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

Abstract

The present invention relates to: a resin composition containing (A) one or more substances selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives thereof, and (B) a compound having a vinyl benzyl group; and a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition, the resin composition containing (A) one or more substances selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives thereof, and (B) a compound having a vinyl benzyl group, the component (B) contains one or more compounds selected from the group consisting of (B1) compounds having one or more vinyl benzyl groups directly bonded to carbon atoms and (B2) compounds having three or more vinyl benzyl groups directly bonded to oxygen atoms, and the ratio of the mass-based content of the component (B) to the mass-based content of the component (A) (component (B) / component (A)) is 0.11 or more.

Description

Technical Field

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

[0002] In recent years, electronic devices have been continuously miniaturized, made lighter, and more functional, while the semiconductor devices integrated into these devices have become increasingly integrated. Along with this, printed circuit boards, semiconductor packages, and other components are increasingly required to achieve higher reliability than ever before.

[0003] For insulating resin materials used in printed circuit boards, semiconductor packages, etc., heat resistance and mechanical properties are required to withstand the manufacturing and usage environments. Therefore, the application of resin compositions using thermosetting resins with excellent heat resistance and mechanical properties has been investigated (for example, see Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-1783 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] When forming a substrate for a printed circuit board using a resin composition containing a thermosetting resin, the resin composition is cured by performing a heat-pressurization treatment in which the resin composition is heated and pressurized simultaneously.

[0009] In recent years, in order to achieve a circular society, there has been a demand to reduce electricity consumption, which necessitates shortening the heating and pressurizing time (hereinafter also referred to as "heating and pressurizing time") of resin compositions. However, simply shortening the heating and pressurizing time of the resin composition may result in insufficient curing of the thermosetting resin, leading to a significant decrease in the glass transition temperature of the cured product. Furthermore, the heating and pressurizing time applied to the resin composition varies depending on the structure of the target semiconductor package; therefore, it is desirable to maintain a stable glass transition temperature even when the heating and pressurizing time is changed.

[0010] In view of this situation, the objective of this embodiment is to provide: a resin composition in which the glass transition temperature changes little even when the heating and pressurization treatment time is changed, a prepreg using the resin composition, a laminate, a resin film, a printed circuit board, and a semiconductor package.

[0011] Methods for solving problems

[0012] In order to solve the above-mentioned problem, the inventors conducted research and found that the problem can be solved by the following embodiments [1] to

[12] .

[0013] [1] A resin composition comprising:

[0014] (A) Selected from one or more maleimide resins and their derivatives having one or more N-substituted maleimide groups; and

[0015] (B) Compounds having a vinyl benzyl group,

[0016] The above-mentioned component (B) contains one or more compounds selected from (B1) compounds having one or more vinyl benzyl groups directly bonded to a carbon atom and (B2) compounds having three or more vinyl benzyl groups directly bonded to an oxygen atom.

[0017] The ratio of the content of the quality standard of component (B) to the content of the quality standard of component (A) [component (B) / component (A)] is 0.11 or more.

[0018] [2] According to the resin composition described in [1] above, wherein the above-mentioned component (B) contains the above-mentioned component (B1).

[0019] [3] According to the resin composition described in [2] above, wherein the above-mentioned (B1) component is a compound comprising a fused polycyclic structure containing an aromatic ring and a non-aromatic ring.

[0020] [4] According to the resin composition described in [3] above, the fused polycyclic structure containing aromatic and non-aromatic rings is an indene ring.

[0021] [5] The resin composition described in any one of [2] to [4] above, wherein the above-mentioned (B1) component is a compound having two or more vinyl benzyl groups directly bonded to carbon atoms.

[0022] [6] The resin composition according to any one of [1] to [5] above, wherein the above-mentioned component (A) is selected from one or more aromatic maleimide resins having two or more N-substituted maleimide groups and their derivatives.

[0023] [7] A prepreg containing the resin composition described in any one of [1] to [5] above or a semi-cured product of the resin composition described above.

[0024] [8] A laminate having a cured resin composition of any one of [1] to [5] and a metal foil.

[0025] [9] A resin film containing the resin composition described in any one of [1] to [5] above or a semi-cured product of the resin composition described above.

[0026]

[10] A printed circuit board having a cured product of the resin composition described in any one of [1] to [5] above.

[0027]

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

[10] above.

[0028]

[12] A semiconductor package having a semiconductor element and a cured resin composition of any one of [1] to [5] described above for sealing the semiconductor element.

[0029] Invention Effects

[0030] According to this embodiment, it is possible to provide: a resin composition in which the glass transition temperature changes little even when the heating and pressurizing treatment time is changed, a prepreg using the resin composition, a laminate, a resin film, a printed circuit board, and a semiconductor package. Detailed Implementation

[0031] In this specification, the numerical range indicated by “~” represents the range of minimum and maximum values ​​recorded before and after the “~”.

[0032] For example, the expression "X~Y" (where X and Y are real numbers) refers to a range of values ​​above X and below Y. Furthermore, the phrase "above X" in this specification refers to X and values ​​exceeding X. Additionally, the phrase "below Y" in this specification refers to Y and values ​​less than Y.

[0033] The lower and upper limits of the numerical ranges described in this specification can be arbitrarily combined with the lower or upper limits of other numerical ranges.

[0034] In the numerical range described in this specification, the lower or upper limit of the numerical range may be replaced with the values ​​shown in the embodiments.

[0035] Unless otherwise specified, each component and material illustrated in this instruction manual may be used alone or in combination of two or more.

[0036] In this specification, the content of each component in the resin composition refers to the total amount of the multiple substances present in the resin composition, unless otherwise specified, when multiple substances equivalent to each component are present in the resin composition.

[0037] In this specification, "solid components" refers to components other than solvents, and components that are liquid at 25°C are also considered solid components.

[0038] The weight-average molecular weight (Mw) in this specification refers to the value determined by gel permeation chromatography (GPC) and converted to polystyrene. Specifically, the weight-average molecular weight (Mw) in this specification can be determined by the methods described in the examples.

[0039] In this specification, "semi-cured product" has the same meaning as resin compositions in the B-stage state in JIS K 6800 (2006), and "cured product" has the same meaning as resin compositions in the C-stage state in JIS K 6800 (2006).

[0040] The mechanisms of action described in this specification are speculative and are not intended to limit the mechanisms by which this embodiment achieves its effects.

[0041] This embodiment also includes any combination of the items described in this specification.

