WO2023053749A1

WO2023053749A1 - Resin composition, adhesive film, bonding sheet for interlayer bonding, resin composition for semiconductor package with antenna, and semiconductor package with antenna

Info

Publication number: WO2023053749A1
Application number: PCT/JP2022/030845
Authority: WO
Inventors: 遼宇佐美; 寛史高杉
Original assignee: ナミックス株式会社
Priority date: 2021-09-30
Filing date: 2022-08-15
Publication date: 2023-04-06
Also published as: TW202317689A

Abstract

Provided is a resin composition that has excellent resistance to soldering heat, has a low dielectric characteristic at an initial state, and can suppress changes in dielectric characteristics when left for an extended period at a high temperature.　The composition includes: (A) polyphenylene ether having a styrene structure at an end; and (B) styrene elastomer having an amino group, where the content of component (B) is 70-1100 parts by mass with respect to 100 parts by mass of component (A).

Description

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

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

　Currently, due to the demand for higher speed transmission signals in the field of electrical and electronic equipment, the frequency of transmission signals is increasing significantly. In order to cope with such a high frequency, various resin compositions have been developed in anticipation of use in a high frequency region (see, for example, Patent Document 1). Patent Document 1 discloses a curable composition containing a specific polyphenylene ether, an epoxy resin, and an elastomer having reactive functional groups that react with epoxy groups.

In addition, in recent years, the standardization of 5G as a next-generation communication technology has progressed, and the market demand for realizing products that support high frequencies is increasing. Technological developments such as multi-element antenna technology and high-speed transmission have accelerated, and the use of high-frequency bands has increased communication capacity. Along with the improvement in information processing capability, the amount of high-frequency noise and heat generated has also increased, and countermeasures are also a major issue. It has become.

For example, in 5G millimeter-wave antennas, a structure that shortens the wiring distance between the antenna and the IC to reduce conductor loss (in other words, less transmission loss) is required in terms of package technology. Therefore, in recent years, a semiconductor package with an antenna (for example, antenna-in-package (AiP) or antenna-on-package (AoP)) in which an antenna section is integrally formed with a semiconductor device section has been developed. In such a package, heat generated from the IC causes the temperature of the insulating layer around the antenna to be higher than that of the conventional structure. Note that "IC" means an integrated circuit.

JP 2016-089137 A

However, conventional adhesives and adhesive films made of resin compositions have the problem that their dielectric properties deteriorate when exposed to high temperatures for a long period of time. For this reason, the adhesives and adhesive films made of conventional resin compositions may not be able to maintain the performance at the time of design.

For example, the curable composition disclosed in Patent Document 1 includes a thermosetting resin having a styrene group at the end and a phenylene ether skeleton, and a hydrogenated polymer such as styrene/ethylene/butylene/styrene block copolymer (SEBS). It contains a styrenic thermoplastic elastomer. Although the curable composition disclosed in Patent Document 1 has a low dielectric loss tangent, no mention is made of changes in the dielectric loss tangent when left at high temperatures or solder heat resistance.

Resin compositions intended for use in the high frequency range described above are required to have excellent solder heat resistance, low dielectric properties in the initial state, suppression of changes in dielectric properties when left at high temperatures for long periods of time, and the like. Development of a resin composition having excellent properties is desired.

The present invention has been made in view of such problems of the prior art. INDUSTRIAL APPLICABILITY The present invention can be suitably used for adhesive films, bonding sheets for interlayer adhesion, interlayer adhesives, etc., has excellent solder heat resistance, has low dielectric properties in the initial state, and has excellent dielectric properties when left at high temperatures for a long period of time. Provided is a resin composition capable of suppressing change. Furthermore, the present invention provides an adhesive film, a bonding sheet for interlayer adhesion, a resin composition for a semiconductor package with an antenna, and a semiconductor package with an antenna using such a resin composition.

According to the present invention, the following resin composition, adhesive film, bonding sheet for interlayer adhesion, resin composition for semiconductor package with antenna, and semiconductor package with antenna are provided.

[1] Contains (A) a polyphenylene ether having a styrene structure at its end and (B) a styrene-based elastomer having an amino group, and the content of the component (B) is less than 100 parts by mass of the component (A) On the other hand, the resin composition is 70 to 1100 parts by mass.

[2] The resin composition according to claim 1, wherein the component (A) has a structure represented by the following general formula (1).

In the above general formula (1),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group;
—(O—X—O)— is represented by the above structural formula (2), and in the structural formula (2), R ⁸ , R ⁹ , R ¹⁰ , R ¹⁴ and R ¹⁵ may be the same or different. R ¹¹ , R ¹² and R ¹³ may be the same or different and may be a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. is the basis,
-(Y-O)- is one type of structure represented by the above structural formula (3), or two or more types of structures represented by the above structural formula (3) arranged randomly, and the structure In formula (3), R ¹⁶ and R ¹⁷ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, R ¹⁸ and R ¹⁹ may be the same or different, a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group;
Z is an organic group having 1 or more carbon atoms, and may optionally contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom;
a and b are integers of 0 to 300, at least one of which is not 0; c and d are integers of 0 or 1;

[3] The resin composition according to [1] or [2] above, further comprising (C) an epoxy resin.

[4] The content of component (C) is 0.01 to 11 parts by mass with respect to a total of 100 parts by mass of component (A), component (B) and component (C). The resin composition according to [3].

[5] The resin composition according to any one of [1] to [4] above, wherein the amino group-containing styrene elastomer of component (B) is a styrene/butadiene/butylene/styrene block copolymer.

[6] The resin composition according to any one of [1] to [5], further comprising (D) a polytetrafluoroethylene filler.

[7] The resin composition according to any one of [1] to [6], further comprising (E) a curing catalyst.

[8] (F) The resin composition according to any one of [1] to [7], further comprising an organic peroxide.

[9] The resin composition according to any one of [1] to [8], further comprising (G) an antioxidant.

[10] An adhesive film using the resin composition according to any one of [1] to [9] above.

[11] A bonding sheet for interlayer adhesion using the resin composition according to any one of [1] to [9].

[12] A laminate or semiconductor device comprising a cured product of the resin composition according to any one of [1] to [9].

[13] An interlayer adhesive using the resin composition according to any one of [1] to [9].

[14] A resin composition for a semiconductor package with an antenna, comprising the resin composition according to any one of [1] to [9].

[15] A cured product of the resin composition according to any one of the above [1] to [9], wherein the amount of change in dielectric loss tangent before and after the heat resistance test calculated by the following formula 1 of the cured product is 0 A cured product of 0.0050 or less.
[Formula 1]
"Amount of change in dielectric loss tangent before and after heat resistance test" = "Dielectric loss tangent at frequency 10 GHz after heat resistance test" - "Dielectric loss tangent at frequency 10 GHz before heat resistance test"
In Formula 1, the heat resistance test is performed under heating conditions of 125° C. and 1000 hours.

[16] The cured product according to [15], wherein the rate of change in dielectric loss tangent before and after the heat resistance test calculated by the following formula 2 of the cured product is 400% or less.
[Formula 2]
"Rate of change in dielectric loss tangent before and after heat resistance test (%)" = "Amount of change in dielectric loss tangent before and after heat resistance test" / "Dielectric loss tangent at frequency 10 GHz before heat resistance test" x 100
In Equation 2, the heat resistance test was performed under the heating conditions of 125° C. and 1000 hours, and the amount of change in dielectric loss tangent before and after the heat resistance test is the value calculated by Equation 1 above.

