Resin composition, resin film, prepreg, laminate, printed wiring board, and semiconductor package

Abstract

Provided is a resin composition which has excellent high-frequency characteristics and is capable of forming a cured product in which the occurrence of recesses in the surface after decontamination treatment is suppressed. Also provided are a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package using the resin composition. Specifically, the resin composition contains a styrene elastomer (A) and a maleimide compound (B), and the component (A) contains 5-15% by mass or 40% by mass or more of structural units derived from a styrene compound based on the total structural units of the component (A).

Description

Technical Field

[0001] This disclosure relates to resin compositions, resin films, prepregs, laminates, printed circuit boards, and semiconductor packages. Background Technology

[0002] The speed and capacity of signals used in mobile communication devices such as mobile phones, their base station devices, network infrastructure equipment such as servers and routers, and mainframe computers are increasing year by year. Along with this, the printed circuit boards (PCBs) mounted on these electronic devices need to cope with the increasing frequency, requiring substrate materials with excellent dielectric properties (low dielectric constant and low dielectric loss tangent; hereinafter sometimes referred to as high-frequency characteristics) in high-frequency bands (e.g., above 10 GHz) to reduce transmission loss. In recent years, in addition to the aforementioned electronic devices, the implementation and practical application of new systems for handling high-frequency wireless signals in the ITS field (automotive and transportation systems) and indoor short-range communication fields are also progressing. Therefore, it is anticipated that low-transmission-loss substrate materials will also be required for the PCBs mounted on these devices in the future.

[0003] Under such circumstances, with the goal of providing resin compositions that have particularly good compatibility, high frequency characteristics, high adhesion to conductors, excellent heat resistance, high glass transition temperature, low coefficient of thermal expansion and high flame retardancy, a resin composition comprising a specific polyphenylene ether derivative, a specific thermosetting resin and a styrene-based thermoplastic elastomer has been proposed (see Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2016 / 175326 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, in the manufacturing process of printed circuit boards, a decontamination treatment using an aqueous oxidizing agent is performed on the insulating layer to remove residues from the opening process of the insulating layer or to roughen the surface to improve the adhesion between the insulating layer and the conductor layer. According to the research of the inventors, it has been found that after the above-mentioned decontamination treatment, copper-clad laminates using resin compositions containing styrene-based elastomers sometimes develop depressions with a diameter exceeding about 1 μm on the surface of the insulating layer.

[0009] In view of this situation, the objective of this disclosure is to provide a resin composition that has excellent high-frequency characteristics and can form a cured product in which the formation of depressions on the surface after decontamination is suppressed, and to provide a resin film, prepreg, laminate, printed circuit board and semiconductor package using the above resin composition.

[0010] Methods for solving problems

[0011] The inventors have conducted repeated and in-depth research and found that the above-mentioned objectives can be achieved with the resin composition disclosed herein.

[0012] This disclosure includes the following embodiments [1] to

[11] .

[0013] [1] A resin composition comprising a styrene-based elastomer (A) and a maleimide compound (B), wherein the (A) component contains 5 to 15% by mass or 40% by mass or more of structural units derived from the styrene-based compound, based on all structural units of the (A) component.

[0014] [2] According to the resin composition described in [1] above, the content of component (A) is 1 to 50 parts by mass relative to 100 parts by mass of solid components in the resin composition.

[0015] [3] According to the resin composition described in [1] or [2] above, wherein the above-mentioned component (B) is selected from one or more maleimide compounds having two or more N-substituted maleimide groups and their derivatives.

[0016] [4] The resin composition described in any one of [1] to [3] above further contains an inorganic filler (C).

[0017] [5] The resin composition according to any one of [1] to [4] above further contains a polyphenylene ether derivative (D) having a group containing an olefinic unsaturated bond.

[0018] [6] The resin composition described in any one of [1] to [5] above further contains a curing accelerator (E).

[0019] [7] A resin film containing the resin composition described in any one of [1] to [6] above or a semi-cured product of the resin composition described above.

[0020] [8] A prepreg containing the resin composition described in any one of [1] to [6] above or a semi-cured product of the resin composition described above.

[0021] [9] A laminate having a cured resin composition of any one of [1] to [6] or a cured prepreg of [8] and a metal foil.

[0022]

[10] A printed circuit board having one or more of the following: a cured resin composition selected from any one of [1] to [6] above, a cured prepreg selected from [8] above, and a laminate selected from [9] above.

[0023]

[11] A semiconductor package having the printed circuit board and semiconductor element described in

[10] above.

[0024] Invention Effects

[0025] According to this disclosure, a resin composition is provided that has excellent high-frequency characteristics and can form a cured product in which the formation of depressions on the surface of the resin layer after decontamination is suppressed, and a resin film, prepreg, laminate, printed circuit board and semiconductor package using the above resin composition are provided. Detailed Implementation

[0026] In the numerical range described in this disclosure, the upper or lower limit of the numerical range can be replaced with the values ​​shown in the embodiments. Furthermore, the lower and upper limits of the numerical range can be arbitrarily combined with the lower or upper limits of other numerical ranges. In the expression "AA~BB", the values ​​AA and BB at both ends are included in the numerical range as the lower and upper limits, respectively.

[0027] In this disclosure, for example, a description such as "10 or more" refers to a value of 10 or more, and this applies even if the value differs. Similarly, a description such as "10 or less" refers to a value of 10 or less, and this applies even if the value differs.

[0028] Furthermore, unless otherwise specified, each component and material exemplified in this disclosure may be used individually or in combination of two or more. In this disclosure, the content of each component in the resin composition refers to the total amount of the various substances present in the resin composition when multiple substances corresponding to each component are present in the resin composition, unless otherwise specified.

[0029] In this disclosure, "resin component" refers to all components in the solid components constituting the resin composition other than inorganic compounds such as inorganic fillers, which will be described later.

[0030] In this disclosure, "solid component" refers to components in the resin composition other than the organic solvents described later.

[0031] Regarding the expression "containing XX" as recorded in this disclosure, if XX can react, it can mean that it contains XX in the state after XX has reacted, or it can mean that it directly contains XX, or it can include both of these methods.

[0032] Any combination of the items described in this disclosure is also included in this disclosure and this embodiment.

[0033] [Resin Composition]

[0034] The resin composition of this embodiment contains a styrene-based elastomer (A) [hereinafter, sometimes also referred to as component (A)] and a maleimide compound (B) [hereinafter, sometimes also referred to as component (B)], wherein component (A) contains 5 to 15% by mass or 40% by mass or more of structural units derived from the styrene-based compound, based on all structural units of component (A).

