WO2024048055A1

WO2024048055A1 - Resin composition, adhesive film, bonding sheet for interlayer adhesion, and resin composition for semiconductor package with antenna

Info

Publication number: WO2024048055A1
Application number: PCT/JP2023/024266
Authority: WO
Inventors: 遼宇佐美; 寛史高杉
Original assignee: ナミックス株式会社
Priority date: 2022-08-31
Filing date: 2023-06-29
Publication date: 2024-03-07

Abstract

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

Description

Resin compositions, adhesive films, interlayer bonding sheets, and resin compositions for semiconductor packages with antennas

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

With the recent demand for higher speed transmission signals in printed wiring boards, the frequency of transmission signals is becoming significantly higher. Accordingly, materials used for printed wiring boards are required to be able to reduce transmission loss in a high frequency region, specifically, in a frequency region of 1 GHz or higher.

As a resin composition used for an insulating layer of a printed wiring board, for example, a thermosetting resin composition containing a thermosetting resin having a styrene group at the end and a styrene thermoplastic elastomer is known. (For example, Patent Document 1). For example, in the thermosetting resin composition disclosed in Patent Document 1, a thermosetting resin having a styrene group at the terminal and having a phenylene ether skeleton is used as the thermosetting resin having a styrene group at the terminal. There is. Furthermore, as the styrene thermoplastic elastomer, a low molecular weight styrene elastomer is used.

Additionally, in recent years, the standardization of 5G as a next-generation communication technology has progressed, and the market demand for products compatible with high frequencies is increasing. Technological developments such as multi-element antenna technology and high-speed transmission are accelerating, and the use of high-frequency bands increases communication capacity.At the same time as information processing capacity improves, high-frequency noise and heat generation also increase, making countermeasures a major issue. It becomes.

For example, 5G millimeter wave antennas require a structure that reduces conductor loss (in other words, has low transmission loss) by shortening the wiring distance between the antenna and the IC in terms of packaging technology. For this reason, in recent years, semiconductor packages with antennas (eg, antenna-in-package (AiP) and antenna-on-package (AoP)) in which the antenna portion is integrally formed with the semiconductor device portion have been developed. In such a package, the insulating layer around the antenna also becomes hotter than in a conventional structure due to heat generation from the IC, so it is required to have low dielectric loss even when placed in a high-temperature environment. Note that "IC" refers to an integrated circuit.

International Publication No. 2019/230531

As described above, the resin composition disclosed in Patent Document 1 contains a thermosetting resin having a styrene group at the end and a styrene thermoplastic elastomer. It is said to contain a thermoplastic resin and a styrene thermoplastic elastomer. On the other hand, soldering heat resistance is sometimes required for insulating layers of printed wiring boards, but the resin composition disclosed in Patent Document 1 does not mention such soldering heat resistance. do not have.

Resin compositions intended for use in the high frequency range mentioned above are required to have excellent solder heat resistance and low dielectric properties, and there is a strong desire to develop resin compositions that have excellent properties. There is.

The present invention has been made in view of the problems of the prior art. The present invention provides a resin composition that can be suitably used for adhesive films, interlayer bonding sheets, interlayer adhesives, etc., and has excellent solder heat resistance and low dielectric properties. Furthermore, the present invention provides an adhesive film, a bonding sheet for interlayer bonding, and a resin composition for a semiconductor package with an antenna using such a resin composition.

According to the present invention, the following resin compositions, adhesive films, interlayer bonding sheets, and resin compositions for semiconductor packages with antennas are provided.

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

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

[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 its terminal.

(However, in the above formula (1), R ¹ represents a hydrogen atom or an alkyl group.)

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

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

[6] The resin composition according to [5] above, 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 [1] to [6] above, 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 [1] to [7] above, 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 [1] to [8], wherein the content of the component (B) is greater than the content of the component (A).

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

[11] The content of the component (C) is 0.1 to 5.0 parts by mass based on a total of 100 parts by mass of the component (A), the component (B), and the component (C) in the resin composition. The resin composition according to [10] above, which contains 0 parts by mass.

[12] The resin composition according to any one of [1] to [11] above, further comprising (D) a curing agent.

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

[14] An interlayer bonding sheet using the resin composition according to any one of [1] to [12] above.

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

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

The resin composition of the present invention has excellent soldering heat resistance and low dielectric properties. Therefore, the resin composition of the present invention can be suitably used for adhesive films, interlayer bonding sheets, interlayer adhesives, and the like. Furthermore, the adhesive film, interlayer adhesion bonding sheet, and resin composition for semiconductor packages with antennas of the present invention are those using the resin composition of the present invention, and are said to have excellent soldering heat resistance and low dielectric properties. be effective.

FIG. 2 is a schematic partial cross-sectional view showing an example of a semiconductor package with an antenna. FIG. 7 is a schematic partial cross-sectional view showing another example of a semiconductor package with an antenna.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. Therefore, it is understood that modifications and improvements made to the following embodiments based on the common knowledge of those skilled in the art without departing from the spirit of the present invention also fall within the scope of the present invention. Should.

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

The resin composition of this embodiment has excellent solder heat resistance and low dielectric properties. In particular, the resin composition of this embodiment includes a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end as the component (A), thereby imparting low dielectric properties to the resin composition. Solder heat resistance can be effectively improved. Further, by including a thermoplastic elastomer having a number average molecular weight of 60,000 or more as component (B), the resin composition becomes difficult to melt, and the soldering heat resistance can be further improved.

In addition to the above-mentioned components (A) and (B), the resin composition of the present embodiment contains (C) an epoxy resin, (D) a curing agent, (E) an organic peroxide, and (F) a hardening agent. Other components such as a refueling agent, (G) a filler, and (H) a crosslinking agent may also be included. Hereinafter, each of the above-mentioned components may be referred to as components (C) to (H) as appropriate.

[(A) component]
Component (A) is a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end. Examples of the functional group containing a carbon-carbon double bond include a terminal vinyl group, a vinylene group, and a vinylidene group. Component (A) is not particularly limited as long as it has a functional group containing a carbon-carbon double bond at its terminal and polyphenylene ether in its skeleton. By including component (A), it is possible to effectively improve solder heat resistance while imparting low dielectric properties to the resin composition.

Examples of component (A) include those containing modified polyphenylene ether having a styrene structure at the end. Such modified polyphenylene ether is not particularly limited as long as it has a styrene structure at its terminal. The styrene structure may be an unsubstituted styrene group having no substituent, or a styrene group having any substituent. By including such component (A), the solder heat resistance of the resin composition can be improved. In particular, modified polyphenylene ether having a styrene structure at its terminal undergoes a curing reaction even without the use of peroxide, and has extremely excellent soldering heat resistance.