[17] A semiconductor package with an antenna in which an antenna section is integrally formed with a semiconductor device section, wherein an insulating layer for connecting the semiconductor device section and the antenna section and an insulating layer inside the antenna section At least one of them is a cured product of a resin composition containing (A) a polyphenylene ether having a styrene structure at its end and (B) a styrene elastomer having an amino group, and the resin composition comprises the ( A semiconductor package with an antenna, containing 70 to 1100 parts by mass of component (B) with respect to 100 parts by mass of component A).

[18] The semiconductor package with an antenna according to [17], wherein the cured product has a dielectric loss tangent change of 0.0050 or less before and after the heat resistance test calculated by the following formula 3.
[Formula 3]
"Amount of change in dielectric loss tangent before and after heat resistance test" = "Dielectric loss tangent at frequency 10 GHz after heat resistance test" - "Dielectric loss tangent at frequency 10 GHz before heat resistance test"
In the calculation formula 3, the heat resistance test is performed under heating conditions of 125° C. and 1000 hours.

[19] The semiconductor package with an antenna according to [18], wherein the rate of change in dielectric loss tangent before and after the heat resistance test calculated by the following formula 4 of the cured product is 400% or less.
[Formula 4]
"Rate of change in dielectric loss tangent before and after heat resistance test (%)" = "Amount of change in dielectric loss tangent before and after heat resistance test" / "Dielectric loss tangent at frequency 10 GHz before heat resistance test" x 100
In Equation 4, the heat resistance test was performed under the heating conditions of 125° C. and 1000 hours, and the amount of change in dielectric loss tangent before and after the heat resistance test is the value calculated by Equation 3 above.

The resin composition of the present invention has excellent solder heat resistance, low dielectric properties in the initial state, and suppresses changes in dielectric properties when left at high temperatures for a long period of time. Therefore, the resin composition of the present invention can be suitably used for adhesive films, bonding sheets for interlayer adhesion, interlayer adhesives, and the like. In addition, the adhesive film, the bonding sheet for interlayer adhesion, and the resin composition for a semiconductor package with an antenna of the present invention use the above resin composition of the present invention, are excellent in solder heat resistance, and have low dielectric properties in the initial state. In addition, it has the effect of suppressing the change in dielectric properties when left at high temperatures for a long period of time.

In the semiconductor package with an antenna of the present invention, the antenna section is formed integrally with the semiconductor device section. is composed of a cured product of the resin composition described above. Therefore, the semiconductor package with an antenna of the present invention has excellent solder heat resistance, has low dielectric properties in the initial state, and suppresses changes in dielectric properties when left at high temperatures for a long period of time.

1 is a schematic partial cross-sectional view showing a semiconductor package with an antenna according to one embodiment of the present invention; FIG. FIG. 10 is a schematic partial cross-sectional view showing a semiconductor package with an antenna according to another embodiment of the invention;

Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. Therefore, it is understood that the following modifications, improvements, etc., to the following embodiments are also included in the scope of the present invention without departing from the spirit of the present invention, based on the ordinary knowledge of those skilled in the art. should.

[Resin composition]
One embodiment of the resin composition of the present invention is a resin composition containing (A) a polyphenylene ether having a styrene structure at its end and (B) a styrene elastomer having an amino group. Hereinafter, the (A) polyphenylene ether having a styrene structure at the terminal may be referred to as the (A) component. Similarly, the (B) amino group-containing styrene elastomer is sometimes referred to as the (B) component. In the resin composition of the present embodiment, the content of component (B) is 70 to 1100 parts by mass per 100 parts by mass of component (A).

The resin composition of the present embodiment has excellent solder heat resistance, low dielectric properties in the initial state, and can suppress changes in dielectric properties when left at high temperatures for a long period of time. In particular, the resin composition of the present embodiment is extremely excellent in soldering heat resistance by containing a polyphenylene ether having a styrene structure at its end as the component (A). Furthermore, the resin composition of the present embodiment contains 70 to 1100 parts by mass of a styrene-based elastomer having an amino group as component (B) with respect to 100 parts by mass of component (A), thereby providing excellent solder heat resistance. In addition, low dielectric properties are realized in the initial state, and changes in the dielectric properties during long-term high-temperature storage are effectively suppressed. For example, according to the resin composition of the present embodiment, when a film made of the resin composition is left under conditions of 125° C. for 1000 hours, the change in the dielectric properties of the film from the initial value can be very effectively suppressed. can be done.

In addition to the components (A) and (B) described above, the resin composition of the present embodiment includes (C) an epoxy resin, (D) a polytetrafluoroethylene filler, (E) a curing catalyst, and (F) Other ingredients such as organic peroxides and (G) antioxidants may also be included. Hereinafter, the respective components described above may be referred to as components (C) to (G) as appropriate.

[(A) component]
Component (A) is a polyphenylene ether having a styrene structure at its end. Component (A) 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 an arbitrary substituent. By including the component (A), the soldering heat resistance of the resin composition can be improved.

As the component (A), for example, a compound having a structure represented by the following general formula (1) can be mentioned.

In general formula (1) above, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group. or a phenyl group. -(O-X-O)- is represented by the above structural formula (2), in which R ⁸ , R ⁹ , R ¹⁰ , R ¹⁴ and R ¹⁵ are the same or different may be a halogen atom, an alkyl group ^having 6 or less carbon atoms ^, or a ^phenyl group; or a phenyl group. In addition, -(Y-O)- is one type of structure represented by the above structural formula (3), or two or more types of structures represented by the above structural formula (3) arranged randomly, In the structural formula (3), R ¹⁶ and R ¹⁷ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and R ¹⁸ and R ¹⁹ may be the same or different. It is often a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may optionally contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b are integers of 0 to 300, at least one of which is not 0; c and d are integers of 0 or 1; For example, the compound represented by general formula (1) is as described in JP-A-2004-59644.

Since the compound represented by general formula (1) has styrene functional groups at both ends, the resin composition containing component (A) is easily cured by heating. From the viewpoint of curability, the compound represented by the general formula (1) preferably has hydrogen as R ¹ to R ⁷ .

In the above structural formula (2) showing the configuration of —(O—X—O)— of the compound represented by general formula (1), R ⁸ , R ⁹ , R ¹⁰ , R ¹⁴ and R ¹⁵ each have 3 carbon atoms. The following alkyl groups are preferred, and methyl groups are particularly preferred. In the above structural formula (2), R ¹¹ , R ¹² and R ¹³ are preferably hydrogen atoms or alkyl groups having 3 or less carbon atoms, particularly preferably methyl groups. Specifically, the following structural formula (4) is mentioned.

In the above structural formula (3) showing the configuration of —(Y—O)— of the compound represented by general formula (1), R ¹⁶ and R ¹⁷ are preferably alkyl groups having 3 or less carbon atoms, methyl is particularly preferred. In the structural formula (3) above, R ¹⁸ and R ¹⁹ are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, particularly preferably a methyl group. Specifically, the following structural formula (5) or structural formula (6) may be mentioned.