[0042] [Resin Composition]

[0043] The resin composition of this embodiment contains:

[0044] (A) Selected from one or more maleimide resins and their derivatives having one or more N-substituted maleimide groups; and

[0045] (B) Compounds having a vinyl benzyl group,

[0046] The above-mentioned component (B) contains one or more compounds selected from (B1) compounds having one or more vinyl benzyl groups directly bonded to a carbon atom and (B2) compounds having three or more vinyl benzyl groups directly bonded to an oxygen atom.

[0047] The ratio of the content of the quality standard of component (B) to the content of the quality standard of component (A) [component (B) / component (A)] is 0.11 or more.

[0048] It should be noted that in this specification, each component is sometimes referred to as component (A), component (B), etc., and the same abbreviation method is sometimes used for other components as well.

[0049] <(A) Selected from one or more maleimide resins and their derivatives having one or more N-substituted maleimide groups>

[0050] The resin composition of this embodiment contains: (A) one or more maleimide resins and their derivatives having one or more N-substituted maleimide groups (hereinafter also referred to as "(A) maleimide resin").

[0051] (A) Maleimide resin can be used alone or in combination of two or more types.

[0052] It should be noted that in the following description, maleimide resins having more than one N-substituted maleimide group are sometimes referred to as "maleimide resin (AX)" or "(AX) component".

[0053] In addition, derivatives of maleimide resins having one or more N-substituted maleimide groups are sometimes referred to as "maleimide resin derivatives (AY)" or "(AY) components".

[0054] (Maleimide resin (AX))

[0055] There are no particular limitations on maleimide resins (AX) as long as they have one or more N-substituted maleimide groups.

[0056] From the viewpoint of conductor adhesion and heat resistance, 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.

[0057] It should be noted that, in this specification, "aromatic maleimide resin" refers to a compound having N-substituted maleimide groups directly bonded to an aromatic ring. Additionally, in this specification, "aromatic bismaleimide resin" refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. Furthermore, in this specification, "aromatic polymaleimide resin" refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. Finally, in this specification, "aliphatic maleimide resin" refers to a compound having N-substituted maleimide groups directly bonded to an aliphatic hydrocarbon.

[0058] As the maleimide resin (AX), the maleimide resin shown in the following general formula (A-1) is preferred.

[0059] [Chemical Formula 1]

[0060]

[0061] (where X) A1 (It is a divalent organic group.)

[0062] As X in the above general formula (A-1)A1 The divalent organic groups shown can be, for example, those shown in the following general formulas (A-2), (A-3), (A-4), (A-5), or (A-6).

[0063] [Chemical Formula 2]

[0064]

[0065] (where R) A1 It consists of an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbon atoms. A1 Integers between 0 and 4. (Indicates the bonding site.)

[0066] R in the above general formula (A-2) A1 Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include: alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; alkenyl groups with 2 to 5 carbon atoms; and alkynyl groups with 2 to 5 carbon atoms. The aliphatic hydrocarbon groups with 1 to 5 carbon atoms can be either straight-chain or branched.

[0067] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0068] In n A1 When R is an integer greater than 2, multiple R A1 They can be the same or different.

[0069] [Chemical Formula 3]

[0070]

[0071] (where R) A2 and R A3 Each is independently an aliphatic hydrocarbon group or halogen atom with 1 to 5 carbon atoms. X A2 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 carbonyl group, a ketone group, a single bond, or a divalent organic group represented by the following general formula (A-3-1). A2 and n A3 Each is an independent integer from 0 to 4. (Indicates the bonding site.)

[0072] R in the above general formula (A-3) A2 and R A3 The aliphatic hydrocarbon groups and halogen atoms with 1 to 5 carbon atoms shown can be exemplified by those related to the above-mentioned R. A1 Same group.

[0073] As X in the above general formula (A-3) A2 Examples of alkyl groups having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentaneene. Methylene is preferred as the alkyl group having 1 to 5 carbon atoms.

[0074] As X in the above general formula (A-3) A2 Examples of alkylidene groups with 2 to 5 carbon atoms include: ethoxyl, propionyl, isopropionyl, butylidene, isobutylidene, pentylidene, isopentyl, etc.

[0075] In the above general formula (A-3), n A2 and n A3 Each is an integer from 0 to 4, and from the point of view of ease of acquisition, they are all preferably integers from 0 to 2.

[0076] In n A2 or n A3 When R is an integer greater than 2, multiple R A2 R to each other or multiple R A3 They can be the same or different.

[0077] In the above general formula (A-3), X A2 The divalent organic groups represented by the general formula (A-3-1) are as follows.

[0078] [Chemical Formula 4]

[0079]

[0080] (where R) A4 and R A5 Each is independently an aliphatic hydrocarbon group or halogen atom with 1 to 5 carbon atoms. X A3 It can be an alkyl group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyl group, a ketone group, or a single bond. A4 and n A5 Each is an independent integer from 0 to 4. (Indicates the bonding site.)

[0081] R in the above general formula (A-3-1) A4 and R A5 The aliphatic hydrocarbon groups and halogen atoms with 1 to 5 carbon atoms shown can be exemplified by those related to the above-mentioned R. A1 Same group.

[0082] X in the above general formula (A-3-1) A3 The alkylene groups having 1 to 5 carbon atoms and the alkylidene groups having 2 to 5 carbon atoms shown can be exemplified by those related to X above. A2 Same group.

[0083] In the above general formula (A-3-1), n A4 and n A5 Each is an integer from 0 to 4, and from the point of view of ease of acquisition, they are all preferably integers from 0 to 2.

[0084] In n A4 or n A5 When R is an integer greater than 2, multiple R A4 R to each other or multiple R A5 They can be the same or different.

[0085] [Chemical Formula 5]

[0086]

[0087] (where n) A6 Integers from 0 to 10. (Indicates the bonding site.)

[0088] [Chemical Formula 6]

[0089]

[0090] (where n) A7 Numbers between 0 and 5. (Indicates the bonding site.)

[0091] [Chemical Formula 7]

[0092]

[0093] (where R) A6 and R A7 Each is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. A8 It is an integer from 1 to 8. (Indicates the bonding site.)

[0094] R in the above general formula (A-6) A6 and R A7 The aliphatic hydrocarbon groups and halogen atoms with 1 to 5 carbon atoms shown can be exemplified by those related to the above-mentioned R. A1 Same group.

[0095] In the above general formula (A-6) n A8 When R is an integer greater than 2, multiple R A6 R to each other or multiple R A7 They can be the same or different.

[0096] Examples of maleimide resins (AX) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins, among which aromatic bismaleimide resins are preferred. That is, component (A) is preferably selected from one or more aromatic maleimide resins and their derivatives having two or more N-substituted maleimide groups.

