Resin composition, and adhesive film for interlayer insulation using same, laminated substrate, electronic component, and semiconductor device

Abstract

Provided is a resin composition which has good embedding properties into a substrate while having low dielectric properties. The thermosetting resin composition contains (A) a thermosetting resin having at least one of a vinyl benzyl group and a maleimide group and (B) a compound having a butadiene skeleton having a 1, 2-vinyl group, and the number average molecular weight of the component (B) is 1000-10000.

Description

Technical Field

[0001] The present invention relates to a resin composition, and an adhesive film for interlayer insulation, a laminated substrate, an electronic component, and a semiconductor device using the resin composition. Background Art

[0002] In recent years, communication speeds and capacities have been increasing for mobile devices such as smartphones and tablets, communication base stations, and advanced driver assistance systems (ADAS). The construction of 5G communication networks, which utilize high-frequency signals, is progressing rapidly. Furthermore, research is actively underway to utilize even higher-frequency signals, such as 6G communications. Electronic circuit boards are essential components for these high-frequency communications.

[0003] On the other hand, common substrate materials (such as FR-4) can result in high transmission losses of electrical signals in high-frequency communications. Therefore, development of substrate materials with reduced transmission losses is ongoing. "FR-4," short for "Flame Retardant Type 4," is a material made by infiltrating epoxy resin into glass fiber cloth and then heat-curing it. Reducing transmission losses in substrate materials requires lowering the dielectric constant and dielectric loss tangent of the copper-clad laminate and the adhesive film used for interlayer insulation. Hereinafter, "adhesive film for interlayer insulation" may be referred to simply as "interlayer adhesive film."

[0004] Furthermore, substrates used in these high-frequency communications require multilayering and high integration for weight reduction and miniaturization.

[0005] For example, a polyphenylene ether resin composition comprising polyphenylene ether and a styrene-butadiene block copolymer having a 1,2-vinyl structure has been proposed as a high-frequency molding material (see, for example, Patent Document 1). The polyphenylene ether resin composition disclosed in Patent Document 1 is believed to have improved heat resistance and water resistance while maintaining low dielectric properties.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2021 / 024679 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] Adhesive films for substrates handling high-frequency signals, such as those containing a high percentage of inorganic fillers such as silica, can increase their melt viscosity, leading to poor embedding into the substrate. For example, high melt viscosity makes it difficult to embed the film into wiring patterns when laminating and bonding substrates.

[0011] Patent Document 1 does not mention the fluidity required of an interlayer adhesive film (in other words, the ability to embed into a substrate). Furthermore, the polyphenylene ether resin composition evaluated in Patent Document 1 is only a methacrylic-modified polyphenylene ether.

[0012] As a resin composition that is focused on use in high-frequency communications, there is a strong demand for the development of a resin composition that has low dielectric properties and good embeddability in a substrate.

[0013] The present invention was developed in response to the problems associated with such prior art. It provides a resin composition that exhibits low dielectric properties and good embeddability in substrates. Furthermore, the present invention provides an adhesive film for interlayer insulation, a laminated substrate, an electronic component, and a semiconductor device using this resin composition.

[0014] Means for solving problems

[0015] According to the present invention, there are provided the following resin compositions, and adhesive films for interlayer insulation, laminated substrates, electronic components, and semiconductor devices using the resin compositions.

[0016] [1] A resin composition comprising (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group and (B) a compound having a butadiene skeleton having a 1,2-vinyl group, wherein the number average molecular weight of the component (B) is 1,000 to 10,000.

[0017] [2] The resin composition according to [1], wherein the resin composition has a minimum melt viscosity of less than 40,000 Pa·s.

[0018] [3] The resin composition according to [1] or [2], wherein the component (A) is a thermosetting resin having a vinylbenzyl group at a terminal and a polyphenylene skeleton.

[0019] [4] The resin composition according to any one of [1] to [3], wherein the component (B) is a compound having a styrene skeleton.

[0020] [5] The resin composition according to any one of [1] to [4], wherein the component (B) is a styrene-butadiene block copolymer.

[0021] [6] The resin composition according to any one of [1] to [5], wherein the component (B) is a styrene-butadiene-styrene block copolymer represented by the following structural formula (1) or a hydrogenated product thereof.

[0022] [Chemistry 1]

[0023]

[0024] (In the above structural formula (1), m, o, p, and q are each independently a positive integer, n is 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.)

[0025] [7] The resin composition according to any one of [1] to [6], wherein the 1,2-vinyl structure in the butadiene skeleton of the component (B) accounts for 5 to 95% by mass.

[0026] [8] The resin composition according to any one of [1] to [7], further comprising (C) a thermoplastic elastomer component.

[0027] [9] The resin composition according to any one of [1] to [8], further comprising (D) a reaction accelerator component.

[0028]

[10] The resin composition according to [9], wherein the component (D) is an organic peroxide.

[0029]

[11] The resin composition according to any one of [1] to

[10] , further comprising (E) an inorganic filler.

[0030]

[12] The resin composition according to

[11] , wherein the component (E) is contained in an amount of 50% by mass or more based on 100% by mass of the non-volatile components in the resin composition.

[0031]

[13] The resin composition according to

[11] , comprising 200 parts by mass or more of the component (E) based on 100 parts by mass of the total of the component (A) and the component (B).

[0032]

[14] The resin composition according to any one of [1] to

[13] , comprising 10 to 200 parts by mass of the component (B) relative to 100 parts by mass of the component (A).

[0033]

[15] The resin composition according to any one of [1] to

[14] , wherein the minimum melting temperature of the resin composition is less than 200°C.

[0034]

[16] An adhesive film for interlayer insulation, comprising the resin composition described in any one of [1] to

[15] .

[0035]

[17] A laminate substrate comprising a cured product of the resin composition described in any one of [1] to

[15] or the adhesive film for interlayer insulation described in

[16] .

[0036]

[18] An electronic component comprising the multilayer substrate described in

[17] .

[0037]

[19] A semiconductor device comprising the multilayer substrate described in

[17] or the electronic component described in

[18] .

[0038] Effects of the Invention

[0039] The resin composition of the present invention has excellent dielectric properties and excellent embeddability into the substrate. 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. In other words, it is believed that the thermosetting resin as the above-mentioned component (A) has high binding energy, so the reaction proceeds slowly, and as a result, the minimum melt viscosity is reduced. In addition, the resin composition of the present invention has excellent dielectric properties, adhesion, thermal expansion coefficient, and heat-resistant reliability after thermal curing. In addition, since the compound having a butadiene skeleton with a 1,2-vinyl group as component (B) has a number average molecular weight of 1000 to 10000, the fluidity and thermal expansion coefficient can be set to appropriate values.