Z is, for example, an alkylene group having 3 or less carbon atoms, specifically a methylene group.

At least one of a and b represents an integer of 0 to 300, preferably an integer of 0 to 30.

In order to control the elastic modulus of the cured product of the resin composition within an appropriate range, the compound represented by general formula (1) preferably has a number average molecular weight of 1,000 to 3,000. Further, the compound represented by the general formula (1) is a functional group having vinyl groups at both ends, and has an equivalent weight per functional group (functional group equivalent weight) of 500 to 1500, which corresponds to 1/2 of the above molecular weight. things are appropriate. The functional group equivalent indicates the degree of cross-linking density of the cured product, and when the functional group equivalent is 500 or more, an appropriate cross-linking density is obtained and sufficient mechanical strength is provided, so cracks occur when formed into a film. There is an advantage that the occurrence of such as can be avoided. Further, when the functional group equivalent is 1500 or less, the compatibility with the component (B) is good and a transparent film can be easily obtained. In addition, it is easy to avoid a situation in which the melt viscosity increases and the reactivity decreases, so that the curing temperature has to be raised to a practically unpreferable temperature, which is advantageous. In this specification, the number average molecular weight is a value obtained by using a standard polystyrene calibration curve by gel permeation chromatography (GPC).

The compound represented by general formula (1) can be prepared by the method described in JP-A-2004-59644. For example, a reaction in which a polycondensate of 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol and 2,6-dimethylphenol is further reacted with chloromethylstyrene. The product can be used.

As the component (A), the compound represented by the general formula (1) may be used alone, or two or more of the compounds represented by the general formula (1) may be used in combination.

As the polyphenylene ether having a styrene structure at the end of component (A), trade names "OPE-2200" and "OPE-1200" manufactured by Mitsubishi Gas Chemical Company, Inc. can be mentioned.

[(B) component]
Component (B) is a styrene-based elastomer having an amino group. The styrene-based elastomer of the component (B) has an amino group as a functional group, thereby improving adhesion and soldering heat resistance. Furthermore, (C) in the system to which the epoxy resin is added, the reaction between the amino group and the epoxy resin can further improve the solder heat resistance.

The content of component (B) is 70 to 1100 parts by mass with respect to 100 parts by mass of component (A). By configuring in this way, it is possible to maintain excellent solder heat resistance, have low dielectric properties in the initial state, and suppress changes in dielectric properties when left at high temperatures for a long period of time. For example, if the content of component (B) is too high, the dielectric properties in the initial state will be low, but the solder heat resistance will be poor. Although not particularly limited, the content of component (B) is preferably 100 to 800 parts by mass, more preferably 200 to 600 parts by mass, with respect to 100 parts by mass of component (A). is more preferred.

The content of component (B) is preferably 40 to 90 parts by mass, more preferably 60 to 85 parts by mass, when the amount of the resin composition excluding the filler is 100 parts by mass.

The styrene-based elastomer of component (B) is preferably a styrene-based elastomer having a double bond. Examples of styrenic elastomers having double bonds include block copolymers containing at least one terminal block of styrene or its analogue block and at least one intermediate block of an elastomeric block of a conjugated diene. can. Examples include styrene/butadiene/styrene block copolymer (SBS) and styrene/butadiene/butylene/styrene block copolymer (SBBS). A cured product of a resin composition containing such a styrene-based elastomer has excellent solder heat resistance. Also, the styrene ratio in component (B) is preferably 10 to 60%, more preferably 20 to 40%. When the styrene ratio of the component (B) is 20 to 40%, the film formability and workability are excellent.

The styrene-based elastomer having an amino group as component (B) is preferably a styrene/butadiene/butylene/styrene block copolymer (SBBS). That is, component (B) is preferably an amine-modified styrene/butadiene/butylene/styrene block copolymer (SBBS). Styrene/butadiene/butylene/styrene block copolymers (SBBS) with amine groups have good solder heat resistance, and since they have amino groups, they react with other components such as epoxy, resulting in better solder heat resistance and adhesion. become a thing. The amine-modified styrene/butadiene/butylene/styrene block copolymer (SBBS) preferably has amino groups at its terminals.

The weight average molecular weight of component (B) is preferably 20,000 to 200,000, more preferably 30,000 to 150,000. The weight average molecular weight is determined by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. If the weight-average molecular weight is less than 20,000, the heat resistance and adhesion may deteriorate. On the other hand, if the weight average molecular weight is more than 200,000, the solubility in solvents may be poor, making it difficult to form a film.

As a styrene-based elastomer having an amino group as the component (B), Asahi Kasei's product name "MP10" can be mentioned.

[(C) component]
(C) Component is an epoxy resin. Epoxy resins are compounds having one or more epoxy groups in the molecule, and can be cured by forming a three-dimensional network structure by reacting the epoxy groups with heating. By including an epoxy resin as the component (C), the solder heat resistance can be further improved. Further, by including the epoxy resin as the component (C), it is possible to improve the adhesiveness even to the smooth surface of the adherend such as the glossy surface of copper.

The content of the epoxy resin of component (C) is not particularly limited, but it is 0.01 to 11 parts by mass per 100 parts by mass of components (A), (B) and (C). preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass. If the content of component (C) is too high, the dielectric loss tangent of the cured product may become high.

Specific examples of epoxy resins include bisphenol compounds such as bisphenol A, bisphenol E, and bisphenol F, or derivatives thereof (eg, alkylene oxide adducts), hydrogenated bisphenol A, hydrogenated bisphenol E, hydrogenated bisphenol F, and cyclohexanediol. , Cyclohexanedimethanol, cyclohexanediethanol and other diols having an alicyclic structure or their derivatives, aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol and decanediol, or their derivatives epoxidized bifunctional epoxidized epoxy resins; trifunctional epoxy resins having a trihydroxyphenylmethane skeleton and aminophenol skeleton; include, but are not limited to. Bisphenol A type epoxy resin, bisphenol F type epoxy resin and aminophenol type epoxy resin are preferred. The compounds exemplified here may be used alone, or two or more of them may be mixed and used.

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

[(D) component]
Component (D) is a polytetrafluoroethylene filler (hereinafter also referred to as "PTFE filler"). The PTFE filler of component (D) is added to the resin composition as a filler to improve the dielectric properties of the resin composition. For example, by adding a PTFE filler to the resin composition, it is possible to improve the dielectric properties such as dielectric constant (ε) and dielectric loss tangent (tan δ) of the film formed using the resin composition.

The content of the PTFE filler of component (D) is not particularly limited, but the content in 100% by mass of the resin composition is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass. and more preferably 20 to 40% by mass. If the content of component (D) is too low, it may be difficult to obtain the effect of improving the dielectric properties of the PTFE filler. On the other hand, if the content of the component (D) is too high, it may become difficult to form a film from the resin composition.

The PTFE filler of component (D) preferably has an average particle size of 20 μm or less. When the average particle size of the PTFE filler is larger than 20 μm, it may become difficult to disperse it uniformly in the resin composition. More preferably, the PTFE filler has an average particle size of 0.01 to 10 μm. The shape of the PTFE filler is not particularly limited, and may be spherical, amorphous, or scale-like. The average particle diameter of the PTFE filler is a volume-based median diameter measured by a laser diffraction method after wet dispersion.

