Resin composition, adhesive film, laminated substrate, electronic component, and semiconductor device

Abstract

To provide a resin composition having low dielectric characteristics and good embedding ability into circuit boards.SOLUTION: A resin composition comprises (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group, and (B) a compound having a butadiene backbone with a 1,2-vinyl group, wherein the number average molecular weight of the component (B) is 1000-10000, the component (B) comprises (B2) a styrene-butadiene block copolymer, and 10-200 pts.mass of the component (B) is contained per 100 pts.mass of the component (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, an adhesive film, a laminated substrate, an electronic component, and a semiconductor device. [Background technology]

[0002] In recent years, communication speeds and capacity have increased for electronic communication devices such as mobile devices like smartphones and tablets, communication base stations, and advanced driving assistance systems (ADAS), and the construction of 5G communication networks that use high-frequency signals is progressing. Furthermore, the use of even higher-frequency signals, such as 6G communication, is also being actively considered. Electronic boards have become essential components for these high-frequency communications.

[0003] On the other hand, common circuit board materials (e.g., FR-4) can have large transmission losses of electrical signals in high-frequency communications. For this reason, development of circuit board materials with low transmission losses is underway. Here, "FR-4" stands for "Flame Retardant Type 4," and refers to a material made by impregnating glass fiber cloth with epoxy resin and then subjecting it to a heat-curing process. To reduce the transmission loss of circuit board materials, it is necessary to lower the dielectric constant and dielectric dissipation factor of the copper-clad laminates used as circuit board materials and the adhesive film for interlayer insulation. Hereinafter, "adhesive film for interlayer insulation" may be simply referred to as "interlayer adhesive film."

[0004] Furthermore, the substrates used for these high frequency communications must be multi-layered and highly integrated in order to reduce weight and size.

[0005] For example, a polyphenylene ether resin composition containing polyphenylene ether and a styrene-butadiene block copolymer having a 1,2-vinyl structure has been proposed as a molding material for high frequency applications (see, for example, Patent Document 1). The polyphenylene ether resin composition disclosed in Patent Document 1 is said to be capable of improving heat resistance and water resistance while having low dielectric properties. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2021 / 024679 Summary of the Invention [Problem to be solved by the invention]

[0007] Adhesive films for substrates that process high-frequency signals have had the problem that, for example, when a resin composition is highly filled with an inorganic filler such as silica filler, the melt viscosity becomes high, which makes it difficult to embed the film into a wiring pattern when laminating and bonding two substrates together.

[0008] Patent Document 1 makes no mention whatsoever of the fluidity (in other words, embeddability into a substrate) required for an interlayer adhesive film. Furthermore, the polyphenylene ether resin composition evaluated in Patent Document 1 is only a methacrylic-modified polyphenylene ether.

[0009] There is a strong demand for the development of resin compositions that have low dielectric properties and good embeddability into substrates, with a view to using them in high-frequency communications.

[0010] The present invention has been made in consideration of the problems of the prior art. The present invention provides a resin composition that has low dielectric properties and good embeddability into substrates. Furthermore, the present invention provides an adhesive film, a laminated substrate, an electronic component, and a semiconductor device that use such a resin composition. [Means for solving the problem]

[0011] According to the present invention, there are provided the following resin compositions, adhesive films, laminated substrates, electronic components, and semiconductor devices.

[0012] [1] (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group; (B) a compound having a butadiene skeleton having a 1,2 vinyl group, The number average molecular weight of the component (B) is 1,000 to 10,000, the component (B) contains (B2) a styrene-butadiene block copolymer, A resin composition comprising 10 to 200 parts by mass of the component (B) per 100 parts by mass of the component (A).

[0013] [2] (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group; (B) a compound having a butadiene skeleton having a 1,2 vinyl group, The number average molecular weight of the component (B) is 1,000 to 10,000, The composition contains 10 to 200 parts by mass of the component (B) relative to 100 parts by mass of the component (A), the component (B) comprises (B1) a butadiene copolymer having 1,2 vinyl groups and / or (B2) a styrene-butadiene block copolymer having a 1,2 vinyl structure, A resin composition having a minimum melt viscosity of 100 Pa·s or more and less than 40,000 Pa·s.

[0014] [3] (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group; (B) a compound having a butadiene skeleton having a 1,2 vinyl group; (E) an inorganic filler, The number average molecular weight of the component (B) is 1,000 to 10,000, The composition contains 10 to 200 parts by mass of the component (B) relative to 100 parts by mass of the component (A), A resin composition comprising 215.7 to 900 parts by mass of the component (E) relative to 100 parts by mass of the total of the components (A) and (B).

[0015] [4] The resin composition according to any one of [1] to [3], wherein the component (B) is a styrene-butadiene-styrene block copolymer represented by the following structural formula (1), or a hydrogenated product thereof:

[0016] [ka] (In the structural formula (1), m, o, p, and q each independently represent a positive integer, n represents 0 or a positive integer, and the relationship of o:p:q=1-20:60-98:1-20 is satisfied, and the relationship of m:n=100:0-80:20 is satisfied.)

[0017] [5] The resin composition according to any one of [1] to [3] above, wherein the content of the component (A) relative to the total amount of the resin components is 20.8 to 48.0 mass %.

[0018] [6] The resin composition according to any one of [1] to [3], wherein a cured product of the resin composition has a dielectric loss tangent (tan δ) of 0.0015 or less at a measurement frequency of 10 GHz.

[0019] [7] An adhesive film made of the resin composition according to any one of [1] to [3] above.

[0020] [8] A laminated substrate comprising a cured product of the adhesive film described in [7] above.

[0021] [9] An electronic component comprising the laminated substrate according to [8] above.

[0022]

[10] A semiconductor device including the electronic component described in [9]. [Effects of the Invention]

[0023] The resin composition of the present invention exhibits excellent dielectric properties and excellent embeddability in substrates. In particular, by including a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as component (A), the minimum melt viscosity can be reduced. That is, the thermosetting resin as component (A) has high bond energy, which allows the reaction to proceed slowly, resulting in a reduced minimum melt viscosity. Furthermore, the resin composition of the present invention exhibits excellent dielectric properties, adhesiveness, thermal expansion coefficient, and heat resistance reliability after thermal curing. Furthermore, the compound having a butadiene skeleton with 1,2-vinyl groups as component (B) has a number-average molecular weight of 1,000 to 10,000, which allows for favorable fluidity and thermal expansion coefficient.

[0024] The adhesive film of the present invention is made of the resin composition of the present invention and exhibits the effects of excellent dielectric properties and embeddability. Furthermore, the laminated substrate, electronic component, and semiconductor device of the present invention contain a cured product of the resin composition or adhesive film of the present invention and enjoy the effects of the present invention described above. DETAILED DESCRIPTION OF THE INVENTION

[0025] While the present invention will be described below with reference to exemplary embodiments, it should be understood that the present invention is not limited to the following exemplary embodiments. Therefore, it should be understood that modifications and improvements to the following exemplary embodiments, based on the ordinary knowledge of those skilled in the art, are also within the scope of the present invention, provided that they do not deviate from the spirit of the present invention.

