CN119604555A - Resin composition, adhesive film, adhesive sheet for interlayer bonding, and resin composition for semiconductor package with antenna - Google Patents

Abstract

Provided is a resin composition having excellent solder heat resistance and low dielectric characteristics. The resin composition comprises (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.

Description

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

Technical Field

The present invention relates to a resin composition, an adhesive film, an adhesive sheet for interlayer adhesion, and a resin composition for a semiconductor package with an antenna.

Background

With recent demands for higher speed of transmission signals in printed wiring boards, significant higher frequencies of transmission signals are being developed. Accordingly, a material used for a printed wiring board is required to be capable of reducing transmission loss in a high frequency range, specifically, in a frequency range of 1GHz or more.

As a resin composition used for an insulating layer or the like of a printed wiring board, for example, a thermosetting resin composition containing a thermosetting resin having a styrene group at a terminal and a styrene-based thermoplastic elastomer is known (for example, patent document 1). For example, as the thermosetting resin composition disclosed in patent document 1, a thermosetting resin having a styrene group at the terminal, a phenyl ether skeleton, or the like is used. Further, as the styrene-based thermoplastic elastomer, a low molecular weight styrene-based elastomer is used.

In recent years, 5G has been standardized as a next-generation communication technology, and market demands for products for realizing high-frequency response have been increasing. The development of multi-element antenna technology, high-speed transmission, and other technologies has been accelerated, and also, the use of high frequency bands has increased communication capacity, information processing capacity has increased, and the amount of high frequency noise and heat generated has increased, which has also been a major problem.

For example, in the 5G millimeter wave antenna, regarding the package technology, a structure is required in which conductor loss (in other words, transmission loss is small) is reduced by shortening the wiring distance between the antenna and the IC. Accordingly, in recent years, semiconductor packages with antennas (for example, antenna-in-Package, aiP), antenna-On-Package (AoP)) in which an Antenna portion is integrally formed with a semiconductor device portion have been developed. In such a package, since the insulating layer around the antenna is also at a higher temperature than in the conventional structure due to heat generated from the IC, the dielectric loss is required to be small even when the package is placed in a high-temperature environment. In addition, "IC" refers to an integrated circuit (INTEGRATED CIRCUIT).

Prior art literature

Patent literature

Patent document 1 International publication No. 2019/230531

Disclosure of Invention

Technical problem to be solved by the invention

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 terminal and a styrene-based thermoplastic elastomer, and is considered to be a resin composition containing a thermosetting resin having a styrene group at the terminal and a styrene-based thermoplastic elastomer. On the other hand, soldering heat resistance is sometimes required for insulating layers and the like of printed wiring boards, but the resin composition disclosed in patent document 1 does not mention such soldering heat resistance.

The resin composition used in the high frequency range is required to have excellent weld heat resistance, low dielectric characteristics, and the like, and development of a resin composition having excellent various characteristics is desired.

The present invention has been made in view of the problems of the prior art as described above. The invention provides a resin composition with excellent welding heat resistance and low dielectric property, which can be applied to adhesive films, adhesive sheets for interlayer adhesion, interlayer adhesives and the like. Further, the present invention provides an adhesive film, an adhesive sheet for interlayer adhesion, and a resin composition for a semiconductor package with an antenna, each of which uses the resin composition.

Technical means for solving the technical problems

According to the present invention, there are provided a resin composition, an adhesive film, an adhesive sheet for interlayer adhesion, and a resin composition for a semiconductor package with an antenna, which are shown below.

[1] 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.

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

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

[ Chemical 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 the above [1] to [3], wherein the component (B) is a styrenic thermoplastic elastomer.

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

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

[7] The resin composition according to any one of the above [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 the above [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 the above [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 the above [1] to [9], wherein the resin composition further comprises (C) an epoxy resin.

[11] The resin composition according to the above [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 the above [1] to [11], wherein the resin composition further comprises (D) a curing agent.

[13] An adhesive film comprising the resin composition according to any one of the above [1] to [12 ].

[14] An adhesive sheet for interlayer adhesion, which comprises the resin composition according to any one of the above items [1] to [12 ].

[15] A resin composition for a semiconductor package with an antenna, which is composed of the resin composition according to any one of the above [1] to [12 ].

[16] A laminate or a semiconductor device comprising the cured product of the resin composition according to any one of the above [1] to [12 ].

Advantageous effects

The resin composition of the present invention achieves the effect of excellent solder heat resistance and low dielectric characteristics. Therefore, the resin composition of the present invention can be applied to an adhesive film, an adhesive sheet for interlayer adhesion, an interlayer adhesive, and the like. The adhesive film, the adhesive sheet for interlayer adhesion, and the resin composition for a semiconductor package with an antenna of the present invention use the resin composition of the present invention, and have the effect of excellent soldering heat resistance and low dielectric characteristics.

Drawings

Fig. 1 is a schematic partial sectional view showing one example of a semiconductor package with an antenna.

Fig. 2 is a schematic partial sectional view showing other examples of the semiconductor package with an antenna.

Detailed Description

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. Accordingly, it is to be understood that the following embodiments are also included in the scope of the present invention, as appropriate, by changing and modifying the following embodiments based on the common knowledge of a person skilled in the art, without departing from the gist of the present invention.

[ 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, the polyphenylene ether resin (A) having a functional group having a carbon-carbon double bond at the terminal is sometimes referred to as component (A). Similarly, the thermoplastic elastomer (B) having a number average molecular weight of 60,000 or more is sometimes referred to as component (B).

The resin composition of the present embodiment is a resin composition having excellent solder heat resistance and low dielectric characteristics. In particular, the resin composition of the present embodiment can effectively improve the solder heat resistance while imparting low dielectric characteristics to the resin composition by including the polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal as the component (a). Further, by containing 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 weld heat resistance can be further improved.

The resin composition of the present embodiment may contain, in addition to the above-described component (a) and component (B), other components such as (C) an epoxy resin, (D) a curing agent, (E) an organic peroxide, (F) a flame retardant, (G) a filler, and (H) a crosslinking agent. Hereinafter, the above-mentioned components may be appropriately referred to as "components (C) - (H)".

[ (A) component ]

(A) The component (a) is a polyphenylene ether resin having a functional group having a carbon-carbon double bond at the terminal. Examples of the functional group containing a carbon-carbon double bond include a terminal vinyl group, a vinylidene group, and a vinylidene group. (A) The component is not particularly limited as long as it has a functional group containing a carbon-carbon double bond at the terminal thereof and polyphenylene ether is present in the skeleton. By containing the component (a), the solder heat resistance can be effectively improved while imparting low dielectric characteristics to the resin composition.

As the component (a), for example, a component (a) including a modified polyphenylene ether having a styrene structure at the terminal is exemplified. Such a modified polyphenylene ether is not particularly limited as long as it has a styrene structure at its terminal. The styrene structure may be unsubstituted styryl group having no substituent, or may be styryl group having an arbitrary substituent. By containing such component (a), the weld heat resistance of the resin composition can be improved. In particular, a modified polyphenylene ether having a styrene structure at the terminal thereof undergoes a curing reaction even without using a peroxide, and is extremely excellent in weld heat resistance.

The modified polyphenylene ether having a styrene structure at the terminal as the component (A) may be, for example, a compound having a structure represented by the following general formula (2).