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

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

In structural formula (3), R ² , R ³ , R ⁴ , R ⁷ , and R ⁸ are an alkyl group or a phenyl group having 6 or less carbon atoms, and may be the same or different from each other. Good too. R ⁵ , R ⁶ , 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 structural formula (4), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and each 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.

Furthermore, in general formula (2), -(YO)- is represented by the above structural formula (5). In -(YO)-, one type of structure or two or more types of structures are arranged randomly. In Structural Formula (5), R ¹⁸ and R ¹⁹ are an alkyl group or a phenyl group having 6 or less carbon atoms, 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.

Furthermore, in the general formula (2), a and b are integers of 0 to 100. At least one of a and b is not 0.

-A- in structural formula (4) is, for example, methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1 -methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene. However, -A- in structural formula (4) is not limited to these.

In the compound represented by general formula (2), R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹⁸ , and R ¹⁹ are alkyl groups having 3 or less carbon atoms, and 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 ²¹ are preferably hydrogen atoms or alkyl groups having 3 or less carbon atoms. In particular, -(O-X-O)- represented by structural formula (3) or (4) is represented by the following structural formula (6), structural formula (7), or structural formula (8). More preferably, it is a compound that Similarly, in particular, -(Y-O)- represented by structural formula (5) is a compound represented by the following structural formula (9) or structural formula (10), or It is more preferable that the compound represented by (9) and the compound represented by Structural Formula (10) be randomly arranged.

The method for producing the compound represented by general formula (2) is not particularly limited. For example, the compound represented by general formula (2) can be produced by the following method. First, a difunctional phenylene ether oligomer is obtained by oxidative coupling of a difunctional phenol compound and a monofunctional phenol compound. Next, the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer is converted into vinylbenzyl ether. In this way, the compound represented by general formula (2) can be produced.

The number average molecular weight of the compound represented by general formula (2) is preferably from 1,000 to 5,000, more preferably from 1,000 to 3,000, and from 1,000 to 2,500. It is even more preferable that there be. When the number average molecular weight is 1000 or more, stickiness is unlikely to occur when the resin composition is formed into a coating film. Moreover, if the number average molecular weight is 5,000 or less, a decrease in solubility in a solvent in the resin composition 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 properties and curability at high frequencies of the resin composition are improved. Here, the above-mentioned number average molecular weight is determined by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

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

Examples of the polyphenylene ether having a styrene structure at the end of component (A) include the product names "OPE-2200" and "OPE-1200" manufactured by Mitsubishi Gas Chemical Company.

In addition, as the component (A), in addition to those containing the modified polyphenylene ether having a styrene structure at the terminal described above (for example, the compound represented by the above general formula (2)), Examples include those containing a modified polyphenylene ether having the group shown in 1).

In the above formula (1), R ¹ represents a hydrogen atom or an alkyl group. Further, the alkyl group for 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. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.

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

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

In the above structural formula (11), m represents 1 to 50. Further, R ²² to R ²⁵ are each independent and may be the same or different from each other. R ²² to R ²⁵ represent 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 these, hydrogen atoms and alkyl groups are preferred.

Specific examples of the functional groups listed in R ²² to R ²⁵ include the following.

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

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

The alkynyl group in R ²² to R ²⁵ is not particularly limited, but is preferably an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples include ethynyl group and prop-2-yn-1-yl group (propargyl group).

The alkylcarbonyl group in R ²² to R ²⁵ is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is preferable. group is more preferred. Specific examples include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, hexanoyl group, octanoyl group, and cyclohexylcarbonyl group.

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

The alkynylcarbonyl group in R ²² to R ²⁵ is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is preferable. group is more preferred. Specifically, for example, a propioloyl group and the like can be mentioned.

As the modified polyphenylene ether having a group represented by the above formula (1), for example, a group represented by the above formula (1) is added to the terminal of a polyphenylene ether represented by the following formula (12) or formula (13). Examples include those that have. Specific examples of the modified polyphenylene ether include modified polyphenylene ether represented by the following formula (14) or formula (15).

In formulas (12) to (15), s and t are preferably such that the total value of s and t is 1 to 30, for example. Further, s is preferably from 0 to 20, and t is preferably from 0 to 20. That is, s preferably represents 0 to 20, t represents 0 to 20, and the sum of s and t preferably represents 1 to 30. In formulas (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. Moreover, in formula (14) and formula (15), R ¹ is the same as R ¹ in the above formula (1), and represents a hydrogen atom or an alkyl group. Further, the alkyl group 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. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.

The number average molecular weight (Mn) of the modified polyphenylene ether having the group represented by formula (1) is not particularly limited. Specifically, it is preferably 500 to 5,000, more preferably 800 to 4,000, and even more preferably 1,000 to 3,000. Here, the number average molecular weight may be one measured by a general molecular weight measurement method, and specifically, a value measured using gel permeation chromatography (GPC), etc. can be mentioned. In addition, when the modified polyphenylene ether having the group represented by formula (1) has a repeating unit represented by formula (11) in the molecule, m is the weight average molecular weight of the modified polyphenylene ether such that It is preferable that the value falls within a certain range. Specifically, m is preferably 1 to 50.

When the weight average molecular weight of the modified polyphenylene ether having the group represented by formula (1) is within the above numerical range, the cured product will have excellent heat resistance while having excellent dielectric properties derived from polyphenylene ether. Furthermore, the moldability of the resin composition can also be improved. For example, if the weight average molecular weight of conventional polyphenylene ether is within the above numerical range, the molecular weight will be relatively low, and the heat resistance of the cured product will tend to decrease. On the other hand, the modified polyphenylene ether having the group represented by formula (1) above has the group represented by formula (1) at the end, and therefore can improve the heat resistance of the cured product. Furthermore, since the weight average molecular weight of the modified polyphenylene ether can be made relatively low, it also has excellent moldability. For this reason, by using component (A) containing a modified polyphenylene ether having a group represented by formula (1) at the terminal, a resin composition having better heat resistance and moldability of the cured product can be obtained. Can be done.

Furthermore, in the modified polyphenylene ether used as component (A), the average number of groups represented by the above formula (1) at the molecular ends (number of terminal functional groups) per molecule of modified polyphenylene ether is not particularly limited. . Specifically, the number is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. In addition, if the number of terminal functional groups is too large, the reactivity becomes too high, which may cause problems such as a decrease in the storage stability of the resin composition or a decrease in the fluidity of the resin composition. . That is, when such modified polyphenylene ether is used, molding defects such as voids occur during multilayer molding due to insufficient fluidity, resulting in poor moldability that makes it difficult to obtain a highly reliable printed wiring board. Problems could have arisen.