[0026] [Resin composition] A first embodiment of the resin composition of the present invention is a resin composition containing (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group, and (B) a compound having a butadiene skeleton and a 1,2-vinyl group. Hereinafter, (A) the thermosetting resin having at least one of a vinylbenzyl group and a maleimide group may be referred to as component (A). Similarly, (B) the compound having a butadiene skeleton and a 1,2-vinyl group may be referred to as component (B). In the resin composition of this embodiment, the number average molecular weight of component (B) is 1,000 to 10,000.

[0027] The resin composition of this embodiment has excellent dielectric properties and good embeddability in substrates. In particular, by including a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as component (A), the minimum melt viscosity can be reduced. That is, the thermosetting resin as component (A) has high bond energy, which allows the reaction to proceed slowly, resulting in a reduced minimum melt viscosity. Furthermore, the resin composition of the present invention exhibits excellent dielectric properties, adhesiveness, thermal expansion coefficient, and heat resistance reliability after thermal curing. Furthermore, the compound having a butadiene skeleton with 1,2-vinyl groups as component (B) has a number-average molecular weight of 1,000 to 10,000, which allows for favorable fluidity and thermal expansion coefficient.

[0028] The resin composition of this embodiment may contain, in addition to the above-described components (A) and (B), other components such as a (C) thermoplastic elastomer component, a (D) reaction accelerator component, and a (E) inorganic filler. Hereinafter, the above-described components may be appropriately referred to as components (C) to (E). Of course, the resin composition of this embodiment may further contain other resin components in addition to component (C).

[0029] [Component (A)] Component (A) is a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group. The inclusion of component (A) can lower the minimum melt viscosity. That is, a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group has high bond energy, which causes the reaction to proceed slowly, presumably resulting in a lower minimum melt viscosity. On the other hand, a thermosetting resin having, for example, a methacryloyl group has low bond energy, which causes the reaction to proceed rapidly, presumably resulting in an increased minimum melt viscosity.

[0030] The vinylbenzyl group-containing thermosetting resin of component (A) can be, for example, a thermosetting resin having a vinylbenzyl group at its terminal, such as a thermosetting resin having a vinylbenzyl group at its terminal and a polyphenylene skeleton.

[0031] The thermosetting resin having a vinylbenzyl group at the terminal and a polyphenylene skeleton may be, for example, a compound having a structure represented by the following general formula (2).

[0032] [ka] [ka] [ka] [ka]

[0033] In the above general formula (2), -(OXO)- is represented by the above structural formula (3) or (4).

[0034] In structural formula (3), R 2 , R 3 , R 4 , R 8 , and R 9R is an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same as or different from each other. 5 , R 6 , and R 7 are hydrogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl groups, and may be the same or different from each other.

[0035] In structural formula (4), R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and may be the same as or different from each other. -A- represents a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0036] In addition, in the general formula (2), -(YO)- is represented by the above structural formula (5). In -(YO)-, one type of structure or two or more types of structures are randomly arranged. In the structural formula (5), R 18 and R 19 R is an alkyl group having 6 or less carbon atoms or a phenyl group, and may be the same as or different from each other. 20 and R 21 are hydrogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl groups, and may be the same as or different from each other.

[0037] In general formula (2), a and b are integers of 0 to 100. At least one of a and b is not 0.

[0038] Examples of -A- in structural formula (4) include divalent organic groups such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene, although -A- in structural formula (4) is not limited thereto.

[0039] The compound represented by general formula (2) includes R 2 , R 3 , R 4 , R 8 , R 9 , R 18 , and R 19 is an alkyl group having 3 or less carbon atoms, and R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 20 , and R 21 is preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms. In particular, it is more preferable that -(OXO)- represented by structural formula (3) or structural formula (4) is a compound represented by the following structural formula (6), structural formula (7), or structural formula (8). Similarly, it is more preferable that -(YO)- represented by structural formula (5) is a compound represented by the following structural formula (9) or structural formula (10), or a structure in which a compound represented by structural formula (9) and a compound represented by structural formula (10) are randomly arranged.

[0040] [ka] [ka] [ka] [ka] [ka]

[0041] The method for producing the compound represented by general formula (2) is not particularly limited. For example, the compound represented by general formula (2) can be produced by the following method. First, a bifunctional phenylene ether oligomer is obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. Next, the terminal phenolic hydroxyl groups of the obtained bifunctional phenylene ether oligomer are converted to vinylbenzyl ether. In this way, the compound represented by general formula (2) can be produced.

[0042] The number-average molecular weight of the compound represented by general formula (2) is preferably 1,000 to 3,000, more preferably 1,000 to 2,500, and particularly preferably 1,000 to 2,000. By setting the number-average molecular weight of the compound represented by general formula (2) within the above range, the compound exhibits excellent solubility, low dielectric constant, fluidity, and heat resistance. For example, a number-average molecular weight of 1,000 or more reduces stickiness when the resin composition is formed into a coating film. Furthermore, a number-average molecular weight of 3,000 or less effectively prevents the resin composition from losing solubility in solvents. Furthermore, by using a compound having a number-average molecular weight within the above range as component (A), the resin composition exhibits improved electrical properties and curability at high frequencies. Here, the number-average molecular weight is a value determined by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0043] As the component (A), a compound represented by general formula (2) may be used alone, or two or more compounds represented by general formula (2) may be used in combination.

[0044] Examples of thermosetting resins having a vinylbenzyl group at the end of the component (A) include the trade names "OPE2St-2200" and "OPE2St-1200" manufactured by Mitsubishi Gas Chemical Company, Inc.

[0045] Furthermore, the thermosetting resin having a maleimide group of the component (A) can be, for example, a thermosetting resin having a maleimide group at its terminal.

[0046] The thermosetting resin having a maleimide group at its terminal, used as component (A), can be, for example, a compound containing one or more maleimide groups in the molecule, as represented by the following general formula (11): Monomaleimide compounds and polymaleimide compounds are preferably used, and are represented by the following general formulas (11), (12), (13), (14), or (15).

[0047] [ka] (However, in the above general formula (11), R 31 is an r-valent aliphatic, alicyclic, aromatic, or heterocyclic monovalent or polyvalent organic group. Xa and Xb are the same or different monovalent atoms or organic groups selected from hydrogen atoms, halogen atoms, and aliphatic organic groups. r is an integer of 1 or greater.

[0048] In the above general formula (11), R 31 is preferably phenyl, alkylphenyl, dialkylphenyl, alkoxyphenyl, benzyl, dodecyl, alkyl, or cycloalkyl. Xa and Xb are preferably hydrogen atoms.

[0049] [ka] (However, in the above general formula (12), R 32 is a monovalent or divalent organic group that is aliphatic, alicyclic, aromatic, or heterocyclic, and s is 0 or 1.

[0050] In the above general formula (12), s is 0, and R 32 When R is a monovalent group, it is preferably phenyl, alkylphenyl, dialkylphenyl, alkoxyphenyl, benzyl, dodecyl, alkyl, or cycloalkyl. 32 When is a divalent group, it is preferably alkylene, fluorene, cyclohexylene-alkylene-cyclohexylene.