[0097] From the viewpoints of heat resistance and dielectric properties, the preferred maleimide resins (AX) are bis(4-maleimidephenyl)methane, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 4-methyl-1,3-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, aromatic bismaleimide resins with an indaminozide skeleton, and biphenyl aralkyl type maleimide resins.

[0098] As a maleimide resin derivative (AY), an aminomaleimide resin having a structure derived from the above-mentioned maleimide resin (AX) and a structure derived from a diamine compound is preferred.

[0099] Aminomaleimide resins are obtained, for example, by Michael addition of maleimide resin (AX) with a diamine compound.

[0100] As a diamine compound, for example, a compound identical to the amine compound having at least two primary amino groups in one molecule listed in Japanese Patent Application Publication 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-methylethylene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylene)]bisaniline, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and organosilicon compounds having primary amino groups at both ends are preferred.

[0101] The content of the structure derived from maleimide resin (AX) in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and even more preferably 70 to 90% by mass.

[0102] In addition, the content of the structure derived from the diamine compound in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and even more preferably 10 to 30% by mass.

[0103] From the viewpoints of heat resistance, formability, processability, conductor adhesion and dielectric properties, the content of (A) maleimide resin in the resin composition of this embodiment is preferably 1 to 90% by mass, more preferably 20 to 80% by mass, further preferably 35 to 75% by mass, and particularly preferably 50 to 70% by mass, relative to the total amount of resin components (100% by mass) in the resin composition of this embodiment.

[0104] In this specification, "resin component" refers to resin and compounds that form resin through a curing reaction.

[0105] In the resin composition of this embodiment, for example, components (A), (B), (C), (D), and (F) are equivalent to resin components.

[0106] In this embodiment, if the resin composition contains, in addition to the above-described components, a resin or a compound that forms a resin through a curing reaction as an arbitrary component, these arbitrary components are also included in the resin composition.

[0107] On the other hand, component (E) is not included in the resin components.

[0108] From the viewpoints of low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, the total content of resin components in the resin composition of this embodiment is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass, relative to the total solid content (100% by mass) of the resin composition of this embodiment.

[0109] <(B) Compounds containing a vinyl benzyl group>

[0110] The resin composition of this embodiment contains (B) a compound having a vinyl benzyl group (hereinafter also referred to as "(B) vinyl benzyl compound"). The (B) vinyl benzyl compound contains one or more compounds selected from (B1) a compound having one or more vinyl benzyl groups directly bonded to a carbon atom and (B2) a compound having three or more vinyl benzyl groups directly bonded to an oxygen atom.

[0111] (B) A vinylbenzyl compound may be used alone or in combination of two or more compounds.

[0112] In the resin composition of this embodiment, the ratio of the mass basis content of component (B) to the mass basis content of component (A) [(B) component / (A) component] (hereinafter also referred to as "content ratio [(B) component / (A) component]") is 0.11 or more.

[0113] If the content ratio of component (B) to component (A) is 0.11 or higher, the glass transition temperature of the resin composition of this embodiment changes little even when the heating and pressurizing treatment time is changed. The reason for this is not yet certain, but it is speculated that the main reason is that the N-substituted maleimide group of the maleimide resin (A) reacts with the vinyl benzyl group of the vinyl benzyl compound (B) at a lower temperature to generate free radicals, which promote the curing reaction of the maleimide resin (A).

[0114] From the viewpoint of further reducing the change in glass transition temperature when the heating and pressurizing treatment time is changed, the content ratio [(B) component / (A) component] is preferably 0.12 or more, more preferably 0.13 or more, and even more preferably 0.14 or more.

[0115] Furthermore, from the viewpoint of conductor adhesion, the content ratio [(B) component / (A) component] is preferably 50 or less, more preferably 10 or less, even more preferably 1 or less, and particularly preferably 0.3 or less.

[0116] Furthermore, from the same point of view as above, the content ratio [(B) component / (A) component] is preferably 0.11 to 50, more preferably 0.12 to 10, even more preferably 0.13 to 1, and particularly preferably 0.14 to 0.3.

[0117] The following describes a suitable manner for (B) vinylbenzyl compounds.

[0118] (B) The vinyl benzyl group in the vinyl benzyl compound may be any of ortho-vinyl benzyl, meta-vinyl benzyl or para-vinyl benzyl, with para-vinyl benzyl or meta-vinyl benzyl preferred from the viewpoint of dielectric properties.

[0119] From the viewpoint of low dielectric loss tangent, in the vinylbenzyl compound (B), the content of p-vinylbenzyl groups is preferably 10-100% by mass, more preferably 20-90% by mass, even more preferably 30-80% by mass, and particularly preferably 40-60% by mass. From the viewpoint of low dielectric loss tangent, in the vinylbenzyl compound (B), the content of meta-vinylbenzyl groups is preferably 10-100% by mass, more preferably 20-90% by mass, even more preferably 30-80% by mass, and particularly preferably 40-60% by mass.

[0120] (B1) Compounds having one or more vinyl benzyl groups directly bonded to a carbon atom)

[0121] (B1) There are no particular restrictions on the composition as long as it is a compound having one or more vinyl benzyl groups directly bonded to a carbon atom.

[0122] The resin composition of this embodiment contains (B1) component as (B) vinyl benzyl compound, thereby reducing the change in glass transition temperature even when the heating and pressurization treatment time is changed, and tends to obtain excellent dielectric properties.

[0123] (B1) The component may have one or more vinyl benzyl groups directly bonded to carbon atoms in one molecule. (B1) The component is preferably a compound having two or more vinyl benzyl groups directly bonded to carbon atoms, more preferably a compound having two to four vinyl benzyl groups directly bonded to carbon atoms, and even more preferably a compound having two or three vinyl benzyl groups directly bonded to carbon atoms.

[0124] From the viewpoint of formability and processability, the weight-average molecular weight (Mw) of component (B1) is preferably 200 to 800, more preferably 250 to 750, and even more preferably 300 to 700.

[0125] (B) The vinyl benzyl compound contains component (B1), which is preferably a compound comprising a fused polycyclic structure containing an aromatic ring and a non-aromatic ring.

[0126] The (B1) component may be a fused polycyclic structure containing aromatic and non-aromatic rings, such as indene rings, fluorene rings, indene rings, phenanthrene rings, and acenaphthene rings. Among these, indene rings and fluorene rings are preferred from the viewpoint of dielectric properties.

[0127] From the viewpoint of dielectric properties, the compound represented by the following general formula (B1-1) is preferred as the (B1) component containing an indene ring.

[0128] [Chemical Formula 8]

[0129]

[0130] (where R) B1 Each is independently vinylbenzyl, n B1 (Integers from 1 to 3.)