The number of terminal functional groups of the above-mentioned modified polyphenylene ether is a numerical value representing the average value of the groups represented by the above formula (1) per molecule of all the modified polyphenylene ethers present in 1 mole of the modified polyphenylene ether. Can be mentioned. The number of 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 from the number of hydroxyl groups in the polyphenylene ether before modification. The number of terminal functional groups is the decrease from the number of hydroxyl groups in the polyphenylene ether before modification. The method for measuring the number of hydroxyl groups remaining in modified polyphenylene ether is to add a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of modified polyphenylene ether, and measure the UV absorbance of the mixed solution. It can be found by

Furthermore, the intrinsic viscosity of the modified polyphenylene ether used as component (A) is not particularly limited. Specifically, it is preferably 0.03 to 0.12 dl/g, more preferably 0.04 to 0.11 dl/g, and even more preferably 0.06 to 0.095 dl/g. preferable. If the intrinsic viscosity is too low, the molecular weight tends to be low, making it difficult to obtain low dielectric properties such as low dielectric constant and low dielectric loss tangent. Furthermore, if the intrinsic viscosity is too high, the viscosity will be high, sufficient fluidity will not be obtained, and the moldability of the cured product will tend to deteriorate. 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 above-mentioned intrinsic viscosity is an intrinsic viscosity measured in methylene chloride at 25°C, and more specifically, for example, a 0.18 g/45ml methylene chloride solution (liquid temperature 25°C) was measured with a viscometer. value etc. Examples of this viscometer include the product name "AVS500 Visco System" manufactured by Schott.

Furthermore, the method for synthesizing the modified polyphenylene ether used as component (A) is not particularly limited as long as it can synthesize a modified polyphenylene ether having a group represented by the above formula (1) at its terminal.

Component (A) may be a modified polyphenylene ether having a group represented by the above formula (1) at its end, or a modified polyphenylene ether having a group represented by the above formula (1) at its end. Two or more types may be used in combination. Furthermore, it may be used in combination with one or more of the compounds represented by the general formula (2) described above.

As the modified polyphenylene ether having a group represented by the above formula (1) at the end of the component (A), the product name "Noryl SA9000" manufactured by SABIC Japan may be mentioned.

In addition, the content of component (A) is 5 to 70 parts per 100 parts by mass of the total of components (A), (B), and (B') from the viewpoint of having excellent low dielectric properties and soldering heat resistance. It is preferably 6 to 60 parts by weight, even more preferably 7 to 50 parts by weight, and particularly preferably 8 to 40 parts by weight. Note that the component (B') will be described later.

[(B) component]
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 component (B), the resin composition becomes difficult to melt, and the soldering heat resistance can be favorably improved. Further, 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, may be referred to as component (B').

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

The thermoplastic elastomer as component (B) preferably has a number average molecular weight of 60,000 or more, more preferably 100,000 or more, even more preferably 110,000 or more, and even more preferably 120,000 or more. It is particularly preferable that it is above. With such a number average molecular weight, the soldering 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, it may become difficult to melt the thermoplastic elastomer, resulting in poor workability. 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, even more preferably 140,000 or less, It is particularly preferred that it is 130,000 or less.

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 frequency range of 1 to 100 GHz. This can contribute to the excellent dielectric properties in the high frequency region of the thermosetting film formed from the resin composition of the present disclosure. The "thermoplastic elastomer having a dielectric loss tangent (tan δ) of less than 0.005 in the frequency range of 1 to 100 GHz" is preferably a styrene-based thermoplastic elastomer, and preferably a hydrogenated styrene-based thermoplastic elastomer. More preferred. Here, the hydrogenated styrene thermoplastic elastomer refers to a hydrogenated styrene thermoplastic elastomer, and examples of the hydrogenated styrene thermoplastic elastomer include, for example, styrene/butadiene/butylene/styrene block copolymer (monomer). Examples include partially hydrogenated, SBBS) and styrene/ethylene/butylene/styrene block copolymers (fully hydrogenated, SEBS). By using a hydrogenated styrene thermoplastic elastomer, dielectric properties can be improved. Note that when component (B) is a styrene thermoplastic elastomer, the styrene ratio of component (B) is preferably 10 to 70%, more preferably 15 to 60%. When the styrene ratio of component (B) is 20 to 50%, film forming properties and workability are excellent.

The hydrogenated styrenic thermoplastic elastomer of component (B) is not particularly limited, but is preferably a styrene/ethylene/butylene/styrene block copolymer (SEBS). Styrene/ethylene/butylene/styrene block copolymer (SEBS) is a fully hydrogenated styrene-based thermoplastic elastomer, and since it is a styrene-based thermoplastic elastomer without double bonds, it can further improve dielectric properties. Can be done. Further, by using a styrene/ethylene/butylene/styrene block copolymer (SEBS) having a number average molecular weight of 60,000 or more, it is possible to improve solder heat resistance while maintaining good dielectric properties. Furthermore, by using styrene/ethylene/butylene/styrene block copolymer (SEBS) as the component (B), when the resin composition is formed into a film, the film is less likely to curl. Another suitable example of the hydrogenated styrene thermoplastic elastomer as component (B) is styrene/ethylene/ethylene/propylene/styrene block copolymer (SEEPS).

There is no particular restriction on the content of component (B), but the mass ratio of component (A) to component (B) (component (A):component (B)) is 5:95 to 70:30. The ratio is preferably 10:90 to 67:33, even more preferably 20:80 to 60:40, and particularly preferably 25:75 to 40:60. Furthermore, from the viewpoint of soldering heat resistance, the content of component (B) is preferably greater than that of component (A). However, if the ratio of component (B) is too high, when the resin composition is formed into a film, the film may be more likely to tack, which may reduce workability. Furthermore, if the ratio of component (B) increases, the dielectric properties of the resin composition may deteriorate, so it is preferably within the above range.

Further, when the amount of the resin composition excluding filler is 100 parts by mass, the content of component (B) is preferably 20 to 95 parts by mass, more preferably 30 to 93 parts by mass, and 35 parts by mass. More preferably, the amount is 80 parts by mass. By being within this range, excellent solder heat resistance can be achieved while maintaining low dielectric properties.

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

Examples of the thermoplastic elastomer in which the component (B) has a number average molecular weight of 60,000 or more include "Septon 8004", "Septon 8006", and "Septon V9461" manufactured by Kuraray Co., Ltd., for example.