[0040] Furthermore, the interlayer insulating adhesive film of the present invention comprises the resin composition of the present invention, exhibiting excellent dielectric properties and embeddability. Furthermore, the laminated substrate, electronic component, and semiconductor device of the present invention comprise a cured product of the resin composition or interlayer insulating adhesive film of the present invention, and enjoy the effects of the present invention described above. DETAILED DESCRIPTION

[0041] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments. Therefore, it should be understood that embodiments obtained by appropriately adding changes, improvements, etc. to the following embodiments based on the common knowledge of those skilled in the art without departing from the scope of the present invention also fall within the scope of the present invention.

[0042] [Resin composition]

[0043] A first embodiment of the resin composition of the present invention is a resin composition comprising (A) a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group, and (B) a compound having a butadiene skeleton containing a 1,2-vinyl group. Hereinafter, the thermosetting resin (A) having at least one of a vinylbenzyl group and a maleimide group may be referred to as component (A). Similarly, the compound (B) having a butadiene skeleton containing a 1,2-vinyl group may be referred to as component (B). Furthermore, the number average molecular weight of component (B) of the resin composition of this embodiment is 1,000 to 10,000.

[0044] The resin composition of this embodiment has excellent dielectric properties and good embedding properties into the substrate. 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, it can be considered that the thermosetting resin as the above-mentioned component (A) has high binding energy, so the reaction proceeds slowly, and as a result, the minimum melt viscosity is reduced. In addition, the resin composition of the present invention has excellent dielectric properties, adhesion, thermal expansion coefficient, and heat-resistant reliability after thermal curing. In addition, since the compound having a butadiene skeleton with a 1,2-vinyl group as component (B) has a number average molecular weight of 1000 to 10000, the fluidity and thermal expansion coefficient can be set to appropriate values.

[0045] It should be noted that the resin composition of this embodiment may contain other components, such as a thermoplastic elastomer component (C), a reaction accelerator component (D), and an inorganic filler (E), in addition to the aforementioned components (A) and (B). Hereinafter, these components may be appropriately referred to as components (C) to (E). Of course, the resin composition of this embodiment may contain other resin components besides component (C).

[0046] [(A) Ingredient]

[0047] Component (A) is a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group. The inclusion of component (A) can reduce the minimum melt viscosity. Specifically, it is believed that thermosetting resins having at least one of a vinylbenzyl group and a maleimide group have high binding energy, which slows the reaction and results in a lower minimum melt viscosity. On the other hand, it is speculated that thermosetting resins having, for example, a methacryloyl group have low binding energy, which rapidly advances the reaction and results in an increase in the minimum melt viscosity.

[0048] Examples of the thermosetting resin having a vinylbenzyl group as component (A) include thermosetting resins having a vinylbenzyl group at a terminal thereof, and thermosetting resins having a polyphenylene skeleton and a vinylbenzyl group at a terminal thereof.

[0049] Examples of the thermosetting resin having a vinylbenzyl group at a terminal and a polyphenylene skeleton include compounds having a structure represented by the following general formula (2).

[0050] [Chemistry 2]

[0051]

[0052] [Chemistry 3]

[0053]

[0054] [Chemistry 4]

[0055]

[0056] [Chemistry 5]

[0057]

[0058] In the above general formula (2), -(OXO)- is represented by the above structural formula (3) or (4).

[0059] In the structural formula (3), R 2 、R 3 、R 4 、R 8 and R 9 is an alkyl group or a phenyl group having 6 or less carbon atoms, and may be the same as or different from each other. 5 、R 6 and R 7 The groups 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.

[0060] In the structural formula (4), R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17 is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and they may be the same or different from each other. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0061] In the general formula (2), -(YO)- is represented by the above-mentioned structural formula (5). In -(YO)-, one structure or two or more structures are randomly arranged. In the structural formula (5), R 18 and R 19 is an alkyl group or a phenyl group having 6 or less carbon atoms, and may be the same as or different from each other. 20 and R21 The groups 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.

[0062] In general formula (2), a and b are integers of 0 to 100. At least one of a and b is not 0.

[0063] 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. However, -A- in structural formula (4) is not limited to these.

[0064] As the compound represented by the general formula (2), R 2 、R 3 、R 4 、R 8 、R 9 、R 18 and R 19 is an alkyl group with a carbon number of 3 or less, 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 A compound in which -(OXO)- represented by Structural Formula (3) or Structural Formula (4) and represented by Structural Formula (6), Structural Formula (7), or Structural Formula (8) are particularly preferred. Similarly, a compound in which -(YO)- represented by Structural Formula (5) and represented by Structural Formula (9) or Structural Formula (10) are particularly preferred, or a structure in which the compound represented by Structural Formula (9) and the compound represented by Structural Formula (10) are randomly arranged.

[0065] [Chemistry 6]

[0066]

[0067] [Chemistry 7]

[0068]

[0069] [Chemistry 8]

[0070]

[0071] [Chemistry 9]

[0072]

[0073] [Chemistry 10]

[0074]

[0075] 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 phenol compound and a monofunctional phenol compound are oxidatively coupled to obtain a bifunctional phenylene ether oligomer. Then, the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer is vinylbenzyl etherified. By operating in this manner, the compound represented by general formula (2) can be produced.

[0076] The number average molecular weight of the compound represented by the general formula (2) is preferably 1000 to 3000, more preferably 1000 to 2500, and particularly preferably 1000 to 2000. By setting the number average molecular weight of the compound represented by the general formula (2) to the above numerical range, the solubility, low dielectric constant, fluidity, and heat resistance are further improved. For example, if the number average molecular weight is 1000 or more, it is less likely to cause stickiness when the resin composition is formed into a coating film. In addition, if the number average molecular weight is 3000 or less, the reduction in the solubility of the resin composition in the solvent can be effectively suppressed. In addition, by using a compound having a number average molecular weight in the above numerical range as the (A) component, the electrical properties and curing properties of the resin composition at high frequencies are improved. Here, the above number average molecular weight is a value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0077] As the component (A), the compound represented by the general formula (2) may be used alone, or two or more compounds represented by the general formula (2) may be used in combination.

[0078] Examples of the thermosetting resin having a vinylbenzyl group at a terminal as the component (A) include "OPE2St-2200" and "OPE2St-1200" manufactured by Mitsubishi Gas Chemical Corporation.

[0079] Examples of the thermosetting resin having a maleimide group as the component (A) include thermosetting resins having a maleimide group at their terminals.

[0080] The thermosetting resin having a maleimide group at the terminal used as component (A) can be, for example, a compound containing one or more maleimide groups in a molecule represented by the following general formula (11). Monomaleimide compounds or polymaleimide compounds represented by the following general formula (11), (12), (13), (14), or (15) can be suitably used.

[0081] [Chemistry 11]

[0082]

[0083] (Wherein, in the above general formula (11), R 31 (i) represents a monovalent or polyvalent organic group, any of which is aliphatic, alicyclic, aromatic, or heterocyclic, with a valence of r. Xa and Xb represent monovalent atoms or organic groups, which may be the same or different, selected from hydrogen atoms, halogen atoms, and aliphatic organic groups. (ii) r represents an integer greater than 1.)