[(E) component]
(E) Component is a curing catalyst. The curing catalyst of the component (E) is not particularly limited as long as it is a curing catalyst that promotes general epoxy reaction, but an imidazole-based curing catalyst is more preferable because it enables appropriate adjustment of curability.

The imidazole-based curing catalyst may be imidazole, and imidazole adducts, inclusion imidazoles, microcapsule-type imidazoles, imidazole compounds coordinated with stabilizers, and the like can also be used. They have nitrogen atoms in their structure that have lone pairs of electrons that can activate epoxy groups and even other co-used epoxy resins, facilitating 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 and the like, It is not limited to these. Adduct treatment, inclusion treatment with foreign molecules, microencapsulation treatment, or imidazole coordinated with a stabilizer is a modification of the imidazole. These can be hardened or accelerated while exhibiting excellent pot life in low-temperature regions by reducing the activity of imidazole by adduct treatment, inclusion treatment with foreign molecules, microencapsulation treatment, or by coordinating a stabilizer. Highly capable.

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, and 2PHZ-PW (above, Shikoku (manufactured by Kasei Kogyo Co., Ltd.), EH2021 (manufactured by ADEKA), and the like, but are not limited thereto. Commercially available imidazole adducts include, for example, PN-50, PN-50J, PN-40, PN-40J, PN-31, and PN-23, which have a ring-opening addition structure of an imidazole compound to an epoxy group of an epoxy resin. , and PN-H (manufactured by Ajinomoto Fine-Techno Co., Inc.), but are not limited to these. Commercially available clathrate imidazoles include, for example, TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, and NIPA-2E4MZ (manufactured by Nippon Soda Co., Ltd.). However, it is not limited to these. Examples of commercial products of microcapsule-type imidazole include Novacure HX3721, HX3722, HX3742, HX3748 (manufactured by Asahi Kasei Corporation), LC-80 (manufactured by A&C Catalysts), and the like.

The content of the curing catalyst can be appropriately selected according to the type of curing catalyst used as component (E). The content of the component (E) is preferably 0.001 to 1.0 parts by mass, more preferably 0.01 to 0.60 parts by mass when the amount of the resin composition other than the filler is 100 parts by mass. . Also, the content of the imidazole-based curing catalyst is preferably 0.1 to 10% by mass, more preferably 1 to 6% by mass, relative to the epoxy resin. If the content of the component (E) 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 the component (E) is too large, the shelf life of the film produced using the resin composition may be deteriorated, and the physical properties inherent in the resin may be impaired in the cured product, resulting in adhesiveness, toughness, etc. There is a risk of deterioration in durability and heat resistance.

[(F) component]
(F) Component is an organic peroxide. By containing such an organic peroxide, the reaction initiation temperature of the component (A) shifts to the low temperature side, and curing of the resin composition is accelerated. Therefore, the soldering heat resistance of the resin composition is further improved. The content of the organic peroxide can be appropriately selected depending on the type, but is typically 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of component (A). part is more preferred.

Examples of organic peroxides include benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, and di(3,5,5-trimethylhexanoyl) peroxide. diacyl peroxides such as; 2,2-di(4,4-di-(di-tert-butylperoxy)cyclohexyl) cyclohexyl) propane and other peroxyketals; isopropyl purge carbonate, di-sec-butyl purge carbonate, Peroxydicarbonates such as di-2-ethylhexyl purgecarbonate, di-1-methylheptyl purgecarbonate, di-3-methoxybutyl purgecarbonate, dicyclohexyl purgecarbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert -butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, 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-2,5 di(t-butylperoxy)hexane, 2,5-dimethyl-2,5di(t-butylperoxy)hexyne-3, 1,1-di(t- dialkyl peroxides such as hexylperoxy)-3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, di(2-tert-butylperoxyisopropyl)benzene; cumene hydroperoxide, tert-butyl hydro Hydroperoxides such as peroxide and p-mentha hydroperoxide can be used. The organic peroxide used is not particularly limited, but when curing the resin composition, for example, a drying step of about 60 to 80 ° C. is often required, so the 10-hour half-life temperature is 100 ° C. It is preferable to use one having a temperature of up to 140°C. Furthermore, the 10-hour half-life temperature is more preferably 110 to 130°C.

Commercially available organic peroxides of component (F) (hereinafter referred to as product names) include Perbutyl H, Perbutyl Z, Perbutipacumyl P, Permyl D, Permyl H, and Perhexa C (manufactured by NOF Chemical Co., Ltd.). etc. can be mentioned.

[(G) component]
The (G) component is an antioxidant. By containing such an antioxidant, oxidation of the resin composition can be reduced, and changes in dielectric properties due to long-term high-temperature storage can be further reduced.

There are no particular restrictions on the type of antioxidant used as the component (G), but examples include phenol antioxidants, sulfur antioxidants, amine antioxidants, phosphorus antioxidants, and the like.

For example, phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H,5H)-trione, 4,4′,4″-(1-methylpropyl-3-ylidene)tris(6-butyl-m-cresol), 1,3,5-tris(3,5-di- tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, octadecyl 3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane and the like.

Sulfur antioxidants include 2,2-bis{[3-(dodecyltino)-1-oxopropoxy]methyl}propane-1,3, diylbis[3-(dodecyltino)propionate], di(tridecyl) 3, 3'-thiodipropionate and the like.

Amine antioxidants include dinonyldiphenylamine, octylbutylphenylamine, 2,6-diterdobutylphenol and their derivatives.

Phosphorus antioxidants include 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]udecane, 3,9-bis( 2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]udecane, 2,2′-methylenebis(4, 6-di-tert-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra-dodecyl (propane-2,2-diylbis (4,1-phenylene))bis(phosphite), tetra-tridecyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), tetra-tetradecyl(propane-2,2-diylbis (4,1-phenylene))bis(phosphite), tetra-pentadecyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 2-ethylhexyldiphenylphosphite, isodecyldiphenylphosphite phyto, triisodecylphosphite, triisodecylphosphite and the like.

Commercially available antioxidants of component (G) (hereinafter referred to as trade names) include AO-20, AO-50, AO-80, AO-503, AO-523S, PEP-8, HP-10, TPP ( above, manufactured by ADEKA) and the like. Among these, an antioxidant having a carbon chain with 10 or more carbon atoms such as an octadecyl group or a dodecyl group in its structure is preferable because of its good dielectric properties. In addition, the antioxidant having a carbon chain of 10 or more carbon atoms has high compatibility with the component (A) and component (B), so that the antioxidant can be prevented from bleeding out of the resin composition. The content of the antioxidant can be appropriately selected depending on the type, but is typically preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total amount of the resin composition.

[Other ingredients]
The resin composition of the present embodiment may further contain components other than components (A) to (G) described above. Examples of other components include various additives such as colorants, dispersants, flame retardants, silane coupling agents, rheology control agents, inorganic fillers and organic fillers.

[Dielectric loss tangent of cured product of resin composition]
The cured product of the resin composition of the present embodiment preferably has a dielectric loss tangent change of 0.0050 or less before and after the heat resistance test calculated by the following formula 1 of the cured product. The amount of change in dielectric loss tangent before and after the heat resistance test calculated by the following formula 1 is more preferably 0.0040 or less, and even more preferably 0.0030 or less. With such a configuration, the cured product of the resin composition of the present embodiment has a small dielectric loss even when placed in a high-temperature environment.

