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

Abstract

The present invention relates to a resin composition, a resin film using the same, a printed wiring board, and a semiconductor package, the resin composition containing: (A) a thermosetting resin; (B) a compound that is liquid at 25 DEG C, has a reactive group, and has a molecular weight of 1000 or less; (C) an elastomer having a reactive group and a molecular weight exceeding 1000; and (D) an inorganic filler.

Description

Technical Field

[0001] The present embodiment relates to a resin composition, a resin film, a printed wiring board, and a semiconductor package. Background Art

[0002] In recent years, due to the miniaturization and performance improvement of electronic devices, the wiring density and integration have been increasing in the field of printed wiring boards and semiconductor packages.

[0003] In these electronic devices, insulating materials such as thermosetting resins can be used as sealing materials for semiconductor chips and substrate materials for printed circuit boards. However, when mounting components, stress caused by the difference in thermal expansion coefficients between the insulating material and the semiconductor chip can sometimes become a problem. The stress generated here can cause warping of the semiconductor package, which is a major cause of reduced reliability.

[0004] Therefore, as a method of making the thermal expansion coefficient of the insulating material close to the thermal expansion coefficient of the semiconductor chip, a method of mixing an inorganic filler into the insulating material has been developed.

[0005] Patent Document 1 discloses a thermosetting resin composition that is a cured product having low thermal expansion and low hygroscopicity. The composition comprises an epoxy resin composition and an inorganic filler. The epoxy resin composition comprises a biphenyl-type epoxy resin monomer, and the biphenyl content in the epoxy resin composition is 31% by weight or more.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2001-302758 Summary of the invention

[0009] Problems to be solved by the invention

[0010] However, when the resin composition is made into a resin film having a thickness that can seal a semiconductor chip, cracks sometimes occur in the resin film during processing. This problem is particularly prone to occur when using a thermosetting resin that is easy to obtain high heat resistance, and when using an inorganic filler material that contributes to low thermal expansion. In order to solve the above problems, it is considered effective to improve the flexibility of the resin composition used to form the resin film. It should be noted that the "flexibility of the resin composition" in this specification refers to the flexibility of the resin composition when it is solid at room temperature (25°C) by drying the organic solvent when the resin composition contains an organic solvent and the like and is in a liquid state.

[0011] As the method for the flexibility of the resin combination when improving the solid state, it is possible to consider making a small amount of the method for the organic solvent containing the degree that can keep solid in the resin combination. However, the resin combination comprising a small amount of organic solvent sometimes produces space in the cured product or appears concavo-convex on the surface of the cured product due to the volatilized organic solvent when heat-curing. In addition, since the organic solvent volatilizes in the heat-curing, it is also necessary to equip the operating environment with higher safety. The thickness of the resin film is larger, and these problems are more obvious, so it is desired to improve.

[0012] Furthermore, in recent years, demands for improved reliability of printed wiring boards and the like have further increased, and it has been desired to further improve low thermal expansion properties while improving the flexibility of the resin composition.

[0013] In view of such a situation, the subject of the present embodiment is to provide: a resin composition whose cured product has excellent low thermal expansion, excellent flexibility in a solid state, and can suppress the generation of volatile components during heat curing; a resin film using the resin composition; a printed wiring board; and a semiconductor package.

[0014] Means for solving problems

[0015] The present inventors have studied to solve the above-mentioned problems, and as a result, have found that the problems can be solved by the present embodiment described below.

[0016] That is, this embodiment relates to the following [1] to

[16] .

[0017] [1] A resin composition comprising:

[0018] (A) Thermosetting resin;

[0019] (B) a compound that is liquid at 25°C, has a reactive group and has a molecular weight of 1000 or less;

[0020] (C) an elastomer having a reactive group and a molecular weight exceeding 1000; and

[0021] (D) Inorganic filling materials.

[0022] [2] The resin composition according to [1] above, wherein the component (A) is one or more selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin.

[0023] [3] The resin composition according to [2], wherein the maleimide resin having one or more N-substituted maleimide groups is a maleimide resin having a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups.

[0024] [4] The resin composition according to any one of [1] to [3], wherein the component (B) has, as the reactive group, one or more selected from a functional group containing an ethylenically unsaturated bond, an epoxy group, a hydroxyl group, a carboxyl group and an amino group.

[0025] [5] The resin composition according to any one of [1] to [4], wherein the component (B) has two or more of the reactive groups in one molecule.

[0026] [6] The resin composition according to any one of [1] to [5], wherein the component (B) is a di(meth)acrylate.

[0027] [7] The resin composition according to any one of [1] to [6], wherein the content of the component (B) is 0.5 to 20% by mass relative to the total solid content (100% by mass) of the resin composition.

[0028] [8] The resin composition according to any one of [1] to [7], wherein the reactive group contained in the component (C) is at least one selected from a functional group containing an ethylenically unsaturated bond and an acid anhydride group.

[0029] [9] The resin composition according to any one of [1] to [8], which is used for forming a resin film having a thickness of 80 μm or more.

[0030]

[10] A resin film comprising the resin composition according to any one of [1] to [9].

[0031]

[11] The resin film according to the above

[10] , wherein the thickness is 80 μm or more.

[0032]

[12] The resin film according to

[10] or

[11] above, which is a resin film with a thickness of 150 μm or more, and the relative dielectric constant (Dk) of the cured product of the resin film at 10 GHz is less than 2.8, and the dielectric loss tangent (Df) is less than 0.0030.

[0033]

[13] The resin film according to any one of

[10] to

[12] , wherein the mass reduction rate after heat drying at 170° C. for 30 minutes in an air atmosphere is 2.0 mass % or less.

[0034]

[14] A printed wiring board comprising a cured product of the resin film according to any one of

[10] to

[13] above.

[0035]

[15] A semiconductor package comprising a cured product of the resin film according to any one of

[10] to

[13] above.

[0036]

[16] The semiconductor package according to

[15] above, comprising a semiconductor chip sealed with the cured product of the resin film.

[0037] Effects of the Invention

[0038] According to this embodiment, there can be provided: a resin composition whose cured product has excellent low thermal expansion, excellent flexibility in a solid state, and can suppress the generation of volatile components during heat curing; a resin film using the resin composition; a printed wiring board; and a semiconductor package. DETAILED DESCRIPTION

[0039] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0040] For example, a numerical range such as "X to Y" (X, Y are real numbers) refers to a numerical range greater than X and less than Y. Also, a description such as "greater than X" in this specification refers to X and a numerical value greater than X. In addition, a description such as "less than Y" in this specification refers to Y and a numerical value less than Y.

[0041] The lower limit and the upper limit of the numerical range described in the present specification can be arbitrarily combined with the lower limit or the upper limit of other numerical ranges, respectively.

[0042] In the numerical range described in the present specification, the lower limit value or the upper limit value of the numerical range may be replaced with the value shown in the Examples.

[0043] Unless otherwise specified, each component and material exemplified in the present specification may be used alone or in combination of two or more.

[0044] In the present specification, when there are plural substances corresponding to each component in the resin composition, the content of each component in the resin composition refers to the total amount of the plural substances present in the resin composition unless otherwise specified.

[0045] In this specification, "resin composition" refers to a mixture containing at least two or more components of resins, and when the resin is a thermosetting resin, it also includes a material in which the mixture is in a B-stage state. The type and content of each component in the resin composition in a B-stage state refer to the type and content of each component before the B-stage state is formed, that is, the type and amount of the component mixed when the resin composition is produced.

[0046] In this specification, "solid content" refers to components other than solvents, and also includes substances that are liquid, syrupy, and waxy at room temperature. Here, in this specification, room temperature means 25°C.

[0047] In this specification, "(meth)acrylate" refers to "acrylate" and its corresponding "methacrylate". Similarly, "(meth)acrylic acid" refers to "acrylic acid" and its corresponding "methacrylic acid", and "(meth)acryloyl" refers to "acryloyl" and its corresponding "methacryloyl".

[0048] The "molecular weight" of a compound in this specification refers to a molecular weight that can be calculated from the structural formula when the compound is not a polymer but the structural formula of the compound can be determined, and refers to a number average molecular weight when the compound is a polymer.

[0049] The number average molecular weight in this specification refers to a value measured by gel permeation chromatography (GPC) and converted to polystyrene. Specifically, the number average molecular weight in this specification can be measured by the method described in Examples.

[0050] The mechanism of action described in this specification is a guess, and does not limit the mechanism by which the effect of the resin composition of the present embodiment is exerted.

[0051] Any combination of the matters described in this specification is also included in this embodiment.

[0052] [Resin composition]

[0053] The resin composition of this embodiment contains:

[0054] (A) Thermosetting resin;

[0055] (B) a compound that is liquid at 25°C, has a reactive group and has a molecular weight of 1000 or less;

[0056] (C) an elastomer having a reactive group and a molecular weight exceeding 1000; and

[0057] (D) Inorganic filling materials.

[0058] In addition, in this specification, each component may be abbreviated as (A) component, (B) component, etc., respectively, and the same abbreviation method may be used for other components.

[0059] In addition, (B) a compound that is liquid at 25°C, has a reactive group and has a molecular weight of 1000 or less is sometimes referred to as a "(B) reactive liquid compound", and (C) an elastomer that has a reactive group and has a molecular weight exceeding 1000 is sometimes referred to as a "(C) reactive elastomer".

[0060] Hereinafter, each component which the resin composition of this embodiment may contain is demonstrated sequentially.

[0061] In the present embodiment, being in a liquid state at 25° C. means that the viscosity calculated by the following measurement method is 100,000 mPa·s or less.

[0062] <Viscosity measurement method>

[0063] Device: E-type viscometer

[0064] Conical rotor: 1°34'×R24

[0065] Temperature: 25℃

[0066] Sample volume: 1.0 mL

[0067] Speed: 20rpm

[0068] Hereinafter, in this specification, the viscosity at 25° C. means the viscosity measured by the above-mentioned method.

[0069] The reasons why the cured product of the resin composition of the present embodiment has excellent low thermal expansion, excellent flexibility in a solid state, and can suppress generation of volatile components during heat curing are presumed as follows.

