To control the elastic modulus of the cured resin composition within an appropriate range, the number average molecular weight of the compound represented by general formula (1) is preferably 1000 to 3000. Furthermore, the compound represented by general formula (1) is preferably a compound with functional groups containing carbon-carbon double bonds at both ends, and the equivalent of each functional group (functional group equivalent) is 500 to 1500, which is equivalent to half of the aforementioned molecular weight. The functional group equivalent indicates the degree of crosslinking density of the cured product. If the functional group equivalent is within this range, an appropriate crosslinking density can be obtained, resulting in sufficient mechanical strength, thus having the advantage of avoiding cracks during film formation. In addition, in this specification, the number average molecular weight is the value obtained using a calibration curve obtained by gel permeation chromatography (GPC) with standard polystyrene.

[0056] The compound represented by general formula (1) can be prepared using the method described in Japanese Patent Application Publication No. 2004-59644. For example, it can be prepared by further reacting a polycondensate of 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol and 2,6-dimethylphenol with chloromethylstyrene.

[0057] (A) The component may be a compound of general formula (1) used alone, or two or more compounds of general formula (1) may be used in combination.

[0058] Of the 100% by mass of non-volatile components in the resin composition, it is preferable to include 15-90% by mass of component (A), more preferably 17-80% by mass, and even more preferably 18-70% by mass. If the content of component (A) in 100% by mass of non-volatile components in the resin composition is within this range, it has the advantage of improved processability, such as improved heat resistance and film formation. Furthermore, the content of component (A) in the non-volatile components can be measured, for example, by methods such as Fourier transform infrared spectroscopy (FTIR) or gas chromatography-mass spectrometry.

[0059] Furthermore, when including component (A) as described so far, it is preferable to include 15 to 95 parts by mass of component (A) relative to the total 100 parts by mass of resin components in the resin composition, more preferably 23 to 90 parts by mass, and most preferably 32 to 85 parts by mass. If the content of component (A) in the total 100 parts by mass of resin components is within this range, there are advantages such as improved heat resistance and film-forming processability of the cured resin composition. In addition, the content of component (A) in the resin composition can be measured, for example, by methods such as Fourier transform infrared spectroscopy (FTIR) or gas chromatography-mass spectrometry. Components (A), (B), and (E) or (F) as arbitrary components can be particularly listed as resin components in the resin composition. Therefore, the content of component (A) relative to the total 100 parts by mass of resin components in the resin composition can be obtained, for example, as the content of component (A) when the total mass of component (A), component (B), and other resin components is set to 100 parts by mass. Furthermore, the content of component (B) as described below relative to the total 100 parts by mass of the resin components can also be calculated using the above method.

[0060] Polyphenylene ether resins having carbon-carbon double bond functional groups at their ends as component (A) include, for example, the trade names "OPE-2St 1200" (number average molecular weight 1200) and "OPE-2St 2200" (number average molecular weight 2200) manufactured by Mitsubishi Gas Chemical Company, Inc. These are polyphenylene ether resins with vinyl groups at their ends.

[0061] Furthermore, polyphenylene ether resins that have a functional group containing a carbon-carbon double bond at the end as component (A) can be listed as polyphenylene ether resins with a group shown in formula (8) at the end.

[0062] [Compound 10] (In formula (8) above, R 20 represents a hydrogen atom or an alkyl group).

[0063] In formula (8) above, R 20 represents a hydrogen atom or an alkyl group. Furthermore, the alkyl group of R 20 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 carbon atom. Specifically, examples include methyl, ethyl, propyl, etc.

[0064] Furthermore, examples of the bases shown in formula (8) include acrylate groups and methacrylate groups.

[0065] Furthermore, the modified polyphenylene ether having the base shown in formula (8) is preferably a polyphenylene ether chain in the molecule, for example, having a repeating unit shown in the following structural formula (9) in the molecule.

[0066] [Compound 11]

[0067] In the above structural formula (9), m represents 1 to 50. Also, R22 to R25 are independent and can be the same or different from each other. R22 to R25 represent hydrogen atoms and alkyl groups.

[0068] The alkyl group in R 22 to R 25 is not particularly limited. For example, it is preferably an alkyl group with 1 to 8 carbons, and more preferably an alkyl group with 1 to 3 carbons. Specifically, examples include methyl, ethyl, propyl, hexyl, and octyl.

[0069] As a modified polyphenylene ether having the group shown in formula (8) above, examples include polyphenylene ethers with the group shown in formula (8) above at the end, as shown in formula (10) or formula (11) below. Specifically, as a modified polyphenylene ether, examples include modified polyphenylene ethers shown in formula (12) or formula (13) below.

[0070] [Compound 12] [Compound 13] [Compound 14] [Compound 15]

[0071] In formulas (10) to (13), regarding s and t, for example, the sum of s and t is preferably 1 to 30. Also, s is preferably 0 to 20, and t is preferably 0 to 20. That is, preferably s represents 0 to 20, t represents 0 to 20, and the sum of s and t represents 1 to 30. Also, in formulas (10) to (13), Y represents an alkyl group with 1 to 3 carbon atoms or a direct bond, and, for example, dimethylmethylene. Also, in formulas (12) and (13), R 20 is the same as R 20 in formula (8) above, representing a hydrogen atom or an alkyl group. Also, the alkyl group is not particularly limited, for example, it is preferably an alkyl group with 1 to 3 carbon atoms, and more preferably an alkyl group with 1 carbon atom. Specifically, examples include methyl, ethyl, propyl, etc.

[0072] The number average molecular weight (Mn) of the modified polyphenylene ether having the group shown in formula (8) is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and even more preferably 1000 to 3000. Here, the number average molecular weight is simply a value measured by a common molecular weight measurement method, such as a value measured by gel permeation chromatography (GPC). Furthermore, when the modified polyphenylene ether having the group shown in formula (8) has repeating units as shown in formula (9) in its molecule, m is preferably a value that makes the weight average molecular weight of the modified polyphenylene ether within the range shown. Specifically, m is preferably 1 to 50.

[0073] If the number average molecular weight of the modified polyphenylene ether having the base shown in formula (8) is within the above-mentioned range, it has excellent dielectric properties derived from polyphenylene ether and excellent embedding properties into the substrate.

[0074] Furthermore, in the modified polyphenylene ether used as component (A), the average number of groups (terminal functional groups) shown in formula (8) at the end of each molecule of modified polyphenylene ether is not particularly limited. Specifically, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3. If the number of terminal functional groups is too small, the curability will be poor, and there is a tendency to have difficulty obtaining sufficient strength, adhesion, and heat resistance of the cured product. Furthermore, if the number of terminal functional groups is too large, the reactivity will be too high, and there is a concern that defects such as reduced storage stability of the resin composition, reduced flowability of the resin composition, or brittleness or reduced adhesion of the cured product may occur. That is, if the modified polyphenylene ether is used, there is a concern that problems such as the formation of pores may occur during multilayer molding, or the substrate may easily crack or delamination may occur, or it may be difficult to obtain a highly reliable printed circuit board.

