Resin composition, cured product of resin composition, resin sheet, printed wiring board, and semiconductor device

Abstract

The object of the present invention is to provide a resin composition that can obtain a cured product having a small dielectric loss tangent value, excellent adhesion to a conductive material after an environmental resistance test, and improved brittleness, a cured product of the resin composition, a resin sheet comprising the resin composition, a printed wiring board comprising an insulating layer formed using the cured product of the resin composition, and a semiconductor device. The solution of the present invention is a resin composition comprising (A) a maleimide compound, (B) an allyl group-containing benzoxazine compound containing a substituted or unsubstituted allyl group, and (C) a high molecular weight component.

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured product of the resin composition, and a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. Background Art

[0002] As a manufacturing technology for a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductive layers are alternately stacked is known.

[0003] As an insulating material for a printed wiring board used for such an insulating layer, for example, Patent Document 1 discloses a resin composition containing a maleimide compound.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent document 1: Japanese Patent Application Publication No. 2016-074871. Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] In recent years, there has been a demand for a smaller value of dielectric loss tangent of the insulating layer (for example, 0.0050 or less) and further improvement in the adhesion between the insulating layer and the conductive material (hereinafter also referred to as “adhesion”).

[0009] Generally speaking, the dielectric loss tangent of the cured product of the resin composition containing maleimide compounds is small. However, maleimide compounds generally have a high softening point, so the cured product of the resin composition containing maleimide compounds tends to be brittle. In addition, the results of the present inventors' research have shown that the cured product of the resin composition containing maleimide compounds tends to have poor adhesion after environmental resistance tests, especially HAST (Highly Accelerated temperature and humidity Stress Test, Highly Accelerated Temperature and Humidity Stress Test, Highly Accelerated Aging Test).

[0010] The present invention aims to provide a resin composition that can produce a cured product having a small dielectric loss tangent value, excellent adhesion to a conductive material after an environmental resistance test, and improved brittleness, a cured product of the resin composition, a resin sheet containing the resin composition, a printed wiring board containing an insulating layer formed using the cured product of the resin composition, and a semiconductor device.

[0011] Technical solutions adopted to solve technical problems

[0012] The present inventors have conducted intensive studies and have found that the above-mentioned problems can be solved by using (A) a maleimide compound, (B) an allyl-containing benzoxazine compound containing a substituted or unsubstituted allyl group, and (C) a high molecular weight component in combination, thereby completing the present invention.

[0013] That is, the present invention includes the following contents:

[0014] [1] A resin composition comprising (A) a maleimide compound, (B) an allyl group-containing benzoxazine compound, and (C) a high molecular weight component;

[0015] [2] The resin composition according to [1], wherein the content of the component (A) is 10% by mass or more and 40% by mass or less, when the non-volatile component in the resin composition is 100% by mass;

[0016] [3] The resin composition according to [1] or [2], wherein the content of the component (B) is 0.01% by mass or more and 15% by mass or less, when the non-volatile component in the resin composition is 100% by mass;

[0017] [4] The resin composition according to any one of [1] to [3], wherein the mass ratio of the component (B) to the component (A) [component (B) / component (A)] is 0.01 to 0.20.

[0018] [5] The resin composition according to any one of [1] to [4], wherein the component (C) is a thermoplastic resin;

[0019] [6] The resin composition according to [5], wherein the thermoplastic resin is at least one selected from a polyimide resin, a polycarbonate resin, and a phenoxy resin;

[0020] [7] The resin composition according to any one of [1] to [6], wherein the weight average molecular weight or number average molecular weight of component (C) is 5,000 or more and 100,000 or less;

[0021] [8] The resin composition according to any one of [1] to [7], wherein the content of the component (C) is 0.1% by mass or more and 10% by mass or less, when the non-volatile component in the resin composition is 100% by mass;

[0022] [9] The resin composition according to any one of [1] to [8], further comprising (D) an inorganic filler;

[0023]

[10] The resin composition according to [9], wherein the component (D) is surface-treated with an amine coupling agent or a (meth)acrylic coupling agent;

[0024]

[11] The resin composition according to [9] or

[10] , wherein the content of the component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass;

[0025]

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

[11] , wherein the resin composition is heat treated at 200°C for 90 minutes to obtain a cured product, and when the cured product is measured by a resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C, the dielectric loss tangent of the cured product is not more than 0.005;

[0026]

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

[12] , wherein the resin composition is heat treated at 200°C for 90 minutes to obtain a cured product, and when the cured product is measured in accordance with Japanese Industrial Standard JIS K7127, the cured product has an elongation at break of 0.7% or more;

[0027]

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

[13] , which is used for forming an insulating layer;

[0028]

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

[14] , which is used to form an insulating layer, and the insulating layer is used to form a conductor layer;

[0029]

[16] A cured product, which is a cured product of the resin composition according to any one of [1] to

[15] ;

[0030]

[17] A resin sheet comprising a support and a resin composition layer comprising the resin composition described in any one of [1] to

[15] and provided on the support;

[0031]

[18] A printed wiring board comprising an insulating layer formed using a cured product of the resin composition described in any one of [1] to

[15] or a cured product described in

[16] ;

[0032]

[19] A semiconductor device comprising the printed wiring board described in

[18] .

[0033] Effects of the Invention

[0034] If the present invention is adopted, it is possible to provide: a resin composition that can produce a cured product having a small dielectric loss tangent value, excellent adhesion to a conductive material after an environmental resistance test, and improved brittleness; a cured product of the resin composition; a resin sheet containing the resin composition; a printed wiring board containing an insulating layer formed using the cured product of the resin composition; and a semiconductor device. DETAILED DESCRIPTION

[0035] Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and their equivalents.

[0036] [Resin composition]

[0037] The resin composition of the present invention comprises (A) a maleimide compound, (B) an allyl group-containing benzoxazine compound, and (C) a high molecular weight component. The resin composition of the present invention comprises the components (A) to (C) to provide a cured product having a small dielectric loss tangent value, excellent adhesion to a conductive material after an environmental resistance test, and improved brittleness.

[0038] The resin composition may further include any component in combination with the components (A) to (C). Examples of the arbitrary component include (D) an inorganic filler, (E) a polymerization initiator, (F) a thermosetting resin (but not including the components (A), (B) and (C), and (G) other additives. The components contained in the resin composition are described in detail below.

[0039] <(A) Maleimide compound>

[0040] The resin composition contains a maleimide compound as the component (A). By making the resin composition contain the component (A), a cured product with a small dielectric loss tangent value can be obtained. The components (A) may be used alone or in combination of two or more.

[0041] Component (A) is a compound containing at least one maleimide group represented by the following formula (1) in its molecule;

[0042] [Chemical formula 1]

[0043]

[0044] From the viewpoint of obtaining a cured product having a small dielectric loss tangent value, the number of maleimide groups per molecule in component (A) is 1 or more, preferably 2 or more, and more preferably 3 or more, with no upper limit, and can be 10 or less, 6 or less, 4 or less, or 3 or less.

[0045] From the viewpoint of obtaining a cured product having a small dielectric loss tangent value, the first example of the component (A) is a maleimide compound having a biphenyl structure (hereinafter also referred to as "first type maleimide compound"). The biphenyl structure refers to a structure represented by the following formula (2);

[0046] [Chemical formula 2]

[0047]

[0048] In formula (2), R 1 and R 2 Each independently represents a substituent. a and b each independently represent an integer of 0 to 4. * represents a bond.

[0049] As R 1 and R 2 The substituents represented by the above-mentioned groups include, for example, halogen atoms, -OH, -OC 1-10 Alkyl, -N(C 1-10 Alkyl)2, C 1-10 Alkyl, C 6-10 Aryl, -NH2, -CN, -C(O)OC 1-10 Alkyl, -COOH, -C(O)H, -NO2, etc. Here, the term "C x-y "" (x and y are positive integers, satisfying x < y) means that the number of carbon atoms in the organic group immediately following the term is x to y. For example, "C 1-10 The expression "alkyl" means an alkyl group having 1 to 10 carbon atoms. These substituents may be combined with each other to form a ring, and the ring structure may include a spiro ring or a condensed ring.

[0050] The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, the same substituents as those mentioned above can be used unless otherwise specified.

[0051] a and b each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1, further preferably 0.

[0052] From the viewpoint of obtaining a cured product having a small dielectric loss tangent value, the first maleimide compound preferably has maleimide groups at both terminals.

[0053] From the viewpoint of obtaining a cured product with a small dielectric loss tangent value, the first type of maleimide compound preferably also has any one of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and more preferably also has both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The term "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not need to be composed only of an aromatic ring, and a chain structure or an alicyclic hydrocarbon group may be included in a part thereof, and the aromatic ring may be any one of a monocyclic ring, a polycyclic ring, and a heterocyclic ring.

[0054] The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and further preferably an alkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, further preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.

[0055] As the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferred, an arylene group and an aralkylene group are more preferred, and an arylene group is further preferred. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is more preferred, and an arylene group having 6 to 10 carbon atoms is further preferred. Examples of such arylene groups include phenylene, naphthylene, anthrylene, biphenylene, and the like. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferred, an aralkylene group having 7 to 20 carbon atoms is more preferred, and an aralkylene group having 7 to 15 carbon atoms is further preferred. Examples of such aralkylene groups include benzylidene, a group having a biphenylene-methylene structure, and the like. Among them, phenylene, benzylidene, a group having a biphenylene-methylene structure is preferred, and phenylene is further preferred.