[0070] The resin composition of the present embodiment contains (B) a compound that is liquid at 25° C. and has a molecular weight of 1000 or less as a component for improving the flexibility of the resin composition. It is believed that the reactive liquid compound (B) is a liquid component with a relatively low molecular weight, and therefore can penetrate well into the molecules of the resin component, effectively weakening the intermolecular interaction of the resin component, thereby improving the flexibility of the resin composition.

[0071] In addition, since the (B) reactive liquid compound has a reactive group, the (B) reactive liquid compound reacts with each other or with other components during the heat curing of the (A) thermosetting resin. That is, the (B) reactive liquid compound helps to improve flexibility and suppresses volatilization through the curing reaction. Therefore, it is believed that the resin composition of the present embodiment can suppress the generation of volatile components and improve flexibility compared to the case where an organic solvent or the like is used as a component for improving flexibility.

[0072] Furthermore, it is presumed that the resin composition of the present embodiment can form crosslinking points while maintaining flexibility by containing the (C) reactive elastomer, and thus can reduce the linear expansion coefficient of the cured product.

[0073] Hereinafter, each component which the resin composition of this embodiment may contain is demonstrated sequentially.

[0074] <(A) Thermosetting resin>

[0075] The resin composition of the present embodiment contains (A) a thermosetting resin.

[0076] (A) Thermosetting resins may be used alone or in combination of two or more.

[0077] (A) Thermosetting resins include, for example, epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins.

[0078] Among them, the (A) thermosetting resin is preferably a maleimide resin from the viewpoint of heat resistance, and more preferably at least one selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin.

[0079] In the following description, “one or more selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin” may be referred to as “maleimide-based resin”.

[0080] In the following description, a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin (AX)" or a "component (AX)".

[0081] In addition, a derivative of a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin derivative (AY)" or a "(AY) component".

[0082] (Maleimide resin (AX))

[0083] The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups.

[0084] From the viewpoint of conductor adhesion and heat resistance, the maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups.

[0085] It should be noted that, in this specification, "aromatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aromatic ring. In addition, in this specification, "aromatic bismaleimide resin" refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, "aromatic polymaleimide resin" refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring.

[0086] In addition, in this specification, "aliphatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0087] As the maleimide resin (AX), from the viewpoints of dielectric properties, conductor adhesion and heat resistance, a maleimide resin having a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups (hereinafter, sometimes referred to as "maleimide resin (A1)" or "(A1) component"). ] is preferred.

[0088] [Maleimide resin (A1)]

[0089] The maleimide resin (A1) is preferably an aromatic maleimide resin having a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups from the viewpoint of dielectric properties, conductor adhesion and heat resistance.

[0090] The maleimide resin (A1) is more preferably an aromatic bismaleimide resin having a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two N-substituted maleimide groups.

[0091] From the viewpoints of dielectric properties, conductor adhesion and ease of production, the condensed ring contained in the maleimide resin (A1) preferably has a condensed bicyclic structure, and more preferably an indane ring.

[0092] As the maleimide resin (A1) containing an indane ring, an aromatic bismaleimide resin containing an indane ring is preferred.

[0093] It should be noted that, in this specification, the indane ring refers to a fused bicyclic structure of an aromatic 6-membered ring and a saturated aliphatic 5-membered ring. At least one of the ring-forming carbon atoms forming the indane ring has a bonding group for bonding to other groups constituting the maleimide resin (A1). The ring-forming carbon atom having the bonding group and other ring-forming carbon atoms may not have a bonding group, a substituent, etc. in addition to the above-mentioned bonding group, but preferably a divalent group is formed by having a bonding group other than the above-mentioned.

[0094] In the maleimide resin (A1), the indane ring is preferably contained in the form of a divalent group represented by the following general formula (A1-1).

[0095] [Chemical formula 1]

[0096]

[0097] (Where R a1 It is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. a1 is an integer from 0 to 3. a2 ~R a4 Each independently represents an alkyl group having 1 to 10 carbon atoms. * represents a bonding site. )

[0098] As R in the above general formula (A1-1) a1 Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. These alkyl groups may be linear or branched.

[0099] As R a1 Examples of the alkyl group contained in the alkoxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms shown in the foregoing examples include the same groups as those for the alkyl group having 1 to 10 carbon atoms.

[0100] As R a1 Examples of the aryl group having 6 to 10 carbon atoms include phenyl and naphthyl.

[0101] As R a1 Examples of the aryl group contained in the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms shown in the above-mentioned example include the same groups as those mentioned above for the aryl group having 6 to 10 carbon atoms.

[0102] As R a1 Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.

[0103] In the above general formula (A1-1), n a1 When R is an integer of 1 to 3, from the viewpoint of solvent solubility and reactivity, a1 An alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0104] As R a2 ~R a4 The alkyl group having 1 to 10 carbon atoms represented by a1 The same alkyl group. a2 ~R a4 An alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is further preferred.

[0105] In the above general formula (A1-1), n a1 is an integer from 0 to 3, n a1 If the value is 2 or 3, multiple R a1 They can be the same or different from each other.

[0106] Among the above, from the viewpoint of ease of production, the divalent group represented by the general formula (A1-1) is preferably n a1 0, R a2 ~R a4 The divalent group represented by the following formula (A1-1a) which is a methyl group is more preferably a divalent group represented by the following formula (A1-1 a′) or a divalent group represented by the following formula (A1-1a″).

[0107] [Chemical formula 2]

[0108]

[0109] (Wherein, * indicates the bonding site.)

[0110] As the maleimide resin (A1) containing a divalent group represented by the general formula (A1-1), a maleimide resin represented by the following general formula (A1-2) is preferred from the viewpoints of dielectric properties, conductor adhesion, heat resistance and ease of production.

[0111] [Chemical formula 3]

[0112]

[0113] (Where R a1 ~R a4 and n a1 and R in the above general formula (A1-1) a1 ~R a4 and n a1 Same. a5 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group. a2 Each independently represents an integer from 0 to 4.a3 A number between 0.95 and 10.0.)

[0114] In the above general formula (A1-2), a plurality of R a1 Each other, multiple n a1 Each other, multiple R a5 Each other, multiple n a2 They may be the same as or different from each other.

[0115] In n a3 If more than 1, multiple R a2 Each other, multiple R a3 Each other and multiple R a4 They may be the same as or different from each other.

[0116] As R in the above general formula (A1-2) a5 The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the alkylthio group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms, the arylthio group having 6 to 10 carbon atoms and the cycloalkyl group having 3 to 10 carbon atoms represented by the alkyl group include the same as the above R a1 The same groups are preferred.

[0117] In the above general formula (A1-2), n a2 It is an integer of 0 to 4, and is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 2, from the viewpoint of compatibility with other resins, dielectric properties, conductor adhesion, and ease of production.

[0118] It should be noted that by making n a2 When n is 1 or more, the benzene ring and the N-substituted maleimide group have a distorted conformation, and the intermolecular stacking is suppressed, thereby tending to further improve the solvent solubility. From the viewpoint of suppressing intermolecular stacking, a2 When R is greater than 1, a5 The substitution position is preferably the ortho position relative to the N-substituted maleimide group.

[0119] From the viewpoints of dielectric properties, conductor adhesion, solvent solubility, handling properties, and heat resistance, n in the general formula (A1-2) is a3 It is preferably a number of 0.98 to 8.0, more preferably a number of 1.0 to 7.0, and still more preferably a number of 1.1 to 6.0. a3 The average value of the number of structural units containing an indane ring is shown.

[0120] From the viewpoints of dielectric properties, conductor adhesion, solvent solubility and ease of production, the maleimide resin (A1) represented by the above general formula (A1-2) is more preferably a maleimide resin represented by the following general formula (A1-3) or a maleimide resin represented by the following general formula (A1-4).

[0121] [Chemical formula 4]

[0122]

[0123] (Where R a1 ~R a5 and n a1 and n a3 and R in the above general formula (A1-2) a1 ~R a5 and n a1 and n a3 same.)

[0124]

[0125] (Where R a1 ~R a4 and n a1 and n a3 and R in the above general formula (A1-2) a1 ~R a4 and n a1 and n a3 same.)

[0126] Examples of the maleimide resin (A1) represented by the general formula (A1-3) include a maleimide resin represented by the following general formula (A1-3-1), a maleimide resin represented by the following general formula (A1-3-2), and a maleimide resin represented by the following general formula (A1-3-3).

[0127] [Chemical formula 5]

[0128]

[0129] (where n a3 With the above general formula (A1-2) in n a3 same.)

[0130] The maleimide resin (A1) represented by the general formula (A1-4) is more preferably a maleimide resin represented by the following general formula (A1-4-1) from the viewpoints of dielectric properties, conductor adhesion, solvent solubility, and ease of production.

[0131] [Chemical formula 6]

[0132]

[0133] (where n a3 With the above general formula (A1-2) in n a3 same.)

[0134] The number average molecular weight of the maleimide resin (A1) is not particularly limited, but is preferably 600 to 3000, more preferably 800 to 2000, and even more preferably 1000 to 1500 from the viewpoint of compatibility with other resins, conductor adhesion, and heat resistance.

[0135] The maleimide resin (AX) may be a maleimide resin (A2) other than the maleimide resin (A1) [hereinafter, sometimes referred to as "maleimide resin (A2)" or "component (A2)".].

[0136] [Maleimide resin (A2)]

[0137] As the maleimide resin (A2), a maleimide resin represented by the following general formula (A2-1) is preferred.

[0138] [Chemical formula 7]

[0139]

[0140] (Where X a11 It is a divalent organic group that does not contain a condensed ring of an aromatic ring and an aliphatic ring.)

[0141] X in the above general formula (A2-1) a11 It is a divalent organic group not including a condensed ring of an aromatic ring and an aliphatic ring.

