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

Abstract

Provided is a resin composition with low dielectric characteristics while having good ability to permeate into circuit boards. This composition comprises (A) a thermosetting resin comprising vinylbenzyl groups and / or maleimide groups, and (B) a compound with a butadiene backbone that has a 1,2-vinyl group, and the number average molecular weight of component (B) is 1000-10000.

Description

Technical Field

[0001] The present invention relates to a resin composition, a film to be adhered, a laminated substrate, an electronic component, and a semiconductor device. connected to

Background Art

[0002] In recent years, for mobile terminals such as smartphones and tablets, communication electronic devices such as communication base stations and advanced driving assistance systems (ADAS), the communication speed has been increased and the communication capacity has been increased, and the construction of a 5G communication network using high-frequency signals has been progressing. Furthermore, studies on the use of higher-frequency signals such as 6G communication have also been actively conducted. Electronic substrates are essential components for these high-frequency communications.

[0003] On the other hand, general substrate materials (for example, FR-4) may have large transmission losses of electrical signals in high-frequency communications. Therefore, the development of substrate materials with low transmission losses has been carried out. Here, "FR-4" is an abbreviation of "Flame Retardant Type 4", which is a material obtained by impregnating a glass fiber cloth with an epoxy resin and performing a thermosetting treatment. In order to reduce the transmission loss of the substrate material, it is necessary to lower the dielectric constant and dielectric tangent of the copper-clad laminate used for the substrate material and the adhesive film for interlayer insulation. Hereinafter, the "adhesive film for interlayer insulation" may be simply referred to as the "interlayer adhesive film".

[0004] In addition, for the substrates used in these high-frequency communications, in order to reduce weight and size, it is also necessary to increase the number of layers and achieve high integration.

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

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] Regarding an adhesive film for a substrate that processes high-frequency signals, for example, when an inorganic filler such as a silica filler is highly filled in a resin composition, there has been a problem that its melt viscosity becomes high and its embeddability into the substrate deteriorates. For example, when the melt viscosity is high, it becomes difficult to embed into a wiring pattern or the like when laminating and adhering substrates.

[0008] Patent Document 1 does not mention anything regarding the fluidity required for an interlayer adhesive film (in other words, embeddability into a substrate). Further, the polyphenylene ether resin composition evaluated in Patent Document 1 is only a methacryl-modified polyphenylene ether.

[0009] As a resin composition for use in high-frequency communication, development of a resin composition having low dielectric characteristics and good embeddability into a substrate is eagerly desired.

[0010] The present invention has been made in view of such problems of the prior art. The present invention provides a resin composition having low dielectric characteristics and good embeddability into a substrate. Further, the present invention uses such a resin composition connected to to provide an adhesive film, a laminated substrate, an electronic component, and a semiconductor device.

Means for Solving the Problems

[0011] According to the present invention, there are provided the following resin compositions, as well as connected to an adhesive film, a laminated substrate, an electronic component, and a semiconductor device.

[0012] [1] A thermosetting resin having at least one of a vinylbenzyl group and a maleimide group, and (B) A compound having a butadiene skeleton with a 1,2-vinyl group, and (C) a thermoplastic elastomer component, containing, the number average molecular weight of the component (B) is from 1000 to 10000 and when the (C) thermoplastic elastomer component is a compound having a butadiene skeleton having a 1,2-vinyl group, its number average molecular weight exceeds 10,000 and is 1,000,000 or less, including 10 to 200 parts by mass of the (B) component with respect to 100 parts by mass of the (A) component , a resin composition (however, excluding a resin composition containing an uncured semi-IPN type composite and a radical reaction initiator, wherein the uncured semi-IPN type composite is a compatibilized uncured semi-IPN type composite formed from polyphenylene ether, a prepolymer formed from a butadiene polymer that contains 40% or more of 1,2-butadiene units having a 1,2-vinyl group in the molecule and is not chemically modified, and a crosslinking agent, and the radical reaction initiator contains a dialkyl peroxide-based radical reaction initiator and a hydroperoxide-based radical reaction initiator). [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 (B) component being 1000 to 10,000, the (B) component including (B2) a styrene-butadiene block copolymer, a resin composition including 10 to 200 parts by mass of the (B) component with respect to 100 parts by mass of the (A) component (however, excluding a thermosetting resin composition containing an uncured semi-IPN type composite and a radical reaction initiator, where the uncured semi-IPN type composite is a compatibilized uncured semi-IPN type composite formed from a polyphenylene ether, a butadiene polymer containing 40% or more of 1,2-butadiene units having a 1,2-vinyl group in the side chain and not chemically modified, and a crosslinking agent, and the radical reaction initiator includes a dialkyl peroxide-based radical reaction initiator and a hydroperoxide-based radical reaction initiator).

[0013] 3 The resin composition according to [1] above, wherein the minimum melt viscosity of the resin composition is less than 40,000 Pa·s.

[0014] 4 The resin composition according to [1] or [2] above, wherein the component (A) is a thermosetting resin having a vinylbenzyl group at the terminal and a polyphenylene skeleton.

[0015] 5 The resin composition according to [1] or [2] above, wherein the component (B) is a compound having a styrene skeleton.

[0016] ​​​ 6 The resin composition according to [1] or [2], wherein the component (B) is a styrene-butadiene block copolymer.

[0017] 7 The resin composition according to [1] or [2], wherein the component (B) is a styrene-butadiene-styrene block copolymer represented by the following structural formula (1) or a hydrogenated product thereof.

[0018]

Chemical formula

[0019] 8 The resin composition according to [1] or [2], wherein the 1,2-vinyl structure in the butadiene skeleton of the component (B) is 5 to 95% by mass.

[0021] [9] The resin composition according to [1], further comprising a (D) reaction accelerator component. Or [2] described above.

[0022]

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

[0023]

[11] The resin composition according to [1], further comprising an (E) inorganic filler. Or [2] described above.

[0024]

[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.

[0025]

[13] The resin composition according to

[11] , wherein the component (E) is contained in an amount of 200 parts by mass or more based on 100 parts by mass of the total of the components (A) and (B). ​​​

[0027] 14 The resin composition according to [1] or [2], wherein the lowest melting temperature of the resin composition is less than 200°C.

[0028] 15 as described in the above [1] or [2] An adhesive film made of the resin composition. 16 An adhesive film for interlayer insulation made of the resin composition described in 15 .

[0029] 17 A laminated substrate containing the resin composition according to [1] or [2]. substance

[18] a laminated substrate including a cured product of the adhesive film for interlayer insulation described in the above

[16] .

[0030] 19 An electronic component containing the laminated substrate described in 18 .

[0031]

[20] A semiconductor device containing the laminated substrate described in

[18] .