[Formula 1]
"Amount of change in dielectric loss tangent before and after heat resistance test" = "Dielectric loss tangent at frequency 10 GHz after heat resistance test" - "Dielectric loss tangent at frequency 10 GHz before heat resistance test"
Here, in Formula 1, the heat resistance test described above is performed under heating conditions of 125° C. and 1000 hours. A more specific method of the heat resistance test is as follows. A cured product of the resin composition is placed in a constant temperature bath at 125° C. and held for 1000 hours. The cured product of the resin composition is obtained by curing the resin composition through a chemical reaction and completing the chemical reaction for curing. Completion of the chemical reaction can be confirmed, for example, by the disappearance of the exothermic peak in differential scanning calorimetry (DSC). Note that the dielectric loss tangent at a frequency of 10 GHz is a measured value at room temperature (23° C.), and examples of measurement methods include the SPDR (split post dielectric resonator) method and the cavity resonance perturbation method.

Further, it is more preferable that the cured product of the resin composition of the present embodiment has a dielectric loss tangent change rate of 400% or less before and after the heat resistance test, which is calculated by the following formula 2. The rate of change in dielectric loss tangent before and after the heat resistance test calculated by Equation 2 below is more preferably 300% or less, and even more preferably 200% or less.

[Formula 2]
"Rate of change in dielectric loss tangent before and after heat resistance test (%)" = "Amount of change in dielectric loss tangent before and after heat resistance test" / "Dielectric loss tangent at frequency 10 GHz before heat resistance test" x 100
Here, in Equation 2 above, the heat resistance test is performed under the heating conditions of 125° C. and 1000 hours, and the amount of change in dielectric loss tangent before and after the heat resistance test is the value calculated by Equation 1 above.

[Method for producing resin composition]
The resin composition of this embodiment can be produced by a conventional method. The resin composition of the present embodiment can be produced by mixing each component described above using, for example, a Laikai machine, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, or the like. .

[Use of resin composition]
The resin composition of the present embodiment can be suitably used as a resin composition for adhesive films used in electronic parts. The resin composition of the present embodiment can also be suitably used as a bonding sheet for interlayer adhesion and an interlayer adhesive for multilayer substrates. When the resin composition of the present embodiment is used for various applications for electronic parts, the electronic parts to be adhered are not particularly limited, and examples thereof include ceramic substrates, organic substrates, semiconductor chips, and semiconductor devices.

The adhesive film, the bonding sheet for interlayer adhesion, the interlayer adhesive, 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 that constitute electronic components and the like. Therefore, laminates and semiconductor devices that constitute electronic parts and the like preferably contain a cured product of the resin composition of the present embodiment.

Further, the resin composition of the present embodiment can also be used as a resin composition (resin composition for a semiconductor package with an antenna) used for manufacturing a semiconductor package with an antenna. Details of the semiconductor package with an antenna will be described later. The resin composition of the present embodiment is suitable as a resin composition for forming an insulating layer for connecting the semiconductor device portion and the antenna portion and an insulating layer inside the antenna portion in such a semiconductor package with an antenna. can be used for

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

As shown in FIG. 1, the semiconductor package 100 with an antenna has a semiconductor device portion 10 and an antenna portion 5 integrally formed thereon. ) A semiconductor package 100 with an antenna 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 by a wiring layer 4 having various wiring patterns.

The semiconductor device portion 10 in the semiconductor package 100 with an antenna shown in FIG. An insulating layer 1 (first insulating layer 1A) for connection, a wiring layer 4 having a multi-layer structure arranged in a core substrate 2, and an insulating layer 1 configured to cover wiring vias in the wiring layer 4. (second insulating layer 1B, third insulating layer 1C, fourth insulating layer 1D, fifth insulating layer 1E). The first insulating layer 1A is not only provided so as to intervene between the semiconductor device section 10 and the antenna section 5, but is also provided so as to extend to the inside of the antenna section 5. may

In the semiconductor package 100 with an antenna, a portion of the wiring layer 4 on the other surface side of the semiconductor device portion 10 is connected to the RF chip 8 that performs millimeter wave transmission/reception communication. 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 . The electrical connection metal 7 is a terminal portion for physically and/or electrically connecting the semiconductor package 100 with an antenna and the outside according to its function through 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 unit 5 to efficiently radiate them into space. It is required to reduce the loss (transmission loss) of the connection that connects the The same is true for reception. In order to transmit the reflected wave of the millimeter wave signal received by the antenna unit 5 to the RF chip 8 as a receiving unit while suppressing the attenuation of the reflected wave, the connection between the antenna unit 5 and the RF chip 8 is required. It is required to reduce the loss (transmission loss) of the part.

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

In the semiconductor package 100 with an antenna, at least one of an insulating layer 1 (for example, a first insulating layer 1A) for connecting the semiconductor device portion 10 and the antenna portion 5 and an insulating layer 1 inside the antenna portion 5 is insulated. There are particular main features regarding the construction of layer 1 . The configuration of the insulating layer 1 in the semiconductor package 100 with an antenna of this embodiment will be described in more detail below. In addition, hereinafter, the insulating layer 1 for connecting the semiconductor device portion 10 and the antenna portion 5 and the insulating layer 1 inside the antenna portion 5 may be collectively referred to simply as the "insulating layer 1".

In the semiconductor package 100 with an antenna, at least one insulating layer 1 is made of a cured product of a resin composition configured in the same manner as the resin composition of the present invention described above. That is, the cured product constituting the insulating layer 1 is a cured resin composition containing polyphenylene ether having a styrene structure at the end as component (A) and a styrene elastomer having an amino group as component (B). It is a thing. This resin composition is prepared so that the content of component (B) is 70 to 1100 parts by mass per 100 parts by mass of component (A).

The semiconductor package 100 with an antenna having the insulating layer 1 configured as described above has excellent solder heat resistance, has low dielectric properties in the initial state, and suppresses changes in dielectric properties when left at high temperatures for a long period of time. can be done. In the semiconductor package 100 with an antenna including the antenna section 5 for 5G millimeter waves, for example, the insulating layer 1 for connecting the antenna section 5 may be subjected to a solder test at 288 ° C., which was not necessary in the past. Solder heat resistance at heat resistant temperature is required. A known high-frequency film is used as an insulating layer in a conventional semiconductor package, but such a high-frequency film does not meet the solder heat resistance described above, and the antenna section 5 for 5G millimeter waves Many of them cannot be used for the semiconductor package 100 with an antenna. In the semiconductor package 100 with an antenna of the present embodiment, the cured product constituting the insulating layer 1 has a dielectric loss tangent (tan δ) of 0.0020 or less measured at a frequency of 10 GHz by an SPDR (split post dielectric resonator) method. It is preferable that the solder 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 constructed in the same manner as the resin composition of the present invention described above. In addition to the components (A) and (B) already described, the resin composition contains an epoxy resin as component (C), a polytetrafluoroethylene filler as component (D), and a curing agent as component (E). Other components such as a catalyst, an organic peroxide as component (F), and an antioxidant as component (G) may be included.