[0142] As X in the above general formula (A2-1) a11 Examples of the divalent organic group represented include a divalent group represented by the following general formula (A2-2), a divalent group represented by the following general formula (A2-3), a divalent group represented by the following general formula (A2-4), a divalent group represented by the following general formula (A2-5), and a divalent group represented by the following general formula (A2-6).

[0143] [Chemical formula 8]

[0144]

[0145] (Where R a11 It is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a11 is an integer from 0 to 4. * indicates a bonding site. )

[0146] As R in the above general formula (A2-2) a11The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by the above-mentioned group includes, for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is further preferred.

[0147] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0148] In the above general formula (A2-2), n a11 It is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of easy availability.

[0149] In n a11 When the integer is 2 or more, multiple R a11 They can be the same or different from each other.

[0150] [Chemical formula 9]

[0151]

[0152] (Where R a12 and R a13 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a12 It is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (A2-3-1). a12 and n a13 Each independently represents an integer from 0 to 4.

[0153] *Indicates bonding location. )

[0154] As R in the above general formula (A2-3) a12 and R a13 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by can be exemplified by the above R a11 Same group.

[0155] As X in the above general formula (A2-3) a12 Examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, a 1,4-butylene group, and a 1,5-pentylene group.

[0156] As X in the above general formula (A2-3) a12Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and isopentylidene.

[0157] In the above general formula (A2-3), n a12 and n a13 Each independently represents an integer of 0 to 4, and is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2, from the viewpoint of easy availability, compatibility with other resins, and suppression of gelation of the product during the reaction.

[0158] In n a12 or a13 When the integer is 2 or more, multiple R a12 Each other or multiple R a13 They may be the same as or different from each other.

[0159] X in the above general formula (A2-3) a12 The divalent group represented by the general formula (A2-3-1) is as follows.

[0160] [Chemical formula 10]

[0161]

[0162] (Where R a14 and R a15 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a13 It is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. a14 and n a15 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0163] As R in the above general formula (A2-3-1) a14 and R a15 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by can be exemplified by the above R a11 Same group.

[0164] As X in the above general formula (A2-3-1) a13 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the formula (X) include the above-mentioned a12 Same group.

[0165] In the above general formula (A2-3-1), n a14 and n a15Each independently represents an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of easy availability.

[0166] In n a14 or a15 When the integer is 2 or more, multiple R a14 Each other or multiple R a15 They may be the same as or different from each other.

[0167] [Chemical formula 11]

[0168]

[0169] (where n a16 is an integer from 0 to 10. * indicates a bonding site. )

[0170] From the viewpoint of easy availability, n in the above general formula (A2-4) is a16 An integer of 0-5 is preferable, an integer of 0-4 is more preferable, and an integer of 0-3 is further preferable.

[0171] [Chemical formula 12]

[0172]

[0173] (where n a17 It is a number from 0 to 5. * indicates a bonding site. )

[0174] [Chemical formula 13]

[0175]

[0176] (Where R a16 and R a17 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. a18 is an integer from 1 to 8. * represents a bonding site. )

[0177] As R in the above general formula (A2-6) a16 and R a17 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by a11 Same group.

[0178] In the above general formula (A2-6), n a18 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and further preferably 1. a18 When the integer is 2 or more, multiple R a16 Each other or multiple R a17 They may be the same as or different from each other.

[0179] The maleimide resin (A2) is preferably a polymaleimide resin represented by the following general formula (A2-7).

[0180] [Chemical formula 14]

[0181]

[0182] (Where X a14 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, n a19 is an integer from 2 to 5.)

[0183] As X in the above general formula (A2-7) a14 Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include divalent aliphatic hydrocarbon groups such as alkylene groups having 1 to 5 carbon atoms and alkylidene groups having 2 to 5 carbon atoms; and divalent hydrocarbon groups including aromatic hydrocarbon groups represented by the following general formula (A2-8).

[0184] Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferred, an alkylene group having 1 or 2 carbon atoms is more preferred, and a methylene group is further preferred.

[0185] The alkylidene group having 2 to 5 carbon atoms is preferably an alkylidene group having 2 to 4 carbon atoms, more preferably an alkylidene group having 2 or 3 carbon atoms, and further preferably an isopropylidene group.

[0186] [Chemical formula 15]

[0187] *——X a15 -Ar a1 -X a16 -* (A2-8)

[0188] (Where Ar a1 is a divalent aromatic hydrocarbon group, X a15 and X a16 Each independently represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. * represents a bonding site. )

[0189] As X in the above general formula (A2-8) a15 and X a16 The divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by a14 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms are the same groups as mentioned above. Among them, the methylene group is preferred.

[0190] As Ar in the above general formula (A2-8) a1 The divalent aromatic hydrocarbon group represented by the present invention includes, for example, phenylene, naphthylene, biphenylene, anthrylene, etc. Among them, biphenylene is preferred. Examples of biphenylene include 4,2'-biphenylene, 4,3'-biphenylene, 4,4'-biphenylene, 3,3'-biphenylene, etc., among which 4,4'-biphenylene is preferred.

[0191] In the above options, X in the above general formula (A2-7) a14 Preferably, it is a divalent hydrocarbon group containing an aromatic hydrocarbon group represented by the above general formula (A2-8), and more preferably, X in the above general formula (A2-8) is a15 and X a16 is a methylene group and Ar a1 It is a divalent hydrocarbon group of 4,4'-biphenylene.

[0192] In the above general formula (A2-7), n a19 It is an integer of 2-5, preferably an integer of 2-4, and more preferably 2 or 3.

[0193] As a maleimide resin (A2), an aromatic bismaleimide resin, an aromatic polymaleimide resin, an aliphatic maleimide resin etc. are mentioned, for example.

[0194] Specific examples of the maleimide resin (A2) include bis(4-maleimidophenyl)methane, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 4-methyl-1,3-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, biphenyl aralkyl maleimide, etc. Among them, biphenyl aralkyl maleimide is preferred.

[0195] (Maleimide resin derivative (AY))

[0196] As the maleimide resin derivative (AY), an aminomaleimide resin having a structural unit derived from the above-mentioned maleimide resin (AX) and a structural unit derived from a diamine compound is preferred.

[0197] The aminomaleimide resin has a structural unit derived from the maleimide resin (AX) and a structural unit derived from a diamine compound.

[0198] The aminomaleimide resin is obtained by, for example, subjecting a maleimide resin (AX) to Michael addition of a diamine compound.

[0199] As the diamine compound, for example, the same diamine compound as the amine compound having at least two primary amino groups in one molecule listed in Japanese Patent Application Laid-Open No. 2020-200406 can be used. Among them, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline, and 3,3'-diethyl-4,4'-diaminodiphenylmethane are preferred.

[0200] Among the thermosetting resins (A) described above, from the viewpoints of dielectric properties, conductor adhesion and heat resistance, the thermosetting resin (A) is preferably a maleimide resin having a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups.

[0201] The (A) thermosetting resin preferably has a viscosity at 25°C measured by the above method exceeding 100,000 mPa·s, and is more preferably solid at 25°C.

[0202] ((A) Content of thermosetting resin)

[0203] In the resin composition of the present embodiment, the content of (A) thermosetting resin is not particularly limited, and is preferably 5 to 60 mass %, more preferably 8 to 40 mass %, further preferably 10 to 30 mass %, and particularly preferably 15 to 25 mass %, relative to the total amount (100 mass %) of the resin components in the resin composition of the present embodiment.

[0204] When the content of the thermosetting resin (A) is above the lower limit, the heat resistance, formability, processability and conductor adhesion tend to be better. In addition, when the content of the thermosetting resin (A) is below the upper limit, the dielectric properties tend to be better.

[0205] In addition, the upper limit of the content of the thermosetting resin (A) may be 80% by mass or less, 70% by mass or less, or 60% by mass or less, relative to the total amount (100% by mass) of the thermosetting resin (A) and the reactive liquid compound (B). In addition, the lower limit of the content of the thermosetting resin (A) may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, relative to the total amount (100% by mass) of the thermosetting resin (A) and the reactive liquid compound (B).

[0206] Here, in this specification, the "resin component" refers to a resin and a compound that forms a resin by a curing reaction.

[0207] For example, in the resin composition of the present embodiment, the component (A), the component (B), and the component (C) correspond to the resin component.

[0208] When the resin composition of the present embodiment contains a resin or a compound that forms a resin by a curing reaction as an optional component in addition to the above components, these optional components are also included in the resin component. As an optional component equivalent to the resin component, there can be mentioned the component (E) and the component (F) described later.

[0209] On the other hand, the component (D) is not included in the resin component.

[0210] The content of the resin component in the resin composition of the present embodiment is not particularly limited, and is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and further preferably 20 to 40% by mass, relative to the total solid content (100% by mass) of the resin composition of the present embodiment from the viewpoint of low thermal expansion, heat resistance, flame retardancy and conductor adhesion.

[0211] The content of the maleimide resin in the (A) thermosetting resin is not particularly limited, but is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, relative to the total amount (100% by mass) of the (A) thermosetting resin.

[0212] When the content of the maleimide resin is above the lower limit, the heat resistance, formability, processability and conductor adhesion tend to be better. In addition, when the content of the maleimide resin is below the upper limit, the dielectric properties tend to be better.

[0213] <(B) Reactive liquid compound>

[0214] (B) The reactive liquid compound is not particularly limited as long as it is a compound that is liquid at 25° C., has a reactive group, and has a molecular weight of 1,000 or less.

[0215] (B) The reactive liquid compound may be used alone or in combination of two or more.

[0216] The reactive liquid compound (B) preferably has two or more reactive groups in one molecule, more preferably has 2 to 5 reactive groups, further preferably has 2 to 4 reactive groups, and particularly preferably has 2 or 3 reactive groups.

[0217] When the number of reactive groups is within the above range, volatilization during heat curing is more effectively suppressed, and excellent flexibility tends to be easily obtained.

[0218] The molecular weight of the reactive liquid compound (B) is 1,000 or less, preferably 100 to 800, more preferably 150 to 600, and even more preferably 200 to 400.

