Resin composition, adhesive film, adhesive sheet for interlayer adhesive and resin composition for semiconductor package with antenna

Abstract

Provided is a resin composition having excellent welding heat resistance and low dielectric properties. The resin composition contains (A) a polyphenylene ether resin having a functional group having a carbon-carbon double bond at a terminal, and (B) a thermoplastic elastomer having a number average molecular weight of 60,000 or more.

Description

Technical Field

[0001] The present invention relates to a resin composition, an adhesive film, an adhesive sheet for interlayer bonding, and a resin composition for a semiconductor package with an antenna. Background Art

[0002] With the recent demand for faster transmission signals in printed wiring boards, transmission signals are becoming increasingly high-frequency, and therefore materials used in printed wiring boards are required to be able to reduce transmission loss in a high-frequency range, specifically, in a frequency range of 1 GHz or more.

[0003] As a resin composition used in an insulating layer of a printed wiring board, for example, a thermosetting resin composition is known, which contains a thermosetting resin having a styrene group at the end and a styrene-based thermoplastic elastomer (for example, Patent Document 1). For example, regarding the thermosetting resin composition disclosed in Patent Document 1, as a thermosetting resin having a styrene group at the end, a thermosetting resin having a styrene group at the end and having a phenylene ether skeleton is used. In addition, as a styrene-based thermoplastic elastomer, a low molecular weight styrene-based elastomer is used.

[0004] In addition, in recent years, as 5G is the next generation of communication technology, its standardization has been continuously developed, and the market demand for products that can support high frequencies has been increasing. The development of technologies such as multi-element antenna technology and high-speed transmission has been accelerated. In addition, due to the use of high-frequency bands, the communication capacity has also increased. While the information processing capacity has increased, the amount of high-frequency noise and heat generated has also increased, and its countermeasures have also become a major issue.

[0005] For example, in 5G millimeter wave antennas, regarding packaging technology, a structure is required to reduce conductor loss (in other words, less transmission loss) by shortening the wiring distance between the antenna and the IC. Therefore, in recent years, semiconductor packages with antennas have been developed in which the antenna part and the semiconductor device part are integrally formed (for example, Antenna-in-Package (AiP), Antenna-On-Package (AoP)). In such a package, due to the heat from the IC, the insulation layer around the antenna is also hotter than in previous structures, so even if it is placed in a high temperature environment, low dielectric loss is required. In addition, "IC" refers to an integrated circuit. Prior art literature Patent Literature

[0006] Patent Document 1: International Publication No. 2019 / 230531 Summary of the invention Technical problem to be solved by the invention

[0007] As described above, the resin composition disclosed in Patent Document 1 is a resin composition containing a thermosetting resin having a styrene group at the end and a styrene-based thermoplastic elastomer, and is considered to be a resin composition containing a thermosetting resin having a styrene group at the end and a styrene-based thermoplastic elastomer. On the other hand, soldering heat resistance is sometimes required for the insulating layer of a printed wiring board, but the resin composition disclosed in Patent Document 1 does not mention such soldering heat resistance.

[0008] The resin compositions used in the high frequency range described above are required to have excellent soldering heat resistance, low dielectric properties, etc., and there is an urgent need to develop resin compositions excellent in these various properties.

[0009] The present invention is an invention made in view of the problems of the prior art. The present invention provides a resin composition having excellent soldering heat resistance and low dielectric properties, and the resin composition can be applied to an adhesive film, an adhesive sheet for interlayer bonding, an interlayer adhesive, etc. Further, the present invention provides an adhesive film, an adhesive sheet for interlayer bonding, and a resin composition for a semiconductor package with an antenna using such a resin composition. Technical means to solve technical problems

[0010] According to the present invention, there are provided the following resin composition, adhesive film, adhesive sheet for interlayer bonding, and resin composition for a semiconductor package with an antenna.

[0011] [1] A resin composition comprising: (A) a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at a terminal, and (B) a thermoplastic elastomer having a number average molecular weight of 60,000 or more.

[0012] [2] The resin composition according to the above [1], wherein the component (A) contains a modified polyphenylene ether having a styrene structure at a terminal.

[0013] [3] The resin composition according to [1] or [2] above, wherein the component (A) contains a modified polyphenylene ether having a group represented by the following formula (1) at a terminal.

[0014] [Chemistry 1] (Wherein, in the formula (1), R 1 represents a hydrogen atom or an alkyl group. )

[0015] [4] The resin composition according to any one of [1] to [3] above, wherein the component (B) is a styrene-based thermoplastic elastomer.

[0016] [5] The resin composition according to the above [4], wherein the component (B) is a hydrogenated styrene-based thermoplastic elastomer.

[0017] [6] The resin composition according to [5] above, wherein the hydrogenated styrene-based thermoplastic elastomer of the component (B) is a styrene / ethylene / butylene / styrene block copolymer.

[0018] [7] The resin composition according to any one of [1] to [6] above, wherein the component (B) is a thermoplastic elastomer having a number average molecular weight of 100,000 or more.

[0019] [8] The resin composition according to any one of [1] to [7] above, wherein the mass ratio of the component (A) to the component (B) is 5:95 to 70:30.

[0020] [9] The resin composition according to any one of [1] to [8] above, wherein the content of the component (B) is greater than the content of the component (A).

[0021]

[10] The resin composition according to any one of [1] to [9] above, further comprising (C) an epoxy resin.

[0022]

[11] The resin composition according to

[10] above, wherein the content of the component (C) is 0.1 to 5.0 parts by mass relative to 100 parts by mass of the total of the component (A), the component (B), and the component (C) in the resin composition.

[0023]

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

[11] above, further comprising (D) a curing agent.

[0024]

[13] An adhesive film comprising the resin composition according to any one of [1] to

[12] above.

[0025]

[14] An interlayer adhesive sheet comprising the resin composition according to any one of [1] to

[12] .

[0026]

[15] A resin composition for a semiconductor package with an antenna, comprising the resin composition according to any one of [1] to

[12] above.

[0027]

[16] A laminate or a semiconductor device comprising a cured product of the resin composition according to any one of [1] to

[12] above. Beneficial Effects

[0028] The resin composition of the present invention achieves excellent soldering heat resistance and has the effect of low dielectric properties. Therefore, the resin composition of the present invention can be applied to adhesive films, interlayer adhesive sheets, interlayer adhesives, etc. In addition, the adhesive film of the present invention, the interlayer adhesive sheet, and the semiconductor package resin composition with antenna use the resin composition of the present invention, and achieve excellent soldering heat resistance and low dielectric properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] [ Figure 1 ] is a schematic partial cross-sectional view showing an example of a semiconductor package with an antenna. [ Figure 2 ] is a schematic partial cross-sectional view showing other examples of semiconductor packages with antennas. DETAILED DESCRIPTION

[0030] The following are embodiments of the present invention, but the present invention is not limited to the following embodiments. Therefore, it should be understood that, within the scope of the gist of the present invention, based on the common sense of those skilled in the art, the following embodiments are appropriately changed, improved, etc., and also belong to the scope of the present invention.

[0031] [Resin composition] One embodiment of the resin composition of the present invention is a resin composition comprising: (A) a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal, and (B) a thermoplastic elastomer having a number average molecular weight of 60,000 or more. Hereinafter, (A) the polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal is sometimes referred to as the (A) component. Similarly, (B) the thermoplastic elastomer having a number average molecular weight of 60,000 or more is sometimes referred to as the (B) component.

[0032] The resin composition of the present embodiment is a resin composition having excellent welding heat resistance and low dielectric properties. In particular, the resin composition of the present embodiment can effectively improve welding heat resistance while giving the resin composition low dielectric properties by including a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end as (A) component. In addition, by including a thermoplastic elastomer having a number average molecular weight of more than 60,000 as (B) component, the resin composition becomes difficult to melt, and welding heat resistance can be further improved.

[0033] In addition, the resin composition of the present embodiment may include other components such as (C) epoxy resin, (D) curing agent, (E) organic peroxide, (F) flame retardant, (G) filler, and (H) crosslinking agent in addition to the above-mentioned (A) component and (B) component. Hereinafter, each of the above-mentioned components may be appropriately referred to as (C) component to (H) component.

