Resin compositions, prepregs, resin sheets, printed circuit boards, semiconductor packages, and semiconductor devices.

Abstract

To provide a resin composition with excellent low thermal expansion and adhesion properties. [Solution] A resin composition comprising a prepolymer-containing composition (A') obtained by heating a raw material mixture containing a maleimide compound and a mercapto-modified silicone, and a thermosetting compound (B'). A resin composition containing a prepolymer (A) formed from a maleimide compound and a mercapto-modified silicone, and a thermosetting compound (B).

Description

[Technical Field]

[0001] The present invention relates to resin compositions, prepregs, resin sheets, printed circuit boards, semiconductor packages, and semiconductor devices. [Background technology]

[0002] As semiconductor packages become more sophisticated, the problem of warping due to the difference in thermal expansion between the semiconductor chip and the substrate is becoming more serious, and there is a strong demand for low thermal expansion in printed circuit boards for semiconductor packages to suppress this warping. One technology for achieving this low thermal expansion is the introduction of a silicone compound into the resin composition (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 6241536 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] On the other hand, silicone compounds generally have poor compatibility with thermosetting resins, and simply adding them to varnish can cause bleed-out, leading to problems such as reduced adhesion to copper foil used in wiring formation and decreased heat resistance.

[0005] To address these challenges, a method has been disclosed in which silicone compounds are prepolymerized with thermosetting resins. However, controlling the reactivity is difficult, and gelation can occur during prepolymerization. Furthermore, when mixed with thermosetting resins, the silicone compounds act as a curing catalyst for the thermosetting resins, severely degrading the varnish life. As a result, the range of applicability has been limited.

[0006] The object of the present invention is to provide a resin composition that exhibits low thermal expansion and excellent adhesion when cured.

Means for Solving the Problem

[0007] In order to achieve the object of the present invention, the present inventors have conducted intensive studies and as a result, have found that when using a prepolymer formed from a maleimide compound and a mercapto-modified silicone as a resin composition, excellent low thermal expansion and adhesion can be imparted when it is made into a cured product, and thus the present invention has been completed.

[0008] That is, the present invention is as follows. [1] A prepolymer-containing composition (A') obtained by heating a raw material mixture containing a maleimide compound and a mercapto-modified silicone, a thermosetting compound (B'), and a resin composition blended therewith. [2] The resin composition according to [1] above, wherein the weight average molecular weight of the prepolymer-containing composition (A') is 7,000 to 30,000. [3] The resin composition according to [1] above, wherein the mass ratio (maleimide compound: mercapto-modified silicone) of the maleimide compound and the mercapto-modified silicone in the raw material mixture is 55:45 to 30:70. [4] The resin composition according to [1] above, wherein the blending amount of the prepolymer-containing composition (A') is 5 to 50 parts by mass with respect to 100 parts by mass of the total blending amount of the prepolymer-containing composition (A') and the thermosetting compound (B'). [5] The resin composition according to [1] above, wherein the heating temperature of the raw material mixture for obtaining the prepolymer-containing composition (A') is 70°C to 100°C. [6] A resin composition containing a prepolymer (A) formed from a maleimide compound and a mercapto-modified silicone, a thermosetting compound (B), and. [7] The resin composition according to [6] above, wherein the mercapto group equivalent of the mercapto-modified silicone for forming the prepolymer (A) is 1,000 to 5,000 g / eq. [8] The resin composition according to [6] or [7], wherein the mercapto-modified silicone for forming the prepolymer (A) comprises a mercapto-modified silicone having a phenyl group. [9] The resin composition according to any one of [6] to [8] above, wherein the mercapto-modified silicone for forming the prepolymer (A) comprises a linear modified silicone having mercapto groups at both ends.

[10] The resin composition according to any one of [6] to [9] above, wherein the maleimide group equivalent of the maleimide compound for forming the prepolymer (A) is 200 to 1,500 g / eq.

[11] The resin composition according to any one of [6] to

[10] above, wherein the prepolymer (A) has a substructure represented by the following formula (a).

[0009] [ka]

[0010] (In formula (a), R independently represents a phenyl group or an alkyl group having 1 to 3 carbon atoms; X independently represents an organic group; and n represents an integer of 1 or more.)

[12] The resin composition according to any one of [6] to

[11] above, wherein the thermosetting compound (B) contains one or more selected from the group consisting of compounds having a terminal ethylenically unsaturated group, maleimide compounds, and cyanate ester compounds.

[13] The resin composition according to any one of [6] to

[12] above, further containing an inorganic filler (C).

[14] The resin composition according to

[13] , wherein the amount of the inorganic filler (C) is 30 parts by mass or more per 100 parts by mass of resin solids in the resin composition.

[15] The resin composition according to any one of [6] to

[14] above, further comprising a silane coupling agent (D).

[16] The mercapto group equivalent of the mercapto-modified silicone for forming the prepolymer (A) is 1,000 to 5,000 g / eq. The mercapto-modified silicone for forming the prepolymer (A) includes a linear modified silicone having mercapto groups at both ends. The maleimide group equivalent of the maleimide compound for forming the aforementioned prepolymer (A) is 200 to 1,500 g / eq. The prepolymer (A) has a substructure represented by the following formula (a), The resin composition according to [6] above, wherein the thermosetting compound (B) contains one or more selected from the group consisting of compounds having a terminal ethylenically unsaturated group, maleimide compounds, and cyanate ester compounds.

[0011] [ka]

[0012] (In formula (a), R independently represents a phenyl group or an alkyl group having 1 to 3 carbon atoms; X independently represents an organic group; and n represents an integer of 1 or more.)

[17] The resin composition according to

[16] , wherein the mercapto-modified silicone for forming the prepolymer (A) comprises a mercapto-modified silicone having a phenyl group.

[18] The resin composition according to

[16] , further comprising an inorganic filler (C), wherein the amount of the inorganic filler (C) is 30 parts by mass or more with respect to 100 parts by mass of the resin solids in the resin composition.

[19] A resin composition according to any of [1] to

[18] above, for forming an insulating layer on a printed circuit board.

[20] A prepreg comprising a substrate and a resin composition according to any one of [1] to

[18] above, which is impregnated or coated onto the substrate.

[21] A resin sheet comprising a support and a resin composition layer formed from any of the resin compositions described in [1] to

[18] above, provided on the support.

[22] A printed circuit board comprising an insulating layer containing a cured product formed by curing any of the resin compositions described in [1] to

[18] above.

[23] A semiconductor package comprising the printed circuit board described in

[22] above and a semiconductor element.

[24] A semiconductor device having the printed circuit board described in

[22] above.

[25] A step (1) to obtain a prepolymer-containing composition (A') by heating a raw material mixture containing a maleimide compound and a mercapto-modified silicone, and Step (2) involves blending the prepolymer-containing composition (A') obtained in step (1) with a thermosetting compound (B') to obtain a resin composition. A method for producing a resin composition containing the above. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a resin composition that exhibits low thermal expansion and excellent adhesion when cured. [Modes for carrying out the invention]

[0014] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be modified and implemented as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0015] In this specification, "resin solids" means the components of a resin composition excluding solvents, inorganic fillers, and organic fillers unless otherwise specified, and 100 parts by mass of resin solids means that the total amount of components of the resin composition excluding solvents, inorganic fillers, and organic fillers is 100 parts by mass.

[0016] [Resin composition] The resin composition of the present invention contains a prepolymer (A) formed from a maleimide compound and a mercapto-modified silicone, and a thermosetting compound (B). Such a resin composition exhibits excellent low thermal expansion and adhesion when cured.

[0017] [Prepolymer (A)] The resin composition of the present invention contains a prepolymer (A) formed from a maleimide compound and a mercapto-modified silicone. The prepolymer (A) includes a structure derived from the maleimide compound and a structure derived from the mercapto-modified silicone.

[0018] (Maleimide compounds) Maleimide compounds are compounds having one or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl groups) in one molecule. From the viewpoint of further improving heat resistance, the maleimide compound for forming prepolymer (A) is preferably a maleimide compound having two or more maleimide groups in one molecule. In one embodiment, the maleimide compound for forming prepolymer (A) is more preferably a maleimide compound having three or more maleimide groups in one molecule.

[0019] The maleimide compound for forming the prepolymer (A) may be an aromatic maleimide compound containing an aromatic carbon ring (especially a benzene ring) in its molecule, an aliphatic maleimide compound not containing an aromatic carbon ring in its molecule, or both. However, in one embodiment, it is preferable to include an aromatic maleimide compound containing an aromatic carbon ring in its molecule. In particular, it is preferable to include an aromatic maleimide compound having a maleimide group directly bonded to an aromatic carbon atom, and especially preferable to include a maleimide compound having two or more aromatic carbon rings (especially a benzene ring) with maleimide groups directly bonded to one molecule.

[0020] Examples of maleimide compounds for prepolymer (A) formation include monofunctional maleimide compounds having one maleimide group in one molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.) and difunctional maleimide compounds having two maleimide groups in one molecule (e.g., bis(4-maleimoidphenyl)methane, 2,2-bis{4-(4-maleimoidphenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimoidphenyl)methane, bis(3,5-dimethyl-4-maleimoidphenyl)methane, bis(3,5-dimethyl-4-maleimoidphenyl)methane, bis(3,5-dimethyl- Examples include 4-4-maleimide (phenyl)methane, m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bisphenol M-type maleimide, maleimide compounds having a carbon skeleton derived from dimer acid, maleimide compounds having an indane ring skeleton, dicyclopentadiene-type maleimide compounds, novolac-type maleimide compounds, and aralkyl-type maleimide compounds (e.g., phenylaralkyl-type maleimide compounds, biphenylaralkyl-type maleimide compounds, etc.).