[0219] If the molecular weight of the reactive liquid compound (B) is above the above lower limit, there is a tendency to easily suppress the volatilization of the reactive liquid compound (B) before the resin composition is heated and cured. In addition, if the molecular weight of the reactive liquid compound (B) is below the above upper limit, there is a tendency to easily obtain better flexibility.

[0220] The viscosity of the reactive liquid compound (B) at 25° C. is preferably 1 to 5000 mPa·s, more preferably 2 to 1000 mPa·s, and even more preferably 4 to 500 mPa·s.

[0221] When the viscosity of the reactive liquid compound (B) at 25°C is at least the above lower limit, volatilization of the reactive liquid compound (B) tends to be easily suppressed. On the other hand, when the viscosity of the reactive liquid compound (B) at 25°C is at most the above upper limit, better flexibility tends to be easily obtained.

[0222] (B) The viscosity of the reactive liquid compound at 25°C can be measured by the above-mentioned measurement method.

[0223] The (B) reactive liquid compound preferably has, as the reactive group, one or more selected from the group consisting of a functional group containing an ethylenically unsaturated bond, an epoxy group, a hydroxyl group, a carboxyl group, and an amino group.

[0224] It should be noted that, in the present specification, the "ethylenically unsaturated bond" refers to a carbon-carbon double bond capable of an addition reaction, and does not include a double bond of an aromatic ring.

[0225] Examples of the functional group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a 1-methylallyl group, an isopropenyl group, a 2-butenyl group, a 3-butenyl group, a styryl group, an N-substituted maleimide group, and a (meth)acryloyl group.

[0226] Among them, the reactive group is more preferably a functional group containing an ethylenically unsaturated bond or an epoxy group. From the viewpoint of easily obtaining more excellent dielectric properties, a functional group containing an ethylenically unsaturated bond is further preferred, and a (meth)acryloyl group is particularly preferred.

[0227] Specific examples of the (B) reactive liquid compound having a (meth)acryloyl group as a reactive group include (meth)acrylates such as mono(meth)acrylate, di(meth)acrylate, and tri- or higher-functional (meth)acrylate.

[0228] Examples of the mono(meth)acrylate include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, cyclohexyl(meth)acrylate, cyclopentyl(meth)acrylate, benzyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate, butoxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.

[0229] Examples of the di(meth)acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, and dioxanediol di(meth)acrylate.

[0230] Examples of the dioxanediol di(meth)acrylate include 2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]-2,2-dimethylethyl acrylate and the like.

[0231] Examples of trifunctional or higher-functional (meth)acrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0232] Among the above options, as the (meth)acrylate, di(meth)acrylate is preferred.

[0233] As the di(meth)acrylate, a diacrylate represented by the following general formula (B-1) or a dimethacrylate represented by the following general formula (B-2) is preferred, and a dimethacrylate represented by the following general formula (B-2) is more preferred.

[0234] [Chemical formula 16]

[0235]

[0236] (Where R b1 is an alkylene group having 1 to 20 carbon atoms. )

[0237] From the viewpoint of flexibility and suppression of volatilization, R in the above general formulas (B-1) and (B-2) b1 The alkylene group having 1 to 20 carbon atoms preferably has 4 to 18 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 8 to 12 carbon atoms.

[0238] Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tetradecylene, pentadecylene, etc. The alkylene group may be linear, branched or cyclic, and is preferably linear.

[0239] ((B) Content of reactive liquid compound)

[0240] In the resin composition of the present embodiment, the content of the reactive liquid compound (B) is not particularly limited, and is preferably 5 to 60% by mass, more preferably 8 to 40% by mass, further preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment.

[0241] In the resin composition of the present embodiment, the content of the reactive liquid compound (B) is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 15% by mass, and even more preferably 1.5 to 10% by mass, relative to the total solid content (100% by mass) of the resin composition.

[0242] If the content of the reactive liquid compound (B) is above the lower limit, it is easy to obtain better flexibility. If the content of the reactive liquid compound (B) is below the upper limit, it is easy to suppress the generation of volatile components during heat curing.

[0243] <(C) Elastomer having a reactive group and a molecular weight exceeding 1000>

[0244] The resin composition of the present embodiment is excellent in low thermal expansion properties by containing the (C) reactive elastomer.

[0245] In addition, the "elastomer" herein refers to a polymer having a glass transition temperature of 25° C. or less as measured by differential scanning calorimetry in accordance with JIS K 6240:2011.

[0246] (C) The reactive elastomer may be used alone or in combination of two or more.

[0247] The (C) reactive elastomer preferably has one or more selected from the group consisting of a functional group containing an ethylenic unsaturated bond, an epoxy group, a carboxyl group, and an acid anhydride group as a reactive group, and more preferably one or more selected from the group consisting of a functional group containing an ethylenic unsaturated bond and an acid anhydride group. Examples of the functional group containing an ethylenic unsaturated bond include the same functional groups as those that the above-mentioned (B) component may have.

[0248] The molecular weight of the reactive elastomer (C) exceeds 1,000, and is preferably 1,050 to 500,000, more preferably 1,100 to 350,000, and even more preferably 1,150 to 200,000.

[0249] When the molecular weight of the reactive elastomer (C) is at least the above lower limit, the heat resistance of the obtained resin composition tends to be more favorably maintained. When the molecular weight of the reactive elastomer (C) is at most the above upper limit, the dielectric properties and conductor adhesion of the obtained resin composition tend to be more favorably improved.

[0250] Preferred examples of the reactive elastomer (C) include a conjugated diene polymer (C1) having a vinyl group (hereinafter, also referred to as “conjugated diene polymer (C1)”), a modified conjugated diene polymer (C2) having a reactive group (hereinafter, also referred to as “modified conjugated diene polymer (C2)”), and a styrene-based elastomer (C3) having a reactive group (hereinafter, also referred to as “styrene-based elastomer”).

[0251] Preferred embodiments of these components are described below.

[0252] (Conjugated diene polymer (C1))

[0253] In this specification, the "conjugated diene polymer" refers to a polymer of a conjugated diene compound.

[0254] The conjugated diene polymer (C1) may be used alone or in combination of two or more.

[0255] Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.

[0256] The conjugated diene polymer (C1) may be a polymer of one conjugated diene compound or a copolymer of two or more conjugated diene compounds.

[0257] Furthermore, the conjugated diene polymer (C1) may be a copolymer of one or more conjugated diene compounds and one or more monomers other than the conjugated diene compound.

[0258] When the conjugated diene polymer (C1) is a copolymer, the polymerization method is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization.

[0259] The conjugated diene polymer (C1) has a reactive group. From the viewpoint of compatibility with other resins and dielectric properties, the reactive group is preferably a conjugated diene polymer having a vinyl group, and more preferably a conjugated diene polymer having a plurality of vinyl groups in a side chain.

[0260] The number of vinyl groups in one molecule of the conjugated diene polymer (C1) is not particularly limited, but is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more, from the viewpoint of compatibility with other resins and dielectric properties.

[0261] The upper limit of the number of vinyl groups in one molecule of the conjugated diene polymer (C1) is not particularly limited, and may be 100 or less, 80 or less, or 60 or less.

[0262] As the conjugated diene polymer (C 1), for example, polybutadiene having 1,2-vinyl group, butadiene-styrene copolymer having 1,2-vinyl group, polyisoprene having 1,2-vinyl group, etc. can be mentioned. Among them, from the viewpoint of dielectric properties and heat resistance, polybutadiene having 1,2-vinyl group and butadiene-styrene copolymer having 1,2-vinyl group are preferred, and polybutadiene having 1,2-vinyl group is more preferred. In addition, as the polybutadiene having 1,2-vinyl group, a polybutadiene homopolymer having 1,2-vinyl group is preferred.

[0263] The 1,2-vinyl group derived from butadiene in the conjugated diene polymer (C1) means a vinyl group contained in the structural unit derived from butadiene represented by the following formula (C1-1).

[0264] [Chemical formula 17]

[0265]

[0266] In the case where the conjugated diene polymer (C1) is a polybutadiene with 1,2-vinyl, relative to all structural units from butadiene constituting the polybutadiene, there is a content of 1,2-vinyl structural units [hereinafter, sometimes referred to as "vinyl content". ] It is not particularly limited, from the viewpoint of compatibility with other resins, dielectric properties and heat resistance, preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 85 mol% or more. In addition, the upper limit of the vinyl content is not particularly limited, and can be 100 mol% or less, 95 mol% or less, or 90 mol% or less. As the structural unit with 1,2-vinyl, the structural unit from butadiene shown in the above formula (C1-1) is preferably.

[0267] From the same viewpoint, the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.

[0268] The number average molecular weight of the conjugated diene polymer (C1) is not particularly limited, but is preferably 1,050 to 3,000, more preferably 1,100 to 2,000, and even more preferably 1,150 to 1,500 from the viewpoint of compatibility with other resins, dielectric properties, and heat resistance.

[0269] (Modified conjugated diene polymer (C2))

[0270] The modified conjugated diene polymer (C2) is a polymer obtained by modifying a conjugated diene polymer.

[0271] The modified conjugated diene polymer (C2) may be used alone or in combination of two or more.

[0272] For example, when the (A) thermosetting resin includes a maleimide-based resin, the modified conjugated diene polymer (C2) is preferably a modified conjugated diene polymer obtained by modifying (c1) a conjugated diene polymer having a vinyl group in a side chain [hereinafter, sometimes referred to as "conjugated diene polymer (c1)"]. with (c2) a maleimide resin having two or more N-substituted maleimide groups [hereinafter, sometimes referred to as "maleimide resin (c2)"].] from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion.

[0273] In this case, the modified conjugated diene polymer (C2) has an N-substituted maleimide group and a vinyl group as reactive groups. From the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion, the modified conjugated diene polymer (C2) preferably has an N-substituted maleimide group and a vinyl group as reactive groups.

[0274] As the conjugated diene polymer (c1), for example, the conjugated diene polymer having a vinyl group in a side chain described as the above conjugated diene polymer (C1) can be used, and the preferred embodiments are also the same.

[0275] The conjugated diene polymer (c1) may be used alone or in combination of two or more.