[ Chemical 2]

[ Chemical 3]

[ Chemical 4]

[ Chemical 5]

In the above general formula (2) - (O-X-O) -is represented by the above structural formula (3) or (4).

In the structural formula (3), R ²、R³、R⁴、R⁷ and R ⁸ are an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same or different from each other. R ⁵、R⁶ and R ⁷ are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same or different from each other.

In the structural formula (4), R ¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶ and R ¹⁷ are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same or different from each other. -A-is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms.

In general formula (2), - (Y-O) -is represented by the above-mentioned structural formula (5). In- (Y-O) -1 structure or more than 2 structures are arranged randomly. In the structural formula (5), R ¹⁸ and R ¹⁹ are an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same or different from each other. R ²⁰ and R ²¹ are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same or different from each other.

In the general formula (2), a and b are integers of 0 to 100. at least one of a and b is other than 0.

Examples of the "A" in the structural formula (4) include 2-valent organic groups such as methylene, ethylene, 1-methylethylene, 1-propylene, 1, 4-phenylenebis (1-methylethylene), 1, 3-phenylenebis (1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene and 1-phenylethylene. However, the structural formula (4) of-A-is not limited to these.

As the compound represented by the general formula (2), R ²、R³、R⁴、R⁸、R⁹、R¹⁸ and R ¹⁹ are preferably an alkyl group ,R⁵、R⁶、R⁷、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R²⁰ having 3 or less carbon atoms and R ²¹ is a hydrogen atom or an alkyl group having 3 or less carbon atoms. In particular, the- (O-X-O) -represented by the following structural formula (3) or structural formula (4) is more preferably a compound represented by the following structural formula (6), structural formula (7) or structural formula (8). In addition, in the same manner, in particular, it is more preferable that- (Y-O) -represented by the following 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.

[ Chemical 6]

[ Chemical 7]

[ Chemical 8]

[ Chemical 9]

[ Chemical 10]

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 oxidatively coupled, whereby a bifunctional phenylene ether oligomer is obtained. Next, the terminal phenolic hydroxyl groups of the obtained bifunctional phenylene ether oligomer were subjected to vinylbenzyl etherization. Thus, the compound represented by the general formula (2) can be produced.

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 still more preferably 1,000 to 2,500. When the number average molecular weight is 1000 or more, tackiness is less likely to occur when the resin composition is formed into a film. Further, if the number average molecular weight is 5,000 or less, the decrease in the solubility of the resin composition in a solvent can be effectively suppressed. Further, by using a compound having a number average molecular weight within the above numerical range as the component (a), the electrical characteristics at high frequencies and curability of the resin composition are improved. Here, the number average molecular weight mentioned above is a value according to Gel Permeation Chromatography (GPC) using a calibration curve based on standard polystyrene.

(A) The component (c) may be used alone or in combination of 2 or more kinds of compounds represented by the general formula (2).

Examples of the polyphenylene ether having a styrene structure at the terminal of the component (A) include those manufactured by Mitsubishi chemical corporation under the trade names "OPE-2200" and "OPE-1200".

The component (a) includes, in addition to the component (a) including a modified polyphenylene ether having a styrene structure at the terminal (for example, a compound represented by the above general formula (2)), the component (a) including a modified polyphenylene ether having a group represented by the following formula (1) at the terminal.

[ Chemical 11]

In the above formula (1), R ¹ represents a hydrogen atom or an alkyl group. The alkyl group of R ¹ is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, examples thereof include methyl, ethyl, propyl, hexyl, decyl, and the like.

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

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

[ Chemical 12]

In the structural formula (11), m represents 1 to 50. R ²²～R²⁵ are independent of each other and may be the same or different from each other. R ²²～R²⁵ 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, hydrogen atoms and alkyl groups are preferable.

In R ²²～R²⁵, the following groups are specifically exemplified as the respective functional groups.

The alkyl group in R ²²～R²⁵ is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, examples thereof include methyl, ethyl, propyl, hexyl, decyl, and the like.

The alkenyl group in R ²²～R²⁵ is not particularly limited, and for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specifically, examples thereof include vinyl, allyl, and 3-butenyl.

The alkynyl group in R ²²～R²⁵ is not particularly limited, and for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specifically, for example, there may be mentioned ethynyl and prop-2-yn-1-yl (propargyl).

The alkylcarbonyl group in R ²²～R²⁵ 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 preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. Specifically, examples thereof include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, and cyclohexylcarbonyl.

The alkenylcarbonyl group in R ²²～R²⁵ 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 preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, an acryl group, a methacryl group, a crotonyl group, and the like are given.

The alkynylcarbonyl group in R ²²～R²⁵ 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 preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, a propynyl group and the like are given.

Examples of the modified polyphenylene ether having a group represented by the above formula (1) include modified polyphenylene ethers having a group represented by the above formula (1) at the terminal of a polyphenylene ether represented by the following formula (12) or formula (13). Specific examples of the modified polyphenylene ether include modified polyphenylene ethers represented by the following formula (14) or (15).

[ Chemical 13]

[ Chemical 14]

[ 15]

[ 16]

In the formulae (12) to (15), s and t are preferably, for example, the sum of s and t is 1 to 30. Preferably, s is 0 to 20, and preferably t is 0 to 20. That is, s preferably represents 0 to 20, t represents 0 to 20, and the total of s and t represents 1 to 30. In the 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 a dimethylmethylene group. In the formula (14) and the formula (15), R ¹ is the same as R ¹ in the formula (1) and 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, more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, examples thereof include methyl, ethyl, propyl, hexyl, decyl, and the like.

The number average molecular weight (Mn) of the modified polyphenylene ether having the group represented by the formula (1) is not particularly limited. Specifically, it is preferably 500 to 5,000, more preferably 800 to 4,000, and still more preferably 1,000 to 3,000. The number average molecular weight may be any value measured by a usual molecular weight measurement method, and specifically, a value measured by Gel Permeation Chromatography (GPC) or the like may be mentioned. In addition, in the case where the modified polyphenylene ether having a group represented by the formula (1) has a repeating unit represented by the 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-mentioned range. Specifically, m is preferably 1 to 50.

If the weight average molecular weight of the modified polyphenylene ether having the group represented by the formula (1) is within the above-mentioned numerical range, the cured product is excellent in heat resistance as well as excellent in dielectric characteristics derived from the polyphenylene ether, and further, the moldability of the resin composition can be improved. For example, in the conventional polyphenylene ether, if the weight average molecular weight is within the above-mentioned numerical range, the molecular weight is relatively low, and the heat resistance of the cured product tends to be lowered. On the other hand, the modified polyphenylene ether having the group represented by the above formula (1) has the group represented by the formula (1) at the terminal, and therefore the heat resistance of the cured product can be improved. Further, since the modified polyphenylene ether can be made to have a relatively low weight average molecular weight, the moldability is also excellent. Therefore, by using the component (A) comprising the modified polyphenylene ether having the group represented by the formula (1) at the terminal, a resin composition having excellent heat resistance and excellent moldability of the cured product can be obtained.