[0021] The maleimide compound for forming prepolymer (A) is particularly preferably one or more selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, novolac-type maleimide compounds, and biphenylaralkyl-type maleimide compounds. The maleimide compound for forming prepolymer (A) may be used alone or in combination of two or more.

[0022] In one embodiment, the maleimide compound for forming the prepolymer (A) preferably contains an aralkyl maleimide compound. When the maleimide compound for forming the prepolymer (A) contains an aralkyl maleimide compound, the content of the structure derived from the aralkyl maleimide compound relative to 100 parts by mass of the total structure derived from the maleimide compound in the prepolymer (A) molecule is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 70 parts by mass.

[0023] In one embodiment, the maleimide compound for forming the prepolymer (A) preferably contains 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane.

[0024] Examples of novolac-type maleimide compounds include maleimide compounds represented by the following formula (M1). Examples of biphenylaralkyl-type maleimide compounds include maleimide compounds represented by the following formula (M2).

[0025] [ka]

[0026] In the formula, R m1 Each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom), and R m2 Each independently represents an alkyl group having 1 to 5 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.) or a phenyl group, n m1 This indicates the number-average degree of polymerization, and 1 <n m1 <10 (preferably 1 <n m1 <6) and n m2 Each of these independently represents 0, 1, or 2 (preferably 0).

[0027] The maleimide compound for forming the prepolymer (A) may be a commercially available product or a preparation made by a known method. Examples of commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" from K.I. Chemicals Co., Ltd., "BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000", and "BMI-2300" from Yamato Chemical Industries, Ltd., "MIR-3000" and "MIR-5000" from Nippon Kayaku Co., Ltd., "NE-X-9470S" and "NE-X-9500" from DIC Corporation, "SFR" from Resonaq Corporation, and "BMI-689", "BMI-3000", and "BMI-5000" from Designer Molecules Inc.

[0028] The maleimide group equivalent of the maleimide compound for prepolymer (A) formation is preferably 1,500 g / eq. or less, more preferably 1,000 g / eq. or less, even more preferably 700 g / eq. or less, even more preferably 500 g / eq. or less, and particularly preferably 300 g / eq. or less. The lower limit is not particularly limited, but may be, for example, 100 g / eq. or more, preferably 130 g / eq. or more, more preferably 160 g / eq. or more, even more preferably 200 g / eq. or more, even more preferably 230 g / eq. or more, and particularly preferably 250 g / eq. or more. The maleimide group equivalent represents the mass of the compound per mole of maleimide groups.

[0029] The weight-average molecular weight of the maleimide compound for prepolymer (A) formation is preferably 4,000 or less, more preferably 2,000 or less, even more preferably 1,500 or less, and particularly preferably 1,000 or less. The lower limit is not particularly limited, but may be, for example, 200 or more, 300 or more, 400 or more, 500 or more, etc. The weight-average molecular weight of the maleimide compound is the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography.

[0030] (Mercapto-modified silicone) Mercapto-modified silicones refer to polymers having a polysiloxane structure (particularly a polydiorganosiloxane structure) and mercapto groups. The main chain of the polysiloxane structure may have a branched structure, and side chains of the polysiloxane structure may be formed. Examples of chain-like polysiloxane structures include structures having repeating units represented by the following formula (S).

[0031] [ka]

[0032] In the formula, R independently represents either a phenyl group or an alkyl group having 1 to 3 carbon atoms. A single molecule of mercapto-modified silicone may contain two or more different repeating units represented by the above formula (S).

[0033] The mercapto-modified silicone for forming prepolymer (A) preferably contains a phenyl group or a methyl group in the polysiloxane structure. From the viewpoint of further improving low thermal expansion and adhesion, the mercapto-modified silicone for forming prepolymer (A) preferably contains a mercapto-modified silicone having a phenyl group in the polysiloxane structure, and preferably contains a mercapto-modified silicone having both a phenyl group and a methyl group.

[0034] The mercapto-modified silicone for forming the prepolymer (A) preferably contains a modified silicone having two or more mercapto groups in part of the main chain or side chain of the polysiloxane structure, more preferably contains a modified silicone having two mercapto groups in part of the main chain or side chain of the polysiloxane structure, and particularly preferably contains a linear modified silicone having mercapto groups at both ends.

[0035] The content of the repeating unit represented by the above formula (S) in the mercapto-modified silicone molecule for forming the prepolymer (A) is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

[0036] The mercapto-modified silicone used for forming the prepolymer (A) may be a commercially available product or a prepared product made by a known method. Examples of commercially available modified silicones include "X-22-167B" and "X-26-1126" manufactured by Shin-Etsu Chemical Co., Ltd.

[0037] The mercapto group equivalent of the mercapto-modified silicone for prepolymer (A) formation is not particularly limited, but is preferably 20,000 g / eq. or less, more preferably 10,000 g / eq. or less, even more preferably 5,000 g / eq. or less, even more preferably 4,000 g / eq. or less, and particularly preferably 3,000 g / eq. or less. The lower limit is preferably 300 g / eq. or more, more preferably 400 g / eq. or more, even more preferably 500 g / eq. or more, even more preferably 700 g / eq. or more, and particularly preferably 1,000 g / eq. The mercapto group equivalent represents the mass of the compound per mole of mercapto groups.

[0038] The weight-average molecular weight of the mercapto-modified silicone for prepolymer (A) formation is not particularly limited, but is preferably 40,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less, with a lower limit of preferably 600 or more, more preferably 800 or more, even more preferably 1,000 or more, and particularly preferably 1,400 or more. The weight-average molecular weight of the mercapto-modified silicone is the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography.

[0039] The content of the repeating unit represented by the above formula (S) contained in the prepolymer (A) molecule is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more.

[0040] The prepolymer (A) preferably has a substructure represented by the following formula (a') consisting of a structure derived from the maleimide group of the maleimide compound and a structure derived from the mercapto group of the mercapto-modified silicone, and it is particularly preferable that it has a substructure represented by the following formula (a) having a structure derived from a linear-chain modified silicone having mercapto groups at both ends.

[0041] [ka]

[0042] [ka]

[0043] In formula (a), R independently represents a phenyl group or an alkyl group having 1 to 3 carbon atoms; X independently represents an organic group; and n represents an integer of 1 or more. Preferably, R independently represents a phenyl group or a methyl group.

[0044] An alkyl group refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Examples of alkyl groups having 1 to 3 carbon atoms include the methyl group, ethyl group, propyl group, and isopropyl group.

[0045] The organic group represented by X is a divalent group consisting of one or more (e.g., 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) skeletal atoms selected from carbon, oxygen, nitrogen, and sulfur atoms, and a hydrogen atom. It may include a linear structure, a branched structure, and / or a cyclic structure, and may be a group that does not contain an aromatic ring or a group that does contain an aromatic ring. The organic group represented by X is preferably an alkylene group.

[0046] An alkylene group is a linear, branched, and / or cyclic divalent aliphatic saturated hydrocarbon group. Preferably, the alkylene group has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. Examples of alkylene groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups.

[0047] [Thermosetting compound (B)] The resin composition of the present invention contains a thermosetting compound (B).

[0048] The thermosetting compound (B) is not particularly limited, but examples include maleimide compounds, cyanate ester compounds, epoxy compounds, compounds having terminal ethylenically unsaturated groups, phenol compounds, oxetane compounds, benzoxazine compounds, and organic group-modified silicone compounds. The thermosetting compound (B) may be used alone or in combination of two or more. Preferably, the thermosetting compound (B) contains one or more selected from the group consisting of compounds having terminal ethylenically unsaturated groups, maleimide compounds, and cyanate ester compounds.

[0049] (Maleimide compounds) For use as thermosetting compound (B), it is preferable to include a maleimide compound having two or more maleimide groups in one molecule, from the viewpoint of further improving heat resistance. In one embodiment, it is even more preferable for the maleimide compound for use as thermosetting compound (B) to include a maleimide compound having three or more maleimide groups in one molecule.

[0050] The maleimide compound to be used as thermosetting compound (B) may be an aromatic maleimide compound containing an aromatic carbon ring (especially a benzene ring) in its molecule, an aliphatic maleimide compound not containing an aromatic carbon ring in its molecule, or both. However, in one embodiment, it is preferable to include an aromatic maleimide compound containing an aromatic carbon ring in its molecule. In particular, it is preferable to include an aromatic maleimide compound having a maleimide group directly bonded to an aromatic carbon atom, and especially preferable to include a maleimide compound having two or more aromatic carbon rings (especially a benzene ring) with maleimide groups directly bonded to one molecule.