[0131] The compound represented by the above general formula (B1-1) can be any of the following: a compound having one vinyl benzyl group, a compound having two vinyl benzyl groups, and a compound having three vinyl benzyl groups, or a mixture thereof.

[0132] In the case of a mixture, the average number of vinyl benzyl groups per molecule of the compound represented by the above general formula (B1-1) is preferably 1.4 to 2.8, more preferably 1.6 to 2.7, and even more preferably 1.8 to 2.6.

[0133] From the viewpoint of dielectric properties, the compound represented by the following general formula (B1-2) is preferred as the (B1) component containing a fluorene ring.

[0134] [Chemical Formula 9]

[0135]

[0136] (where X) B1 It is an alkyl group with 1 to 10 carbon atoms, R B2 (It can be a hydrogen atom or a vinyl benzyl group.)

[0137] As X in the above general formula (B1-2) B1 Examples of alkyl groups with 1 to 10 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentene, and 1,6-hexene.

[0138] (B2) Compounds having three or more vinyl benzyl groups directly bonded to oxygen atoms)

[0139] (B2) There are no particular restrictions on the composition as long as it is a compound having three or more vinyl benzyl groups directly bonded to oxygen atoms.

[0140] The resin composition of this embodiment contains (B2) component as (B) vinyl benzyl compound, thereby reducing the change in glass transition temperature even when the heating and pressurization treatment time is changed, and tends to improve dielectric properties and curability.

[0141] (B) The vinyl benzyl compound contains component (B2), and from the viewpoint of curability, formability and processability, component (B2) is preferably a compound represented by the following general formula (B2-1).

[0142] [Chemical Formula 10]

[0143]

[0144] (where X) B2 Each is an independent divalent hydrocarbon group, n B2 (Integers from 1 to 5.)

[0145] X in the above general formula (B2-1) B2 Examples of divalent hydrocarbon groups include alkylene groups with 1 to 5 carbon atoms, alkylidene groups with 2 to 5 carbon atoms, divalent alicyclic hydrocarbon groups with 5 to 12 carbon atoms, arylene groups with 6 to 12 carbon atoms, and divalent groups formed by combining them.

[0146] Examples of alkyl groups having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentylene.

[0147] Examples of alkylidene groups with 2 to 5 carbon atoms include ethoxyl, propionyl, isopropionyl, butylidene, isobutylidene, pentylidene, and isopentylidene.

[0148] Examples of divalent alicyclic hydrocarbon groups with 5 to 12 carbon atoms include those formed by losing two hydrogen atoms bonded to two different carbon atoms from alicyclic hydrocarbon compounds such as norbornene, decahydronaphthalene, bicycloundecane, and saturated dicyclopentadiene.

[0149] Examples of arylene groups with 6 to 12 carbon atoms include phenylene, naphthylene, and biphenylene.

[0150] X B2 Preferably, it is a group formed by combining an alkyl group having 1 to 5 carbon atoms with an arylene group having 6 to 12 carbon atoms, and more preferably, it is a divalent group shown in the following general formula (B2-2-1).

[0151] [Chemical Formula 11]

[0152]

[0153] (where X) B3 Each is an alkyl group with 1 to 5 carbon atoms, Ar B1 It is an arylene group with 6 to 12 carbon atoms. (Indicates the bonding site.)

[0154] X B3 The alkyl group having 1 to 5 carbon atoms shown is preferably used as X above. B2 The methylene group is listed among the alkyl groups.

[0155] Ar B1 The arylene group with 6 to 12 carbon atoms shown is preferably used as X above. B2 The listed arylene groups include phenylene and biphenylene. Furthermore, 1,4-phenylene is preferred, and 4,4'-biphenylene is preferred.

[0156] In the above general formula (B2-1), n B2 It is an integer from 1 to 50, preferably an integer from 1 to 30, and more preferably an integer from 1 to 20.

[0157] (B) Vinylbenzyl compounds may be commercially available or synthesized by known methods.

[0158] Examples of methods for synthesizing (B) vinylbenzyl compounds include: reacting a base compound containing a vinylbenzyl group with styrene having a halomethyl group in the presence of a basic compound. Examples of base compounds include: compounds having phenolic hydroxyl groups; compounds having fused polycyclic structures containing aromatic and non-aromatic rings, such as fluorene, indene, indane, phenanthrene, and acenaphthene.

[0159] Examples of styrene having a halogenated methyl group include o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, and mixtures thereof.

[0160] Examples of basic compounds include alkali metal hydroxides and alkali metal alkoxides.

[0161] In the above reaction, a phase transfer catalyst can be used. Examples of phase transfer catalysts include tetrabutylammonium bromide.

[0162] The reaction is preferably carried out under heating and stirring, and the resulting product can be purified as needed by known methods such as concentration, reprecipitation, and washing.

[0163] From the viewpoint of dielectric properties, based on the total amount of (B) vinylbenzyl compound, the total content of one or more selected from (B1) and (B2) components in (B) vinylbenzyl compound is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.

[0164] Relative to the total amount of resin components (100% by mass) in the resin composition of this embodiment, the content of (B) vinyl benzyl compound in the resin composition of this embodiment is preferably 1 to 80% by mass, more preferably 3 to 50% by mass, even more preferably 6 to 35% by mass, and particularly preferably 8 to 20% by mass.

[0165] If the content of (B) vinylbenzyl compound is above the lower limit mentioned above, the resin composition of this embodiment tends to exhibit a smaller change in glass transition temperature even when the heating and pressurization treatment time is changed. Furthermore, if the content of (B) vinylbenzyl compound is below the upper limit mentioned above, there is a tendency for the conductor adhesion to become better.

[0166] <(C) Epoxy Resin>

[0167] The resin composition of this embodiment preferably further contains (C) epoxy resin.

[0168] (C) One type of epoxy resin can be used alone, or two or more types can be used in combination.

[0169] Examples of (C) epoxy resins include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and other bisphenol-type epoxy resins; linear phenolic epoxy resins such as bisphenol A linear phenolic epoxy resin, bisphenol F linear phenolic epoxy resin, phenol linear phenolic epoxy resin, cresol linear phenolic epoxy resin, biphenyl linear phenolic epoxy resin, and naphthol linear phenolic epoxy resin; phenol aromatic... Aryl alkyl epoxy resins, biphenyl aralkyl epoxy resins, naphthol aralkyl epoxy resins, and other aralkyl-type epoxy resins; stilbene epoxy resins; naphthylene ether epoxy resins; biphenyl epoxy resins; dihydroanthracene epoxy resins; epoxy resins containing a saturated dicyclopentadiene backbone; cyclohexanediol epoxy resins; spirocyclic epoxy resins; heterocyclic epoxy resins; alicyclic epoxy resins; aliphatic chain epoxy resins; rubber-modified epoxy resins, etc.