[0051] [ka] (However, in the above general formula (13), R 33 represents -C(Xc)2-, -CO-, -O-, -S-, -SO2-, or a linking bond, and may be the same or different. Xc represents an alkyl group having 1 to 4 carbon atoms, -CF3, -OCH3, -NH2, a halogen atom, or a hydrogen atom, and may be the same or different. In the general formula (13), the substitution positions of the benzene rings are mutually independent. Furthermore, t and u represent 0 or an integer of 1 to 10.

[0052] Specific examples of the monomaleimide compound represented by general formula (11) or (12) include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide.

[0053] Specific examples of the polymaleimide compound represented by general formula (13) or (12) include 1,2-dimaleimidoethane, 1,3-dimaleimidopropane, bis(4-maleimidophenyl)methane, bis(3-ethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,7-dimaleimidofluorene, N,N'-(1,3-phenylene)bismaleimide, N,N'-(1,3-(4-methylphenylene))bismaleimide, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ether, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(3-(3-maleimidophenoxy)phenoxy)benzene, bis(4-maleimidophenyl)ketone, 2,2 bis(4-(4-maleimidophenoxy)phenyl)propane, bis(4-(4-maleimidophenoxy)phenyl)sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, 4,4'-bis(3-maleimidophenoxy)biphenyl, 1,3-bis(2-(3-maleimidophenyl)propyl)benzene, 1,3-bis(1-(4-(3-maleimidophenoxy)phenyl)-1-propyl)benzene, bis(maleimidocyclohexyl)methane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis(maleimidophenyl)thiophene, aliphatic, alicyclic, aromatic, and heterocyclic polymaleimides such as those represented by the following general formulas (14) and (15) (however, each includes isomers).

[0054] [ka] (However, in the above general formula (14), v has an average value of 0 to 10.)

[0055] [ka] (However, in the general formula (15), w has an average value of 0 to 10.)

[0056] Aromatic polymaleimides are preferred from the viewpoints of moisture resistance, heat resistance, breaking strength, metal foil peel strength, and low thermal expansion characteristics when formed into a printed wiring board. Among them, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane is more preferred in terms of further reducing the thermal expansion coefficient, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane is more preferred in terms of further increasing breaking strength and metal foil peel strength.

[0057] Furthermore, monomaleimides, which undergo a slow curing reaction, are preferred in terms of improving formability when formed into an adhesive film. Among them, N-phenylmaleimide is more preferred in terms of cost. The above maleimide compounds may be used alone or in combination of two or more, or at least one of these maleimide compounds may be used in combination with one or more crosslinking agents.

[0058] When a maleimide compound is used in combination with another crosslinking agent, the proportion of the maleimide compound in component (A) is preferably 50% by mass or more, and more preferably 80% by mass or more. However, it is more preferable to use the maleimide compound alone than to use it in combination with another crosslinking agent.

[0059] The thermosetting resin having a maleimide group at its terminal, used as component (A), may be, for example, a maleimide compound represented by the following general formula (16).

[0060] [ka] (In the above general formula (16), y is the number of repetitions, and <y<5である。)

[0061] The content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide compound represented by general formula (16), as determined by GPC analysis (RI), is typically 90 area % or less, preferably 10 to 80 area %, more preferably 20 to 80 area %, and even more preferably 30 to 70 area %. When the content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide is 90 area % or less, crystallinity decreases, thereby improving solvent solubility. On the other hand, the lower limit of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide may be 0 area %, but when it is 10 area % or more, a decrease in reactivity can be suppressed.

[0062] The content of y=1 in the maleimide compound represented by general formula (16) as determined by GPC analysis (RI) is preferably 98 area% or less, more preferably 20 to 98 area%, even more preferably 30 to 90 area%, and particularly preferably 40 to 80 area%. When the content of y=1 is 98 area% or less, heat resistance is improved. On the other hand, the lower limit of y=1 may be 0 area%, but when it is 20 area% or more, the viscosity of the resin solution decreases and impregnation properties are improved.

[0063] The softening point of the maleimide compound represented by general formula (16) is preferably 50 to 150° C., more preferably 80 to 120° C., even more preferably 90 to 110° C., and particularly preferably 95 to 100° C. The melt viscosity at 150° C. is 0.05 to 100 Pa s, preferably 0.1 to 40 Pa s.

[0064] The maleimide compound represented by general formula (16) more preferably has a structure represented by the following general formula (17), because the crystallinity is lower than when the substitution position of the propyl group relative to the benzene ring to which the maleimide group is not bonded in general formula (16) is para-positioned.

[0065] [ka] (In the above general formula (17), y is the number of repetitions, and <y<5である。)

[0066] The number-average molecular weight of the maleimide compound as component (A) described above is preferably 400 to 3,000, and more preferably 700 to 2,500. By setting the number-average molecular weight of the maleimide compound within the above numerical range, the solubility, low dielectric constant, fluidity, and heat resistance are improved. Here, the number-average molecular weight of the maleimide compound described above is a value obtained by gel permeation chromatography (GPC) using a calibration curve with standard polystyrene.

[0067] As the maleimide compound as component (A), the maleimide compounds explained above may be used alone or in combination of two or more compounds.

[0068] Examples of the thermosetting resin having a maleimide group as component (A) include a maleimide resin manufactured by K.I. Chemical Industry Co., Ltd. (trade name "BMI70") and a maleimide resin manufactured by Nippon Kayaku Co., Ltd. (trade name "MIR-5000-60T").

[0069] [(B) component] Component (B) is a compound having a butadiene skeleton with 1,2 vinyl groups. By including component (B), adhesive properties can be improved. In particular, when a butadiene-containing resin having 1,2 vinyl groups is formed into a copolymer or block copolymer structure with styrene, superior adhesive properties can be achieved. Furthermore, the compound having a butadiene skeleton with 1,2 vinyl groups as component (B) has a number-average molecular weight of 1,000 to 10,000. By achieving such a number-average molecular weight, good fluidity and thermal expansion coefficient can be achieved. Here, the number-average molecular weight of the compound as component (B) is determined by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0070] Examples of the compound as component (B) include the following components (B1), (B2), and (B3).

[0071] The component (B1) is a butadiene copolymer having a 1,2-vinyl group. For example, by using such a component (B1), it is possible to reduce the amount of monomer used, and for example, a suitable cured product can be obtained without using a monomer. On the other hand, since the butadiene copolymer having a 1,2-vinyl group does not have a styrene skeleton, it tends to have weak adhesion (especially the peel strength of the roughened surface (M surface)). Such a butadiene copolymer is not particularly limited as long as it has a 1,2-vinyl group and its number average molecular weight is 1,000 to 10,000.

[0072] Examples of the component (B1) include 1,2-polybutadiene homopolymers (trade names "B-3000" and "B-1000") manufactured by Nippon Soda Co., Ltd., and partially hydrogenated products (trade name "BI-3015").

[0073] Component (B2) is a styrene-butadiene block copolymer having a 1,2 vinyl structure. For example, by using such component (B2), it is possible to improve peel strength and reduce the thermal expansion coefficient.

[0074] The component (B2) is a block copolymer containing a butadiene block and a styrene block. The styrene block is a block obtained by polymerizing styrene, and the butadiene block is a block obtained by polymerizing butadiene. Such a styrene-butadiene block copolymer is not particularly limited as long as it has 1,2 vinyl groups and a number average molecular weight of 1,000 to 10,000. The butadiene block consists solely of a 1,2 bond structure represented by the following formula (18), or consists of a 1,2 bond structure represented by the formula (18) and a 1,4 bond structure represented by the formula (19).