[0056] From the perspective of obtaining a cured product with a small dielectric loss tangent value, the number of maleimide groups per molecule in the first type of maleimide compound is 1 or more, preferably 2 or more, and more preferably 3 or more. The upper limit is not limited and can be set to 10 or less, 6 or less, 4 or less, or 3 or less.

[0057] From the viewpoint of significantly obtaining the desired effects of the present invention, in the first class of maleimide compounds, the nitrogen atom of the maleimide group is preferably directly bonded to the aromatic hydrocarbon group. Here, the term "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

[0058] The first type of maleimide compound preferably has a structure represented by the following formula (A1-1);

[0059] [Chemical formula 3]

[0060]

[0061] In formula (A1-1), R 3 and R 8 Represents maleimide group, R 4 , R 5 , R 6 and R 7 Each independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 9 and R 10 a1 and b1 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 1 to 10, and n represents an integer of 1 to 100.

[0062] R 4 , R 5 , R 6 and R 7Each independently represents a hydrogen atom, an alkyl group or an aryl group, and is preferably a hydrogen atom.

[0063] As R 4 , R 5 , R 6 and R 7 The alkyl group in is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl and the like.

[0064] R 4 , R 5 , R 6 and R 7 The aryl group in is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, anthracenyl, and the like.

[0065] R 4 , R 5 , R 6 and R 7 The alkyl and aryl groups in formula (2) may have substituents. 1 Same (same meaning).

[0066] R 9 and R 10 Each independently represents a substituent, and R in formula (2) 1 and R 2 same.

[0067] a1 and b1 each independently represent an integer of 0 to 4, and are the same as a and b in formula (2).

[0068] m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2, further preferably 1.

[0069] n represents an integer of 1-100, preferably 1-50, more preferably 1-20, further preferably 1-5.

[0070] R 3 and R 8 It represents a maleimide group, and the maleimide group is directly bonded to an aromatic hydrocarbon group. m1 or (CH2) m2 The binding position of R 3 and R 8The maleimide group represented is preferably directly bonded to any of the ortho-position, meta-position and para-position, more preferably directly bonded to the para-position.

[0071] As the first type of maleimide compound, it is preferred to have a structure represented by formula (A1-1a);

[0072] [Chemical formula 4]

[0073]

[0074] In formula (A1-1a), R 11 and R 16 Represents maleimide group, R 12 , R 13 , R 14 and R 15 Each independently represents a hydrogen atom, an alkyl group, or an aryl group. m3 and m4 each independently represent an integer of 1 to 10, and n1 represents an integer of 1 to 100.

[0075] R 11 and R 16 represents a maleimide group, and R in formula (A1-1) 3 , R 8 same.

[0076] R 12 , R 13 , R 14 and R 15 Each independently represents a hydrogen atom, an alkyl group, or an aryl group, and R in formula (A1-1) 4 , R 5 , R 6 and R 7 same.

[0077] m3 and m4 each independently represent an integer of 1 to 10, and are the same as m1 and m2 in formula (A1-1).

[0078] n1 represents an integer of 1 to 100, which is the same as n in formula (A1-1).

[0079] As the first type of maleimide compound, it is preferred to have a structure represented by formula (A1-1b);

[0080] [Chemical formula 5]

[0081]

[0082] In formula (A1-1b), R 17 and R 18 represents a maleimide group. n2 represents an integer of 1 to 100.

[0083] R17 and R 18 represents a maleimide group, and R in formula (A1-1) 3 , R 8 same.

[0084] n2 represents an integer of 1 to 100, which is the same as n in formula (A1-1).

[0085] The first type of maleimide compound can be a commercially available product. Examples of commercially available products include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. (main component: a compound of the following formula (A1-1c));

[0086] [Chemical formula 6]

[0087]

[0088] (where s 1 Indicates 1 or 2).

[0089] From the viewpoint of obtaining a cured product having a small dielectric loss tangent value, the second example of the component (A) is a maleimide compound containing at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms (hereinafter also referred to as "second-class maleimide compound"). However, the second-class maleimide compound does not have a biphenyl structure and is not included in the first-class maleimide compound (is excluded from the first-class maleimide compound).

[0090] The carbon number of the alkyl group with the carbon number of 5 or more possessed by the second type of maleimide compound is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. The alkyl group may be any one of straight chain, branched chain, and cyclic, wherein straight chain is preferred. As such an alkyl group, for example, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. may be cited. The alkyl group with the carbon number of 5 or more may be a substituent of an alkylene group with the carbon number of 5 or more.

[0091] The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. The alkylene group may be any of a straight chain, a branched chain, and a cyclic group, wherein a straight chain is preferred. Here, a cyclic alkylene group refers to a concept including "a situation formed only by a cyclic alkylene group" and "a situation including both a straight chain alkylene group and a cyclic alkylene group". As such an alkylene group, for example, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecanylene group, a heptadecanylene group, a trihexadecylene group, a group having an octylene-cyclohexylene structure, a group having a propylene-cyclohexylene-octylene structure, etc. can be cited.

[0092] From the viewpoint of significantly obtaining the effects of the present invention, the second maleimide compound preferably contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

[0093] The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure may include a spiro ring or a condensed ring. Examples of the ring formed by bonding to each other include a cyclohexane ring.

[0094] The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may or may not have a substituent. As a substituent, R in the above formula (2) 1 Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms.

[0095] In the second maleimide compound, the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are preferably directly bonded to the nitrogen atom of the maleimide group.

[0096] The number of maleimide groups per molecule of the second maleimide compound may be 1, preferably 2 or more, preferably 10 or less, more preferably 6 or less, particularly preferably 3 or less. By allowing the second maleimide compound to have 2 or more maleimide groups per molecule, the effect of the present invention can be significantly obtained.

[0097] The second type of maleimide compound is preferably a maleimide compound represented by the following general formula (A2-1);

[0098] [Chemical formula 7]

[0099]

[0100] In the general formula (A2-1), M represents an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

[0101] M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms described above. 1 The substituents represented are the same as those represented by , and the substituent is preferably an alkyl group having at least 5 carbon atoms. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkylene group having at least 5 carbon atoms.

[0102] L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR 0 -, oxygen atom, sulfur atom, C(=O)NR 0 -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group composed of two or more divalent groups thereof, wherein R 0 It is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkylene group, alkenylene group, alkynylene group, arylene group, divalent group derived from phthalimide, divalent group derived from pyromellitic acid diimide, and a group composed of two or more divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide means a divalent group derived from phthalimide, specifically a group represented by the general formula (3). The divalent group derived from pyromellitic acid diimide means a divalent group derived from pyromellitic acid diimide, specifically a group represented by the general formula (4). In the formula, "*" represents a bond;

[0103] [Chemical formula 8]

[0104]

[0105] The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be any of a linear, branched, or cyclic type. Examples of such alkylene groups include methylethylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, trihexadecylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

[0106] The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. The alkenylene group may be any of a linear, branched, or cyclic type. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, and octenylene.

[0107] The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. The alkynylene group may be any of a linear, branched, or cyclic group. Examples of such alkynylene groups include methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, and octynylene.

[0108] The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, further preferably an arylene group having 6 to 14 carbon atoms, and further preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, anthrylene, and the like.

[0109] The divalent linking group in L, such as the alkylene group, alkenylene group, alkynylene group, and arylene group, may have a substituent. 1 The substituents represented are the same and are preferably alkyl groups having 5 or more carbon atoms.

[0110] As the group composed of two or more divalent groups in L, for example, a divalent group composed of an alkylene group, a divalent group derived from phthalimide and an oxygen atom, a divalent group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group and an alkylene group, a divalent group composed of an alkylene group and a divalent group derived from pyromellitic acid diimide, etc. can be listed. The group composed of two or more divalent groups can form a ring such as a condensed ring by combining the groups. In addition, the group composed of two or more divalent groups can be a repeating unit having a repeating unit number of 1 to 10.

[0111] Among them, L in the general formula (A2-1) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a divalent group composed of two or more of these groups. Among them, L is more preferably an alkylene group, a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide, a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-an oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-a divalent group derived from phthalimide, or a divalent group having a structure of an alkylene group-a divalent group derived from pyromellitic acid diimide.

[0112] The second type of maleimide compound is preferably a maleimide compound represented by the following general formula (A2-2);

[0113] [Chemical formula 9]

[0114]

[0115] In the general formula (A2-2), M 1 Each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, and each A independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. t represents an integer of 1-10.

[0116] M 1 Each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. 1 The same as M in the general formula (A2-1).

[0117] A represents independently an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. As the alkylene group in A, it can be any one of linear, branched, and cyclic, wherein preferably cyclic, i.e., a cyclic alkylene group having 5 or more carbon atoms which may have a substituent. The carbon number of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. As such an alkylene group, for example, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, etc.

[0118] As the aromatic ring in the divalent group having an aromatic ring represented by A, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, an aromatic heterocyclic ring, etc., preferably a benzene ring, a phthalimide ring, a pyromellitic acid diimide ring. That is, as the divalent group that may have an aromatic ring, preferably a divalent group having a benzene ring that may have a substituent, a divalent group having a phthalimide ring that may have a substituent, or a divalent group having a pyromellitic acid diimide ring that may have a substituent. Examples of the divalent group having an aromatic ring include a group composed of a divalent group derived from phthalimide and an oxygen atom, a group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group, a group composed of an alkylene group and a divalent group derived from pyromellitic acid diimide, a divalent group derived from pyromellitic acid diimide, and a group composed of a divalent group derived from phthalimide and an alkylene group. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (A2-1).

[0119] The alkylene group represented by A and the divalent group having an aromatic ring may have a substituent. As a substituent, R in the above formula (2) 1 The substituents represented are the same.