[(C) component]
Component (C) is an epoxy resin. Epoxy resin is a compound having one or more epoxy groups in its molecule, and when heated, the epoxy groups react to form a three-dimensional network structure and can be cured. By including an epoxy resin as component (C), the soldering heat resistance can be further improved. Furthermore, by including the epoxy resin as component (C), it is possible to improve the adhesion even to a smooth surface such as the shiny surface of copper.

There is no particular restriction on the content of the epoxy resin as component (C), but 0.1 to 5.0 parts by mass per 100 parts by mass of the total of components (A), (B), and (C). The amount is preferably from 0.5 to 4.0 parts by weight, and even more preferably from 0.7 to 3.0 parts by weight. If the content of component (C) is too large, the dielectric loss tangent of the cured product may become high.

Further, when the amount of the resin composition excluding the filler is 100 parts by mass, the content of component (C) is preferably 0.1 to 5.0 parts by mass, and 0.5 to 3.0 parts by mass. More preferably, the amount is 0.6 to 2.0 parts by mass.

Specific examples of epoxy resins include bisphenol compounds such as bisphenol A, bisphenol E, and bisphenol F, or derivatives thereof (e.g., alkylene oxide adducts), hydrogenated bisphenol A, hydrogenated bisphenol E, hydrogenated bisphenol F, and cyclohexanediol. , diols with alicyclic structures such as cyclohexanedimethanol and cyclohexanediethanol, or derivatives thereof; difunctional diols obtained by epoxidizing aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, and decanediol, or derivatives thereof, etc. trifunctional epoxy resin having a trihydroxyphenylmethane skeleton and an aminophenol skeleton; polyfunctional epoxy resin obtained by epoxidizing phenol novolak resin, cresol novolac resin, phenol aralkyl resin, biphenylaralkyl resin, naphthol aralkyl resin, etc. These include, but are not limited to: Preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and aminophenol type epoxy resin. The compounds exemplified here may be used alone or in combination of two or more.

The epoxy resin of component (C) is preferably liquid at room temperature (25°C).

[(D) component]
Component (D) is a curing agent. The curing agent of component (D) is not particularly limited as long as it generally cures epoxy resins, and the curing agent in the present application includes a curing catalyst that promotes the reaction of epoxy resins. Although there are no particular limitations on the curing agent, imidazole-based curing catalysts are more preferable because they allow for appropriate adjustment of curing properties.

The imidazole curing catalyst may be imidazole, and imidazole adducts, clathrated imidazole, microcapsule imidazole, imidazole compounds coordinated with stabilizers, etc. can also be used. These have a nitrogen atom with a lone pair of electrons in their structure, which can activate the epoxy group and also activate other epoxy resins used together, promoting curing. be able to.

Specific examples of imidazole-based curing catalysts 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-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-undecyl imidazolyl-(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-di(2-cyanoethoxy)methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. It is not limited to these. Imidazole that has been subjected to adduct treatment, inclusion treatment with a different molecule, microcapsule treatment, or coordination with a stabilizer is a modification of the above-mentioned imidazole. These are made by reducing the activity of imidazole by adduct treatment, inclusion treatment with different molecules, microcapsule treatment, or by coordinating a stabilizer, thereby achieving an excellent pot life at low temperatures while curing and accelerating hardening. High ability.

In addition, commercial products of imidazole (hereinafter referred to as trade names) include 2E4MZ, 2P4MZ, 2PZ-CN, C11Z-CNS, C11Z-A, 2MZA-PW, 2MA-OK, 2P4MHZ-PW, 2PHZ-PW (the above, Shikoku (manufactured by Kasei Kogyo Co., Ltd.), EH2021 (manufactured by ADEKA Co., Ltd.), etc., but is not limited to these. Commercially available imidazole adducts include, for example, PN-50, PN-50J, PN-40, PN-40J, PN-31, and PN-23, which have a structure in which an imidazole compound is ring-opened and added to the epoxy group of an epoxy resin. , PN-H (manufactured by Ajinomoto Fine Techno, Inc.), but is not limited to these. Examples of commercially available clathrate imidazoles include TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, and NIPA-2E4MZ (all manufactured by Nippon Soda). However, it is not limited to these. Examples of commercially available microcapsule imidazoles include Novacure HX3721, HX3722, HX3742, HX3748 (manufactured by Asahi Kasei Corporation), and LC-80 (manufactured by A&C Catalysts).

The content of the curing agent can be appropriately selected depending on the type of curing agent used as component (D). Further, when the amount of the resin composition other than the filler is 100 parts by mass, the content of component (D) is preferably 0.001 to 1.0 parts by mass, more preferably 0.005 to 0.60 parts by mass. . Further, the content of the imidazole curing catalyst is preferably 0.1 to 10% by mass, more preferably 1 to 6% by mass based on the epoxy resin. If the content of component (D) is too small, the curability of the film produced using the resin composition may deteriorate, and the adhesiveness, toughness, and heat resistance may deteriorate. On the other hand, if the content of component (D) is too large, there is a risk that the shelf life of the film produced using the resin composition will deteriorate, and the original physical properties of the resin will be impaired in the cured product, resulting in poor adhesiveness and toughness. There is a risk that the properties and heat resistance may decrease.

[(E) component]
Component (E) is an organic peroxide. By containing such an organic peroxide, the reaction initiation temperature of component (A) is shifted to a lower 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 can be appropriately selected depending on the type, but typically it is preferably 0.1 to 10 parts by weight, and 0.5 to 5 parts by weight, based on 100 parts by weight of component (A). part is more preferable.

Examples of organic peroxides include benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide. diacyl peroxides such as; peroxyketals such as 2,2-di(4,4-di-(di-tert-butylperoxy)cyclohexyl)propane; isopropyl purge carbonate, di-sec-butyl purge carbonate, Peroxy dicarbonates such as di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3-methoxybutyl purge carbonate, dicyclohexyl purge carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert -Butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diper adipate, cumyl perneodecanoate, tert-butyl peroxybenzoate, 2,5-dimethyl - Peroxy esters such as 2,5 di(benzoylperoxy)hexane; Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide Oxide, 2,5-dimethyl-2,5di(t-butylperoxy)hexane, 2,5-dimethyl-2,5di(t-butylperoxy)hexane-3,1,1-di(t- Dialkyl peroxides such as (hexylperoxy)-3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, di(2-tert-butylperoxyisopropyl)benzene; cumene hydroxy peroxide, tert-butyl hydro Hydroperoxides such as peroxide and p-mentha hydroperoxide can be used. There are no particular restrictions on the organic peroxide used, but when curing the resin composition, a drying process at about 60 to 80°C is often required, so the 10-hour half-life temperature is 100°C. It is preferable to use a temperature between 140°C and 140°C. Furthermore, the 10-hour half-life temperature is more preferably 110 to 130°C.