[0075] The terminal functional groups of the aforementioned modified polyphenylene ether can be represented by the average value of the groups shown in formula (8) in each molecule of all modified polyphenylene ether present in 1 mole of modified polyphenylene ether. This terminal functional group can be measured, for example, by measuring the number of residual hydroxyl groups in the modified polyphenylene ether and calculating the reduction in the number of hydroxyl groups from the original polyphenylene ether. This reduction in the number of hydroxyl groups from the original polyphenylene ether is the terminal functional group. The number of residual hydroxyl groups in the modified polyphenylene ether can then be measured by adding a fourth-order ammonium salt (tetraethylammonium hydroxide) associated with hydroxyl groups to a solution of the modified polyphenylene ether and measuring the UV absorbance of the mixed solution.

[0076] Furthermore, the method for synthesizing the modified polyphenylene ether used as component (A) is not particularly limited as long as it can synthesize modified polyphenylene ether with the group shown in formula (8) above at the end.

[0077] (A) The component may be a modified polyphenylene ether having a group at the end of the above formula (8) used alone, or two or more modified polyphenylene ethers having a group at the end of the above formula (8) may be used in combination.

[0078] Furthermore, there are no particular limitations on the content of component (A) with the base shown in formula (8) at the end as described so far. For example, it is preferable to include 15 to 95 parts by mass of component (A) relative to the total 100 parts by mass of the resin composition, more preferably 23 to 90 parts by mass, and even more preferably 32 to 85 parts by mass. If the content of component (A) in the total 100 parts by mass of the resin composition is within this range, the cured resin composition has the advantages of improved heat resistance, film formation and other processability, and the cured composition does not lose its toughness and adhesion does not decrease.

[0079] Modified polyphenylene ethers with the base shown in formula (8) at the end of component (A) can be exemplified by the trade name "Noryl SA9000" manufactured by SABIC Innovative Plastics.

[0080] Furthermore, as described below, this resin composition may also contain inorganic fillers. When this resin composition contains inorganic fillers, it is preferable to contain 40 to 90 parts by mass of component (A) relative to 100 parts by mass of the total resin components, more preferably 45 to 85 parts by mass, and most preferably 50 to 80 parts by mass. Within this range, there is an advantage of increased coefficient of thermal expansion of the resin composition.

[0081] [(B) Component] Component (B) is a compound having an isocyanate ring structure and two allyl groups in one molecule, and is liquid at 25°C. By including component (B), the melt viscosity of the resin composition can be reduced, and the embedding properties for wiring can be improved. Furthermore, the compound as component (B), by having two allyl groups, can obtain excellent low dielectric properties. For example, when a compound having an isocyanate ring structure and three allyl groups in one molecule is used instead of component (B), sufficient low dielectric properties cannot be obtained. Although the detailed reason is unclear, it is speculated that when a compound with three allyl groups is used, it becomes a three-dimensional cross-linked structure, thus the dielectric properties become insufficient. On the other hand, it is speculated that if the compound (B) of the resin composition of this embodiment is a compound with two functional allyl groups, it will become a linear cross-linked structure, indicating that the dipole torque of the molecular polarization reference is reduced, thus obtaining low dielectric properties. Furthermore, while the exact reasons are unclear, it is speculated that the heat resistance of the resin composition is improved due to the isocyanuric acid ring structure of component (B). In addition, since component (B) of the resin composition in this embodiment is a liquid compound at 25°C, its embedding properties are improved. On the other hand, when using a compound where component (B) is solid at 25°C, film formation becomes difficult and undesirable. Component (B) is particularly advantageous because it can react with component (A) without the use of a polymerization initiator.

[0082] The molecular weight of component (B) is preferably 300-400, and more preferably 320-400. By keeping the molecular weight of component (B) within the above range, excellent dielectric properties and fluidity are achieved.

[0083] (B) The preferred composition is a compound represented by the following general formula (4).

[0084] [Compound 16]

[0085] In the above general formula (4), R series are alkyl groups with 4 to 14 carbons, preferred series are alkyl groups with 8 to 14 carbons, and particularly preferred series are alkyl groups with 10 to 12 carbons.

[0086] The content of component (B) is preferably 10 to 70 parts by mass relative to 100 parts by mass of component (A). This configuration reduces the melt viscosity of the resin composition, improves wiring embedding, and enhances heat resistance. Furthermore, while not particularly limited, the content of component (B) is preferably 15 to 65 parts by mass relative to 100 parts by mass of component (A), and more preferably 20 to 60 parts by mass. Additionally, the non-volatile components in the resin composition preferably contain 2 to 50% by mass of component (B), more preferably 3 to 40% by mass, and most preferably 4 to 30% by mass. If the content of component (B) in 100% by mass of non-volatile components in the resin composition falls within this range, the dielectric properties of the resin composition are excellent. Furthermore, the content of component (B) in the non-volatile components can be measured, for example, by methods such as Fourier transform infrared spectroscopy (FTIR) or gas chromatography-mass spectrometry.

[0087] Relative to 100 parts by mass of the total resin components in the resin composition, it is preferable to include 5 to 50 parts by mass of component (B), more preferably 7 to 45 parts by mass, and most preferably 8 to 40 parts by mass. If the content ratio of component (B) relative to 100 parts by mass of the total resin components is within this range, the film-forming properties and flowability of the resin composition become good. Furthermore, from the viewpoint of obtaining the flexibility and heat resistance of the heat-hardened resin composition, it is preferable.

[0088] Furthermore, as described below, this resin composition may also contain inorganic fillers. When this resin composition contains inorganic fillers, it is preferable to contain 1 to 30 parts by weight of component (B) relative to 100 parts by weight of the total resin components, more preferably 2 to 25 parts by weight, and most preferably 3 to 20 parts by weight. Within this range, there are the following advantages: the presence of inorganic fillers can improve the fluidity of the resin composition and enhance its embeddability.

[0089] The compound that is a component (B) having an isocyanate ring structure and two allyl groups in one molecule and is liquid at 25°C can be listed as "L-DAIC" manufactured by Shikoku Chemical Co., Ltd.