[0035] The components contained in the resin composition of this embodiment will be described below.

[0036] <Styrene-based elastomers (A)>

[0037] The resin composition of this embodiment contains a styrene-based elastomer, which contains 5 to 15% by mass or 40% by mass or more of structural units derived from styrene-based compounds, based on all structural units of component (A).

[0038] By including a styrene-based elastomer, the high-frequency characteristics are improved, and by ensuring that the content of structural units from styrene-based compounds is at the specified amount, the formation of depressions on the surface of the resin layer after cleaning is suppressed.

[0039] From the viewpoint of suppressing the formation of depressions on the surface of the resin layer after the cleaning treatment, based on all structural units of component (A), the content of structural units derived from styrene compounds is preferably 7-15% by mass or 40-55% by mass, more preferably 10-15% by mass or 40-50% by mass, and even more preferably 10-15% by mass or 40-45% by mass. That is, the above-mentioned "5-15% by mass" can be independently 7-15% by mass or 10-15% by mass, and the above-mentioned "40% by mass or more" can be independently 40-55% by mass, 40-50% by mass, or 40-45% by mass.

[0040] (A) The preferred component is a styrene-based thermoplastic elastomer.

[0041] As described above, component (A) contains structural units derived from styrene compounds, and is preferably a copolymer having structural units derived from styrene compounds and structural units derived from conjugated diene compounds.

[0042] Examples of the aforementioned styrene compounds include styrene, α-methylstyrene, p-methylstyrene, and p-tert-butylstyrene. Among these, from the viewpoint of availability and productivity, styrene, α-methylstyrene, and 4-methylstyrene are preferred, with styrene being more preferred.

[0043] Examples of the aforementioned conjugated diene compounds include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene (isoprene), 1-phenyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3,4-dimethyl-1,3-hexadiene, and 4,5-diethyl-1,3-octadiene. From the viewpoint of availability and productivity, 1,3-butadiene and isoprene are preferred, with 1,3-butadiene being more preferred.

[0044] (A) The component may be a hydrogenated styrene-based elastomer from which at least a portion of the structural units derived from the conjugated diene compound has been hydrogenated. It should be noted that, in this disclosure, the term "styrene-based elastomer" also includes hydrogenated styrene-based elastomers. The hydrogenation rate of the hydrogenated styrene-based elastomer is not particularly limited, but is preferably 50-100 mol%, more preferably 70-100 mol%, even more preferably 80-100 mol%, particularly preferably 90-100 mol%, and may also be 95-100 mol%.

[0045] Examples of hydrogenated styrene-based elastomers include styrene-butadiene-styrene block copolymers (SEBS) and styrene-isoprene-styrene block copolymers (SEPS). SEBS is preferred. Commercially available SEBS products include Asahi Kasei Corporation's TUFTEC (registered trademark) H and M series, Kuraray Corporation's SEPTON (registered trademark) series, and Kraton Polymer Japan Corporation's Kraton (registered trademark) G Polymer series.

[0046] Styrene-based elastomers can be modified with compounds containing functional groups, such as maleic anhydride.

[0047] For example, maleic anhydride-modified styrene elastomers can be manufactured by reacting styrene elastomers or hydrogenated styrene elastomers with maleic anhydride, or commercially available products can be used.

[0048] As a styrene-based elastomer, a styrene-based elastomer with a number average molecular weight of 5,000 to 200,000 is preferred, a styrene-based elastomer with a number average molecular weight of 10,000 to 150,000 is more preferred, and a styrene-based elastomer with a number average molecular weight of 50,000 to 100,000 is even more preferred.

[0049] In this disclosure, the number-average molecular weight is a value calculated by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, converted to standard polystyrene.

[0050] (Content of component (A))

[0051] The content of component (A) in the resin composition of this embodiment is not particularly limited. From the viewpoint of high-frequency characteristics and suppressing the formation of depressions on the surface of the resin layer after cleaning treatment, it is preferably 1 to 50 parts by mass relative to 100 parts by mass of solid components in the resin composition, more preferably 3 to 40 parts by mass, further preferably 3 to 35 parts by mass, particularly preferably 3 to 25 parts by mass, and most preferably 3 to 15 parts by mass.

[0052] <Maleimide compound (B)>

[0053] The resin composition of this embodiment contains a maleimide compound as component (B). By including a maleimide compound in the resin composition of this embodiment, a resin composition with excellent heat resistance and low thermal expansion is obtained.

[0054] As a maleimide compound, it is preferably selected from one or more maleimide compounds having two or more N-substituted maleimide groups [hereinafter, sometimes simply referred to as "maleimide compound (b1)" or "(b1) component"]. and their derivatives.

[0055] It should be noted that, as the aforementioned "derivatives", examples include the addition reaction products of maleimide compounds having two or more N-substituted maleimide groups and amine compounds such as diamine compounds described later.

[0056] As a specific example of maleimide compound (b1), there is no particular limitation as long as it is a maleimide compound having two or more N-substituted maleimide groups. Examples include: bis(4-maleimidephenyl)methane, polyphenylmethane maleimide, bis(4-maleimidephenyl) ether, bis(4-maleimidephenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis(maleimidephenyl) Aromatic maleimide compounds include maleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane, and aromatic bismaleimides containing indene rings; and aliphatic maleimide compounds include 1,6-bismaleimide-(2,2,4-trimethyl)hexane and pyrophosphate binder-type long-chain alkyl bismaleimides. From the viewpoint of adhesion to conductors and mechanical properties, aromatic maleimide compounds are preferred, aromatic bismaleimide compounds are more preferred, and 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide are even more preferred.

[0057] It should be noted that aromatic maleimide compounds refer to compounds in which the maleimide group is directly bonded to an aromatic hydrocarbon group, while aliphatic maleimide compounds refer to compounds in which the maleimide group is directly bonded to an aliphatic hydrocarbon group.

[0058] From the viewpoints of solubility in organic solvents, compatibility, adhesion to conductors, and high-frequency properties, derivatives of maleimide compound (b1) are preferred as maleimide compounds.

[0059] As a derivative of maleimide compound (b1), a modified maleimide compound (hereinafter sometimes simply referred to as "modified maleimide compound (X)" or "(X) component") having structural units derived from maleimide compound (b1) and structural units derived from an amine compound having a primary amino group [hereinafter sometimes simply referred to as "(b2) component"].