The average number of groups (terminal functional groups) represented by the above formula (1) per molecule of the modified polyphenylene ether used as the component (a) is not particularly limited. Specifically, 1 to 5 are preferable, 1 to 3 are more preferable, and 1.5 to 3 are still more preferable. If the number of the terminal functional groups is too small, it tends to be difficult to obtain a sufficient heat resistance of the cured product. Further, if the number of terminal functional groups is too large, the reactivity becomes too high, and there is a possibility that problems such as a decrease in the storage stability of the resin composition, a decrease in the fluidity of the resin composition, and the like may occur. That is, if such a modified polyphenylene ether is used, there is a possibility that a problem of moldability may occur due to insufficient fluidity or the like, for example, a molding defect such as void formation occurs at the time of multilayer molding, and it is difficult to obtain a printed wiring board with high reliability.

Examples of the terminal functional group number of the modified polyphenylene ether include a value represented by an average value of the groups represented by the above formula (1) per 1mol of all modified polyphenylene ethers present in the modified polyphenylene ether. The number of the terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether and calculating the decrease in the number of hydroxyl groups compared with the number of hydroxyl groups of the polyphenylene ether before modification. The decrease in the hydroxyl number of the polyphenylene ether before modification is the terminal functional group number. The method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether can be obtained by adding a quaternary 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.

The intrinsic viscosity of the modified polyphenylene ether used as the component (A) is not particularly limited. Specifically, the ratio is preferably 0.03 to 0.12dL/g, more preferably 0.04 to 0.11dL/g, and still more preferably 0.06 to 0.095dL/g. If the intrinsic viscosity is too low, the molecular weight tends to be low, and low dielectric characteristics such as low dielectric constant and low dielectric loss tangent tend to be difficult to obtain. If the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to be lowered. Therefore, if the intrinsic viscosity of the modified polyphenylene ether is within the above range, excellent heat resistance and moldability of the cured product can be achieved.

The intrinsic viscosity mentioned above means an intrinsic viscosity measured in methylene chloride at 25 ℃, and more specifically, a value obtained by measuring a methylene chloride solution (liquid temperature 25 ℃) of 0.18g/45mL with a viscometer, for example. Examples of the viscometer include "AVS500 Visco System" manufactured by Schott corporation.

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

(A) The modified polyphenylene ether having a group represented by the above formula (1) at the terminal may be used alone or 2 or more kinds of modified polyphenylene ethers having a group represented by the above formula (1) at the terminal may be used in combination. Further, it may be used in combination with 1 or more of the compounds represented by the general formula (2) described above.

Examples of the modified polyphenylene ether having a group represented by the above formula (1) at the terminal of the component (a) include "Noryl SA9000" manufactured by SABIC.

From the viewpoint of excellent low dielectric characteristics and solder heat resistance, the content of the component (a) is preferably 5 to 70 parts by mass, more preferably 6 to 60 parts by mass, still more 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 the components (a), (B) and (B'). The component (B') will be described later.

[ (B) component ]

(B) The component (A) is a thermoplastic elastomer having a number average molecular weight of 60,000 or more. By containing 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 weld heat resistance can be improved satisfactorily. In the following, 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, may be referred to as a component (B').

The number average molecular weight of the thermoplastic elastomer as the component (B) is a value according to Gel Permeation Chromatography (GPC) using a calibration curve based on standard polystyrene. In addition, in the case of measuring the number average molecular weight of a film formed from the resin composition, for example, the film may be dissolved in a solvent, and the number average molecular weight of a component dissolved in the solvent may be measured.

The number average molecular weight of the thermoplastic elastomer as the component (B) is preferably 60,000 or more, more preferably 100,000 or more, still more preferably 110,000 or more, and particularly preferably 120,000 or more. If the number average molecular weight is such, the weld heat resistance is further improved. The upper limit of the number average molecular weight of the thermoplastic elastomer as the component (B) is not particularly limited. However, if the number average molecular weight of the thermoplastic elastomer becomes too large, the thermoplastic elastomer may be difficult to melt and the processability may be deteriorated. Accordingly, the number average molecular weight of the thermoplastic elastomer as the 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.

The thermoplastic elastomer as the component (B) is not particularly limited, but is preferably a thermoplastic elastomer having a dielectric loss tangent (tan. Delta.) of less than 0.005 in the frequency range of 1GHz to 100 GHz. Thereby, excellent dielectric characteristics in a high frequency range of the thermosetting film formed from the resin composition of the present disclosure can be facilitated. The "thermoplastic elastomer having a dielectric loss tangent (tan. Delta.) of less than 0.005 in the frequency range of 1GHz to 100 GHz" is preferably a styrene-based thermoplastic elastomer, more preferably a hydrogenated styrene-based thermoplastic elastomer. The hydrogenated styrenic thermoplastic elastomer herein means a hydrogenated styrenic thermoplastic elastomer, and examples of the hydrogenated styrenic thermoplastic elastomer include a styrene/butadiene/butylene/styrene block copolymer (partially hydrogenated, SBBS) and a styrene/ethylene/butylene/styrene block copolymer (fully hydrogenated, SEBS). The use of the hydrogenated styrenic thermoplastic elastomer can improve dielectric characteristics. In the case where 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%. The styrene ratio of the component (B) is 20% -50%, and the film forming property and the processing property are excellent.

(B) The hydrogenated styrene-based thermoplastic elastomer of the component (b) is not particularly limited, but is preferably a styrene/ethylene/butylene/styrene block copolymer (SEBS). The styrene/ethylene/butylene/styrene block copolymer (SEBS) is a completely hydrogenated styrene thermoplastic elastomer, and has no double bond, and thus can further improve dielectric characteristics. In addition, by using a styrene/ethylene/butylene/styrene block copolymer (SEBS) having a number average molecular weight of 60,000 or more, not only dielectric characteristics are good, but also soldering heat resistance is improved. Further, by using a styrene/ethylene/butylene/styrene block copolymer (SEBS) as the component (B), the film becomes less liable to curl when the resin composition is formed into a film. Further, as another preferable example of the hydrogenated styrene thermoplastic elastomer of the component (B), a styrene/ethylene/propylene/styrene block copolymer (SEEPS) may be mentioned.

The content of the component (B) is not particularly limited, but the mass ratio of the component (A) to the component (B) (component (A)) is preferably 5:95 to 70:30, more preferably 10:90 to 67:33, still more preferably 20:80 to 60:40, particularly preferably 25:75 to 40:60. In addition, from the viewpoint of weld heat resistance, the content of the component (B) is preferably larger than the content of the component (a). However, if the ratio of the component (B) is excessively large, when the resin composition is formed into a film, tackiness may easily occur on the film, and workability may be deteriorated. In addition, if the ratio of the component (B) is increased, the dielectric characteristics of the resin composition may be deteriorated, and therefore the above range is preferable.

When the amount of the resin composition other than the filler is 100 parts by mass, the content of the component (B) is preferably 20 parts by mass to 95 parts by mass, more preferably 30 parts by mass to 93 parts by mass, and still more preferably 35 parts by mass to 80 parts by mass. In this range, the solder heat resistance is excellent while maintaining the low dielectric characteristics.

The resin composition of the present embodiment may contain a plurality of thermoplastic elastomers as the component (B). The component (B) may contain a plurality of thermoplastic elastomers having a number average molecular weight of 60,000 or more. The resin composition of the present embodiment may contain a thermoplastic elastomer ((B') component) having a number average molecular weight of less than 60,000 as a thermoplastic elastomer other than the (B) component. In the case where the resin composition of the present embodiment contains a plurality of thermoplastic elastomers, it is preferable that the content (mass basis) of the thermoplastic elastomer having a number average molecular weight of 60,000 or more is larger than the content of the thermoplastic elastomer having a number average molecular weight of 60,000 or less.