[0120] As specific examples of the group represented by A, the following groups can be cited. In the formula, "*" represents a bond;

[0121] [Chemical formula 10]

[0122]

[0123] [Chemical formula 11]

[0124]

[0125] The maleimide compound represented by the general formula (A2-2) is preferably any one of a maleimide compound represented by the following general formula (A2-2a) and a maleimide compound represented by the following general formula (A2-2b);

[0126] [Chemical formula 12]

[0127]

[0128] In the general formula (A2-2a), M 2 and M 3 Each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, R 30Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group composed of two or more of these groups. t1 represents an integer of 1 to 10;

[0129] [Chemical formula 13]

[0130]

[0131] In the general formula (A2-2b), M 4 、M 6 and M 7 Each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, M 5 Each independently represents a divalent group having an aromatic ring which may have a substituent, R 31 and R 32 Each independently represents an alkyl group having at least 5 carbon atoms. t2 represents an integer of 1 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

[0132] M 2 and M 3 Each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. 2 and M 3 The alkylene group having 5 or more carbon atoms represented by M in the general formula (A2-1) is the same as that of the alkylene group having 5 or more carbon atoms, and is preferably hexatriadecylene.

[0133] R 30 Each independently represents an oxygen atom, an arylene group, an alkylene group, or a group composed of two or more divalent groups thereof. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (A2-1). 30 , preferably a group composed of two or more divalent groups or an oxygen atom.

[0134] As R 30 The group composed of two or more divalent groups in the formula may include a combination of an oxygen atom, an arylene group, and an alkylene group. As specific examples of the group composed of two or more divalent groups, the following groups may be mentioned. In the formula, "*" represents a bond;

[0135] [Chemical formula 14]

[0136]

[0137] M 4 、M 6 and M 7 Each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. 4 、M 6 and M 7The alkylene group having 5 or more carbon atoms which may have a substituent and which is represented by M in the general formula (A2-1) is the same as that of the alkylene group which may have a substituent, preferably hexylene, heptylene, octylene, nonylene or decylene, and more preferably octylene.

[0138] M 5 Each independently represents a divalent group having an aromatic ring which may have a substituent. 5 The same as the divalent group having an aromatic ring which may have a substituent represented by A in the general formula (A2-2), preferably a group composed of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide, a group composed of a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a group composed of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (A2-1).

[0139] As M 5 Specific examples of the group represented by include the following groups. In the formula, "*" represents a bond;

[0140] [Chemical formula 15]

[0141]

[0142] R 31 and R 32 Each independently represents an alkyl group having 5 or more carbon atoms. 31 and R 32 As with the above-mentioned alkyl group having 5 or more carbon atoms, preferably, it is hexyl, heptyl, octyl, nonyl or decyl, more preferably, hexyl or octyl.

[0143] u1 and u2 each independently represent an integer of 1-15, preferably an integer of 1-10.

[0144] Specific examples of the second type of maleimide compounds include the following compounds (A2-2c), (A2-2d), and (A2-2e). However, the second type of maleimide compounds are not limited to these specific examples. In the formula, v represents an integer of 1 to 10;

[0145] [Chemical formula 16]

[0146]

[0147] [Chemical formula 17]

[0148]

[0149] Specific examples of the second type of maleimide compounds include "BMI-1500" (a compound of formula (A2-2c)), "BMI-1700" (a compound of formula (A2-2d)), and "BMI-689" (a compound of formula (A2-2e)) manufactured by Designer Molecules, Inc. From the viewpoint of more significantly achieving the effects of the present invention, it is preferred to use a compound of formula (A2-2c) as the second type of maleimide compound.

[0150] The third example of the component (A) is a maleimide compound that does not belong to the first maleimide compound and the second maleimide compound (hereinafter also referred to as the "third maleimide compound"). That is, the third maleimide compound is a maleimide compound that does not have a biphenyl structure and does not contain any of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms. As the third maleimide compound, for example, a maleimide compound having a substituted or unsubstituted aromatic hydrocarbon group (for example: N-phenylmaleimide compound, a maleimide compound represented by the following formula (A3-1)) and a maleimide compound containing any of an alkyl group having 4 or less carbon atoms and an alkylene group having 4 or less carbon atoms (for example: N-methylmaleimide) can be listed.

[0151] [Chemical formula 18]

[0152]

[0153] (where s 2 Indicates 1 or 2).

[0154] From the viewpoint of significantly obtaining the desired effect of the present invention, the maleimide group equivalent of the component (A) is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., and further preferably 150 g / eq. to 500 g / eq. The maleimide group equivalent is the mass of the maleimide compound containing 1 equivalent of maleimide groups.

[0155] From the viewpoint of obtaining a cured product having a small value of dielectric loss tangent, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (A) is preferably more than 10% by mass, more preferably more than 20% by mass, preferably less than 40% by mass, and more preferably less than 35% by mass. It should be noted that in the present invention, as long as it is not otherwise expressly stated, the content of each component in the resin composition is the value when the non-volatile component in the resin composition is set to 100% by mass.

[0156] As the component (A), one or more selected from the above-mentioned first class maleimide compounds, second class maleimide compounds and third class maleimide compounds can be used, and preferably one or more selected from the first class maleimide compounds and second class maleimide compounds. From the viewpoint of making the adhesion between the conductive material after the environmental resistance test better and / or the viewpoint of further improving the brittleness, it is preferred to use at least the first class maleimide compound as the component (A).

[0157] <(B) Benzoxazine compounds containing an allyl group>

[0158] For the resin composition, a benzoxazine compound containing an allyl group is included as component (B). The benzoxazine compound containing an allyl group refers to a benzoxazine compound containing a substituted or unsubstituted allyl group. The benzoxazine compound refers to a compound having a benzoxazine ring described later. The benzoxazine compound containing an allyl group acts as a curing agent for thermally curing the resin composition through the reactivity of the allyl group and the reactivity of the benzoxazine ring. By making the resin composition contain component (B), a cured product with excellent adhesion to the conductive material after the environmental resistance test can be obtained. In addition, by making the resin composition contain component (B) and component (C) described later, a cured product with better adhesion to the conductive material after the environmental resistance test and improved brittleness can be obtained. Component (B) can be used alone or in combination of two or more.

[0159] (B) component contains at least one benzoxazine ring in the molecule. As long as the ring-opening reaction of the benzoxazine ring is not excessively hindered, the benzoxazine ring may be substituted by any substituent. In addition, a portion of the double bond contained in the benzoxazine ring may be hydrogenated. The benzoxazine ring includes, for example, 1,2-benzoxazine ring and 1,3-benzoxazine ring. From the viewpoint of obtaining the desired effect of the present invention, 3,4-dihydro-2H-1,3-benzoxazine ring (structure shown in the following formula (5)) is preferred. In the structure shown in the following formula (5), one of the three bonds of the nitrogen atom that is not bonded to other atoms represents a single bond.

[0160] [Chemical formula 19]

[0161]

[0162] From the viewpoint of excellent adhesion and / or improved brittleness, the number of benzoxazine rings per molecule in component (B) is 1 or more, preferably 2 or more, and the upper limit is not limited and can be 10 or less, 6 or less, 4 or less, or 3 or less.

[0163] In addition, component (B) contains at least one substituted or unsubstituted allyl group in the molecule. The unsubstituted allyl group is 2-propenyl. As long as its reactivity is not excessively hindered, the allyl group may have any substituent. An example of a substituted allyl group is 2-methylpropenyl. From the viewpoint of excellent adhesion and / or the viewpoint of obtaining improved brittleness, the number of allyl groups per molecule in component (B) is preferably the same as or more than the number of benzoxazine rings per molecule in component (B), preferably more than 2, more preferably more than 4, and the upper limit is not limited, and can be set to less than 20, less than 12, less than 8 or less than 6.

[0164] In the component (B), from the viewpoint of remarkably obtaining the desired effect of the present invention, the allyl group is preferably bonded to any of a nitrogen atom constituting the benzoxazine ring and a carbon atom constituting the benzoxazine ring, more preferably bonded to a carbon atom constituting the benzoxazine ring.

[0165] The first example of the component (B) is a first type of allyl group-containing benzoxazine compound represented by the following formula (B1-1); [Chemical Formula 20]

[0166]

[0167] In formula (B1-1), R 20 and R 21 Each independently represents a substituted or unsubstituted allyl group, R 22 represents a q-valent group. q represents an integer of 1 to 10, p1s each independently represent an integer of 0 to 4, and p2s each independently represent an integer of 0 to 2.

[0168] R 22 The q-valent group represented by is preferably a q-valent group selected from a substituted or unsubstituted allyl group, a q-valent aromatic hydrocarbon group, a q-valent aliphatic hydrocarbon group, an oxygen atom, and a combination thereof. At least one of the hydrogen atoms possessed by the q-valent aromatic hydrocarbon group and the q-valent aliphatic hydrocarbon group may be substituted by a halogen atom. 22 In the case of a substituted or unsubstituted allyl group, q=1, and in this case, both p1 and p2 may be 0. 22 In the case of a substituted or unsubstituted allyl group, the allyl group may be any substituent of a q-valent aromatic hydrocarbon group or a q-valent aliphatic hydrocarbon group. 22 An arylene group, an alkylene group, an oxygen atom or a group composed of two or more divalent groups among these groups is preferred, an arylene group or a group composed of two or more divalent groups is more preferred, and a group composed of two or more divalent groups is further preferred.

[0169] As R 22The arylene group in is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include phenylene, naphthylene, anthrylene, biphenylene and the like, and phenylene is particularly preferred.