[0034] [(A) ingredient] (A) component is a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end. As the functional group containing a carbon-carbon double bond, for example, terminal vinyl, vinylidene (vinylene) or vinylidene (vinylidene) etc. can be cited. (A) component is not particularly limited as long as it has a functional group containing a carbon-carbon double bond at its end and there is polyphenylene ether in the skeleton. By including (A) component, it is possible to effectively improve the welding heat resistance while giving the resin composition low dielectric properties.

[0035] As the (A) component, for example, there can be mentioned a component (A) including a modified polyphenylene ether having a styrene structure at the end. Such a modified polyphenylene ether is not particularly limited as long as it has a styrene structure at its end. The styrene structure may be an unsubstituted styrene group having no substituent, or a styrene group having any substituent. By including such a (A) component, the welding heat resistance of the resin composition can be improved. In particular, the modified polyphenylene ether having a styrene structure at the end will undergo a curing reaction even without using peroxide, and will become a modified polyphenylene ether having extremely excellent welding heat resistance.

[0036] Examples of the modified polyphenylene ether having a styrene structure at the terminal used as the component (A) include compounds having a structure represented by the following general formula (2).

[0037] [Chemistry 2] [Chemistry 3] [Chemistry 4] [Chemistry 5]

[0038] In the above general formula (2), -(OXO)- is represented by the above structural formula (3) or (4).

[0039] In the structural formula (3), R 2 , R 3 , R 4 , R 7 and R 8 is an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same as or different from each other. 5 , R 6 and R 7 It is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and they may be the same as or different from each other.

[0040] In the structural formula (4), R10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and they may be the same or different from each other. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0041] In the general formula (2), -(YO)- is represented by the above structural formula (5). In -(YO)-, one structure or two or more structures are randomly arranged. In the structural formula (5), R 18 and R 19 is an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same as or different from each other. 20 and R 21 It is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and they may be the same as or different from each other.

[0042] In the general formula (2), a and b are integers of 0 to 100. At least one of a and b is not zero.

[0043] Examples of -A- in the structural formula (4) include divalent organic groups such as methylene, ethylene, 1-methylethylene, 1,1-propylene, 1,4-phenylenebis(1-methylethylene), 1,3-phenylenebis(1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, and 1-phenylethylene. However, -A- in the structural formula (4) is not limited to these.

[0044] As the compound represented by the general formula (2), R 2 , R 3 , R 4 , R 8 , R 9 , R 18 and R 19 is an alkyl group having 3 or less carbon atoms, R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 20 and R 21is a hydrogen atom or an alkyl group having 3 or less carbon atoms. In particular, it is more preferred that -(OXO)- represented by the structural formula (3) or the structural formula (4) is a compound represented by the following structural formula (6), structural formula (7), or structural formula (8). In addition, similarly, it is particularly preferred that -(YO)- represented by the structural formula (5) is a compound represented by the following structural formula (9) or structural formula (10), or a structure in which the compound represented by the structural formula (9) and the compound represented by the structural formula (10) are randomly arranged.

[0045] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] [Chemistry 10]

[0046] The method for producing the compound represented by the general formula (2) is not particularly limited. For example, the compound represented by the general formula (2) can be produced by the following method. First, a bifunctional phenol compound and a monofunctional phenol compound are subjected to oxidative coupling to obtain a bifunctional phenyl ether oligomer. Next, the terminal phenolic hydroxyl group of the obtained bifunctional phenyl ether oligomer is subjected to vinylbenzyl etherification. Thus, the compound represented by the general formula (2) can be produced.

[0047] The number average molecular weight of the compound represented by the general formula (2) is preferably 1,000 to 5,000, more preferably 1,000 to 3,000, and further preferably 1,000 to 2,500. If the number average molecular weight is 1,000 or more, it is not easy to produce stickiness when the resin composition is made into a coating film. In addition, if the number average molecular weight is 5,000 or less, the reduction in the solubility of the resin composition in the solvent can be effectively suppressed. In addition, by using a compound having a number average molecular weight within the above numerical range as component (A), the electrical properties and curability of the resin composition at high frequencies are improved. Here, the above number average molecular weight is a value based on a calibration curve based on standard polystyrene according to gel permeation chromatography (GPC).

[0048] As the component (A), the compound represented by the general formula (2) may be used alone, or two or more compounds represented by the general formula (2) may be used in combination.

[0049] Examples of the polyphenylene ether having a styrene structure at the terminal of the component (A) include trade names "OPE-2200" and "OPE-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0050] In addition, as the component (A), in addition to the component (A) including the modified polyphenylene ether having a styrene structure at the terminal (for example, the compound represented by the above general formula (2), etc.), there can also be mentioned the component (A) including the modified polyphenylene ether having a group represented by the following formula (1) at the terminal.

[0051] [Chemistry 11]

[0052] In the above formula (1), R 1 represents a hydrogen atom or an alkyl group. 1 The alkyl group is not particularly limited, and is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, hexyl, and decyl groups.

[0053] Examples of the group represented by formula (1) include an acrylate group and a methacrylate group.

[0054] The modified polyphenylene ether having a group represented by formula (1) preferably has a polyphenylene ether chain in the molecule, for example, has a repeating unit represented by the following structural formula (11) in the molecule.

[0055] [Chemistry 12]

[0056] In the above structural formula (11), m represents 1 to 50. In addition, R 22 ~R 25 They are independent of each other and can be the same or different from each other. 22 ~R 25 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among them, a hydrogen atom and an alkyl group are preferred.

[0057] In R 22 ~R 25 In the above, as each functional group listed, specifically, the following groups can be mentioned.

[0058] R 22 ~R 25 The alkyl group in is not particularly limited, and is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, hexyl, and decyl groups.

[0059] R 22 ~R 25 The alkenyl group in is not particularly limited, and is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Specific examples thereof include vinyl, allyl, and 3-butenyl.

[0060] R 22 ~R 25 The alkynyl group in is not particularly limited, and for example, an alkynyl group having 2 to 18 carbon atoms is preferred, and an alkynyl group having 2 to 10 carbon atoms is more preferred. Specific examples include ethynyl and prop-2-yn-1-yl (propargyl).

[0061] R 22 ~R 25 The alkylcarbonyl group in is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, and for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferred, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferred. Specifically, for example, acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, and cyclohexylcarbonyl groups can be cited.

[0062] R 22 ~R 25 The alkenylcarbonyl group in is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, and for example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specific examples include acryloyl, methacryloyl, and crotonoyl groups.

[0063] R 22 ~R 25 The alkynylcarbonyl group in is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, and for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specific examples thereof include propioloyl and the like.

[0064] As the modified polyphenylene ether having the group represented by the above formula (1), for example, a modified polyphenylene ether having the group represented by the above formula (1) at the end of a polyphenylene ether represented by the following formula (12) or formula (13) can be mentioned. As the modified polyphenylene ether, specifically, a modified polyphenylene ether represented by the following formula (14) or formula (15) can be mentioned.

[0065] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16]

[0066] In formulae (12) to (15), regarding s and t, for example, the total value of s and t is preferably 1 to 30. In addition, 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 total value of s and t represents 1 to 30. In formulae (12) to (15), Y represents an alkylene group having 1 to 3 carbon atoms or a direct bond, and examples of the alkylene group include dimethylmethylene and the like. In formulae (14) and (15), R 1 R in the above formula (1) 1 The same represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, for example, methyl, ethyl, propyl, hexyl, and decyl groups can be cited.

[0067] The number average molecular weight (Mn) of the modified polyphenylene ether having a group represented by formula (1) is not particularly limited. Specifically, it is preferably 500 to 5,000, more preferably 800 to 4,000, and further preferably 1,000 to 3,000. Here, the number average molecular weight can be any value measured by a conventional molecular weight measurement method, and specifically, a value measured using gel permeation chromatography (GPC) can be cited. In addition, in the case where the modified polyphenylene ether having a group represented by formula (1) has a repeating unit represented by formula (11) in the molecule, m is preferably a value such that the weight average molecular weight of the modified polyphenylene ether is within the above range. Specifically, m is preferably 1 to 50.