[21] A semiconductor device containing the electronic component described in

[19] . 。 [Advantages of the Invention]

[0032] The resin composition of the present invention has the effects of excellent dielectric properties and excellent embeddability into a substrate. In particular, by including a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as the component (A), the lowest melt viscosity can be lowered. That is, since the thermosetting resin as the above-described component (A) has a high binding energy and the reaction proceeds slowly, as a result, the lowest melt viscosity is considered to decrease. Further, the resin composition of the present invention has excellent dielectric properties, adhesiveness, thermal expansion coefficient, and heat resistance reliability after thermosetting. In addition, since the compound having a butadiene skeleton having a 1,2-vinyl group as the component (B) has a number average molecular weight of 1000 to 10000, the fluidity and the thermal expansion coefficient can be set to suitable values.​​​​​​

[0033] Also, the present invention connected The adherent film is made of the resin composition of the present invention, and has the effects of excellent dielectric properties and excellent embedability. Furthermore, the laminated substrate, electronic component, and semiconductor device of the present invention contain the resin composition of the present invention or connected the cured product of the adherent film, and enjoy the effects of the present invention described so far.

Mode for Carrying Out the Invention

[0034] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. Therefore, it should be understood that those obtained by appropriately changing, improving, etc. the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention also fall within the scope of the present invention.

[0035] 〔Resin Composition〕 The 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 having a 1,2-vinyl group. Hereinafter, the thermosetting resin having at least one of a vinylbenzyl group and a maleimide group may be referred to as the (A) component. Similarly, the compound having a butadiene skeleton having a 1,2-vinyl group may be referred to as the (B) component. And, in the resin composition of the present embodiment, the number average molecular weight of the (B) component is 1000 to 10000.

[0036] The resin composition of this embodiment has excellent dielectric properties and good embedability in a substrate. In particular, by containing a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group as the component (A), the minimum melt viscosity can be lowered. That is, since the thermosetting resin as the above-mentioned component (A) has a high bond energy and the reaction proceeds slowly, it is considered that the minimum melt viscosity decreases as a result. In addition, the resin composition of the present invention has excellent dielectric properties, adhesiveness, thermal expansion coefficient, and heat resistance reliability after thermosetting. Further, since the compound having a butadiene skeleton having a 1,2-vinyl group as the component (B) has a number average molecular weight of 1000 to 10000, the fluidity and the thermal expansion coefficient can be set to suitable values.

[0037] In addition, the resin composition of this embodiment may contain other components such as a (C) thermoplastic elastomer component, a (D) reaction accelerator component, and an (E) inorganic filler in addition to the above-mentioned components (A) and (B). Hereinafter, each of the above-mentioned components may be referred to as a component (C) to a component (E) as appropriate. Of course, the resin composition of this embodiment may contain other resin components in addition to the component (C).

[0038] [Component (A)] The component (A) is a thermosetting resin having at least one of a vinylbenzyl group and a maleimide group. By containing the component (A), the minimum melt viscosity can be lowered. That is, since the thermosetting resin having at least one of a vinylbenzyl group and a maleimide group has a high bond energy and the reaction proceeds slowly, it is considered that the minimum melt viscosity decreases as a result. On the other hand, for example, a thermosetting resin having a methacryloyl group has a low bond energy and the reaction proceeds rapidly, so it is presumed that the minimum melt viscosity increases as a result.

[0039] Examples of the thermosetting resin having a vinylbenzyl group in component (A) include a thermosetting resin having a vinylbenzyl group at its terminal. Examples of such a thermosetting resin include a thermosetting resin having a vinylbenzyl group at its terminal and a polyphenylene skeleton.

[0040] Examples of the thermosetting resin having a vinylbenzyl group at its terminal and a polyphenylene skeleton include a compound having a structure represented by the following general formula (2).

[0041]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0042] In the above general formula (2), -(O-X-O)- is represented by the above structural formula (3) or (4).

[0043] In structural formula (3), R 2 , R 3 , R 4 , R 8 , and R 9 are an alkyl group having 6 or fewer carbon atoms or a phenyl group, and may be the same as or different from each other. R 5 , R 6 , and R 7 are a hydrogen atom, an alkyl group having 6 or fewer carbon atoms, or a phenyl group, and may be the same as or different from each other.

[0044] In 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 as each other or different from each other. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0045] Also, in the general formula (2), -(Y-O)- is represented by the above structural formula (5). In -(Y-O)-, one type of structure or two or more types of structures are randomly arranged. In the structural formula (5), R 18 and R 19 are an alkyl group having 6 or less carbon atoms or a phenyl group, and they may be the same as each other or different from each other. R 20 and R 21 are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and they may be the same as each other or different from each other.

[0046] Also, in the general formula (2), a and b are integers from 0 to 100. At least one of a and b is not 0.

[0047] Examples of -A- in the 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 the structural formula (4) is not limited to these.

[0048] Examples of the compound represented by the general formula (2) include cases where R 2 , R 3 , R 4 , R 8 , R 9 , R 18 , and R 19 are alkyl groups having 3 or less carbon atoms, and R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R13 , 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, -(O-X-O)- represented by the structural formula (3) or the structural formula (4) is more preferably a compound represented by the following structural formula (6), structural formula (7), or structural formula (8). Similarly, in particular, -(Y-O)- represented by the structural formula (5) is preferably a compound represented by the following structural formula (9) or structural formula (10), or more preferably a structure in which the compound represented by the structural formula (9) and the compound represented by the structural formula (10) are randomly arranged.

[0049] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0050] The method for producing the compound represented by the general formula (2) is not particularly limited. For example, the compound represented by the general formula (2) can be produced by the following method. First, a difunctional phenol compound and a monofunctional phenol compound are subjected to oxidative coupling to obtain a difunctional phenylene ether oligomer. Next, the terminal phenolic hydroxyl group of the obtained difunctional phenylene ether oligomer is vinyl benzyl etherified. In this way, the compound represented by the general formula (2) can be produced.

[0051] The number average molecular weight of the compound represented by the general formula (2) is preferably from 1,000 to 3,000, more preferably from 1,000 to 2,500, and particularly preferably from 1,000 to 2,000. By setting the number average molecular weight of the compound represented by the general formula (2) within the above numerical range, the solubility, low dielectric property, fluidity, and heat resistance are further improved. For example, if the number average molecular weight is 1,000 or more, stickiness is less likely to occur when the resin composition is formed into a coating film. Further, if the number average molecular weight is 3,000 or less, a decrease in solubility of the resin composition in a solvent can be effectively suppressed. Further, by using a compound having a number average molecular weight within the above numerical range as the component (A), the electrical properties at high frequencies and the curability in the resin composition are improved. Here, the above-mentioned number average molecular weight is a value obtained by using a calibration curve with standard polystyrene by gel permeation chromatography (GPC).

[0052] (A) The component may be used alone with a compound represented by the general formula (2), or may be used in combination of two or more compounds represented by the general formula (2).

[0053] Examples of the thermosetting resin having a vinylbenzyl group at the terminal of the component (A) include "OPE2St-2200" and "OPE2St-1200" manufactured by Mitsubishi Gas Chemical Company, Inc. under their trade names.

[0054] Further, examples of the thermosetting resin having a maleimide group of the component (A) include a thermosetting resin having a maleimide group at its terminal.

[0055] (A) The thermosetting resin having a maleimide group at the terminal used as the component may be, for example, a compound containing one or more maleimide groups in the molecule represented by the following general formula (11). Monomaleimide compounds and polymaleimide compounds can be preferably used, and are shown in the following general formulas (11), (12), (13), (14), or (15).