[0170] As R 22 The alkylene group in is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the alkylene group include methylene, ethylene, and propylene, and methylene is preferred.

[0171] As R 22 The group composed of two or more divalent groups in the group may include, for example, a group composed of one or more arylene groups bonded to one or more oxygen atoms, a group composed of one or more arylene groups bonded to one or more alkylene groups such as a group having an arylene-alkylene-arylene structure, a group composed of one or more alkylene groups bonded to one or more oxygen atoms, a group composed of one or more arylene groups, one or more alkylene groups, and one or more oxygen atoms, etc., preferably a group composed of one or more arylene groups bonded to one or more oxygen atoms, and a group composed of one or more arylene groups bonded to one or more alkylene groups.

[0172] q represents an integer of 1 to 10, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, further preferably 1 or 2.

[0173] p1 each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, further preferably 1. p2 each independently represents an integer of 0 to 2, 0 or 1, preferably 0.

[0174] From the viewpoint of obtaining the desired effects of the present invention, the benzoxazine compound represented by the general formula (B1-1) is preferably an allyl group-containing benzoxazine compound represented by the following general formula (B1-1a).

[0175] [Chemical formula 21]

[0176]

[0177] In formula (B1-1a), R 20 , R 21 and R 23Each independently represents a substituted or unsubstituted allyl group, p1' each independently represents an integer of 0 to 4, p2' each independently represents an integer of 0 to 2, and p3' each independently represents an integer of 0 to 4. However, if a plurality of p1', p2' and p3' exist, at least one of them represents an integer of 1 or more.

[0178] The allyl group-containing benzoxazine compound represented by the general formula (B1-1a) is preferably a benzoxazine compound represented by the formula (B1-1b).

[0179] [Chemical formula 22]

[0180]

[0181] In formula (B1-1b), R 20 , R 21 , p1' and p2' are respectively the same as R in the above formula (B1-1a) 20 , R 21 , p1' and p2' are the same.

[0182] The first type of benzoxazine compound containing an allyl group can use a commercial product. As a commercial product, for example, "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd. (a Pd-type benzoxazine compound containing an allyl group having a structure of the above formula (B1-1a)) can be cited. In addition, the first type of benzoxazine compound containing an allyl group can use, for example, a benzoxazine compound disclosed in Japanese Patent Laid-Open No. 2016-074871 or a derivative thereof. It should be noted that the first type of benzoxazine compound containing an allyl group can be manufactured according to the method described in Japanese Patent Laid-Open No. 2016-074871, for example.

[0183] The second example of the component (B) is a second type of allyl group-containing benzoxazine compound represented by the following formula (B2-1); [Chemical Formula 23]

[0184]

[0185] In formula (B2-1), R 20a , R 21a and R 22a Each independently represents a substituted or unsubstituted allyl group, R 22’ represents a q'-valent group bonded to a carbon atom of the benzoxazine ring. q' represents an integer of 1 to 10, p1a each independently represents an integer of 0 to 4, p2a each independently represents an integer of 0 to 2, and R 22’ The maximum value of the sum of p1a and p2a for each combined benzoxazine ring is 5.

[0186] R is better 20a , R21a and R 22a At least one of them is a substituted or unsubstituted allyl group, R 20a , R 21a and R 22a When neither R 22 'Has at least one substituted or unsubstituted allyl group.

[0187] R 22 The q'-valent group represented by ' is preferably a q'-valent group selected from a q'-valent aromatic hydrocarbon group, a q'-valent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and a combination thereof. At least one of the hydrogen atoms possessed by the q'-valent aromatic hydrocarbon group and the q'-valent aliphatic hydrocarbon group may be substituted by a halogen atom or a substituted or unsubstituted allyl group. For example, when q' is 2, R 22 'It is preferably a group selected from an arylene group, an alkylene group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group and a combination of two or more divalent groups thereof.

[0188] As R 22 The arylene group in ' is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include phenylene, naphthylene, anthrylene, biphenylene, and the like, and phenylene is particularly preferred.

[0189] As R 22 The alkylene group in ' is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the alkylene group include methylene, ethylene, propylene, etc., and methylene is preferred.

[0190] As R 22 The group composed of two or more divalent groups in ' can include, for example, a group composed of one or more arylene groups combined with one or more oxygen atoms, a group composed of one or more arylene groups combined with one or more alkylene groups such as a group having an arylene-alkylene-arylene structure, a group composed of one or more alkylene groups combined with one or more oxygen atoms, a group composed of one or more arylene groups, one or more alkylene groups and one or more oxygen atoms, etc., preferably a group composed of one or more arylene groups combined with one or more oxygen atoms, and a group composed of one or more arylene groups combined with one or more alkylene groups.

[0191] q' represents an integer of 1 to 10, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and further preferably 1 or 2. When q' is an integer of 2 or more, 22The 'combined q' benzoxazine rings and their substituents may be the same or different.

[0192] p1a each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 1. p2a each independently represents an integer of 0 to 2, 0 or 1, and preferably 0. 22 The maximum value of the sum of p1a and p2a for each combined benzoxazine ring is 5.

[0193] The second type of allyl group-containing benzoxazine compound may be, for example, a benzoxazine compound disclosed in JP-A-2016-074871 or a derivative thereof. The second type of allyl group-containing benzoxazine compound may be produced by the method described in JP-A-2016-074871, for example.

[0194] The third example of the component (B) is a third type of allyl group-containing benzoxazine compound that does not belong to the first type of allyl group-containing benzoxazine compound and the second type of allyl group-containing benzoxazine compound. Examples of the third type of allyl group-containing benzoxazine compound include allyl group-containing benzoxazine compounds that contain a 1,2-benzoxazine ring or a 1,4-benzoxazine ring and can undergo a ring-opening reaction.

[0195] The molecular weight of the component (B) is preferably at least 200, more preferably at least 300, further preferably at least 400, and is preferably at most 1,000, more preferably at most 800, further preferably at most 500, from the viewpoint of improving the adhesion.

[0196] From the viewpoint of significantly obtaining the desired effect of the present invention, the equivalent weight of the benzoxazine ring of the component (B) (hereinafter also referred to as "ring-opening reaction participating group equivalent weight") is preferably 100 g / eq. to 1000 g / eq., more preferably 150 g / eq. to 500 g / eq., and further preferably 200 g / eq. to 300 g / eq. The ring-opening reaction participating group equivalent weight is the mass of the allyl-containing maleimide compound containing 1 equivalent of the ring-opening reaction participating group (benzoxazine ring).

[0197] From the viewpoint of significantly obtaining the desired effect of the present invention, the allyl equivalent of component (B) is preferably 100 to 1000 g / eq., more preferably 150 to 500 g / eq., and further preferably 200 to 300 g / eq. The allyl equivalent is the mass of the allyl-containing maleimide compound containing 1 equivalent of allyl groups.

[0198] When the non-volatile component in the resin combination is set to 100 mass %, the content of (B) component is preferably more than 0.01 mass %, more preferably more than 0.02 mass %, and further more preferably more than 0.03 mass %. The upper limit is preferably less than 15 mass %, more preferably less than 10 mass %, and further more preferably less than 7 mass % or less than 5 mass %. By making the content of (B) component within the range, the performance of the cured product, particularly the adhesion between the cured product and the conductor layer can be improved. In addition, the content of (B) component is preferably set according to the maleimide equivalent of (A) component and the ring-opening reaction participating group equivalent and allyl equivalent of (B) component.

[0199] From the viewpoint of exerting the desired effect of the present invention, the mass ratio of component (B) to component (A) in the resin composition [component (B) / component (A)] is preferably 0.01 or more, more preferably 0.02 or more, and from the viewpoint of suppressing excessive crosslinking reaction and improving adhesion, it is preferably 0.20 or less, more preferably 0.19 or less. In addition, the mass ratio of component (B) to component (A) [component (B) / component (A)] is preferably set according to the maleimide equivalent of component (A) and the ring-opening reaction participating group equivalent and allyl equivalent of component (B).

[0200] <(C) High molecular weight component>

[0201] For the resin composition, as (C) component, a high molecular weight component is contained. By making the resin composition contain (C) component, the stress of the resin composition is relaxed, thereby being able to obtain a cured product that can maintain a smaller value of the dielectric loss tangent of the cured product obtained by (A) component and having improved brittleness. In addition, by making the resin composition contain (B) component and (C) component at the same time, a cured product with better adhesion to the conductive material after environmental resistance test and further improved brittleness can be obtained. (C) component can be used alone or in combination of two or more.

[0202] As (C) component, a component having a weight average molecular weight or a number average molecular weight as a high molecular weight can be used. As such a component, thermoplastic resins such as polyimide resin, polycarbonate resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polyetheretherketone resin, polystyrene resin, polyester resin can be cited. Wherein, as (C) component, from the viewpoint of obtaining a cured product having a more significant effect of the present invention, it is preferably selected from at least one of polyimide resin, polycarbonate resin and phenoxy resin.

[0203] The polyimide resin may be a resin having an imide structure. The polyimide resin generally includes a resin obtained by an imidization reaction of a diamine compound and an acid anhydride.

[0204] The diamine compound used for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0205] Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 1,5-diaminopentane, and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; alicyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4′-methylenebis(cyclohexylamine); and dimer acid type diamines (hereinafter also referred to as “dimer diamines”). Dimer acid type diamine refers to a diamine compound obtained by replacing the two terminal carboxyl groups (-COOH) of dimer acid with aminomethyl (-CH2-NH2) or amino (-NH2). Dimer acid is a compound obtained by dimerizing unsaturated fatty acids (preferably unsaturated fatty acids with 11 to 22 carbon atoms, particularly preferably unsaturated fatty acids with 18 carbon atoms), and its industrial production process is also well known.