The semiconductor package 100 with an antenna of this embodiment has excellent solder heat resistance and excellent dielectric properties in the initial state and after long-term high temperature exposure. It is suitably used as a semiconductor package in which the frequency) chip 8 is mounted.

In the semiconductor package 100 with an antenna, the first insulating layer 1A for connecting the semiconductor device portion 10 and the antenna portion 5, the second insulating layer 1B configured to cover the wiring via in the wiring layer 4, the second Each of the third insulating layer 1C, the fourth insulating layer 1D, and the fifth insulating layer 1E is preferably configured in the same manner as the insulating layer 1 made of the cured material described above.

Next, the method of manufacturing the insulating layer 1 in the semiconductor package 100 with an antenna is not particularly limited, but for example, the following method can be used.

First, a resin composition for a semiconductor package with an antenna containing at least component (A) and component (B) is prepared. Hereinafter, the "resin composition for a semiconductor package with an antenna" may be simply referred to as the "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 obtained by, for example, applying a solution obtained by adding an organic solvent to a resin composition containing components (A) and (B) on a PET film that is a support and has been subjected to a release treatment. and dried at 80 to 130°C. The obtained film for a semiconductor package with an antenna is peeled off from the support, attached to the semiconductor device portion 10, and subjected to heat treatment at 200° C. for 30 to 60 minutes, for example, to produce a semiconductor package with an antenna. can.

The configuration of the wiring layer 4 and the like in the semiconductor device portion 10 in the semiconductor package 100 with an antenna is not limited to the configuration shown in FIG. can be done. For example, FIG. 2 is a schematic partial cross-sectional view showing a semiconductor package with an antenna according to another embodiment of the invention.

A semiconductor package 200 with an antenna shown in FIG. 2 is obtained by integrally forming

antenna sections

25 and 26 with a semiconductor device section 30 . In the semiconductor device section 10, the

antenna sections

25 and 26 are connected to an RF chip 28 that performs millimeter wave communication and a wiring layer 24 having various wiring patterns.

The semiconductor device portion 30 includes a core substrate 22, an antenna portion 25 provided on one surface side of the semiconductor device portion 30, and an insulating layer 21 for connecting the semiconductor device portion 30 and the antenna portion 25. have. An RF chip 28 that performs 5G millimeter wave transmission/reception communication is accommodated in the core substrate 22 and is wired by a wiring layer 24 arranged in the core substrate 22 . At both ends of the semiconductor device portion 30, an antenna portion 26 is provided as a dipole antenna in which linear conductors (elements) are arranged symmetrically. The other surface side of the semiconductor device portion 30 is connected to an electrical connection metal 27 for physically and/or electrically connecting the semiconductor package 200 with an antenna and the outside.

Also in the semiconductor package 200 with an antenna as shown in FIG. By using a cured product of a resin composition containing, it is possible to have excellent solder heat resistance, have low dielectric properties in the initial state, and suppress changes in dielectric properties when left at high temperatures for a long period of time. As the cured material used as the insulating layer 21, the cured material having the same structure as the cured material used as the insulating layer 1 of the semiconductor package 100 with an antenna shown in FIG. 1 can be adopted.

Further, the cured product of the resin composition containing the (A) component and the (B) component, which is used as the insulating layer 21 of the semiconductor package 100 with an antenna as shown in FIG. The calculated amount of change in dielectric loss tangent before and after the heat resistance test is preferably 0.0050 or less. The amount of change in dielectric loss tangent before and after the heat resistance test calculated by the following formula 3 is more preferably 0.0040 or less, and even more preferably 0.0030 or less. With such a configuration, the antenna-equipped semiconductor package 100 of the present embodiment has a small dielectric loss even when placed in a high-temperature environment.

[Formula 3]
"Amount of change in dielectric loss tangent before and after heat resistance test" = "Dielectric loss tangent at frequency 10 GHz after heat resistance test" - "Dielectric loss tangent at frequency 10 GHz before heat resistance test"
Here, in Formula 3 above, the heat resistance test is performed under the heating conditions of 125° C. and 1000 hours. As a more specific method for the heat resistance test, the same method as the method described in Equation 1 above can be used.

Further, it is more preferable that the cured product of this resin composition has a dielectric loss tangent change rate of 400% or less before and after the heat resistance test, which is calculated by the following formula 4. The rate of change in dielectric loss tangent before and after the heat resistance test calculated by Equation 4 below is more preferably 300% or less, and even more preferably 200% or less.

[Formula 4]
"Rate of change in dielectric loss tangent before and after heat resistance test (%)" = "Amount of change in dielectric loss tangent before and after heat resistance test" / "Dielectric loss tangent at frequency 10 GHz before heat resistance test" x 100
Here, in Equation 4 above, the heat resistance test is performed under the heating conditions of 125° C. and 1000 hours, and the amount of change in dielectric loss tangent before and after the heat resistance test is the value calculated by Equation 3 above.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited by these examples. In the following examples, parts and % represent parts by weight and % by weight unless otherwise specified.

(Examples 1 to 16, Comparative Examples 1 to 7)
[Sample preparation]
After weighing and blending each component so that the blending ratio (parts by mass) shown in Tables 1 to 4 below, they are put into a reaction kettle heated to 80 ° C. and rotated at a rotation speed of 150 rpm. Pressure mixing was carried out for 4 hours. When the curing catalyst of component (E) and/or the organic peroxide of component (F) were added, the curing catalyst of component (E) and/or the organic peroxide of component (F) were added after cooling. . As described above, varnishes containing the resin compositions of Examples 1 to 16 and Comparative Examples 1 to 7 were prepared.

The raw materials used to prepare the resin compositions in Examples 1-16 and Comparative Examples 1-7 are as follows.

[Component (A): polyphenylene ether having a styrene structure at the end]
(A1): trade name "OPE-2200" manufactured by Mitsubishi Gas Chemical Company.
(A2): manufactured by Mitsubishi Gas Chemical Company, trade name "OPE-1200".
[(A') component: polyphenylene ether having no styrene structure at the end]
(A'3): Trade name "Noryl SA90" manufactured by SABIC Japan.
(A'4): Trade name "Noryl SA9000" manufactured by SABIC Japan.

[Component (B): Styrene-based elastomer having an amino group]
(B1): Styrene-based elastomer having an amino group (SBBS), manufactured by Asahi Kasei Chemicals, trade name "MP10". (Styrene ratio: 30%) Molecular weight: Mw: 52,000.
[(B') component: styrene-based elastomer having no amino group]
(B'2): Styrene-based elastomer (SBS (styrene ratio: 43%)) manufactured by JSR, trade name "TR2003".
(B'3): Styrene-based elastomer (SBBS (styrene ratio: 30%)) manufactured by Asahi Kasei Chemicals, trade name "P1500".
(B'4): Styrene-based elastomer (SEBS (styrene ratio: 30%)) manufactured by Kraton Polymer Co., Ltd., trade name "G1652".