[0084] In the above general formula (11), R 31 Preferred are phenyl, alkylphenyl, dialkylphenyl, alkoxyphenyl, benzyl, dodecyl, alkyl, and cycloalkyl. Xa and Xb are preferably hydrogen atoms.

[0085] [Chemistry 12]

[0086]

[0087] (Wherein, in the above general formula (12), R 32 is a monovalent or divalent organic group that is any of aliphatic, alicyclic, aromatic, and heterocyclic. s is 0 or 1.

[0088] In the above general formula (12), when s is 0 and R 32 When it is a monovalent group, it is preferably a phenyl group, an alkylphenyl group, a dialkylphenyl group, an alkoxyphenyl group, a benzyl group, a dodecyl group, an alkyl group, or a cycloalkyl group. 32 In the case of a divalent group, an alkylene group, a fluorenylene group, or a cyclohexylene-alkylene-cyclohexylene group is preferred.

[0089] [Chemistry 13]

[0090]

[0091] (Wherein, in the above general formula (13), R 33represents -C(Xc)2-, -CO-, -O-, -S-, -SO2-, or a connecting bond, and each of them 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 each of them may be the same or different. It should be noted that in the above general formula (13), the substitution positions of the benzene ring are independent of each other. In addition, t and u represent 0 or an integer from 1 to 10.

[0092] Specific examples of the monomaleimide compound represented by the 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.

[0093] Specific examples of the polymaleimide compound represented by the general formula (13) or (12) include 1,2-dimaleimide ethane, 1,3-dimaleimide propane, bis(4-maleimide phenyl) methane, bis(3-ethyl-4-maleimide phenyl) methane, bis(3-ethyl-5-methyl-4-maleimide phenyl) methane, 2,7-dimaleimide fluorene, 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)sulfide phenyl) 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-maleimidophenyl) 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), etc. (each including isomers).

[0094] [Chemistry 14]

[0095]

[0096] (In the above general formula (14), v is an average value of 0 to 10.)

[0097] [Chemistry 15]

[0098]

[0099] (In the above general formula (15), w is an average value of 0 to 10.)

[0100] Aromatic polymaleimides are preferred from the perspectives of moisture resistance, heat resistance, breaking strength, metal foil peel strength, and low thermal expansion properties when used in printed wiring boards. Among these, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane is more preferred from the perspective of further reducing the thermal expansion coefficient, while 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane is more preferred from the perspective of further improving breaking strength and metal foil peel strength.

[0101] In addition, from the perspective of improving the formability of the adhesive film, monomaleimides with a slow curing reaction are preferred. Among them, N-phenylmaleimide is more preferred from the perspective of cost. Furthermore, the above-mentioned maleimide compounds may be used alone or in combination of two or more, or at least one maleimide compound and one or more crosslinking agents may be used in combination.

[0102] When a maleimide compound and another crosslinking agent are used in combination, the proportion of the maleimide compound in component (A) is preferably 50% by mass or greater, more preferably 80% by mass or greater. However, it is more preferable to use the maleimide compound alone than in combination with another crosslinking agent.

[0103] The thermosetting resin having a maleimide group at the terminal used as the component (A) may be, for example, a maleimide compound represented by the following general formula (16).

[0104] [Chemistry 16]

[0105]

[0106] (In the above general formula (16), y is the number of repetitions, and 1<y<5.)

[0107] The content of N,N'-(phenylene-di(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide compound represented by general formula (16) based on GPC analysis (RI) is generally 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, the crystallinity decreases, thereby improving the solvent solubility. On the other hand, although the lower limit of the content of N,N'-(phenylene-di(2,2-propylidene)-di-p-phenylene)bismaleimide may be 0 area %, a content of 10 area % or more can suppress a decrease in reactivity.

[0108] The content of y=1 in the maleimide compound represented by general formula (16) based on GPC analysis (RI) is preferably 98 area % or less, more preferably 20 to 98 area %, further 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, while the lower limit of y=1 may be 0 area %, a content of 20 area % or more reduces the viscosity of the resin solution, improving impregnation properties.

[0109] The softening point of the maleimide compound represented by the general formula (16) is preferably 50 to 150°C, more preferably 80 to 120°C, further preferably 90 to 110°C, and particularly preferably 95 to 100°C. Furthermore, the melt viscosity at 150°C is 0.05 to 100 Pa·s, preferably 0.1 to 40 Pa·s.

[0110] The maleimide compound represented by the general formula (16) more preferably has a structure represented by the following general formula (17). This is because the crystallinity is lowered compared to when the substitution position of the propyl group to the benzene ring not bonded to the maleimide group in the general formula (16) is para.

[0111] [Chemistry 17]

[0112]

[0113] (In the above general formula (17), y is the number of repetitions, and 1<y<5.)

[0114] The number average molecular weight of the maleimide compound described above as component (A) is preferably 400 to 3000, more preferably 700 to 2500. By setting the number average molecular weight of the maleimide compound within this numerical range, solubility, low dielectric constant, flowability, and heat resistance are further improved. The number average molecular weight of the maleimide compound is determined by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0115] As the maleimide compound as the component (A), the maleimide compounds described above may be used alone, or two or more compounds may be used in combination.

[0116] Examples of the thermosetting resin having a maleimide group as the component (A) include maleimide resin manufactured by KI Chemicals (trade name “BMI70”) and maleimide resin manufactured by Nippon Kayaku Co., Ltd. (trade name “MIR-5000-60T”).

[0117] [Ingredient (B)]

[0118] Component (B) is a compound having a butadiene skeleton with a 1,2-vinyl group. By including component (B), adhesion can be improved. In particular, by setting the butadiene-containing resin having a 1,2-vinyl group as a copolymer or block copolymer with styrene, even better adhesion can be achieved. In addition, the number average molecular weight of the compound having a butadiene skeleton with a 1,2-vinyl group as component (B) is 1,000 to 10,000. By setting such a number average molecular weight, fluidity and thermal expansion coefficient can be improved. Here, the number average molecular weight of the compound as component (B) is set to a value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0119] Examples of the compound of the component (B) include the component (B1), the component (B2), and the component (B3) shown below.

[0120] Component (B1) is a butadiene copolymer containing a 1,2-vinyl group. For example, using this component (B1) can reduce the amount of monomer used, allowing for a suitable cured product to be obtained even without the use of monomers. On the other hand, since butadiene copolymers containing a 1,2-vinyl group lack a styrene backbone, their adhesion (particularly the peel strength of the roughened surface (M surface)) tends to be weak. The butadiene copolymer is not particularly limited as long as it contains a 1,2-vinyl group and has a number average molecular weight of 1,000 to 10,000.

[0121] 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 1,2-polybutadiene homopolymers (trade name "BI-3015").