[0170] When the resin composition of this embodiment contains (C) epoxy resin, from the viewpoints of heat resistance, formability, processability, conductor adhesion and dielectric properties, the content of (C) epoxy resin is preferably 1 to 25% by mass relative to the total amount (100% by mass) of the resin component in the resin composition of this embodiment, more preferably 5 to 20% by mass, and even more preferably 8 to 15% by mass.

[0171] <(D) Phenolic Resin>

[0172] The resin composition of this embodiment preferably further contains (D) phenolic resin.

[0173] (D) Phenolic resins can be used alone or in combination of two or more.

[0174] Examples of (D) phenolic resins include: linear phenolic resins such as phenol linear phenolic resin and cresol linear phenolic resin; naphthalene-type phenolic resin, high-ortho-type linear phenolic resin, terpene-modified phenolic resin, terpene-phenol-modified phenolic resin, aralkyl-type phenolic resin, dicyclopentadiene-type phenolic resin, salicylaldehyde-type phenolic resin, benzaldehyde-type phenolic resin, etc.

[0175] When the resin composition of this embodiment contains (D) phenolic resin, from the viewpoints of heat resistance, formability, processability, conductor adhesion and dielectric properties, the content of (D) phenolic resin is preferably 3 to 30% by mass relative to the total amount (100% by mass) of the resin component in the resin composition of this embodiment, more preferably 8 to 25% by mass, and even more preferably 12 to 20% by mass.

[0176] <(E) Inorganic filler materials>

[0177] The resin composition of this embodiment preferably also contains (E) inorganic filler material.

[0178] The resin composition of this embodiment tends to have better low thermal expansion and heat resistance by containing (E) inorganic filler material.

[0179] (E) Inorganic filler materials can be used alone or in combination with two or more.

[0180] Examples of inorganic filler materials (E) include: silica, alumina, titanium dioxide, 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, and silicon carbide. From the viewpoints of low thermal expansion, heat resistance, and flame retardancy, silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred.

[0181] From the viewpoint of dispersibility and formability, molten silica is preferred as the silica.

[0182] From the perspective of the dispersibility and micro-wiring properties of (E) inorganic filler materials, (E) the average particle size of inorganic filler materials (D 50 The preferred size is 0.1–10 μm, more preferably 0.2–1 μm, and even more preferably 0.3–0.8 μm.

[0183] It should be noted that in this specification, (E) refers to the average particle size of the inorganic filler material (D) 50 (E) The average particle size of inorganic filler materials can be measured, for example, using a particle size distribution measuring device that employs laser diffraction scattering.

[0184] The shape of the inorganic filler material (E) can be, for example, spherical or fragmented, with spherical being preferred.

[0185] From the perspective of improving dispersibility and adhesion to organic components, (E) inorganic filler materials can be surface treated with surface treatment agents such as silane coupling agents.

[0186] When the resin composition of this embodiment contains (E) inorganic filler, the content of (E) inorganic filler is preferably 20 to 95% by mass relative to the total solid content (100% by mass) of the resin composition, more preferably 40 to 90% by mass, and even more preferably 60 to 80% by mass.

[0187] If the content of inorganic filler (E) is above the lower limit mentioned above, there is a tendency for lower thermal expansion and heat resistance to become better. Furthermore, if the content of inorganic filler (E) is below the upper limit mentioned above, there is a tendency for better formability and conductor adhesion to become better.

[0188] <(F) Curing Accelerator>

[0189] The resin composition of this embodiment preferably further contains (F) a curing accelerator.

[0190] The resin composition of this embodiment tends to have improved curability, better dielectric properties, better heat resistance and better conductor adhesion by containing a (F) curing accelerator.

[0191] (F) Curing accelerators can be used alone or in combination with two or more.

[0192] Examples of (F) curing accelerators include: acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazolium, phenylimidazolium, 2-undecylimidazolium, 1-cyanoethyl-2-phenylimidazolium, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate-masked imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazolium; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine and quaternary phosphorus compounds that are the addition reaction product of p-benzoquinone and tri-n-butylphosphine; and dicumyl peroxide. Organic peroxides such as 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylperoxyisopropyl monocarbonate, and α,α'-bis(tert-butylperoxy)diisopropylbenzene; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanitrile), and 2,2'-azobis(4-methoxy-2'-dimethylpentanitrile); carboxylates of manganese, cobalt, and zinc; and acidic catalysts such as p-toluenesulfonic acid.

[0193] From the perspective of curing promotion effect and storage stability, isocyanate-masked imidazole compounds are preferred.

[0194] When the resin composition of this embodiment contains curing accelerator (F), the content of curing accelerator (F) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, and even more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of thermosetting resin (A).

[0195] If the content of curing accelerator (F) is above the lower limit mentioned above, there is a tendency to easily obtain a sufficient curing accelerator effect. Furthermore, if the content of curing accelerator (F) is below the upper limit mentioned above, there is a tendency for storage stability to become better.

[0196] <Other arbitrary ingredients>

[0197] The resin composition of this embodiment may further contain, as needed, resin materials other than those mentioned above, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, silane coupling agents, organic solvents, and other additives.

[0198] Any other ingredient may be used alone or in combination with two or more.

[0199] The content of any of the above-mentioned components in the resin composition of this embodiment is not particularly limited, and can be used as needed within the range that does not impair the effect of this embodiment.

[0200] Furthermore, the resin composition of this embodiment may be made without any of the above-mentioned components, depending on the desired performance.

[0201] From a processability point of view, the resin composition of this embodiment may contain organic solvents.

[0202] Examples of organic solvents include: alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester solvents such as γ-butyrolactone.

[0203] From the viewpoint of solubility, alcohol solvents, ketone solvents, nitrogen-containing solvents, and aromatic hydrocarbon solvents are preferred, ketone solvents are more preferred, and methyl ethyl ketone is even more preferred.

[0204] <Method for manufacturing resin composition>

[0205] The resin composition of this embodiment can be manufactured by mixing the components using a known method. In this process, the components can be dissolved or dispersed while stirring. The mixing order, temperature, time, and other conditions are not particularly limited and can be arbitrarily set according to the type of raw materials.

[0206] <Physical Properties of Resin Compositions>

[0207] (Rate of change of glass transition temperature based on heating and pressurization treatment time)

[0208] In the resin composition of this embodiment, the rate of change of glass transition temperature based on the heating and pressurization treatment time, measured under the following conditions, is preferably -20% to +20%, more preferably -15% to +15%, further preferably -12% to +12%, even more preferably -10% to +10%, even more preferably -8% to +8%, even more preferably -7% to +7%, even more preferably -6% to +6%, and particularly preferably -5% to +5%.