Examples of the thermoplastic elastomer having a number average molecular weight of 60,000 or more as the component (B) include "seta 8004", "seta 8006", and "seta V9461" manufactured by kuh-yu.

[ (C) component ]

(C) The component is epoxy resin. Epoxy resins are compounds having 1 or more epoxy groups in the molecule, which react by heating, thereby forming a 3-dimensional network structure and being curable. By containing an epoxy resin as the component (C), further improvement in solder heat resistance can be achieved. In addition, by the epoxy resin containing the component (C), the adhesion can be improved even if the adherend is smooth with respect to a glossy surface such as copper.

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 even more preferably 0.7 to 3.0 parts by mass, based on 100 parts by mass of the total of the component (A), the component (B) and the component (C). If the content of the component (C) is too large, the dielectric loss tangent of the cured product may become high.

When the amount of the resin composition other than the filler is 100 parts by mass, the content of the component (C) is preferably 0.1 parts by mass to 5.0 parts by mass, more preferably 0.5 parts by mass to 3.0 parts by mass, and still more preferably 0.6 parts by mass to 2.0 parts by mass.

Specific examples of the epoxy resin include 2-functional epoxy resins obtained by epoxidizing bisphenol compounds such as bisphenol a, bisphenol E, bisphenol F, or derivatives thereof (for example, alkylene oxide adducts), diols having an alicyclic structure such as hydrogenated bisphenol a, hydrogenated bisphenol E, hydrogenated bisphenol F, cyclohexanediol, cyclohexanedimethanol, and cyclohexanediethanol, aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, and decanediol, or derivatives thereof, 3-functional epoxy resins having a trihydroxyphenyl methane skeleton and an aminophenol skeleton, and polyfunctional epoxy resins obtained by epoxidizing phenol novolac resins (phenolic resin), cresol novolac resins, phenol aralkyl resins (phenolic resin), biphenyl resins, and naphthol aralkyl resins, but are not limited to these. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, and aminophenol type epoxy resin are preferable. The compounds shown here may be used alone or in combination of 2 or more.

(C) The epoxy resin of the composition is preferably liquid at room temperature (25 ℃).

[ (D) component ]

(D) The component is a curing agent. (D) The curing agent of the component (a) is not particularly limited as long as it is a curing agent that usually cures an epoxy resin, and a curing catalyst that accelerates the reaction of the epoxy resin is also included in the curing agent in the present application. The curing agent is not particularly limited, but is preferably an imidazole-based curing catalyst because the curability can be appropriately adjusted.

The imidazole-based curing catalyst may be imidazole, or an imidazole adduct, an inclusion imidazole, a microcapsule imidazole, an imidazole compound obtained by coordinating a stabilizer, or the like may be used. They have nitrogen atoms in their structure that contain non-common electron pairs, which can activate epoxy groups, and can also activate other co-used epoxy resins, thereby enabling curing to be promoted.

Specific examples of the imidazole-based 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, trimellitic acid 1-cyanoethyl-2-undecylimidazolium, trimellitic acid 1-cyanoethyl-2-phenylimidazolium, 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 '-undecylimidazolyl- (1') -ethyl-s-triazine, 2, 4-diamino-6- (2 '-methylethyl-2' -methyl-triazinyl) -s, and trimellitic acid 1-cyanoethyl-2-undecylium, trimellitic acid 1-cyanoethyl-2-cyanoethyl-phenylimidazole, trimellitic acid, and trimellitic acid 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, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like, but are not limited thereto. The imidazole obtained by addition treatment, inclusion treatment with different molecules, microcapsule treatment, or complexation of the stabilizer is an imidazole obtained by modification of the above-mentioned imidazole. They reduce the activity by subjecting imidazole to addition treatment, inclusion treatment with different molecules, microcapsule treatment, or complexation of a stabilizer, thereby exhibiting excellent pot life in a low temperature range while also having high curing and curing accelerating ability.

Examples of commercially available imidazoles (trade names) include, but are not limited to, 2E4MZ, 2P4MZ, 2PZ-CN, C11Z-CNS, C11Z-A, 2MZA-PW, 2MA-OK, 2P4MHZ-PW, 2PHZ-PW (manufactured by Kyowa Co., ltd., for four countries, above), EH2021 (manufactured by ADEKA Co., ltd.). Examples of the commercially available imidazole adducts include, but are not limited to, PN-50J, PN-40, PN-40J, PN-31, PN-23, PN-H (manufactured by Takara Shuzo Co., ltd.) having a structure in which an imidazole compound is ring-opened added to an epoxy group of an epoxy resin. Examples of commercially available products including imidazole include TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, NIPA-2E4MZ (manufactured by Japanese Caoshe, supra), and the like, but are not limited thereto. Examples of the commercially available microencapsulated imidazoles include iroki HX3721, HX3722, HX3742, HX3748 (manufactured by Asahi chemical Co., ltd.), LC-80 (manufactured by A & CCATALYSTS Co., ltd.).

The content of the curing agent may be appropriately selected depending on the kind of the curing agent used as the component (D). When the amount of the resin composition other than the filler is 100 parts by mass, the content of the component (D) is preferably 0.001 parts by mass to 1.0 parts by mass, more preferably 0.005 parts by mass to 0.60 parts by mass. The content of the imidazole-based curing catalyst is preferably 0.1 to 10 mass%, more preferably 1 to 6 mass%, based on the epoxy resin. If the content of the component (D) is too small, the curability of a film produced using the resin composition may deteriorate, and the adhesiveness, toughness, and heat resistance may be lowered. On the other hand, if the content of the component (D) is too large, the pot life of a film produced using the resin composition may be deteriorated, and the physical properties inherent to the resin in the cured product may be impaired, and the adhesiveness, toughness and heat resistance may be lowered.

[ (E) component ]

(E) The component is an organic peroxide. By containing such an organic peroxide, the reaction initiation temperature of the component (a) is shifted to a low temperature side, and curing of the resin composition is promoted. Therefore, the solder heat resistance of the resin composition is further improved. The content of the organic peroxide may be appropriately selected depending on the type, but is typically preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the component (a).

Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, bis (3, 5-trimethylhexanoyl) peroxide, peroxy ketals such as 2, 2-bis (4, 4-di- (di-t-butylperoxy) cyclohexyl) propane, isopropyl peroxydicarbonate, di-sec-butyl peroxide, bis (2-ethylhexyl) peroxydicarbonate, bis (1-methylheptyl) peroxydicarbonate, bis (3-methoxybutyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, t-butyl peroxybenzoate, t-butyl peroxyacetate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl diperoxyiate, dicumyl peroxyneodecanoate, t-butyl peroxybenzoate, 2, 5-dimethyl-2, 5-di-benzoyl peroxide, di-t-butyl peroxy-2, 5-methyl-cyclohexyl) peroxide, 3-methyl-peroxy-3-cyclohexyl peroxide, 3-methyl-peroxy-2-tert-butyl peroxy-2, 5-methyl-peroxy-3-methyl-n-hexyl peroxide, 3-methyl-peroxy-2-methyl-peroxy-3-n-butyl peroxide, 3-methyl-peroxy-n-peroxy-3-peroxy ketone and the like, dialkyl peroxides such as di (2-t-butylperoxyisopropyl) benzene, hydroperoxides such as cumene hydroperoxide, t-butyl hydroperoxide, and terpene hydroperoxide. The organic peroxide to be used is not particularly limited, but in curing the resin composition, for example, a drying step of about 60 to 80 ℃ is often required, and therefore, an organic peroxide having a half-life temperature of 100 to 140 ℃ in 10 hours is preferably used. Further, an organic peroxide having a 10-hour half-life temperature of 110 ℃ to 130 ℃ is more preferable.