[0056]

Chemical formula

[0057] In the general formula (11) above, R 31 is preferably phenyl, alkylphenyl, dialkylphenyl, alkoxyphenyl, benzyl, dodecyl, alkyl, or cycloalkyl. Also, Xa and Xb are preferably hydrogen atoms.)

[0058] [Chemical formula] (However, in the general formula (12) above, R 32 is a monovalent or divalent organic group that is either aliphatic, alicyclic, aromatic, or heterocyclic. Also, s is 0 or 1.)

[0059] In the general formula (12) above, when s is 0 and R 32 is a monovalent group, it is preferably phenyl, alkylphenyl, dialkylphenyl, alkoxyphenyl, benzyl, dodecyl, alkyl, or cycloalkyl. Also, in the general formula (12), when s is 1 and R 32 is a divalent group, it is preferably alkylene, fluorene, or cyclohexylene-alkylene-cyclohexylene.)

[0060] [Chemical formula] (However, in the general formula (13) above, R 33is -C(Xc)2-, -CO-, -O-, -S-, -SO2-, or a connecting bond, which may be the same or different from each other. Xc represents an alkyl group having 1 to 4 carbon atoms, -CF3, -OCH3, -NH2, a halogen atom, or a hydrogen atom, which may be the same or different from each other. In the general formula (13), the substitution positions of the benzene rings are independent of each other. Also, t and u represent 0 or an integer of 1 to 10.)

[0061] Specific examples of the monomer maleimide 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, N-cyclohexylmaleimide, and the like.

[0062] Specific examples of the polymaleimide compound represented by the 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 the following general formulas (14) and (15) etc. (however, each includes isomers).

[0063] [Chemical formula] (However, in the above general formula (14), v is an average value of 0 to 10.)

[0064] [Chemical formula] (However, in the above general formula (15), w is an average value of 0 to 10.)

[0065] From the viewpoints of moisture resistance, heat resistance, fracture strength, metal foil peel strength, and low coefficient of thermal expansion when used as a printed wiring board, aromatic polyimide is preferred. Among them, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane is more preferred particularly in terms of further lowering the coefficient of thermal expansion, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane is more preferred in terms of further increasing the fracture strength and metal foil peel strength.

[0066] Also, from the viewpoint of enhancing moldability when used as an adhesive film, monomer maleimide that gives a gentle curing reaction is preferred. Among them, N-phenylmaleimide is more preferred in terms of cost. And the above maleimide compounds may be used alone, in combination of two or more kinds, or in combination with at least one of these maleimide compounds and one or more crosslinking agents.

[0067] When using a maleimide compound in combination with other crosslinking agents, the proportion of the maleimide compound in component (A) is preferably 50% by mass or more, more preferably 80% by mass or more. However, it is more preferable to use the maleimide compound alone rather than in combination with other crosslinking agents.

[0068] Also, the thermosetting resin having a maleimide group at the terminal used as component (A) may be, for example, a maleimide compound represented by the following general formula (16).

[0069]

Chemical formula

[0070] The content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide by GPC analysis (RI) in the maleimide compound represented by the general formula (16) is usually 90 area% or less, preferably in the range of 10 - 80 area%, more preferably 20 - 80 area%, still more preferably 30 - 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 and the solvent solubility improves. On the other hand, the lower limit of the content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide may be 0 area%, but when it is 10 area% or more, the decrease in reactivity can be suppressed.

[0071] The content by GPC analysis (RI) of y = 1 in the maleimide compound represented by the general formula (16) is preferably 98 area% or less, more preferably in the range of 20 - 98 area%, still more preferably 30 - 90 area%, particularly preferably 40 - 80 area%. When the content of y = 1 is 98 area% or less, the heat resistance is good. On the other hand, the lower limit of the content of y = 1 may be 0 area%, but when it is 20 area% or more, the viscosity of the resin solution decreases and the impregnation property becomes good.

[0072] The softening point of the maleimide compound represented by the general formula (16) is preferably 50 - 150 °C, more preferably 80 - 120 °C, still more preferably 90 - 110 °C, particularly preferably 95 - 100 °C. Also, the melt viscosity at 150 °C is 0.05 - 100 Pa·s, preferably 0.1 - 40 Pa·s.

[0073] 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 decreases compared to the case where the substitution position of the propyl group with respect to the benzene ring to which the maleimide group is not bonded in the general formula (16) is the para position.

[0074]

Chemical formula

[0075] The number average molecular weight of the maleimide compound as the component (A) described so far 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 property, fluidity, and heat resistance will be more excellent. Here, the number average molecular weight of the maleimide compound described above is a value using a calibration curve with standard polystyrene by the gel permeation chromatography (GPC) method.)

[0076] (A) As the maleimide compound as the component, the maleimide compounds described so far may be used alone, or two or more compounds may be used in combination.)

[0077] (A) Examples of the thermosetting resin having a maleimide group as the component include a maleimide resin (trade name "BMI70") manufactured by Kayaku Kasei Co., Ltd. and a maleimide resin (trade name "MIR-5000-60T") manufactured by Nippon Kayaku Co., Ltd.)

[0078] [(B) component] (B) The component is a compound having a butadiene skeleton having a 1,2-vinyl group. By including the component (B), the adhesiveness can be improved. In particular, a butadiene-containing resin having a 1,2-vinyl group can achieve more excellent adhesiveness by having a structure of a copolymer with styrene or a block copolymer. In addition, the compound having a butadiene skeleton having a 1,2-vinyl group as the component (B) has a number average molecular weight of 1,000 to 10,000. By setting such a number average molecular weight, the fluidity and the coefficient of thermal expansion can be made good. Here, the number average molecular weight of the compound as the component (B) is a value using a calibration curve with standard polystyrene by the gel permeation chromatography (GPC) method.)

[0079] (B) Examples of the compound as the component include the following (B1) component, (B2) component, and (B3) component.)

[0080] (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 monomers used. For example, a suitable cured product can be obtained without using monomers. On the other hand, since the butadiene copolymer having a 1,2-vinyl group does not have a styrene skeleton, the adhesion (especially the peel strength of the roughened surface (M surface)) tends to be weak. Such a butadiene copolymer having a 1,2-vinyl group is not particularly limited as long as its number average molecular weight is from 1000 to 10000.)

[0081] Examples of the component (B1) include 1,2-polybutadiene homopolymers (trade names "B-3000" and "B-1000") manufactured by Nippon Soda Co., Ltd., and a partially hydrogenated product with the trade name "BI-3015".

[0082] (Component (B2) is a styrene-butadiene block copolymer having a 1,2-vinyl structure. For example, by using such a component (B2), the peel strength can be improved and the coefficient of thermal expansion can be reduced.)

[0083] (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 having a 1,2-vinyl group is not particularly limited as long as its number average molecular weight is from 1000 to 10000. The butadiene block consists of only the 1,2-bond structure represented by the following formula (18) or the 1,2-bond structure represented by the formula (18) and the 1,4-bond structure represented by the formula (19).)