[0075] [ka]

[0076] The molar ratio of the 1,2 bond structure represented by formula (18) to the 1,4 bond structure represented by formula (19) contained in the styrene-butadiene block copolymer having a 1,2 vinyl structure of component (B2) is preferably 80:20 to 100:0.

[0077] The weight ratio of the styrene block to the butadiene block in component (B2) is not particularly limited, but examples include 10:90 to 80:20, 10:90 to 70:30, 10:90 to 60:40, 10:90 to 50:50, 20:80 to 80:20, 30:70 to 80:20, 40:60 to 80:20, etc. Of these, 10:90 to 80:20, 10:90 to 70:30, 10:90 to 60:40, and 10:90 to 50:50 are preferred, and 10:90 to 50:50 is more preferred.

[0078] The component (B2) is preferably a styrene-butadiene-styrene block copolymer represented by the following structural formula (1), or a hydrogenated product thereof.

[0079] [ka] (In the structural formula (1), m, o, p, and q are each independently a positive integer, n is 0 or a positive integer, the relationship of o:p:q=1-20:60-98:1-20 is satisfied, and the relationship of m:n=100:0-80:20 is satisfied.)

[0080] By using a styrene-butadiene-styrene block copolymer such as that represented by the above structural formula (1) as component (B), it is possible to improve peel strength and reduce the thermal expansion coefficient.

[0081] The method for producing component (B2) is not particularly limited. For example, a styrene-butadiene-styrene block copolymer can be produced by the methods described in JP-A-6-192502, JP-A-2000-514122, JP-A-2007-302901, etc., or methods equivalent thereto.

[0082] Examples of the component (B2) include the trade names "1,2-SBS-L42" and "1,2-H-SBS-L" manufactured by Nippon Soda Co., Ltd.

[0083] Component (B3) is a styrene-butadiene copolymer having 1,2-vinyl groups. There are no particular limitations on the styrene-butadiene copolymer, so long as it has 1,2-vinyl groups and a number-average molecular weight of 1,000 to 10,000. Such styrene-butadiene copolymers are hydrophobic and contain few polar groups. Therefore, adding them to resin compositions can improve their low dielectric properties. Furthermore, due to their relatively small molecular weight, they exhibit high solubility in not only nonpolar organic solvents such as toluene but also polar organic solvents such as methyl ethyl ketone, despite their hydrophobic backbone. Therefore, they are easily dissolved in various solvents when used in resin compositions, and when dissolved in a solvent to form a resin varnish, they have the advantage of excellent varnish stability. However, because component (B3) is a random copolymer rather than a block copolymer, it tends to have poor adhesion (peel strength on the glossy surface (S surface)). It is presumed that if the phenyl groups are not aligned, it is difficult to achieve sufficient strength on a flat surface.

[0084] Furthermore, since the styrene-butadiene copolymer is liquid, the flexibility of the resin composition is improved, and there is also the advantage that the handleability (reduction of powder falling, etc.) of the resin composition when it is in a semi-cured state is improved.

[0085] Component (B3) is preferably a styrene-butadiene copolymer containing crosslinkable 1,2-vinyl groups in the molecule, which makes it more reactive than typical styrene-butadiene polymers with many 1,4-bonds in the main chain. Furthermore, because the number-average molecular weight is low (10,000 or less), the reactivity of the 1,2-vinyl groups in the styrene-butadiene copolymer is also thought to be higher. These factors contribute to the curing reaction, preventing resin bleeding and resulting in an excellent appearance after molding.

[0086] More specifically, the component (B3) may be, for example, a styrene-butadiene copolymer having the structure shown in the following formula (20).

[0087] [ka]

[0088] The above formula (20) is an example of a styrene-butadiene copolymer, and in the above formula (20), d represents a 1,2 vinyl group, e represents a styrene group, and f represents a 1,4-bond.

[0089] Examples of structural units having a 1,2-vinyl group include a structural unit of the following formula (21): Examples of structural units having a 1,4-bond include a structural unit of the following formula (22): Examples of styrene groups include a structural unit of the following formula (23):

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] The styrene-butadiene copolymer having a 1,2-vinyl group preferably has a repeating structure of the structural unit of formula (21) and a repeating structure of the structural unit of formula (23). It may further contain a repeating structure of the structural unit of formula (22).

[0094] In the styrene-butadiene copolymer of component (B3), the styrene content in the molecule is preferably 50% by mass or less and the butadiene content is preferably 50% by mass or more, and more preferably 20 to 50% by mass and 50 to 80% by mass, respectively. That is, the relationship between d, e, and f shown in the above formula (20) is as follows: e / (d+e+f)=20~50% (d+f) / (d+e+f)=50~80% It is preferable that the above-mentioned range of styrene content makes it possible to obtain a resin composition with a good balance of high Tg, adhesion, and the like. Furthermore, the above-mentioned range of butadiene content reliably reduces the elastic modulus of the resin composition, and thus reduces the thermal expansion coefficient in the in-plane direction when the resin composition is made into a laminate. If the thermal expansion coefficient in the in-plane direction can be reduced, warpage of the substrate, such as in a package substrate, can be reduced. The styrene and butadiene contents in the styrene-butadiene copolymer can be measured, for example, by nuclear magnetic resonance spectroscopy (NMR).

[0095] Examples of styrene-butadiene copolymers of component (B3) include those available under the trade names "Ricon 181" and "Ricon 100" manufactured by Cray Valley.

[0096] The compound as component (B) is preferably a compound having a styrene skeleton. For example, among the components (B1), (B2), and (B3) described above, the styrene-butadiene block copolymer having a 1,2-vinyl structure as component (B2) is more preferred from the viewpoints of thermal expansion coefficient, adhesion strength, and heat resistance reliability.

[0097] The number average molecular weight of component (B) is not particularly limited as long as it is 1000 to 10000, but is, for example, preferably 1000 to 8000, more preferably 1000 to 5000, and particularly preferably 3500 to 5000. When measuring the number average molecular weight of a film made of the resin composition, for example, the film may be dissolved in a solvent and the number average molecular weight of the component dissolved in the solvent may be measured.

[0098] Furthermore, the compound serving as component (B) preferably contains 5 to 95% by mass, more preferably 10 to 95% by mass, and particularly preferably 20 to 95% by mass of 1,2-vinyl structures in its butadiene skeleton. Setting the content of 1,2-vinyl structures in the butadiene skeleton within the above range is advantageous in terms of lowering the minimum melt viscosity. For example, such a compound may be a butadiene resin containing 5 to 95% by mass of 1,2-vinyl structures. The content of 1,2-vinyl structures can be measured by FT-IR, NMR, or the like.

[0099] The content of component (B) is preferably 10 to 200 parts by mass per 100 parts by mass of component (A). This composition provides advantages in terms of heat resistance and chemical resistance due to the reaction with component (A). Although not particularly limited, the content of component (B) is more preferably 15 to 190 parts by mass, and even more preferably 20 to 100 parts by mass per 100 parts by mass of component (A).