Examples of the commercial products (trade names) of the organic peroxide as the component (E) include a case H, a case Z, a case pair, a case P, a case D, a case H, a case C (above manufactured by day oil chemical company), and the like.

[ (F) component ]

(F) The component is a flame retardant. The flame retardant as the component (F) is any component appropriately contained within a range that does not impair the effects of the resin composition of the present embodiment described hereinabove. For example, flame retardancy may be required in a resin composition used for an insulating layer of a printed wiring board or the like, in addition to the solder heat resistance and low dielectric characteristics described above. In response to such a demand, the flame retardant is further contained as the component (F), which can contribute to the improvement of the flame retardancy of the cured product of the resin composition of the present embodiment.

The kind of the flame retardant is not particularly limited. Examples of the flame retardant of the component (F) include inorganic phosphorus flame retardants, organic phosphorus flame retardants, metal hydrates such as aluminum hydroxide hydrate and magnesium hydroxide hydrate. The flame retardant (F) may be used alone or in combination of 1 or more than 2.

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, phosphine oxide and the like.

Examples of the organic phosphorus flame retardant include phosphate flame retardants, 1-substituted phosphonic acid diesters, 2-substituted phosphinates, metal salts of 2-substituted phosphinic acids, organic nitrogen-and phosphorus-containing compounds, and cyclic organic phosphorus compounds. Examples of the "metal salt" include lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, zinc salt, and the like.

The content of the flame retardant may be appropriately selected depending on the kind of the flame retardant used as the component (F). When the amount of the resin composition other than the filler is 100 parts by mass, the content of the component (F) is preferably 15 parts by mass to 50 parts by mass, more preferably 20 parts by mass to 40 parts by mass. Further, examples of the flame retardant of the component (F) include a phosphinate metal salt (for example, brand name "OP-935" manufactured by kurahen corporation).

[ (G) component ]

(G) The component is a filler material. The type of the filler as the component (G) is not particularly limited, and examples thereof include known inorganic fillers. The filler as the component (G) is required to have insulation properties and a low thermal expansion coefficient.

As the inorganic filler of the component (G), a general inorganic filler can be used. Examples of the inorganic filler include silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium carbonate, barium sulfate, barium carbonate, calcium sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. The inorganic filler may be used alone or in combination of 2 or more. In particular, silica fillers and alumina fillers are preferable from the viewpoint of insulation. Further, from the viewpoint of dielectric characteristics, a silica filler is preferable. The inorganic filler may be surface-treated with a silane coupling agent having at least one functional group selected from the group consisting of an acrylic group, a methacrylic group, a styrene group, an amino group, an epoxy group, and a vinyl group. For example, the inorganic filler is preferably surface-treated with a surface-treating agent such as an aminosilane-based coupling agent, an ureido silane-based coupling agent, an epoxy silane-based coupling agent, a mercapto silane-based coupling agent, a vinyl silane-based coupling agent, a styryl silane-based coupling agent, an acrylate silane-based coupling agent, an isocyanate silane-based coupling agent, a sulfide silane-based coupling agent, an organosilane compound, or a titanate-based coupling agent, to improve heat resistance, moisture resistance, and dispersibility. They may be used in 1 kind or in combination of more than 2 kinds. More preferably, among the surface-treated silica fillers, a silica filler surface-treated with a vinyl silane coupling agent is preferably used. The use of the silica filler surface-treated with the vinyl silane coupling agent can improve the thermal expansion coefficient.

The shape of the inorganic filler is not particularly limited, and examples thereof include spherical, scaly, needle-like, irregular, and the like. From the viewpoint of workability, a spherical shape is preferable. The average particle diameter is preferably 0.1 μm to 10. Mu.m, more preferably 0.1 μm to 4. Mu.m. The average particle diameter of the inorganic filler is within this range, and thus the embeddability between fine structures is excellent. The average particle diameter is the particle diameter at 50% of the cumulative value in the particle size distribution on a volume basis, measured by the laser diffraction/scattering method. The average particle diameter can be measured by, for example, a laser diffraction/scattering particle size distribution measuring apparatus LS13320 (manufactured by the company コ, inc., wet type).

When the component (G) is contained, the content of the component (G) is preferably 0.1 to 90 parts by mass, more preferably 20 to 85 parts by mass, still more preferably 30 to 80 parts by mass, and particularly preferably 50 to 80 parts by mass, based on 100 parts by mass of the nonvolatile component in the resin composition. By configuring in this way, the thermal expansion coefficient can be improved well.

[ (H) component ]

(H) The component (c) is a crosslinking agent. By containing the crosslinking agent as the component (H), cracking of the film formed from the resin composition can be effectively prevented. Further, by crosslinking with the polyphenylene ether resin as the component (a), further improvement in the weld heat resistance of the resin composition can be expected.

As the crosslinking agent of the component (H), for example, polybutadiene, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl isocyanurate, 2' -diallyl bisphenol a, and the like can be used, and among these crosslinking agents, a crosslinking agent having an isocyanurate ring structure and 2 allyl groups in 1 molecule is preferably used. (H) The crosslinking agent of the component (A) has 2 allyl groups, and therefore, the dielectric characteristics are low and the solder heat resistance can be improved. Although the detailed reasons are not clear, it is assumed that the heat resistance of the resin composition is improved because the (H) component has an isocyanurate ring structure. Further, the component (H) may be a compound having an isocyanurate ring structure and 2 allyl groups in 1 molecule. Thus, the solder has good heat resistance while having low dielectric characteristics, and further, can obtain better film forming property, thereby facilitating film formation. In addition, component (H) may be a liquid compound at 25 ℃.

Further, the component (H) may be a flame retardant crosslinking agent which is a crosslinking agent of the polyphenylene ether resin as the component (A) while imparting flame retardancy. For example, a flame retardant crosslinking agent having an isocyanurate ring structure and 2 allyl groups in 1 molecule and having a phosphorus-based substituent at the terminal can be used. This can crosslink the polyphenylene ether resin as the component (A), thereby improving the weld heat resistance of the resin composition and imparting flame retardancy.

The component (H) is preferably a compound represented by the following general formula (16).

[ Chemical 17]

In the 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.