[0084] [Chemical formula]

[0085] The molar ratio of the 1,2-bond structure represented by the formula (18) to the 1,4-bond structure represented by the formula (19) contained in the styrene-butadiene block copolymer having a 1,2-vinyl structure of the (B2) component is preferably from 80:20 to 100:0.

[0086] The weight ratio of the styrene block to the butadiene block in the (B2) component 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, 40:60 to 80:20, and the like. Among these, 10:90 to 80:20, 10:90 to 70:30, 10:90 to 60:40, 10:90 to 50:50 are preferable, and 10:90 to 50:50 is more preferable.

[0087] The (B2) component is preferably a styrene-butadiene-styrene block copolymer represented by the following structural formula (1) or a hydrogenated product thereof.

[0088] [Chemical formula] (However, 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 to 20:60 to 98:1 to 20 is satisfied, and the relationship of m:n = 100:0 to 80:20 is satisfied.)

[0089] By using the styrene-butadiene-styrene block copolymer represented by the above structural formula (1) as the (B) component, the peel strength can be improved and the coefficient of thermal expansion can be reduced.

[0090] The production method of the (B2) component is not particularly limited. For example, the styrene-butadiene-styrene block copolymer can be produced by the methods described in JP-A-6-192502, JP-T-2000-514122, JP-A-2007-302901, and the like and methods analogous thereto.

[0091] Examples of the component (B2) include the products named "1,2-SBS-L42" and "1,2-H-SBS-L" manufactured by Nippon Soda Co., Ltd.

[0092] The component (B3) is a styrene-butadiene copolymer having a 1,2-vinyl group. Such a styrene-butadiene copolymer having a 1,2-vinyl group is not particularly limited as long as its number average molecular weight is from 1,000 to 10,000. Such a styrene-butadiene copolymer is hydrophobic and has few polar groups. Therefore, by adding it to the resin composition, the low dielectric properties can be improved. Further, due to its relatively small molecular weight, it exhibits high solubility not only in nonpolar organic solvents such as toluene but also in polar organic solvents such as methyl ethyl ketone despite its hydrophobic skeleton. Therefore, when forming a resin composition, it is easily dissolved in various solvents, and when dissolved in a solvent to form a resin varnish, it has an advantage of excellent varnish stability. On the other hand, since the component (B3) is a random copolymer rather than a block copolymer, the adhesion (peel strength of the glossy surface (S surface)) tends to be weak. That is, it is presumed that when phenyl groups are not aligned, it becomes difficult to develop the strength in a plane.

[0093] In addition, since the styrene-butadiene copolymer is liquid, there is also an advantage that the flexibility of the resin composition is improved and the handleability (such as powder falling) of the resin composition in a semi-cured state is improved.

[0094] The component (B3) is particularly preferably a styrene-butadiene copolymer having crosslinkable 1,2-vinyl in the molecule, whereby it has reactivity as compared with a general styrene-butadiene polymer having many 1,4-bonds in the main chain. Further, since the number average molecular weight is as low as 10,000 or less, it is considered that the reactivity of the 1,2-vinyl group in the styrene-butadiene copolymer becomes higher. From these facts, it is considered that it contributes to the curing reaction and the appearance after molding without bleeding of the resin is excellent.

[0095] More specifically, examples of the component (B3) include styrene-butadiene copolymers having a structure represented by the following formula (20).

[0096] [Chemical formula]

[0097] Although 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 styrene group, and f represents a 1,4-bond, respectively.

[0098] Examples of the structural unit having a 1,2-vinyl group include a structural unit represented by the following formula (21). Examples of the structural unit having a 1,4-bond include a structural unit represented by the following formula (22). Further, examples of the styrene group include a structural unit represented by the following formula (23).

[0099] [Chemical formula]

[0100] [Chemical formula]

[0101] [Chemical formula]

[0102] As the styrene-butadiene copolymer having a 1,2-vinyl group, those having a repeating structure of the structural unit of formula (21) and a repeating structure of the structural unit of formula (23) are preferable. Further, it may include a repeating structure of the structural unit of formula (22).

[0103] In the styrene-butadiene copolymer of component (B3), the styrene content in its molecule is preferably 50% by mass or less, and the butadiene content is preferably 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. That is, the relationships of d, e, and f represented by the above formula (20) are respectively: e / (d + e + f)=20~50% (d + f) / (d + e + f)=50~80% It is preferably such. By the styrene content being within the above range, it is considered that a resin composition excellent in balance in high Tg, adhesiveness, etc. can be obtained. Further, by the butadiene content being within the above range, it is considered that the elastic modulus of the resin composition can be surely reduced, and thus the coefficient of thermal expansion in the plane direction when made into a laminate can be reduced. If the coefficient of thermal expansion in the plane direction can be reduced, the warpage of the substrate can be reduced in a package substrate or the like. The styrene and butadiene contents in the styrene-butadiene copolymer can be measured, for example, by nuclear magnetic resonance spectroscopy (NMR).

[0104] Examples of the styrene-butadiene copolymer of component (B3) include the products named "Ricon181" and "Ricon100" manufactured by CRAY VALLEY.

[0105] The compound as component (B) is preferably a compound having a styrene skeleton. For example, among the components (B1), (B2), and (B3) described so far, from the viewpoints of coefficient of thermal expansion, adhesive strength, and heat resistance reliability, the styrene-butadiene block copolymer having a 1,2 vinyl structure of component (B2) is more preferable.

[0106] (B) The number average molecular weight of the component is not particularly limited as long as it is from 1,000 to 10,000. For example, it is preferably from 1,000 to 8,000, more preferably from 1,000 to 5,000, and particularly preferably from 3,500 to 5,000. When measuring the number average molecular weight in a film made of the resin composition, for example, the film may be dissolved in a solvent and the number average molecular weight in the components dissolved in the solvent may be measured.

[0107] Also, the compound as the (B) component preferably has a 1,2-vinyl structure in the butadiene skeleton in an amount of 5 to 95% by mass, more preferably 10 to 95% by mass, and particularly preferably 20 to 95% by mass. By setting the 1,2-vinyl structure in the butadiene skeleton within the above numerical range, there is an advantage in terms of lowering the minimum melt viscosity. For example, such a compound includes a butadiene resin containing 5 to 95% by mass of the 1,2-vinyl structure. The content ratio of the 1,2-vinyl structure can be measured by FT-IR, NMR, etc.

[0108] (B) The content of the component is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the (A) component. By configuring in this way, there are advantages in terms of heat resistance and chemical resistance due to the reaction with the (A) component. Although not particularly limited, the content of the (B) component is more preferably 15 to 190 parts by mass and even more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the (A) component.

[0109] [(C) Component] (C) component is a thermoplastic elastomer component. As the thermoplastic elastomer component, for example, a styrene-based thermoplastic elastomer or a hydrogenated styrene-based thermoplastic elastomer is preferable. Here, the hydrogenated styrene-based thermoplastic elastomer is 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). By using the hydrogenated styrene-based thermoplastic elastomer, the dielectric properties can be improved. When the (C) component is a styrene-based thermoplastic elastomer, the styrene ratio of the (C) component is preferably 10 to 50%, more preferably 15 to 40%, and still more preferably 20 to 35%. By setting the styrene ratio of the (C) component within the above numerical range, excellent film-forming properties and workability can be achieved.