[0051] Examples of maleimide compounds for use as thermosetting compound (B) include monofunctional maleimide compounds having one maleimide group in one molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.) and difunctional maleimide compounds having two maleimide groups in one molecule (e.g., bis(4-maleimoidphenyl)methane, 2,2-bis{4-(4-maleimoidphenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimoidphenyl)methane, bis(3,5-dimethyl-4-maleimoidphenyl)methane, bis(3,5-diethyl-4-maleimoidphenoxy) Examples include (methane), m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bisphenol M-type maleimide, maleimide compounds having a carbon skeleton derived from dimer acid, maleimide compounds having an indane ring skeleton, etc., dicyclopentadiene-type maleimide compounds, novolac-type maleimide compounds, aralkyl-type maleimide compounds (e.g., phenylaralkyl-type maleimide compounds, biphenylaralkyl-type maleimide compounds, etc.), and prepolymers of these maleimide compounds with amine compounds.

[0052] The maleimide compound used as thermosetting compound (B) is particularly preferably one or more selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, novolac-type maleimide compounds, and biphenylaralkyl-type maleimide compounds. The maleimide compound used as thermosetting compound (B) may be used alone or in combination of two or more.

[0053] The maleimide compound used as thermosetting compound (B) may be a commercially available product or a preparation made by a known method.

[0054] The maleimide group equivalent of the maleimide compound used as the thermosetting compound (B) is preferably 1,500 g / eq. or less, more preferably 1,000 g / eq. or less, even more preferably 700 g / eq. or less, even more preferably 500 g / eq. or less, and particularly preferably 300 g / eq. or less. The lower limit is not particularly limited, but may be, for example, 100 g / eq. or more, preferably 130 g / eq. or more, more preferably 160 g / eq. or more, even more preferably 200 g / eq. or more, even more preferably 230 g / eq. or more, and particularly preferably 250 g / eq. or more.

[0055] The weight-average molecular weight of the maleimide compound used as thermosetting compound (B) is preferably 4,000 or less, more preferably 2,000 or less, even more preferably 1,500 or less, and particularly preferably 1,000 or less. The lower limit is not particularly limited, but may be, for example, 200 or more, 300 or more, 400 or more, 500 or more, etc.

[0056] (Cyanate ester compounds) A cyanate ester compound is a compound having one or more cyanate ester groups (cyanato groups) in one molecule. Preferably, the cyanate ester compound contains two or more cyanato groups in one molecule. In one embodiment, the cyanate ester compound preferably contains one or more aromatic carbon rings (particularly benzene rings and naphthalene rings) in one molecule, more preferably contains two or more aromatic carbon rings (particularly benzene rings and naphthalene rings) in one molecule, and particularly preferably contains two or more aromatic carbon rings (particularly benzene rings and naphthalene rings) to which cyanato groups are directly bonded in one molecule. In one embodiment, the cyanate ester compound preferably contains three or more cyanato groups in one molecule.

[0057] Examples of cyanate ester compounds include benzene compounds substituted with two or three cyanato groups (e.g., 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, etc.), naphthalene compounds substituted with two or three cyanato groups (e.g., 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricinatonaphthalene, etc.), biphenyl compounds substituted with two or three cyanato groups (e.g., 4,4'-dicyanatobiphenyl, etc.), novolac-type cyanate esters, aralkyl-type cyanate esters (e.g., phenol aralkyl-type cyanate esters, naphthol aralkyl-type cyanate esters). Examples include biphenylaralkyl type cyanate esters, bisphenol type cyanate esters (e.g., bisphenol A type cyanate ester, bisphenol E type cyanate ester, bisphenol F type cyanate ester, bisphenol AD ​​type cyanate ester, bisnophenol B type cyanate ester, bisphenol AP type cyanate ester, bisphenol S type cyanate ester, bisphenol Z type cyanate ester, bisphenol TMC type cyanate ester, etc.), diallylbisphenol type cyanate esters (e.g., diallylbisphenol A type cyanate ester, diallylbisphenol F type cyanate ester, diallylbisphenol E type cyanate ester, diallylbisphenol S type cyanate ester, etc.), and prepolymers of these cyanate esters. In particular, from the viewpoint of even better heat resistance and flame retardancy, the cyanate ester compound preferably contains one or more selected from the group consisting of bisphenol A type cyanate ester, novolac type cyanate ester, naphthol aralkyl type cyanate ester, biphenylaralkyl type cyanate ester, and diallylbisphenol type cyanate ester. Cyanate ester compounds may be used individually or in combination of two or more.

[0058] Examples of novolak type cyanate esters include compounds represented by the following formula (C1). Examples of phenol aralkyl type cyanate esters include compounds represented by the following formula (C2). Examples of naphthol aralkyl type cyanate esters include compounds represented by the following formula (C3). Examples of biphenyl aralkyl type cyanate esters include compounds represented by the following formula (C4).

[0059] [Chemical formula]

[0060] In the formula, R c1 each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom), R c2 each independently represents an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, an isopropyl group, etc.) or a phenyl group, n c1 represents the number average degree of polymerization, 1 < n c1 < 10 (preferably 1 < n c1 < 6, more preferably 1 < n c1 < 3), and n c2 each independently represents 0, 1, or 2 (preferably 0).

[0061] Commercially available products may be used for the cyanate ester compound, or products synthesized by known methods may also be used. Examples of commercially available products of the cyanate ester compound include "CA210", "NCN-M", etc. manufactured by Mitsubishi Gas Chemical Company, Inc.

[0062] The cyanate group equivalent of the cyanate ester compound is preferably 1,500 g / eq. or less, more preferably 1,000 g / eq. or less, even more preferably 500 g / eq. or less, even more preferably 300 g / eq. or less, and particularly preferably 250 g / eq. or less, from the viewpoint of increasing the crosslinking points and more effectively improving the heat resistance of the resulting cured product. The lower limit is not particularly limited, but may be, for example, 100 g / eq. or more, 130 g / eq. or more, 150 g / eq. or more, 170 g / eq. or more, etc. The cyanate group equivalent represents the mass of the compound per mole of cyanate groups.

[0063] The weight-average molecular weight of the cyanate ester compound is preferably 4,000 or less, more preferably 2,000 or less, even more preferably 1,500 or less, even more preferably 1,200 or less, and particularly preferably 1,000 or less, from the viewpoint of increasing the number of crosslinking points and more effectively improving the heat resistance of the resulting cured product. The lower limit is not particularly limited, but may be, for example, 200 or more, 300 or more, 400 or more, etc. The weight-average molecular weight of the cyanate ester compound is the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography.

[0064] (Compounds having terminal ethylenically unsaturated groups) Compounds having terminal ethylenically unsaturated groups are compounds that have one or more terminal ethylenically unsaturated groups in one molecule, such as acryloyl groups, methacryloyl groups, vinylbenzyl groups (2-vinylbenzyl groups, 3-vinylbenzyl groups, or 4-vinylbenzyl groups), or allyl groups. Examples of compounds having terminal ethylenically unsaturated groups include polyphenylene ether compounds and allyl-substituted nadiimide compounds. Examples of polyphenylene ether compounds having terminal ethylenically unsaturated groups include polyphenylene ether compounds with a vinylbenzyl group at the end and polyphenylene ether compounds with a methacryloyl group at the end.

[0065] Compounds having terminal ethylenically unsaturated groups preferably include polyphenylene ether compounds having terminal ethylenically unsaturated groups. Polyphenylene ether compounds having terminal ethylenically unsaturated groups preferably include polyphenylene ether compounds having vinyl benzyl groups at the terminals, and particularly preferably include modified polyphenylene ethers represented by formula (V).

[0066] [ka]

[0067] In the formula, R 11 and R 12 Each of these independently represents an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 , and R 24 Each of these independently represents a hydrogen atom or an alkyl group; X v is a coupling, -C(R v ) indicates 2-, -O-, -CO-, -S-, or -SO2-; R v Each of these independently represents a hydrogen atom or an alkyl group, or two R v These elements are bonded together to form a cycloalkane ring, which may be substituted with an alkyl group; s represents 0 or 1; and t and u each independently represent an integer greater than or equal to 1.

[0068] Unless otherwise specified, alkyl groups having 1 to 6 carbon atoms are preferred. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, cyclopentyl, and cyclohexyl groups. A cycloalkane ring refers to a saturated carbon ring in which only carbon atoms constitute the ring atoms. Cycloalkane rings having 3 to 20 carbon atoms are preferred, and cycloalkane rings having 5 to 12 carbon atoms are more preferred. Examples of cycloalkane rings include monocyclic saturated carbocyclic rings such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, and cyclododecane rings; bicyclic saturated carbocyclic rings such as norbornane, decalin, and hydrindane rings; and tricyclic saturated carbocyclic rings such as adamantane rings.

[0069] R 11 and R 12 Each of these independently represents an alkyl group, preferably a methyl group. 13 and R 14 Each of these independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. 21 and R 22 Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. 23 and R 24 Each of these independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. v This is a single bond, -C(R v )2-, -O-, -CO-, -S-, or -SO2-, preferably a single bond, -C(R v )2-, or -O-. vEach independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. s represents 0 or 1, preferably 1. t and u each independently represent an integer of 1 or more, preferably an integer between 1 and 200, more preferably an integer between 1 and 100.

[0070] The equivalent of terminal ethylenically unsaturated groups in polyphenylene ether compounds having terminal ethylenically unsaturated groups is not particularly limited, but is preferably 300 g / eq. or more, more preferably 400 g / eq. or more, even more preferably 450 g / eq. or more, and particularly preferably 500 g / eq. or more, with an upper limit of preferably 5,000 g / eq. or less, more preferably 2,500 g / eq. or less, even more preferably 1,500 g / eq. or less, and particularly preferably 1,000 g / eq. or less. The equivalent of terminal ethylenically unsaturated groups represents the mass of the compound per mole of terminal ethylenically unsaturated groups.