[(C) component: epoxy resin]
(C1): Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, trade name "828EL".
(C2): Biphenyl-type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., trade name "NC3000H".
(C3): Naphthalene-type epoxy resin, manufactured by DIC, trade name "HP-4032D".
(C4): novolac type epoxy resin, trade name "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd.;

[(D) component: polytetrafluoroethylene filler]
(D1): Trade name “Lubron L-5F” manufactured by Daikin Industries, Ltd.
[(E) component: curing catalyst]
(E1): Made by ADEKA, trade name "EH2021".
[(F) component: organic peroxide]
(F1): manufactured by NOF Chemical Co., Ltd., trade name "PERBUTYL Z".
(F2): manufactured by NOF Chemical Co., Ltd., trade name "Percumyl D".
[(G) component: antioxidant]
(G1): manufactured by ADEKA, trade name "AO-50".

The column "ratio of raw materials" in Tables 1 to 4 shows the ratio of the raw materials used to prepare the resin compositions in Examples 1 to 16 and Comparative Examples 1 to 7. The ratios in each column of "raw material ratio" in Tables 1 to 4 are as follows. The column of "B/A x 100 (mass ratio)" indicates the content (parts by mass) of component (B) with respect to 100 parts by mass of component (A). The column of "B/(A+B) x 100 (mass ratio)" indicates the content (parts by mass) of component (B) with respect to a total of 100 parts by mass of components (A) and (B). The column "C / (A + B + C) × 100 (mass ratio)" shows the content (parts by mass) of component (B) with respect to a total of 100 parts by mass of components (A), (B) and (C). .

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

The following dielectric properties were evaluated for the adhesive film with support thus obtained. For the evaluation of dielectric properties, the dielectric constant (ε) and dielectric loss tangent (tan δ) were measured before and after the heat resistance test described below. Also, from the dielectric loss tangent (tan δ) before and after the heat resistance test, the amount of change in the dielectric loss tangent before and after the heat resistance test and the rate of change (%) in the dielectric loss tangent before and after the heat resistance test were calculated. The amount of change in the dielectric loss tangent before and after the heat resistance test is obtained by subtracting the value of the dielectric loss tangent at a frequency of 10 GHz before the heat resistance test from the dielectric loss tangent at a frequency of 10 GHz after the heat resistance test (heating condition of 125° C. for 1000 hours). Also, the rate of change in dielectric loss before and after the heat resistance test is obtained by dividing the amount of change in the dielectric loss tangent before and after the heat resistance test by the value of the dielectric loss tangent at a frequency of 10 GHz before the heat resistance test (heating condition of 125°C for 1000 hours). is preferably 0.0050 or less, more preferably 0.0040 or less, and even more preferably 0.0030 or less. The rate of change in dielectric loss tangent before and after the heat resistance test is preferably 400% or less, more preferably 300% or less, and even more preferably 200% or less. Each result is shown in Tables 1 to 4.

[Dielectric properties (dielectric constant (ε), dielectric loss tangent (tan δ))]
The adhesive film before the heat resistance test was heat-cured at 200° C. for 60 minutes at 10 kgf/cm ² , peeled off from the support, and then cut out from the adhesive film into a test piece (50±0.5 mm×100±2 mm), Thickness was measured. The dielectric constant (ε) and dielectric loss tangent (tan δ) of the film whose thickness was measured were measured by the dielectric resonator method (SPDR method). In the measurement by the dielectric resonator method, the measurement frequency was 10 GHz. The dielectric constant (ε) is preferably 2.6 or less. The dielectric loss tangent (tan δ) is preferably 0.0020 or less, more preferably 0.0010 or less.

[Dielectric properties after heat resistance test (dielectric constant (ε), dielectric loss tangent (tan δ))]
A heat resistance test was performed by placing the adhesive film in a constant temperature bath at 125° C. and holding it for 1000 hours. After conducting such a heat resistance test, the adhesive film was taken out from the constant temperature bath, and when the surface temperature of the adhesive film reached room temperature, the dielectric resonator method (SPDR method) was performed.
, the dielectric constant (ε) and dielectric loss tangent (tan δ) were measured. In evaluating the dielectric properties after the heat resistance test, the dielectric constant (ε) is preferably 2.6 or less. The dielectric loss tangent (tan δ) is preferably 0.0050 or less, more preferably 0.0040 or less, and even more preferably 0.0030 or less.

In addition, the following solder heat resistance test and peel strength evaluation were performed on the obtained adhesive film with support. Each result is shown in Tables 1 to 4.

[Solder heat resistance]
It was carried out according to JIS C5012 (1993). Specifically, a copper foil was pasted on both sides of the adhesive film with the roughened surface facing inward, and was thermocompressed with a press. The thermocompression bonding conditions were 200° C., 60 minutes, and 10 kgf/cm ² . The obtained test piece was cut into a size of 25 mm×25 mm, floated in a solder bath heated to 288° C., and the presence or absence of swelling was confirmed for 4 minutes. The results (seconds) shown in Tables 1 to 4 show the time (seconds) until the test pieces blister visually. In addition, when swelling did not generate|occur|produce for 4 minutes, it described as "240<". In the evaluation of solder heat resistance, it is preferable that swelling does not occur for 120 seconds or more.

[Peel strength (M)]
It was carried out in accordance with JIS C 6471. Specifically, a copper foil was pasted on both sides of the adhesive film with the roughened surface facing inward, and was thermocompressed with a press. A copper foil of 18 μm, trade name “CF-T9” manufactured by Fukuda Metal Foil Industry Co., Ltd. was used. The thermocompression bonding conditions were 200° C., 60 minutes, and 10 kgf/cm ² . The obtained test piece was cut into a width of 10 mm, peeled off by an autograph, and the peel strength was measured. An average value of each N=5 was calculated for the measurement results.

[Peel strength (S)]
A copper foil was pasted on both sides of the adhesive film with the glossy side facing inward, and was thermocompression bonded with a press. A copper foil of 18 μm, trade name “CF-T9” manufactured by Fukuda Metal Foil Industry Co., Ltd. was used. The thermocompression bonding conditions were 200° C., 60 minutes, and 10 kgf/cm ² . The obtained test piece was cut into a width of 10 mm, peeled off by an autograph, and the peel strength was measured. An average value of each N=5 was calculated for the measurement results.

〔result〕
As shown in Tables 1 to 3, the resin compositions of Examples 1 to 16 consisted of polyphenylene ether having a styrene structure at the terminal as component (A) and a styrene elastomer having an amino group as component (B). and was included. In the resin compositions of Examples 1 to 16, as shown in the column of "B/A x 100 (mass ratio)", the content of component (B) with respect to 100 parts by mass of component (A) is within a specific numerical range. In each evaluation of dielectric properties (permittivity (ε) and dielectric loss tangent (tan δ)), soldering heat resistance, and peel strength before and after the heat resistance test, good results were obtained.

In addition, the resin compositions of Examples 1 to 16 show a small amount of change in dielectric loss tangent before and after the heat resistance test, and the change rate (%) of the dielectric loss tangent before and after the heat resistance test is a small value of 400% or less at maximum. there were. In addition, all the examples except Example 3 showed a very small value of 300% or less at the maximum of the rate of change (%). Especially in a semiconductor package with an antenna, it is expected that the temperature of the insulating layer around the antenna will rise due to the heat generated from the IC. can be expected. In addition, it was confirmed that the resin composition of Example 4 had a relatively low content of the component (B) and tended to have slightly higher dielectric properties. On the other hand, it was confirmed that the resin composition of Example 5 had a relatively large content of the component (B) and tended to have low dielectric properties.