[0068] If the weight average molecular weight of the modified polyphenylene ether with the group shown in formula (1) is within the above numerical range, the heat resistance of the cured product is also excellent while having excellent dielectric properties from the polyphenylene ether, and further, the formability of the resin composition can be improved. For example, in the existing polyphenylene ether, if its weight average molecular weight is within the above numerical range, the molecular weight is relatively low, and there is a tendency that the heat resistance of its cured product is reduced. On the other hand, the modified polyphenylene ether with the group shown in the above formula (1) can improve the heat resistance of the cured product because it has the group represented by formula (1) at the end. In addition, since the weight average molecular weight of the modified polyphenylene ether can be made into a relatively low molecular weight, the formability is also excellent. Therefore, by using the (A) component of the modified polyphenylene ether with the group shown in formula (1) at the end, a resin composition having excellent heat resistance and excellent formability can be made.

[0069] In addition, the average number of groups represented by the above formula (1) possessed by each molecule of the modified polyphenylene ether used as the (A) component at the molecular end (the number of terminal functional groups) is not particularly limited. Specifically, it is preferably 1 to 5, more preferably 1 to 3, and further preferably 1.5 to 3. If the number of terminal functional groups is too small, there is a tendency that it is difficult to obtain sufficient heat resistance of the cured product. In addition, if the number of terminal functional groups is too large, the reactivity becomes too high, and undesirable conditions such as reduced storage stability of the resin composition and reduced fluidity of the resin composition may occur. That is, if such a modified polyphenylene ether is used, problems with formability may arise due to insufficient fluidity, for example, forming defects such as formation of voids occur during multilayer forming, and it is difficult to obtain a printed wiring board with high reliability.

[0070] Regarding the number of terminal functional groups of the above-mentioned modified polyphenylene ether, the numerical value represented by the following average value can be cited, and the average value is the average value of the group represented by the above formula (1) per molecule of all modified polyphenylene ethers present in 1 mol of modified polyphenylene ether. The number of terminal functional groups can be determined, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether and calculating the reduction compared with the number of hydroxyl groups of the polyphenylene ether before modification. The reduction compared with the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups. In addition, the method for determining the number of hydroxyl groups remaining in the modified polyphenylene ether can be obtained by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with the hydroxyl group to the solution of the modified polyphenylene ether and measuring the UV absorbance of the mixed solution.

[0071] In addition, the intrinsic viscosity of the modified polyphenylene ether used as (A) component is not particularly limited. Specifically, it is preferably 0.03-0.12dL / g, more preferably 0.04-0.11dL / g, and further preferably 0.06-0.095dL / g. If the intrinsic viscosity is too low, there is a tendency for the molecular weight to be low, and there is a tendency for low dielectric properties such as low dielectric constant or low dielectric loss tangent to be difficult to obtain. In addition, if the intrinsic viscosity is too high, there is a tendency for the viscosity to be high, sufficient fluidity to be unable to be obtained, and the formability of the cured product to be reduced. Therefore, if the intrinsic viscosity of the modified polyphenylene ether is within the above range, excellent heat resistance and formability of the cured product can be achieved.

[0072] The intrinsic viscosity is the intrinsic viscosity measured in dichloromethane at 25°C, and more specifically, for example, a value obtained by measuring a 0.18 g / 45 mL dichloromethane solution (liquid temperature 25°C) using a viscometer. Examples of such a viscometer include the product "AVS500 Visco System" manufactured by Schott.

[0073] The method for synthesizing the modified polyphenylene ether used as the component (A) is not particularly limited as long as a modified polyphenylene ether having a group represented by the above formula (1) at a terminal can be synthesized.

[0074] The component (A) may be a modified polyphenylene ether having a group represented by the above formula (1) at the terminal alone, or two or more modified polyphenylene ethers having a group represented by the above formula (1) at the terminal may be used in combination. Furthermore, it may be used in combination with one or more compounds represented by the above general formula (2).

[0075] As the modified polyphenylene ether having a group represented by the above formula (1) at the terminal of the component (A), there can be mentioned "Noryl SA9000" (trade name) manufactured by SABIC Japan.

[0076] In addition, from the viewpoint of excellent low dielectric properties and soldering heat resistance, the content of component (A) is preferably 5 to 70 parts by mass, more preferably 6 to 60 parts by mass, further preferably 7 to 50 parts by mass, and particularly preferably 8 to 40 parts by mass, relative to 100 parts by mass of the total of component (A), component (B), and component (B'). In addition, component (B') will be described later.

[0077] [(B) ingredient] The component (B) is a thermoplastic elastomer having a number average molecular weight of 60,000 or more. By including a thermoplastic elastomer having a number average molecular weight of 60,000 or more as the component (B), the resin composition becomes less likely to melt, and the welding heat resistance can be improved well. In addition, hereinafter, a thermoplastic elastomer other than the above-mentioned component (B), that is, a thermoplastic elastomer having a number average molecular weight of less than 60,000, is sometimes referred to as the component (B').

[0078] The number average molecular weight of the thermoplastic elastomer as component (B) is a value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene. In addition, when measuring the number average molecular weight in a film formed by a resin composition, for example, the film may be dissolved in a solvent and the number average molecular weight in the component dissolved in the solvent may be measured.

[0079] The number average molecular weight of the thermoplastic elastomer as component (B) is preferably 60,000 or more, more preferably 100,000 or more, further preferably 110,000 or more, and particularly preferably 120,000 or more. With such a number average molecular weight, the welding heat resistance is further improved. There is no particular restriction on the upper limit of the number average molecular weight of the thermoplastic elastomer as component (B). However, if the number average molecular weight of the thermoplastic elastomer becomes too large, there is a case where the thermoplastic elastomer becomes difficult to melt and the processability deteriorates. Therefore, the number average molecular weight of the thermoplastic elastomer as component (B) is preferably 200,000 or less, more preferably 150,000 or less, further preferably 140,000 or less, and particularly preferably 130,000 or less.

[0080] The thermoplastic elastomer as component (B) is not particularly limited, but is preferably a thermoplastic elastomer having a dielectric loss tangent (tan δ) of less than 0.005 in the range of frequency 1 GHz to 100 GHz. Thus, it is possible to contribute to the excellent dielectric properties of the thermosetting film formed by the resin composition of the present disclosure in the high frequency range. As "a thermoplastic elastomer having a dielectric loss tangent (tan δ) of less than 0.005 in the range of frequency 1 GHz to 100 GHz", it is preferably a styrene-based thermoplastic elastomer, and more preferably a hydrogenated styrene-based thermoplastic elastomer. Here, the hydrogenated styrene-based thermoplastic elastomer refers to a hydrogenated styrene-based thermoplastic elastomer, and as a hydrogenated styrene-based thermoplastic elastomer, for example, styrene / butadiene / butylene / styrene block copolymer (partially hydrogenated, SBBS) or styrene / ethylene / butylene / styrene block copolymer (completely hydrogenated, SEBS) can be cited. By using a hydrogenated styrene-based thermoplastic elastomer, the dielectric properties can be improved. When the component (B) is a styrene-based thermoplastic elastomer, the styrene ratio of the component (B) is preferably 10% to 70%, more preferably 15% to 60%. When the styrene ratio of the component (B) is 20% to 50%, excellent film-forming properties and processability are achieved.

[0081] The hydrogenated styrene thermoplastic elastomer of (B) component is not particularly limited, but preferably styrene / ethylene / butylene / styrene block copolymer (SEBS). Styrene / ethylene / butylene / styrene block copolymer (SEBS) is a styrene thermoplastic elastomer that is fully hydrogenated. Since it is a styrene thermoplastic elastomer without double bonds, it is possible to further improve dielectric properties. In addition, by using a styrene / ethylene / butylene / styrene block copolymer (SEBS) having a number average molecular weight of more than 60,000, not only dielectric properties are good, but also welding heat resistance can be improved simultaneously. Further, by using styrene / ethylene / butylene / styrene block copolymer (SEBS) as (B) component, when the resin composition is filmized, the film becomes difficult to curl. In addition, as other preferred examples of the hydrogenated styrene thermoplastic elastomer of (B) component, styrene / ethylene / ethylene / propylene / styrene block copolymer (SEEPS) can be cited.