[0060] It should be noted that the structural units from component (b1) and structural units from component (b2) contained in the modified maleimide compound (X) can be one type or a combination of two or more types.

[0061] The modified maleimide compound (X) is preferably a compound containing the structure shown in the following formula (B-1) formed by the addition reaction of the maleimide group of component (b1) and the primary amino group of component (b2).

[0062] [Chemical Formula 1]

[0063]

[0064] ( Indicates the bonding location with other structures.

[0065] The amine compound (b2) is preferably a compound having two or more amino groups, and more preferably a diamine compound having two amino groups.

[0066] Examples of amine compounds (b2) include: 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis... (3-Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1- Aromatic diamine compounds such as 4,4'-[1,4-phenylenebis(1-methylethylene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, and 9,9-bis(4-aminophenyl)fluorene; amine-modified siloxane compounds with primary amino groups, etc.

[0067] Here, aromatic diamine compounds refer to compounds in which two amino groups are directly bonded to an aromatic hydrocarbon group.

[0068] Of these, as component (b2), from the viewpoint of excellent solubility in organic solvents, reactivity with component (b1), and heat resistance, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylene)]bisaniline, and 4,4'-[1,4-phenylenebis(1-methylethylene)]bisaniline are preferred. Furthermore, from the viewpoint of excellent high-frequency characteristics and low water absorption, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane is preferred. Furthermore, from the viewpoint of excellent mechanical properties such as high adhesion to conductors, elongation, and tensile strength, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is preferred. Furthermore, from the viewpoints of excellent solubility in organic solvents, reactivity during synthesis, heat resistance, high adhesion to conductors, and excellent high-frequency characteristics and low hygroscopicity, 4,4'-[1,3-phenylenebis(1-methylethylene)]bisaniline and 4,4'-[1,4-phenylenebis(1-methylethylene)]bisaniline are preferred. Additionally, from the viewpoint of low thermal expansion, amine-modified siloxane compounds are preferred.

[0069] The functional group equivalent of the above-mentioned amine-modified siloxane compound is not particularly limited, but is preferably 300-3000 g / mol, more preferably 400-2000 g / mol, and even more preferably 600-1000 g / mol.

[0070] As component (b2), from the viewpoint of heat resistance and low thermal expansion, it is preferable to use a combination of aromatic diamine compounds and amine-modified siloxane compounds.

[0071] The ratio of aromatic diamine compound to amine-modified siloxane compound used [aromatic diamine compound / amine-modified siloxane compound] is not particularly limited, but is preferably 20 / 80 to 80 / 20 by mass, more preferably 40 / 60 to 70 / 30, and even more preferably 50 / 50 to 65 / 35.

[0072] The content of structural units derived from component (b2) in the modified maleimide compound (X) is not particularly limited, but is preferably 5 to 50% by mass, more preferably 8 to 30% by mass, and even more preferably 10 to 15% by mass. If the content of structural units derived from component (b2) is within the above range, there is a tendency to obtain better high-frequency characteristics, as well as better heat resistance, flame retardancy and glass transition temperature.

[0073] The total content of structural units from component (b1) and structural units from component (b2) in the modified maleimide compound (X) is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 100% by mass (i.e., it consists only of structural units from component (b1) and structural units from component (b2)).

[0074] The ratio of structural units from component (b1) to structural units from component (b2) in the modified maleimide compound (X) is not particularly limited. The equivalence ratio (Ta1 / Ta2) of the total equivalent amount (Ta1) of maleimide groups (including maleimide groups) derived from component (b1) to the total equivalent amount (Ta2) of -NH2 groups (including -NH2 groups) derived from component (b2) is preferably 0.05 to 10, more preferably 1 to 5. If the equivalence ratio (Ta1 / Ta2) is within the above range, there is a tendency to obtain excellent high-frequency characteristics, as well as better heat resistance, flame retardancy, and glass transition temperature.

[0075] (Method for manufacturing modified maleimide compound (X))

[0076] Component (X) can be obtained as a reaction product of components (b1) and (b2), for example, by reacting components (b1) and (b2) in an organic solvent.

[0077] Specifically, a predetermined amount of component (b1), component (b2), and other components as needed are added to a reactor, and component (b1) and component (b2) undergo a Michael addition reaction [hereinafter sometimes simply referred to as the "pre-reaction"]. This yields a modified maleimide compound (X).

[0078] The reaction conditions in the pre-reaction are not particularly limited. From the viewpoint of inhibiting gelation and obtaining good reactivity and operability, the reaction temperature is preferably 50 to 160°C and the reaction time is preferably 1 to 10 hours.

[0079] In the pre-reaction process, a reaction catalyst may be used as needed. Examples of reaction catalysts include: acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazolium and phenylimidazolium; and phosphorus-based catalysts such as triphenylphosphine. One catalyst may be used alone, or two or more may be used in combination. Furthermore, there is no particular limitation on the amount of reaction catalyst used, which is, for example, 0.01 to 5 parts by mass relative to 100 parts by mass of the combined amount of components (b1) and (b2).

[0080] The weight-average molecular weight (Mw) of the modified maleimide compound (X) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, even more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.

[0081] It should be noted that, in this disclosure, the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) based on a standard curve using standard polystyrene, or more specifically, a value obtained by the determination method described in the examples.

[0082] (Content of component (B))

[0083] The content of thermosetting resin (B) in the resin composition of this embodiment is not particularly limited. From the viewpoints of high-frequency characteristics, heat resistance, low thermal expansion and formability, it is preferably 10 to 70 parts by mass relative to 100 parts by mass of solid components in the resin composition, more preferably 15 to 60 parts by mass, further preferably 20 to 50 parts by mass, and particularly preferably 25 to 45 parts by mass.

[0084] <Inorganic filler materials (C)>

[0085] The resin composition of this embodiment may contain an inorganic filler as component (C). By including component (C) in the resin composition of this embodiment, there is a tendency to improve the low coefficient of thermal expansion, heat resistance, and flame retardancy.

[0086] Component (C) is not particularly limited and can include: silicon dioxide, aluminum oxide, titanium oxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (fired clay, etc.), molybdate compounds (zinc molybdate, etc.), talc, aluminum borate, silicon carbide, etc. Component (C) can be used alone or in combination of two or more. From the viewpoint of coefficient of thermal expansion, heat resistance, and flame retardancy, silicon dioxide, aluminum oxide, mica, and talc are preferred, silicon dioxide and aluminum oxide are more preferred, and silicon dioxide is even more preferred. Examples of silicon dioxide include crushed silicon dioxide, fumed silicon dioxide, and molten silicon dioxide (molten spherical silicon dioxide).