[0100] [(C) component] Component (C) is a thermoplastic elastomer component. Examples of the thermoplastic elastomer component include styrene-based thermoplastic elastomers and hydrogenated styrene-based thermoplastic elastomers. Here, the hydrogenated styrene-based thermoplastic elastomer refers to a hydrogenated styrene-based thermoplastic elastomer. Examples of the hydrogenated styrene-based thermoplastic elastomer include styrene / butadiene / butylene / styrene block copolymer (partially hydrogenated, SBBS) and styrene / ethylene / butylene / styrene block copolymer (fully hydrogenated, SEBS). The use of a hydrogenated styrene-based thermoplastic elastomer can improve dielectric properties. When component (C) is a styrene-based thermoplastic elastomer, the styrene ratio of component (C) is preferably 10 to 50%, more preferably 15 to 40%, and even more preferably 20 to 35%. By setting the styrene ratio of component (C) within the above range, excellent film-forming properties and workability can be achieved.

[0101] The thermoplastic elastomer component of component (C) is not particularly limited, but is preferably a styrene / ethylene / butylene / styrene block copolymer (SEBS). By using a styrene / ethylene / butylene / styrene block copolymer (SEBS) as component (C), the resulting product has excellent heat resistance and film properties.

[0102] The number average molecular weight of the thermoplastic elastomer component (C) is not particularly limited, but is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 200,000. When component (C) is a compound having a butadiene skeleton with 1,2 vinyl groups, the number average molecular weight of component (C) exceeds 10,000.

[0103] There are no particular restrictions on the amount of component (C), but for example, the amount of component (C) is preferably 10 to 150 parts by mass, and more preferably 15 to 100 parts by mass, per 100 parts by mass of the total of components (A) and (B). By having the amount of component (C) in this range, the effects of containing component (C) such as improved heat resistance and film properties can be achieved.

[0104] [(D) component] Component (D) is a reaction accelerator component. Component (D) is an additive for accelerating the reaction between components (A) and (B). By including component (D), the reaction initiation temperature is shifted to a lower temperature, accelerating the curing of the resin composition.

[0105] The reaction accelerator component for component (D) may be any component that accelerates the reaction between components (A) and (B), and any conventionally known reaction accelerator component can be used. Examples of reaction accelerator components include organic peroxides, inorganic peroxides, and azo compounds. Organic peroxides are preferred as the reaction accelerator component for component (D).

[0106] Examples of organic peroxides include diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, and di(3,5,5-trimethylhexanoyl) peroxide; peroxyketals such as 2,2-di(4,4-di(di-tert-butylperoxy)cyclohexyl)propane; isopropyl percarbonate, di- Peroxydicarbonates such as sec-butyl purged carbonate, di-2-ethylhexyl purged carbonate, di-1-methylheptyl purged carbonate, di-3-methoxybutyl purged carbonate, and dicyclohexyl purged carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, and tert-butyl Peroxyesters such as diperadipate, cumyl perneodecanoate, tert-butyl peroxybenzoate, and 2,5-dimethyl-2,5-di(benzoylperoxy)hexane; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, and di(2-tert-butylperoxyisopropyl)benzene; and hydroperoxides such as cumene hydroxyperoxide, tert-butyl hydroperoxide, and p-menthahydroperoxide can be used. There are no particular restrictions on the organic peroxide used, but since a drying step at, for example, about 60 to 80°C is often required when curing the resin composition, it is preferable to use one with a 10-hour half-life temperature of 100 to 140°C.More preferably, one with a 10-hour half-life temperature of 110 to 130°C is used.

[0107] Examples of the organic peroxide of component (D) include organic peroxides manufactured by NOF Corporation under the trade names "Percumyl D" and "Perbutyl C." Component (D) may be used alone or in combination of two or more types.

[0108] Furthermore, when component (D) is contained, the content of component (D) is preferably 0.1 to 5.0 parts by mass, and more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of the resin components in the composition. By configuring in this way, it is possible to satisfactorily improve heat resistance and adhesiveness.

[0109] [(E) component] Component (E) is an inorganic filler. The inorganic filler is required to have insulating properties and a low thermal expansion coefficient. As the inorganic filler, a general inorganic filler can be used. Examples of inorganic fillers include silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. These inorganic fillers may be used alone or in combination. Silica fillers and alumina fillers are particularly preferred from the viewpoint of insulating properties. Silica fillers are also preferred from the viewpoint of dielectric properties and thermal expansion coefficient. The inorganic fillers may be surface-treated with a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styryl, amino, epoxy, and vinyl. For example, inorganic fillers are preferably surface-treated with a surface treatment agent such as an aminosilane coupling agent, a ureidosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, a vinylsilane coupling agent, a styrylsilane coupling agent, an acrylate silane coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, or a titanate coupling agent to improve their heat resistance, moisture resistance, and dispersibility. These may be used alone or in combination of two or more. More preferably, among surface-treated silica fillers, silica fillers surface-treated with a vinylsilane coupling agent are preferably used. The use of a silica filler surface-treated with a vinylsilane coupling agent can improve the thermal expansion coefficient.

[0110] The shape of the inorganic filler is not particularly limited, and examples include spherical, scaly, needle-like, and amorphous shapes. From the viewpoint of fluidity, spherical shapes are preferred. The average particle diameter is preferably 0.1 to 10 μm, and more preferably 0.1 to 4 μm. When the average particle diameter of the inorganic filler is within this range, excellent embedding properties are achieved between fine structures. The average particle diameter is the particle diameter at 50% of the cumulative value in the particle size distribution on a volume basis, measured by a laser diffraction / scattering method. The average particle diameter can be measured, for example, using a laser scattering / diffraction particle size distribution analyzer: LS13320 (manufactured by Beckman Coulter, Inc., wet type).

[0111] When the resin composition contains component (E), the resin composition preferably contains 50% by mass or more of component (E) per 100% by mass of nonvolatile components, more preferably 50 to 90% by mass, and even more preferably 50 to 85% by mass. Furthermore, when the content of component (E) is defined as a ratio to the total amount of components (A) and (B), the resin composition preferably contains 200 parts by mass or more of component (E), more preferably 200 to 900 parts by mass, and even more preferably 400 to 900 parts by mass, per 100 parts by mass of the total of components (A) and (B). This configuration allows for a good thermal expansion coefficient.

[0112] [Other ingredients] The resin composition of this embodiment may further contain components other than the components (A) to (E) described above. For example, these other components may include various additives such as solvents, silane coupling agents, flame retardants, and pigments. Furthermore, the resin composition may further contain other compounds (e.g., other resin components) in addition to the components (A) to (C). For example, these other resin components include isocyanuric acid (diallylated isocyanuric acid derivatives) from the viewpoint of further improving embeddability in substrates, and a commercially available product thereof is the trade name "L-DAIC" from Shikoku Chemicals Corporation.

[0113] [Characteristics of Resin Composition] The resin composition of this embodiment preferably has the following properties, for example: The minimum melt viscosity of the resin composition is preferably less than 40,000 Pa s. This configuration provides excellent embeddability into a substrate.