[0082] About the content of (B) component, there is no particular restriction, but preferably the mass ratio of (A) component to (B) component ((A) component: (B) component) is 5:95~70:30, more preferably 10:90~67:33, further preferably 20:80~60:40, and particularly preferably 25:75~40:60. In addition, from the viewpoint of welding heat resistance, the content of (B) component is preferably more than the content of (A) component. However, if the ratio of (B) component excessively becomes more, when the resin composition is filmized, sometimes viscosity is easily generated on the film, and there is a situation where processability is reduced. In addition, if the ratio of (B) component becomes more, there is also a situation where the dielectric properties of the resin composition deteriorate, so it is preferably in the above range.

[0083] In addition, when the amount of the resin composition other than the filler is set to 100 parts by mass, the content of the component (B) is preferably 20 to 95 parts by mass, more preferably 30 to 93 parts by mass, and further preferably 35 to 80 parts by mass. By keeping it within this range, the soldering heat resistance is excellent while maintaining the low dielectric properties.

[0084] The resin composition of the present embodiment may contain a plurality of thermoplastic elastomers as the (B) component. As the (B) component, a plurality of thermoplastic elastomers having a number average molecular weight of 60,000 or more may be contained. In addition, the resin composition of the present embodiment may contain a thermoplastic elastomer having a number average molecular weight of less than 60,000 ((B') component) as a thermoplastic elastomer other than the (B) component. In addition, when the resin composition of the present embodiment contains a plurality of thermoplastic elastomers, it is preferred that the content (by mass) of the thermoplastic elastomer having a number average molecular weight of 60,000 or more is greater than the content of the thermoplastic elastomer having a number average molecular weight of less than 60,000.

[0085] Examples of the thermoplastic elastomer having a number average molecular weight of 60,000 or more as the component (B) include trade names "Cepton 8004", "Cepton 8006" and "Cepton V9461" manufactured by CLARE Corporation.

[0086] [(C) ingredient] Component (C) is an epoxy resin. Epoxy resin is a compound having one or more epoxy groups in the molecule, and the epoxy groups react by heating to form a three-dimensional network structure and can be cured. By containing epoxy resin as component (C), it is possible to further improve the welding heat resistance. In addition, by containing epoxy resin as component (C), even if the adherend is relative to a smooth surface such as the glossy surface of copper, it is possible to improve the adhesion.

[0087] The content of the epoxy resin of the component (C) is not particularly limited, but is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 4.0 parts by mass, and further preferably 0.7 to 3.0 parts by mass, relative to 100 parts by mass of the total of the components (A), (B) and (C). If the content of the component (C) is too high, the dielectric loss tangent of the cured product may become high.

[0088] The content of the component (C) is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, and even more preferably 0.6 to 2.0 parts by mass, based on 100 parts by mass of the resin composition excluding the filler.

[0089] Specific examples of epoxy resins include bisphenol compounds such as bisphenol A, bisphenol E, bisphenol F, or their derivatives (e.g., alkylene oxide adducts), hydrogenated bisphenol A, hydrogenated bisphenol E, hydrogenated bisphenol F, diols having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, or their derivatives, and aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, or their derivatives. The present invention can be used as a bifunctional epoxy resin obtained by epoxidizing phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, etc.; trifunctional epoxy resin having a trihydroxyphenylmethane skeleton and an aminophenol skeleton; polyfunctional epoxy resin obtained by epoxidizing phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, etc., but is not limited to these. Preferably, bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol type epoxy resin. The compounds exemplified here can be used alone or in combination of two or more.

[0090] The epoxy resin of the component (C) is preferably in a liquid state at room temperature (25° C.).

[0091] [(D) ingredient] (D) component is a curing agent. The curing agent of component (D) is not particularly limited as long as it is a curing agent that generally cures epoxy resins. Regarding the curing agent in the present application, a curing catalyst that promotes the reaction of epoxy resins is also included in the curing agent. There are no particular restrictions on the curing agent, but since the curability can be appropriately adjusted, an imidazole-based curing catalyst is more preferred.

[0092] The imidazole curing catalyst may be imidazole, or imidazole adducts, inclusion imidazoles, microcapsule-type imidazoles, imidazole compounds obtained by coordinating stabilizers, etc. These have nitrogen atoms with non-shared electron pairs in their structures, which can activate epoxy groups and other epoxy resins used in combination, thereby promoting curing.

[0093] Specific examples of the imidazole curing catalyst include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methyl, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, trimellitic acid 1-cyanoethyl-2-undecylimidazole, trimellitic acid 1-cyanoethyl-2-phenylimidazole, 2,4-diamino The present invention includes, but is not limited to, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-undecylimidazolyl-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-ethyl-4-methylimidazolyl-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 1-cyanoethyl-2-phenyl-4,5-bis(2-cyanoethoxy)methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Imidazoles treated with addition, inclusion, microencapsulation or coordination with stabilizers are modified imidazoles. They are treated with addition, inclusion, microencapsulation or coordination with stabilizers to reduce the activity of imidazoles, thereby showing excellent pot life in a low temperature range and high curing and curing acceleration capabilities.

[0094] In addition, as commercially available products of imidazole (hereinafter referred to as trade names), 2E4MZ, 2P4MZ, 2PZ-CN, C11Z-CNS, C11Z-A, 2MZA-PW, 2MA-OK, 2P4MHZ-PW, 2PHZ-PW (all manufactured by Shikoku Chemical Industry Co., Ltd.), EH2021 (manufactured by ADEKA Co., Ltd.), etc. can be cited, but they are not limited to these. As commercially available products of imidazole adducts, for example, PN-50, PN-50J, PN-40, PN-40J, PN-31, PN-23, PN-H (all manufactured by Ajinomoto Ficinone Co., Ltd.) having a structure formed by ring-opening addition of an imidazole compound to an epoxy group of an epoxy resin can be cited, but they are not limited to these. As commercially available products of inclusion imidazole, for example, TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, NIPA-2E4MZ (above, manufactured by Nippon Soda Co., Ltd.), etc. can be cited, but it is not limited to these. As commercially available products of microcapsule type imidazole, for example, Novacura HX3721, HX3722, HX3742, HX3748 (above, manufactured by Asahi Kasei Co., Ltd.), LC-80 (above, manufactured by A&C Catalysts Co., Ltd.), etc. can be cited.

[0095] The content of curing agent can be appropriately selected according to the type of curing agent used as (D) component. In addition, when the amount of the resin composition except filler is set to 100 mass parts, the content of (D) component is preferably 0.001 mass part ~ 1.0 mass part, more preferably 0.005 mass part ~ 0.60 mass part. In addition, relative to epoxy resin, the content of imidazole curing catalyst is preferably 0.1 mass % ~ 10 mass %, more preferably 1 mass % ~ 6 mass %. If the content of (D) component is too little, the curability of the film made using the resin composition may deteriorate, and adhesion, toughness, heat resistance may be reduced. On the other hand, if the content of (D) component is too much, the shelf life of the film made using the resin composition may deteriorate, and in addition, the physical properties inherent to the resin in the cured product may be damaged, and adhesion, toughness, heat resistance may be reduced.

[0096] [(E) ingredient] (E) component is an organic peroxide. By containing such an organic peroxide, the reaction start temperature of the (A) component moves to the low temperature side, promoting the curing of the resin composition. Therefore, the soldering heat resistance of the resin composition is further improved. The content of the organic peroxide can be appropriately selected according to the type, but representatively, relative to 100 parts by mass of the (A) component, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass.

[0097] As the organic peroxide, diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide; peroxyketals such as 2,2-bis(4,4-di-(di-tert-butylperoxy)cyclohexyl)propane; peroxydicarbonates such as isopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(1-methylheptyl) peroxydicarbonate, di(3-methoxybutyl) peroxydicarbonate, and dicyclohexyl peroxydicarbonate; tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, and peroxy Peroxyesters such as tert-butyl pivalate, tert-butyl diperoxyadipate, isopropyl peroxyneodecanoate, tert-butyl perbenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; di-tert-butyl peroxide, diisopropyl peroxide, tert-butyl isopropyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, di(2-tert-butylperoxyisopropyl)benzene; hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, terpane hydroperoxide, etc. The organic peroxide used is not particularly limited, but when curing the resin composition, for example, a drying step at about 60° C. to 80° C. is often required, so it is preferred to use an organic peroxide having a 10-hour half-life temperature of 100° C. to 140° C. Furthermore, an organic peroxide having a 10-hour half-life temperature of 110° C. to 130° C. is more preferred.