[0071] The number-average molecular weight of polyphenylene ether compounds having terminal ethylenically unsaturated groups is not particularly limited, but is preferably 600 or more, more preferably 800 or more, even more preferably 900 or more, and particularly preferably 1,000 or more, with an upper limit of preferably 10,000 or less, more preferably 5,000 or less, even more preferably 3,000 or less, and particularly preferably 2,000 or less. The number-average molecular weight of polyphenylene ether compounds having terminal ethylenically unsaturated groups is the number-average molecular weight in terms of polystyrene, measured by gel permeation chromatography.

[0072] Polyphenylene ether compounds having terminal ethylenically unsaturated groups may be produced by known methods or commercially available products may be used. Examples of commercially available products include "SA9000" manufactured by SABIC Innovative Plastics, which has a methacryloyl group at the end, and "OPE-2St1200" and "OPE-2St2200" manufactured by Mitsubishi Gas Chemical Company, which have a vinylbenzyl group at the end. Furthermore, as polyphenylene ether compounds having a vinylbenzyl group at the end, it is also possible to use polyphenylene ether compounds with hydroxyl groups at the end, such as "SA90" manufactured by SABIC Innovative Plastics, which have been modified to have a vinylbenzyl group at the end using vinylbenzyl chloride or the like.

[0073] The allyl-substituted nadiimide compound may be a commercially available product or a manufactured product prepared according to known methods. Examples of commercially available products include "BANI-M" and "BANI-X" from Maruzen Petrochemical Co., Ltd.

[0074] (Phenol compounds) Phenol compounds are compounds having two or more phenolic hydroxyl groups in one molecule. Examples of phenol compounds include bisphenols (e.g., bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.), diallylbisphenols (e.g., diallylbisphenol A, diallylbisphenol E, diallylbisphenol F, diallylbisphenol S, etc.), biphenols (biphenyl-type phenol compounds), novolac resins (e.g., phenol novolac resin, naphthol novolac resin, cresol novolac resin, etc.), naphthalene-type phenol resins, dihydroanthracene-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins (e.g., phenol aralkyl-type phenol resin, naphthol aralkyl-type phenol resin, biphenyl aralkyl-type phenol resin, etc.). These phenol compounds can be used individually or in combination of two or more. Phenol compounds may be commercially available products or products synthesized by known methods. Commercially available phenolic compounds include "KAYAHARD GPH-65," "KAYAHARD GPH-78," and "KAYAHARD GPH-103" (biphenyl aralkyl type phenolic resins) from Nippon Kayaku Co., Ltd., and "SN-495" (naphthol aralkyl type phenolic resin) from Nippon Steel Chemical Co., Ltd.

[0075] (Benzoxazine compound) Benzooxazine compounds are compounds that have two or more dihydrobenzoxazine rings in one molecule. Examples include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ" from Konishi Chemical Co., Ltd.

[0076] (Epoxy compound) An epoxy compound is a compound having one or more epoxy groups in one molecule. Preferably, the epoxy compound includes an epoxy compound having two or more epoxy groups in one molecule.

[0077] Examples of epoxy compounds include bisphenol-type epoxy resins (e.g., bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin), diallylbisphenol-type epoxy resins (e.g., diallylbisphenol A epoxy resin, diallylbisphenol E epoxy resin, diallylbisphenol F epoxy resin, diallylbisphenol S epoxy resin, etc.), trisphenolmethane-type epoxy resins, novolac-type epoxy resins (e.g., phenol novolac epoxy resin, bisphenol A novolac epoxy resin, cresol novolac epoxy resin, naphth Examples include bisphenol-cresol novolac epoxy resins, aralkyl epoxy resins (e.g., biphenyl aralkyl epoxy resins, phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, etc.), biphenyl epoxy resins, naphthylene ether epoxy resins, anthracene epoxy resins, glycidyl ester epoxy resins, polyol epoxy resins, isocyanurate ring-containing epoxy resins, dicyclopentadiene epoxy resins, epoxy resins consisting of bisphenol A type structural units and hydrocarbon structural units, and halogen compounds thereof (e.g., brominated bisphenol A type epoxy resins, brominated phenol novolac type epoxy resins).

[0078] The epoxy compound may be a commercially available product or a preparation prepared by a known method. Examples of commercially available epoxy compounds include "NC-7000", "NC-7300", and "NC-7300L" from Nippon Kayaku Co., Ltd., "HP-9540" and "HP-9500" (naphthol-cresol novolac type epoxy resin) from DIC Corporation, "Epotote ESN-155", "Epotote ESN-355", "Epotote ESN-375", "Epotote ESN-475V", "Epotote ESN-485", and "Epotote ESN-175" from Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "HP-5000" and "HP- Examples include "9900" (naphthol aralkyl type epoxy resin); "NC-3000", "NC-3000H", "NC-3000L", and "NC-3000FH" (biphenyl aralkyl type epoxy resin) from Nippon Kayaku Co., Ltd.; "HP-4710" (naphthalene type epoxy resin) from DIC Corporation; and "HP-4032", "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L", and "EXA7311-G3" (naphthylene ether type epoxy resin) from DIC Corporation.

[0079] If the resin composition contains an epoxy compound, it may further contain an epoxy resin curing agent other than maleimide compounds, cyanate ester compounds, phenol compounds, and benzoxazine compounds as a thermosetting compound (B). Examples of such epoxy resin curing agents include active ester compounds, carbodiimide compounds, and acid anhydrides.

[0080] (Oxetane compounds) Examples of oxetane compounds include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, as well as 3-methyl-3-methoxymethyloxetane, 3,3'-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, and biphenyl-type oxetanes. The oxetane compound may be a commercially available product or a manufactured product produced according to known methods. Examples of commercially available products include "OXT-101" and "OXT-121" from Toagosei Co., Ltd.

[0081] (Organogroup-modified silicone compound) Examples of organic group-modified silicone compounds include bis(methylamino)polydimethylsiloxane, bis(propylamino)polydimethylsiloxane, bis(octylamino)polydimethylsiloxane, bis(glycidoxypropyl)polydimethylsiloxane, and bis(glycidoxyoctyl)polydimethylsiloxane. Commercially available organic group-modified silicone compounds may be used, or manufactured products produced according to known methods may be used.

[0082] [Inorganic filler (C)] From the viewpoint of further improving low thermal expansion properties, the resin composition of the present invention preferably further contains an inorganic filler (C).

[0083] The inorganic filler (C) is not particularly limited and may include, for example, silica compounds, silicon compounds (e.g., white carbon), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides (e.g., boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, etc.), metal sulfides (e.g., barium sulfate, etc.), metal hydroxides (e.g., aluminum hydroxide, heat-treated aluminum hydroxide (e.g., aluminum hydroxide that has been heat-treated to reduce some of its crystal water), etc. Examples of inorganic fillers (C) include boehmite, magnesium hydroxide, etc., molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), zinc compounds (e.g., zinc borate, zinc stainate, etc.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass powders such as E-glass, T-glass, D-glass, S-glass, Q-glass, etc.), hollow glass, spherical glass, etc. Inorganic fillers (C) may be used individually or in combination of two or more types.

[0084] From the viewpoint of further improving low thermal expansion, the inorganic filler (C) preferably contains one or more selected from the group consisting of silicas, metal hydroxides and metal oxides, more preferably contains one or more selected from the group consisting of silicas, boehmite and alumina, and even more preferably contains silicas.

[0085] Examples of silica types include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. Silica types can be used individually or in combination of two or more. Among these, fused silica is preferred from the viewpoint of dispersibility, and two or more types of fused silica with different particle sizes are more preferred from the viewpoint of packing and fluidity. Examples of commercially available fused silica include "SFP-120MC" and "SFP-130MC" from Denka Corporation, and "SC1050-MLQ", "SC2050-MB", "SC2050-MNU", "SC2050-MTX", "SE2053-SQ", "YA050C-MJF", and "YA050C-MJA" from Admatex Corporation. The inorganic filler (C) may be surface-treated with a silane coupling agent or the like.

[0086] The average particle size of the inorganic filler (C) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, even more preferably 1 μm or less, and particularly preferably 0.8 μm or less. The lower limit is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, even more preferably 0.3 μm or more, and particularly preferably 0.5 μm or more. The average particle size of the inorganic filler (C) refers to the median diameter (D50) of the inorganic filler (C). Here, the median diameter refers to the particle size such that, when the particle size distribution of the powder is divided into two parts based on a certain particle size, the volume of the larger particle size and the volume of the smaller particle size each account for 50% of the total powder volume. The average particle size (median diameter) of the inorganic filler (C) is measured by the wet laser diffraction-scattering method.

[0087] The specific surface area of ​​the inorganic filler (C) is not particularly limited, but is preferably 0.1 m². 2 / g or more, comfortably 1m 2 / g or more, more preferably 3m 2 / g or more, particularly preferably 4m 2 The amount is 100m or more, and the upper limit is not particularly limited, but preferably 100m 2 / g or less, more preferably 50m 2 / g or less, more preferably 30m 2 Less than or equal to / g, and more preferably 20m 2 / g or less, particularly preferably 10m 2 It is less than / g. The specific surface area of ​​the inorganic filler (C) can be calculated using the BET multipoint method with a specific surface area measuring device.