[0110] (C) component's thermoplastic elastomer component is not particularly limited, but a styrene / ethylene / butylene / styrene block copolymer (SEBS) is preferably used. By using the (C) component as a styrene / ethylene / butylene / styrene block copolymer (SEBS), it will have excellent heat resistance and film properties.

[0111] (C) component's thermoplastic elastomer component's number average molecular weight is not particularly limited, but for example, it is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 200,000. When the (C) component is a compound having a butadiene skeleton with a 1,2 vinyl group, the number average molecular weight of the (C) component shall exceed 10,000.

[0112] (C) component content is not particularly limited. For example, with respect to a total of 100 parts by mass of (A) component and (B) component, (C) component is preferably 10 to 150 parts by mass, and more preferably 15 to 100 parts by mass. When the content of (C) component is within this range, heat resistance and film properties, which are the effects of containing (C) component, become more excellent.

[0113] 〔(D) component〕 (D) component is a reaction accelerator component. The reaction accelerator component as (D) component is an additive for promoting the reaction of (A) component and (B) component. By including such (D) component, the reaction start temperature shifts to the low temperature side and the curing of the resin composition is promoted.

[0114] (D) component's reaction accelerator component may be any one that can promote the reaction of (A) component and (B) component, and conventionally known reaction accelerator components can be used. For example, examples of the reaction accelerator component include organic peroxides, inorganic peroxides, and azo compounds. As (D) component's reaction accelerator component, organic peroxides are preferred.

[0115] Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, and di(3,5,5-trimethylhexanoyl) peroxide; peroxyketals such as 2,2-bis(4,4-di-(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, and dicyclohexyl peroxydicarbonate; peroxy esters such as tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, cumyl perneodecanoate, tert-butyl peroxybenzoate, 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-butyl cumyl 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-menthane hydroperoxide. Although there is no particular limitation on the organic peroxide to be used, when curing the resin composition, for example, a drying step at about 60 to 80°C is often required, and thus it is preferable to use one having a 10-hour half-life temperature of 100 to 140°C. Further, it is more preferable to use one having a 10-hour half-life temperature of 110 to 130°C.

[0116] Examples of the organic peroxide as the component (D) include organic peroxides manufactured by NOF Corporation, trade names "Perk Mill D" and "Perbutyl C", etc. The component (D) may be used alone or in combination of two or more kinds.

[0117] Further, when the component (D) is contained, the content of the component (D) is preferably 0.1 to 5.0 parts by mass, and more preferably 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the resin component in the composition. By configuring in this way, the heat resistance and adhesiveness can be improved satisfactorily.

[0118] 〔Component (E)〕 The component (E) is an inorganic filler. Insulating property and low coefficient of thermal expansion are required for the inorganic filler. As the inorganic filler, general inorganic fillers can be used. For example, inorganic fillers include silica, alumina, 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. The inorganic fillers may be used alone or in combination of two or more. Particularly, from the viewpoint of insulation, silica fillers and alumina fillers are preferred. Also, from the viewpoints of dielectric properties and thermal expansion coefficient, silica fillers are preferred. 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, the inorganic fillers are preferably surface-treated with a surface treatment agent such as an aminosilane-based coupling agent, a ureidosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, a vinylsilane-based coupling agent, a styrylsilane-based coupling agent, an acrylate silane-based coupling agent, an isocyanatosilane-based coupling agent, a sulfidesilane-based coupling agent, an organosilazane compound, a titanate-based coupling agent, etc. to improve their heat resistance, moisture resistance, and dispersibility. These may be used alone or in combination of two or more. More preferably, among the surface-treated silica fillers, it is preferable to use a silica filler surface-treated with a vinylsilane-based coupling agent. By using a silica filler surface-treated with a vinylsilane-based coupling agent, the thermal expansion coefficient can be improved.

[0119] The shape of the inorganic filler is not particularly limited, and examples thereof include spherical, flaky, acicular, and amorphous shapes. From the viewpoint of fluidity, a spherical shape is preferred. The average particle diameter is preferably from 0.1 to 10 μm, more preferably from 0.1 to 4 μm. When the average particle diameter of the inorganic filler is within this range, it has excellent embedding properties between fine structures. The average particle diameter is the particle diameter at 50% of the integrated value in the volume-based particle size distribution measured by the laser diffraction / scattering method. The average particle diameter can be measured, for example, by a laser scattering diffraction method particle size distribution measuring device: LS13320 (manufactured by Beckman Coulter, wet type).

[0120] When the resin composition contains the component (E), it is preferably contained in an amount of 50% by mass or more, more preferably 50 to 90% by mass, and still more preferably 50 to 85% by mass, based on 100% by mass of the non-volatile components in the resin composition. Further, when the content of the component (E) is defined as a ratio to the total amount of the components (A) and (B), it is preferably contained in an amount of 200 parts by mass or more, more preferably 200 to 900 parts by mass, and still more preferably 400 to 900 parts by mass, based on 100 parts by mass in total of the components (A) and (B). By configuring in this way, the coefficient of thermal expansion can be improved favorably.

[0121] 〔Other components〕 The resin composition of the present embodiment may further contain components other than the components (A) to (E) described so far. For example, examples of other components include various additives such as solvents, silane coupling agents, flame retardants, and pigments. Further, in addition to the components (A) to (C), other compounds (for example, other resin components) may be further contained. Examples of other resin components include isocyanuric acid (diallylated isocyanuric acid derivative) from the viewpoint of further improving the embedding property into the substrate, and a commercially available product is "L-DAIC" under the trade name of Shikoku Kasei Kogyo Co., Ltd.

[0122] 〔Properties of resin composition〕 The resin composition of this embodiment preferably has, for example, the following characteristics. The minimum melt viscosity of the resin composition is preferably less than 40,000 Pa·s. By configuring it in this way, the embedability into the substrate becomes extremely good.

[0123] When the resin composition does not contain an inorganic filler as the (E) component, the minimum melt viscosity of the resin composition is more preferably 10 Pa·s or more and less than 40,000 Pa·s, still 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 ratio of the (E) component 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 more preferably 10 Pa·s or more and less than 40,000 Pa·s as in the above-described case, and still more preferably 100 Pa·s or more and less than 30,000 Pa·s.

[0124] On the other hand, when the content ratio of the (E) component in 100% by mass of the non-volatile 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, still 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.

[0125] The minimum melt temperature of the resin composition is preferably less than 200°C, more preferably 80°C or more and less than 200°C, and still more preferably 100°C or more and less than 180°C.