[0206] Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalenediamine compounds, and diphenylamine compounds.

[0207] A phenylenediamine compound refers to a compound formed by a benzene ring having two amino groups, and the benzene ring may have 1 to 3 substituents. The substituents are not particularly limited. Specific examples of phenylenediamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

[0208] The naphthalene diamine compound refers to a compound formed by a naphthalene ring having two amino groups, and the naphthalene ring may have 1 to 3 substituents. The substituents are not particularly limited. Specific examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

[0209] A diphenylamine compound refers to a compound containing two aniline structures in the molecule, and the two benzene rings in the two aniline structures may each have 1 to 3 substituents. The substituents are not particularly limited. The two aniline structures in the diphenylamine compound may be linked via a single bond and / or 1 or 2 linking group structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The diphenylamine compound also includes compounds in which the two aniline structures are linked via two bonds.

[0210] Specific examples of the "linker structure" in the diphenylamine compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -CO-, -SO2-, -NH-, -Ph-, -Ph-Ph-, -C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -C(CH3)2-Ph-C(CH3)2-,

[0211] [Chemical formula 24]

[0212]

[0213] wait.

[0214] In the present specification, "Ph" represents 1,4-phenylene, 1,3-phenylene, or 1,2-phenylene.

[0215] In one embodiment, specific examples of the diphenylamine compound include 4,4'-diamino-2,2'-bis(trifluoromethyl)-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminobenzoic acid-4-aminophenyl ester, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane,

[0045] The following are some examples of the invention:

[0046] bis(4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, etc.

[0216] A commercially available diamine compound may be used, or a compound synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

[0217] The acid anhydride used to prepare the polyimide resin is not particularly limited, and in a preferred embodiment, it is aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic dianhydride, and the like, preferably diphthalic dianhydride.

[0218] Pyromellitic dianhydride refers to a dianhydride of benzene having four carboxyl groups, wherein the benzene ring may optionally have 1 to 3 substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups and -X 33 -R 33 (The same as the definition of the following formula (6)) The pyromellitic dianhydride includes, specifically, trimellitic dianhydride, 1,2,3,4-pyromellitic dianhydride, and the like.

[0219] Naphthalenetetracarboxylic dianhydride refers to naphthalene dianhydride having four carboxyl groups, wherein the naphthalene ring may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from halogen atoms, cyano groups and -X 33 -R 33(The same as the definition of the following formula (6)) The naphthalenetetracarboxylic dianhydride includes, specifically, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

[0220] Anthracenetetracarboxylic dianhydride refers to an anthracene dianhydride having four carboxyl groups, wherein the anthracene ring may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group and -X 33 -R 33 (The same as the definition of the following formula (6)) The anthracenetetracarboxylic dianhydride includes, specifically, 2,3,6,7-anthracenetetracarboxylic dianhydride and the like.

[0221] Diphthalic anhydride refers to a compound containing two phthalic anhydrides in the molecule, and the two benzene rings in the two phthalic anhydrides may each have 1 to 3 substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups and -X 33 -R 33 (same as defined in the following formula (6)) The two phthalic anhydrides in diphthalic dianhydride may be linked via a single bond or a linker structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

[0222] As diphthalic dianhydride, for example, a compound represented by formula (6) can be cited;

[0223] [Chemical formula 25]

[0224]

[0225] In formula (6),

[0226] R 31 and R 32 Each independently represents a halogen atom, a cyano group, a nitro group or -X 33 -R 33 ,

[0227] X 33 Each independently represents a single bond, -NR 33 '-, -O-, -S-, -CO-, -SO2-, -NR 33 'CO-、-CONR 33 '-, -OCO- or -COO-,

[0228] R 33 Each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, and R 33'respectively independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond or a linking group structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms,

[0229] n10 and m10 each independently represent an integer of 0 to 3.

[0230] Y preferably has a linker structure having 1 to 100 skeleton atoms selected from the group consisting of carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

[0231] The "linker structure" in Y has 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The "linker structure" is preferably -[A1-Ph] a10 -A1-[Ph-A1] b10 -represented a divalent group; wherein A1 independently represents a single bond, -(substituted or unsubstituted alkylene)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO- or -OCO-, a10 and b10 independently represent an integer from 0 to 2, preferably 0 or 1.

[0232] Specific examples of the "linking group structure" in Y include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc. In the present specification, "Ph" represents 1,4-phenylene, 1,3-phenylene, or 1,2-phenylene.

[0233] Specific examples of diphthalic dianhydride include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, and 2,3,3', 4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenyl ethertetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride , 2,2-propylene-4,4'-diphthalic anhydride, 1,2-ethylene-4,4'-diphthalic anhydride, 1,3-propylene-4,4'-diphthalic anhydride, 1,4-butylene-4,4'-diphthalic anhydride, 1,5-pentylene-4,4'-diphthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1 ,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, etc.

[0234] As the acid anhydride, a commercially available compound may be used, or a compound synthesized by a known method or a method based thereon may be used. The acid anhydride may be used alone or in combination of two or more.

[0235] A commercially available product may be used as the polyimide resin. Examples of the commercially available product include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Co., Ltd.

[0236] Polycarbonate resin is a resin having a carbonate structure. As such resin, carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing carbamate groups, and carbonate resins containing epoxy groups can be cited. Here, reactive groups refer to functional groups that can react with other components such as hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, anhydride groups, isocyanate groups, carbamate groups, and epoxy groups.

[0237] Commercially available products may be used as the carbonate resin, and examples of the commercially available products include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd. and "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation.

[0238] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0239] Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton), "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton), "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton), "FX280" and "FX293" manufactured by Nippon Steel Chemical Materials Co., Ltd., "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation, etc.

[0240] The polyamide-imide resin can use a resin with an amide-imide structure. From the viewpoint of compatibility with other components in the resin combination, the polyamide-imide resin preferably uses a polyamide-imide resin with an alicyclic structure in the molecular structure, a polyamide-imide resin with a siloxane structure recorded in Japanese Patent Laid-Open No. 05-112760 communique, a polyamide-imide resin with a larger branched structure, a polyamide-imide resin with an asymmetric monomer as a raw material, a polyamide-imide resin with a multi-branched structure, etc.

[0241] Among them, from the viewpoint of improving the compatibility and dispersibility of the resin varnish by having an isocyanurate ring structure, the polyamide-imide resin is more preferably (i) a polyamide-imide resin having an isocyanurate ring structure in its molecular structure (i.e., a polyamide-imide resin having an "isocyanurate ring structure" and an "imide skeleton or an amide skeleton"), (ii) a polyamide-imide resin having an isocyanurate ring structure and an alicyclic structure in its molecular structure (i.e., a polyamide-imide resin having an "isocyanurate ring structure", an "alicyclic structure" and an "imide skeleton or an amide skeleton"), or (iii) a polyamide-imide resin having a repeating unit containing an isocyanurate ring structure and an alicyclic structure (i.e., a polyamide-imide resin having a repeating unit containing an "isocyanurate ring structure", an "alicyclic structure" and an "imide skeleton or an amide skeleton").

[0242] Preferred embodiments of the polyamide-imide resins of (i) to (iii) include: (1) a compound obtained by reacting an isocyanurate ring-containing polyisocyanate compound derived from an alicyclic diisocyanate with an acid anhydride derived from a polycarboxylic acid having three or more carboxyl groups (e.g., a carboxylic dianhydride having one or more carboxyl groups), i.e., a branched polyamide-imide containing a carboxylic acid group (hereinafter, this compound is also referred to as “compound (C-1)”); (2) a polyamide-imide having one epoxy group and one or more free radical polyisocyanates; and (3) a polyamide-imide having one epoxy group and one or more free radical polyisocyanates. (C-2) or (3) a compound obtained by reacting a compound having one hydroxyl group and one or more free radical polymerizable unsaturated groups with an isocyanate group remaining in the synthesis process of compound (C-1), i.e., a branched polymerizable polyamideimide containing a carboxylic acid group (hereinafter, this compound is also referred to as "compound (C-3)").

[0243] Specific examples of compound (C-1) include compounds represented by the following general formula (I): wherein the structural units enclosed in parentheses in the general formula (I) are referred to as repeating units (I-1);

[0244] [Chemical formula 26]

[0245]

[0246] (In formula (I), w represents 0 to 15).

[0247] As compound (C-2), there can be mentioned compounds (II) having a structure represented by the following formula (I-2) by adding GMA (glycidyl methacrylate) to any part of the carboxyl group and / or the terminal carboxyl group of the repeating unit (I-1) in the general formula (I). That is, compound (II) is a compound obtained by modifying the carboxyl group of the compound represented by the general formula (I) with GMA. Here, the terminal carboxyl group refers to a carboxyl group located at a position not included in the repeating unit (I-1) in the general formula (I).

[0248] [Chemical formula 27]

[0249]

[0250] In formula (I-2), * represents a bond.

[0251] The structure represented by the above formula (I-2) is bonded to a group having a structure obtained by removing a hydrogen atom from a carboxyl group and / or a terminal carboxyl group of any part of the repeating unit (I-1) in the general formula (I).

[0252] The ratio of GMA modification of carboxyl groups, i.e., the ratio of GMA addition relative to the molar number of carboxyl groups of compound (C-1) is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, further preferably 0.7 mol% or more or 0.9 mol% or more. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less or 20 mol% or less.