[0088] From the viewpoint of low thermal expansion and moldability, the content of inorganic filler (C) is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 100 parts by mass or more, and particularly preferably 150 parts by mass or more, per 100 parts by mass of resin solids in the resin composition. The upper limit of the content is not particularly limited, but is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, even more preferably 500 parts by mass or less, even more preferably 300 parts by mass or less, and particularly preferably 200 parts by mass or less.

[0089] [Silane coupling agent (D)] The resin composition of the present invention may further contain a silane coupling agent (D). By including a silane coupling agent (D), if the resin composition contains an inorganic filler (C), the dispersibility of the inorganic filler (C) is further improved, and furthermore, the adhesive strength between the components of the resin composition and the substrate tends to be further improved.

[0090] The silane coupling agent (D) is not particularly limited, and examples include silane coupling agents generally used for surface treatment of inorganic fillers, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylicsilane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane compounds (e.g., styryltrimethoxysilane, etc.), vinylsilane compounds (e.g., vinyltrimethoxysilane, etc.), and phenylsilane compounds. The silane coupling agent (D) may be used alone or in combination of two or more. Among these, the silane coupling agent (D) is preferably an epoxy-based silane coupling agent. Examples of epoxy-based silane coupling agents include "KBM-403," "KBM-303," "KBM-402," and "KBE-403" from Shin-Etsu Chemical Co., Ltd.

[0091] The content of the silane coupling agent (D) is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of resin solids.

[0092] [Wetting and dispersing agent (E)] The resin composition of the present invention may further contain a wetting and dispersing agent (E). By including a wetting and dispersing agent (E), the dispersibility of the inorganic filler (C) in the resin composition tends to be further improved. The wetting and dispersing agent (E) can be any known dispersant (dispersion stabilizer) used to disperse inorganic fillers, such as metal phosphate salt wetting and dispersing agents, polyurethane wetting and dispersing agents, and acrylic wetting and dispersing agents. Examples of commercially available products include "DISPER BYK-110", "DISPER BYK-111", "DISPER BYK-118", "DISPER BYK-180", "DISPER BYK-161", "BYK-W996", "BYK-W9010", and "BYK-W903" from Big Chemie Japan. The content of the wetting and dispersing agent (E) is not particularly limited, but is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 0.7 to 3 parts by mass, per 100 parts by mass of resin solids.

[0093] [Curing accelerator (F)] The resin composition of the present invention may further contain a curing accelerator (F). The curing accelerator (F) is not particularly limited, but examples include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; tertiary amines such as N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenol, xylenol, cresol, Examples include phenols such as resorcinol and catechol; organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; compounds obtained by dissolving these organometallic salts in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; and organotin compounds such as dioctyl tin oxide, other alkyltins, and alkyltin oxides. Among these, imidazoles and / or organometallic salts are preferred, imidazoles are more preferred, and triphenylimidazole is particularly preferred because it has excellent pot life, promotes the curing reaction, and tends to improve the glass transition temperature. The content of the curing accelerator (F) is not particularly limited, but is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 2 parts by mass, and even more preferably 0.05 to 1 part by mass, per 100 parts by mass of resin solids.

[0094] [Elastomer (G)] The resin composition of the present invention may further contain elastomer (G). Examples of elastomer (G) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and derivatives thereof. The elastomer consists of a hard segment component and a soft segment component, with the former generally contributing to heat resistance and strength, and the latter contributing to flexibility and toughness. From the viewpoint of further improving heat resistance and insulation reliability, elastomer (G) is preferably a styrene-based elastomer, an olefin-based elastomer, a polyamide-based elastomer, or a silicone-based elastomer, and more preferably a styrene-based elastomer. Elastomer (G) can be used alone or in combination of two or more types.

[0095] As the elastomer (G), one having reactive functional groups at the molecular ends or in the molecular chain can be used. Examples of reactive functional groups include epoxy groups, hydroxyl groups, carboxyl groups, amino groups, amide groups, isocyanate groups, acryloyl groups, methacryloyl groups, vinyl groups, and the like. By having these reactive functional groups at the molecular ends or in the molecular chain of the elastomer, compatibility with thermosetting compounds is improved, and internal stress generated during the curing of the resin composition can be more effectively reduced, resulting in a significant reduction in substrate warping. From the viewpoint of adhesion to metals, the reactive functional group is preferably an epoxy group, hydroxyl group, carboxyl group, amino group, or amide group, and from the viewpoint of further improving heat resistance and insulation reliability, it is more preferably an epoxy group, hydroxyl group, carboxyl group, or amino group.

[0096] From the viewpoint of effectively exhibiting low shrinkage and low thermal expansion of the cured product, the elastomer (G) content is preferably 0.1 to 30 parts by mass per 100 parts by mass of resin solids in the resin composition. The amount is parts by mass, more preferably 2 to 20 parts by mass.

[0097] 〔solvent〕 The resin composition of the present invention may further contain a solvent. The inclusion of a solvent tends to lower the viscosity during preparation of the resin composition, further improving handling and impregnation into the substrate. The solvent is not particularly limited as long as it can dissolve some or all of the components in the resin composition, but examples include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g., toluene, xylene, etc.), amides (e.g., dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetate. These solvents can be used individually or in combination of two or more. A method for producing the resin composition includes, for example, a method of mixing each component in the solvent all at once or sequentially and stirring. In this case, known treatments such as stirring, mixing, and kneading are used to uniformly dissolve or disperse each component.

[0098] [Other additives] The resin composition of the present invention may further contain any additives. Examples of such additives include thermoplastic resins, organic fillers, colorants, radical polymerization initiators, polymerization inhibitors, leveling agents, thickeners, defoamers, ultraviolet absorbers, adhesion enhancers, adhesion-improving agents, antioxidants, fluorescent whitening agents, surfactants, flame retardants, stabilizers, and the like. Other additives may be used individually or in combination of two or more in any ratio. The content of other additives can be appropriately determined by those skilled in the art.

[0099] [Method for producing resin compositions] In one embodiment, the resin composition of the present invention is produced by a method comprising the steps of (1) heating a raw material mixture containing a maleimide compound and a mercapto-modified silicone to obtain a prepolymer-containing composition (A'), and (2) blending the prepolymer-containing composition (A') obtained in step (1) with a thermosetting compound (B') to obtain a resin composition.

[0100] In this embodiment, the resin composition of the present invention is a blend of a prepolymer-containing composition (A') obtained by heating a raw material mixture containing a maleimide compound and a mercapto-modified silicone, and a thermosetting compound (B'). The prepolymer-containing composition (A') contains a prepolymer (A) formed from the maleimide compound and the mercapto-modified silicone.

[0101] The maleimide compound in the raw material mixture is the same as the maleimide compound for forming prepolymer (A). The content of the maleimide compound in the raw material mixture is not particularly limited, but is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less, per 100 parts by mass of solid content of the raw material mixture, with a lower limit of preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and particularly preferably 35 parts by mass or more.

[0102] In one embodiment, it is preferable that the raw material mixture contains an aralkyl maleimide compound. When the raw material mixture contains an aralkyl maleimide compound, the content of the aralkyl maleimide compound is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 70 parts by mass, based on 100 parts by mass of the total maleimide compounds in the raw material mixture.

[0103] The mercapto-modified silicone in the raw material mixture is the same as the mercapto-modified silicone for forming prepolymer (A). The content of the mercapto-modified silicone in the raw material mixture is not particularly limited, but is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and particularly preferably 65 parts by mass or less, per 100 parts by mass of solid content of the raw material mixture, with a lower limit of preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and particularly preferably 50 parts by mass or more.

[0104] The mass ratio of the maleimide compound to the mercapto-modified silicone in the raw material mixture (maleimide compound:mercapto-modified silicone) is preferably 70:30 to 10:90, more preferably 60:40 to 20:80, even more preferably 55:45 to 30:70, and particularly preferably 50:50 to 35:65, from the viewpoint of suppressing the residue of terminal mercapto groups and improving varnish life.

[0105] The raw material mixture may contain a curing accelerator (F), a solvent, and other additives.

[0106] The heating temperature of the raw material mixture to obtain the prepolymer-containing composition (A') is preferably 70°C to 100°C, more preferably 70°C to 90°C, even more preferably 75°C to 90°C, and particularly preferably 75°C to 85°C.

[0107] The heating time for the raw material mixture to obtain the prepolymer-containing composition (A') is preferably 0.5 to 6 hours, more preferably 1 to 5 hours, even more preferably 1 to 3 hours, and particularly preferably 1 to 2 hours. Here, the heating time of the raw material mixture means the time for which the heating temperature of the raw material mixture is maintained.

[0108] The weight-average molecular weight of the prepolymer-containing composition (A') is preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 15,000 or less, with a lower limit of preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, even more preferably 7,000 or more, and particularly preferably 8,000 or more. The weight-average molecular weight of the prepolymer-containing composition (A') is the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography.

[0109] The amount of prepolymer-containing composition (A') relative to 100 parts by mass of the resin solids content of all components is not particularly limited, but is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less. The lower limit is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more. The amount of prepolymer-containing composition (A') is expressed on a solids basis.

[0110] Thermosetting compound (B') is the same as thermosetting compound (B).