[0114] When the resin composition does not contain an inorganic filler as component (E), the minimum melt viscosity of the resin composition is more preferably 10 Pa·s or more and less than 40,000 Pa·s, even more preferably 100 Pa·s or more and less than 30,000 Pa·s, and particularly preferably 1,000 Pa·s or more and less than 10,000 Pa·s. Even when the content of component (E) in 100 mass% of nonvolatile components in the resin composition is less than 50 mass%, the minimum melt viscosity of the resin composition is, as in the above case, more preferably 10 Pa·s or more and less than 40,000 Pa·s, and even more preferably 100 Pa·s or more and less than 30,000 Pa·s.

[0115] On the other hand, when the content of component (E) in 100% by mass of nonvolatile components in the resin composition is 50% by mass or more, the minimum melt viscosity of the resin composition is more preferably 100 Pa·s or more and less than 40,000 Pa·s, even more preferably 1,000 Pa·s or more and less than 40,000 Pa·s, and particularly preferably 5,000 Pa·s or more and less than 30,000 Pa·s.

[0116] The minimum melting temperature of the resin composition is preferably less than 200°C, more preferably 80°C or higher and lower than 200°C, and even more preferably 100°C or higher and lower than 180°C.

[0117] The minimum melt viscosity (Pa·s) and minimum melt temperature (°C) of a resin composition can be measured using the following method. First, a solution containing the resin composition is applied to a release-treated PET film using a knife. The solution on the PET film is then dried consecutively at temperatures of 80°C for 2 minutes, 100°C for 2 minutes, and 130°C for 2 minutes to produce a 50 μm-thick resin film. The resin film thus prepared is laminated to a thickness of 300 μm, and the melt viscosity is measured using a rheometer. The minimum melt viscosity and minimum melt temperature are then read and used as the minimum melt viscosity (Pa·s) and minimum melt temperature (°C) of the resin composition. The measurement conditions are as follows: parallel plates with a diameter of 5 mm are used; a load of 50 gf, a strain of 1%, a frequency of 10 Hz, and a temperature change rate of 5°C / min from 50 to 200°C. The solution to be applied to the PET film (solution containing the resin composition) can be prepared by dissolving each component of the resin composition in toluene as a solvent. In this case, when the resin composition does not contain an inorganic filler as component (E), the solution is prepared so that the solids concentration in the solution becomes 30% by mass, whereas when the resin composition contains an inorganic filler as component (E), the solution is prepared by dissolving and dispersing each component so that the solids concentration in the solution becomes 60% by mass.

[0118] [Method for producing resin composition] The resin composition of this embodiment can be produced by a conventional method, for example, by mixing the components described above using a mortar and pestle mixer, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, or the like.

[0119] [Uses of resin composition] The resin composition of this embodiment can be suitably used as a resin composition for adhesives or adhesive films used in electronic components. The resin composition of this embodiment can also be suitably used as a bonding sheet for interlayer bonding or an interlayer adhesive for multilayer wiring boards. In particular, the resin composition of this embodiment can be suitably used as an adhesive film for interlayer insulation. When the resin composition of this embodiment is used for various applications for electronic components, there are no particular restrictions on the electronic components to be bonded, and examples include various printed wiring boards such as ceramic substrates and organic substrates, semiconductor chips, and semiconductor devices. The resin composition of this embodiment can also be suitably used as a dielectric layer in the rewiring layer of FO-WLP (fan-out wafer-level package).

[0120] An adhesive film for interlayer insulation or an interlayer adhesive using the resin composition of this embodiment is contained as a cured product of the resin composition in a laminate substrate or semiconductor device that constitutes electronic components, etc. Therefore, it is preferable that a cured product of the resin composition of this embodiment is contained in a laminate substrate or semiconductor device that constitutes electronic components, etc.

[0121] The resin composition of the present embodiment can also be used as a prepreg using a cured product of the resin composition, or as a high frequency electronic component having a cured product of the resin composition. [Example]

[0122] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0123] (Examples 1 to 17, Comparative Examples 1 to 7) [Sample preparation] The components were weighed and mixed to the blending ratios (parts by mass) shown in Tables 1 to 4 below, and then dissolved in toluene as a solvent to prepare solutions containing the resin compositions of Examples 1 to 17 and Comparative Examples 1 to 7. When the resin composition did not contain an inorganic filler as component (E), the solution was prepared so that the solids concentration in the solution was 30% by mass. On the other hand, when the resin composition contained an inorganic filler as component (E), the solution was prepared by dissolving and dispersing the components so that the solids concentration in the solution was 60% by mass.

[0124] In Examples 1 to 17 and Comparative Examples 1 to 7, the raw materials used to prepare solutions containing resin compositions are as follows.

[0125] [Component (A)] A1(1): Mitsubishi Gas Chemical Company, Inc., trade name "OPE2St-2200", number average molecular weight (Mn) = 2200, modified polyphenylene ether resin having vinylbenzyl groups at the terminals. A1(2): Mitsubishi Gas Chemical Company, Inc., trade name "OPE2St-1200", number average molecular weight (Mn) = 1200, modified polyphenylene ether resin having vinylbenzyl groups at the terminals. A2(1): Manufactured by K.I. Chemical Co., Ltd., product name "BMI70", maleimide resin. A2(2): Nippon Kayaku Co., Ltd., product name "MIR-5000-60T", maleimide resin (solid content 60%, toluene soluble).

[0126] [Component (A')] A1': SABIC, trade name "SA-9000", number average molecular weight (Mn) = 1700, modified polyphenylene ether resin having methacrylic groups at the terminals.

[0127] [(B) component] B1(1): Nippon Soda Co., Ltd., product name "B-1000", number average molecular weight (Mn) = 1200, butadiene resin (1,2 vinyl structure 85%). B1(2): Nippon Soda Co., Ltd., product name "B-3000", number average molecular weight (Mn) = 3200, butadiene resin (1,2 vinyl structure 92%). B1(3): Nippon Soda Co., Ltd., product name "BI-3015", number average molecular weight (Mn) = 3200, butadiene resin (1,2 vinyl structure 7%). B2(1): Nippon Soda Co., Ltd., product name "1,2-SBS-L42", number average molecular weight (Mn) = 4300, styrene-butadiene block copolymer (20% styrene, 90% 1,2 vinyl structure). B2(2): Nippon Soda Co., Ltd., product name "1,2-H-SBS-L", number average molecular weight (Mn) = 4300, styrene-butadiene block copolymer (20% styrene, 30% 1,2 vinyl structure). B3: CRAY VALLEY, trade name "Ricon 100", number average molecular weight (Mn) = 4500, styrene-butadiene copolymer (1,2 vinyl structure 70%).

[0128] [Other resin components] Manufactured by Shikoku Chemicals Corporation, product name "L-DAIC", isocyanuric acid (diallylated isocyanuric acid derivative).

[0129] [(C) component] C1: Kraton Polymers, trade name "G1652", number average molecular weight (Mn): 54,000, thermoplastic elastomer (SEBS: styrene 30%). C2: Asahi Kasei Corporation, product name "P1500", number average molecular weight (Mn): 49,000, thermoplastic elastomer (SBBS: styrene 30%). C3: ENEOS Materials Corporation, product name "TR2003", number average molecular weight (Mn): 100,000, styrene-butadiene block copolymer (styrene 43%).

[0130] [(D) component] D1: Product name "Perkmyl D" manufactured by Nippon Oil & Fats Corporation, organic peroxide.