[0253] As compound (C-3), there can be cited compounds (III) having a structure represented by the following formula (I-3) obtained by adding a hydroxyl group of pentaerythritol triacrylate to these isocyanate groups, among the compounds in which any part of the repeating unit (I-1) in the above formula (I) and / or the terminal imide group is an isocyanate group. Here, the terminal imide group refers to an imide group located at a position not included in the repeating unit (I-1) in the general formula (I). The compound in which any part and / or the terminal imide group is an isocyanate group can be obtained by preliminarily leaving an isocyanate group when obtaining the branched polyamide-imide containing a carboxylic acid group of the general formula (1).

[0254] [Chemical formula 28]

[0255]

[0256] In formula (I-3), * represents a bond.

[0257] The structure represented by the above formula (I-3) bonds to an isocyanate group to form a urethane bond.

[0258] The addition amount of pentaerythritol triacrylate is preferably 40 mol% or less, more preferably 38 mol% or less, and further preferably 35 mol% or less, relative to the molar number of the isocyanate group of the polyisocyanate when added. On the other hand, from the viewpoint of fully obtaining the effect produced by the addition, the addition amount of pentaerythritol triacrylate is preferably 0.3 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more, relative to the molar number of the isocyanate group of the polyisocyanate when added.

[0259] The polyamide-imide resin can be synthesized by various known methods, for example. As a method for synthesizing the polyamide-imide resin, for example, the description in paragraphs 0020 to 0030 of International Publication No. 2010 / 074197 can be referred to, and the contents are incorporated herein.

[0260] Commercially available polyamide-imide resins can be used. Examples of commercially available products include EPICLON (registered trademark) "V-8000" and "V8001" manufactured by DIC Corporation, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd., and modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

[0261] As the polystyrene resin, any resin containing a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. The polystyrene resin is preferably an elastomer. In addition, the polystyrene resin can be a copolymer containing any repeating unit different from the styrene unit in addition to the styrene unit, or can be a hydrogenated polystyrene resin.

[0262] As any repeating unit, for example, a repeating unit (conjugated diene unit) having a structure obtained by polymerizing a conjugated diene, a repeating unit (hydrogenated conjugated diene unit) having a structure obtained by hydrogenating the conjugated diene, etc. can be cited. As a conjugated diene, for example, aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, halogenated aliphatic conjugated dienes such as chloroprene, etc. can be cited. As a conjugated diene, from the viewpoint of significantly obtaining the effect of the present invention, it is preferably an aliphatic conjugated diene, and more preferably butadiene. Conjugated dienes can be used alone or in combination of two or more. In addition, the polystyrene resin can be a random copolymer or a block copolymer.

[0263] Examples of the polystyrene resin include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), styrene-butadiene-butylene-styrene block copolymers (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, and styrene-maleic anhydride copolymers. Among them, the polystyrene resin is preferably a styrene-maleic anhydride copolymer.

[0264] Specific examples of the polystyrene resin include "EF-40" manufactured by Cray Valley and "H1043" manufactured by Asahi Kasei Corporation.

[0265] The polyester resin preferably has a fluorene structure in its molecular structure, and preferably has a structural unit derived from a diol and a structural unit derived from a dicarboxylic acid in addition to the fluorene structure, from the viewpoint of compatibility with other components in the resin composition.

[0266] Specific examples of the polyester resin include "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd. and the like.

[0267] Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0268] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, preferably polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0269] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

[0270] From the perspective of obtaining a cured product that more significantly exerts the desired effect of the present invention, the weight average molecular weight (Mw) of component (C) is preferably 5000 or more, more preferably 8000 or more, particularly preferably 10000 or more, preferably 100000 or less, more preferably 80000 or less, particularly preferably 50000 or less. The weight average molecular weight of component (C) is the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

[0271] From the viewpoint of reducing the melt viscosity of the resin composition, the number average molecular weight (Mn) of the component (C) is preferably 5000 or more, more preferably 8000 or more, particularly preferably 10000 or more, preferably 100000 or less, more preferably 80000 or less, particularly preferably 50000 or less. The number average molecular weight can be measured according to the following <Determination of number average molecular weight>. It should be noted that the component (C) can be used as long as one of the weight average molecular weight and the number average molecular weight is within the above-mentioned range. For example, when the weight average molecular weight is generally used as the molecular weight of the component (C), the number average molecular weight does not need to be within the above-mentioned range. Similarly, when the number average molecular weight is generally used as the molecular weight of the component (C), the weight average molecular weight does not need to be within the above-mentioned range.

[0272] <Determination of number average molecular weight>

[0273] 100 mg of component (C) and 5 g of a dispersant ("N-methylpyrrolidone" manufactured by Kanto Chemical Co., Ltd.) were weighed into a vial, dispersed by ultrasonic wave for 20 minutes, and filtered using a membrane filter ("ADVANTEC" manufactured by Toyo Filter Paper Co., Ltd., 0.5 μm pore size (cut)). The number average molecular weight (Mn) was calculated using a gel permeation chromatography measuring apparatus ("Shodex GPC-101" manufactured by Shoko Science Co., Ltd.).

[0274] From the viewpoint of obtaining a cured product having the desired effect of the present invention, the content of component (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less, when the non-volatile component in the resin composition is set to 100% by mass.

[0275] When the content of the nonvolatile components in the resin composition of the component (C) is 100% by mass is c1, and the content of the nonvolatile components in the resin composition of the component (A) is 100% by mass is a1, a1 / c1 is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, preferably 50 or less, more preferably 40 or less, further preferably 30 or less. By setting a1 / c1 within the above range, the effect of the present invention can be significantly obtained.

[0276] <(D) Inorganic fillers>

[0277] The resin composition may contain an inorganic filler as a component (D) as an arbitrary component in addition to the above-mentioned components.

[0278] As the material of the inorganic filler, an inorganic compound is used. As examples of the material of the inorganic filler, silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc., can be listed. Among them, silicon dioxide is particularly preferred. As silicon dioxide, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc. can be listed. In addition, as silicon dioxide, spherical silicon dioxide is preferred. (D) The inorganic filler can be used alone or in combination of two or more.

[0279] (D) As commercially available products of the component, for example, "UFP-30" manufactured by DENKA Corporation, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation, "YC100C", "YA050C", "YA050C-MJE" and "YA010C" manufactured by Yaduma Co., Ltd., "SILFIL NSS-3N", "SILFIL NSS-4N" and "SILFIL NSS-5N" manufactured by Tokuyama Co., Ltd., "SC2500SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Yaduma Co., Ltd., etc.

[0280] From the viewpoint of improving moisture resistance and dispersibility, component (D) is preferably treated by a surface treatment agent. As a surface treatment agent, for example, an amine coupling agent, a (meth) acrylic coupling agent, and a vinyl coupling agent can be cited. From the point of view of obtaining a cured product with excellent environmental test resistance (HAST resistance), it is preferably to use an amine coupling agent and a (meth) acrylic coupling agent. Here, an amine coupling agent refers to a coupling agent with an amino group. A (meth) acrylic coupling agent refers to a coupling agent with a methacryloyloxy group or an acryloxy group. A vinyl coupling agent refers to a coupling agent with a vinyl group and is a coupling agent that does not belong to a (meth) acrylic coupling agent. The above-mentioned amine coupling agent, (meth) acrylic coupling agent, and vinyl coupling agent can be cited as silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc., respectively, and can belong to any one of the silane coupling agents. As silane coupling agents, for example, fluorine-containing silane coupling agents, epoxy silane coupling agents, and mercapto silane coupling agents can be cited. Among them, from the viewpoint of significantly obtaining the effect of the present invention, silane coupling agents are preferred, and amine coupling agents belonging to silane coupling agents and (meth) acrylic coupling agents belonging to silane coupling agents are more preferred. In addition, the surface treatment agent can be used alone or in any combination of two or more.

[0281] Examples of commercially available surface treatment agents include "KBM1003" (vinyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBE903" (3-aminopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM503" (a (methyl) acrylic acid coupling agent) and "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (a long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc. Among them, it is preferably selected from one or more of "KBM503" belonging to a (meth) acrylic coupling agent and "KBM573" and "KBE903" belonging to an amine coupling agent, and it is more preferable to use at least one of "KBM503" and "KBM573".

[0282] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment performed by the surface treatment agent is preferably within a specified range. Specifically, 100 parts by mass of the inorganic filler is preferably surface treated with 0.2 to 5 parts by mass of a surface treatment agent, more preferably with 0.2 to 3 parts by mass of a surface treatment agent, and further preferably with 0.3 to 2 parts by mass of a surface treatment agent.

[0283] The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More than 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of suppressing the increase of the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m 2 Below, preferably 0.8mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0284] The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, a carbon analyzer can be used to measure the amount of carbon per unit surface area of ​​the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0285] The specific surface area of ​​the component (D) is preferably 1 m 2 / g or more, preferably 2m 2 / g or more, particularly preferably 3m 2 There is no particular upper limit, but 60 m 2 / g or less, 50m 2 / g or below or 40m 2 The specific surface area can be obtained by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area by the BET multipoint method.

[0286] From the viewpoint of significantly obtaining the desired effect of the present invention, the average particle size of the component (D) is preferably at least 0.01 μm, more preferably at least 0.05 μm, particularly preferably at least 0.1 μm, preferably at most 5 μm, more preferably at most 2 μm, further preferably at most 1 μm.

[0287] The average particle size of (D) component can be measured by laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of inorganic filler can be made into a volume basis by laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The sample can be measured using a sample obtained by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. For the sample, a laser diffraction particle size distribution measuring device can be used, and the light source wavelength is blue and red, and the volume-based particle size distribution of (D) component is measured in a flow cell (flow cell) manner, and the average particle size is calculated as the median particle size according to the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" made by Horiba Manufacturing Co., Ltd. can be cited.