[0276] As the maleimide resin (c2), for example, the maleimide resin having two or more N-substituted maleimide groups described as the maleimide resin (AX) can be used, and the preferred embodiments are also the same.

[0277] The maleimide resin (c2) may be used alone or in combination of two or more.

[0278] The modified conjugated diene polymer (C2) preferably has a substituent (hereinafter sometimes referred to as "substituent (x)") formed by reacting a vinyl group of the conjugated diene polymer (c1) with an N-substituted maleimide group of the maleimide resin (c2) in a side chain.

[0279] From the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, the substituent (x) is preferably a group containing a structure represented by the following general formula (C2-1) or (C2-2) as a structure derived from the maleimide resin (c2).

[0280] [Chemical formula 18]

[0281]

[0282] (Where X c1 A divalent group obtained by removing two N-substituted maleimide groups from the maleimide resin (c2), * c1 This is a site that bonds to a carbon atom derived from a vinyl group in a side chain of the conjugated diene polymer (c1).* c2 The site for bonding with other atoms.)

[0283] The modified conjugated diene polymer (C2) preferably has a substituent (x) and a vinyl group (y) in a side chain.

[0284] The extent to which the substituent (x) exists in the modified conjugated diene polymer (C2) can be determined by the extent to which the vinyl groups of the conjugated diene polymer (c1) are modified by the maleimide resin (c2) (hereinafter sometimes referred to as "vinyl modification ratio").

[0285] The vinyl modification rate is not particularly limited, but is preferably 20 to 70%, more preferably 30 to 60%, and further preferably 35 to 50%, from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. Here, the vinyl modification rate is a value obtained by the method described in the Examples.

[0286] The vinyl group (y) is preferably a 1,2-vinyl group contained in the structural unit derived from butadiene.

[0287] The number average molecular weight of the modified conjugated diene polymer (C2) is not particularly limited, but is preferably 1,100 to 6,000, more preferably 1,300 to 4,000, and even more preferably 1,500 to 2,000 from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance.

[0288] The modified conjugated diene polymer (C2) can be produced by reacting the conjugated diene polymer (c1) with the maleimide resin (c2).

[0289] The method for reacting the conjugated diene polymer (c1) and the maleimide resin (c2) is not particularly limited. For example, the conjugated diene polymer (c1), the maleimide resin (c2), a reaction catalyst and an organic solvent can be put into a reaction vessel, and reacted while heating, keeping warm, stirring, etc. as required, thereby obtaining a modified conjugated diene polymer (C2).

[0290] The reaction temperature of the above reaction is preferably 70 to 120°C, more preferably 80 to 110°C, and even more preferably 85 to 105°C, from the viewpoint of workability and suppression of gelation of the product during the reaction.

[0291] From the viewpoint of productivity and sufficient progress of the reaction, the reaction time of the above reaction is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, and even more preferably 3 to 7 hours.

[0292] However, these reaction conditions can be appropriately adjusted according to the types of raw materials used, and are not particularly limited.

[0293] When the above reaction is carried out, the molar number (M m ) relative to the molar number of the side chain vinyl groups possessed by the conjugated diene polymer (c1) (M v ) ratio (M m / M v) is not particularly limited, but is preferably 0.001 to 0.5, more preferably 0.005 to 0.1, and further preferably 0.008 to 0.05, from the viewpoint of compatibility of the obtained modified conjugated diene polymer (C2) with other resins and suppression of gelation of the product during the reaction.

[0294] (Styrene elastomer (C3))

[0295] The styrene-based elastomer (C3) is not particularly limited as long as it has a reactive group and a structural unit derived from a styrene-based compound.

[0296] The styrene-based elastomer (C3) may be used alone or in combination of two or more.

[0297] The styrene-based elastomer (C3) is preferably a substance having a structural unit derived from a styrene-based compound represented by the following general formula (C3-1).

[0298] [Chemical formula 19]

[0299]

[0300] (Where R c1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R c2 It is an alkyl group having 1 to 5 carbon atoms. c1 is an integer from 0 to 5.)

[0301] As R in the above general formula (C3-1) c1 and R c2 The alkyl group having 1 to 5 carbon atoms represented by the present invention includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. The alkyl group having 1 to 5 carbon atoms may be straight-chain or branched. Among them, the alkyl group having 1 to 3 carbon atoms is preferred, the alkyl group having 1 or 2 carbon atoms is more preferred, and the methyl group is still more preferred.

[0302] In the above general formula (C3-1), n c1 It is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 0.

[0303] The reactive group of the styrene-based elastomer (C3) is not particularly limited, but is preferably a vinyl group, an N-substituted maleimide group, a (meth)acryloyl group, an epoxy group, a carboxyl group or an acid anhydride group.

[0304] The carboxyl group can be introduced into the molecule by, for example, allowing the styrene elastomer (C3) to contain a structural unit derived from maleic acid, and the acid anhydride group can be introduced into the molecule by allowing the styrene elastomer (C3) to contain a structural unit derived from maleic anhydride.

[0305] When the styrene-based elastomer (C3) contains a structural unit derived from maleic anhydride, the content of the structural unit derived from maleic anhydride in the styrene-based elastomer (C3) is not particularly limited, but is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, and even more preferably 0.7 to 1.5% by mass.

[0306] As other structural units which the styrene-based elastomer (C3) may contain, for example, a structural unit derived from butadiene, a structural unit derived from isoprene, etc. are mentioned.

[0307] The structural units derived from butadiene and the structural units derived from isoprene may be hydrogenated. When hydrogenated, the structural units derived from butadiene become structural units in which ethylene units and butene units are mixed, and the structural units derived from isoprene become structural units in which ethylene units and propylene units are mixed.

[0308] As the styrene-based elastomer (C3), from the viewpoints of dielectric properties, conductor adhesion, heat resistance, glass transition temperature and low thermal expansion, SEBS having a reactive group and SEPS having a reactive group are preferred, SEBS having a reactive group is more preferred, and as the reactive group, SEBS having an acid anhydride group is further preferred.

[0309] It should be noted that SEBS is a styrene-ethylene / butylene-styrene block copolymer obtained by hydrogenating a styrene-butadiene-styrene block copolymer, and SEPS is a styrene-ethylene / propylene-styrene block copolymer obtained by hydrogenating a styrene-isoprene-styrene block copolymer.

[0310] In the styrene-based elastomer (C3), the content of the structural unit derived from the styrene-based compound [hereinafter sometimes referred to as "styrene content"] is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and further preferably 10 to 20% by mass.

[0311] The melt flow rate (MFR) of the styrene elastomer (C3) is not particularly limited, but is preferably 10 to 80 g / 10 min, more preferably 20 to 60 g / 10 min, and further preferably 30 to 50 g / 10 min under the measurement conditions of 230°C and a load of 5 kgf.

[0312] The number average molecular weight of the styrene elastomer (C3) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 350,000, and even more preferably 100,000 to 200,000.

[0313] ((C) Content of reactive elastomer)

[0314] In the resin composition of the present embodiment, the content of the reactive elastomer (C) is not particularly limited, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment.

[0315] When the content of the reactive elastomer (C) is at least the above lower limit, there is a tendency to easily obtain more excellent low thermal expansion properties. On the other hand, when the content of the reactive elastomer (C) is at most the above upper limit, there is a tendency to easily obtain more excellent heat resistance.

[0316] <(D) Inorganic fillers>

[0317] The resin composition of the present embodiment can easily obtain more excellent low thermal expansion property, heat resistance and flame retardancy by containing the (D) inorganic filler.

[0318] In particular, since the resin composition of the present embodiment is excellent in flexibility, the content of the (D) inorganic filler can be increased to further improve the low thermal expansion property.

[0319] (D) The inorganic filler may be used alone or in combination of two or more.

[0320] (D) Inorganic fillers include, for example, silica, alumina, titanium oxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc. Among them, from the viewpoint of low thermal expansion, heat resistance and flame retardancy, silica, alumina, mica and talc are preferred, and silica and alumina are more preferred.

[0321] Examples of silica include precipitated silica with a high water content produced by a wet process, dry-process silica that contains almost no bound water, etc. Dry-process silica, further including crushed silica, fumed silica, fused silica, etc., depending on the production method.

[0322] From the viewpoint of improving dispersibility and adhesion with organic components, the (D) inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent.

[0323] The average particle size of the inorganic filler (D) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm from the viewpoint of dispersibility and fine wiring properties of the inorganic filler (D).

[0324] It should be noted that, in this specification, the average particle size of the inorganic filler (D) refers to the particle size corresponding to the point of 50% volume when the total volume of the particles is set to 100% and the cumulative frequency distribution curve based on the particle size is obtained. The average particle size of the inorganic filler (D) can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method.

[0325] Examples of the shape of the (D) inorganic filler include spherical shapes and crushed shapes, and a spherical shape is preferred.

[0326] ((D) Content of inorganic filler)

[0327] In the resin composition of the present embodiment, the content of the (D) inorganic filler is not particularly limited, but is preferably 20 to 95% by mass, more preferably 40 to 90% by mass, and even more preferably 60 to 80% by mass relative to the total solid content (100% by mass) of the resin composition.

[0328] If the content of (D) inorganic filler is above the above lower limit, low thermal expansion, heat resistance and flame retardancy tend to become better. In addition, if the content of (D) inorganic filler is below the above upper limit, formability and conductor adhesion tend to become better.

[0329] <(E) Elastomer having no reactive group>

[0330] The resin composition of the present embodiment may further contain (E) an elastomer having no reactive group.

[0331] (E) The elastomer having no reactive group may be used alone or in combination of two or more.

[0332] (E) The elastomer having no reactive group is described in the same manner as the styrene-based elastomer (C3) except that the elastomer has no reactive group.

[0333] That is, the (E) elastomer having no reactive group is preferably a styrene-based elastomer having no reactive group.

[0334] The type of the elastomer, the structural units constituting the elastomer, the styrene content, the melt flow rate and the preferred aspects of the number average molecular weight are also the same as those of the styrene elastomer (C3).