[0098] Examples of commercially available organic peroxides (hereinafter referred to as trade names) of the component (E) include Bade H, Bade Z,パーブチパークミルP, パークミルD, パークミルH, パーヘキサC (the above, manufactured by NOF Chemical Co., Ltd.), etc.

[0099] [(F)INGREDIENT] (F) component is a flame retardant. The flame retardant as (F) component is any component suitably contained within the scope of the effect of the resin combination of the present embodiment described before without damaging. For example, in the resin combination used in the insulating layer of a printed wiring board, in addition to the soldering heat resistance and low dielectric properties described before, flame retardancy is sometimes required. For such requirements, by further containing a flame retardant as (F) component, it is possible to contribute to improving the flame retardancy of the cured product consisting of the resin combination of the present embodiment.

[0100] There is no particular limitation on the type of flame retardant. For example, as the flame retardant of component (F), inorganic phosphorus flame retardants, organic phosphorus flame retardants, aluminum hydroxide hydrates, magnesium hydroxide hydrates and other metal hydrates can be cited. As the flame retardant of component (F), one type can be used alone, or two or more types can be used in combination.

[0101] Examples of the inorganic phosphorus flame retardant include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide; phosphoric acid; and phosphine oxide.

[0102] Examples of organic phosphorus flame retardants include phosphate flame retardants, monosubstituted phosphonic acid diesters and disubstituted phosphinates; metal salts of disubstituted phosphinates, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc. Examples of "metal salts" include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, zinc salts, etc.

[0103] The content of the flame retardant can be appropriately selected according to the type of the flame retardant used as (F) component. In addition, when the amount of the resin composition other than the filler is set to 100 parts by mass, the content of the (F) component is preferably 15 to 50 parts by mass, more preferably 20 to 40 parts by mass. In addition, as the flame retardant of the (F) component, metal phosphinate (for example, the trade name "OP-935" manufactured by Clariant Japan) etc. can be cited.

[0104] [(G) ingredient] The component (G) is a filler. There are no particular restrictions on the type of filler used as the component (G), and examples thereof include known inorganic fillers. The filler used as the component (G) is required to have insulating properties and a low thermal expansion coefficient.

[0105] As the inorganic filler material of component (G), general inorganic fillers can be used. For example, as the inorganic filler, silicon dioxide, aluminum oxide, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, calcium sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride, etc. can be cited. The inorganic filler can be used alone or in combination of two or more. In particular, from the viewpoint of insulation, silica fillers and aluminum oxide fillers are preferred. In addition, from the viewpoint of dielectric properties, silica fillers are preferred. The inorganic filler can be surface treated with a silane coupling agent having one or more functional groups selected from acrylic acid groups, methacrylic acid groups, styryl groups, amino groups, epoxy groups, and vinyl groups. For example, inorganic fillers are preferably surface treated with surface treatment agents such as aminosilane coupling agents, urea silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, silane coupling agents, vinyl silane coupling agents, styryl silane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, organic silazane compounds, titanate coupling agents, so as to improve their heat resistance, moisture resistance, and dispersibility. They can be used in one or in combination of two or more. More preferably, in the surface-treated silica filler, it is preferred to use a silica filler surface-treated with a vinyl silane coupling agent. By using a silica filler surface-treated with a vinyl silane coupling agent, the thermal expansion coefficient can be made good.

[0106] The shape of the inorganic filler is not particularly limited, and spherical, flaky, needle-shaped, irregular shapes, etc. can be cited. From the viewpoint of processability, a spherical shape is preferred. The average particle size is preferably 0.1 μm to 10 μm, and more preferably 0.1 μm to 4 μm. When the average particle size of the inorganic filler is within this range, the embedding property between the fine structures is excellent. The average particle size is the particle size at which the cumulative value in the particle size distribution based on volume is 50% as measured by a laser diffraction scattering method. The average particle size can be measured, for example, by a laser diffraction scattering particle size distribution measuring device: LS13320 (manufactured by Beckman Colter, wet type).

[0107] In addition, when the (G) component is contained, the content of the (G) component is preferably 0.1 to 90 parts by mass, more preferably 20 to 85 parts by mass, further preferably 30 to 80 parts by mass, and particularly preferably 50 to 80 parts by mass, relative to 100 parts by mass of the non-volatile components in the resin composition. By constituting in this way, the thermal expansion coefficient can be well improved.

[0108] [(H) ingredient] (H) component is a cross-linking agent. By containing a cross-linking agent as component (H), cracking of the film formed by the resin composition can be effectively prevented. In addition, by cross-linking with the polyphenylene ether resin as component (A), further improvement of the soldering heat resistance of the resin composition can be expected.

[0109] As the cross-linking agent of the (H) component, for example, polybutadiene, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl isocyanurate, 2,2'-diallyl bisphenol A, etc. can be used. Among these cross-linking agents, it is preferred to use a cross-linking agent having an isocyanuric acid ring structure and two allyl groups in one molecule. The cross-linking agent of the (H) component can improve the welding heat resistance while having two allyl groups, while having low dielectric properties. Although the detailed reason is unclear, it is speculated that since the (H) component has an isocyanuric acid ring structure, the heat resistance of the resin composition is improved. In addition, the (H) component can be a compound having an isocyanuric acid ring structure and two allyl groups in one molecule. As a result, while the dielectric properties are low, the welding heat resistance is good, and further better film forming properties can be obtained, so that it can be easily filmized. In addition, the (H) component can be a liquid compound at 25°C.

[0110] Furthermore, the component (H) may be a flame retardant crosslinking agent, which is a crosslinking agent for the polyphenylene ether resin as the component (A) and also imparts flame retardancy. For example, a flame retardant crosslinking agent having an isocyanuric acid ring structure and two allyl groups in one molecule and a phosphorus-based substituent at the end may be used. Thus, it can be crosslinked with the polyphenylene ether resin as the component (A), thereby improving the soldering heat resistance of the resin composition and imparting flame retardancy.

[0111] Furthermore, the component (H) is preferably a compound represented by the following general formula (16).

[0112] [Chemistry 17]

[0113] In the above general formula (16), R is an alkyl group having 4 to 14 carbon atoms, preferably an alkyl group having 8 to 14 carbon atoms, and particularly preferably an alkyl group having 10 to 12 carbon atoms. In addition, R may be a phosphorus-based substituent.

[0114] Relative to 100 parts by mass of (A) component, the content of (H) component is preferably 10 parts by mass to 70 parts by mass. By constituting in this way, while the dielectric properties are low, the welding heat resistance can be improved. In addition, although not particularly limited, relative to 100 parts by mass of (A) component, the content of (H) component is more preferably 15 parts by mass to 65 parts by mass, and further preferably 20 parts by mass to 60 parts by mass. In addition, in the non-volatile component 100% by mass in the resin composition, it is preferred to contain 2% by mass to 50% by mass of (H) component, more preferably 3% by mass to 40% by mass, and particularly preferably 4% by mass to 30% by mass. If the content ratio of (H) component in 100% by mass of the non-volatile component in the resin composition is within this range, the dielectric properties of the resin composition are excellent. In addition, the content ratio of (H) component in the non-volatile component can be measured, for example, by methods such as infrared spectrophotometer (FTIR) or gas chromatography-mass spectrometry. In addition, if the number average molecular weight of the thermoplastic elastomer of the component (B) becomes too large, there is a situation where the thermoplastic elastomer becomes difficult to melt and the workability deteriorates. However, by containing a compound having an isocyanuric acid ring structure and two allyl groups in one molecule and being liquid at 25°C, even when a thermoplastic resin with a large molecular weight is used, the melt viscosity of the resin composition can be reduced and filmization can be easily performed. In addition, for example, when 50 parts by mass or more of the (G) filler is added relative to 100 parts by mass of the non-volatile component in the resin composition, there is a situation where the cured resin composition tends to become brittle and cracks are generated when the resin composition is filmized. For this, by adding the (H) component in the above range, the generation of cracks when the resin composition is filmized can be suppressed. Furthermore, by adding the (H) component in the above range, when the resin composition is filmized, the curling property described later can be suppressed. From the above viewpoints, the amount of the component (H) is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, further preferably 5 to 20 parts by mass, and particularly preferably 7 to 15 parts by mass, relative to 100 parts by mass of the filler (G).