[0126] The minimum melt viscosity (Pa·s) and the minimum melt temperature (°C) of the resin composition can be measured by the following method. First, a solution containing the resin composition is applied onto the peeled PET film by a knife coating method. Then, the solution on the PET film is continuously dried at 80°C for 2 minutes, 100°C for 2 minutes, and 130°C for 2 minutes to produce a resin film with a thickness of 50 μm. The resin films thus produced are laminated to a thickness of 300 μm, and the melt viscosity is measured using a rheometer. The minimum melt viscosity and the minimum melt temperature at that time are read, and the read values are taken as the minimum melt viscosity (Pa·s) and the minimum melt temperature (°C) of the resin composition. The measurement conditions are as follows: using a parallel plate with a diameter of 5 mm, a load of 50 gf, a strain of 1%, a frequency of 10 Hz, and measuring from 50 to 200°C at 5°C / min. The solution (solution containing the resin composition) applied onto the PET film can be prepared by dissolving each component constituting the resin composition in toluene as a solvent. At this time, when the resin composition does not contain an inorganic filler as the (E) component, 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 the (E) component, each component is dissolved and dispersed so that the solid content concentration in the solution is 60% by mass to prepare the solution.

[0127] [Manufacturing method of resin composition] The resin composition of the present embodiment can be manufactured by a conventional method. The resin composition of the present embodiment can be manufactured by mixing the respective components described so far using, for example, a Lycra machine, a pot mill, a three-roll mill, a rotary mixer, a twin-screw mixer, or the like.

[0128] [Uses of resin composition] The resin composition of this embodiment can be suitably used as an adhesive for electronic components or a resin composition for an adhesive film. Further, the resin composition of this embodiment can also be suitably used as an interlayer bonding sheet or an interlayer adhesive for a multilayer wiring board. 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 is no particular limitation on the electronic components to be adhered, and various printed wiring boards such as ceramic substrates and organic substrates, semiconductor chips, semiconductor devices, etc. can be mentioned. Further, 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).

[0129] An adhesive film for interlayer insulation, an interlayer adhesive, etc. using the resin composition of this embodiment are included as a cured product of the resin composition in a laminated substrate or a semiconductor device constituting an electronic component or the like. Therefore, in a laminated substrate or a semiconductor device constituting an electronic component or the like, it is preferable to include a cured product of the resin composition of this embodiment.

[0130] Further, the resin composition of this embodiment can also be used as a prepreg using a cured product of the resin composition and an electronic component for high frequencies having a cured product of the resin composition.

Examples

[0131] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited by these examples in any way. In the following examples, parts and % indicate parts by mass and mass % unless otherwise specified.

[0132] (Examples 1 to 17, Comparative Examples 1 to 7) 〔Sample Preparation〕 After weighing and mixing the respective components so as to have the compounding ratios (parts by mass) shown in Tables 1 to 4 below, they were dissolved in toluene as a solvent to prepare a solution containing the resin compositions of Examples 1 to 17 and Comparative Examples 1 to 7. In the case where the resin composition did not contain an inorganic filler as the component (E) in the solution, the solution was prepared so that the solid content concentration in the solution was 30% by mass. On the other hand, in the case where the resin composition contained an inorganic filler as the component (E), each component was dissolved and dispersed so that the solid content concentration in the solution was 60% by mass to prepare a solution.

[0133] The raw materials used for preparing the solution containing the resin composition in Examples 1 to 17 and Comparative Examples 1 to 7 are as follows.

[0134] [Component (A)] A1(1): Modified polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Company, Inc., trade name "OPE2St-2200", number average molecular weight (Mn) = 2200, having a vinylbenzyl group at the terminal. A1(2): Modified polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Company, Inc., trade name "OPE2St-1200", number average molecular weight (Mn) = 1200, having a vinylbenzyl group at the terminal. A2(1): Maleimide resin manufactured by K.I. Kasei Co., Ltd., trade name "BMI70". A2(2): Maleimide resin (solid content 60%, toluene solution product) manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-5000-60T".

[0135] [Component (A')] A1': Modified polyphenylene ether resin manufactured by SABIC, trade name "SA-9000", number average molecular weight (Mn) = 1700, having a methacryl group at the terminal.

[0136] [Component (B)] B1(1): Butadiene resin manufactured by Nippon Soda Co., Ltd., trade name "B-1000", number average molecular weight (Mn) = 1200, (1,2 vinyl structure 85%). B1(2): Butadiene resin manufactured by Nippon Soda Co., Ltd., trade name "B-3000", number average molecular weight (Mn) = 3200, (1,2 vinyl structure 92%). 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%). B2(1): Manufactured by Nippon Soda Co., Ltd., trade name "1,2-SBS-L42", number average molecular weight (Mn) = 4300, styrene-butadiene block copolymer (styrene 20%, 1,2 vinyl structure 90%). B2(2): Manufactured by Nippon Soda Co., Ltd., trade name "1,2-H-SBS-L", number average molecular weight (Mn) = 4300, styrene-butadiene block copolymer (styrene 20%, 1,2 vinyl structure 30%). B3: Manufactured by CRAY VALLEY, trade name "Ricon100", number average molecular weight (Mn) = 4500, styrene-butadiene copolymer (1,2 vinyl structure 70%).

[0137] 〔Other resin components〕 Manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name "L-DAIC", isocyanuric acid (diallylated isocyanuric acid derivative).

[0138] 〔Component (C)〕 C1: Manufactured by Kraton Polymers, trade name "G1652", number average molecular weight (Mn): 54,000, thermoplastic elastomer (SEBS: styrene 30%). C2: Manufactured by Asahi Kasei Corporation, trade name "P1500", number average molecular weight (Mn): 49,000, thermoplastic elastomer (SBBS: styrene 30%). C3: Manufactured by ENEOS MATERIALS, trade name "TR2003", number average molecular weight (Mn): 100,000, styrene-butadiene block copolymer (styrene 43%).

[0139] 〔Component (D)〕 D1: Manufactured by NOF Corporation, trade name "Parkmill D", organic peroxide.

[0140] 〔Component (E)〕 E1: Manufactured by Admatechs Co., Ltd., trade name "20SV-C9", silica filler (average particle size 2μm, vinyl silane surface treatment). E2: Manufactured by Admatechs Co., Ltd., product name "SC4050SX", silica filler (average particle size 1 μm, aminopropylsilane surface treatment). E3: Manufactured by Denka Co., Ltd., product name "FB-3SDXHOL2", silica filler (average particle size 3 μm, vinylsilane surface treatment).

[0141] In the columns of "Total resin components (A + B + C + other resins)" in Tables 1 to 4, the total amounts (parts by mass) of component (A), component (B), component (C), and other resin components in the raw materials used for the preparation of the resin composition are shown. In the columns of "Amount of filler (parts by mass) based on 100 parts by mass of the total of (A + B)" in Tables 2 to 3, the ratio (parts by mass) of component (E) to 100 parts by mass of the total of component (A) and component (B) used for the preparation of the resin composition is shown.

[0142] Regarding the solution containing the resin compositions of Examples 1 to 17 and Comparative Examples 1 to 7 obtained as described above, the "minimum melt viscosity (Pa·s)" and the "minimum melt temperature (°C)" were measured by the method shown below. The results are shown in Tables 1 to 4.

[0143] Also, regarding the solution containing the resin compositions of Examples 6 to 17 and Comparative Examples 3 to 7, the "copper foil peel strength M (N / cm)" and the "copper foil peel strength S (N / cm)" were measured by the method shown below. The results are shown in Tables 2 to 4.