[0335] ((E) Content of elastomer having no reactive group)

[0336] When the resin composition of the present embodiment contains component (E), the content of component (E) is not particularly limited, but is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and further preferably 30 to 50% by mass, relative to the total solid content (100% by mass) of the resin composition.

[0337] When the content of the component (E) is at least the above lower limit, more excellent dielectric properties tend to be easily obtained. On the other hand, when the content of the component (E) is at most the above upper limit, more excellent heat resistance tends to be easily obtained.

[0338] <(F) Curing accelerator>

[0339] The resin composition of the present embodiment further contains (F) a curing accelerator.

[0340] The resin composition of the present embodiment contains the (F) curing accelerator, whereby the curability is improved, and there is a tendency that more excellent dielectric properties, heat resistance, and conductor adhesion are easily obtained.

[0341] (F) The curing accelerator may be used alone or in combination of two or more.

[0342] From the viewpoint of efficiently forming the chemical bond of the resin component during heating, as (F) curing accelerator, it is preferred to include a free radical polymerization initiator. The free radical polymerization initiator acts as a polymerization initiator for free radical polymerization, and when exposed to energy such as light and heat, it decomposes into a substance with unpaired electrons. As the free radical polymerization initiator, organic peroxides, inorganic peroxides, azo compounds, etc. described later can be cited, preferably organic peroxides.

[0343] Examples of the curing accelerator (F) include: acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, tributylamine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, and 1-cyanoethyl-2-phenylimidazole; isocyanate-masked imidazole compounds such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; diisopropyl peroxide, 2,5-dimethylbenzene peroxide, Organic peroxides such as 2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylperoxyisopropyl monocarbonate, 1,3-di(tert-butylperoxyisopropyl)benzene; inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile); carboxylates of manganese, cobalt, zinc, etc.

[0344] Among them, from the viewpoint of the curing accelerating effect and storage stability, imidazole compounds, isocyanate-masked imidazole compounds, organic peroxides, and carboxylates are preferred, and isocyanate-masked imidazole compounds and organic peroxides are more preferred.

[0345] When the resin composition of the present embodiment contains (F) a curing accelerator, the content of the (F) curing accelerator is not particularly limited, and is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and further preferably 4 to 8 parts by mass, relative to the total amount (100 parts by mass) of the (A) thermosetting resin and the (B) reactive liquid compound.

[0346] When the content of the curing accelerator (F) is at least the above lower limit, a sufficient curing acceleration effect tends to be easily obtained. On the other hand, when the content of the curing accelerator (F) is at most the above upper limit, storage stability tends to be further improved.

[0347] When the resin composition of the present embodiment contains a free radical polymerization initiator as the (F) curing accelerator, the content of the free radical polymerization initiator is not particularly limited, and is preferably 0.05 to 7 parts by mass, more preferably 0.5 to 5 parts by mass, and further preferably 2 to 4 parts by mass, relative to the total amount (100 parts by mass) of the (A) thermosetting resin and the (B) reactive liquid compound.

[0348] If the content of the radical polymerization initiator is above the lower limit, sufficient curing acceleration effect is easily obtained and the generation of volatile components is more easily suppressed. In addition, if the content of the radical polymerization initiator is below the upper limit, storage stability tends to be better.

[0349] <Other ingredients>

[0350] The resin composition of the present embodiment may further contain one or more arbitrary components selected from resin materials other than the above-mentioned components, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, organic solvents and additives other than these, as needed.

[0351] The above-mentioned optional components may be used alone or in combination of two or more.

[0352] The content of the above-mentioned optional components in the resin composition of the present embodiment is not particularly limited, and may be used as needed within a range that does not inhibit the effects of the present embodiment.

[0353] In addition, the resin composition of the present embodiment may not contain the above-mentioned arbitrary components depending on the desired performance.

[0354] The resin composition of the present embodiment is excellent in flexibility and therefore is suitable as a resin composition constituting a resin film.

[0355] From the viewpoint of more effectively exhibiting the characteristics of the resin composition of the present embodiment of excellent flexibility, the resin composition of the present embodiment is preferably used to form a resin film with a thickness of 10 μm or more, more preferably used to form a resin film with a thickness of 50 μm or more, further preferably used to form a resin film with a thickness of 80 μm or more, further preferably used to form a resin film with a thickness of 100 μm or more, further preferably used to form a resin film with a thickness of 130 μm or more, and particularly preferably used to form a resin film with a thickness of 150 μm or more.

[0356] In addition, from the viewpoint of handling properties, the resin composition of the present embodiment is preferably used to form a resin film having a thickness of 1000 μm or less, more preferably used to form a resin film having a thickness of 700 μm or less, and further preferably used to form a resin film having a thickness of 500 μm or less.

[0357] [Resin film]

[0358] The resin film of the present embodiment is a resin film containing the resin composition of the present embodiment.

[0359] The resin film of the present embodiment can be produced, for example, by applying the resin composition of the present embodiment containing an organic solvent (hereinafter, the resin composition containing an organic solvent is also referred to as “resin varnish”) on a support and then heating and drying it.

[0360] Examples of the support include plastic films, metal foils, and release papers.

[0361] Examples of the plastic film include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate [hereinafter, sometimes referred to as "PET"]. and polyethylene naphthalate; polycarbonate films, polyimide films, etc. Among them, polyethylene terephthalate films are preferred from the viewpoints of economic efficiency and handling properties.

[0362] As metal foil, for example, copper foil, aluminum foil, etc. can be cited. When copper foil is used as a support, the copper foil can also be used directly as a conductor layer to form a circuit. In this case, as copper foil, rolled copper foil, electrolytic copper foil, etc. can be used. When using a thin copper foil, from the viewpoint of improving workability, a copper foil with a carrier can be used.

[0363] The support may be a support subjected to a surface treatment such as matte treatment or corona treatment. Alternatively, the support may be a support subjected to a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like.

[0364] The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 20 to 100 μm, and even more preferably 25 to 50 μm from the viewpoint of handling ease and economic efficiency.

[0365] As the coating device for coating the resin varnish, for example, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, etc. These coating devices may be appropriately selected according to the film thickness to be formed.

[0366] The drying conditions after applying the resin varnish may be appropriately determined according to the content, boiling point, etc. of the organic solvent, and are not particularly limited.

[0367] For example, in the case of a resin varnish containing 40 to 60% by mass of an aromatic hydrocarbon solvent, the drying temperature is not particularly limited, but is preferably 50 to 200°C, more preferably 80 to 150°C, and further preferably 100 to 130°C from the viewpoint of productivity and making the resin composition of the present embodiment appropriately B-staged.

[0368] In the case of the resin varnish, the drying time is not particularly limited, but is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes from the viewpoint of productivity and making the resin composition of the present embodiment appropriately B-staged.

[0369] The content of the organic solvent in the resin film of this embodiment is preferably 2 mass % or less, more preferably 1 mass % or less, further preferably 0.5 mass % or less, and may be 0 mass % relative to the total amount of the resin film (100 mass %).

[0370] When the content of the organic solvent in the resin film is within the above range, the amount of the organic solvent volatilized during heat curing tends to be easily suppressed sufficiently.

[0371] The mass reduction rate of the resin film of the present embodiment when heated and dried at 170° C. for 30 minutes in an air atmosphere [hereinafter sometimes referred to as “170° C. mass reduction rate”] is preferably 2.0 mass % or less, more preferably 1.5 mass % or less, further preferably 1.0 mass % or less, and may be 0 mass %.

[0372] When the mass reduction rate at 170° C. is within the above range, the amount of volatile components during heat curing tends to be easily suppressed.

[0373] The mass reduction rate at 170° C. can be measured by the method described in Examples.

[0374] The thickness of the resin film of the present embodiment can be appropriately determined according to the purpose of the resin film, and from the viewpoint of obtaining sufficient insulation reliability and the viewpoint of being able to embed semiconductor chips, etc., it is preferably 10 μm or more, more preferably 50 μm or more, further preferably 80 μm or more, further preferably 100 μm or more, further preferably 130 μm or more, and particularly preferably 150 μm or more.

[0375] In addition, from the viewpoint of handling properties, the thickness of the resin film of the present embodiment is preferably 1000 μm or less, more preferably 700 μm or less, and even more preferably 500 μm or less.

[0376] The resin film of this embodiment may have a protective film. The protective film is provided on the surface of the resin film of this embodiment opposite to the surface provided with the support, and is used for the purpose of preventing foreign matter from adhering to and damaging the resin film.

[0377] The relative dielectric constant (Dk) of the cured product of the resin composition and resin film of the present embodiment at 10 GHz may be less than 3.0, less than 2.9, or less than 2.8. The smaller the relative dielectric constant (Dk), the more preferred it is. The lower limit is not particularly limited, and considering the balance with other physical properties, it may be, for example, 2.4 or more, or 2.5 or more.

[0378] The dielectric loss tangent (Df) of the cured product of the resin composition and resin film of the present embodiment at 10 GHz may be less than 0.0030, less than 0.0025, or less than 0.0015. The smaller the dielectric loss tangent (Df), the more preferred it is. The lower limit thereof is not particularly limited, and in consideration of the balance with other physical properties, it may be, for example, 0.0010 or more, or 0.0015 or more.

[0379] In addition, from the perspective of obtaining sufficient insulation reliability and being able to embed semiconductor chips, the resin film of this embodiment is preferably a resin film with a thickness of 150 μm or more, and the relative dielectric constant (Dk) of the cured product of the resin film at 10 GHz is less than 2.8, and the dielectric loss tangent (Df) is less than 0.0030.

[0380] It should be noted that the relative dielectric constant (Dk) and the dielectric loss tangent (Df) are values ​​based on the cavity resonator perturbation method, and more specifically, are values ​​measured by the method described in the Examples.

[0381] The resin film of this embodiment is suitable as a resin film for forming an insulating layer of a printed circuit board such as a multilayer printed circuit board, or a semiconductor sealing resin film for a semiconductor package. In particular, the resin film of this embodiment has excellent flexibility and excellent handling properties when made into a thick resin film, and is therefore suitable as a semiconductor sealing resin film.