The content of the component (H) is preferably 10 to 70 parts by mass based on 100 parts by mass of the component (A). By configuring in this way, the solder heat resistance can be improved while the dielectric characteristics are low. The content of the component (H) is more preferably 15 parts by mass to 65 parts by mass, and still more preferably 20 parts by mass to 60 parts by mass, based on 100 parts by mass of the component (a), although not particularly limited. The nonvolatile component in the resin composition preferably contains 2 to 50% by mass of the component (H), more preferably 3 to 40% by mass, and particularly preferably 4 to 30% by mass, based on 100% by mass of the nonvolatile component. If the content ratio of the (H) component in 100 mass% of the nonvolatile component in the resin composition is within this range, the resin composition is excellent in dielectric characteristics. The content of the component (H) in the nonvolatile component can be measured by, for example, infrared spectrophotometry (FTIR) or gas chromatography/mass spectrometry. If the number average molecular weight of the thermoplastic elastomer of the component (B) is too large, the thermoplastic elastomer may be difficult to melt and may deteriorate workability. However, by containing a compound having an isocyanurate ring structure and 2 allyl groups in 1 molecule and being liquid at 25 ℃, even when a thermoplastic resin having a large molecular weight is used, the melt viscosity of the resin composition can be reduced and film formation can be easily performed. Further, for example, when 50 parts by mass or more of the filler (G) is added to 100 parts by mass of the nonvolatile component in the resin composition, the resin composition after curing may be fragile and cracks may occur when the resin composition is formed into a film. In contrast, by adding the component (H) in the above range, occurrence of cracks when the resin composition is formed into a film can be suppressed. Further, by adding the component (H) in the above range, curling, which will be described later, can be suppressed when the resin composition is formed into a film. From the above point of view, the component (H) is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, still more 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).

As the component (H), a compound having an isocyanurate ring structure and 2 allyl groups in 1 molecule and being liquid at 25 ℃, for example, the trade name "L-DAIC" manufactured by Kagaku Kogyo Co., ltd. Further, as a flame retardant crosslinking agent having an isocyanurate ring structure and 2 allyl groups in 1 molecule and having a phosphorus-based substituent at the terminal, there is exemplified a product name "P-DAIC" manufactured by four chemical industry, inc.

[ Other Components ]

The resin composition of the present embodiment may further contain components other than the components (a) to (H) described above. Examples of the other components include various additives such as a colorant, a dispersant, a silane coupling agent, an antioxidant, and a rheology control agent.

[ 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 above-described components using, for example, a kneader, a pot mill, a three-roll mill, a rotary mixer, a twin-shaft mixer, or the like.

[ Use of resin composition ]

The resin composition of the present embodiment can be preferably used as a resin composition for an adhesive film used for an electronic component. The resin composition of the present embodiment can be preferably used as an interlayer adhesive sheet or an interlayer adhesive for multilayered substrates. When the resin composition of the present embodiment is used for various applications for electronic components, the electronic components to be bonded are not particularly limited, and examples thereof include ceramic substrates, organic substrates, semiconductor chips, semiconductor devices, and the like.

An adhesive film, an adhesive sheet for interlayer adhesion, an interlayer adhesive, and the like using the resin composition of the present embodiment are included as cured products of the resin composition in a laminate or a semiconductor device constituting an electronic component or the like. Therefore, the cured product of the resin composition of the present embodiment is preferably contained in a laminate or a semiconductor device constituting an electronic component or the like.

The resin composition according to the present embodiment can also be used as a resin composition for manufacturing a semiconductor package with an antenna (a resin composition for a semiconductor package with an antenna). The details of the semiconductor package with the antenna will be described later. In such a semiconductor package with an antenna, the resin composition of the present embodiment can be preferably used as a resin composition for connecting the semiconductor device portion and the insulating layer of the antenna portion or for forming the insulating layer inside the antenna portion.

[ Semiconductor Package with antenna ]

Next, an embodiment of the semiconductor package with an antenna will be described. One embodiment of the semiconductor package with an antenna is a semiconductor package with an antenna 100 as shown in fig. 1. Fig. 1 is a schematic partial sectional view showing one example of a semiconductor package with an antenna.

As shown in fig. 1, the semiconductor package with antenna 100 has an antenna portion 5 integrally formed in a semiconductor device portion 10, and in particular, the semiconductor package with antenna 100 is a high-frequency substrate on which an RF (radio frequency) chip 8 for performing transmission/reception communication of 5G millimeter waves is mounted. In the semiconductor device section 10, the antenna section 5 is connected to the RF chip 8 that performs millimeter wave communication through the wiring layer 4 having various wiring patterns.

The semiconductor device 10 in the semiconductor package with antenna 100 shown in fig. 1 includes a core substrate 2, an antenna 5 provided on one surface side of the semiconductor device 10, an insulating layer 1 (first insulating layer 1A) for connecting the semiconductor device 10 and the antenna 5, a wiring layer 4 having a multilayer structure disposed in the core substrate 2, and insulating layers 1 (second insulating layer 1B, third insulating layer 1C, fourth insulating layer 1D, and fifth insulating layer 1E) configured to cover wiring holes in the wiring layer 4. The first insulating layer 1A may be provided not only so as to be interposed between the semiconductor device section 10 and the antenna section 5, but also so as to extend into the antenna section 5.

In the semiconductor package with antenna 100, on the other surface side of the semiconductor device section 10, one portion of the wiring layer 4 is connected to the RF chip 8 that performs transmission/reception communication of millimeter waves, and the other portion of the wiring layer 4 is connected to the electrical connection metal 7. In the example shown in fig. 1, the wiring layer 4 and the RF chip 8 are electrically connected via a hemispherical connection pad 9. The electric connection metal 7 is a terminal portion for physically and/or electrically connecting the semiconductor package 100 with an antenna to the outside through the electric connection metal 7 in combination with its function.

The insulating layer 1 suppresses attenuation of a current or millimeter wave signal output from the RF chip 8 at the time of transmission, and transmits the same to the antenna section 5 and efficiently radiates the same to space, so that it is required to reduce loss (transmission loss) of a connection section connecting the antenna section 5 and the RF chip 8. In order to suppress attenuation of the reflected wave of the millimeter wave signal received by the antenna unit 5 and transmit the same to the RF chip 8 as the receiving unit, it is also required to reduce loss (transmission loss) of the connection unit connecting the antenna unit 5 and the RF chip 8.

The antenna section 5 is provided as a patch antenna of a planar antenna on one surface side of the semiconductor device section 10.

The semiconductor package with antenna 100 has particularly main features in terms of the structure of at least one insulating layer 1 among the insulating layers 1 (for example, the first insulating layer 1A) for connecting the semiconductor device section 10 and the antenna section 5, and the insulating layer 1 inside the antenna section 5. The structure of the insulating layer 1 in the semiconductor package with antenna 100 according to the present embodiment will be described in more detail below. Hereinafter, the insulating layer 1 for connecting the semiconductor device unit 10 and the antenna unit 5 and the insulating layer 1 inside the antenna unit 5 may be simply referred to as "insulating layer 1".

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

The semiconductor package with antenna 100 equipped with the insulating layer 1 configured as described above is excellent in solder heat resistance and has low dielectric characteristics. In the semiconductor package with antenna 100 equipped with the antenna portion 5 for 5G millimeter wave, for example, there is a case where a soldering test at 288 ℃ is performed on the insulating layer 1 for connecting the antenna portion 5, and soldering heat resistance at a heat-resistant temperature, which has been conventionally unnecessary, is required. Conventional high-frequency films are used for the insulating layer in the semiconductor package, but there are films that do not satisfy the above-described soldering heat resistance, including many films that cannot be used for the semiconductor package 100 with an antenna equipped with the 5G millimeter wave antenna section 5. In the semiconductor package with antenna 100 of the present embodiment, it is preferable that the dielectric loss tangent (tan δ) measured by the SPDR (split column dielectric resonator) method at a frequency of 10GHz is 0.0020 or less and the solder heat resistance is 290 ℃ or more for 2 minutes with respect to the cured product constituting the insulating layer 1.