[0144] Furthermore, regarding the solution containing the resin compositions of Examples 6 to 8, as an evaluation of "heat resistance reliability", the evaluation and measurement of "dielectric constant (ε)" and "dissipation factor (tanδ)" were performed by the method shown below. The results are shown in Table 4.

[0145] [Production of resin film] First, a solution containing the resin composition was applied onto the peeled PET film by a knife method. 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.

[0146] [Minimum melt viscosity (Pa·s), minimum melt temperature (°C)] The produced resin film was laminated to a thickness of 300 μm, and the melt viscosity was measured using a rheometer. The minimum melt viscosity and the minimum melt temperature at that time were read, and the read values were taken as the minimum melt viscosity (Pa·s) and the minimum melt temperature (°C) of the resin composition. The measurement conditions were as follows: using a parallel plate with a diameter of 5 mm, a load of 50 gf, a strain of 1%, a frequency of 10 Hz, and measuring from 50 to 200 °C at a rate of 5 °C / min.

[0147] 〔Copper foil peel strength M (N / cm)〕 The produced resin film was sandwiched between the roughened surfaces of copper foils with a thickness of 18 μm, cured at 200 °C for 60 minutes under a pressure of 1 MPa, and a double-sided copper-clad plate was produced. The produced double-sided copper-clad plate was cut into strips 1 cm wide, and the strength when one-sided copper foil was peeled off in the 180-degree direction was measured. The measurement condition was a tensile speed of 50 mm / min.

[0148] 〔Copper foil peel strength S (N / cm)〕 The produced resin film was sandwiched between the shiny surfaces of copper foils with a thickness of 18 μm, cured at 200 °C for 60 minutes under a pressure of 1 MPa, and a double-sided copper-clad plate was produced. The produced double-sided copper-clad plate was cut into strips 1 cm wide, and the strength when one-sided copper foil was peeled off in the 180-degree direction was measured. The measurement condition was a tensile speed of 50 mm / min.

[0149] 〔Heat resistance reliability〕 The prepared resin film was cured at 200 °C for 60 minutes under 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 by the dielectric resonator method (SPDR method). Each value measured after the test piece was prepared as described above was taken as the initial value before the heat resistance test. The results are shown in the "Initial value" column of Table 4. Next, the sample was placed in an oven heated to 125 °C for 24 hours, and then the sample was taken out of the oven and cooled to room temperature. For the sample cooled to room temperature, the dielectric constant (ε) and dielectric loss tangent (tanδ) were measured in the same manner as the method described above. The values measured in this way were taken as the measured values after the heat resistance test and are shown in the column of "After 125 °C × 24 h" in Table 4. Also, for the values of the dielectric constant (ε) and dielectric loss tangent (tanδ) measured before and after the heat resistance test, the value obtained by subtracting the initial value from the measured value after the heat resistance test was taken as the "change amount relative to the initial value". Furthermore, the percentage of the value obtained by dividing the "change amount relative to the initial value" by the initial value was taken as the "change amount relative to the initial value (%)". Each result is shown in Table 4. The measurement by the dielectric resonator method was carried out at a measurement frequency of 20 GHz.

[0150] Also, for some of the examples among Examples 6 to 17 and Comparative Examples 3 to 7, the evaluation and measurement of the "thermal expansion coefficient (ppm / K)", "thermal expansion coefficient (thickness) (ppm / K)", and "solder heat resistance" were carried out by the method shown below. Also, for Examples 6 to 16 and Comparative Examples 3 to 7, the measurement of the initial values of the dielectric constant (ε) and dielectric loss tangent (tanδ) in the above-mentioned heat resistance reliability was carried out. Furthermore, for Examples 9 to 16 and Comparative Examples 3 to 7, the measurement frequency by the dielectric resonator method was changed to 10 GHz, and the measurement of the initial values of the dielectric constant (ε) and dielectric loss tangent (tanδ) in the above-mentioned heat resistance reliability was carried out.

[0151] 〔Thermal expansion coefficient (ppm / K)〕 The fabricated resin films were laminated to a thickness of 100 μm and cured at a temperature of 200 °C for 60 minutes under a pressure of 1 MPa to prepare a sample for measuring the coefficient of thermal expansion. For the prepared sample, measurement was performed by the tensile method using a TMA (Thermomechanical Analyzer), and the average coefficient of thermal expansion from 90 to 100 °C was taken as the reading value (i.e., the measured value of the coefficient of thermal expansion). The measurement conditions were as follows: After annealing to 230 °C at a tensile load of 2 gf and a rate of 20 °C / min, it was once returned to room temperature, and then measured up to 230 °C at a rate of 5 °C / min. The measured coefficient of thermal expansion is the coefficient of thermal expansion in the plane direction (i.e., the XY direction).

[0152] [Coefficient of Thermal Expansion (Thickness) (ppm / K)] The fabricated resin films were laminated to a thickness of approximately 2 mm and cured at a temperature of 200 °C for 60 minutes under a pressure of 1 MPa to prepare a sample for measuring the coefficient of thermal expansion (thickness). For the prepared sample, measurement was performed by the compression method using a TMA (Thermomechanical Analyzer), and the average coefficient of thermal expansion from 90 to 100 °C was taken as the reading value (i.e., the measured value of the coefficient of thermal expansion (thickness)). The measurement conditions were as follows: After annealing to 250 °C at a compression load of 1 gf and a rate of 20 °C / min, it was once returned to room temperature, and then measured up to 250 °C at a rate of 5 °C / min. The coefficient of thermal expansion is the coefficient of thermal expansion in the thickness direction (i.e., the Z direction).

[0153] [Soldering Heat Resistance] After attaching copper foils to both sides of the fabricated adhesive film, test pieces were prepared by cutting them into squares of 2 cm × 2 cm. The prepared test pieces were floated in a solder bath heated to 260, 270, 280, 290, and 300 °C for 1 minute, and their appearance was visually confirmed. The temperature (highest temperature) of the solder bath at which no change was observed in the appearance was taken as the evaluation value of soldering heat resistance.

[0154] [Table 1]

[0155] [Table 2]

[0156]

Table 3

[0157]

Table 4

[0158] 〔Results〕 As shown in Table 1, the resin compositions of Examples 1 to 5 had a lower minimum melt viscosity and a lower minimum melt temperature compared to the resin composition of Comparative Example 2. Note that it was impossible to measure the minimum melt viscosity and the minimum melt temperature of the resin composition of Comparative Example 1.

[0159] As shown in Tables 2 to 3, the resin compositions of Examples 9 to 17 had an extremely low minimum melt viscosity 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 the (E) component, and the resin compositions of Comparative Examples 3 to 7 showed a very high minimum melt viscosity. On the other hand, since 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 the (A) component, an increase in the minimum melt viscosity was suppressed, and they were excellent in embeddability into the substrate.