[0131] [(E) component] E1: Product name "20SV-C9" manufactured by Admatechs Co., Ltd., silica filler (average particle size 2 μm, vinyl silane surface treatment). E2: Product name "SC4050SX", manufactured by Admatechs Co., Ltd., silica filler (average particle size 1 μm, aminosilane surface treatment). E3: Manufactured by Denka Company Limited, product name "FB-3SDXHOL2", silica filler (average particle diameter 3 μm, vinyl silane surface treatment).

[0132] The column "Total Resin Components (A+B+C+Other Resins)" in Tables 1 to 4 shows the total amounts (parts by mass) of components (A), (B), (C), and other resin components in the raw materials used to prepare the resin compositions. The column "Amount of Filler (parts by mass) per 100 parts by mass of the total of (A+B)" in Tables 2 to 3 shows the ratio (parts by mass) of component (E) per 100 parts by mass of the total of components (A) and (B) used to prepare the resin compositions.

[0133] The solutions containing the resin compositions of Examples 1 to 17 and Comparative Examples 1 to 7 obtained as described above were measured for "minimum melt viscosity (Pa s)" and "minimum melting temperature (°C)" by the methods described below. The results are shown in Tables 1 to 4.

[0134] Furthermore, the "copper foil peel strength M (N / cm)" and "copper foil peel strength S (N / cm)" were measured by the following method for the solutions containing the resin compositions of Examples 6 to 17 and Comparative Examples 3 to 7. The results are shown in Tables 2 to 4.

[0135] Furthermore, for the solutions containing the resin compositions of Examples 6 to 8, the dielectric constant (ε) and dielectric loss tangent (tanδ) were evaluated and measured by the following method to evaluate the heat resistance reliability. The results are shown in Table 4.

[0136] [Preparation of resin film] First, a solution containing the resin composition was applied to a release-treated PET film using a knife, and then the solution on the PET film was dried at a temperature of 80 to 130°C to produce a resin film with a thickness of 50 to 100 μm.

[0137] [Minimum melt viscosity (Pa·s), minimum melt temperature (℃)] The prepared resin films were laminated to a thickness of 300 μm, and the melt viscosity was measured using a rheometer. The minimum melt viscosity and minimum melt temperature were read and recorded as the minimum melt viscosity (Pa·s) and minimum melt temperature (°C) of the resin composition. The measurement conditions were as follows: parallel plates with a diameter of 5 mm were used, a load of 50 gf, a strain of 1%, a frequency of 10 Hz, and a temperature change of 5°C / min from 50 to 200°C.

[0138] [Copper foil peel strength M (N / cm)] The resin film was sandwiched between the roughened surfaces of 18 μm thick copper foil and cured at 200°C for 60 minutes under a pressure of 1 MPa to produce a double-sided copper-clad board. The double-sided copper-clad board was cut into 1 cm wide pieces, and the strength was measured when the copper foil on one side was peeled off in a 180° direction at a pulling speed of 50 mm / min.

[0139] [Copper foil peel strength S (N / cm)] The resin film was sandwiched between the shiny sides of 18 μm thick copper foil and cured at 200°C for 60 minutes under a pressure of 1 MPa to produce a double-sided copper-clad board. The double-sided copper-clad board was cut into 1 cm wide pieces, and the strength was measured when the copper foil on one side was peeled off in a 180° direction at a pulling speed of 50 mm / min.

[0140] [Heat resistance reliability] The prepared resin film was cured at 200°C for 60 minutes under a pressure of 1 MPa to prepare samples for evaluating heat resistance reliability. The dielectric constant (ε) and dielectric dissipation factor (tanδ) of the prepared samples were measured using a dielectric resonator (SPDR) method. The values ​​measured after preparing the test specimens as described above were used as the initial values ​​before the heat resistance test. The results are shown in the "Initial Value" column of Table 4. Next, the samples were placed in an oven heated to 125°C for 24 hours, then removed from the oven and allowed to cool to room temperature. The dielectric constant (ε) and dielectric dissipation factor (tanδ) of the cooled samples were measured using the same method as described above. The values ​​measured in this way were used as the measured values ​​after the heat resistance test and are shown in the "After 125°C x 24h" column of Table 4. The dielectric constant (ε) and dielectric dissipation factor (tanδ) measured before and after the heat resistance test were subtracted from the initial values ​​to obtain the "change from the initial value." Furthermore, the percentage of the "amount of change from the initial value" divided by the initial value was calculated as the "amount of change from the initial value (%)." The results are shown in Table 4. The measurement frequency by the dielectric resonator method was 20 GHz.

[0141] Furthermore, for some examples among Examples 6 to 17 and Comparative Examples 3 to 7, the "thermal expansion coefficient (ppm / K)," "thermal expansion coefficient (thickness) (ppm / K)," and "solder heat resistance" were evaluated and measured by the methods described below. Furthermore, for Examples 6 to 16 and Comparative Examples 3 to 7, the initial values ​​of the dielectric constant (ε) and dielectric dissipation factor (tanδ) in the heat resistance reliability described above were measured. Furthermore, for Examples 9 to 16 and Comparative Examples 3 to 7, the measurement frequency was changed to 10 GHz using the dielectric resonator method, and the initial values ​​of the dielectric constant (ε) and dielectric dissipation factor (tanδ) in the heat resistance reliability described above were measured.

[0142] [Coefficient of thermal expansion (ppm / K)] The prepared resin films were laminated to a thickness of 100 μm and cured at 200°C for 60 minutes under a pressure of 1 MPa to prepare a sample for measuring the thermal expansion coefficient. The prepared sample was measured using the tensile method with a TMA (thermomechanical analyzer), and the average thermal expansion coefficient from 90 to 100°C was read (i.e., the measured value of the thermal expansion coefficient). The measurement conditions were a tensile load of 2 gf, annealing at 20°C / min up to 230°C, then returning to room temperature, and then measurement was performed at 5°C / min up to 230°C. The measured thermal expansion coefficient was the thermal expansion coefficient in the planar direction (i.e., the XY direction).

[0143] [Thermal expansion coefficient (thickness) (ppm / K)] The prepared resin films were laminated to a thickness of approximately 2 mm and cured at 200°C for 60 minutes under a pressure of 1 MPa to prepare a sample for measuring the thermal expansion coefficient (thickness). The prepared sample was measured using a TMA (thermomechanical analyzer) compression method, and the average thermal expansion coefficient from 90 to 100°C was read (i.e., the measured value of the thermal expansion coefficient (thickness)). The measurement conditions were a compressive load of 1 gf, annealing at 20°C / min up to 250°C, then returning to room temperature, and then measurement was performed at 5°C / min up to 250°C. The thermal expansion coefficient was measured in the thickness direction (i.e., Z direction).

[0144] [Solder heat resistance] Copper foil was laminated to both sides of the prepared adhesive film, and then cut into a 2 cm x 2 cm square to prepare test pieces. The prepared test pieces were floated in solder baths heated to 260, 270, 280, 290, and 300°C for 1 minute, and their appearance was visually inspected. The solder bath temperature (maximum temperature) at which no change in appearance was observed was used as the evaluation value for solder heat resistance.