Commercially available organic peroxides for component (E) include Perbutyl H, Perbutyl Z, Perbutypercyl P, Percyl D, Percyl H, and Perhexa C (manufactured by NOF Chemical Co., Ltd.). Examples include.

[(F) component]
Component (F) is a flame retardant. The flame retardant as component (F) is an optional component that is appropriately contained within a range that does not impair the effects of the resin composition of the present embodiment described above. For example, in resin compositions used for insulating layers of printed wiring boards, in addition to the solder heat resistance and low dielectric properties described above, flame retardance may be required. In response to such demands, further inclusion of a flame retardant as component (F) can contribute to improving the flame retardancy of the cured product made of the resin composition of this embodiment.

There are no particular restrictions on the type of flame retardant. For example, as the flame retardant as component (F), inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, metal hydrates such as aluminum hydroxide hydrate, magnesium hydroxide hydrate, etc. can be mentioned. The flame retardant as component (F) may be used alone or in combination of two or more.

Examples of inorganic phosphorus-based flame retardants 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; Acids; examples include phosphine oxide.

Examples of organic phosphorus-based flame retardants include phosphate ester flame retardants, mono-substituted phosphonic acid diesters and 2-substituted phosphinic esters; metal salts of 2-substituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc. Can be mentioned. Examples of "metal salts" include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, zinc salts, and the like.

The content of the flame retardant can be appropriately selected depending on the type of flame retardant used as component (F). Furthermore, when the amount of the resin composition other than the filler is 100 parts by mass, the content of component (F) is preferably 15 to 50 parts by mass, more preferably 20 to 40 parts by mass. Further, examples of the flame retardant as component (F) include phosphinate metal salts (eg, trade name "OP-935" manufactured by Clariant Japan).

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

As the inorganic filler as component (G), a general inorganic filler can be used. For example, inorganic fillers include silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, oxidized Examples include titanium, zinc oxide, silicon carbide, silicon nitride, and boron nitride. The inorganic fillers may be used alone or in combination of two or more. In particular, from the viewpoint of insulation, silica filler and alumina filler are preferable. Moreover, from the viewpoint of dielectric properties, silica filler is preferable. The inorganic filler may be surface-treated with a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styryl, amino, epoxy, and vinyl. For example, inorganic fillers include aminosilane coupling agents, ureidosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, vinylsilane coupling agents, and styrylsilane coupling agents. Surface treatment agents such as acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, organosilazane compounds, and titanate coupling agents improve heat resistance, moisture resistance, and dispersion. Those with improved properties are preferred. These may be used alone or in combination of two or more. More preferably, among the surface-treated silica fillers, it is preferable to use a silica filler surface-treated with a vinyl silane coupling agent. By using a silica filler whose surface has been treated with a vinyl silane coupling agent, the coefficient of thermal expansion can be improved.

The shape of the inorganic filler is not particularly limited, and examples include spherical, scaly, acicular, and amorphous shapes. From the viewpoint of workability, a spherical shape is preferable. The average particle diameter is preferably 0.1 to 10 μm, more preferably 0.1 to 4 μm. When the average particle size of the inorganic filler is within this range, it has excellent embedding properties between fine structures. The average particle diameter is the particle diameter at an integrated value of 50% in a volume-based particle size distribution measured by a laser diffraction/scattering method. The average particle diameter can be measured, for example, using a laser scattering diffraction particle size distribution analyzer: LS13320 (manufactured by Beckman Coulter, wet type).

In addition, when containing component (G), the content of component (G) is preferably 0.1 to 90 parts by mass, and preferably 20 to 85 parts by mass, based on 100 parts by mass of nonvolatile components in the resin composition. It is more preferably 30 to 80 parts by weight, particularly preferably 50 to 80 parts by weight. With this configuration, the coefficient of thermal expansion can be improved satisfactorily.

[(H) component]
Component (H) is a crosslinking agent. By including a crosslinking agent as the component (H), cracking of the film made of the resin composition can be effectively prevented. Furthermore, by crosslinking with the polyphenylene ether resin as component (A), further improvement in the solder heat resistance of the resin composition can be expected.

As the crosslinking agent as component (H), for example, polybutadiene, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl isocyanurate, 2,2'-diallyl bisphenol A, etc. can be used. However, among these crosslinking agents, it is preferable to use a crosslinking agent having an isocyanuric ring structure and two allyl groups in one molecule. By having two allyl groups, the crosslinking agent (H) component can improve soldering heat resistance while having low dielectric properties. Although the details are not clear, it is presumed that the heat resistance of the resin composition is improved because the component (H) has an isocyanuric ring structure. Moreover, the (H) component may be a compound having an isocyanuric ring structure and two allyl groups in one molecule. As a result, it is possible to obtain good solder heat resistance while having low dielectric properties, and also to obtain good film formability, making it easy to form into a film. Moreover, the (H) component may be a liquid compound at 25°C.

Furthermore, the (H) component may be a flame-retardant cross-linking agent that is a cross-linking agent with the polyphenylene ether resin as the (A) component and also imparts flame retardancy. For example, a flame-retardant crosslinking agent having an isocyanuric ring structure and two allyl groups in one molecule and a phosphorus-based substituent at the terminal can be used. Thereby, it can crosslink with the polyphenylene ether resin as component (A), improve the solder heat resistance of the resin composition, and also impart flame retardancy.

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

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 R is an alkyl group having 10 to 12 carbon atoms. It is particularly preferable that Further, R may be a phosphorus-based substituent.