[0087] (C) The shape and particle size of the component are not particularly limited, but the particle size is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm. Here, particle size refers to the average particle size, which is the particle size at the point corresponding to 50% of the volume when the total volume of the particles is set to 100% and the cumulative frequency distribution curve based on the particle size is obtained. (C) The particle size of the component can be measured by a particle size distribution measuring device using laser diffraction scattering method, etc.

[0088] (C) Content of component

[0089] When the resin composition of this embodiment contains component (C), the content of component (C) is not particularly limited. From the viewpoint of coefficient of thermal expansion, heat resistance and flame retardancy, it is preferably 5 to 70 parts by mass relative to 100 parts by mass of solid components in the resin composition, more preferably 15 to 65 parts by mass, further preferably 20 to 60 parts by mass, and particularly preferably 30 to 55 parts by mass.

[0090] Furthermore, when using component (C), coupling agents can be used in combination as needed to improve the dispersibility of component (C) and the adhesion between component (C) and the organic components in the resin composition. There are no particular limitations on the coupling agent used; for example, silane coupling agents or titanate coupling agents can be appropriately selected. One coupling agent can be used alone, or two or more can be used in combination. Furthermore, there are no particular limitations on the amount of coupling agent used.

[0091] It should be noted that when using a coupling agent, it can be a so-called integral blending treatment where the coupling agent is added after component (C) is incorporated into the resin composition. Preferably, the inorganic filler material has been pre-treated with a coupling agent using a dry or wet method. By employing this method, the advantages of component (C) can be more effectively expressed.

[0092] In this embodiment, when using component (C), for the purpose of improving the dispersibility of component (C) in the resin composition, it can be used in the form of a slurry prepared by pre-dispersing component (C) in an organic solvent, as needed. Examples of organic solvents include those described below.

[0093] <Polyphenylene ether derivatives with groups containing olefinic unsaturated bonds (D)>

[0094] The resin composition of this embodiment may contain a polyphenylene ether derivative (hereinafter, sometimes simply referred to as "polyphenylene ether derivative (D)") having a group containing an olefinic unsaturated bond as component (D). By including component (D) in the resin composition of this embodiment, there is a tendency for the high-frequency characteristics to be further improved, and the compatibility between component (A) and component (B) to be improved.

[0095] (D) The preferred component is a polyphenylene ether derivative having a group containing an olefinic unsaturated bond at the end, and more preferably a polyphenylene ether derivative having a group containing an olefinic unsaturated bond at both ends.

[0096] It should be noted that, in this disclosure, "groups containing olefinic unsaturated bonds" refers to substituents containing carbon-carbon double bonds capable of undergoing addition reactions, excluding double bonds in aromatic rings.

[0097] Polyphenylene ether derivatives (D) can be used alone or in combination of two or more.

[0098] Examples of groups containing olefinic unsaturated bonds include: vinyl, allyl, 1-methylallyl, isopropenyl, 2-butenyl, 3-butenyl, styryl, and other unsaturated aliphatic hydrocarbon groups; maleimide groups; and groups containing heteroatoms and olefinic unsaturated bonds, such as those shown in the following general formula (D-1). From the viewpoints of high-frequency characteristics, adhesion to conductors, and compatibility between components (A) and (B), groups containing olefinic unsaturated bonds are preferably those shown in the following general formula (D-1).

[0099] [Chemical Formula 2]

[0100]

[0101] (where R) d1 (This refers to an alkyl group having 1 to 20 hydrogen atoms or carbon atoms.)

[0102] R d1 The alkyl group having 1 to 20 carbon atoms shown can be any one of straight-chain alkyl, branched alkyl, or cyclic alkyl, preferably a straight-chain alkyl.

[0103] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1.

[0104] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, pentadecyl, hexadecyl, heptadecanyl, etc., with methyl being preferred.

[0105] From the viewpoints of high-frequency characteristics, adhesion to the conductor, and compatibility between component (A) and component (B), the group represented by the above general formula (D-1) is preferably (meth)acryloyl (i.e., R in the above general formula (D-1)). d1 (A group consisting of a hydrogen atom or a methyl group), more preferably a methacryloyl group.

[0106] It should be noted that, in this disclosure, groups such as maleimide groups and groups represented by the above general formula (D-1), which have unsaturated aliphatic hydrocarbon groups but cannot be called unsaturated aliphatic hydrocarbon groups when viewed as a whole, are not included in the above "unsaturated aliphatic hydrocarbon groups".

[0107] The polyphenylene ether derivative (D) preferably has groups represented by the above general formula (D-1) at one or both ends.

[0108] When the polyphenylene ether derivative (D) has groups containing olefinic unsaturated bonds at one or both ends, it may further have groups containing olefinic unsaturated bonds in addition to the groups at one or both ends, but preferably only at the two ends. The polyphenylene ether derivative (D) is preferably a polyphenylene ether having methacryl groups at both ends.

[0109] The number of olefinically unsaturated groups in one molecule of the polyphenylene ether derivative (D) is not particularly limited, but is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2. If the number of olefinically unsaturated groups is above the lower limit mentioned above, there is a tendency to obtain excellent heat resistance and compatibility between component (A) and component (B), and if it is below the upper limit mentioned above, there is a tendency to obtain excellent flowability and formability.

[0110] The polyphenylene ether derivative (D) has phenylene ether bonds, and preferably has structural units shown in the following general formula (D-2).

[0111] [Chemical Formula 3]

[0112]

[0113] (where R) d2 This refers to an aliphatic hydrocarbon group or halogen atom with 1 to 5 carbon atoms. d1 (Represents integers from 0 to 4.)

[0114] R in the above general formula (D-2) d2 Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. As this aliphatic hydrocarbon group, an aliphatic hydrocarbon group with 1 to 3 carbon atoms is preferred, an alkyl group with 1 to 3 carbon atoms is more preferred, and methyl is even more preferred.

[0115] n d1 Represents an integer from 0 to 4, preferably 1 or 2, more preferably 2. It should be noted that in n... d1 When R is 1 or 2, d2 Preferably, the substitution occurs at the ortho position on the benzene ring (wherein the substitution position of the oxygen atom is used as a reference). Additionally, in n... d1 When R is an integer greater than 2, multiple R d2 They can be the same or different.

[0116] The structural unit shown in the above general formula (D-2) is preferably the structural unit shown in the following general formula (D-2').