[0122] The component (B2) is a styrene-butadiene block copolymer having a 1,2-vinyl structure. For example, the use of the component (B2) can improve the peel strength and reduce the thermal expansion coefficient.

[0123] Component (B2) is a block copolymer comprising 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. This styrene-butadiene block copolymer is not particularly limited as long as it has a 1,2-vinyl group and a number average molecular weight of 1,000 to 10,000. The butadiene block is composed solely of a 1,2-bonded structure represented by the following formula (18), or contains a 1,2-bonded structure represented by formula (18) and a 1,4-bonded structure represented by formula (19).

[0124] [Chemistry 18]

[0125]

[0126] 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 as component (B2) is preferably 80:20 to 100:0.

[0127] The weight ratio of the styrene block to the butadiene block in the component (B2) is not particularly limited, and examples thereof 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, and 40:60 to 80:20. Among 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.

[0128] The component (B2) is preferably a styrene-butadiene-styrene block copolymer represented by the following structural formula (1), or a hydrogenated product thereof.

[0129] [Chemistry 19]

[0130]

[0131] (In the above structural formula (1), m, o, p, and q are each independently a positive integer, n is 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.)

[0132] By using a styrene-butadiene-styrene block copolymer such as that represented by the above structural formula (1) as the component (B), the peel strength can be improved and the thermal expansion coefficient can be reduced.

[0133] The method for producing component (B2) is not particularly limited. For example, styrene-butadiene-styrene block copolymers can be produced by methods described in JP-A-6-192502, JP-A-2000-514122, JP-A-2007-302901, and the like, or equivalent methods.

[0134] As the component (B2), trade names "1,2-SBS-L42" and "1,2-H-SBS-L" manufactured by Nippon Soda Co., Ltd. can be mentioned.

[0135] Component (B3) is a styrene-butadiene copolymer containing a 1,2-vinyl group. This styrene-butadiene copolymer is not particularly limited as long as it contains a 1,2-vinyl group and has a number average molecular weight of 1,000 to 10,000. This styrene-butadiene copolymer is hydrophobic and has few polar groups. Therefore, by adding it to a resin composition, it can optimize low dielectric properties. Furthermore, due to its low molecular weight, despite its hydrophobic backbone, it exhibits high solubility not only in non-polar organic solvents such as toluene, but also in polar organic solvents such as methyl ethyl ketone. Therefore, when formulated into a resin composition, it easily dissolves in various solvents, and when dissolved in a solvent to form a resin varnish, it has the advantage of excellent varnish stability. On the other hand, component (B3) is not a block copolymer but a random copolymer, and therefore tends to have weak adhesion (peel strength from the glossy surface (S surface)). This is presumably because if the phenyl groups are not neatly arranged, it is difficult to exhibit strength in a flat surface.

[0136] In addition, since the styrene-butadiene copolymer is in liquid form, there are advantages in that the flexibility of the resin composition is improved, and the handling properties of the resin composition (such as particle shedding) are improved when the resin composition is in a semi-cured state.

[0137] Component (B3) is particularly preferably a styrene-butadiene copolymer containing 1,2-vinyl groups with crosslinking properties within the molecule. This makes it more reactive than typical styrene-butadiene polymers, which have numerous 1,4-linkages in the main chain. Furthermore, the low number-average molecular weight of 10,000 or less is believed to enhance the reactivity of the 1,2-vinyl groups in the styrene-butadiene copolymer. These factors are believed to facilitate the curing reaction, resulting in an excellent appearance after molding without resin bleed-out.

[0138] More specifically, as the component (B3), for example, a styrene-butadiene copolymer having a structure represented by the following formula (20) can be cited.

[0139] [Chemistry 20]

[0140]

[0141] The above formula (20) is an example of a styrene-butadiene copolymer. In the above formula (20), d represents a 1,2-vinyl group, e represents a styryl group, and f represents a 1,4-bond.

[0142] Examples of the structural unit having a 1,2-vinyl group include the structural unit of the following formula (21). Examples of the structural unit having a 1,4-bond include the structural unit of the following formula (22). Examples of the structural unit having a styryl group include the structural unit of the following formula (23).

[0143] [Chemistry 21]

[0144]

[0145] [Chemistry 22]

[0146]

[0147] [Chemistry 23]

[0148]

[0149] As the styrene-butadiene copolymer having a 1,2-vinyl group, a copolymer having a repeating structure of the structural unit of formula (21) and a repeating structure of the structural unit of formula (23) is preferred. It may further contain a repeating structure of the structural unit of formula (22).

[0150] 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 50% by mass or more. More preferably, the styrene content is 20 to 50% by mass and the butadiene content is 50 to 80% by mass. Specifically, the relationships among d, e, and f expressed in formula (20) are preferably:

[0151] e / (d+e+f)=20~50%

[0152] (d+f) / (d+e+f)=50~80%

[0153] It is believed that a styrene content within the above range can produce a resin composition with a high Tg and well-balanced adhesion. It is also believed that a butadiene content within the above range can reliably reduce the elastic modulus of the resin composition, thereby reducing the in-plane thermal expansion coefficient when formed into a laminate. Reducing the in-plane thermal expansion coefficient can reduce warping of substrates, such as package substrates. The styrene and butadiene contents in styrene-butadiene copolymers can be measured, for example, using nuclear magnetic resonance spectroscopy (NMR).

[0154] Examples of the styrene-butadiene copolymer of the component (B3) include "Ricon 181" and "Ricon 100" manufactured by Cray Valley Corporation.

[0155] The compound as component (B) is preferably a compound having a styrene skeleton. For example, among the components (B1), (B2), and (B3) described above, a 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-resistant reliability.

[0156] The number average molecular weight of component (B) is not particularly limited as long as it is 1,000 to 10,000. For example, it is preferably 1,000 to 8,000, more preferably 1,000 to 5,000, and particularly preferably 3,500 to 5,000. It should be noted that when measuring the number average molecular weight of a film comprising a resin composition, for example, the film can be dissolved in a solvent and the number average molecular weight of the component dissolved in the solvent can be measured.

[0157] Furthermore, the compound as component (B) preferably contains 5 to 95% by mass of 1,2-vinyl structures within its butadiene skeleton, more preferably 10 to 95% by mass, and particularly preferably 20 to 95% by mass. By setting the 1,2-vinyl structure within the butadiene skeleton within the above numerical range, it is advantageous in lowering the minimum melt viscosity. For example, a butadiene resin containing 5 to 95% by mass of a 1,2-vinyl structure can be used as such. The content of the 1,2-vinyl structure can be measured using FT-IR, NMR, or the like.

[0158] The content of component (B) is preferably 10 to 200 parts by mass per 100 parts by mass of component (A). This configuration provides advantages in heat resistance and chemical resistance due to its reaction with component (A). While 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).