[0115] As the component (H), the compound having an isocyanuric acid ring structure and two allyl groups in one molecule and being liquid at 25° C. may be exemplified by the trade name “L-DAIC” manufactured by Shikoku Chemicals Co., Ltd. Also, as a flame retardant crosslinking agent having an isocyanuric acid ring structure and two allyl groups in one molecule and having a phosphorus-based substituent at the terminal, the trade name “P-DAIC” manufactured by Shikoku Chemicals Co., Ltd. may be exemplified.

[0116] [Other ingredients] The resin composition of the present embodiment may further contain components other than the components (A) to (H) described above. For example, various additives such as colorants, dispersants, silane coupling agents, antioxidants, and rheology control agents are mentioned as other components.

[0117] [Method for producing resin composition] The resin composition of the present embodiment can be produced by a conventional method. The resin composition of the present embodiment can be produced by mixing the components described above using, for example, a grinder, a pot mill, a three-roll mill, a rotary mixer, a twin-shaft mixer, or the like.

[0118] [Application of resin composition] The resin composition of the present embodiment can be preferably used as a resin composition for adhesive films used in electronic components. In addition, the resin composition of the present embodiment can also be preferably used as an interlayer bonding sheet or interlayer adhesive for multilayer substrates. When the resin composition of the present embodiment is used for various purposes of electronic components, there is no particular limitation on the electronic components to be bonded, and ceramic substrates, organic substrates, semiconductor chips, semiconductor devices, etc. can be cited.

[0119] The adhesive film, interlayer adhesive sheet, and interlayer adhesive using the resin composition of the present embodiment are contained in a laminate or semiconductor device constituting an electronic component as a cured product of the resin composition. Therefore, the laminate or semiconductor device constituting an electronic component preferably contains a cured product of the resin composition of the present embodiment.

[0120] In addition, the resin composition of the present embodiment can also be used as a resin composition for making a semiconductor package with an antenna (resin composition for a semiconductor package with an antenna). In addition, the details of the semiconductor package with an antenna will be described later. In such a semiconductor package with an antenna, the resin composition of the present embodiment can preferably be used as a resin composition for connecting the semiconductor device part and the antenna part, or for forming an insulating layer inside the antenna part.

[0121] [Semiconductor package with antenna] Next, an embodiment of a semiconductor package with an antenna is described. One embodiment of a semiconductor package with an antenna is as follows Figure 1 A semiconductor package 100 with an antenna is shown. Figure 1 is a schematic partial cross-sectional view showing an example of a semiconductor package with an antenna.

[0122] like Figure 1As shown, the semiconductor package 100 with an antenna has an antenna portion 5 integrally formed in the semiconductor device portion 10, and is particularly a semiconductor package 100 with an antenna as a high-frequency substrate on which an RF (radio frequency) chip 8 for transmitting and receiving 5G millimeter-wave communications is mounted. In the semiconductor device portion 10, the antenna portion 5 is connected to the RF chip 8 for millimeter-wave communications via a wiring layer 4 having various wiring patterns.

[0123] Figure 1 The semiconductor device portion 10 in the semiconductor package 100 with an antenna shown includes: a core substrate 2, an antenna portion 5 provided on one surface side of the semiconductor device portion 10, an insulating layer 1 (first insulating layer 1A) for connecting the semiconductor device portion 10 and the antenna portion 5, a wiring layer 4 of a multilayer structure arranged in the core substrate 2, and an insulating layer 1 (second insulating layer 1B, third insulating layer 1C, fourth insulating layer 1D, fifth insulating layer 1E) configured in a manner covering the wiring through-holes in the wiring layer 4. In addition, the first insulating layer 1A is not only provided in a manner interposed between the semiconductor device portion 10 and the antenna portion 5, but can also be provided in a manner extending to the inside of the antenna portion 5.

[0124] In the semiconductor package 100 with an antenna, on the other surface side of the semiconductor device portion 10, one portion of the wiring layer 4 is connected to the RF chip 8 for transmitting and receiving millimeter-wave communications, while the other portion of the wiring layer 4 is connected to the electrical connection metal 7. Figure 1 In the example shown, the wiring layer 4 and the RF chip 8 are electrically connected via hemispherical connection pads 9. The electrical connection metal 7 is a terminal portion for physically and / or electrically connecting the semiconductor package 100 with an antenna to the outside via the electrical connection metal 7 in combination with its function.

[0125] The insulating layer 1 suppresses the attenuation of the current or millimeter wave signal output from the RF chip 8 during transmission, and transmits it to the antenna unit 5 and radiates it effectively into space, so it is required to reduce the loss (transmission loss) of the connection portion connecting the antenna unit 5 and the RF chip 8. Similarly, during reception, in order to suppress the attenuation of the reflected wave of the millimeter wave signal received by the antenna unit 5 and transmit it to the RF chip 8 as the receiving unit, it is required to reduce the loss (transmission loss) of the connection portion connecting the antenna unit 5 and the RF chip 8.

[0126] The antenna portion 5 is provided on one surface side of the semiconductor device portion 10 as a patch antenna that is a planar antenna.

[0127] The semiconductor package 100 with an antenna has a particularly main feature in terms of the structure of at least one of the insulating layer 1 (for example, the first insulating layer 1A) for connecting the semiconductor device portion 10 and the antenna portion 5, and the insulating layer 1 inside the antenna portion 5. The structure of the insulating layer 1 in the semiconductor package 100 with an antenna of this embodiment will be described in more detail below. In addition, below, the insulating layer 1 for connecting the semiconductor device portion 10 and the antenna portion 5, and the insulating layer 1 inside the antenna portion 5 are sometimes simply collectively referred to as "insulating layer 1".

[0128] In the semiconductor package 100 with an antenna, at least one insulating layer 1 is composed of a cured product of a resin composition, and the resin composition is composed in the same manner as the resin composition of the present invention described above. That is, the cured product constituting the insulating layer 1 is a cured product of a resin composition comprising a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal as component (A), and a thermoplastic elastomer having a number average molecular weight of 60,000 or more as component (B).

[0129] The semiconductor package 100 with an antenna equipped with the insulating layer 1 constructed in the above manner has excellent soldering heat resistance and low dielectric properties. In the semiconductor package 100 with an antenna equipped with the antenna part 5 for 5G millimeter waves, for example, there is a case where the insulating layer 1 for connecting the antenna part 5 is subjected to a soldering test at 288°C, requiring soldering heat resistance at a heat-resistant temperature that was not previously required. The insulating layer in the conventional semiconductor package uses a well-known high-frequency film, but there are films that do not satisfy the above-mentioned soldering heat resistance among such high-frequency films, including many films that cannot be used for the semiconductor package 100 with an antenna equipped with the antenna part 5 for 5G millimeter waves. In the semiconductor package 100 with an antenna of the present embodiment, for the cured product constituting the insulating layer 1, it is preferred that the dielectric loss tangent (tanδ) measured at a frequency of 10 GHz by the SPDR (separated pillar dielectric resonator) method is less than 0.0020, and the soldering heat resistance is 290°C for more than 2 minutes.

[0130] The insulating layer 1 can be obtained by heat curing the resin composition containing the above-mentioned (A) component and (B) component. The resin composition for forming the insulating layer 1 is a resin composition constructed in the same manner as the resin composition of the present invention described above. In addition to the already described (A) component and (B) component, the resin composition may further contain any other component among the (C) component to the (H) component, and other components other than these.

[0131] The semiconductor package 100 with an antenna of the present embodiment is excellent in soldering heat resistance and dielectric properties, and therefore is preferably used as a semiconductor package on which an RF (radio frequency) chip 8 for performing 5G millimeter wave transmission and reception communications is mounted.

[0132] In a semiconductor package 100 with an antenna, a first insulating layer 1A for connecting a semiconductor device portion 10 and an antenna portion 5, and a second insulating layer 1B, a third insulating layer 1C, a fourth insulating layer 1D and a fifth insulating layer 1E which are formed in a manner covering wiring through holes in a wiring layer 4 are preferably formed in the same manner as the insulating layer 1 formed of a cured material as described previously.