[0111] The amount of thermosetting compound (B) per 100 parts by mass of resin solids of all components is not particularly limited, but is preferably 99 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, and particularly preferably 75 parts by mass or less, with a lower limit of preferably 10 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 60 parts by mass or more, and particularly preferably 65 parts by mass or more.

[0112] The amount of prepolymer-containing composition (A') relative to 100 parts by mass of the total amount of prepolymer-containing composition (A') and thermosetting compound (B') is not particularly limited, but is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less, with a lower limit of preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more. The total amount of prepolymer-containing composition (A') and thermosetting compound (B') is calculated on a solid content basis.

[0113] When a maleimide compound is incorporated as the thermosetting compound (B') in the resin composition, the amount of the maleimide compound relative to 100 parts by mass of the total amount of thermosetting compound (B') is not particularly limited, but is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and particularly preferably 55 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more.

[0114] When a cyanate ester compound is incorporated as the thermosetting compound (B') in the resin composition, the amount of the cyanate ester compound relative to 100 parts by mass of the total amount of thermosetting compound (B') is not particularly limited, but is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less. The lower limit is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more.

[0115] When both a cyanate ester compound and a maleimide compound are blended as a thermosetting compound (B') in a resin composition, the blending mass ratio of the cyanate ester compound to the maleimide compound (cyanate ester compound / maleimide compound) is not particularly limited, but is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.3 or more, and particularly preferably 0.5 or more, with an upper limit of preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 1 or less.

[0116] When a compound having a terminal ethylenically unsaturated group is incorporated as a thermosetting compound (B') into a resin composition, the amount of the compound having a terminal ethylenically unsaturated group relative to 100 parts by mass of the total amount of thermosetting compound (B) is not particularly limited, but is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, with a lower limit of preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and particularly preferably 12 parts by mass or more.

[0117] When a resin composition contains both a compound having a terminal ethylenically unsaturated group and a maleimide compound as the thermosetting compound (B'), the blending mass ratio of the compound having a terminal ethylenically unsaturated group to the maleimide compound (compound having a terminal ethylenically unsaturated group / maleimide compound) is not particularly limited, but is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and particularly preferably 0.2 or more, with an upper limit of preferably 10 or less, more preferably 3 or less, even more preferably 1 or less, and particularly preferably 0.4 or less.

[0118] In step (2), the prepolymer-containing composition (A') and the thermosetting compound (B') may be further combined with, if necessary, components such as an inorganic filler (C), a silane coupling agent (D), a wetting and dispersing agent (E), a curing accelerator (F), an elastomer (G), a solvent, and other additives. The resin composition of the present invention can be produced in step (2) by sequentially combining these components and stirring thoroughly.

[0119] In step (2), known treatments (such as stirring, mixing, and kneading) can be performed to uniformly dissolve or disperse each component. For example, when using a filler, the dispersibility of the filler in the resin composition can be improved by performing a stirring and dispersion treatment using a stirring tank equipped with a stirrer having appropriate stirring capacity. The above stirring, mixing, and kneading treatments can be appropriately performed using, for example, equipment intended for mixing such as a ball mill or bead mill, or known equipment such as a revolving or rotating type mixing device.

[0120] [Physical properties of cured resin compositions] In one embodiment, the cured product of the resin composition of the present invention may have the characteristic of low thermal expansion. Therefore, in one embodiment, for example, the linear thermal expansion coefficient (CTE) of the cured product when measured as in Test Example 1 below may be preferably 20.0 ppm / °C or less, more preferably 15.0 ppm / °C or less, even more preferably 10.0 ppm / °C or less, and particularly preferably 8.0 ppm / °C or less in the range of 60°C to 120°C.

[0121] In one embodiment, the cured product of the resin composition of the present invention may have the characteristic of excellent heat resistance. Therefore, in one embodiment, for example, the glass transition temperature (Tg) of the cured product when measured in accordance with JIS C6481 as shown in Test Example 2 below may be preferably 200°C or higher, more preferably 230°C or higher, even more preferably 250°C or higher, and particularly preferably 260°C or higher.

[0122] [Application] The resin composition of the present invention is suitably used in the manufacture of printed circuit boards. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of printed circuit boards. The resin composition of the present invention can be used in a wide range of applications such as resin sheets, prepregs, laminates thereof, metal foil-clad laminates, solder resist materials, underfill materials, die bonding materials, and semiconductor encapsulants.

[0123] [Prepreg] The prepreg comprises a substrate and a resin composition (the resin composition of the present invention) impregnated or coated onto the substrate. The prepreg may be a prepreg obtained by a known method, specifically by impregnating or coating the substrate with the resin composition and then heating and drying it at a temperature of 100 to 200°C to bring it to a semi-cured (B-stage) state.

[0124] The term "prepreg" also includes the form of a cured product obtained by heat-curing a semi-cured prepreg at a heating temperature of 180-230°C and a heating time of 60-180 minutes.

[0125] The content of the resin composition (including fillers) in the prepreg is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and even more preferably 40 to 80% by mass, relative to the total amount of the prepreg. Having a resin composition content within this range tends to improve moldability.

[0126] The substrate is not particularly limited, and examples include known substrates used in the materials for various printed circuit boards. Specific examples of substrates include glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass, such as quartz), and organic substrates (for example, organic substrates composed of organic fibers such as fully aromatic polyamides, polyesters, poly(p-phenylenebenzoxazole), and polyimides). These substrates can be used individually or in combination of two or more. Among these, glass substrates are preferred from the viewpoint of having even better dimensional stability when heated.

[0127] Examples of fibers constituting the glass substrate include E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among these, it is preferable that the fibers constituting the glass substrate are one or more fibers selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass, from the viewpoint of having superior strength and low water absorption.

[0128] The form of the base material is not particularly limited, but examples include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, and surfacing mats. The weaving method of woven fabrics is not particularly limited, but examples include plain weave, twill weave, etc., and these known methods can be appropriately selected and used depending on the intended application and performance. Glass woven fabrics that have been opened or surface-treated with silane coupling agents are also preferably used. The thickness and mass of the base material are not particularly limited, but typically a thickness of about 0.01 to 0.1 mm is preferably used.

[0129] [Resin sheet] The resin sheet comprises a support and a resin composition layer formed from a resin composition (the resin composition of the present invention) provided on the support. The resin sheet may be formed, for example, by coating the resin composition on one or both sides of the support. The resin sheet can be manufactured, for example, by directly coating and drying a resin composition used for prepregs, etc., onto a support such as a metal foil or film.

[0130] The support material is not particularly limited, but for example, known materials used in various printed circuit boards can be used, and it is preferably a resin film or a metal foil. Examples of resin films and metal foils include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, polyethylene (PE) films, and other resin films, as well as metal foils such as aluminum foil, copper foil, and gold foil. Among these, electrolytic copper foil and PET film are preferred as the support material.

[0131] Resin sheets can be obtained, for example, by applying a resin composition to a support and then allowing it to reach a semi-cured (B-stage) state. Generally, a preferred method for manufacturing resin sheets is to produce a composite of a B-stage resin composition layer and a support. Specifically, for example, a method can be used to produce a resin sheet by applying the resin composition to a support such as copper foil, and then semi-curing it by heating it in a dryer at 100-200°C for 1-60 minutes. The amount of resin composition adhering to the support is preferably in the range of 1.0 μm to 300 μm in terms of the resin thickness of the resin sheet. Alternatively, a single-layer resin sheet can be obtained by peeling or etching the support from the resin sheet. A single-layer resin sheet can also be obtained by supplying a varnish-like resin composition containing a solvent into a mold having a sheet-shaped cavity and drying it to form a sheet. Resin sheets and single-layer resin sheets can be used as build-up materials for printed circuit boards.

[0132] [Metal foil-clad laminate] A metal foil-clad laminate includes a laminate formed from one or more selected from the group consisting of prepregs and resin sheets, and metal foil disposed on one or both sides of the laminate. The laminate may be formed from one prepreg or resin sheet, or from multiple prepregs and / or resin sheets. The laminate is formed by curing the resin composition of the prepreg and resin sheet. That is, a metal foil-clad laminate includes a cured layer containing a cured product formed by curing a resin composition (the resin composition of the present invention), and metal foil disposed on one or both sides of the cured layer.

[0133] The metal foil (conductor layer) can be any metal foil used in various printed circuit board materials, such as copper or aluminum foil. Examples of copper foil include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

[0134] The molding method and molding conditions for metal foil-clad laminates are not particularly limited, and general methods and conditions for laminates and multilayer boards for printed circuit boards can be applied. For example, when molding laminates or metal foil-clad laminates, multi-stage presses, multi-stage vacuum presses, continuous molding machines, autoclave molding machines, etc., can be used. In addition, in the molding (lamination) of laminates or metal foil-clad laminates, the temperature should be 100 to 300°C and the pressure should be a surface pressure of 2 to 100 kgf / cm². 2 The heating time is generally in the range of 0.05 to 5 hours. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300°C. In particular, when using a multi-stage press, from the viewpoint of sufficiently promoting the curing of the prepreg, a temperature of 200°C to 250°C and a pressure of 10 to 40 kgf / cm² are recommended. 2 A heating time of 80 to 130 minutes is preferable, with a temperature of 215°C to 235°C and a pressure of 25 to 35 kgf / cm². 2 A heating time of 90 to 120 minutes is more preferable. Furthermore, it is possible to create a multilayer board by laminating the above-mentioned prepreg with a separately prepared wiring board for the inner layer.