In the resin composition of Comparative Example 1, a polyphenylene ether having a terminal hydroxyl group (OH group) was used as the (A') component instead of a polyphenylene ether having a styrene structure at the terminal. In the resin composition of Comparative Example 2, a polyphenylene ether having a terminal methacrylic group was used as the component (A') instead of the polyphenylene ether having a terminal styrene structure. The resin compositions of Comparative Examples 1 and 2 were extremely poor in solder heat resistance. In addition, the resin composition of Comparative Example 1 exhibited a high dielectric loss tangent (tan δ) before the heat resistance test and a high dielectric constant (ε) after the heat resistance test. The resin composition of Comparative Example 2 exhibited a high dielectric constant (ε) after the heat resistance test.

In the resin compositions of Comparative Examples 3 to 5, a styrene-based elastomer having no amino group was used as the component (B') instead of the styrene-based elastomer having an amino group. The resin composition of Comparative Example 3 exhibited high values of dielectric loss tangent (tan δ) before the heat resistance test, and dielectric constant (ε) and dielectric loss tangent (tan δ) after the heat resistance test. The resin composition of Comparative Example 4 exhibited a high dielectric loss tangent (tan δ) after the heat resistance test. For this reason, the resin compositions of Comparative Examples 3 and 4 exhibited extremely large values of change in dielectric loss tangent (tan δ) before and after the heat resistance test. The resin composition of Comparative Example 5 was extremely poor in solder heat resistance.

In the resin composition of Comparative Example 6, the content of component (B) was 61.67 parts by mass with respect to 100 parts by mass of component (A). The resin composition of Comparative Example 6 was inferior in soldering heat resistance and showed a high dielectric loss tangent (tan δ) before the heat resistance test.

In the resin composition of Comparative Example 7, the content of component (B) was 1895 parts by mass with respect to 100 parts by mass of component (A). The resin composition of Comparative Example 7 was extremely poor in solder heat resistance.

The resin composition of the present invention can be used as a resin composition for adhesive films used in electronic parts. The resin composition of the present invention can also be used as a bonding sheet for interlayer adhesion and an interlayer adhesive for multilayer substrates. Moreover, the semiconductor package with an antenna 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 the insulating layer of the semiconductor package with an antenna of the present invention.

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

semiconductor device part

100, 200 semiconductor package with antenna

Claims

(A) a polyphenylene ether having a styrene structure at its end;
(B) a styrene-based elastomer having an amino group,
A resin composition in which the content of component (B) is 70 to 1100 parts by mass per 100 parts by mass of component (A).
The resin composition according to claim 1, wherein the component (A) has a structure represented by the following general formula (1).

(In the above general formula (1),
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group;
—(O—X—O)— is represented by the above structural formula (2), and in the structural formula (2), R 8 , R 9 , R 10 , R 14 and R 15 may be the same or different. R 11 , R 12 and R 13 may be the same or different and may be a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. is the basis,
-(Y-O)- is one type of structure represented by the above structural formula (3), or two or more types of structures represented by the above structural formula (3) arranged randomly, and the structure In formula (3), R 16 and R 17 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, R 18 and R 19 may be the same or different, a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group;
Z is an organic group having 1 or more carbon atoms, optionally containing an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom,
a and b are integers of 0 to 300, at least one of which is not 0; c and d are integers of 0 or 1; )
(C) The resin composition according to claim 1 or 2, further comprising an epoxy resin.
Claim 3, wherein the content of component (C) is 0.01 to 11 parts by mass with respect to a total of 100 parts by mass of component (A), component (B) and component (C). The described resin composition.
The resin composition according to any one of claims 1 to 4, wherein the amino group-containing styrene elastomer of component (B) is a styrene/butadiene/butylene/styrene block copolymer.
(D) The resin composition according to any one of claims 1 to 5, further comprising a polytetrafluoroethylene filler.
(E) The resin composition according to any one of claims 1 to 6, further comprising a curing catalyst.
(F) The resin composition according to any one of claims 1 to 7, further comprising an organic peroxide.
(G) The resin composition according to any one of claims 1 to 8, further comprising an antioxidant.
An adhesive film using the resin composition according to any one of claims 1 to 9.
A bonding sheet for interlayer adhesion using the resin composition according to any one of claims 1 to 9.
A laminate or semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 9.
An interlayer adhesive using the resin composition according to any one of claims 1 to 9.
A resin composition for a semiconductor package with an antenna, comprising the resin composition according to any one of claims 1 to 9.
A cured product of the resin composition according to any one of claims 1 to 9, wherein the amount of change in dielectric loss tangent before and after the heat resistance test calculated by the following formula 1 of the cured product is 0.0050 or less. There is a hardened material.
[Formula 1]
"Amount of change in dielectric loss tangent before and after heat resistance test" = "Dielectric loss tangent at frequency 10 GHz after heat resistance test" - "Dielectric loss tangent at frequency 10 GHz before heat resistance test"
In Formula 1, the heat resistance test is performed under heating conditions of 125° C. and 1000 hours.
16. The cured product according to claim 15, wherein the cured product has a dielectric loss tangent change rate of 400% or less before and after the heat resistance test calculated by the following formula 2.
[Formula 2]
"Rate of change in dielectric loss tangent before and after heat resistance test (%)" = "Amount of change in dielectric loss tangent before and after heat resistance test" / "Dielectric loss tangent at frequency 10 GHz before heat resistance test" x 100
In Equation 2, the heat resistance test was performed under the heating conditions of 125° C. and 1000 hours, and the amount of change in dielectric loss tangent before and after the heat resistance test is the value calculated by Equation 1 above.
A semiconductor package with an antenna in which an antenna section is integrally formed with a semiconductor device section, wherein at least one of an insulating layer for connecting the semiconductor device section and the antenna section and an insulating layer inside the antenna section on the one hand,
A cured product of a resin composition containing (A) a polyphenylene ether having a styrene structure at its end and (B) a styrene elastomer having an amino group, wherein the resin composition contains 100 parts by mass of the component (A). A semiconductor package with an antenna, containing 70 to 1100 parts by mass of the component (B).
18. The semiconductor package with an antenna according to claim 17, wherein the amount of change in dielectric loss tangent before and after the heat resistance test calculated by the following formula 3 of the cured product is 0.0050 or less.
[Formula 3]
"Amount of change in dielectric loss tangent before and after heat resistance test" = "Dielectric loss tangent at frequency 10 GHz after heat resistance test" - "Dielectric loss tangent at frequency 10 GHz before heat resistance test"
In the calculation formula 3, the heat resistance test is performed under heating conditions of 125° C. and 1000 hours.
19. The semiconductor package with an antenna according to claim 18, wherein a rate of change in dielectric loss tangent of said cured product before and after said heat resistance test calculated by the following formula 4 is 400% or less.
[Formula 4]
"Rate of change in dielectric loss tangent before and after heat resistance test (%)" = "Amount of change in dielectric loss tangent before and after heat resistance test" / "Dielectric loss tangent at frequency 10 GHz before heat resistance test" x 100
In Equation 4, the heat resistance test was performed under the heating conditions of 125° C. and 1000 hours, and the amount of change in dielectric loss tangent before and after the heat resistance test is the value calculated by Equation 3 above.