[0090] [(C) Component] (C) The component is an inorganic filler. The inorganic filler is required to have insulating properties and a low coefficient of thermal expansion. Common inorganic fillers can be used. Examples of inorganic fillers include: silicon dioxide, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, calcium sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium dioxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. The inorganic filler can be used alone or in combination with two or more types. From an insulation perspective, silicon dioxide and alumina fillers are preferred. From a dielectric property perspective, silicon dioxide filler is preferred. The inorganic filler can also be surface-treated with a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styrene, amino, epoxy, and vinyl groups. For example, inorganic fillers are preferably surface-treated with surface-treatment agents such as aminosilane coupling agents, ureasilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, vinylsilane coupling agents, styrenesilane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, thioether silane coupling agents, organosilazane compounds, and titanate coupling agents to improve their heat resistance, moisture resistance, and dispersibility. One or more of these agents can also be used. More preferably, among the surface-treated silica fillers, silica fillers surface-treated with vinylsilane coupling agents are used. By using silica fillers that have been surface-treated with vinyl silane coupling agents, a good coefficient of thermal expansion (thickness) can be achieved.

[0091] The shape of the inorganic filler is not particularly limited, and examples include spherical, flaky, needle-like, and irregular shapes. From an operational point of view, spherical shapes are preferred. The average particle size is preferably 0.1~10 μm, and more preferably 0.1~4 μm. By keeping the average particle size of the inorganic filler within this range, excellent embedding properties between fine structures are achieved. The average particle size is the particle size of the cumulative 50% of the particle size distribution on a volume basis, measured by laser diffraction / scattering method. The average particle size can be measured, for example, using a laser diffraction particle size distribution measuring device: LS13320 (manufactured by BECKMAN COULTER, wet type).

[0092] Furthermore, when component (C) is present, the content of component (C) is preferably 1 to 90 parts by mass relative to 100 parts by mass of non-volatile components in the resin composition. This configuration effectively improves the coefficient of thermal expansion. Additionally, while not particularly limited, the content of component (C) is more preferably 20 to 80 parts by mass relative to 100 parts by mass of non-volatile components in the resin composition, and even more preferably 30 to 75 parts by mass.

[0093] Furthermore, in order to reduce the coefficient of thermal expansion of the resin composition, when component (C) contains 50 or more parts by mass relative to 100 parts by mass of non-volatile components in the resin composition, a high filling of inorganic filler tends to increase the melt viscosity of the resin composition and worsen its embedding properties to the substrate. However, by using component (B), which contains a compound having an isocyanate ring structure and two allyl groups in one molecule and is liquid at 25°C, the melt viscosity of the resin composition can be reduced and the embedding properties to the wiring can be improved even with a high filling of inorganic filler.

[0094] Examples of silica fillers used as components (C) include fused silica, ordinary silica, spherical silica, crushed silica, crystalline silica, and amorphous silica, without particular limitation. From the viewpoints of dispersibility, flowability of the thermosetting resin composition, surface smoothness of the cured product, dielectric properties, low coefficient of thermal expansion, and adhesion, spherical fused silica is preferred.

[0095] There are no particular limitations on the method of surface treatment of silica filler using the above-mentioned coupling agent; examples include dry method and wet method.

[0096] The dry method involves placing silica filler and a silane coupling agent of appropriate surface area relative to the silica filler into a stirring device and stirring under suitable conditions. Alternatively, the silica filler can be placed into the stirring device beforehand, and while stirring under suitable conditions, an appropriate amount of silane coupling agent of appropriate surface area relative to the silica filler is added dropwise or by spraying, and the silane coupling agent is uniformly adhered to the surface of the silica filler by stirring (through hydrolysis) to achieve surface treatment. Examples of stirring devices include Henschel mixers and other mixers capable of high-speed rotation for stirring and mixing, but there are no particular limitations.

[0097] The wet process involves dissolving a silane coupling agent, which is sufficient to cover the surface area of ​​the silica filler to be surface-treated, in water or an organic solvent to form a surface treatment solution. Silica filler is then added to the solution and stirred to form a slurry, thereby allowing the silane coupling agent and silica filler to react fully. The silica filler is then separated from the surface treatment solution by filtration or centrifugation, and finally heated and dried to complete the surface treatment.

[0098] [(D) component] Component (D) is a polymerization initiator. The polymerization initiator, as component (D), is an additive used to facilitate the polymerization of components (A) and (B). By including component (D), the degree of curing of the resin composition relative to a given curing temperature / time can be improved. Therefore, the resin composition of this embodiment preferably further includes the polymerization initiator as component (D).

[0099] The polymerization initiator for component (D) only needs to have the ability to cure components (A) and (B), and conventionally known polymerization initiators can be used. Examples of polymerization initiators include: organic peroxides, inorganic peroxides, and azo compounds. Examples of polymerization initiators for component (D) include: organic peroxides manufactured by Nippon Yushi Co., Ltd., under the trade names "PERCUMYL D" and "PERBUTYL C," etc. Component (D) can be used alone or in combination with two or more.

[0100] Furthermore, when component (D) is present, the content of component (D) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of non-volatile components in the resin composition. This configuration effectively improves heat resistance and adhesion. Additionally, while not particularly limited, the content of component (D) is more preferably 0.1 to 8 parts by mass relative to 100 parts by mass of non-volatile components in the resin composition, and even more preferably 0.1 to 5 parts by mass.

[0101] [(E) component] (E) is a thermoplastic resin. While there is no particular limitation on the thermoplastic resin used as component (E), it is preferably a thermoplastic resin having a dielectric loss tangent (tanδ) of less than 0.005 in the frequency range of 1 to 100 GHz. This imparts excellent dielectric properties to the thermosetting film formed from the resin composition of this embodiment in the high-frequency region. The term "thermoplastic resin having a dielectric loss tangent (tanδ) of less than 0.005 in the frequency range of 1 to 100 GHz" is not particularly limited, but styrene-based thermoplastic elastomers can be cited as examples. As a styrene-based thermoplastic elastomer, a block copolymer can be cited as an example, containing at least one end block of styrene or similar substances and at least one intermediate block of an elastomer containing a conjugated diene. Examples include styrene / butadiene / styrene block copolymers (SBS), styrene / butadiene / butene / styrene block copolymers (SBBS), styrene / ethylene / butene / styrene block copolymers (SEBS), and styrene / ethylene / ethylene / propylene / styrene block polymers (SEEPS). By including styrene-based thermoplastic elastomers, resin compositions can be made more flexible, the cured product can maintain its toughness, adhesion can be improved, and dielectric properties can be reduced.

[0102] The number average molecular weight of component (E) is preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more. Furthermore, the number average molecular weight of component (E) is preferably 30,000 to 150,000, more preferably 40,000 to 120,000, and particularly preferably 50,000 to 100,000. By maintaining the number average molecular weight within this range, the heat resistance of the solder is improved. While there is no particular upper limit to the number average molecular weight of component (E), if the number average molecular weight of the thermoplastic resin is too high, the thermoplastic resin may become difficult to melt. Therefore, the number average molecular weight of the thermoplastic resin used as component (E) is preferably 150,000 or less, even more preferably 120,000 or less, and particularly preferably 100,000 or less. Furthermore, the higher the molecular weight of component (E), the higher the melt viscosity of the resin composition, which tends to worsen the embedding properties into the substrate. However, by using component (B), which contains a compound having an isocyanate ring structure and two allyl groups in one molecule and is liquid at 25°C, the melt viscosity of the resin composition can be reduced and the embedding properties of the wiring can be improved, even when using thermoplastic resins with larger molecular weights.