[0135] [Printed wiring board] The printed circuit board includes an insulating layer containing a cured product formed by curing a resin composition (the resin composition of the present invention). The printed circuit board has an insulating layer and a conductive layer formed on the surface of the insulating layer. The printed circuit board can be formed, for example, by etching the metal foil of a metal foil-clad laminate into a predetermined wiring pattern to form a conductive layer. The printed circuit board may also include an insulating layer formed from one or more materials selected from the group consisting of the above-mentioned prepreg and single-layer resin sheets, and a conductive layer formed on the surface of the insulating layer.

[0136] Printed circuit boards can be manufactured by, for example, the following method. First, a metal foil-clad laminate is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to create an inner layer substrate having a conductor layer (inner layer circuit). Next, a predetermined number of prepreg and / or single-layer resin sheets that will serve as insulating layers, and metal foil for the outer layer circuit are laminated in this order on the surface of the conductor layer (inner layer circuit) of the inner layer substrate, and a laminate is obtained by integral molding (lamination molding) by heating and pressing. The lamination molding method and molding conditions are the same as those for the metal foil-clad laminate described above. Next, holes for through-holes and via holes are drilled into the laminate, and a plated metal film is formed on the walls of the resulting holes to allow conductivity between the conductor layer (inner layer circuit) and the metal foil for the outer layer circuit. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to create an outer layer substrate having a conductor layer (outer layer circuit). A printed circuit board is manufactured in this way.

[0137] Furthermore, if a metal foil laminate is not used, a conductive layer forming a circuit may be formed on the insulating layer to create a printed wiring board. In this case, electroless plating can be used to form the conductive layer.

[0138] [Semiconductor Packages] A semiconductor package is a semiconductor package comprising a printed circuit board and semiconductor elements. A semiconductor package can be manufactured by mounting semiconductor elements such as semiconductor chips and memory at specific locations on the printed circuit board.

[0139] [Semiconductor device] Printed circuit boards can be used in the manufacture of semiconductor devices that have printed circuit boards. Examples of semiconductor devices include personal computers, smartphones, smartwatches, digital cameras, televisions, car navigation systems, printers, liquid crystal displays, electronic dictionaries, game consoles, automobiles, ships, trains, and aircraft. [Examples]

[0140] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, the temperature condition is room temperature (25°C), and unless otherwise specified, the pressure condition is atmospheric pressure (1 atm). In the following description, the "parts by mass" of each component other than the solvent is based on the mass on a solid content basis.

[0141] (Synthesis Example 1: Synthesis of naphthol aralkyl cyanate compounds (SNCNs)) 300 g of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) (1.28 mol in terms of OH groups) and 194.6 g of triethylamine (1.92 mol) (1.5 mol per 1 mol of hydroxyl groups) were dissolved in 1800 g of dichloromethane to prepare Solution 1. Solution 1 was added over 30 minutes while stirring, maintaining the liquid temperature at -2 to -0.5°C, by adding 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per mol of hydroxyl groups), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per mol of hydroxyl groups), and 1205.9 g of water. After adding Solution 1, the mixture was stirred at the same temperature for 30 minutes, and then Solution 2, a solution of 65 g (0.64 mol) of triethylamine (0.5 mol per mol of hydroxyl groups) dissolved in 65 g of dichloromethane, was added over 10 minutes. After adding Solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction. The reaction mixture was then allowed to stand to separate the organic and aqueous phases. The resulting organic phase was washed five times with 1300 g of water. The electrical conductivity of the wastewater after the fifth wash was 5 μS / cm, confirming that the ionic compounds to be removed were sufficiently removed by washing with water. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90°C for 1 hour to obtain 331 g of the target naphthol aralkyl-type cyanate compound (SNCN) (orange viscous substance). The weight-average molecular weight of the obtained SNCN was 600. The IR spectrum of SNCN was obtained at 2250 cm⁻¹. -1 Absorption of the cyanate ester group was observed, but absorption of the hydroxyl group was not.

[0142] (Synthesis Example 2; Synthesis of Prepolymer A) 15 parts by mass of mercapto-modified silicone (Shin-Etsu Chemical Co., Ltd. "X-22-167B", dimethylpolysiloxane having mercapto groups at both ends), 7.5 parts by mass of a bifunctional maleimide compound (K.I. Chemicals Co., Ltd. "BMI-80", 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane), 7.5 parts by mass of a biphenyl aralkyl type maleimide compound (Nippon Kayaku Co., Ltd. "MIR-3000-70MT", solid content 70% by mass), 0.075 parts by mass of imidazole catalyst (Shikoku Chemicals Co., Ltd. "2E4MZ", 2-ethyl-4-methylimidazole), and 30 parts by mass of methyl ethyl ketone were charged into a reactor and stirred under reflux for 2 hours to obtain a prepolymer A-containing composition. The weight-average molecular weight of the prepolymer A-containing composition was 9,000.

[0143] (Synthesis Example 3: Synthesis of Prepolymer B) In Synthesis Example 2, 15 parts by mass of mercapto-modified silicone (Shin-Etsu Chemical Co., Ltd. "X-22-167B", a dimethylpolysiloxane with mercapto groups at both ends) was replaced with 19 parts by mass of mercaptosilicone (Shin-Etsu Chemical Co., Ltd. "X-22-1126", a methylphenylpolysiloxane with mercapto groups at both ends), and 5.5 parts by mass (on a solid content basis) each of a difunctional maleimide compound (K.I. Chemicals Co., Ltd. "BMI-80", 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane) and a biphenylaralkyl type maleimide compound (Nippon Kayaku Co., Ltd. "MIR-3000-70MT", solid content 70% by mass) were added. The composition was synthesized in the same manner as in Synthesis Example 1 to obtain a prepolymer B-containing composition. The weight-average molecular weight of the prepolymer B-containing composition was 12,000.

[0144] (Example 1) 10.5 parts by mass of vinyl benzyl-modified polyphenylene ether resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", number average molecular weight 1187, vinyl benzyl group equivalent 590 g / eq.), 17.5 parts by mass of bifunctional maleimide compound (K.I. Chemicals Co., Ltd. "BMI-80", 2,2'-bis-[4-(4-maleimidophenoxy)phenyl]propane), 17.5 parts by mass of biphenyl aralkyl type maleimide compound (Nippon Kayaku Co., Ltd. "MIR-3000-70MT", solid content 70% by mass), 24.5 parts by mass of naphthol aralkyl type cyanate ester compound (SNCN) obtained in Synthesis Example 1, 30 parts by mass of prepolymer A-containing composition obtained in Synthesis Example 2, polyurethane-based wetting and dispersing agent (BIC Chemie Japan "DISPER A varnish-like resin composition was obtained by mixing 1 part by mass of BYK-161, 2.5 parts by mass of epoxy silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.01 parts by mass of manganese octoate, 0.1 parts by mass of imidazole catalyst (TPIZ, manufactured by Tokyo Chemical Industry Co., Ltd., 2,4,5-triphenylimidazole), and 50 parts by mass (calculated on a solid content basis) of silica (SC2050MB, manufactured by Admatex, Inc., average particle size 0.5 μm, solid content 70% by mass) with 100 parts by mass of methyl ethyl ketone (solvent).

[0145] (Example 2) A varnish-like resin composition was obtained in the same manner as in Example 1, except that 30 parts by mass of the prepolymer B-containing composition obtained in Synthesis Example 3 was used instead of 30 parts by mass of the prepolymer A-containing composition obtained in Synthesis Example 2, and the amount of silica (Admatex "SC2050MB", average particle size 0.5 μm, solid content 70% by mass) used was changed from 50 parts by mass to 150 parts by mass (on a solid content basis).

[0146] (Comparative Example 1) 15 parts by mass of vinyl benzyl-modified polyphenylene ether resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", number average molecular weight 1187, vinyl benzyl group equivalent 590 g / eq.), 25 parts by mass of bifunctional maleimide compound (K.I. Chemicals Co., Ltd. "BMI-80", 2,2'-bis-[4-(4-maleimidophenoxy)phenyl]propane), 25 parts by mass of biphenyl aralkyl type maleimide compound (Nippon Kayaku Co., Ltd. "MIR-3000-70MT", solid content 70% by mass) (on a solid content basis), 35 parts by mass of naphthol aralkyl type cyanate ester compound (SNCN) obtained in Synthesis Example 1, polyurethane wetting and dispersing agent (BIC Chemie Japan "DISPER A varnish-like resin composition was obtained by mixing 1 part by mass of BYK-161, 2.5 parts by mass of epoxy silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.01 parts by mass of manganese octoate, 0.1 parts by mass of imidazole catalyst (TPIZ, manufactured by Tokyo Chemical Industry Co., Ltd., 2,4,5-triphenylimidazole), and 150 parts by mass (solid content equivalent) of silica (SC2050MB, manufactured by Admatex, average particle size 0.5 μm, solid content 70% by mass) with 100 parts by mass of methyl ethyl ketone (solvent).