The content of component (H) is preferably 10 to 70 parts by mass based on 100 parts by mass of component (A). With this configuration, it is possible to improve solder heat resistance while maintaining low dielectric properties. Although not particularly limited, the content of component (H) is more preferably 15 to 65 parts by mass, and 20 to 60 parts by mass, based on 100 parts by mass of component (A). More preferably. Further, it is preferable that the component (H) is contained in 2 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 4 to 30% by mass in 100% by mass of the nonvolatile components in the resin composition. preferable. When the content ratio of the (H) component in 100% by mass of nonvolatile components in the resin composition is within this range, the dielectric properties of the resin composition are excellent. Note that the content ratio of the (H) component in the nonvolatile components can be measured by, for example, an infrared spectrophotometer (FTIR) or a gas chromatograph mass spectrometry method. Note that if the number average molecular weight of the thermoplastic elastomer as component (B) becomes too large, the thermoplastic elastomer may be difficult to melt, resulting in poor workability. However, by including a compound that has an isocyanuric ring structure and two allyl groups in one molecule and is liquid at 25°C, even when a thermoplastic resin with a large molecular weight is used, the melting of the resin composition The viscosity can be lowered and it can be easily formed into a film. In addition, for example, when adding 50 parts by mass or more of the filler (G) to 100 parts by mass of the nonvolatile components in the resin composition, the resin composition after curing tends to become brittle, and the resin composition may be formed into a film. Cracks may occur when On the other hand, by adding the component (H) in the above range, it is possible to suppress the occurrence of cracks when the resin composition is formed into a film. Furthermore, by adding component (H) in the above range, curling, which will be described later, can be suppressed when the resin composition is formed into a film. In addition, from the above viewpoint, the component (H) is preferably added in an amount of 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, and 5 to 20 parts by weight, based on 100 parts by weight of the filler (G). More preferably, the amount is 7 to 15 parts by mass.

An example of a compound that has an isocyanuric ring structure and two allyl groups in one molecule of component (H) and is liquid at 25°C is the product name "L-DAIC" manufactured by Shikoku Kasei Co., Ltd. In addition, as a flame-retardant crosslinking agent that has an isocyanuric ring structure and two allyl groups in one molecule and has a phosphorus-based substituent at the terminal, the product name "P-DAIC" manufactured by Shikoku Kasei Co., Ltd. is cited. It will be done.

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

[Method for manufacturing resin composition]
The resin composition of this embodiment can be manufactured by a conventional method. The resin composition of this embodiment can be manufactured by mixing the components described above using, for example, a Raikai machine, a pot mill, a three-roll mill, a rotary mixer, a twin-shaft mixer, etc. .

[Applications of resin composition]
The resin composition of this embodiment can be suitably used as a resin composition for adhesive films used in electronic components. Further, the resin composition of the present embodiment can be suitably used as an interlayer bonding sheet or an interlayer adhesive for multilayer substrates. When the resin composition of this embodiment is used for various purposes for electronic parts, there are no particular restrictions on the electronic parts to be bonded, and examples thereof include ceramic substrates, organic substrates, semiconductor chips, semiconductor devices, and the like.

Adhesive films, interlayer bonding sheets, interlayer adhesives, and the like using the resin composition of the present embodiment are included as cured products of the resin composition in laminates and semiconductor devices constituting electronic components and the like. Therefore, it is preferable that a cured product of the resin composition of this embodiment be included in a laminate or a semiconductor device constituting an electronic component or the like.

Moreover, the resin composition of this embodiment can also be used as a resin composition used for producing a semiconductor package with an antenna (resin composition for a semiconductor package with an antenna). Note that details of the semiconductor package with antenna will be described later. The resin composition of this embodiment is suitable as a resin composition for forming an insulating layer for connecting the semiconductor device part and the antenna part and an insulating layer inside the antenna part in such a semiconductor package with an antenna. It can be used for.

[Semiconductor package with antenna]
Next, an embodiment of a semiconductor package with an antenna will be described. One embodiment of a semiconductor package with an antenna is a semiconductor package with an antenna 100 as shown in FIG. FIG. 1 is a schematic partial cross-sectional view showing an example of a semiconductor package with an antenna.

As shown in FIG. 1, the antenna-equipped semiconductor package 100 has an antenna section 5 integrally formed with a semiconductor device section 10, and is particularly designed for RF (radio frequency) communication for transmitting and receiving 5G millimeter waves. ) A semiconductor package 100 with an antenna serves as a high frequency substrate on which a chip 8 is mounted. In the semiconductor device section 10, the antenna section 5 is connected to an RF chip 8 that performs millimeter wave communication through a wiring layer 4 having various wiring patterns.

The semiconductor device section 10 in the semiconductor package with antenna 100 shown in FIG. An insulating layer 1 for connection (first insulating layer 1A), a wiring layer 4 with a multilayer structure arranged in the core substrate 2, and an insulating layer 1 configured to cover wiring vias in the wiring layer 4. (a second insulating layer 1B, a third insulating layer 1C, a fourth insulating layer 1D, and a fifth insulating layer 1E). Note that the first insulating layer 1A is not only provided to be interposed between the semiconductor device section 10 and the antenna section 5, but also to extend into the inside of the antenna section 5. It's okay.

In the semiconductor package with antenna 100, on the other surface side of the semiconductor device section 10, a part of the wiring layer 4 is connected to an RF chip 8 that performs communication for transmitting and receiving millimeter waves, and the other part of the wiring layer 4 is 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 hemispherical connection pads 9. In the example shown in FIG. 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 depending on the function of the electrical connection metal 7.

The insulating layer 1 suppresses the attenuation of the current and millimeter wave signals output from the RF chip 8 during transmission, and transmits them to the antenna section 5 to efficiently radiate them into space. It is required to reduce the loss (transmission loss) in the connection section that connects the The same goes for reception, and in order to suppress the attenuation of the reflected wave of the millimeter wave signal received by the antenna section 5 and transmit it to the RF chip 8 as the reception section, the connection between the antenna section 5 and the RF chip 8 is necessary. It is required to reduce the loss (transmission loss) in the transmission area.

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

The semiconductor package with antenna 100 includes an insulating layer 1 for connecting the semiconductor device section 10 and the antenna section 5 (for example, a first insulating layer 1A), and an insulating layer 1 inside the antenna section 5. The structure of layer 1 has particularly important characteristics. Hereinafter, the structure of the insulating layer 1 in the semiconductor package with antenna 100 of this embodiment will be explained in more detail. Note that hereinafter, the insulating layer 1 for connecting the semiconductor device section 10 and the antenna section 5 and the insulating layer 1 inside the antenna section 5 may be collectively referred to simply as "insulating layer 1."

In the semiconductor package with antenna 100, at least one insulating layer 1 is made of a cured product of a resin composition configured similarly to the resin composition of the present invention described above. That is, the cured product constituting the insulating layer 1 is composed of a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end as the component (A), and a number average molecular weight of 60,000 as the component (B). This is a cured product of a resin composition containing the above thermoplastic elastomer.