[0209] A method for determining the rate of change of glass transition temperature based on heating and pressurization time.

[0210] Seven sheets containing the above-mentioned resin composition and glass cloth (glass type: T glass, unit area weight: 114g / m²) were prepared. 2 The thickness of the glass cloth is 0.098 mm. Prepregs with a thickness of 0.1 mm are stacked and subjected to heating and pressurization treatment for 100 minutes or 40 minutes at a temperature of 240℃ and a pressure of 3.0 MPa, respectively, to obtain a laminate (100) made with a heating and pressurization treatment time of 100 minutes and a laminate (40) made with a heating and pressurization treatment time of 40 minutes.

[0211] The obtained laminates (40) and (100) were cut into 4mm × 30mm pieces according to their planar dimensions, and dried at 105℃ for 1 hour. The resulting pieces were used as test specimens. The test specimens were used as the test objects, and dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device at a heating rate of 5℃ / min, a frequency of 10Hz, and a measurement temperature range of 40~400℃. The temperature at which tanδ reaches its maximum value in the obtained temperature-loss tangent (tanδ) curve was taken as the glass transition temperature (Tg).

[0212] The rate of change of glass transition temperature based on the heating and pressurization treatment time is calculated using the following formula (1) based on the glass transition temperature Tg(100) of the laminate (100) and the glass transition temperature Tg(40) of the laminate (40).

[0213] The rate of change of glass transition temperature based on heating and pressurization time (%) = [Tg(100) - Tg(40)] × 100 / Tg(100) (1)

[0214] A more detailed method for determining the rate of change of glass transition temperature based on heating and pressurization treatment time is described in the examples.

[0215] It should be noted that, in this embodiment, "T glass" refers to glass composed of SiO2 (64-66% by mass), Al2O3 (24-26% by mass), and MgO (9-11% by mass).

[0216] <Glass transition temperature of laminate (40)>

[0217] When the resin composition of this embodiment is made into the form of the laminate (40) described in the above-mentioned "method for determining the rate of change of glass transition temperature based on heating and pressurizing treatment time", from the viewpoint of heat resistance and ease of manufacture, the glass transition temperature Tg (40) of the laminate (40) is preferably 200 to 400°C, more preferably 240 to 370°C, even more preferably 255 to 360°C, and particularly preferably 260 to 350°C.

[0218] <Coefficient of thermal expansion of laminate (40)>

[0219] When the resin composition of this embodiment is made into the form of the laminate (40) described in the above-mentioned "method for determining the rate of change of glass transition temperature based on heating and pressurizing treatment time", from the viewpoint of low thermal expansion and ease of manufacture, the coefficient of thermal expansion of the laminate (40) is preferably 4.5 to 25.0 ppm / ℃, more preferably 5.0 to 20.0 ppm / ℃, even more preferably 5.5 to 13.0 ppm / ℃, and particularly preferably 6.0 to 11.0 ppm / ℃.

[0220] The coefficient of thermal expansion of the laminate (40) can be determined by the method described in the examples.

[0221] <Flexural modulus of elasticity of laminate (40)>

[0222] When the resin composition of this embodiment is made into the form of the laminate (40) described in the above-mentioned "method for determining the rate of change of glass transition temperature based on heating and pressurizing treatment time", from the viewpoint of mechanical strength and ease of manufacture, the flexural modulus of the laminate (40) is preferably 25 to 50 GPa, more preferably 30 to 45 GPa, even more preferably 33 to 42 GPa, and particularly preferably 34 to 40 GPa.

[0223] The flexural modulus of the laminate (40) can be determined by the method described in the examples.

[0224] [Prepreg]

[0225] The prepreg in this embodiment is a prepreg containing the resin composition of this embodiment or a semi-cured product of the above-described resin composition.

[0226] The prepreg in this embodiment may contain, for example, the resin composition of this embodiment or a semi-cured product of the above-described resin composition, and a fiber substrate.

[0227] The fiber substrate contained in the prepreg of this embodiment can be, for example, a known fiber substrate used in various electrical insulation material laminates.

[0228] Examples of materials that can be used as fiber substrates include: inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These fiber substrates can take the form of woven fabrics, nonwoven fabrics, rovings, chopped strand mats, or surface mats. The fiber substrate is preferably in sheet form.

[0229] The prepreg of this embodiment can be manufactured, for example, by impregnating or coating the resin composition of this embodiment onto a fiber substrate and then heating and drying it to achieve B-step formation.

[0230] From the viewpoint of productivity and to moderately B-stage the resin composition of this embodiment, the temperature and time for heating and drying can be set, for example, to 50–200°C and 1–30 minutes.

[0231] From the viewpoint that good formability can be easily obtained when making laminates, the content of the resin composition in the prepreg of this embodiment is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 75% by mass.

[0232] From the viewpoint of formability and the ability to perform high-density wiring, the thickness of the prepreg in this embodiment is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and even more preferably 0.05 to 0.2 mm.

[0233] [Resin film]

[0234] The resin film of this embodiment is a resin film containing the resin composition of this embodiment or a semi-cured product of the above-described resin composition.

[0235] The resin film of this embodiment can be manufactured, for example, by coating a resin composition of this embodiment containing an organic solvent onto a support and then heating and drying it.

[0236] Examples of suitable supports include plastic film, metal foil, and release paper.

[0237] From the viewpoint of productivity and to adequately B-stage the resin composition of this embodiment, the temperature and time for heating and drying can be set to 50–200°C and 1–30 minutes.

[0238] In the case of manufacturing printed circuit boards, the resin film of this embodiment is preferably used to form an insulating layer.

[0239] [Laminated Board]

[0240] The laminate of this embodiment is a laminate having a cured resin composition of this embodiment and a metal foil.

[0241] It should be noted that laminates with metal foil are sometimes also called metal-clad laminates.

[0242] Metals that can be used as foils include, for example, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements.

[0243] The laminate of this embodiment can be manufactured, for example, by heat and pressure treatment after metal foil is arranged on one or both sides of the prepreg of this embodiment.

[0244] Typically, the laminate of this embodiment is obtained by curing the B-stage prepreg through this heating and pressurizing process.

[0245] When performing heat and pressure treatment, only one sheet of prepreg can be used, or two or more sheets of prepreg can be stacked.

[0246] Heating and pressurizing processes can be performed using multi-stage presses, multi-stage vacuum presses, continuous forming machines, autoclave forming machines, etc.

[0247] The conditions for heating and pressurizing treatment can be set, for example, a temperature of 100–300°C, a time of 10–300 minutes, and a pressure of 1.5–5 MPa.