[0145] [Table 1]

[0146] [Table 2]

[0147] [Table 3]

[0148] [Table 4]

[0149] 〔result〕 As shown in Table 1, the resin compositions of Examples 1 to 5 had lower minimum melt viscosities and lower minimum melting temperatures than the resin composition of Comparative Example 2. It was impossible to measure the minimum melt viscosity and minimum melting temperature of the resin composition of Comparative Example 1.

[0150] As shown in Tables 2 and 3, the resin compositions of Examples 9 to 17 had extremely low minimum melt viscosities compared to the resin compositions of Comparative Examples 3 to 7. In particular, the resin compositions of Examples 9 to 16 and Comparative Examples 3 to 7 contained an inorganic filler (silica filler) as component (E), and the resin compositions of Comparative Examples 3 to 7 exhibited extremely high minimum melt viscosities. On the other hand, the resin compositions of Examples 9 to 16 contained a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as component (A), and therefore the increase in minimum melt viscosity was suppressed, and the resin compositions had excellent embeddability into a substrate.

[0151] The resin compositions of Examples 9 to 17 also exhibited good values ​​for copper foil peel strength M (N / cm) and copper foil peel strength S (N / cm), demonstrating excellent adhesiveness. The resin compositions of Examples 9 to 16 also exhibited good results in terms of thermal expansion coefficient and solder heat resistance. For example, the thermal expansion coefficients (ppm / K) of the resin compositions of Examples 9 to 16 were 102, 123, 46, 50, 56, 44, 50, and 55, respectively (all units: ppm / K). The thermal expansion coefficients (thickness) (ppm / K) of the resin compositions of Examples 9 to 16 were 39, 55, 46, 56, 50, 38, 42, and 59, respectively (all units: ppm / K).

[0152] The resin compositions of Examples 9 to 14 had dielectric constants (ε) of 3.05, 3.12, 3.10, 3.10, 2.89, and 3.06, respectively, at a measurement frequency of 10 GHz, and dielectric dissipation factors (tanδ) of 0.0014, 0.0015, 0.0013, 0.0011, 0.0015, and 0.0014, respectively. The resin compositions of Examples 13 to 16 had dielectric constants (ε) of 3.01, 3.08, 3.07, and 3.09, respectively, at a measurement frequency of 20 GHz, and dielectric dissipation factors (tanδ) of 0.0016, 0.0015, 0.0015, and 0.0013, respectively. Furthermore, the resin compositions of Examples 9 to 14 also showed favorable values ​​of 300°C or 290°C in solder heat resistance evaluation.

[0153] The resin composition of Example 17 does not contain any other resin components and contains components (A) and (B) as resin components. The resin composition of Example 17 also does not contain an inorganic filler as component (E). The resin composition of Example 17 also had a low minimum melt viscosity and a low minimum melting temperature. The resin composition of Example 17 had a thermal expansion coefficient (ppm / K) of 102 ppm / K and a thermal expansion coefficient (thickness) (ppm / K) of 73 ppm / K. The resin composition of Example 17 can also be suitably used as a dielectric layer in a redistribution layer of a FO-WLP (fan-out wafer-level package), for example.

[0154] On the other hand, the resin compositions of Comparative Examples 3 to 7 had thermal expansion coefficients (ppm / K) of 51, 35, 36, 51, and 50, respectively, and thermal expansion coefficients (thickness) (ppm / K) of 37, 47, 29, 37, and 64, respectively (all units are ppm / K). The resin compositions of Comparative Examples 3 to 7 also had dielectric constants (ε) of 3.12, 3.06, 3.11, 3.12, and 3.12, respectively, at a measurement frequency of 10 GHz, and dielectric dissipation factors (tanδ) of 0.0014, 0.0012, 0.0013, 0.0014, and 0.0019, respectively. The resin composition of Comparative Example 7 also showed a low value of 270°C in the evaluation of solder heat resistance.

[0155] As shown in Table 4, the resin composition of Example 6 used a styrene-butadiene block copolymer (B2) as the component (B). The resin composition of Example 8 used a butadiene resin (B1) as the component (B). The resin composition of Example 7 used a styrene-butadiene copolymer (B3) as the component (B). Comparing the resin compositions of Examples 6 to 8, the resin composition of Example 6 using the styrene-butadiene block copolymer (B2) had better heat resistance reliability (rate of change in tan δ) than the other (B) components, and also showed good results in peel strength M from the matte side (M side) of the electrolytic copper foil. The resin compositions of Examples 6 to 8 had thermal expansion coefficients (ppm / K) of 149, 146, and 154, respectively, and thermal expansion coefficients (thickness) (ppm / K) of 194, 207, and 196, respectively (all units are ppm / K). [Industrial Applicability]

[0156] The resin composition of the present invention can be used as a resin composition for adhesives or adhesive films used in electronic components. It can also be used as a bonding sheet or interlayer adhesive for multilayer wiring boards. The resin composition of the present invention can also be used as a prepreg using a cured product of the resin composition or as a high-frequency electronic component having a cured product of the resin composition.

Claims

1. (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group; (B) a compound having a butadiene skeleton containing a 1,2-vinyl group, The number average molecular weight of the component (B) is 1,000 to 10,000, the component (B) contains (B2) a styrene-butadiene block copolymer, A resin composition comprising 10 to 200 parts by mass of the component (B) per 100 parts by mass of the component (A).

2. (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group; (B) a compound having a butadiene skeleton having a 1,2-vinyl group, The number average molecular weight of the component (B) is 1,000 to 10,000, The composition contains 10 to 200 parts by mass of the component (B) relative to 100 parts by mass of the component (A), the component (B) comprises (B1) a butadiene copolymer having 1,2 vinyl groups and / or (B2) a styrene-butadiene block copolymer having a 1,2 vinyl structure, A resin composition having a minimum melt viscosity of 100 Pa·s or more and less than 40,000 Pa·s.

3. (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group; (B) a compound having a butadiene skeleton containing a 1,2-vinyl group; (E) an inorganic filler, The number average molecular weight of the component (B) is 1,000 to 10,000, The composition contains 10 to 200 parts by mass of the component (B) relative to 100 parts by mass of the component (A), A resin composition comprising 215.7 to 900 parts by mass of the component (E) relative to 100 parts by mass of the total of the component (A) and the component (B).

4. The resin composition according to any one of claims 1 to 3, wherein the component (B) is a styrene-butadiene-styrene block copolymer represented by the following structural formula (1), or a hydrogenated product thereof: 【Chemistry 1】 (In the structural formula (1), m, o, p, and q each independently represent a positive integer, n represents 0 or a positive integer, and the relationship of o:p:q = 1-20:60-98:1-20 is satisfied, and the relationship of m:n = 100:0-80:20 is satisfied.)

5. The resin composition according to any one of claims 1 to 3, wherein the content of the component (A) relative to the total resin components is 20.8 to 48.0 mass%.

6. The resin composition according to any one of claims 1 to 3, wherein a dielectric loss tangent (tanδ) of a cured product of the resin composition at a measurement frequency of 10 GHz is 0.0015 or less.

7. An adhesive film comprising the resin composition according to any one of claims 1 to 3.

8. A laminated substrate comprising a cured product of the adhesive film according to claim 7.

9. An electronic component comprising the laminate substrate according to claim 8 .

10. A semiconductor device comprising the electronic component according to claim 9.

Images