[0288] From the viewpoint of reducing the value of dielectric loss tangent, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (D) is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. As long as dispersibility can be ensured, the upper limit is not limited and can be set to 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less.

[0289] <(E) Polymerization initiator>

[0290] The resin composition may further contain a polymerization initiator as a component (E) as an optional component in addition to the above-mentioned components. The component (E) may be used alone or in combination of two or more.

[0291] Examples of the component (E) include peroxides such as tert-butylcumyl peroxide, tert-butyl peroxyacetate, α,α′-di(tert-butylperoxy)diisopropylbenzene, tert-butyl peroxylaurate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxybenzoate, and di-tert-hexyl peroxide.

[0292] Examples of commercially available products of the component (E) include “PERBUTYL (registered trademark) C”, “PERBUTYL (registered trademark) A”, “PERBUTYL (registered trademark) P”, “PERBUTYL (registered trademark) L”, “PERBUTYL (registered trademark) O”, “PERBUTYL (registered trademark) ND”, “PERBUTYL (registered trademark) Z”, “PERBUTYL (registered trademark) I”, “PERCUMYL P”, “PERCUMYL D”, “PERHEXYL (registered trademark) D”, “PERHEXYL (registered trademark) A”, “PERHEXYL (registered trademark) I”, “PERHEXYL (registered trademark) Z”, “PERHEXYL (registered trademark) ND”, “PERHEXYL (registered trademark) O”, “PERHEXYL (registered trademark) PV”, and “PERHEXYL (registered trademark) O” manufactured by NOF Corporation.

[0293] From the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is set to 100 mass %, the content of the component (E) is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 0.1 mass % or more, preferably 1 mass % or less, more preferably 0.5 mass % or less, further preferably 0.3 mass % or less.

[0294] <(F) Thermosetting resin>

[0295] For the resin composition, in addition to the above-mentioned components, as an arbitrary component, a thermosetting resin may be further contained as the (F) component. However, the (F) component does not include any component belonging to the (A) component, the (B) component and the (C) component. Thermosetting resin refers to a heat-curable resin. Here, the heat-curable compound includes a compound that can be polymerized by heat curing, a compound that is reactive with the components contained in the resin composition of the present invention, and a compound that can react with the component according to the reactivity of the components contained in the resin composition of the present invention.

[0296] The first example of the component (F) is epoxy resin. Examples of the epoxy resin include biphenylol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butylcatechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, cresol novolac epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, naphthylene ether epoxy resins, trimethylol epoxy resins, and tetraphenylethane epoxy resins. The epoxy resins may be used alone or in combination of two or more.

[0297] For resin combination, it is better to include an epoxy resin having more than 2 epoxy groups in 1 molecule as epoxy resin. From the viewpoint of significantly obtaining the desired effect of the present invention, relative to 100 mass % of the non-volatile component of (F) component, the ratio of the epoxy resin having more than 2 epoxy groups in 1 molecule is preferably more than 50 mass %, more preferably more than 60 mass %, and particularly preferably more than 70 mass %.

[0298] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter also referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin as the component (F), and preferably contains a combination of a liquid epoxy resin and a solid epoxy resin. However, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferred to contain only a liquid epoxy resin.

[0299] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0300] As liquid epoxy resins, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, and better are bisphenol A type epoxy resins and bisphenol F type epoxy resins.

[0301] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US", "jER828EL", "825", and "EPIKOTE 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "630" and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals, Ltd., and Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX Corporation, "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation, "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel Corporation, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation, etc. These epoxy resins may be used alone or in combination of two or more.

[0302] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0303] As solid epoxy resins, preferred are biphenylol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, and better is naphthalene type epoxy resin.

[0304] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation, "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, "HP-7200HH", "HP-7200H", "HP-7200H" and "HP-7200H" manufactured by DIC Corporation. 00" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation, "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC3000H" manufactured by Nippon Kayaku Co., Ltd. , "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YX4000HK" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation ), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These epoxy resins may be used alone or in combination of two or more.

[0305] As epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, their amount ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:20 by mass ratio, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10. By making the amount ratio of liquid epoxy resin and solid epoxy resin within the described range, the desired effect of the present invention can be significantly obtained. In addition, when it is usually used in the form of a resin sheet, appropriate adhesion is brought. In addition, when it is usually used in the form of a resin sheet, sufficient flexibility can be obtained and operability is improved. In addition, a cured product with sufficient fracture strength can usually be obtained.

[0306] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and further preferably 110 g / eq. to 1000 g / eq.. By making it within this range, the crosslinking density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

[0307] From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the epoxy resin is preferably 100 or more and less than 5000, more preferably 250 or more and less than 3000, further preferably 400 or more and less than 1500. The weight average molecular weight of the component (F) can be measured by the same method as the weight average molecular weight of the component (C).

[0308] From the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the content of the epoxy resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less.

[0309] The second example of the component (F) is a resin other than epoxy resin. As an example of a resin other than epoxy resin, a resin having a weight average molecular weight or a number average molecular weight smaller than the resin that can be used as a high molecular weight component listed as the component (C) (also referred to as a "low molecular weight resin" for convenience) can be cited. As an example of a low molecular weight resin, a polyphenylene ether resin can be cited. As a specific example of a polyphenylene ether resin, an oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited.

[0310] The third example of the component (F) is a curing agent other than the component (B), that is, a second curing agent that can be used together with the component (B).

[0311] Examples of the second curing agent include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents not containing an allyl group, cyanate curing agents, carbodiimide curing agents, amine curing agents, and acid anhydride curing agents. The second curing agent may be used alone or in combination of two or more.

[0312] As active ester curing agent, a compound having more than one active ester group in one molecule can be used. Among them, as active ester curing agent, preferably a compound having more than two highly reactive ester groups in one molecule such as esters of phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxy compounds. The active ester curing agent is preferably a compound obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improved heat resistance, it is preferably an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound, and more preferably an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound.

[0313] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0314] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenol novolacs. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0315] As preferred specific examples of active ester curing agents, active ester curing agents containing dicyclopentadiene type diphenol structures, active ester curing agents containing naphthalene structures, active ester curing agents containing acetylated products of phenol novolacs, and active ester curing agents containing benzoylated products of phenol novolacs are preferred. Among them, active ester curing agents containing naphthalene structures and active ester curing agents containing dicyclopentadiene type diphenol structures are more preferred. "Dicyclopentadiene type diphenol structure" represents a divalent structural unit formed by phenylene-dicyclopentylene (ジシクロペンチレン)-phenylene.

[0316] As commercially available active ester curing agents, active ester curing agents containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", "HPC8000H-65TM", "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC Corporation), etc., active ester curing agents containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC Corporation), and active ester curing agents containing acetylated products of phenol novolacs include "EXB9416-70BK" (manufactured by DIC Corporation). Examples include "DC808" (manufactured by Mitsubishi Chemical Corporation), examples include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), examples include "DC808" (manufactured by Mitsubishi Chemical Corporation), examples include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), examples include "YLH1030" (manufactured by Mitsubishi Chemical Corporation), examples include "YLH1048" (manufactured by Mitsubishi Chemical Corporation), examples include "DC808" (manufactured by Mitsubishi Chemical Corporation), examples include "DC808" (manufactured by Mitsubishi Chemical Corporation), examples include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0317] As the phenolic curing agent and naphthol curing agent, those having a novolac structure are preferred from the viewpoint of heat resistance and water resistance, and nitrogen-containing phenolic curing agents are preferred from the viewpoint of adhesion to the conductor layer, and phenolic curing agents containing a triazine skeleton are more preferred.

[0318] Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals Co., Ltd., "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN495V", and "SN375" manufactured by Nippon Steel & Sumitomo Metal Chemicals Corporation, and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

[0319] Specific examples of the benzoxazine curing agent not containing an allyl group (ie, benzoxazine compounds other than the component (B)) include "ODA-BOZ" manufactured by JFE Chemical Corporation, and "Pd" and "Fa" manufactured by Shikoku Chemicals Co., Ltd.

[0320] Examples of cyanate curing agents include difunctional cyanate resins such as bisphenol A dicyanate, 4,4'-methylenebis(2,6-dimethylphenylcyanate), hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, and bis(4-cyanatephenyl)sulfide; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers obtained by triazinizing a portion of these cyanate resins.

[0321] Specific examples of cyanate curing agents include "PT60" (phenol novolac type multifunctional cyanate resin), "ULL-950S" (multifunctional cyanate resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-treated to form a trimer) manufactured by Lonza Japan Co., Ltd.

[0322] Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0323] As the amine curing agent, there can be cited curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of exerting the desired effect of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-diaminodiphenylmethane, diphenyldiaminosulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. As the amine curing agent, a commercially available product can be used, and examples thereof include "KAYABON DC-100" manufactured by Nippon Kayaku Co., Ltd. and the like.

[0324] As the acid anhydride curing agent, there can be cited curing agents having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, Polymer-type acid anhydrides such as benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), and styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid.

[0325] From the viewpoint of significantly obtaining the desired effect of the present invention, the content of the second curing agent relative to 100 mass % of the non-volatile component in the resin composition is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more, preferably 5 mass % or less, more preferably 4 mass % or less, further preferably 3 mass % or less.

[0326] From the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the content of the component (F) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 15% by mass or less, more preferably 13% by mass or less, and particularly preferably 10% by mass or less.