[0103] There is no particular limitation on the content of component (E), but when component (E) is included, it is preferable to include 1 to 50% by mass of component (E) relative to 100% by mass of non-volatile components in the resin composition, and even more preferably 1 to 30% by mass. By keeping the content of component (E) within this range, the fluidity of the resin composition is improved, thereby improving the embedding properties to the substrate.

[0104] Furthermore, the resin composition may also contain inorganic fillers. When the resin composition contains inorganic fillers, it is preferable to contain 1 to 60 parts by mass of component (E) relative to the total 100 parts by mass of the resin components, more preferably 10 to 55 parts by mass, and even more preferably 20 to 50 parts by mass.

[0105] [(F)INGREDIENT] (F) is polybutadiene. By including polybutadiene as component (F), the coefficient of thermal expansion in the thickness direction of the cured resin composition or cured layer can be reduced. Component (F) is preferred because the side chains of polybutadiene contain vinyl components that react with components (A) or (B). Although the exact reason is unclear, it is speculated that the reaction between components (A) or (B) and the side chains of polybutadiene reduces the coefficient of thermal expansion in the thickness direction. Therefore, by including polybutadiene as component (F), the breakage 24 on the conductor layer 14, as shown in FIG1(b), can be suppressed very effectively.

[0106] The number average molecular weight (Mn) of the polybutadiene as component (F) is preferably 500 to 3000, more preferably 600 to 2000, and even more preferably 700 to 1800. If the number average molecular weight (Mn) of the polybutadiene as component (F) is within this range, the coefficient of thermal expansion in the thickness direction of the cured resin composition or cured layer can be smaller.

[0107] As a component (F), polybutadiene can be exemplified by polybutadiene (1,2-ethylene) manufactured by Nippon Soda Corporation under the trade name "B-1000".

[0108] Furthermore, when containing component (F), the content of component (F) is preferably 1 to 20 parts by mass relative to 100 parts by mass of non-volatile components in the resin composition. This configuration allows for a favorable coefficient of thermal expansion. Additionally, while not particularly limited, the content of component (F) is more preferably 1 to 10 parts by mass relative to 100 parts by mass of non-volatile components in the resin composition, and even more preferably 1 to 5 parts by mass.

[0109] [Other ingredients] The resin composition of this embodiment may further include components other than those described so far (A) to (F). For example, other components may include: solvents, dispersants, silane coupling agents, antioxidants, flame retardants, fluxes, and various additives.

[0110] [Manufacturing method of resin composition] The resin composition of this embodiment can be manufactured using conventional methods. The resin composition of this embodiment can be manufactured by dissolving and mixing the various components described so far with a solvent using, for example, a crusher, ball mill, three-roll mill, rotary mixer, or twin-shaft mixer.

[0111] [Applications of Resin Compositions] The resin composition of this embodiment can be appropriately used as an adhesive for use in electronic components or as a resin composition for bonding thin films. Furthermore, the resin composition of this embodiment can also be appropriately used as an adhesive sheet or interlayer adhesive for multilayer wiring boards. When the resin composition of this embodiment is used for various applications in electronic components, there are no particular limitations on the electronic components to which it is bonded; examples include various printed circuit boards such as ceramic substrates or organic substrates, semiconductor wafers, and semiconductor devices.

[0112] The adhesive films, interlayer adhesive sheets, and interlayer adhesives made using the resin composition of this embodiment are contained in multilayer boards or semiconductor devices constituting electronic components as cured products of the resin composition. Therefore, in multilayer boards or semiconductor devices constituting electronic components, it is preferable to include cured products of the resin composition of this embodiment.

[0113] Furthermore, the resin composition of this embodiment can also be used as a prepreg made from a cured resin composition, or as a high-frequency electronic component having a cured resin composition. [Example]

[0114] The present invention will be described in more detail below with reference to the embodiments, but the present invention is not limited to these embodiments. In the following embodiments, unless otherwise specified, parts and % represent parts by mass and percentage by mass.

[0115] (Examples 1-15, Comparative Examples 1-6) [Sample Creation] After measuring and mixing each component in the proportions (parts by mass) shown in Tables 1 to 4 below, the components were placed in a container heated to 70°C to dissolve them. The mixture was then stirred at atmospheric pressure for 3 to 6 hours while rotating at 100 to 400 rpm. A solution containing the resin compositions of Examples 1 to 15 and Comparative Examples 1 to 6 was prepared in the above manner.

[0116] In Examples 1-15 and Comparative Examples 1-6, the raw materials used to prepare the solutions containing the resin composition are as follows.

[0117] [(A) Composition: Polyphenylene ether resin with terminal functional groups (vinyl groups) containing carbon-carbon double bonds] (A1): Manufactured by Mitsubishi Gas Chemical Company, trade name "OPE-2St", quantity average molecular weight (Mn) = 1200. (A2): Manufactured by Mitsubishi Gas Chemical Company, trade name "OPE-2St", quantity average molecular weight (Mn) = 2200. (A3): Manufactured by SABIC Japan LLC., trade name "Noryl SA9000", quantity average molecular weight (Mn) = 1850~1950. [(A') Composition: Polyphenylene ether without terminal functional groups containing carbon-carbon double bonds] (A'3): Manufactured by Saudi Basic Industries Corporation of Japan, trade name "Noryl SA90", a polyphenylene ether with hydroxyl groups at the end.

[0118] [(B) Composition: A compound containing an isocyanuric acid ring structure and two allyl groups in one molecule] (B1): Manufactured by Shikoku Chemical Co., Ltd., trade name "L-DAIC", the compound shown in the above general formula (4). In the above general formula (4), R is an alkyl group with 4 to 14 carbon atoms. [(B') component: Compounds other than the (B) component containing an allyl group in one molecule] (B'2): Manufactured by Yamato Chemical Industry Co., Ltd., trade name "DABPA", a compound that does not have an isocyanate ring structure and has phenolic hydroxyl and allyl groups in one molecule. (B'3): Manufactured by Mitsubishi Gas Chemical Company, trade name "TAIC", a compound having an isocyanate ring structure and 3 allyl groups in one molecule.