The semiconductor package 100 with an antenna including the insulating layer 1 configured as described above has excellent solder heat resistance and low dielectric properties. In the semiconductor package 100 with an antenna equipped with the antenna section 5 for 5G millimeter waves, for example, a 288° C. solder test may be performed on the insulating layer 1 for connecting the antenna section 5, which was not necessary in the past. Soldering heat resistance at heat-resistant temperatures is required. Known high-frequency films are used as insulation layers in conventional semiconductor packages, but some of these high-frequency films do not meet the above-mentioned solder heat resistance. There are many things that cannot be used for the semiconductor package 100 with an antenna. In the semiconductor package with antenna 100 of the present embodiment, the cured material constituting the insulating layer 1 has a dielectric loss tangent (tan δ) of 0.0020 or less when measured at a frequency of 10 GHz using the SPDR (split post dielectric resonator) method. It is preferable that the soldering heat resistance is 290° C. for 2 minutes or more.

The insulating layer 1 can be obtained by heating and curing a resin composition containing the above-described components (A) and (B). The resin composition for forming the insulating layer 1 is a resin composition configured similarly to the resin composition of the present invention described above. In addition to the already explained components (A) and (B), the resin composition contains any of the components (C) to (H), and further other components. Good too.

The antenna-equipped semiconductor package 100 of this embodiment has excellent solder heat resistance and dielectric properties, so it is a semiconductor package with an RF (radio frequency) chip 8 mounted thereon that performs communication for transmitting and receiving 5G millimeter waves. Suitable for use as a package.

In the semiconductor package with antenna 100, a first insulating layer 1A for connecting the semiconductor device part 10 and the antenna part 5, a second insulating layer 1B configured to cover the wiring via in the wiring layer 4, and a second insulating layer 1B configured to cover the wiring via in the wiring layer 4. It is preferable that each of the third insulating layer 1C, the fourth insulating layer 1D, and the fifth insulating layer 1E have the same structure as the insulating layer 1 made of the cured material described above.

Next, there is no particular restriction on the method for manufacturing the insulating layer 1 in the semiconductor package with antenna 100, but for example, the following method can be mentioned.

First, a resin composition for a semiconductor package with an antenna is prepared, which includes at least component (A) and component (B). Hereinafter, the "resin composition for a 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. This film for a semiconductor package with an antenna is produced by coating a solution of a resin composition containing components (A) and (B) with an organic solvent on a PET film that has undergone mold release treatment as a support. It can be obtained by drying at 80 to 130°C. The obtained antenna-equipped semiconductor package film is peeled from the support, attached to the semiconductor device part 10, and heat-treated at 200° C. for 30 to 60 minutes to produce an antenna-equipped semiconductor package. can.

The configuration of the wiring layer 4, etc. in the semiconductor device section 10 in the semiconductor package with antenna 100 is not limited to the configuration shown in FIG. 1, and can be applied to various semiconductor packages equipped with a 5G millimeter wave antenna. Can be done. For example, FIG. 2 is a schematic partial cross-sectional view showing another example of a semiconductor package with an antenna.

A semiconductor package with an antenna 200 shown in FIG. 2 has

antenna parts

25 and 26 formed integrally with a semiconductor device part 30. The

antenna sections

25 and 26 are connected to an RF chip 28 that performs millimeter wave communication in the semiconductor device section 10 by a wiring layer 24 having various wiring patterns.

The semiconductor device section 30 includes a core substrate 22, an antenna section 25 disposed 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. have An RF chip 28 that performs 5G millimeter wave transmission/reception communication is housed within the core substrate 22 and is wired by a wiring layer 24 disposed within the core substrate 22 . At both ends of the semiconductor device section 30, an antenna section 26 is provided as a dipole antenna in which linear conducting wires (elements) are arranged symmetrically. The other surface side of the semiconductor device section 30 is connected to an electrical connection metal 27 for physically and/or electrically connecting the semiconductor package with antenna 200 to the outside.

Also in the semiconductor package with antenna 200 as shown in FIG. 2, the insulating layer 21 is made of a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end as the component (A) and a polyphenylene ether resin as the component (B). A cured product of a resin composition containing a thermoplastic elastomer having a number average molecular weight of 60,000 or more has excellent solder heat resistance and low dielectric properties. The cured product used as the insulating layer 21 can be configured similarly to the cured product used as the insulating layer 1 of the semiconductor package 100 with antenna shown in FIG.

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In the following examples, parts and % indicate parts by mass and % by mass unless otherwise specified.

(Examples 1 to 20, Comparative Examples 1 to 2)
[Sample preparation]
After weighing and blending each component to the proportions (parts by mass) shown in Tables 1 to 4 below, they were placed in a reaction vessel heated to 80°C, and constantly rotated at a rotation speed of 150 rpm. Pressure mixing was carried out for 4 hours. When adding the curing agent (D) and/or the organic peroxide (E), the curing agent (D) and/or the organic peroxide (E) are added after cooling. . As described above, varnishes containing the resin compositions of Examples 1 to 20 and Comparative Examples 1 to 2 were prepared.

The raw materials used to prepare the resin compositions in Examples 1 to 20 and Comparative Examples 1 to 2 are as follows. The number average molecular weights (Mn) of component (A), component (B), and component (B') were determined by a chromatography method.

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

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

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

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

[Component (D): Curing agent]
(D1): Manufactured by ADEKA, product name "EH2021".
[Component (E): organic peroxide]
(E1): Manufactured by NOF Chemical Co., Ltd., trade name "Perbutyl Z".
(E2): Manufactured by NOF Chemical Co., Ltd., trade name "Perc Mill D".
[(F) component: flame retardant]
(F1): Manufactured by Clariant Japan, product name "OP935".
[(G) component: filler]
(G1): Spherical silica surface-treated with an aminosilane coupling agent, manufactured by Admatex, trade name "SC4050 SX", average particle diameter 1.0 μm.
[(H) component: crosslinking agent]
(H1): Manufactured by Shikoku Kasei Co., Ltd., trade name "L-DAIC".
(H2): Manufactured by Shikoku Kasei Co., Ltd., product name "P-DAIC".

The "raw material ratio" column in Tables 1 to 4 shows the ratio of the raw materials used to prepare the resin compositions in Examples 1 to 17 and Comparative Examples 1 to 2. The ratios in each column of "raw material ratio" in Tables 1 to 4 are as follows. The column "A/(A+B+B') x 100 (mass ratio)" indicates the content (parts by mass) of component (A) relative to the total of 100 parts by mass of component (A), component (B), and component (B'). shows. The column "B/(A+B)×100 (mass ratio)" indicates the content (parts by mass) of component (B) relative to the total of 100 parts by mass of components (A) and (B). The column “C/(A+B+C)×100 (mass ratio)” indicates the content (parts by mass) of component (C) based on the total of 100 parts by mass of component (A), component (B), and component (C). .

Next, a varnish containing the resin composition prepared as described above is applied to one side of the support (PET film subjected to mold release treatment) and dried at 100°C to form an adhesive film with the support. Obtained.