[0117] [Chemical Formula 4]

[0118]

[0119] From the viewpoints of high-frequency characteristics, adhesion to conductors, and compatibility between components (A) and (B), the polyphenylene ether derivative (D) is preferably a compound represented by the following general formula (D-3).

[0120] [Chemical Formula 5]

[0121]

[0122] (where R) d2 and n d1 As explained in the general formula (D-2) above. R d3 and R d4 Each group independently represents an aliphatic hydrocarbon group or halogen atom with 1 to 5 carbon atoms. d2 and n d3 Each of the n integers from 0 to 4 can be represented independently. d4 and n d5 Each represents an integer from 0 to 20 independently, n d4 and n d5 The sum is an integer from 1 to 30. X d1 Y represents an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyl group, a ketone group, or a single bond. d1 and Y d2 Each of these groups independently represents one of the aforementioned groups containing an alkene unsaturated bond.

[0123] Regarding R in the above general formula (D-3) d3 and R d4 The description of the aliphatic hydrocarbon groups with 1 to 5 carbon atoms shown is related to R in the above general formula (D-2). d2 The descriptions for aliphatic hydrocarbon groups with 1 to 5 carbon atoms are the same.

[0124] n d2 and n d3 Represents an integer from 0 to 4, preferably an integer from 0 to 3, and more preferably 2 or 3. In n d2 or n d3 When R is an integer greater than 2, multiple R d3 R to each other or multiple R d4 They can be the same or different.

[0125] n d4 and n d5 It represents an integer from 0 to 20, preferably an integer from 1 to 20, more preferably an integer from 2 to 15, and even more preferably an integer from 3 to 10. In n d4 or n d5 When n is an integer greater than or equal to 2, multiple n d1 They can be the same or different.

[0126] n d4 and n d5 The total is an integer from 1 to 30, preferably an integer from 2 to 25, more preferably an integer from 5 to 20, and even more preferably an integer from 7 to 15.

[0127] As X in the above general formula (D-3) d1 Examples of alkylene groups with 1 to 5 carbon atoms include methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, and 1,5-pentamethylene.

[0128] As X d1 Examples of alkylidenes with 2 to 5 carbon atoms include ethoxyl, propionyl, isopropionyl, butylidene, isobutylidene, pentylidene, and isopentylidene.

[0129] X d1 Of the groups shown, isopropylidene is preferred from the viewpoints of high-frequency characteristics, adhesion to conductors, and compatibility between components (A) and (B).

[0130] About Y d1 and Y d2 The preferred embodiment of the group containing an olefinic unsaturated bond is as described above.

[0131] From the viewpoints of high-frequency characteristics, adhesion to conductors, and compatibility between component (A) and component (B), the compound represented by the above general formula (D-3) is preferably the compound represented by the following general formula (D-4).

[0132] [Chemical Formula 6]

[0133]

[0134] (where n) d4 and n d5 As explained in the general formula (D-3) above. R d5 and R d6 Each can independently represent a hydrogen atom or a methyl group. X d2 (This indicates a methylene or isopropylidene group.)

[0135] [Weight-average molecular weight (Mw) of polyphenylene ether derivative (D)]

[0136] The weight-average molecular weight (Mw) of the polyphenylene ether derivative (D) is not particularly limited, but is preferably 500 to 7000, more preferably 800 to 5000, even more preferably 1000 to 3000, and particularly preferably 1200 to 2500. If the weight-average molecular weight (Mw) of component (D) is above the lower limit mentioned above, there is a tendency to obtain a cured product with excellent dielectric properties of polyphenylene ether and excellent heat resistance; if it is below the upper limit mentioned above, there is a tendency to obtain excellent formability.

[0137] The synthesis of polyphenylene ether derivatives (D) can be carried out using known methods for the synthesis and modification of polyphenylene ethers, without any particular limitation.

[0138] (Content of component (D))

[0139] When the resin composition of this embodiment contains component (D), the content of component (D) is not particularly limited. It is preferably 0.1 to 40 parts by mass relative to 100 parts by mass of the solid content in the resin composition, more preferably 0.5 to 20 parts by mass, further preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass. If the content of component (D) is above the lower limit mentioned above, there is a tendency to obtain better high-frequency characteristics and compatibility; if it is below the upper limit mentioned above, there is a tendency to obtain better heat resistance, formability, and processability.

[0140] <Curing Accelerator (E)>

[0141] The resin composition of this embodiment tends to have improved curability, superior high-frequency properties, heat resistance, adhesion to conductors, elastic modulus and glass transition temperature by further containing a curing accelerator as component (E).

[0142] When the resin composition of this embodiment contains a curing accelerator (E), a suitable curing accelerator (E) can be appropriately selected according to the type of thermosetting resin (B) component used.

[0143] Curing accelerator (E) can be used alone or in combination of two or more.

[0144] Examples of components (E) include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organometallic salts, acidic catalysts, and organic peroxides. It should be noted that, in this embodiment, imidazole-based curing accelerators are not classified as amine-based curing accelerators.

[0145] Examples of amine-based curing accelerators include: triethylamine, pyridine, tributylamine, dicyandiamide, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and other amine compounds with primary to tertiary amines; quaternary ammonium compounds, etc.

[0146] Examples of imidazole-based curing accelerators include: methylimidazolium, phenylimidazolium, 2-undecylimidazolium, and isocyanate-masked imidazolium (such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazolium).

[0147] Examples of phosphorus-based curing accelerators include: tertiary phosphines such as triphenylphosphine; and quaternary phosphorus compounds such as the tri-n-butylphosphine addition reaction product of p-benzoquinone.

[0148] Examples of organometallic salts include carboxylates of manganese, cobalt, and zinc.

[0149] Examples of acidic catalysts include p-toluenesulfonic acid.

[0150] Examples of organic peroxides include: dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxide)-3-hexyne, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane, tert-butylperoxide isopropyl monocarbonate, and α,α'-di(tert-butylperoxide)diisopropylbenzene.

[0151] From the viewpoint of obtaining superior high-frequency characteristics, heat resistance, adhesion to conductors, elastic modulus, and glass transition temperature, amine-based curing accelerators, imidazole-based curing accelerators, and phosphorus-based curing accelerators are preferred; dicyandiamide, imidazole-based curing accelerators, and quaternary phosphorus compounds are more preferred; and combinations thereof are even more preferred. Organic peroxides may also be used in combination, but from the viewpoint of the physical properties of the cured product, it is preferable that the product does not contain organic peroxides.