[0248] Printed Circuit Board

[0249] The printed circuit board of this embodiment is a printed circuit board having a cured form of the resin composition of this embodiment.

[0250] The printed circuit board of this embodiment can be manufactured, for example, by forming conductor circuits on one or more of the cured prepreg of this embodiment, the cured resin film of this embodiment, and the laminate of this embodiment using known methods. Alternatively, a multilayer printed circuit board can be manufactured by further performing multilayer bonding processing as needed. Conductor circuits can be formed, for example, by appropriately performing hole processing, metal plating processing, etching of metal foil, etc.

[0251] [Semiconductor Package]

[0252] The semiconductor package of the first embodiment is a semiconductor package having a printed circuit board and semiconductor elements of this embodiment.

[0253] The semiconductor package of the first aspect of this embodiment can be manufactured, for example, by mounting semiconductor components, memory, etc. on the printed circuit board of this embodiment using known methods.

[0254] The second type of semiconductor package in this embodiment is a semiconductor package having a semiconductor element and a cured resin composition of this embodiment that seals the semiconductor element.

[0255] The semiconductor package of the second aspect of this embodiment can be manufactured, for example, by covering at least a portion of a semiconductor element mounted on a printed circuit board with the resin composition of this embodiment and curing the resin composition.

[0256] Example

[0257] The following examples illustrate this implementation method in detail. However, this implementation method is not limited to the following examples.

[0258] It should be noted that, in each case, the weight-average molecular weight (Mw) was determined according to the following steps.

[0259] (Method for determining weight-average molecular weight (Mw))

[0260] Weight-average molecular weight (Mw) was calculated by gel permeation chromatography (GPC) using a calibration curve employing standard polystyrene. The calibration curve used standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-20, F-80) [manufactured by Tosoh Corporation, trade name], approximated using a cubic formula. The determination conditions for GPC are shown below.

[0261] Device: High-speed GPC device HLC-8320GPC

[0262] Detector: UV-8320 ultraviolet absorbance detector [manufactured by Tosoh Corporation]

[0263] Columns: Protective columns; TSKgel guardcolumn Super (HZ)-M+ columns; TSKgel SuperMultiporeHZ-M (2 columns); Reference columns; TSKgel SuperH-RC (2 columns) (all manufactured by Tosoh Corporation, trade names)

[0264] Column dimensions: 4.6×20mm (protective column), 4.6×150mm (column), 6.0×150mm (reference column)

[0265] Eluent: Tetrahydrofuran

[0266] Sample concentration: 10 mg / 1 mL

[0267] Injection volume: 20 μL or 2 μL

[0268] Flow rate: 0.35 mL / min

[0269] Measurement temperature: 40℃

[0270] [Manufacturing of aminomaleimide resin]

[0271] Manufacturing Example 1

[0272] 100 g of a diamine-terminated siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A, an organosilicon compound with primary amino groups at both ends, functional group equivalent of amino groups: 800 g / mol), 450 g of 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, and 550 g of propylene glycol monomethyl ether were added to a 2 L reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, and capable of heating and cooling. The reaction was carried out at 120 °C for 3 hours to produce a solution containing aminomaleimide resin. The weight-average molecular weight (Mw) of the obtained aminomaleimide resin was 2,500.

[0273] [Manufacturing of Vinylbenzyl Compounds]

[0274] Manufacturing Example 2

[0275] 35.6 g of indene (as the base compound), 101.2 g of chloromethylstyrene (manufactured by AGC SEIMI CHEMICAL Co., Ltd., a mixture of m-body and p-body, with m-body content of 50% by mass and p-body content of 50% by mass) as the base compound, 7.1 g of tetrabutylammonium bromide (as the phase transfer catalyst), 0.1 g of phenothiazine (as the polymerization inhibitor), and 77.6 g of toluene (as the solvent) were added to a 500 mL reaction vessel equipped with a stirrer, thermometer, reflux pipe, and nitrogen purging inlet. The mixture was heated and stirred at 40 °C while nitrogen was purged at a flow rate of 50 mL / min.

[0276] Next, a solution prepared by adding 46.5 g of sodium hydroxide (as a basic compound) to form a 48% (w / w) aqueous solution was added dropwise over 20 minutes, and the mixture was further stirred at 60°C for 9 hours. Note that nitrogen was continuously purged during the reaction. The mixture was then cooled to room temperature (25°C), neutralized with 10% hydrochloric acid, and washed twice with pure water. Next, toluene was removed by vacuum distillation, and the resulting viscous liquid was washed with methanol and then dried under vacuum to obtain vinylbenzyl compound 1.

[0277] pass 1¹H-NMR analysis confirmed that vinylbenzyl compound 1 has a structure in which the two hydrogen atoms directly bonded to the carbon atom at position 1 of indene, as shown in formulas (B1-3), are substantially entirely replaced by vinylbenzyl groups, corresponding to composition (B1). Furthermore, GPC analysis confirmed that vinylbenzyl compound 1 is a mixture of compounds with two vinylbenzyl groups and compounds with three vinylbenzyl groups, with a weight-average molecular weight (Mw) of 500.

[0278] [Chemical Formula 12]

[0279]

[0280] [Preparation of the resin composition]

[0281] Examples 1-9, Comparative Examples 1-3

[0282] Mix the components listed in Table 1 in powder form or with methyl ethyl ketone according to the proportions listed in Table 1, and stir and mix at 25°C to prepare a varnish-like resin composition (solid component concentration: approximately 60% by mass). It should be noted that the proportions of each component in Table 1 are in parts by mass; in the case of a solution, they refer to the parts by mass converted from solid components.

[0283] [Prepreg Manufacturing]

[0284] The varnish-like resin composition obtained above was impregnated with glass cloth (manufactured by Nitto Boshoku Co., Ltd., trade name "T2118", thickness 0.098 mm, unit area weight 114 g / m²). 2 The glass type (T glass) was heated and dried at 110°C for 3 minutes to obtain a prepreg. The thickness of the obtained prepreg was 0.1 mm, and the content of the resin composition in the prepreg was 48.5% by mass.

[0285] Manufacturing of copper-clad laminates

[0286] Seven sheets of the prepreg obtained above were overlapped, and copper foil with a thickness of 12 μm (manufactured by Mitsui Metals Corporation, trade name "3EC-M3-VLP-12", roughened surface Rz: 3.0 μm) was placed on top and bottom of them with the roughened surface in contact with the prepreg. The laminate was then heated and pressurized at 240°C and 3.0 MPa for 100 minutes or 40 minutes to produce a copper-clad laminate (thickness: 0.7 mm).