The insulating layer 1 can be obtained by heat curing a resin composition containing the above-mentioned component (a) and component (B). The resin composition used for forming the insulating layer 1 is a resin composition configured in the same manner as the resin composition of the present invention described hereinabove. The resin composition may contain any other component of the components (C) to (H) and other components other than the components (A) and (B) described above.

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

In the semiconductor package with antenna 100, it is preferable that the first insulating layer 1A for connecting the semiconductor device section 10 and the antenna section 5 and the second insulating layer 1B, the third insulating layer 1C, the fourth insulating layer 1D, and the fifth insulating layer 1E each be configured so as to cover the wiring through-hole in the wiring layer 4 are configured in the same manner as the insulating layer 1 composed of the cured product described above.

Next, the method for producing the insulating layer 1 in the semiconductor package with antenna 100 is not particularly limited, and the following method is exemplified.

First, a resin composition for a semiconductor package with an antenna, which contains at least a component (a) and a component (B), is prepared. Hereinafter, the "resin composition for semiconductor package with antenna" may be simply referred to as "resin composition". From the viewpoint of handling, the resin composition is preferably in the form of a film. 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 a component (A) and a component (B) to a PET film which is a support and subjected to a mold release treatment, and drying the film at 80 to 130 ℃. The obtained film for the semiconductor package with an antenna is peeled off from the support and attached to the semiconductor device 10, and heat treatment is performed at 200 ℃ for 30 minutes to 60 minutes, for example, to thereby manufacture the semiconductor package with an antenna.

The structure of the wiring layer 4 and the like in the semiconductor device section 10 in the semiconductor package with antenna 100 is not limited to the structure shown in fig. 1, and can be applied to various semiconductor packages equipped with antennas for 5G millimeter waves. For example, fig. 2 is a schematic partial cross-sectional view showing other examples of a semiconductor package with an antenna.

The semiconductor package 200 with an antenna shown in fig. 2 has the antenna portions 25 and 26 integrally formed in the semiconductor device portion 30. In the semiconductor device 10, the antenna portions 25 and 26 are connected to an RF chip 28 for millimeter wave communication through a wiring layer 24 having various wiring patterns.

The semiconductor device section 30 includes a core substrate 22, an antenna section 25 provided on one surface side of the semiconductor device section 30, and an insulating layer 21 for connecting the semiconductor device section 30 and the antenna section 25. An RF chip 28 for transmitting/receiving communication of 5G millimeter waves is accommodated in the core substrate 22, and wiring is performed through a wiring layer 24 disposed in the core substrate 22. The antenna portions 26 are provided at both ends of the semiconductor device portion 30 as dipole antennas in which linear wires (elements) are provided symmetrically. The other surface side of the semiconductor device portion 30 is connected to an electric connection metal 27, and the electric connection metal 27 is used to physically and/or electrically connect the semiconductor package 200 with an antenna to the outside.

In the semiconductor package 200 with an antenna shown in FIG. 2, the insulating layer 21 is made of a cured product of a resin composition containing a polyphenylene ether resin having a carbon-carbon double bond-containing functional group at the terminal as the component (A) and a thermoplastic elastomer having a number average molecular weight of 60,000 or more as the component (B), whereby the solder heat resistance is excellent and the dielectric characteristics are low. The cured product used for the insulating layer 21 may be a cured product configured in the same manner as the cured product used for the insulating layer 1 of the semiconductor package with antenna 100 shown in fig. 1.

Examples

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples, parts,% means parts by mass, mass% unless otherwise indicated.

(Examples 1 to 20, comparative examples 1 to 2)

[ Sample preparation ]

The components were measured and blended in accordance with the blending ratios (parts by mass) shown in tables 1 to 4 below, and then the components were put into a reaction vessel heated to 80℃and rotated at 150rpm, and simultaneously mixed at normal pressure for 4 hours. In the case of adding the curing agent of the component (D) and/or the organic peroxide of the component (E), after cooling, the curing agent of the component (D) and/or the organic peroxide of the component (E) are added. In the above manner, varnishes containing the resin compositions of examples 1 to 20 and comparative examples 1 to 2 were prepared.

In examples 1 to 20 and comparative examples 1 to 2, raw materials used for the preparation of the resin compositions are as follows. The number average molecular weight (Mn) of the component (a), the component (B) and the component (B') was determined by chromatography.

[ Component (A) [ polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the terminal ]

(A1) Polyphenylene ether resin having methacrylic group at the terminal, SABIC, trade name "Noryl SA9000", number average molecular weight (Mn): 1,700.

(A2) Polyphenylene ether resin having a styryl group at the terminal, trade name "OPE-2200" manufactured by Mitsubishi chemical corporation, number average molecular weight (Mn): 2,200.

(A3) Polyphenylene ether resin having a styryl group at the terminal, trade name "OPE-1200", number average molecular weight (Mn): 1,200, manufactured by Mitsubishi chemical corporation.

[ (B) component: thermoplastic elastomer having a number average molecular weight of 60,000 or more ]

(B1) Styrene elastomer (SEBS (styrene ratio: 31%)), trade name "setan 8004", number average molecular weight (Mn): 76,495, manufactured by Laura's society.

(B2) Styrene elastomer (SEBS (styrene ratio: 33%)), trade name "setan 8006", number average molecular weight (Mn): 125,769, manufactured by Laura's society.

(B3) Styrene elastomer (SEEPS, styrene ratio: 30%), brand name "setan V9461", number average molecular weight (Mn): 129,783, manufactured by Laura's society.

[ (B') component: thermoplastic elastomer having number average molecular weight of less than 60,000 ]

(B' 4) styrene elastomer (SEBS (styrene ratio: 30%)), trade name "G1652" manufactured by Takara Shuzo, and number average molecular weight (Mn): 53,864.

(B' 5) styrene elastomer (SEEPS-OH (styrene ratio: 28%)), trade name "HG-252", number average molecular weight (Mn): 54,029, manufactured by Kyoro Lae.

[ (C) component: epoxy resin ]

(C1) Bisphenol A type epoxy resin, mitsubishi chemical, trade name "828EL".

(C2) Novolac epoxy resin manufactured by kayaku corporation under the trade name "EPPN-502H".

[ (D) component, curing agent ]

(D1) Manufactured by ADEKA corporation under the trade name "EH2021".

[ Component (E): organic peroxide ]

(E1) The trade name is "dock Z" manufactured by Nikki chemical Co., ltd.

(E2) The trade name "ring D" is manufactured by Nikko chemical Co., ltd.

[ (F) component, flame retardant ]

(F1) The trade name "OP935" manufactured by the Umbelliferae company.

[ (G) component, filler ]

(G1) Spherical silica surface-treated with an aminosilane coupling agent, trade name "SC4050 SX", average particle diameter 1.0. Mu.m, manufactured by UK.

[ (H) component, crosslinker ]

(H1) Manufactured by four kingdoms chemical industry Co., ltd., trade name "L-DAIC".

(H2) Manufactured by four kingdoms chemical industry Co., ltd., trade name "P-DAIC".

The "raw material ratio" column of tables 1 to 4 shows the ratios of raw materials used in the preparation of the resin compositions in examples 1 to 17 and comparative examples 1 to 2. The ratios in the columns of "raw material ratios" in tables 1 to 4 are as follows. The column "a/(a+b+b ')×100 (mass ratio)" shows the content (parts by mass) of the component (a) relative to 100 parts by mass of the total of the components (a), (B) and (B'). The column "B/(a+b) ×100 (mass ratio)" shows the content (parts by mass) of the component (B) relative to 100 parts by mass of the total of the components (a) and (B). The column "C/(a+b+c) ×100 (mass ratio)" shows the content (parts by mass) of the component (C) relative to 100 parts by mass of the total of the component (a), the component (B), and the component (C).