[0119] [(C) Composition: Inorganic filler] (C1): Spherical silica surface-treated with aminosilane coupling agent, SC4050 SX (product name), manufactured by Admatechs Co., Ltd., with an average particle size of 1.0 μm. (C2): Spherical silica surface-treated with a vinyl silane coupling agent, 10SV-C12 (product name), manufactured by Admatechs Co., Ltd., with an average particle size of 1.0 μm.

[0120] [(D) Component: Polymerization Initiator] (D1): Manufactured by Nippon Oil Chemical Company, trade name "PERCUMYL D".

[0121] [(E) Composition: Thermoplastic resin] (E1): Hydrogenated styrene thermoplastic elastomer manufactured by Asahi Kasei Corporation, trade name "TAFTEC P1500", quantity average molecular weight (Mn) = 49,000. (E2): Hydrogenated styrene thermoplastic elastomer manufactured by KURARAY, trade name "SEPTON 8006", quantity average molecular weight (Mn) = 125,000. (E3): Hydrogenated styrene thermoplastic elastomer produced by KRATON CORPORATION, trade name "G1652", quantity average molecular weight (Mn) = 53,000.

[0122] [(F) Composition: Polybutadiene] (F1): Polybutadiene manufactured by Nippon Soda Co., Ltd., trade name "B-1000". Polybutadiene has vinyl groups on its side chains. Number average molecular weight (Mn) = 1200.

[0123] [(G) Component: Solvent] (G1): Toluene.

[0124] Furthermore, the column "Ratio of Filler in Solid Components (mass %)" in Tables 1-4 displays the ratio (mass %) of component (C) in the solid raw materials used to prepare the resin composition. Additionally, "Ratio of Filler in Solid Components (mass %)" refers to the ratio (mass %) of filler relative to the non-volatile components in the resin composition. The column "Ratio of Component (A) in Non-volatile Components (mass %)" in Tables 1-4 displays the ratio (mass %) of component (A) in the non-volatile components of the raw materials used to prepare the resin composition. The column "Ratio of Component (B) in Non-volatile Components (mass %)" in Tables 1-4 displays the ratio (mass %) of component (B) in the non-volatile components of the raw materials used to prepare the resin composition.

[0125] The solutions containing the resin compositions of Examples 1-15 and Comparative Examples 1-6 obtained in accordance with the above method were evaluated and measured for "film-forming properties", "dielectric constant", "dielectric loss tangent", "coefficient of thermal expansion [10⁻⁵ / K]", "copper foil peel strength [N / cm]" and "solder heat resistance (300°C × 3 minutes)" according to the methods shown below. The results are shown in Tables 1-4.

[0126] Further, for the formed films of the resin compositions containing Examples 5, 8, 10, and 13, the "thermal expansion coefficient (thickness) [10⁻⁵ / K]" was measured by the following method. Furthermore, for the formed films of the resin compositions containing Examples 1 to 11, Example 13, Comparative Examples 1 to 3, and 5, the "minimum melt viscosity [Pa･s]" and "minimum melting temperature [°C]" were measured by the following method.

[0127] [Film-forming property] First, the solution containing each resin composition was applied onto a peeled PET film by knife coating. After that, the solution on the PET film was dried at a temperature of 80 to 130°C to produce a resin film with a thickness of 20 to 50 μm. The shape of the produced resin film was visually confirmed and evaluated according to the following evaluation criteria. When the evaluation result is "〇", it is regarded as qualified. 〇: Excellent film. △: Film with stripes / spots. ×: Cracks.

[0128] [Dielectric constant, dielectric loss tangent] The resin film produced in the evaluation of film-forming property was cured at a temperature of 200°C for 1 hour to produce a specimen for measuring the dielectric constant and dielectric loss tangent. For the produced specimen, a 10 GHz resonator of the cavity resonator perturbation method was used to measure the dielectric constant and dielectric loss tangent. The dielectric constant is preferably less than 3.5, more preferably less than 3.0. Also, the dielectric loss tangent is preferably less than 0.0020, more preferably less than 0.0018.

[0129] [Thermal expansion coefficient [10⁻⁵ / K]] The resin film produced in the evaluation of film-forming property was laminated to a thickness of 50 to 100 μm and cured at a temperature of 200°C for 1 hour to produce a specimen for measuring the thermal expansion coefficient. For the produced specimen, measurement was carried out by the tensile method of TMA (thermomechanical analysis device), and the average thermal expansion coefficient from 100 to 110°C was taken as the reading value (i.e., the measured value of the thermal expansion coefficient). The measurement conditions were annealing to 230°C at a tensile load of 2 gf and 20°C / min, then temporarily returning to room temperature, and then measuring to 230°C at 5°C / min. In addition, the thermal expansion coefficient evaluated here is the thermal expansion coefficient in the planar direction. The thermal expansion coefficient is preferably less than 20 [10⁻⁵ / K], more preferably less than 10 [10⁻⁵ / K].

[0130] [Coefficient of thermal expansion (thickness) [10⁻⁵ / K]] The resin film prepared for the film-forming property evaluation was laminated to a thickness of approximately 2 mm and cured at 200°C for 1 hour to prepare a sample for measuring the coefficient of thermal expansion (thickness). The prepared sample was compressed using a TMA (Thermomechanical Analysis Apparatus), and the average coefficient of thermal expansion from 100 to 110°C was used as the reading (i.e., the measured value of the coefficient of thermal expansion (thickness)). The measurement conditions were: annealing to 250°C with a compression load of 1 gf and a rate of 20°C / min, followed by a temporary return to room temperature, and then measurement at 5°C / min up to 250°C. Furthermore, the coefficient of thermal expansion evaluated here is the coefficient of thermal expansion in the thickness direction (i.e., the Z-direction). The coefficient of thermal expansion in the thickness direction is preferably less than 20 [10⁻⁵ / K], more preferably less than 10 [10⁻⁵ / K].

[0131] [Copper foil peel strength [N / cm]] A double-sided copper-clad laminate (CCL) for measuring copper foil peel strength was fabricated by sandwiching a resin film prepared in the film-forming property evaluation with a copper foil of 18 μm thickness and curing it at 200°C for 1 hour and 1 MPa. The CCL was cut into 1 cm wide pieces, and the strength when a single-sided copper foil was peeled off at 180 degrees was measured. The measurement conditions were set at a tensile speed of 50 mm / min. The preferred copper foil peel strength was 3.0 N / cm or higher, and more preferably 4.0 N / cm or higher.

[0132] [Solder heat resistance (300℃ x 3 minutes)] For the evaluation of copper foil peel strength, the double-sided copper-clad laminate prepared in the experiment is cut into 2cm squares and floated in a 300°C solder bath for 3 minutes. Its appearance is visually inspected, and it is evaluated according to the following evaluation criteria. An evaluation result of "PASS" is considered acceptable. PASS: No change. ×: There is expansion and peeling of copper foil.