[0159] [Ingredient (C)]

[0160] Component (C) is a thermoplastic elastomer component. Preferred thermoplastic elastomer components include, for example, styrene-based thermoplastic elastomers and hydrogenated styrene-based thermoplastic elastomers. A hydrogenated styrene-based thermoplastic elastomer is a hydrogenated styrene-based thermoplastic elastomer. Examples of hydrogenated styrene-based thermoplastic elastomers include styrene / butadiene / butylene / styrene block copolymers (partially hydrogenated, SBBS) and styrene / ethylene / butylene / styrene block copolymers (fully hydrogenated, SEBS). The use of a hydrogenated styrene-based thermoplastic elastomer can improve dielectric properties. It should be noted that when component (C) is a styrene-based thermoplastic elastomer, the styrene ratio of component (C) is preferably 10-50%, more preferably 15-40%, and even more preferably 20-35%. By setting the styrene ratio of component (C) within the above numerical range, excellent film-forming properties and workability are achieved.

[0161] The thermoplastic elastomer component (C) is not particularly limited, but is preferably a styrene / ethylene / butylene / styrene block copolymer (SEBS). Using a styrene / ethylene / butylene / styrene block copolymer (SEBS) as component (C) improves heat resistance and film properties.

[0162] The number average molecular weight of the thermoplastic elastomer component (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. Note that when component (C) is a compound having a butadiene skeleton containing a 1,2-vinyl group, the number average molecular weight of component (C) is set to be greater than 10,000.

[0163] The content of component (C) is not particularly limited. For example, the content of component (C) is preferably 10 to 150 parts by mass, and more preferably 15 to 100 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). When the content of component (C) is within this range, the heat resistance and film properties, which are the effects of the inclusion of component (C), are further improved.

[0164] [Ingredient (D)]

[0165] Component (D) is a reaction accelerator. Component (D) is an additive that accelerates the reaction between components (A) and (B). The inclusion of component (D) shifts the reaction start temperature toward a lower temperature, accelerating the curing of the resin composition.

[0166] The reaction accelerator component (D) can be any component as long as it accelerates the reaction between component (A) and component (B), and any conventionally known reaction accelerator component can be used. Examples of the reaction accelerator component include organic peroxides, inorganic peroxides, and azo compounds. As the reaction accelerator component (D), an organic peroxide is preferred.

[0167] As the organic peroxide, diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide; peroxyketals such as 2,2-bis(4,4-bis(di-tert-butylperoxy)cyclohexyl)propane; peroxydicarbonates such as isopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(1-methylheptyl) peroxydicarbonate, di(3-methoxybutyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate; tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, neopentyl peroxide Peroxyesters such as tert-butyl valerate, tert-butyl diperoxyadipate, isopropyl peroxyneodecanoate, tert-butyl perbenzoate, 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, diisopropyl peroxide, tert-butyl isopropyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, di(2-tert-butylperoxyisopropyl)benzene; hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, and p-menthane hydroperoxide, etc. The organic peroxide used is not particularly limited. However, since curing the resin composition often requires a drying step at, for example, about 60 to 80°C, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 100 to 140°C. Furthermore, an organic peroxide having a 10-hour half-life temperature of 110 to 130°C is more preferable.

[0168] Examples of the organic peroxide as the component (D) include organic peroxides manufactured by NOF Corporation, trade names "PERCUMYL D" and "PERBUTYL C." The component (D) may be used alone or in combination of two or more.

[0169] When component (D) is contained, the content of component (D) is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, relative to 100 parts by mass of the resin component in the composition. With such a configuration, heat resistance and adhesiveness can be improved.

[0170] [Ingredient (E)]

[0171] Component (E) is an inorganic filler. Inorganic fillers are required to have insulating properties and a low thermal expansion coefficient. Common inorganic fillers can be used.

[0172] For example, as inorganic fillers, silicon dioxide, aluminum oxide, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, calcium sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride, etc. can be enumerated. The inorganic filler can be used alone or in combination of two or more. In particular, from the aspect of insulation, silica fillers and aluminum oxide fillers are preferred. In addition, from the viewpoint of dielectric properties and thermal expansion coefficient, silica fillers are preferred. The inorganic filler can be surface treated with a silane coupling agent having one or more functional groups selected from acrylic acid, methacrylic acid, styryl, amino, epoxy, and vinyl. For example, inorganic filler is preferably surface treated with surface treatment agents such as aminosilane coupling agent, urea silane coupling agent, epoxy silane coupling agent, mercapto silane coupling agent, silane coupling agent, vinyl silane coupling agent, styryl silane coupling agent, acrylate silane coupling agent, isocyanate silane coupling agent, sulfide silane coupling agent, organosilazane compound, titanate coupling agent, so as to improve its heat resistance, moisture resistance, dispersibility. They can use one or two or more in combination. More preferably, in the silica filler that has been surface treated, it is preferred to use a silica filler that has been surface treated with a vinyl silane coupling agent. By using a silica filler that has been surface treated with a vinyl silane coupling agent, the thermal expansion coefficient can be made good.

[0173] The shape of the inorganic filler is not particularly limited, and examples thereof include spherical, flaky, needle-shaped, and irregular shapes. From the perspective of fluidity, a spherical shape is preferred. The average particle size is preferably 0.1 to 10 μm, more preferably 0.1 to 4 μm. By setting the average particle size of the inorganic filler within this range, the embedding property between the microstructures is excellent. The average particle size is the particle size at 50% of the cumulative value in the particle size distribution based on volume, measured by a laser diffraction / scattering method. The average particle size can be measured, for example, using a laser scattering diffraction particle size distribution measuring device: LS13320 (manufactured by Beckman Coulter, wet type).

[0174] When the resin composition contains component (E), it preferably contains 50% by mass or more of component (E) per 100% by mass of the non-volatile components in the resin composition, more preferably 50 to 90% by mass, and even more preferably 50 to 85% by mass. Furthermore, when the content of component (E) is specified as a ratio relative to the total amount of components (A) and (B), it preferably contains 200 parts by mass or more of component (E) per 100 parts by mass of the total of components (A) and (B), more preferably 200 to 900 parts by mass, and even more preferably 400 to 900 parts by mass. This configuration can improve the thermal expansion coefficient.

[0175] [Other ingredients]

[0176] The resin composition of this embodiment may further contain components other than the components (A) to (E) described above. For example, various additives such as solvents, silane coupling agents, flame retardants, and pigments may be included as other components. Furthermore, in addition to components (A) to (C), other compounds (such as other resin components) may be included. For example, isocyanuric acid (a diallyl isocyanuric acid derivative) can be used as an example of an other resin component to improve substrate embedding properties. A commercially available product is the trade name "L-DAIC" from Shikoku Chemical Industry Co., Ltd.

[0177] [Characteristics of resin composition]

[0178] 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. With such a configuration, embedding properties into a substrate become extremely good.