Next, a varnish containing the resin composition prepared in the above manner was applied to one surface of a support (a PET film subjected to a mold release treatment), and dried at 100 ℃.

The adhesive film with a support obtained in the above manner was evaluated for dielectric characteristics by the following method. The measurement results are shown in tables 1 to 4.

[ Dielectric characteristics (dielectric constant (. Epsilon.), dielectric loss tangent (tan. Delta)) ]

The release-treated PET film was sandwiched between both sides of the adhesive film, and the adhesive film was thermally cured using a press machine. The conditions were set to 200℃for 60 minutes and 10kgf/cm ² by heat curing with a press. Thereafter, the PET film which was disposed on both sides of the cured adhesive film and subjected to the release treatment was removed, and test pieces (50.+ -. 0.5 mm. Times.100.+ -. 2 mm) were cut out from the adhesive film to measure the thickness. The "film thickness" columns of tables 1 to 4 show the film thicknesses of the adhesive films measured. Next, the dielectric constant (epsilon) and the dielectric loss tangent (tan δ) of the film (test piece) of which the thickness was measured were measured by a dielectric resonator method (SPDR method). The measurement frequency was set to 10GHz by the dielectric resonator method. For the dielectric constant (. Epsilon.), 2.50 or less is regarded as "excellent", more than 2.50 and 3.00 or less as "good", and more than 3.00 as "poor". In addition, the dielectric loss tangent (tan δ) is regarded as "excellent", 0.00010 or more and less than 0.0020 are regarded as "good", 0.0020 or more and less than 0.0030 are regarded as "fair", and 0.030 or more are regarded as "poor".

The following weld heat resistance test and evaluation of peel strength and curling property were performed on the obtained adhesive film with a support. The results are shown in tables 1 to 4.

[ Soldering Heat resistance ]

According to JIS C5012 (1993). Specifically, copper foil is attached to both surfaces of the adhesive film with the roughened surface as the inner side, and thermocompression bonding is performed by a press machine. The conditions of the thermocompression bonding were 200℃for 60 minutes and 10kgf/cm ². The test piece obtained was cut into 25mm×25mm pieces, and the pieces were floated in a solder bath heated to 288 ℃ to confirm whether or not expansion occurred for 4 minutes. 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 swelling occurred for 4 minutes, it was described as "4 min.ltoreq.4". The weld heat resistance was evaluated as "excellent" when no expansion occurred for 4 minutes or more. The time until the occurrence of swelling was 3 minutes or more and less than 4 minutes was regarded as "good", the time of 2 minutes or more and less than 3 minutes was regarded as "fair", and the time of less than 2 minutes was regarded as "poor".

[ Peel Strength ]

According to JIS C6471. Specifically, copper foil is attached to both surfaces of the adhesive film with the roughened surface as the inner side, and thermocompression bonding is performed by a press machine. The copper foil was manufactured by Fufield Metal foil Co., ltd. With a trade name of "CF-T9", 18. Mu.m. The conditions of the thermocompression bonding were 200℃for 60 minutes and 10kgf/cm ². The obtained test piece was cut into a width of 10mm, and peeled off using a universal tester (zebra), and the peel strength was measured. For the measurement results, an average value of each n=5 was calculated.

[ Curling property ]

First, a varnish containing a resin composition was applied to one surface of a support (a PET film having a thickness of 38 μm subjected to a mold release treatment), and dried at 100 ℃. After the obtained adhesive film with a support was returned to normal temperature, the adhesive film with a support was cut into a size of 30cm×50cm, and a test piece for evaluating curling was produced. The prepared test piece was placed on a horizontal table with the support side of the test piece being the lower side, and the length (warpage amount) of the test piece shortened by curling was measured as follows. First, a side of one front end portion of a test piece placed on a horizontal stage is fixed to the stage. In this way, for the test piece to which the edge of one front end portion is fixed, the length of the edge of the opposite front end portion of the test piece shortened by the curl is measured. The test piece was considered to be satisfactory (good; "poor") when the length (warpage) of the test piece, which was shortened by curling, was less than 5cm, and also considered to be satisfactory (fair; ". DELTA.") when it was 5cm or more and less than 7cm, and considered to be poor ("×") when it was 7cm or more.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

Results (results)

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 the component (A) and a thermoplastic elastomer having a number average molecular weight of 60,000 or more as the component (B). The resin compositions of examples 1 to 20 showed good results in each evaluation of dielectric properties (dielectric constant (. Epsilon.) and dielectric loss tangent (tan. Delta)), solder heat resistance, peel strength, and curling property.

Among the resin compositions of examples 1 to 17, the resin compositions using SEBS styrene-based elastomer as the component (B) (i.e., examples 1 to 5 and examples 7 to 17) showed particularly good results in evaluation of curling property. The resin compositions of examples 16 and 18 to 20 also satisfied the qualification criteria in each evaluation of weld heat resistance, peel strength, and curling properties, and particularly the resin compositions of examples 16,18, and 19 containing a predetermined amount or more of the crosslinking agent of component (H) exhibited good results in all the evaluations including the evaluation of curling properties.

The resin compositions of comparative examples 1 and 2 were resin compositions using a thermoplastic elastomer having a number average molecular weight of less than 60,000 as component (B'), and were extremely inferior in weld heat resistance to the resin compositions of examples 1 to 17. In addition, in the evaluation of the curling property, the resin composition of comparative example 2 had a very large length (amount of warpage) shortened by the curling, and the evaluation result of the curling property was very poor. The reason why the resin composition of comparative example 2 had deteriorated in curling properties is presumed to be that an SEEPS-OH styrene elastomer was used as the thermoplastic elastomer.

Industrial applicability

The resin composition of the present invention can be used as a resin composition for an adhesive film used for electronic parts. The resin composition of the present invention can be used as an adhesive sheet for interlayer adhesion or an interlayer adhesive for multilayered substrates. Further, the semiconductor package with an antenna using the resin composition of the present invention can be used as a high-frequency substrate on which an RF chip for performing transmission/reception communication of 5G millimeter waves is mounted. 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.

Symbol description

1. Insulating layer

1A first insulating layer

1B second insulating layer

1C third insulating layer

1D fourth insulating layer

1E fifth insulating layer

2. Core substrate

4 Wiring layer

5 Antenna part (Patch antenna)

7. Electrically connecting metal

8 RF chip

9. Connecting pad

10. Semiconductor device unit

21. Insulating layer

22-Core substrate

24. Wiring layer

25 Antenna (Patch antenna)

26 Antenna (dipole antenna)

27. Electrically connecting metal

28 RF chip

30. Semiconductor device unit

100. 200 Semiconductor package with antenna

Claims (16)

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] In the formula (1), ^R1 represents a hydrogen atom or an alkyl group. 4 . The resin composition according to claim 1 , 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 claim 1 , 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 claim 1 , wherein the mass ratio of the component (A) to the component (B) is 5:95 to 70:30. 9 . The resin composition according to claim 1 , wherein the content of the component (B) is larger than the content of the component (A). 10 . The resin composition according to claim 1 , further comprising (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 claim 1 , further comprising (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 .