[0133] [Minimum melt viscosity [Pa·s], Minimum melt temperature [°C]] The resin film prepared for the film-forming property evaluation was laminated with a thickness of 200-300 μm, and the melt viscosity was measured using a rheometer. The lowest melt viscosity [Pa·s] and lowest melting temperature [°C] at the time of measurement were then recorded. Measurements were performed using a parallel plate with a diameter of 5 mm, a load of 2 gf, a strain of 1%, a frequency of 1 Hz, and a speed of 5 °C / min, at temperatures ranging from 30 to 160 °C. The lowest melting temperature was preferably less than 200 °C, more preferably less than 160 °C. Furthermore, the lowest melt viscosity was preferably less than 10,000 Pa·s, more preferably less than 5,000 Pa·s.

[0134] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Raw materials (parts by weight) (A)Ingredients (A1) OPE-2St, Mn=1200 48.0 48.0 43.2 48.0 48.0 48.0 (A2) OPE-2St, Mn=2200 - - - - - - (A')Ingredient (A'3) SA90 - - - - - - (B) Ingredients (B1) L-DAIC 23.0 20.0 18.0 20.0 20.0 5.0 (B') component (B'2) DABPA - - - - - - (B'3) TAIC - - - - - - (C) Components (C1) SC4050-SX - - - - 146.7 - (C2) 10SV-C12 - - - - - - (D) Components (D1) PERCUMYL D - - 0.20 0.48 0.48 - (E) Components (E1) TAFTEC P1500 - 20.0 - 20.0 32.0 - (E2) SEPTON 8006 - - - - - - (F)Ingredients (F1) B-1000 - - - - - - (G) component (G1) Solvent (toluene) 40 80 40 80 120 40 total 111.00 168.00 101.40 168.48 367.18 93.00 The filler ratio (mass %) in the solid component 0.00% 0.00% 0.00% 0.00% 59.35% 0.00% The ratio (mass%) of component (A) in the non-volatile components 67.61% 54.55% 70.36% 54.25% 19.42% 90.57% The ratio (mass%) of component (B) in the non-volatile components 32.39% 22.73% 29.32% 22.60% 8.09% 9.43% evaluate Film-forming properties 〇 〇 〇 〇 〇 〇 Dielectric constant 2.38 2.55 2.41 2.49 2.96 2.46 Dielectric loss tangent 0.00182 0.00161 0.00197 0.00156 0.00140 0.00190 Coefficient of thermal expansion [10⁻⁵ / K] 19.5 18.1 19.6 15.5 4.7 10.8 Copper foil peel strength [N / cm] 5.0 5.6 3.9 5.7 4.6 4.2 Solder heat resistance (300℃ × 3 minutes) PASS PASS PASS PASS PASS PASS

[0135] [Table 2] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Raw materials (parts by weight) (A)Ingredients (A1) OPE-2St, Mn=1200 48.0 42.0 48.0 48.0 48.0 - 47.0 (A2) OPE-2St, Mn=2200 - - - - - 48.0 - (A')Ingredient (A'3) SA90 - - - - - - - (B) Ingredients (B1) L-DAIC 32.0 10.0 20.0 10.0 20.0 21.0 19.6 (B') component (B'2) DABPA - - - - - - - (B'3) TAIC - - - - - - - (C) Components (C1) SC4050-SX - 146.7 - 147.0 140.0 - - (C2) 10SV-C12 - - - - - - 144.6 (D) Components (D1) PERCUMYL D - 0.42 - 0.48 - - 0.47 (E) Components (E1) TAFTEC P1500 - 28.0 - 32.0 - - 31.4 (E2) SEPTON 8006 - - 20.0 - - - - (F)Ingredients (F1) B-1000 - 20.0 - 10.0 - - - (G) component (G1) Solvent (toluene) 40 160 300 160 80 40 156.8 total 120.00 407.12 388.00 407.48 288.00 108.00 399.87 The filler ratio (mass %) in the solid component 0.00% 59.36% 0.00% 59.40% 67.31% 0.00% 59.49% The ratio (mass%) of component (A) in the non-volatile components 60.00% 17.00% 54.55% 19.40% 23.08% 69.57% 19.34% The ratio (mass%) of component (B) in the non-volatile components 40.00% 4.05% 22.73% 4.04% 9.62% 30.43% 8.06% evaluate Film-forming properties 〇 〇 〇 〇 〇 〇 〇 Dielectric constant 2.24 2.84 2.28 2.98 2.89 2.36 2.87 Dielectric loss tangent 0.00184 0.00149 0.00154 0.00143 0.00154 0.00162 0.00122 Coefficient of thermal expansion [10⁻⁵ / K] 22.0 7.8 17.3 3.2 7.0 20.1 5.6 Copper foil peel strength [N / cm] 5.1 3.1 6.1 4.8 3.2 5.3 3.9 Solder heat resistance (300℃ × 3 minutes) PASS PASS PASS PASS PASS PASS PASS

[0136] [Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Raw materials (parts by weight) (A)Ingredients (A1) OPE-2St, Mn=1200 48.0 48.0 48.0 49.0 48.0 - (A2) OPE-2St, Mn=2200 - - - - - - (A')Ingredient (A'3) SA90 - - - - - 48.0 (B) Ingredients (B1) L-DAIC - - - - - 20.0 (B') component (B'2) DABPA - - 20.0 21.0 20.0 - (B'3) TAIC 20.0 20.0 - - - - (C) Components (C1) SC4050-SX - - - - 146.7 - (C2) 10SV-C12 - - - - - - (D) Components (D1) PERCUMYL D - 0.48 0.48 0.49 0.48 - (E) Components (E1) TAFTEC P1500 - - - 21.0 32.0 - (E2) SEPTON 8006 - - - - - - (F)Ingredients (F1) B-1000 - - - - - - (G) component (G1) Solvent (toluene) 40 40 40 130 120 40 total 108.00 108.48 108.48 221.49 367.18 108.00 The filler ratio (mass %) in the solid component 0.00% 0.00% 0.00% 0.00% 59.35% 0.00% The ratio (mass%) of component (A) in the non-volatile components 70.59% 70.09% 70.09% 53.56% 19.42% 70.59% The ratio (mass%) of component (B) in the non-volatile components 29.41% 29.21% 29.21% 22.95% 8.09% 29.41% evaluate Film-forming properties △ △ 〇 〇 〇 〇 Dielectric constant 2.45 2.51 - 2.56 3.00 - Dielectric loss tangent 0.00220 0.00251 - 0.00676 0.00297 - Coefficient of thermal expansion [10⁻⁵ / K] 11.8 11.6 - 13.0 4.1 - Copper foil peel strength [N / cm] 5.5 3.5 × (expansion) 2.1 1.5 0 Solder heat resistance (300℃ × 3 minutes) PASS PASS ✕ PASS PASS ✕ Uncured