[0179] 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, further preferably 100 Pa·s or more and less than 30,000 Pa·s, and particularly preferably 1000 Pa·s or more and less than 10,000 Pa·s. Note that even when the content of component (E) in 100% by mass of the non-volatile components in the resin composition is less than 50% by mass, the minimum melt viscosity of the resin composition is still, as in the above case, more preferably 10 Pa·s or more and less than 40,000 Pa·s, and further preferably 100 Pa·s or more and less than 30,000 Pa·s.

[0180] On the other hand, when the content of component (E) in 100% by mass of the non-volatile matter 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, further 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.

[0181] The lowest melting temperature of the resin composition is preferably lower 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.

[0182] The minimum melt viscosity (Pa·s) and minimum melting temperature (°C) of a resin composition can be measured using the following method. First, a solution containing the resin composition is applied onto a release-treated PET film using a doctor blade. The solution on the PET film is then dried sequentially at 80°C for 2 minutes, 100°C for 2 minutes, and 130°C for 2 minutes to produce a 50μm thick resin film. The resulting resin film is laminated to a thickness of 300μm and the melt viscosity is measured using a rheometer. The minimum melt viscosity and minimum melting temperature are read and defined as the minimum melt viscosity (Pa·s) and minimum melting temperature (°C) of the resin composition. Measurements are performed using a 5mm diameter parallel plate at a load of 50gf, a strain of 1%, and a frequency of 10Hz at a rate of 5°C / min at 50-200°C. The solution (containing the resin composition) applied to the PET film can be prepared by dissolving the components of the resin composition in toluene as a solvent. At this time, when the resin composition does not contain an inorganic filler as component (E), the solution is prepared so that the solid content concentration in the solution is 30% by mass. On the other hand, when the resin composition contains an inorganic filler as component (E), the components are dissolved and dispersed so that the solid content concentration in the solution is 60% by mass to prepare the solution.

[0183] [Method for producing resin composition]

[0184] The resin composition of this embodiment can be produced by a conventional method. The resin composition of this embodiment can be produced by mixing the components described above using, for example, a pestle, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, or the like.

[0185] [Application of resin composition]

[0186] The resin composition of this embodiment can be suitably used as an adhesive or a resin composition for an adhesive film used in electronic components. In addition, the resin composition of this embodiment can also be suitably used as an adhesive sheet or an interlayer adhesive for interlayer bonding of a multilayer wiring substrate. 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 in electronic components, there is no particular limitation on the electronic components to be bonded, and examples thereof include various printed circuit boards such as ceramic substrates and organic substrates, semiconductor chips, semiconductor devices, and the like. In addition, the resin composition of this embodiment can also be suitably used as a dielectric layer in the redistribution layer of FO-WLP (fan-out wafer-level package).

[0187] Adhesive films and interlayer adhesives for interlayer insulation using the resin composition of this embodiment are incorporated into laminated substrates or semiconductor devices that constitute electronic components, etc., as a cured product of the resin composition. Therefore, laminated substrates or semiconductor devices that constitute electronic components, etc. preferably incorporate a cured product of the resin composition of this embodiment.

[0188] Furthermore, the resin composition of the present embodiment can also be used as a prepreg using a cured product of the resin composition or a high-frequency electronic component having a cured product of the resin composition.

[0189] Example

[0190] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited in any way by these Examples. In the following Examples, parts and % represent parts by mass or mass % unless otherwise indicated.

[0191] (Examples 1 to 17, Comparative Examples 1 to 7)

[0192] 〔Sample production〕

[0193] After the components were blended to the proportions (parts by mass) shown in Tables 1 to 4 below, they were dissolved in toluene as a solvent to prepare solutions containing the resin compositions of Examples 1 to 17 and Comparative Examples 1 to 7. It should be noted that when the resin composition did not contain an inorganic filler as component (E), the solutions were 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 components were dissolved and dispersed so that the solids concentration in the solution was 60% by mass.

[0194] The raw materials used in the preparation of the dissolved liquid containing the resin composition in Examples 1 to 17 and Comparative Examples 1 to 7 are as follows.

[0195] [(A) Ingredient]

[0196] A1 (1): manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name “OPE2St-2200”, number average molecular weight (Mn) = 2200, modified polyphenylene ether resin having a vinylbenzyl group at the terminal.

[0197] A1(2): manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name “OPE2St-1200”, number average molecular weight (Mn) = 1200, modified polyphenylene ether resin having a vinylbenzyl group at the terminal.

[0198] A2 (1): manufactured by KI Chemicals Co., Ltd., trade name "BMI70", maleimide resin.

[0199] A2 (2): manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-5000-60T", maleimide resin (solid content 60%, toluene soluble product).

[0200] [(A') ingredient]

[0201] A1′: a modified polyphenylene ether resin manufactured by SABIC, trade name “SA-9000”, number average molecular weight (Mn)=1700, having a methacrylic acid group at the terminal.

[0202] [Ingredient (B)]

[0203] B1 (1): manufactured by Nippon Soda Co., Ltd., trade name "B-1000", number average molecular weight (Mn) = 1200, butadiene resin (1,2-vinyl structure 85%).

[0204] B1 (2): manufactured by Nippon Soda Co., Ltd., trade name "B-3000", number average molecular weight (Mn) = 3200, butadiene resin (1,2-vinyl structure 92%).

[0205] B1 (3): manufactured by Nippon Soda Co., Ltd., trade name “BI-3015”, number average molecular weight (Mn) = 3200, butadiene resin (1,2-vinyl structure 7%).

[0206] B2 (1): Made by Nippon Soda Co., Ltd., trade name “1,2-SBS-L42”, number average molecular weight (Mn) = 4300, styrene-butadiene block copolymer (20% styrene, 90% 1,2-vinyl structure).

[0207] B2 (2): Made by Nippon Soda Co., Ltd., trade name “1,2-H-SBS-L”, number average molecular weight (Mn) = 4300, styrene-butadiene block copolymer (20% styrene, 30% 1,2-vinyl structure).

[0208] B3: manufactured by Cray Valley Co., Ltd., trade name “Ricon 100”, number average molecular weight (Mn) = 4500, styrene-butadiene copolymer (1,2-vinyl structure 70%).

[0209] 〔Other resin components〕

[0210] Isocyanuric acid (diallylated isocyanuric acid derivative), manufactured by Shikoku Chemical Industry Co., Ltd., trade name "L-DAIC."

[0211] [Ingredient (C)]

[0212] C1: manufactured by Kraton Polymer Co., Ltd., trade name “G1652”, number average molecular weight (Mn): 54,000, thermoplastic elastomer (SEBS: 30% styrene).

[0213] C2: manufactured by Asahi Kasei Corporation, trade name “P1500”, number average molecular weight (Mn): 49,000, thermoplastic elastomer (SBBS: 30% styrene).

[0214] C3: manufactured by ENEOS Materials, trade name “TR2003”, number average molecular weight (Mn): 100,000, styrene-butadiene block copolymer (styrene 43%).