[0382] [Printed circuit board]

[0383] The printed wiring board of the present embodiment is a printed wiring board having a cured product of the resin composition of the present embodiment.

[0384] The printed wiring board of the present embodiment can be manufactured, for example, by forming a conductor circuit on the cured product of the resin film of the present embodiment using a known method. In addition, a multilayer printed wiring board can also be manufactured by further performing a multilayer bonding process as required. The conductor circuit can be formed, for example, by appropriately performing a hole opening process, a metal plating process, an etching of a metal foil, etc.

[0385] [Semiconductor package]

[0386] The semiconductor package of the present embodiment is a semiconductor package having a cured product of the resin film of the present embodiment. That is, the semiconductor package of the present embodiment can also be said to be a semiconductor package including the resin film of the present embodiment.

[0387] The semiconductor package of the present embodiment may be, for example, a semiconductor package in which a semiconductor chip is mounted on a printed wiring board of the present embodiment, or may be a semiconductor package including a semiconductor chip sealed with a cured product of the resin film of the present embodiment.

[0388] The semiconductor package formed by mounting a semiconductor chip on the printed wiring board of this embodiment can be manufactured by mounting a semiconductor chip, a memory, etc. on the printed wiring board of this embodiment by a known method. The printed wiring board of this embodiment used in manufacturing the semiconductor package is preferably a multilayer printed wiring board.

[0389] A semiconductor package including a semiconductor chip sealed with a cured product of the resin film of the present embodiment can be produced by, for example, the following method.

[0390] First, the resin film of the present embodiment is arranged on the semiconductor chip. Next, the resin film is heated and melted, and the semiconductor chip is embedded in the resin composition constituting the resin film. Then, the resin composition embedded with the semiconductor chip is cured by heating, so that a semiconductor package in which the semiconductor chip is sealed by the cured product of the resin composition can be manufactured.

[0391] Example

[0392] Hereinafter, the present embodiment will be described in detail with reference to examples, but the present embodiment is not limited to the following examples.

[0393] In addition, the number average molecular weight is measured by the following procedure.

[0394] (Method for determining number average molecular weight)

[0395] The number average molecular weight is converted by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve uses standard polystyrene: TSKstandard POLYSTYRENE (model: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) (manufactured by Tosoh Corporation, trade name), and is approximated by a cubic formula. The measurement conditions of GPC are shown below.

[0396] [GPC measurement conditions]

[0397] Device: High-speed GPC device HLC-8320GPC

[0398] Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation]

[0399] Column: Guard column; TSK Guardcolumn SuperHZ-L + column; TSKgel SuperHZM-N + TSKgelSuperHZM-M + TSKgel SuperH-RC (all manufactured by Tosoh Corporation, trade names)

[0400] Column size: 4.6×20mm (guard column), 4.6×150mm (column), 6.0×150mm (reference column)

[0401] Eluent: Tetrahydrofuran

[0402] Sample concentration: 10mg / 5mL

[0403] Injection volume: 25 μL

[0404] Flow rate: 1.00mL / min

[0405] Measuring temperature: 40℃

[0406] [Manufacturing of modified conjugated diene polymer]

[0407] Production Example 1

[0408] Into a 2L glass flask container equipped with a thermometer, a reflux condenser and a stirring device, which can be heated and cooled, 33.8 parts by mass of 1,2-polybutadiene homopolymer (number average molecular weight = 1200, vinyl content = 85% or more), 1.43 parts by mass of an aromatic bismaleimide resin containing an indane ring (the compound represented by the above general formula (A1-4-1), number average molecular weight = 1300), 0.0035 parts by mass of tert-butyl peroxyisopropyl carbonate and toluene as an organic solvent were added. Next, under a nitrogen atmosphere, the mixture was reacted at 90 to 100° C. while stirring for 5 hours, thereby obtaining a solution of a modified conjugated diene polymer (solid content concentration: 35% by mass). The number average molecular weight of the obtained modified conjugated diene polymer was 1700.

[0409] In addition, for the 1,2-polybutadiene homopolymer before the start of the reaction and the solution of the aromatic bismaleimide resin containing indane rings, and the solution after the reaction, GPC is measured by the above method to obtain the peak area of ​​the aromatic bismaleimide resin containing indane rings before and after the reaction. Next, the vinyl modification rate of the aromatic bismaleimide resin containing indane rings is calculated by the following formula. It should be noted that the vinyl modification rate is equivalent to the reduction rate of the peak area of ​​the aromatic bismaleimide resin containing indane rings based on the reaction.

[0410] Vinyl modification rate (%) = [(peak area derived from the aromatic bismaleimide resin containing an indane ring before the reaction) - (peak area derived from the aromatic bismaleimide resin containing an indane ring after the reaction)] × 100 / (peak area derived from the aromatic bismaleimide resin containing an indane ring before the reaction)

[0411] The vinyl modification ratio determined from the above formula was 40%.

[0412] [Manufacturing of resin composition]

[0413] Examples 1 to 15, Comparative Examples 1 to 3

[0414] The components listed in Table 1 were mixed with toluene in the amounts listed in Table 1, and then stirred and mixed while heating at 25° C. or 50 to 80° C., thereby preparing a resin composition having a solid content concentration of about 50% by mass. It should be noted that in Table 1, the unit of the amount of each component is part by mass, and in the case of a solution, it refers to part by mass in terms of solid content.

[0415] [Manufacturing of resin film]

[0416] The resin composition obtained in each example was applied on one side of a 50 μm thick PET film (manufactured by Toyobo Co., Ltd., trade name "Purex A53") so that the thickness of the resin layer after drying was 150 μm. Then, the resin composition was heated and dried at 105° C. for 5 minutes to be in a B-stage state, thereby preparing a resin film (1) with a PET film on one side (the thickness of the resin film was 150 μm).

[0417] Next, the obtained single-sided PET film (1) was cut into 200 mm × 200 mm, and the two films were overlapped so that the two films faced each other. Next, a vacuum laminator was used to laminate the two films at a temperature of 100° C. and a press time of 5 seconds, thereby obtaining a double-sided PET film (2) (the thickness of the resin film was 300 μm).

[0418] [Manufacturing of resin sheets with copper foil on both sides]

[0419] The resin film (2) with PET film on both sides obtained above was cut into a size of 90 mm in length × 50 mm in width, and the PET films on both sides were peeled off and removed. A Teflon (registered trademark) sheet with a thickness of 0.3 mm punched out into a size of 90 mm in length × 50 mm in width was placed on the copper foil, and the resin film after the PET film was peeled off was put into the punched out part, and further, the copper foil was placed thereon to obtain a laminate. It should be noted that the copper foil used was a low-profile copper foil with a thickness of 18 μm (manufactured by Mitsui Mining and Smelting Co., Ltd., trade name "3EC-VLP-18"), and was placed in a manner such that the M side became the resin film side. Next, the above laminate was heated and pressurized under the conditions of a temperature of 180° C., a pressure of 2.0 MPa, and a time of 60 minutes, and the resin film was formed into a resin plate while being cured, thereby producing a resin plate with copper foil on both sides. The thickness of the resin plate portion of the obtained resin plate with copper foil on both sides was 0.3 mm.

[0420] [Measurement and evaluation methods]

[0421] The resin films and the resin plates with copper foil on both sides obtained in the above-mentioned Examples and Comparative Examples were used to perform various measurements and evaluations according to the following methods.

[0422] (1. Evaluation method of flexibility of resin film)

[0423] The single-sided PET film obtained in each example (1) was wound around a resin cylinder with a diameter of 85 mm at 25° C. with the resin film surface facing outward. The appearance of the wound resin film was visually observed and evaluated according to the following criteria. In the following criteria, A indicates the best.

[0424] <Flexibility Criteria>

[0425] A: No cracks in the resin film or peeling from the PET film were observed.

[0426] B: Cracks of the resin film or peeling from the PET film was observed.

[0427] (2. Determination and evaluation method of linear expansion coefficient and glass transition temperature)

[0428] The resin plate with copper foil on both sides obtained in each example was immersed in a 10% by mass solution of ammonium persulfate (Mitsubishi Gas Chemical Co., Ltd.) as a copper etching solution to remove the copper foil. The obtained resin plate was cut into a width of 0.4 mm and a length of 20 mm, and then dried at 105°C for 1 hour to serve as a test piece. The test piece was clamped at both ends of the long side direction of the test piece with upper and lower clamps in a manner that the interval between the clamps was 10 mm. Next, a thermomechanical measuring device (TMA) (Seiko Instruments Co., Ltd., trade name "SS6100") was used to measure the dimensional change under the conditions of tensile mode, temperature range of 30 to 300°C, heating rate of 5°C / min, and load of 4g. The inflection point of the dimensional change relative to temperature was taken as the glass transition temperature, and the average value of the dimensional change per unit temperature of 30 to 150°C was taken as the linear expansion coefficient, and evaluated according to the following criteria. In the following criteria, A represents the best.

[0429] <Determination criteria of linear expansion coefficient>

[0430] A: less than 20ppm / K

[0431] B: 20ppm / K or more and less than 40ppm / K

[0432] C: 40ppm / K or more and less than 60ppm / K

[0433] <Criteria for determining glass transition temperature>

[0434] A: Above 180℃

[0435] B: less than 180℃

[0436] (3.25℃ tensile elastic modulus measurement and evaluation method)

[0437] The resin plate with copper foil on both sides obtained in each example was immersed in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a copper etching solution to remove the copper foil. The obtained resin plate was cut into a width of 10 mm and a length of 40 mm, and then dried at 105°C for 1 hour to serve as a test piece. The test piece was clamped at both ends of the long side direction of the test piece with upper and lower clamps in a manner that the interval between the clamps was 20 mm. Next, a small desktop testing machine (manufactured by Shimadzu Corporation, trade name "EZ-TEST") was used to obtain the tensile modulus of the above test piece under an environment of 25°C and a tensile speed of 2 mm / min. Five identical samples were made, and the tensile modulus was obtained under the same conditions as above, and the average value was used as the 25°C tensile modulus. Other detailed conditions and the calculation method of the tensile modulus were carried out in accordance with the international standard ISO5271 (1993). The obtained 25°C tensile modulus was evaluated according to the following judgment criteria. In the following criteria, A indicates the best.