[0287] [Evaluation Methods and Measurement Methods]

[0288] Using the copper-clad laminates fabricated in each example, the following measurements and evaluations were performed. The results are shown in Table 1.

[0289] (Methods for determining glass transition temperature and methods for calculating the rate of change of glass transition temperature based on heating and pressurization time)

[0290] The copper foil on both sides of the copper-clad laminate fabricated in each example is removed by etching to obtain the laminate. It should be noted that, in the laminate with the copper foil removed, the copper-clad laminate fabricated with a heating and pressurization treatment time of 40 minutes is referred to as "Laminated Laminate (40)" and the copper-clad laminate fabricated with a heating and pressurization treatment time of 100 minutes is referred to as "Laminated Laminate (100)".

[0291] The obtained laminates were cut into 4mm × 30mm pieces according to their planar dimensions, and dried at 105°C for 1 hour. These pieces were then used as test specimens. These specimens were used for testing, and dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device (UBM Rheogel-E4000) at a heating rate of 5°C / min, a frequency of 10Hz, and a measurement temperature range of 40–400°C. The temperature at which tanδ reaches its maximum value in the obtained temperature-loss tangent (tanδ) curve was taken as the glass transition temperature (Tg).

[0292] In addition, based on the glass transition temperature Tg(100) of the laminate (100) and the glass transition temperature Tg(40) of the laminate (40), the rate of change of glass transition temperature based on the heating and pressurization treatment time is calculated by the following formula (1).

[0293] The rate of change of glass transition temperature based on heating and pressurization time (%) = [Tg(100) - Tg(40)] × 100 / Tg(100) (1)

[0294] (Methods for determining the coefficient of thermal expansion)

[0295] The laminated plates (40) and (100) were cut into 5 mm squares and dried at 105°C for 1 hour. The resulting pieces were used as test pieces. The test pieces were mounted on a thermomechanical analysis (TMA) apparatus (manufactured by TA Instruments Japan Co., Ltd., trade name "TMA450") with the displacement in the thickness direction of the laminated plates being measured. The thermomechanical analysis was performed twice, with a compression method, under a load of 0.01 N and a heating rate of 10°C / min. The temperature range for the first measurement was set to 25–260°C, and the temperature range for the second measurement was set to -20–300°C. The average coefficient of thermal expansion from 30–260°C in the second measurement was taken as the coefficient of thermal expansion.

[0296] (Method for determining flexural modulus)

[0297] The aforementioned laminated plates (40) and (100) were cut into 20mm × 50mm pieces according to their surface dimensions, and dried at 105°C for 1 hour. The resulting pieces were used as test pieces. Using these test pieces as the test objects, the flexural modulus was measured at room temperature (25°C) using a 5t Tensilon (manufactured by ORIENTEC Corporation, trade name "RTC-1350A") with a crosshead speed of 1mm / min and a distance between support points of 20mm.

[0298] [Table 1]

[0299]

[0300] It should be noted that the details of each material in Table 1 are as follows.

[0301] [(A) Ingredient]

[0302] Maleimide resin 1: 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane

[0303] • Maleimide resin 2: The aminomaleimide resin obtained in manufacturing example 1

[0304] Maleimide Resin 3: Polyphenylmethane maleimide (manufactured by Daiwa Chemical Industry Co., Ltd., trade name "BMI-2300")

[0305] Maleimide resin 4: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide

[0306] Maleimide Resin 5: Bis(4-maleimidephenyl)methane

[0307] Maleimide Resin 6: Biphenyl aralkyl type maleimide (manufactured by Nippon Kayaku Co., Ltd., "MIR-3000")

[0308] [(B) Component]

[0309] Vinylbenzyl compound 1: Vinylbenzyl compound 1 obtained in manufacturing example 2

[0310] • Vinylbenzyl compound 2: A mixture of a compound having two vinylbenzyl groups directly bonded to the indene ring and a vinylbenzyl compound having three vinylbenzyl groups directly bonded to the indene ring (equivalent to component (B1)).

[0311] • Vinylbenzyl compound 3: A mixture of compounds having two vinylbenzyl groups directly bonded to the indene ring and vinylbenzyl compounds having three vinylbenzyl groups directly bonded to the indene ring (equivalent to component (B1)).

[0312] [(C) Component]

[0313] • Epoxy resin: Manufactured by DIC Corporation, trade name "HP-9540"

[0314] [(D) component]

[0315] • Phenolic resin: Manufactured by Shikoku Chemical Industry Co., Ltd., trade name "Benzoxazine Pd"

[0316] [(E) component]

[0317] • Inorganic filler material: spherical fused silica, average particle size (D 50 ): 0.5μm

[0318] [(F)Component]

[0319] • Curing accelerator: Isocyanate-masked imidazole (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name "G-8009L")

[0320] As shown in Table 1, the glass transition temperature of the resin compositions of Examples 1 to 9 of this embodiment has a small rate of change based on the heating and pressurization treatment time.

Claims

1. A resin composition comprising: (A) Selected from one or more maleimide resins and their derivatives having one or more N-substituted maleimide groups; and (B) Compounds having a vinyl benzyl group, The (B) component contains one or more compounds selected from (B1) compounds having one or more vinyl benzyl groups directly bonded to a carbon atom and (B2) compounds having three or more vinyl benzyl groups directly bonded to an oxygen atom. The ratio of the content of the mass reference of component (B) to the content of the mass reference of component (A), i.e., component (B) / component (A), is 0.11 or higher.

2. The resin composition according to claim 1, wherein, The (B) component contains the (B1) component.

3. The resin composition according to claim 2, wherein, The (B1) component is a compound comprising a fused polycyclic structure containing aromatic and non-aromatic rings.

4. The resin composition according to claim 3, wherein, The fused polycyclic structure containing aromatic and non-aromatic rings is an indene ring.

5. The resin composition according to claim 2, wherein, The (B1) component is a compound having two or more vinyl benzyl groups directly bonded to carbon atoms.

6. The resin composition according to any one of claims 1 to 5, wherein, The component (A) is selected from one or more aromatic maleimide resins and their derivatives having two or more N-substituted maleimide groups.

7. A prepreg comprising the resin composition of any one of claims 1 to 5 or a semi-cured product of the resin composition.

8. A laminate comprising a cured resin composition according to any one of claims 1 to 5 and a metal foil.

9. A resin film comprising the resin composition of any one of claims 1 to 5 or a semi-cured product of the resin composition.

10. A printed circuit board having a cured product of the resin composition according to any one of claims 1 to 5.

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

12. A semiconductor package having a semiconductor element and a cured resin composition of any one of claims 1 to 5 for sealing the semiconductor element.

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