[0133] Next, the method for manufacturing the insulating layer 1 in the semiconductor package 100 with an antenna is not particularly limited, and for example, the following method may be mentioned.

[0134] First, a resin composition for a semiconductor package with an antenna is prepared, which contains at least components (A) and (B). Hereinafter, the "resin composition for a semiconductor package with an antenna" is sometimes referred to as the "resin composition". From the viewpoint of operability, the resin composition is preferably in a film-like form. The film for a semiconductor package with an antenna can be obtained, for example, by applying a solution obtained by adding an organic solvent to a resin composition containing components (A) and (B) to a release-treated PET film as a support, and drying it at 80°C to 130°C. The obtained film for a semiconductor package with an antenna is peeled off from the support, attached to the semiconductor device part 10, and heat-treated at, for example, 200°C for 30 minutes to 60 minutes, thereby making a semiconductor package with an antenna.

[0135] The structure of the wiring layer 4 and the like in the semiconductor device portion 10 in the semiconductor package 100 with an antenna is not limited to Figure 1 The structure shown can be applied to various semiconductor packages equipped with 5G millimeter wave antennas. For example, Figure 2 is a schematic partial cross-sectional view showing another example of a semiconductor package with an antenna.

[0136] Figure 2 The semiconductor package 200 with antenna shown has antenna units 25 and 26 integrally formed in a semiconductor device unit 30. In the semiconductor device unit 10, the antenna units 25 and 26 are connected to an RF chip 28 that performs millimeter wave communication via a wiring layer 24 having various wiring patterns.

[0137] The semiconductor device unit 30 has a core substrate 22, an antenna unit 25 provided on one surface side of the semiconductor device unit 30, and an insulating layer 21 for connecting the semiconductor device unit 30 and the antenna unit 25. The core substrate 22 contains an RF chip 28 for transmitting and receiving 5G millimeter waves, and wiring is performed through a wiring layer 24 configured in the core substrate 22. Antenna units 26 as dipole antennas are provided at both ends of the semiconductor device unit 30, and the dipole antennas are symmetrically arranged with straight wires (elements). The other surface side of the semiconductor device unit 30 is connected to an electrical connection metal 27, and the electrical connection metal 27 is used to physically and / or electrically connect the semiconductor package 200 with an antenna to the outside.

[0138] exist Figure 2 In the semiconductor package 200 with antenna shown in FIG. 1 , the insulating layer 21 is made into a cured product containing the following resin composition: a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal as component (A) and a thermoplastic elastomer having a number average molecular weight of 60,000 or more as component (B), thereby having excellent soldering heat resistance and low dielectric properties. The cured product used as the insulating layer 21 can be used in the same manner as used as the Figure 1 The cured product is constructed in the same manner as the cured product of the insulating layer 1 of the semiconductor package 100 with an antenna shown. Example

[0139] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0140] (Example 1 to Example 20, Comparative Example 1 to Comparative Example 2) [Sample production] After each component was weighed and mixed according to the mixing ratio (mass parts) shown in Tables 1 to 4 below, they were put into a reactor heated to 80°C and rotated at 150 rpm while mixing under normal pressure for 4 hours. When a curing agent of component (D) and / or an organic peroxide of component (E) were added, the curing agent of component (D) and / or the organic peroxide of component (E) were added after cooling. In the above manner, varnishes containing the resin compositions of Examples 1 to 20 and Comparative Examples 1 to 2 were prepared.

[0141] The raw materials used in the preparation of the resin compositions in Examples 1 to 20 and Comparative Examples 1 and 2 are as follows: The number average molecular weights (Mn) of the components (A), (B) and (B') were determined by chromatography.

[0142] [Component (A): polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal] (A1): a polyphenylene ether resin having a methacrylic acid group at the terminal, manufactured by SABIC Japan Co., Ltd., trade name “Noryl SA9000”, number average molecular weight (Mn): 1,700. (A2): a polyphenylene ether resin having a styrene group at the end, manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "OPE-2200", number average molecular weight (Mn): 2,200. (A3): a polyphenylene ether resin having a styrene group at the terminal, manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "OPE-1200", number average molecular weight (Mn): 1,200.

[0143] [Component (B): thermoplastic elastomer having a number average molecular weight of 60,000 or more] (B1): Styrene-based elastomer (SEBS (styrene ratio: 31%)), manufactured by Kuraray Co., Ltd., trade name: "Septone 8004", number average molecular weight (Mn): 76,495. (B2): Styrene-based elastomer (SEBS (styrene ratio: 33%)), manufactured by Kuraray Co., Ltd., trade name: "Septone 8006", number average molecular weight (Mn): 125,769. (B3): Styrene-based elastomer (SEEPS (styrene ratio: 30%)), manufactured by Kuraray Co., Ltd., trade name: "SEEPS V9461", number average molecular weight (Mn): 129,783.

[0144] [Component (B'): thermoplastic elastomer having a number average molecular weight of less than 60,000] (B'4): Styrene-based elastomer (SEBS (styrene ratio: 30%)), manufactured by CLETON Corporation, trade name "G1652", number average molecular weight (Mn): 53,864. (B'5): Styrene-based elastomer (SEEPS-OH (styrene ratio: 28%)), manufactured by Kuraray Co., Ltd., trade name "HG-252", number average molecular weight (Mn): 54,029.

[0145] [Component (C): epoxy resin] (C1): Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, trade name "828EL". (C2): Novolac type epoxy resin, manufactured by Nippon Chemical Industries, Ltd., trade name “EPPN-502H”.

[0146] [Component (D): Curing agent] (D1): Made by ADEKA, trade name “EH2021”. [Ingredient (E): organic peroxide] (E1): manufactured by NOF Chemical Co., Ltd., trade name: "Parbular Z". (E2): Manufactured by NOF Chemical Co., Ltd., trade name "Balconium D". [(F) ingredient: flame retardant] (F1): Manufactured by クラリアントジャパン Co., Ltd., trade name "OP935". [(G) Component: Filler] (G1): Spherical silica surface-treated with an aminosilane coupling agent, manufactured by Advantex Corporation, trade name “SC4050SX”, average particle size 1.0 μm. [Component (H): cross-linking agent] (H1): Manufactured by Shikoku Chemical Industry Co., Ltd., trade name "L-DAIC". (H2): Manufactured by Shikoku Chemical Industry Co., Ltd., trade name "P-DAIC".

[0147] The "Raw Material Ratio" column of Tables 1 to 4 shows the ratio of the raw materials used in the preparation of the resin composition in Examples 1 to 17 and Comparative Examples 1 to 2. The ratios in each column of "Raw Material Ratio" of Tables 1 to 4 are as follows. The "A / (A+B+B')×100 (mass ratio)" column shows the content (mass parts) of the (A) component relative to 100 parts by mass of the total of the (A) component, the (B) component, and the (B') component. The "B / (A+B)×100 (mass ratio)" column shows the content (mass parts) of the (B) component relative to 100 parts by mass of the total of the (A) component and the (B) component. The "C / (A+B+C)×100 (mass ratio)" column shows the content (mass parts) of the (C) component relative to 100 parts by mass of the total of the (A) component, the (B) component, and the (C) component.

[0148] Next, a varnish containing the resin composition prepared as described above was applied to one side of a support (a PET film subjected to a release treatment) and dried at 100° C. to obtain an adhesive film with a support.

[0149] The dielectric properties of the adhesive films with support obtained as described above were evaluated by the following method. The measurement results are shown in Tables 1 to 4.

[0150] [Dielectric properties (dielectric constant (ε), dielectric loss tangent (tanδ))] The two sides of the adhesive film were sandwiched by PET films subjected to mold release treatment, and the adhesive film was thermally cured using a press. The thermal curing conditions by the press were set at 200°C, 60 minutes, 10 kgf / cm 2. Afterwards, the PET films that were subjected to demolding treatment and arranged on both sides of the cured adhesive film were removed, and a test piece (50±0.5mm×100±2mm) was cut out from the adhesive film to measure the thickness. The "Thin Film Thickness" column in Tables 1 to 4 shows the measured thickness of the adhesive film. Next, the dielectric constant (ε) and dielectric loss tangent (tanδ) of the film (test piece) whose thickness was measured were measured by the dielectric resonator method (SPDR method). In addition, the measurement frequency of the measurement performed by the dielectric resonator method was set to 10 GHz. For the dielectric constant (ε), 2.50 or less is considered "excellent", greater than 2.50 and less than 3.00 is considered "good", and greater than 3.00 is considered "poor". In addition, regarding the dielectric loss tangent (tan δ), less than 0.00010 is considered "excellent", 0.00010 or more and less than 0.0020 is considered "good", 0.0020 or more and less than 0.0030 is considered "fair", and 0.030 or more is considered "poor".