[0215] [Ingredient (D)]

[0216] D1: manufactured by NOF Corporation, trade name "PERCUMYL D", organic peroxide.

[0217] [Ingredient (E)]

[0218] E1: manufactured by Admatechs, trade name “20SV-C9”, silica filler (average particle size 2 μm, vinylsilane surface treated).

[0219] E2: manufactured by Admatechs, trade name “SC4050SX”, silica filler (average particle size 1 μm, aminosilane surface treated).

[0220] E3: manufactured by Denka, trade name “FB-3SDXHOL2”, silica filler (average particle size 3 μm, vinylsilane surface treated).

[0221] The "Total Resin Components (A+B+C+Other Resins)" column in Tables 1 to 4 shows the total amount (parts by mass) of component (A), component (B), component (C), and other resin components in the raw materials used to prepare the resin composition. The "Amount of Filler (parts by mass) per 100 parts by mass of the total of (A+B)" column in Tables 2 and 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 composition.

[0222] The "minimum melt viscosity (Pa·s)" and "minimum melt temperature (° C.)" of the resin composition solutions obtained in Examples 1 to 17 and Comparative Examples 1 to 7 were measured by the following methods. The results are shown in Tables 1 to 4.

[0223] Furthermore, the copper foil peel strength M (N / cm) and copper foil peel strength S (N / cm) were measured for the solutions containing the resin compositions of Examples 6 to 17 and Comparative Examples 3 to 7 by the following methods. The results are shown in Tables 2 to 4.

[0224] Furthermore, the dielectric constant (ε) and dielectric loss tangent (tan δ) of the solutions containing the resin compositions of Examples 6 to 8 were evaluated and measured as “heat resistance reliability” by the following method. The results are shown in Table 4.

[0225] [Production of resin film]

[0226] First, a solution containing the resin composition is applied to a release-treated PET film using a doctor blade method. The solution on the PET film is then dried at a temperature of 80 to 130° C. to produce a resin film with a thickness of 50 to 100 μm.

[0227] 〔Minimum melt viscosity (Pa·s), minimum melting temperature (℃)〕

[0228] The prepared resin film was laminated to a thickness of 300 μm, and the melt viscosity was measured using a rheometer. The minimum melt viscosity and minimum melting temperature at this point were recorded, and the read values ​​were used as the minimum melt viscosity (Pa·s) and minimum melting temperature (°C) of the resin composition. The measurement conditions were: using a 5 mm diameter parallel plate, a load of 50 gf, a strain of 1%, and a frequency of 10 Hz, at a rate of 5°C / min at 5°C / min, at a temperature between 50 and 200°C.

[0229] 〔Copper foil peel strength M (N / cm)〕

[0230] The prepared resin film was sandwiched between a roughened copper foil (18 μm thick) and cured at 200°C for 60 minutes under a pressure of 1 MPa to produce a double-sided copper-clad laminate. The laminate was cut into 1 cm widths, and the strength of the copper foil on one side was measured when pulled 180 degrees. The measurement was performed at a tensile speed of 50 mm / min.

[0231] [Copper foil peel strength S (N / cm)]

[0232] The prepared resin film was sandwiched between the shiny side of an 18μm-thick copper foil and cured at 200°C for 60 minutes under a pressure of 1 MPa to produce a double-sided copper-clad laminate. The laminate was cut into 1cm widths, and the strength of the copper foil on one side was measured when it was pulled 180 degrees. The measurement conditions were a tensile speed of 50 mm / min.

[0233] [Heat resistance and reliability]

[0234] The prepared resin film was cured at 200°C for 60 minutes and a pressure of 1 MPa to prepare a sample for heat resistance reliability evaluation. The dielectric constant (ε) and dielectric loss tangent (tanδ) of the prepared sample were measured using the dielectric resonator method (SPDR method). The values ​​measured after the test piece was prepared as described above were set as the initial values ​​before the heat resistance test. The results are shown in the "Initial Value" column of Table 4. Then, the sample was placed in an oven heated to 125°C for 24 hours, after which the sample was taken out of the oven and cooled to room temperature. The dielectric constant (ε) and dielectric loss tangent (tanδ) of the sample cooled to room temperature were measured in the same manner as described above. The values ​​measured in this way were set as the measured values ​​after the heat resistance test and are shown in the "125°C×24h after" column of Table 4. The dielectric constant (ε) and dielectric loss tangent (tanδ) values ​​measured before and after the heat resistance test were calculated by subtracting the initial values ​​from the values ​​measured after the heat resistance test. The resulting value was used as the "change from the initial value." The percentage of the resulting value was divided by the initial value and calculated as the "change from the initial value (%)." The results are shown in Table 4. The measurement frequency for the dielectric resonator method was 20 GHz.

[0235] In addition, for some of Examples 6-17 and Comparative Examples 3-7, the "thermal expansion coefficient (ppm / K)", "thermal expansion coefficient (thickness) (ppm / K)", and "solder heat resistance" were evaluated and measured using the methods described below. Furthermore, for Examples 6-16 and Comparative Examples 3-7, the initial values ​​of the dielectric constant (ε) and dielectric loss tangent (tanδ) in the heat resistance reliability test described above were measured. Subsequently, for Examples 9-16 and Comparative Examples 3-7, the measurement frequency using the dielectric resonator method was changed to 10 GHz, and the initial values ​​of the dielectric constant (ε) and dielectric loss tangent (tanδ) in the heat resistance reliability test described above were measured.

[0236] [Coefficient of thermal expansion (ppm / K)]

[0237] 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 produce samples for thermal expansion coefficient measurement. The prepared samples were measured using a tensile method using a TMA (thermomechanical analyzer), with the average thermal expansion coefficient between 90°C and 100°C being the reading (i.e., the measured thermal expansion coefficient). The measurement conditions were: annealing to 230°C at a tensile load of 2 gf and 20°C / min, followed by a temporary return to room temperature and subsequent measurement at 5°C / min until 230°C. The measured thermal expansion coefficient is the thermal expansion coefficient in the planar direction (i.e., the XY direction).

[0238] [Coefficient of thermal expansion (thickness) (ppm / K)]

[0239] 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 produce samples for measuring the thermal expansion coefficient (thickness). The samples were measured using a compression method using a TMA (thermomechanical analyzer), with the average thermal expansion coefficient between 90°C and 100°C being the reading (i.e., the measured thermal expansion coefficient (thickness) value). The measurement conditions were: annealing to 250°C at a compressive load of 1 gf and 20°C / min, followed by a temporary return to room temperature and subsequent measurement at 5°C / min until 250°C. The thermal expansion coefficient is measured in the thickness direction (i.e., the Z direction).

[0240] 〔Resistant to soldering heat〕

[0241] After laminating copper foil on both sides of the prepared adhesive film, the film was cut into 2 cm x 2 cm squares to create test pieces. The test pieces were floated in flux baths heated to 260, 270, 280, 290, and 300°C for 1 minute, and their appearance was visually inspected. The temperature (maximum temperature) at which no change in appearance was observed was used as the evaluation value for soldering heat resistance.