The dielectric properties of the thus obtained adhesive film with a support were evaluated using the method shown below. The measurement results are shown in Tables 1 to 4.

[Dielectric properties (permittivity (ε), dielectric loss tangent (tanδ))]
Both sides of the adhesive film were sandwiched between release-treated PET films, and the adhesive film was heat-cured using a press. Thermal curing using a press was carried out at 200° C., 60 minutes, and 10 kgf/cm ² . Thereafter, the release-treated PET films placed on both sides of the cured adhesive film were removed, and a test piece (50±0.5 mm x 100±2 mm) was cut out from the adhesive film and its thickness was measured. The "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 (tan δ) of the film (test piece) whose thickness was measured were measured using a dielectric resonator method (SPDR method). Note that in the measurement using the dielectric resonator method, the measurement frequency was 10 GHz. Regarding the dielectric constant (ε), 2.50 or less is considered "excellent", more than 2.50 and 3.00 or less is considered "good", and more than 3.00 is considered "poor". In addition, the dielectric loss tangent (tan δ) is defined as "excellent" if it is less than 0.00010, "good" if it is 0.00010 or more and less than 0.0020, "fair" if it is 0.0020 or more and less than 0.0030, and 0. A score of .030 or higher is considered "impossible".

Furthermore, the obtained adhesive film with a support was subjected to the following soldering heat resistance test and evaluation of peel strength and curling property. The results are shown in Tables 1 to 4.

[Solder heat resistance]
It was conducted in accordance with JIS C5012 (1993). Specifically, copper foil was pasted on both sides of the adhesive film with the roughened side facing inside, and then hot-pressed using a press. The conditions for thermocompression bonding were 200° C., 60 minutes, and 10 kgf/cm ² . The obtained test piece was cut into a size of 25 mm x 25 mm, floated on a solder bath heated to 288° C., and the presence or absence of blisters was checked for 4 minutes. The results (seconds) shown in Tables 1 to 4 indicate the time (seconds) until the test piece visually bulges. In addition, when no blistering occurred for 4 minutes, it was written as "4min≦". The solder heat resistance is evaluated as "excellent" if no blistering occurs for 4 minutes or more. In addition, if the time until swelling occurs is 3 minutes or more but less than 4 minutes, it is considered "good", if it is 2 minutes or more but less than 3 minutes, it is considered "acceptable", and if it is less than 2 minutes, it is "unacceptable". And so.

[Peel strength]
It was conducted in accordance with JIS C 6471. Specifically, copper foil was pasted on both sides of the adhesive film with the roughened side facing inside, and then hot-pressed using a press. The copper foil used was 18 μm, trade name “CF-T9”, manufactured by Fukuda Metal Foil Industry Co., Ltd. The conditions for thermocompression bonding were 200° C., 60 minutes, and 10 kgf/cm ² . The obtained test piece was cut to a width of 10 mm and peeled off using an autograph to measure the peel strength. Regarding the measurement results, the average value of each N=5 was calculated.

[Curling property]
First, a varnish containing a resin composition was coated on one side of a support (38 μm thick PET film subjected to mold release treatment) and dried at 100° C. to obtain an adhesive film with a support. After the obtained adhesive film with a support was returned to room temperature, the adhesive film with a support was cut into a size of 30 cm x 50 cm to prepare a test piece for evaluating curlability. Place the prepared test piece on a horizontal table with the support side of the test piece facing down, and measure the length shortened by curling of the test piece (amount of warpage) using the method below. did. First, one edge of the tip of a test piece placed on a horizontal table is fixed on the table. In this way, for a test piece with one side of the tip fixed, the length shortened by curling on the side of the opposite tip of the test piece was measured. If the length shortened by curling of the test piece (amount of warpage) is less than 5 cm, it is considered a pass (good; "〇"), if it is 5 cm or more but less than 7 cm, it is also considered a pass (fair; "△"), and if it is 7 cm or more Cases were marked as not possible (“x”).

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

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

The resin compositions of Comparative Examples 1 and 2 used a thermoplastic elastomer with a number average molecular weight of less than 60,000 as the component (B'), and compared with the resin compositions of Examples 1 to 17. , the soldering heat resistance was very poor. Further, in the curling evaluation of the resin composition of Comparative Example 2, the length shortened by curling (the amount of warpage) was extremely large, and the curling evaluation results were very poor. The deterioration in curling properties of the resin composition of Comparative Example 2 is presumed to be due to the use of SEEPS-OH styrene elastomer as the thermoplastic elastomer.

The resin composition of the present invention can be used as a resin composition for adhesive films used in electronic components. Furthermore, the resin composition of the present invention can be used as an interlayer bonding sheet or an interlayer adhesive for multilayer substrates. Further, a 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 that performs 5G millimeter wave transmission/reception communication 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.

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 section (patch antenna)
7 Electrical connection metal 8 RF chip 9 Connection pad 10 Semiconductor device section 21 Insulating layer 22 Core substrate 24 Wiring layer 25 Antenna section (patch antenna)
26 Antenna section (dipole antenna)
27 Electrical connection metal 28 RF chip 30

Semiconductor device section

100, 200 Semiconductor package with antenna

Claims

(A) a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end;
(B) A resin composition containing a thermoplastic elastomer having a number average molecular weight of 60,000 or more.
The resin composition according to claim 1, wherein the component (A) contains a modified polyphenylene ether having a styrene structure at the end.
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 its terminal.

(However, in the above formula (1), R 1 represents a hydrogen atom or an alkyl group.)
The resin composition according to any one of claims 1 to 3, wherein the component (B) is a styrenic thermoplastic elastomer.
The resin composition according to claim 4, wherein the component (B) is a hydrogenated styrenic thermoplastic elastomer.
The resin composition according to claim 5, wherein the hydrogenated styrenic thermoplastic elastomer of the component (B) is a styrene/ethylene/butylene/styrene block copolymer.
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.
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.
The resin composition according to any one of claims 1 to 8, wherein the content of the component (B) is greater than the content of the component (A).
The resin composition according to any one of claims 1 to 9, further comprising (C) an epoxy resin.
The content of the component (C) is 0.1 to 5.0 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C) in the resin composition. The resin composition according to claim 10.
The resin composition according to any one of claims 1 to 11, further comprising (D) a curing agent.
An adhesive film using the resin composition according to any one of claims 1 to 12.
An interlayer bonding sheet using the resin composition according to any one of claims 1 to 12.
A resin composition for a semiconductor package with an antenna, comprising the resin composition according to any one of claims 1 to 12.
A laminate or a semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 12.