[0147] (Comparative Example 2) 12.6 parts by mass of vinyl benzyl-modified polyphenylene ether resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", number average molecular weight 1187, vinyl benzyl group equivalent 590 g / eq.), 21 parts by mass of bifunctional maleimide compound (K.I. Chemicals Co., Ltd. "BMI-80", 2,2'-bis-[4-(4-maleimidophenoxy)phenyl]propane), 21 parts by mass of biphenyl aralkyl type maleimide compound (Nippon Kayaku Co., Ltd. "MIR-3000-70MT", solid content 70% by mass) (calculated on a solid content basis), 29.4 parts by mass of naphthol aralkyl type cyanate ester compound (SNCN) obtained in Synthesis Example 1, 16 parts by mass of mercapto-modified silicone (Shin-Etsu Chemical Co., Ltd. "X-22-167B", dimethylpolysiloxane having mercapto groups at both ends), polyurethane-based wetting and dispersing agent (BIC Chemie Japan "DISPER A varnish-like resin composition was obtained by mixing 1 part by mass of BYK-161, 2.5 parts by mass of epoxy silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.01 parts by mass of manganese octoate, 0.1 parts by mass of imidazole catalyst (TPIZ, manufactured by Tokyo Chemical Industry Co., Ltd., 2,4,5-triphenylimidazole), and 50 parts by mass (calculated on a solid content basis) of silica (SC2050MB, manufactured by Admatex, Inc., average particle size 0.5 μm, solid content 70% by mass) with 100 parts by mass of methyl ethyl ketone (solvent).

[0148] (Preparation of metal foil-clad laminates) The varnish-like resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were impregnated and coated onto S glass woven fabric (thickness 100 μm), and heated and dried at 140°C for 3 minutes to obtain a prepreg with a resin composition solid content (including filler) of 45.8% by mass.

[0149] Two of the resulting prepregs were stacked, and electrolytic copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) with a thickness of 12 μm was placed above and below them, and a pressure of 30 kgf / cm² was applied. 2 Lamination molding was performed at a temperature of 230°C for 100 minutes to obtain a double-sided copper foil laminated board containing an insulating layer with a thickness of 0.2 mm, as a metal foil laminated board.

[0150] Separately, eight of the obtained prepregs were stacked, and electrolytic copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) with a thickness of 12 μm was placed above and below them, and a pressure of 30 kgf / cm² was applied. 2 Lamination molding was performed at a temperature of 230°C for 100 minutes to obtain a double-sided copper foil laminated board containing an insulating layer with a thickness of 0.8 mm, as a metal foil-clad laminate.

[0151] (Test Example 1: CTE (Coefficient of Linear Thermal Expansion)) The double-sided copper foil laminate, including the 0.2 mm thick insulating layer obtained above, was subjected to full-surface etching to remove the copper foil. The laminate was then heated from 40°C to 340°C at a rate of 10°C per minute using a thermomechanical analyzer (TA Instruments Inc.). The linear thermal expansion coefficient in the planar direction was measured between 60°C and 120°C, and the resulting value was used as the evaluation value for linear thermal expansion coefficient (ppm / °C). The measurement direction was the longitudinal direction (Warp) of the glass cloth in the laminate. A value of "○" was given if the measured linear thermal expansion coefficient was 8.0 ppm / °C or less, and a value of "×" was given if the linear thermal expansion coefficient exceeded 8.0 ppm / °C. The measurement results and evaluation results are shown in Table 1.

[0152] (Test Example 2: Tg (Glass Transition Temperature)) After removing the copper foil from both sides of the double-sided copper foil laminate (20mm × 5mm × 0.2mm) containing the 0.2mm thick insulating layer obtained above by etching, the glass transition temperature (Tg) (unit: °C) was measured using a dynamic viscoelasticity measuring device (manufactured by TA Instruments) in accordance with JIS C6481. A glass transition temperature of 250°C or higher was evaluated as "○", and a glass transition temperature of less than 250°C was evaluated as "×". The measurement results and evaluation results are shown in Table 1.

[0153] (Test Example 3: Peel Strength) Using a double-sided copper foil laminate (30mm × 150mm × 0.8mm) containing an insulating layer with a thickness of 0.8mm obtained as described above, the copper foil peel strength was measured in accordance with JIS C6481. If the measured peel strength was 0.4kN / m or higher, it was evaluated as "○", and if the peel strength was less than 0.4kN / m, it was evaluated as "×". The measurement results and evaluation results are shown in Table 1.

[0154] Table 1 summarizes the raw material usage amounts for each of the resin compositions in Examples 1 and 2 and Comparative Examples 1 and 2, as well as the measurement and evaluation results for Test Examples 1 to 3.

[0155] [Table 1]

[0156] Examples 1 and 2, which used a prepolymer formed from a maleimide compound and mercapto-modified silicone, achieved both excellent low thermal expansion and excellent adhesion. In contrast, Comparative Example 1, which did not use a prepolymer, resulted in high thermal expansion. Furthermore, Comparative Example 2, which used silicone, a prepolymer raw material, instead of the prepolymer, resulted in both high thermal expansion and low heat resistance.

Claims

1. A prepolymer-containing composition (A') obtained by heating a raw material mixture containing a maleimide compound and a mercapto-modified silicone, Thermosetting compound (B'), A resin composition containing [a certain compound].

2. The resin composition according to claim 1, wherein the weight-average molecular weight of the prepolymer-containing composition (A') is 7,000 to 30,000.

3. The resin composition according to claim 1, wherein the mass ratio of the maleimide compound to the mercapto-modified silicone in the raw material mixture (maleimide compound:mercapto-modified silicone) is 55:45 to 30:

70.

4. The resin composition according to claim 1, wherein the amount of the prepolymer-containing composition (A') is 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of the prepolymer-containing composition (A') and the thermosetting compound (B').

5. The resin composition according to claim 1, wherein the heating temperature of the raw material mixture for obtaining the prepolymer-containing composition (A') is 70°C to 100°C.

6. A prepolymer (A) formed from a maleimide compound and a mercapto-modified silicone, Thermosetting compound (B), A resin composition containing the following:

7. The resin composition according to claim 6, wherein the mercapto group equivalent of the mercapto-modified silicone for forming the prepolymer (A) is 1,000 to 5,000 g / eq.

8. The resin composition according to claim 6, wherein the mercapto-modified silicone for forming the prepolymer (A) comprises a mercapto-modified silicone having a phenyl group.

9. The resin composition according to claim 6, wherein the mercapto-modified silicone for forming the prepolymer (A) comprises a linear modified silicone having mercapto groups at both ends.

10. The resin composition according to claim 6, wherein the maleimide group equivalent of the maleimide compound for forming the prepolymer (A) is 200 to 1,500 g / eq.

11. The resin composition according to claim 6, wherein the prepolymer (A) has a substructure represented by the following formula (a). 【Chemistry 1】 (In formula (a), R independently represents a phenyl group or an alkyl group having 1 to 3 carbon atoms; X independently represents an organic group; and n represents an integer of 1 or more.)

12. The resin composition according to claim 6, wherein the thermosetting compound (B) contains one or more selected from the group consisting of compounds having terminal ethylenically unsaturated groups, maleimide compounds, and cyanate ester compounds.

13. The resin composition according to claim 6, further containing an inorganic filler (C).

14. The resin composition according to claim 13, wherein the amount of the inorganic filler (C) is 30 parts by mass or more with respect to 100 parts by mass of resin solids in the resin composition.

15. The resin composition according to claim 6, further containing a silane coupling agent (D).

16. The mercapto group equivalent of the mercapto-modified silicone for forming the aforementioned prepolymer (A) is 1,000 to 5,000 g / eq. The mercapto-modified silicone for forming the prepolymer (A) includes a linear modified silicone having mercapto groups at both ends. The maleimide group equivalent of the maleimide compound for forming the aforementioned prepolymer (A) is 200 to 1,500 g / eq. The prepolymer (A) has a substructure represented by the following formula (a), The resin composition according to claim 6, wherein the thermosetting compound (B) contains one or more selected from the group consisting of compounds having terminal ethylenically unsaturated groups, maleimide compounds, and cyanate ester compounds. 【Chemistry 2】 (In formula (a), R independently represents a phenyl group or an alkyl group having 1 to 3 carbon atoms; X independently represents an organic group; and n represents an integer of 1 or more.)

17. The resin composition according to claim 16, wherein the mercapto-modified silicone for forming the prepolymer (A) comprises a mercapto-modified silicone having a phenyl group.

18. The resin composition according to claim 16, further containing an inorganic filler (C), wherein the amount of the inorganic filler (C) is 30 parts by mass or more with respect to 100 parts by mass of the resin solids in the resin composition.

19. A resin composition according to any one of claims 1 to 18, for forming an insulating layer on a printed wiring board.

20. A prepreg comprising a substrate and a resin composition according to any one of claims 1 to 18 impregnated or coated onto the substrate.

21. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 18, provided on the support.

22. A printed circuit board comprising an insulating layer containing a cured product formed by curing a resin composition according to any one of claims 1 to 18.

23. A semiconductor package comprising a printed circuit board as described in claim 22 and a semiconductor element.

24. A semiconductor device having a printed circuit board as described in claim 22.

25. Step (1) to obtain a prepolymer-containing composition (A') by heating a raw material mixture containing a maleimide compound and a mercapto-modified silicone, and Step (2) to obtain a resin composition by blending the prepolymer-containing composition (A') obtained in step (1) with a thermosetting compound (B'). A method for producing a resin composition containing the resin composition.

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