[0242]

[0243]

[0244]

[0245]

[0246] 〔result〕

[0247] As shown in Table 1, the resin compositions of Examples 1 to 5 have lower minimum melt viscosities and lower minimum melt temperatures than the resin composition of Comparative Example 2. Note that the minimum melt viscosity and minimum melt temperature of the resin composition of Comparative Example 1 could not be measured.

[0248] As shown in Tables 2 and 3, the resin compositions of Examples 9 to 17 exhibited significantly lower minimum melt viscosities than 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), resulting in the resin compositions of Comparative Examples 3 to 7 exhibiting significantly higher minimum melt viscosities. Meanwhile, the resin compositions of Examples 9 to 16, which contained a thermosetting resin containing at least one of a vinylbenzyl group and a maleimide group as component (A), exhibited a suppressed increase in minimum melt viscosity and exhibited excellent substrate embedding properties.

[0249] 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 adhesive properties. Furthermore, the resin compositions of Examples 9 to 16 also demonstrated excellent 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 are ppm / K). Furthermore, the thermal expansion coefficients (per 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 are ppm / K).

[0250] The dielectric constants (ε) of the resin compositions of Examples 9 to 14 at a measured frequency of 10 GHz were 3.05, 3.12, 3.10, 3.10, 2.89, and 3.06, respectively, and the dielectric loss tangents (tan δ) were 0.0014, 0.0015, 0.0013, 0.0011, 0.0015, and 0.0014, respectively. The dielectric constants (ε) of the resin compositions of Examples 13 to 16 at a measured frequency of 20 GHz were 3.01, 3.08, 3.07, and 3.09, respectively, and the dielectric loss tangents (tan δ) were 0.0016, 0.0015, 0.0015, and 0.0013, respectively. Furthermore, the resin compositions of Examples 9 to 14 also exhibited good values ​​of resistance to solder heat at either 300°C or 290°C.

[0251] The resin composition of Example 17 is a resin composition that contains components (A) and (B) as resin components and does not contain other resin components. In addition, the resin composition of Example 17 does not contain an inorganic filler as component (E). This resin composition of Example 17 also has a low minimum melt viscosity and a low minimum melting temperature. The coefficient of thermal expansion (ppm / K) of the resin composition of Example 17 is 102 ppm / K, and the coefficient of thermal expansion (thickness) (ppm / K) is 73 ppm / K. The resin composition of Example 17 can also be suitably used, for example, as a dielectric layer in the redistribution layer of FO-WLP (fan-out wafer-level package).

[0252] Meanwhile, the coefficients of thermal expansion (ppm / K) of the resin compositions of Comparative Examples 3 to 7 were 51, 35, 36, 51, and 50, respectively, and the coefficients of thermal expansion (thickness) (ppm / K) were 37, 47, 29, 37, and 64, respectively (all units expressed in ppm / K). Furthermore, the dielectric constants (ε) of the resin compositions of Comparative Examples 3 to 7 at a measurement frequency of 10 GHz were 3.12, 3.06, 3.11, 3.12, and 3.12, respectively, and the dielectric loss tangents (tan δ) were 0.0014, 0.0012, 0.0013, 0.0014, and 0.0019, respectively. Furthermore, the resin composition of Comparative Example 7 exhibited a low value of 270°C in solder heat resistance evaluation.

[0253] As shown in Table 4, the resin composition of Example 6 uses a styrene-butadiene block copolymer as the (B) component (B2). The resin composition of Example 8 uses a butadiene resin as the (B) component (B1). The resin composition of Example 7 uses a styrene-butadiene copolymer as the (B) component (B3). Comparing the resin compositions of Examples 6 to 8, the resin composition of Example 6, which uses a styrene-butadiene block copolymer as the (B2) component, exhibits superior heat resistance reliability (rate of change in tan δ) compared to the other (B) components. It also exhibits excellent results for peel strength M against the matte surface (M surface) of the electrolytic copper foil. The coefficients of thermal expansion (ppm / K) of the resin compositions of Examples 6 to 8 are 149, 146, and 154, respectively, and the coefficients of thermal expansion (thickness) (ppm / K) are 194, 207, and 196, respectively (all units are ppm / K).

[0254] Industrial applicability

[0255] The resin composition of the present invention can be used as an adhesive for use in electronic components or as a resin composition for adhesive films. Furthermore, it can be used as an adhesive sheet or interlayer adhesive for use between layers of multilayer wiring boards. Furthermore, the resin composition of the present invention can 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 resin composition comprising: A thermosetting resin having at least one of a vinylbenzyl group and a maleimide group, and B is 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.

2. The resin composition according to claim 1, wherein The resin composition has a minimum melt viscosity of less than 40,000 Pa·s.

3. The resin composition according to claim 1 or 2, wherein The component A is a thermosetting resin having a vinylbenzyl group at a terminal and a polyphenylene skeleton.

4. The resin composition according to any one of claims 1 to 3, wherein The component B is a compound having a styrene skeleton.

5. The resin composition according to any one of claims 1 to 4, wherein The component B is a styrene-butadiene block copolymer.

6. The resin composition according to any one of claims 1 to 5, wherein The component B is a styrene-butadiene-styrene block copolymer or its hydrogenated product represented by the following structural formula (1): In the structural formula (1), m, o, p, and q are each independently a positive integer, n is 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.

7. The resin composition according to any one of claims 1 to 6, wherein The 1,2-vinyl structure accounts for 5% to 95% by mass in the butadiene skeleton of the component B. 8 . The resin composition according to claim 1 , further comprising a thermoplastic elastomer component (C). 9 . The resin composition according to claim 1 , further comprising a reaction accelerator component (D).

10. The resin composition according to claim 9, wherein The component D is an organic peroxide. 11 . The resin composition according to claim 1 , further comprising an inorganic filler (E).

12. The resin composition according to claim 11, wherein The component E is contained in an amount of 50% by mass or more based on 100% by mass of the non-volatile components in the resin composition.

13. The resin composition according to claim 11, wherein The component E is contained in an amount of 200 parts by mass or more relative to 100 parts by mass of the total of the component A and the component B.

14. The resin composition according to any one of claims 1 to 13, wherein The component B is contained in an amount of 10 to 200 parts by mass based on 100 parts by mass of the component A.

15. The resin composition according to any one of claims 1 to 14, wherein The resin composition has a minimum melting temperature of less than 200°C. 16 . An adhesive film for interlayer insulation, comprising the resin composition according to claim 1 . 17 . A laminate substrate comprising a cured product of the resin composition according to claim 1 or the adhesive film for interlayer insulation according to claim 16 . An electronic component comprising the laminate substrate according to claim 17 . 19 . A semiconductor device comprising the multilayer substrate according to claim 17 or the electronic component according to claim 18 .

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