[0151] The obtained adhesive film with a support was subjected to the following solder heat resistance test, and evaluations of peel strength and curling properties.

[0152] [Welding heat resistance] The method was carried out according to JIS C5012 (1993). Specifically, copper foil was attached to both sides of the adhesive film with the rough surface facing the inside, and the copper foil was thermally pressed using a press. The thermal pressing conditions were 200°C, 60 minutes, 10 kgf / cm 2 . The obtained test piece was cut into 25mm×25mm pieces, floated in a solder bath heated to 288°C, and confirmed for 4 minutes whether there was any expansion. The results (seconds) shown in Tables 1 to 4 show the time (seconds) until the expansion of the test piece was visually confirmed. In addition, when no expansion occurs within 4 minutes, it is recorded as "4min≤". The evaluation of welding heat resistance regards the case where no expansion occurs for more than 4 minutes as "excellent". In addition, the case where the time until expansion occurs is 3 minutes or more and less than 4 minutes is regarded as "good", the case where it is 2 minutes or more and less than 3 minutes is regarded as "acceptable", and the case where it is less than 2 minutes is regarded as "poor".

[0153] [Peel strength] According to JIS C 6471. Specifically, copper foil was attached to both sides of the adhesive film with the rough surface on the inside, and thermally pressed using a press. The copper foil used was trade name "CF-T9", manufactured by Fukuda Metal Foil Industry Co., Ltd., 18 μm. The thermal pressing conditions were 200°C, 60 minutes, 10 kgf / cm 2 The obtained test piece was cut into a width of 10 mm, and peeled using a universal testing machine to measure the peel strength. The average value of each N=5 was calculated for the measurement results.

[0154] [Curling] First, a varnish containing a resin composition is applied to one side of a support (a PET film with a thickness of 38 μm that has been subjected to a demolding treatment), and dried at 100°C to obtain an adhesive film with a support. After the obtained adhesive film with a support is restored to room temperature, the adhesive film with a support is cut into a size of 30 cm × 50 cm to prepare a test piece for evaluating curling. The prepared test piece is placed on a horizontal table with the support side of the test piece as the lower side, and the length (warping amount) of the test piece shortened due to curling is measured according to the following method. First, an edge of one front end of the test piece placed on a horizontal table is fixed on the table. In this way, for a test piece with an edge of one front end fixed, the length shortened due to curling on the edge of the opposite front end of the test piece is measured. The case where the length (warping amount) of the test piece shortened due to curling is less than 5 cm is considered qualified (good; "0"), the case where it is more than 5 cm and less than 7 cm is also considered qualified (acceptable; "△"), and the case where it is more than 7 cm is considered poor ("×").

[0155] [Table 1]

[0156] [Table 2]

[0157] [Table 3]

[0158] [Table 4]

[0159] [result] As shown in Tables 1 to 4, the resin compositions of Examples 1 to 20 are resin compositions containing a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal as component (A) and a thermoplastic elastomer having a number average molecular weight of 60,000 or more as component (B). The resin compositions of Examples 1 to 20 showed good results in the evaluation of dielectric properties (dielectric constant (ε) and dielectric loss tangent (tanδ)), soldering heat resistance, peel strength, and curling properties.

[0160] In addition, among the resin compositions of Examples 1 to 17, the resin compositions using SEBS styrene elastomer as the (B) component (i.e., Examples 1 to 5, and Examples 7 to 17) all showed particularly good results in the evaluation of curling. In addition, the resin compositions containing 50 parts by mass or more of the filler (G) component, such as the resin compositions of Examples 16 and 18 to 20, also met the pass criteria in the evaluations of soldering heat resistance, peel strength, and curling. In particular, the resin compositions containing a crosslinking agent (H) component in a predetermined amount or more, such as Examples 16, 18, and 19, showed good results in all evaluations including the evaluation of curling.

[0161] The resin compositions of Comparative Examples 1 and 2 are resin compositions using a thermoplastic elastomer having a number average molecular weight of less than 60,000 as the (B') component, and have very poor welding heat resistance compared to the resin compositions of Examples 1 to 17. In addition, in the evaluation of curling, the length shortened by curling (warping amount) of the resin composition of Comparative Example 2 becomes extremely large, and the evaluation result of curling is very poor. It is speculated that the reason for the deterioration of the curling of the resin composition of Comparative Example 2 is that SEEPS-OH styrene elastomer is used as the thermoplastic elastomer. Industrial Applicability

[0162] The resin composition of the present invention can be used as a resin composition for an adhesive film used in an electronic component. In addition, the resin composition of the present invention can be used as an interlayer adhesive sheet or interlayer adhesive for a multilayer substrate. In addition, a semiconductor package with an antenna using the resin composition of the present invention can be used as a high-frequency substrate equipped with an RF chip for transmitting and receiving communications of 5G millimeter waves. The resin composition for a semiconductor package with an antenna of the present invention can be used for an insulating layer of a semiconductor package with an antenna. Explanation of symbols

[0163] 1 Insulation layer 1A First insulation layer 1B Second insulation layer 1C Third insulation layer 1D Fourth insulation layer 1E Fifth insulation layer 2-core substrate 4 wiring layers 5Antenna part (patch antenna) 7 Electrically bonded metal 8 RF chip 9 Connection pads 10 Semiconductor Devices Division 21 Insulation layer 22-core substrate 24 wiring layers 25 Antenna part (patch antenna) 26 Antenna unit (dipole antenna) 27 Electrically connected metal 28 RF Chip 30 Semiconductor Devices 100, 200 Semiconductor package with antenna

Claims

1. A resin composition, comprising: (A) a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at a terminal; and (B) A thermoplastic elastomer having a number average molecular weight of 60,000 or more.

2. The resin composition according to claim 1, wherein The component (A) contains a modified polyphenylene ether having a styrene structure at a terminal.

3. The resin composition according to claim 1 or 2, wherein The component (A) contains a modified polyphenylene ether having a group represented by the following formula (1) at the terminal. [Chemistry 1] Wherein, in the formula (1), R 1 represents a hydrogen atom or an alkyl group.

4. The resin composition according to any one of claims 1 to 3, wherein The component (B) is a styrene-based thermoplastic elastomer.

5. The resin composition according to claim 4, wherein The component (B) is a hydrogenated styrene-based thermoplastic elastomer.

6. The resin composition according to claim 5, wherein The hydrogenated styrene-based thermoplastic elastomer of the component (B) is a styrene / ethylene / butylene / styrene block copolymer.

7. The resin composition according to any one of claims 1 to 6, wherein The component (B) is a thermoplastic elastomer having a number average molecular weight of 100,000 or more.

8. The resin composition according to any one of claims 1 to 7, wherein The mass ratio of the component (A) to the component (B) is 5:95 to 70:

30.

9. The resin composition according to any one of claims 1 to 8, wherein The content of the component (B) is larger than the content of the component (A).

10. The resin composition according to any one of claims 1 to 9, wherein The resin composition further comprises (C) an epoxy resin.

11. The resin composition according to claim 10, wherein The content of the component (C) is 0.1 to 5.0 parts by mass based on 100 parts by mass of the total of the component (A), the component (B), and the component (C) in the resin composition.

12. The resin composition according to any one of claims 1 to 11, wherein The resin composition further includes (D) a curing agent. 13 . An adhesive film comprising the resin composition according to claim 1 . 14 . An interlayer adhesive sheet, comprising the resin composition according to claim 1 . 15 . A resin composition for a semiconductor package with an antenna, comprising the resin composition according to claim 1 . 16 . A laminate or a semiconductor device, comprising a cured product of the resin composition according to claim 1 .

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