[0438] <25℃ tensile modulus of elasticity determination criteria>

[0439] A: less than 1.5GPa

[0440] B: 1.5GPa or above

[0441] (4. Determination and evaluation method of peel strength)

[0442] After the copper foil of the resin plate with copper foil on both sides obtained in each example is processed into a straight line with a width of 5 mm by etching, it is dried at 105°C for 1 hour and used as a test piece. The formed straight copper foil is installed in a small desktop testing machine (manufactured by Shimadzu Corporation, trade name "EZ-TEST"), peeled in a 90° direction, and the peel strength of the copper foil is measured. The tensile speed when peeling the copper foil is set to 50 mm / min. The peel strength obtained is evaluated according to the following judgment criteria. In the following criteria, A represents the best.

[0443] <Determination criteria of peel strength>

[0444] A: 0.5kN / m or more

[0445] B: 0.4kN / m or more and less than 0.5kN / m

[0446] (5. Measurement and evaluation method of relative dielectric constant (Dk) and dielectric loss tangent (Df))

[0447] The resin plate with copper foil on both sides obtained in each example is immersed in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a copper etching solution to remove the copper foil. The obtained resin plate is cut into 2 mm × 50 mm pieces, dried at 105°C for 1 hour, and used as a test piece. Next, according to the cavity resonator perturbation method, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the above test piece are measured at an atmosphere temperature of 25°C using a 10 GHz band, and evaluated according to the following criteria. In the following criteria, A represents the best.

[0448] <Criteria for determining relative dielectric constant (Dk)>

[0449] A: less than 2.8

[0450] B: 2.8 or above

[0451] <Determination criteria of dielectric loss tangent (Df)>

[0452] A: less than 0.0015

[0453] B: 0.0015 or more and less than 0.0025

[0454] C: 0.0025 or more and less than 0.0030

[0455] D: 0.0030 or more

[0456] (6. Determination and evaluation method of thermal conductivity)

[0457] The resin plate obtained by etching away the copper foil of the resin plate with copper foil on both sides obtained in each example was cut into 10 mm in length and 10 mm in width, and used as a test piece. After the test piece was blackened using graphite spray, the thermal diffusivity was evaluated using a xenon flash analyzer (NETZSCH company, trade name "LFA447 nanoflash"). According to this value, the density measured using the Archimedean method, and the product of the specific heat measured using DSC (differential scanning calorimetry; Perkin Elmer company, trade name "DSC Pyris1"), the thermal conductivity of the test piece was obtained. The obtained thermal conductivity was evaluated according to the following judgment criteria. In the following benchmarks, A represents the best.

[0458] <Criteria for determining thermal conductivity>

[0459] A: 3.0W / m·K or above

[0460] B: less than 3.0W / m·K

[0461] (7.170℃ mass reduction rate determination method)

[0462] After the PET film was peeled off from the resin film (1) with a PET film on one side obtained in each example, a powder in a B-stage state obtained by crushing the resin film was used as an evaluation sample. Using this evaluation sample, the mass reduction rate when heated and dried at 170°C for 30 minutes in an air atmosphere [{(mass before heating - mass after heating at 170°C for 30 minutes) / (mass before heating)}×100] was taken as the mass reduction rate at 170°C. The results are shown in Table 1. It should be noted that in Table 1, "≤1.0" means that the mass reduction rate at 170°C is 1.0% by mass or less.

[0463] [Table 1]

[0464] Table 1

[0465]

[0466] It should be noted that the details of the components shown in Table 1 are as follows.

[0467] [(A) ingredient]

[0468] Maleimide resin A: an aromatic bismaleimide resin containing an indane ring represented by the general formula (A1-4-1): number average molecular weight = 1300, solid at 25°C

[0469] Maleimide resin B: manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-3000", a compound represented by the above general formula (A2-7), X a14 X in the above general formula (A2-8) a15 and X a16 is a methylene group and Ar a1 It is a divalent hydrocarbon group of 4,4'-biphenylene: number average molecular weight = 500, solid at 25°C

[0470] [(B) ingredient]

[0471] Bisphenol F epoxy resin: Epoxy equivalent: 155-165 g / eq, liquid at 25°C (viscosity at 25°C = 393 mPa·s), number average molecular weight: 300

[0472] 1,9-nonanediol diacrylate: liquid at 25°C (viscosity at 25°C = 8 mPa·s), molecular weight: 268.35

[0473] 1,10-Decanediol diacrylate: liquid at 25°C (viscosity at 25°C = 12 mPa·s), molecular weight: 282.38

[0474] ·Dioxanediol diacrylate: 2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]-2,2-dimethylethyl acrylate, liquid at 25°C (viscosity at 25°C = 310 mPa·s), molecular weight: 326.38

[0475] 1,9-nonanediol dimethacrylate: liquid at 25°C (viscosity at 25°C = 8 mPa·s), molecular weight: 296.4

[0476] 1,12-Dodecanediol dimethacrylate: liquid at 25°C (viscosity at 25°C = 11 mPa·s), molecular weight: 338.5

[0477] [(C) ingredient]

[0478] Modified conjugated diene polymer: the modified conjugated diene polymer obtained in Preparation Example 1, number average molecular weight 1700

[0479] · Conjugated diene polymer: 1,2-polybutadiene homopolymer (number average molecular weight = 1200, vinyl content = 85% or more)

[0480] Maleic acid-modified styrene elastomer: an anhydride-modified product of hydrogenated styrene thermoplastic elastomer (styrene-ethylene-butylene-styrene copolymer), trade name "FG-1924", styrene content = 13% by mass, MFR under the measurement conditions of 230°C and a load of 5 kgf = 40 g / 10 min, maleic anhydride content = 1.0% by mass

[0481] [(D) ingredient]

[0482] Silica: Spherical silica treated with aminosilane coupling agent, average particle size 0.5 μm

[0483] Alumina: Alumina 1 (average particle size 18 μm, polyhedral spherical shape), Alumina 2 (average particle size 3 μm, polyhedral spherical shape), Alumina 3 (average particle size 0.4 μm, polyhedral spherical shape) are mixed in a mass ratio of 66:24:10

[0484] [(E) ingredient]

[0485] Unmodified styrene elastomer: hydrogenated styrene thermoplastic elastomer (styrene-ethylene-butylene-styrene copolymer), trade name "Tuftec H1221", styrene content = 12% by mass, MFR under the measurement conditions of 230°C and a load of 2.16 kgf = 4.5 g / 10 min, number average molecular weight = 170,000

[0486] [(F)INGREDIENT]

[0487] Organic peroxide: 1,3-di(tert-butylperoxyisopropyl)benzene

[0488] Imidazole curing accelerator: Isocyanate-masked imidazole, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "G-8009L"

[0489] According to the above results, the cured products of the resin compositions obtained in Examples 1 to 15 of the present embodiment have excellent low thermal expansion properties, and the resin films formed from the resin compositions have excellent flexibility. In addition, it is known that the mass reduction rate at 170°C of the resin films of Examples 1 to 15 is less than 1.0% by mass, and the generation of volatile components during heat curing is suppressed. On the other hand, the flexibility of the resin films of Comparative Examples 1 and 2 is poor, and the low thermal expansion properties of the resin composition of Comparative Example 3 are poor.

[0490] Industrial Applicability

[0491] The cured product of the resin composition of the present embodiment has excellent low thermal expansion, excellent flexibility in a solid state, and can suppress the generation of volatile components during heat curing. Therefore, the resin composition of the present embodiment is useful for printed wiring boards, semiconductor packages, and the like.

Claims

1. A resin composition comprising: A thermosetting resin; B is a compound that is liquid at 25°C, has a reactive group and has a molecular weight of 1000 or less; C an elastomer having a reactive group and a molecular weight exceeding 1000; and D Inorganic filling material.

2. The resin composition according to claim 1, in, The component A is one or more selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin.

3. The resin composition according to claim 2, in, The maleimide resin having one or more N-substituted maleimide groups is a maleimide resin having a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups.

4. The resin composition according to any one of claims 1 to 3, in, The component B has, as the reactive group, one or more selected from the group consisting of a functional group including an ethylenically unsaturated bond, an epoxy group, a hydroxyl group, a carboxyl group, and an amino group.

5. The resin composition according to any one of claims 1 to 3, in, The component B has two or more reactive groups in one molecule.

6. The resin composition according to any one of claims 1 to 3, in, The component B is di(meth)acrylate.

7. The resin composition according to any one of claims 1 to 3, in, The content of the component B is 0.5% by mass to 20% by mass based on 100% by mass, which is the total solid content of the resin composition.

8. The resin composition according to any one of claims 1 to 3, in, The reactive group contained in the component C is one or more selected from the group consisting of a functional group containing an ethylenically unsaturated bond and an acid anhydride group. 9 . The resin composition according to claim 1 , which is used for forming a resin film having a thickness of 80 μm or more. 10 . A resin film comprising the resin composition according to claim 1 . The resin film according to claim 10 , which has a thickness of 80 μm or more. 12 . The resin film according to claim 10 , which is a resin film having a thickness of 150 μm or more, wherein a relative dielectric constant Dk of a cured product of the resin film at 10 GHz is less than 2.8, and a dielectric loss tangent Df of a cured product of the resin film at 10 GHz is less than 0.0030. 13 . The resin film according to claim 10 , wherein the mass reduction rate after heat drying at 170° C. for 30 minutes in an air atmosphere is 2.0 mass % or less. 14 . A printed wiring board comprising a cured product of the resin film according to claim 10 . 15 . A semiconductor package comprising a cured product of the resin film according to claim 10 . 16 . The semiconductor package according to claim 15 , comprising a semiconductor chip sealed by the cured product of the resin film.

Images