[0160] Also, the resin compositions of Examples 9 to 17 showed good values for the copper foil peel strength M (N / cm) and the copper foil peel strength S (N / cm), and had excellent adhesiveness. Further, the resin compositions of Examples 9 to 16 also showed good results in terms of the coefficient of thermal expansion and heat resistance to solder. For example, the coefficients of thermal expansion (ppm / K) of the resin compositions of Examples 9 to 16 were 102, 123, 46, 50, 56, 44, 50, 55 in sequence (all units are ppm / K). Also, the coefficients of thermal expansion (thickness) (ppm / K) of the resin compositions of Examples 9 to 16 were 39, 55, 46, 56, 50, 38, 42, 59 in sequence (all units are ppm / K).

[0161] 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, and dielectric tangents (tanδ) of 0.0014, 0.0015, 0.0013, 0.0011, 0.0015, and 0.0014, respectively, at a measurement frequency of 10 GHz. The resin compositions of Examples 13 to 16 had dielectric constants (ε) of 3.01, 3.08, 3.07, and 3.09, and dielectric tangents (tanδ) of 0.0016, 0.0015, 0.0015, and 0.0013, respectively, at a measurement frequency of 20 GHz. Also, the resin compositions of Examples 9 to 14 showed good values at 300 °C or 290 °C in the evaluation of solder heat resistance.

[0162] The resin composition of Example 17 does not contain other resin components and is a resin composition containing component (A) and component (B) as resin components. Also, the resin composition of Example 17 does not contain an inorganic filler as component (E). Such a resin composition of Example 17 also had a low minimum melt viscosity and a low minimum melt temperature. The resin composition of Example 17 had a coefficient of thermal expansion (ppm / K) of 102 ppm / K and a coefficient of thermal expansion (thickness) (ppm / K) of 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).

[0163] On the other hand, the resin compositions of Comparative Examples 3 to 7 had coefficients of thermal expansion (ppm / K) of 51, 35, 36, 51, and 50, and coefficients of thermal expansion (thickness) (ppm / K) of 37, 47, 29, 37, and 64, respectively (all units are ppm / K). Also, the resin compositions of Comparative Examples 3 to 7 had dielectric constants (ε) of 3.12, 3.06, 3.11, 3.12, and 3.12, and dielectric tangents (tanδ) of 0.0014, 0.0012, 0.0013, 0.0014, and 0.0019, respectively, at a measurement frequency of 10 GHz. Also, the resin composition of Comparative Example 7 showed a low value of 270 °C in the evaluation of solder heat resistance.

[0164] As shown in Table 4, the resin composition of Example 6 uses a styrene-butadiene block copolymer as the (B2) component as the (B) component. The resin composition of Example 8 uses a butadiene resin as the (B1) component as the (B) component. The resin composition of Example 7 uses a styrene-butadiene copolymer as the (B3) component as the (B) component. When comparing the resin compositions of Examples 6 to 8, the resin composition of Example 6 using a styrene-butadiene block copolymer as the (B2) component has good heat resistance reliability (change rate of tanδ) compared to other (B) components, and also shows good results for the peel strength M with respect to the matte surface (M surface) of the electrolytic copper foil. The resin compositions of Examples 6 to 8 had thermal expansion coefficients (ppm / K) of 149, 146, and 154 in sequence, and thermal expansion coefficients (thickness) (ppm / K) of 194, 207, and 196 in sequence (all units are ppm / K).

Industrial Applicability

[0165] 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 an interlayer bonding sheet or interlayer adhesive for multilayer wiring boards. Further, the resin composition of the present invention can also be used as a prepreg using a cured product of the resin composition or an electronic component for high frequencies 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 with a 1,2-vinyl group; (C) A thermoplastic elastomer component, and comprising: The number average molecular weight of the component (B) is from 1,000 to 10,000; When the thermoplastic elastomer component (C) is a compound having a butadiene skeleton with a 1,2-vinyl group, its number average molecular weight exceeds 10,000 and is 1,000,000 or less; The resin composition contains 10 to 200 parts by mass of the component (B) with respect to 100 parts by mass of the component (A) (however, a thermosetting resin composition containing an uncured semi-IPN type composite and a radical reaction initiator, the uncured semi-IPN type composite is a polyphenylene ether, and 1,2-butadiene units having a 1,2-vinyl group in the side chain are contained in the molecule by 40% or more and are not chemically modified. An uncured semi-IPN type composite formed by compatibilizing a butadiene polymer and a prepolymer formed from a crosslinking agent, and excluding a resin composition in which the radical reaction initiator contains a dialkyl peroxide-based radical reaction initiator and a hydroperoxide-based radical reaction initiator).

2. (A) A thermosetting resin having at least one of a vinylbenzyl group and a maleimide group; (B) A compound having a butadiene skeleton with a 1,2-vinyl group, and comprising: The number average molecular weight of the component (B) is from 1,000 to 10,000; The component (B) contains (B2) a styrene-butadiene block copolymer; The resin composition contains 10 to 200 parts by mass of the component (B) with respect to 100 parts by mass of the component (A) (however, a thermosetting resin composition containing an uncured semi-IPN type composite and a radical reaction initiator, the uncured semi-IPN type composite is a polyphenylene ether, and 1,2-butadiene units having a 1,2-vinyl group in the side chain are contained in the molecule by 40% or more and are not chemically modified. An uncured semi-IPN type composite formed by compatibilizing a butadiene polymer and a prepolymer formed from a crosslinking agent, and excluding a resin composition in which the radical reaction initiator contains a dialkyl peroxide-based radical reaction initiator and a hydroperoxide-based radical reaction initiator).

3. The resin composition according to claim 1 or 2, wherein the minimum melt viscosity of the resin composition is less than 40,000 Pa·s.

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

5. The resin composition according to claim 1, wherein the component (B) is a compound having a styrene skeleton.

6. The resin composition according to claim 1, wherein the component (B) is a styrene-butadiene block copolymer.

7. The resin composition according to claim 1 or 2, wherein the component (B) is a styrene-butadiene-styrene block copolymer represented by the following structural formula (1) or a hydrogenated product thereof. 【Chemical 1】 (However, 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 o:p:q = 1 to 20:60 to 98:1 to 20 is satisfied, and the relationship m:n = 100:0 to 80:20 is satisfied.)

8. The resin composition according to claim 1 or 2, wherein the 1,2-vinyl structure in the butadiene skeleton of the component (B) is 5 to 95% by mass.

9. The resin composition according to claim 1 or 2, further comprising a (D) reaction accelerator component.

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

11. The resin composition according to claim 1 or 2, further comprising an (E) inorganic filler.

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 based on 100 parts by mass in total of the component (A) and the component (B).

14. The resin composition according to claim 1 or 2, wherein the minimum melting temperature of the resin composition is less than 200°C.

15. An adhesive film comprising the resin composition according to claim 1 or 2.

16. The adhesive film according to claim 15, which is for interlayer insulation.

17. A laminated substrate comprising the resin composition according to claim 1 or 2.

18. A laminated substrate comprising a cured product of the adhesive film for interlayer insulation according to claim 16.

19. An electronic component comprising the laminated substrate according to claim 18.

20. A semiconductor device comprising the laminated substrate according to claim 18.

21. A semiconductor device comprising the electronic component according to claim 19.

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