[0137] [Table 4] Experimental Example 14 Experimental Example 15 Raw materials (parts by weight) (A)Ingredients (A1) OPE-2St, Mn=1200 - - (A2) OPE-2St, Mn=2200 17.0 - (A3) SA9000 - 17.0 (B) Ingredients (B1) L-DAIC 11.0 11.0 (B') component (B'2) DABPA - - (B'3) TAIC - - (C) Components (C1) SC4050-SX - - (C2) 10SV-C12 150.0 150.0 (D) Components (D1) PERCUMYL D 0.4 0.4 (E) Components (E3) G1652 20.0 20.0 - - (F)Ingredients (F1) B-1000 - - (G) component (G1) Solvent (toluene) 160 160 total 358.40 358.40 The filler ratio (mass %) in the solid component 75.60% 75.60% The ratio (mass%) of component (A) in the non-volatile components 8.57% 8.57% The ratio (mass%) of component (B) in the non-volatile components 5.54% 5.54% evaluate Film-forming properties 〇 〇 Dielectric constant 3.15 3.18 Dielectric loss tangent 0.00130 0.00133 Coefficient of thermal expansion [10⁻⁵ / K] 4.8 6.6 Copper foil peel strength [N / cm] 5.1 5.0 Solder heat resistance (300℃ × 3 minutes) PASS PASS

[0138] [result] As shown in Tables 1 to 4, the resin compositions of Examples 1 to 15 showed good results in the evaluation and measurement of "film-forming properties", "dielectric constant", "dielectric loss tangent", "coefficient of thermal expansion [10⁻⁵ / K]", "copper foil peel strength [N / cm]" and "solder heat resistance (300°C × 3 minutes)".

[0139] In the measurement results of "coefficient of thermal expansion (thickness) [10⁻⁵ / K]", Example 5 is 8.5 [10⁻⁵ / K], Example 8 is 12.3 [10⁻⁵ / K], Example 10 is 6.0 [10⁻⁵ / K], and Example 13 is 6.6 [10⁻⁵ / K].

[0140] In the measurement results of "lowest melt viscosity [Pa·s]", Example 1 was 68 Pa·s, Example 2 was 1130 Pa·s, Example 3 was 45 Pa·s, Example 4 was 1166 Pa·s, Example 5 was 6168 Pa·s, Example 6 was 124 Pa·s, Example 7 was 8 Pa·s, Example 8 was 3495 Pa·s, Example 9 was 797 Pa·s, Example 10 was 9980 Pa·s, Example 11 was 164 Pa·s, and Example 13 was 5037 Pa·s. Comparative Example 1 was 85 Pa·s, Comparative Example 2 was 86 Pa·s, Comparative Example 3 was 94 Pa·s, and Comparative Example 5 was 2735 Pa·s.

[0141] In the measurement results of "lowest melting temperature [°C]", Example 1 was 91°C, Example 2 was 120°C, Example 3 was 100°C, Example 4 was 116°C, Example 5 was 125°C, Example 6 was 100°C, Example 7 was 121°C, Example 8 was 131°C, Example 9 was 134°C, Example 10 was 127°C, Example 11 was 110°C, and Example 13 was 122°C. Comparative Example 1 was 104°C, Comparative Example 2 was 102°C, Comparative Example 3 was 102°C, and Comparative Example 5 was 141°C.

[0142] The resin composition of Example 1, consisting only of solvents for components (A), (B), and (G), exhibits low dielectric loss tangent, excellent heat resistance, and a particularly low minimum melting temperature. The resin composition of Example 6, obtained by reducing the amount of component (B) compared to the resin composition of Example 1, still exhibits low dielectric loss tangent and excellent heat resistance even with a smaller amount of component (B). On the other hand, the resin composition of Example 7, obtained by increasing the amount of component (B) compared to the resin composition of Example 1, still exhibits low dielectric loss tangent, excellent heat resistance, and a particularly low minimum melt viscosity even with the increased amount of component (B).

[0143] The resin composition of Example 2 further includes a styrene-based thermoplastic elastomer containing component (E). Even with the inclusion of component (E), it still exhibits a low dielectric loss tangent and excellent heat resistance. The resin composition of Example 9 is derived by changing the type of styrene-based thermoplastic elastomer containing component (E). Compared to Example 2, its minimum melt viscosity has increased, but within a range that does not impede flowability. It also exhibits a low dielectric loss tangent, excellent heat resistance, and excellent copper foil peel strength.

[0144] The resin composition of Example 3 further includes a polymerization initiator of component (D). Even with the inclusion of component (D), it still exhibits a low dielectric loss tangent and excellent heat resistance. The resin composition of Example 4 includes both components (D) and (E), exhibiting a low dielectric loss tangent and excellent heat resistance. The resin compositions of Examples 5, 8, and 10, in addition to components (D) and (E), further include an inorganic filler (silicon dioxide filler) of component (C), which has a particularly excellent coefficient of thermal expansion, a low dielectric loss tangent, and excellent heat resistance.

[0145] The resin composition of Example 11 contains only the solvents of components (A), (B), (C), and (G), exhibiting particularly excellent coefficients of thermal expansion and minimum melt viscosity, low dielectric loss tangent, and excellent heat resistance. The resin composition of Example 12 uses a polyphenylene ether resin with a number-average molecular weight of 2200 as component (A), exhibiting a lower dielectric loss tangent and excellent heat resistance compared to Example 1. The resin composition of Example 13 further includes an inorganic filler (silica filler treated with vinyl silane) as component (C), exhibiting particularly excellent coefficients of thermal expansion (thickness), low dielectric loss tangent, and excellent heat resistance. The resin composition of Example 14 contains component (E) (styrene-based thermoplastic elastomer), which differs from the components used in Examples 1-13, but is the same as that described so far in Examples 1-13, showing good results in various evaluations and measurements. Furthermore, the resin composition of Example 15 contains component (A), which is different from the components used in Examples 1-13, but is the same as that in Examples 1-13, and shows good results in various evaluations and measurements.

[0146] Example 6, in which the content of component (A) in 100% by mass of non-volatile components in the resin composition is 90.57% by mass, exhibits relatively low film-forming properties compared to Example 1. Similarly, Examples 3 and 12, in which the content of component (A) in 100% by mass of non-volatile components is approximately 70% by mass, show improved film-forming properties compared to Example 6, but still relatively low film-forming properties compared to Example 1. Example 8, in which the content of component (A) in 100% by mass of non-volatile components is 17.00% by mass, exhibits relatively low copper foil peel strength.