[0152] (Content of component (E))

[0153] When the resin composition of this embodiment contains component (E), the content of component (E) is not particularly limited, but is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the resin component, more preferably 0.05 to 5 parts by weight, further preferably 0.1 to 4 parts by weight, and particularly preferably 0.5 to 3 parts by weight. If the content of the curing accelerator (E) is within the above range, there is a tendency to obtain better high-frequency characteristics, heat resistance, storage stability, and formability.

[0154] <Other Ingredients>

[0155] The resin composition of this embodiment may further contain, as needed, one or more of the resin materials other than those mentioned above, flame retardants, flame retardant additives, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, silane coupling agents, and other optional components.

[0156] Each of the above optional ingredients can be used alone or in combination of two or more.

[0157] As resin materials other than the components mentioned above, examples include thermosetting resins other than maleimide compounds. Preferably, the aforementioned thermosetting resin contains one or more selected from epoxy resins, phenolic resins, polyimide resins, cyanate ester resins, isocyanate ester resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins.

[0158] When the resin composition of this embodiment contains the optional components described above, their content is not particularly limited. Relative to the total amount of resin components (100 parts by mass), the content can be 0.01 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more. In addition, it can be 30 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less.

[0159] In addition, the resin composition of this embodiment may be omitted from the above-mentioned optional components, depending on the desired performance.

[0160] The total content of components (A) to (E) in the resin composition of this embodiment is not particularly limited. It is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and even more preferably 95 parts by mass or more, and can be 100 parts by mass, relative to 100 parts by mass of solid components in the resin composition.

[0161] (Organic solvent)

[0162] From the viewpoint of ease of operation and ease of manufacturing the prepreg described later, the resin composition of this embodiment can be a varnish-like resin composition containing organic solvents.

[0163] Examples of organic solvents include: alcohols such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran; aromatics such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and esters such as γ-butyrolactone. These organic solvents can be used individually or in combination of two or more.

[0164] When the resin composition of this embodiment contains an organic solvent, its content is not particularly limited. Preferably, the solid content concentration of the resin composition of this embodiment is 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass. If the content of the organic solvent is within the above range, the processability of the resin composition becomes easier, the impregnation of the substrate and the appearance of the manufactured prepreg become better. In addition, the adjustment of the solid content concentration of the resin in the prepreg described later becomes easier, and the manufacture of prepregs with the desired thickness tends to become easier.

[0165] <Dielectric Properties>

[0166] When the resin composition of this embodiment is used to prepare test pieces using the methods described in the embodiments described later, the dielectric constant (Dk) at 10 GHz is not particularly limited, but is preferably 4.0 or less, more preferably 3.7 or less, even more preferably 3.3 or less, and may also be 3.1 or less. A smaller dielectric constant (Dk) is preferred, and its lower limit is not particularly limited; considering the balance with other properties, it may be 2.5 or more, or 2.8 or more. That is, the dielectric constant (Dk) can be from 2.5 to 4.0.

[0167] When preparing test pieces of the resin composition of this embodiment using the methods described in the embodiments below, the dielectric loss tangent (Df) at 10 GHz is not particularly limited, but is preferably 0.0040 or less, more preferably 0.0038 or less, further preferably 0.0035 or less, particularly preferably 0.0034 or less, most preferably 0.0033 or less, and may also be 0.0032 or less. A smaller dielectric loss tangent (Df) is preferred, and its lower limit is not particularly limited. Considering the balance with other physical properties, it may be 0.0020 or more, 0.0025 or more, 0.0028 or more, or 0.0029 or more. That is, the dielectric loss tangent (Df) can be 0.0025 to 0.0040.

[0168] It should be noted that the dielectric constant (Dk) and dielectric loss tangent (Df) are values ​​based on the cavity resonator perturbation method, and more specifically, values ​​measured by the method described in the embodiments. Furthermore, in this disclosure, when referred to simply as dielectric constant, it refers to the relative dielectric constant.

[0169] The resin composition of this embodiment can be manufactured by mixing components (A) to (B) and any other components as needed using a known method. At this time, each component can be dissolved or dispersed in the aforementioned organic solvent while stirring. The mixing order, temperature, time, and other conditions are not particularly limited and can be set arbitrarily.

[0170] [Resin film]

[0171] The resin film of this embodiment may be a resin film containing the resin composition of this embodiment or a semi-cured product of the above-described resin composition.

[0172] The resin film of this embodiment can be manufactured, for example, by coating a resin composition containing an organic solvent, i.e., a varnish, onto a support, heating and drying it, and then semi-curing it as needed (B-stage curing). The thickness of the resin film is not particularly limited, but is preferably 1 to 100 μm, more preferably 3 to 70 μm, and even more preferably 5 to 35 μm.

[0173] Examples of suitable support materials include plastic film, metal foil, and release paper.

[0174] The drying temperature and drying time can be appropriately determined based on the amount of organic solvent used and the boiling point of the organic solvent. A resin film can be properly formed by drying at 50-200℃ for about 1-10 minutes.

[0175] [Prepreg]

[0176] The prepreg in this embodiment is a prepreg containing the resin composition of this embodiment or a semi-cured product of the above-described resin composition.

[0177] The prepreg of this embodiment contains, for example, the resin composition of this embodiment or a semi-cured product of the above-described resin composition, and a sheet fiber substrate. This prepreg is formed using the resin composition of this embodiment or the above-described resin film, and the sheet fiber substrate. For example, it can be obtained by impregnating the resin composition of this embodiment or the above-described resin film into the sheet fiber substrate, heating and drying it, and then semi-curing it as needed (B-stage curing). More specifically, for example, the prepreg of this embodiment can be manufactured by heating and drying it in a drying oven at a temperature typically between 80 and 200°C for 1 to 30 minutes to semi-cur it (B-stage curing). Here, in this disclosure, B-stage curing refers to forming a state defined in JIS K6900 (1994).

[0178] The amount of resin composition used can be appropriately determined for the purpose of achieving a solids concentration of 30-90% by mass in the dried prepreg. By setting the solids concentration within the above range, there is a tendency to obtain better formability when producing laminates.

[0179] As a prepreg, the sheet fiber substrate can be any known sheet fiber substrate used in laminates for various electrical insulation materials. Examples of materials for the sheet fiber substrate include: inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet fiber substrates can be in the form of woven fabric, nonwoven fabric, roving, chopped strand mat, or surface mat.

[0180] The thickness of the sheet fiber substrate is not particularly limited; it can be 1–100 μm, 3–70 μm, 5–55 μm, 15–55 μm, or 25–55 μm.