[0147] Example 10, which has the lowest content of component (B) in 100% by mass of non-volatile components, has a higher minimum melt viscosity than the other examples. Then, as can be seen from Examples 1, 6, and 7, a tendency to increase the dielectric loss tangent is observed as the content of component (B) in 100% by mass of non-volatile components increases.

[0148] In Comparative Examples 1 and 2, instead of component (B), a compound having an isocyanate ring structure and three allyl groups in one molecule was used as component (B'). The resin compositions of Comparative Examples 1 and 2 using the aforementioned compound showed poor film-forming properties. Furthermore, the resin compositions of Comparative Examples 1 and 2 exhibited higher dielectric loss tangent values.

[0149] In Comparative Examples 3-5, instead of component (B), a compound having a phenolic hydroxyl group and an allyl group in one molecule without an isocyanate ring structure was used as component (B'). In the evaluation of solder heat resistance, copper foil peeling was confirmed in the resin composition of Comparative Example 3. Furthermore, the copper foil in the copper foil peel strength measurement of the resin composition of Comparative Example 3 also peeled off, making it impossible to measure the copper foil peel strength. The resin compositions of Comparative Examples 4 and 5 showed higher dielectric loss tangent values. Also, the copper foil peel strength values ​​of the resin compositions of Comparative Examples 4 and 5 were lower, and the copper foil peeled off easily.

[0150] In Comparative Example 6, polyphenylene ether with terminal hydroxyl groups was used as component (A') instead of component (A). In the resin composition of Comparative Example 6, the film-forming component containing the resin composition was not cured, making it difficult to produce a cured resin film. Therefore, it was impossible to perform any evaluation or measurement other than film-forming property evaluation on the resin composition of Comparative Example 6. [Industry availability]

[0151] The resin composition of this invention can be used as an adhesive or a resin composition for bonding films in electronic components. Furthermore, the resin composition of this invention can also be used as an adhesive sheet or interlayer adhesive for multilayer wiring boards. Additionally, the resin composition of this invention can also be used as a prepreg made from a cured resin composition, or as a high-frequency electronic component having a cured resin composition.

[0152] 10: Multilayer wiring board 12,12a,12b,12c,12d,12e:Substrate 14: Conductor layer 16, 16a, 16b, 16c, 16d: Adhesive layer 22: Through hole 24: Fracture Z: Thickness direction

Claims

1. A resin composition comprising: (A) a polyphenylene ether resin having a functional group comprising a carbon-carbon double bond at its end; and (B) a resin composition comprising a compound having an isocyanate ring structure, two allyl groups, and an alkyl group having 4 to 14 carbon atoms in one molecule, and being liquid at 25°C, having a molecular weight of 300 to 400, and further comprising (E) a styrene-based thermoplastic elastomer having an average molecular weight of 30,000 or more, wherein 1 to 50% by mass of the non-volatile components in the aforementioned resin composition comprises the component (E) in 100% by mass.

2. A resin composition comprising: (A) a polyphenylene ether resin having a functional group comprising a carbon-carbon double bond at its end; and (B) a resin composition having a 1 molecule having an isocyanate ring structure and two allyl groups and an alkyl group having 4 to 14 carbon atoms, and being liquid at 25°C, having a molecular weight of 300 to 400, wherein the dielectric loss tangent of the cured resin composition at 10 GHz is less than 0.0020.

3. A resin composition comprising: (A) a polyphenylene ether resin having a functional group comprising a carbon-carbon double bond at the end; and (B) a resin composition comprising a compound having an isocyanate ring structure, two allyl groups and an alkyl group having 4 to 14 carbon atoms in one molecule, being liquid at 25°C, and having a molecular weight of 300 to 400, and further comprising (C) an inorganic filler, wherein the content of the aforementioned component (A) is 40 to 90 parts by mass relative to 100 parts by mass of the total resin composition, and the coefficient of thermal expansion in the thickness direction of the aforementioned cured product is less than 20 [10⁻⁵ / K].

4. The resin composition of any one of claims 1 to 3, wherein, Component (A) is a thermosetting resin.

5. The resin composition of any one of claims 1 to 3, wherein, The component (A) is polyphenylene ether as shown in the following general formula (1); [Compound 1] [Compound 2] [Compound 3] In the above general formula (1), R1, R2, R3, R4, R5, R6, and R7 may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups, halogenated alkyl groups, or phenyl groups; -(OXO)- is represented by the above structural formula (2), in which R8, R9, R10, R14, and R15 may be the same or different, and are halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups; R11, R12, and R13 may be the same or different, and are hydrogen atoms, halogen atoms, alkyl groups with 6 or fewer carbon atoms, or phenyl groups. -(YO)- is a random arrangement of one structure shown in the above structural formula (3) or two or more structures shown in the above structural formula (3). In the structural formula (3), R16 and R17 may be the same or different, and are halogen atoms, alkyl or phenyl with 6 or fewer carbon atoms. R18 and R19 may be the same or different, and are hydrogen atoms, halogen atoms, alkyl or phenyl with 6 or fewer carbon atoms. Z is an organic group with 1 or more carbon atoms, and may sometimes contain oxygen atoms, nitrogen atoms, sulfur atoms, or halogen atoms. At least one of a and b is not 0, and it represents an integer from 0 to 300. c and d represent integers 0 or 1.

6. The resin composition of any one of claims 1 to 3, wherein, The component (B) is a compound represented by the following general formula (4); [Compound 4] wherein, in the above general formula (4), the R series is an alkyl group with 4 to 14 carbon atoms.

7. The resin composition of any one of claims 1 to 3, wherein, The content of the aforementioned component (B) is 3 to 20 parts by mass relative to the total 100 parts by mass of the resin components.

8. The resin composition as claimed in claim 3, wherein, The non-volatile components in the resin composition contain more than 50% by mass of component (C) per 100% by mass.

9. The resin composition of any one of claims 1 to 3 further comprises a polymerization initiator (D) that initiates the polymerization of component (A) and component (B).

10. The resin composition of any one of claims 1 to 3 further comprises (F) polybutadiene.

11. The resin composition of any one of claims 1 to 3, wherein, The non-volatile components in the resin composition contain 15 to 90% by mass of component (A) per 100% by mass.

12. The resin composition of any one of claims 1 to 3, wherein, The component (B) comprises 10 to 70 parts by mass relative to 100 parts by mass of component (A).

13. The resin composition as claimed in claim 1 or 2, wherein, The coefficient of thermal expansion in the thickness direction of the aforementioned cured material is less than 20 [10-5 / K].

14. A printed circuit board having a cured layer composed of a resin composition as claimed in any one of claims 1 to 13.

15. A cured product, which is a cured product of the resin composition of any one of claims 1 to 13.

16. A prepreg made using a resin composition as claimed in any one of claims 1 to 13.

17. A high-frequency electronic component having a cured product as claimed in claim 15.

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