[0181] [Laminated Board]

[0182] The laminate in this embodiment is a laminate containing a cured resin composition or a cured prepreg of the resin composition of this embodiment and a metal foil.

[0183] The laminate of this embodiment can be manufactured, for example, by placing metal foil on one or both sides of a resin film of this embodiment, or by placing metal foil on one or both sides of a laminate obtained by overlapping two or more resin films of this embodiment, followed by heating and pressing to form the laminate. In the laminate obtained by this manufacturing method, the resin film of this embodiment is C-graded.

[0184] Another embodiment of the laminate of this embodiment can be manufactured, for example, by placing metal foil on one or both sides of a prepreg of this embodiment, or on one or both sides of a laminate obtained by overlapping two or more prepregs of this embodiment, followed by heating and pressing to form the laminate. In the laminate obtained by this manufacturing method, the prepreg of this embodiment is C-graded.

[0185] In this disclosure, C-order refers to the formation of a C-order state as defined in JIS K6900 (1994). It should be noted that laminates with metal foil are sometimes also referred to as metal-clad laminates.

[0186] The metal used as the foil is not particularly limited. From the viewpoint of conductivity, it can be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements. Copper and aluminum are preferred, and copper is more preferred.

[0187] There are no particular limitations on the implementation method of the above-mentioned heating and pressurizing forming. For example, it can be carried out under conditions of temperature of 100 to 300°C, pressure of 0.2 to 10 MPa, and time of 0.1 to 5 hours. In addition, heating and pressurizing forming can be carried out by using a method such as vacuum pressing to maintain a vacuum state for 0.5 to 5 hours.

[0188] Printed Circuit Board

[0189] The printed circuit board of this embodiment has a cured product of the resin composition of this embodiment. Alternatively, the printed circuit board of this embodiment may also be described as a printed circuit board having one or more of the following: a cured product of the thermosetting resin composition of this embodiment, a cured product of the prepreg of this embodiment, and a laminate of this embodiment.

[0190] The printed circuit board of this embodiment can be manufactured by using one or more of the prepreg, resin film, and laminate selected from this embodiment, and performing circuit forming processes such as hole-making, metal plating, and metal foil etching using known methods. Furthermore, a multilayer printed circuit board can also be manufactured by further performing multilayer bonding processes as needed. In the printed circuit board of this embodiment, the prepreg and resin film of this embodiment are C-graded.

[0191] [Semiconductor Package]

[0192] The semiconductor package of this embodiment is a semiconductor package having a printed circuit board and semiconductor elements as described in this embodiment. The semiconductor package of this embodiment can be manufactured by mounting semiconductor elements such as semiconductor chips and memory at predetermined locations on the printed circuit board of this embodiment.

[0193] The resin composition, resin film, prepreg, laminate, printed circuit board, and semiconductor package of this embodiment are suitable for use in electronic devices that process high-frequency signals above 10 GHz. In particular, the printed circuit board is useful as a printed circuit board for millimeter-wave radar.

[0194] The preferred embodiments have been described above, but these are merely illustrative examples and are not intended to limit the scope of this disclosure to these embodiments. This disclosure also includes various other embodiments different from those described above without departing from its spirit.

[0195] Example

[0196] The following examples illustrate this implementation in more detail. However, this disclosure is not limited to the following examples.

[0197] It should be noted that, in each case, the weight-average molecular weight (Mw) was determined by the following method.

[0198] The results were obtained by gel permeation chromatography (GPC) from a standard curve using standard polystyrene. The standard curve used standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name], approximated using a cubic formula. The determination conditions for GPC are shown below.

[0199] Device:

[0200] Pump: L-6200 type [Manufactured by Hitachi High-Technologies Co., Ltd.]

[0201] Detector: L-3300 RI [Manufactured by Hitachi High-Technologies Co., Ltd.]

[0202] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]

[0203] Columns: Protective columns; TSK Guardcolumn HHR-L+ column; TSKgel G4000HHR+ TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade names)

[0204] Column dimensions: 6.0×40mm (protective column), 7.8×300mm (column)

[0205] Eluent: Tetrahydrofuran

[0206] Sample concentration: 30 mg / 5 mL

[0207] Injection volume: 20μL

[0208] Flow rate: 1.00 mL / min

[0209] Measurement temperature: 40℃

[0210] [Manufacturing Example 1: Manufacturing of Modified Maleimide Compound (X-1) (Component (B))]

[0211] In a 5L reaction vessel equipped with a thermometer, stirrer, reflux condenser, and moisture meter, capable of heating and cooling, 100 parts by mass of 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane, 5.6 parts by mass of a siloxane compound with amino groups at both ends (functional equivalent 750 g / mol), 7.9 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by mass of propylene glycol monomethyl ether were added, and the mixture was refluxed for 2 hours. The mixture was then concentrated at reflux temperature for 3 hours to prepare a modified maleimide compound (X-1) solution with a solid content of 65% by mass. The weight-average molecular weight (Mw) of the obtained modified maleimide compound (X-1) was approximately 2700.

[0212] [Examples 1-2, Comparative Examples 1-3]

[0213] (Preparation of resin composition)

[0214] The components listed in Table 1 were mixed with 58 parts by mass of toluene and 10 parts by mass of methyl isobutyl ketone at room temperature to prepare a resin composition with a solid component concentration of 55-65% by mass.

[0215] (Manufacturing of resin film)

[0216] Using a coating machine, the above-mentioned resin composition was coated onto a PET film with a thickness of 0.050 mm, and then heated and dried at 120°C for 3 minutes to produce a resin-coated PET film with a resin thickness of 25 μm.

[0217] (Manufacturing of double-sided copper-clad laminates)

[0218] The resin surfaces of the resin-coated PET films were bonded together using vacuum pressure lamination (temperature 110°C, pressure 0.5 MPa). Further, the process of peeling off one side of the PET film and bonding the resin surface of another resin-coated PET film to the exposed resin surface was repeated until the resin thickness reached 325 μm. The PET films on both sides of the 325 μm resin-coated PET film were peeled off, and a 18 μm thick low-profile copper foil (BF-ANP18, M-side Rz: 1.5 μm, manufactured by CIRCUIT FOIL) was laminated on the top and bottom with the M-side in contact with the resin. This laminate was then placed in a 300 μm thick mold frame. Next, a double-sided copper-clad laminate was fabricated by heat and pressure molding at 230°C, 3.0 MPa, and 90 minutes.

[0219] [Evaluation Method]

[0220] Using the double-sided copper-clad laminates obtained in each example, the evaluations were performed according to the following methods. The results are shown in Table 1.

[0221] (1. Confirmation of the presence or absence of dents)

[0222] The copper foil was removed by immersing the double-sided copper-clad laminate obtained in each example in a copper etching solution, and the following (1) to (4) were performed in sequence to carry out the decontamination treatment, and a resin board was made.

[0223] (1) Immerse in swelling solution (manufactured by Atotech Japan Co., Ltd., trade name "Swelling Dip Securiganth P", glycol ether, aqueous solution of sodium hydroxide) at 60°C for 10 minutes, then wash with water.

[0224] (2) After soaking in the roughening solution (manufactured by Atotech Japan Co., Ltd., trade name "Concentrate Compact P", aqueous solution of KMnO4: 60g / L, NaOH: 40g / L) at 80°C for 20 minutes, wash with water.

[0225] (3) Soak in neutralization solution (Atotech Japan Co., Ltd., “Reduction Solution Securiganth P”, an aqueous solution of sulfuric acid) at 40°C for 5 minutes, then wash with water.

[0226] (4) Dry at 80℃ for 10 minutes.

[0227] The surface of the decontamination-treated resin board (resin layer) obtained above was observed using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies, Ltd., trade name: SV-4700) under secondary electron mode, accelerating voltage of 10 kV, and magnification of 5000x. In the obtained surface SEM images, the presence of depressions larger than 1.0 μm on the surface of the resin board (resin layer) was marked as "present" depressions, and the absence of depressions larger than 1.0 μm on the surface of the resin board (resin layer) was marked as "absent" depressions.

[0228] It should be noted that the size of the depression here refers to the length of the longest straight line drawn within the depression area when viewed from above the resin board.

[0229] (2. High-frequency characteristics)

[0230] Resin plates were prepared under the same conditions as those used in the "Confirmation of the Presence or Absence of Dents" procedure described above. These plates were cut into 60mm long and 2mm wide pieces to serve as test specimens. The dielectric constant and dielectric loss tangent were determined using the cavity resonator perturbation method. The measuring instrument used was an Agilent Technologies N5227A vector network analyzer, and the cavity resonator used was a CP129 (10GHz band resonator) manufactured by Kanto Electron Applications Development Co., Ltd. The measurement program used was CPMA-V2. Measurements were performed at a frequency of 10GHz and a measurement temperature of 25°C.

[0231] (3. Evaluation of copper foil peel strength)

[0232] For the copper foil peel strength of the double-sided copper-clad laminates obtained in each example, the peel strength was determined by peeling the copper foil along a 90° direction according to JIS C6481 (1996). It should be noted that the stretching speed was set to 50 mm / min.

[0233] The copper foil peel strength should be above 0.5 kN / m.

[0234] [Table 1]

[0235]

[0236] It should be noted that the abbreviations for the materials in Table 1 are as follows.

[0237] [(A) Ingredient]

[0238] SEBS_A-1: Hydrogenated styrene-based elastomer (manufactured by Asahi Kasei Corporation, trade name "TUFTEC (registered trademark) H1221"), styrene content 12%.

[0239] SEBS_A-2: Hydrogenated styrene-based elastomer (manufactured by Asahi Kasei Corporation, trade name "TUFTEC (registered trademark) H1517"), styrene content 43%.

[0240] [Component (A'): Styrene-based elastomers that are not part of component (A)]

[0241] • SEBS_A'-3: Hydrogenated styrene-based elastomer (manufactured by Asahi Kasei Corporation, trade name "TUFTEC (registered trademark) H1052"), styrene content 20%.

[0242] • SEBS_A'-4: Hydrogenated styrene-based elastomer (manufactured by Asahi Kasei Corporation, trade name "TUFTEC (registered trademark) H1041"), styrene content 30%.

[0243] SEBS_A'-5: Maleic anhydride-modified hydrogenated styrene elastomer (manufactured by Asahi Kasei Corporation, trade name "TUFTEC (registered trademark) M1913"), acid value 10 mg CH3ONa / g, styrene content 30%.

[0244] [(B) Component]

[0245] • Modified maleimide compound: Modified maleimide compound (X-1) prepared in Manufacturing Example 1

[0246] [(C) Component]

[0247] • Silica: Spherical fused silica, average particle size: 0.5 μm, 70% by mass methyl isobutyl ketone slurry

[0248] [(D) component]

[0249] • Polyphenylene ether derivatives with groups containing olefinic unsaturated bonds: Polyphenylene ethers with methacryl groups at both ends (weight average molecular weight (Mw): 1700)

[0250] [(E) component]

[0251] • Curing accelerator E-1: a product of the tri-n-butylphosphine addition reaction of p-benzoquinone

[0252] • Curing accelerator E-2: 2-Undecylimidazol

[0253] • Curing accelerator E-3: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane

[0254] The results shown in Table 1 clearly demonstrate that the copper-clad laminates of Examples 1-2, prepared using the resin composition of this embodiment, exhibit excellent high-frequency characteristics and do not produce the depressions on the resin layer that occurred in the copper-clad laminates of Comparative Examples 1-3. Furthermore, the copper-clad laminates of Examples 1-2 also showed excellent copper foil peel strength.

Claims

1. A resin composition comprising a styrene-based elastomer (A) and a maleimide compound (B), wherein the (A) component contains 5% to 15% by mass or more or 40% by mass of structural units derived from the styrene-based compound, based on all structural units of the (A) component.

2. The resin composition according to claim 1, wherein, The content of component (A) is 1 to 50 parts by mass relative to 100 parts by mass of solid components in the resin composition.

3. The resin composition according to claim 1, wherein, The component (B) is selected from one or more maleimide compounds and their derivatives having two or more N-substituted maleimide groups.

4. The resin composition according to claim 1, further comprising an inorganic filler (C).

5. The resin composition according to claim 1, further comprising a polyphenylene ether derivative (D) having a group containing an olefinically unsaturated bond.

6. The resin composition according to claim 1, further comprising a curing accelerator (E).

7. A resin film comprising the resin composition of claim 1 or a semi-cured product of the resin composition.

8. A prepreg comprising the resin composition of claim 1 or a semi-cured product of the resin composition.

9. A laminate comprising a cured resin composition of claim 1 or a cured prepreg of claim 8 and a metal foil.

10. A printed circuit board having a cured product of the resin composition of claim 1.

11. A semiconductor package having the printed circuit board and semiconductor element as described in claim 10.

Images