[0327] <(G) Other additives>

[0328] For resin combination, except comprising above-mentioned composition, as arbitrary composition, other additives can be further included.As such additive, for example, resin additives such as thickener, defoamer, leveler, adhesion imparting agent, curing accelerator etc. can be listed.These additives can be used alone or in combination of two or more.If those skilled in the art, the content of each additive can be appropriately set.

[0329] Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. The component (F) may be used alone or in combination of two or more.

[0330] Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

[0331] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]-undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-undecene are preferred.

[0332] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Imidazole compounds such as diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

[0333] As the imidazole-based curing accelerator, a commercially available item may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0334] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine and 1-(o-tolyl)biguanidine, and dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0335] As metal curing accelerators, for example, metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin, organic metal complexes or organic metal salts can be cited. As specific examples of organic metal complexes, organic cobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II). As organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0336] <Method for preparing resin composition>

[0337] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent etc. to the blended components as needed and mixing and dispersing them using a rotary mixer etc. The resin composition can be obtained as a resin varnish, for example, by including a solvent.

[0338] <Physical properties and uses of resin composition>

[0339] The resin composition comprises (A) a maleimide compound, (B) a benzoxazine compound containing an allyl group, and (C) a high molecular weight component. By using these components in combination, a cured product having a small dielectric loss tangent value, excellent adhesion to a conductive material after an environmental resistance test, and improved brittleness can be obtained. As described above, in general, the cured product of a resin composition containing a maleimide compound has a small dielectric loss tangent value. However, maleimide compounds generally have a high softening point, so the cured product of a resin composition containing a maleimide compound tends to be more brittle. In addition, the cured product of a resin composition containing a maleimide compound tends to have poor adhesion after an environmental resistance test, especially after a HAST (Highly Accelerated temperature and humidity Stress Test). However, by making the resin composition containing (A) component contain (B) benzoxazine compound containing allyl group and (C) high molecular weight component, as illustrated in the embodiment, the following cured product can be obtained: maintain the smaller value of dielectric loss tangent obtained by containing (A) component, and the excellent adhesion between the conductive material after environmental resistance test, and the brittleness is improved. This is inferred to be by the presence of (B) component containing allyl group and benzoxazine ring that can react with (A) component in the same molecule in the resin composition, so that a cross-linked structure can be formed under the state of containing (C) component, and the cross-linked structure has a structure that can successfully pass (pass) environmental resistance test (such as HAST test), and the desired effect of the present invention can be exerted as a result. Here, about the improvement of brittleness, it is believed that the stress in the cured product (cross-linked structure) can be relaxed by the presence of (C) high molecular weight component, which is also one of the reasons, and thus the improvement of adhesion and environmental resistance (HAST resistance) are also helpful.

[0340] The cured product obtained by heat curing the resin composition described in the present embodiment at 200° C. for 90 minutes shows the property of a small value of dielectric loss tangent. Specifically, the value of dielectric loss tangent (Df) is preferably 0.005 or less, more preferably 0.0049 or less, and further preferably 0.0048 or less. The value of dielectric loss tangent (Df) can be measured by the method described in the examples described later.

[0341] The cured product obtained by heat curing the resin composition described in the present embodiment at 200° C. for 90 minutes shows improved brittleness. Specifically, the value (%) of the elongation at break as an example of the brittleness evaluation item is preferably higher than 0.6%, more preferably 0.7% or more, further preferably 1.0% or more, and particularly preferably 1.2% or more. The value of the elongation at break can be measured by the method described in the examples described later.

[0342] The cured product obtained by heat curing the resin composition described in the present embodiment at 200° C. for 90 minutes shows excellent adhesion to the conductive material before the environmental resistance test, especially the conductive material (such as copper foil) of the film. Therefore, the cured product brings an insulating layer with excellent peel strength of the conductive material as an example of the adhesion evaluation project. The peel strength before the environmental resistance test is preferably higher than 0.49kgf / cm, more preferably more than 0.50kgf / cm, and further preferably more than 0.51kgf / cm. The upper limit of the peel strength before the environmental resistance test can be set to less than 10kgf / cm, etc. The peel strength before the environmental test can be measured according to the method described in the embodiment described later. The unit of peel strength can use N / cm of the SI unit system instead of kgf / cm.

[0343] The cured product obtained by thermally curing the resin composition described in the present embodiment at 200° C. for 90 minutes shows excellent adhesion to the conductive material after the environmental resistance test, especially the conductive material of the film (such as copper foil). Therefore, the cured product brings an insulating layer with excellent peel strength of the conductive material after the environmental resistance test. The peel strength after the environmental resistance test is preferably higher than 0.38kgf / cm, more preferably more than 0.39kgf / cm, and further preferably more than 0.40kgf / cm. The upper limit of the peel strength after the environmental resistance test can be set to less than 10kgf / cm, etc. Regarding the determination of the peel strength after the environmental resistance test, it can be measured according to the method described in the embodiments described later.

[0344] The cured product obtained by heat curing the resin composition described in this embodiment at 200°C for 90 minutes shows that it can maintain the adhesion between the conductive material before the environmental resistance test, especially the adhesion with the conductive material of the film (such as copper foil) after the environmental resistance test. Therefore, the cured product brings an insulating layer that can maintain the peel strength of the conductive material after the environmental resistance test. The ratio (percentage) of "the value obtained by subtracting the peel strength after the environmental resistance test from the value of the peel strength before the environmental resistance test" to "the value of the peel strength before the environmental resistance test" is preferably less than 30%, more preferably less than 28%, and further preferably less than 17%, especially preferably less than 15%, even if the test environment of the environmental resistance test is a harsh environment (for example, 100 hours under high temperature and high humidity conditions of 130°C and 85%RH).

[0345] The resin composition of the present invention can bring about an insulating layer with a small value of dielectric loss tangent, excellent adhesion with conductive materials after environmental resistance test, and improved brittleness. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, it can be suitably used as: a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer), the insulating layer is an insulating layer for forming a conductor layer (including a rewiring layer), and the conductor layer is formed on the insulating layer. The resin composition of the present invention can bring about a cured product with improved brittleness. Therefore, the resin composition of the present invention can also be suitably used as a resin composition other than insulating purposes.

[0346] Furthermore, in the multilayer printed wiring board described later, it can be suitably used as: a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), and a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).

[0347] Furthermore, when a semiconductor chip package is manufactured through the following steps (1) to (6), for example, the resin composition of the present invention can also be suitably used as a resin composition for a rewiring forming layer (resin composition for forming a rewiring forming layer) as an insulating layer for forming a rewiring layer, and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer;

[0348] (1) A step of laminating a temporary fixing film on a substrate;

[0349] (2) a step of temporarily fixing the semiconductor chip to a temporary fixing film;

[0350] (3) a step of forming a sealing layer on a semiconductor chip;

[0351] (4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;

[0352] (5) forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled off; and

[0353] (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0354] [Resin sheet]

[0355] The resin sheet of the present invention comprises a support and a resin composition layer comprising the resin composition of the present invention provided on the support.

[0356] In addition to the resin composition of the present invention, the resin composition layer may also contain any material, such as a sheet-like reinforcing member such as glass cloth, as long as the effect of the present invention is not greatly damaged. However, if the resin composition layer contains a sheet-like reinforcing member, there is a tendency for the thickness of the resin composition layer to increase, so from the viewpoint of reducing the thickness, the resin composition layer preferably does not contain a sheet-like reinforcing member, for example, the resin composition layer is composed only of the resin composition. It should be noted that the properties of the aforementioned cured product are the properties of the cured product obtained by curing the resin composition layer of the resin composition that does not contain a sheet-like reinforcing member.

[0357] From the viewpoint of thinning of the printed wiring board and the cured product of the resin composition having excellent insulation properties even as a thin film, the thickness of the resin composition layer is preferably below 70 μm, preferably below 50 μm, more preferably below 45 μm, and further preferably below 40 μm. The lower limit of the thickness of the resin composition layer is not particularly limited, and can usually be set to more than 1 μm, more than 1.5 μm, more than 2 μm or more than 5 μm, etc.

[0358] Examples of the support include films formed of a plastic material, metal foil and release paper, and films formed of a plastic material and metal foil are preferred.

[0359] When a film formed of a plastic material is used as a support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter also referred to as "PET") and polyethylene naphthalate (hereinafter also referred to as "PEN"), polycarbonate (hereinafter also referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0360] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. As the copper foil, a foil formed of a single metal of copper can be used, or a foil formed of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used. As a specific example of a polyethylene terephthalate film, "LUMIRROR R80" manufactured by Toray Industries, Inc. can be cited.

[0361] The surface of the support to be in contact with the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0362] In addition, as a support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent for the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins and silicone resins can be cited. As an alkyd resin release agent, "AL-5" manufactured by Lintec Co., Ltd. can be cited. Commercial products can be used for the support with a release layer, for example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Co., Ltd., which is a PET film having a release layer with an alkyd resin release agent as the main component, "LUMIRROR T60" manufactured by Toray Industries, Ltd., "Purex" manufactured by Teijin Co., Ltd., "Unipeel" manufactured by UNITIKA Co., Ltd., etc.

[0363] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the entire thickness of the support with a release layer is preferably within the above range.

[0364] In one embodiment, the resin sheet may further include other layers as needed. As the other layers, for example, a protective film selected according to the support and disposed on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the side opposite to the support) can be cited. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of garbage or the formation of damage to the surface of the resin composition layer.

[0365] The resin sheet can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish on a support using a die coater or the like, and drying the varnish to form a resin composition layer.

[0366] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone, etc. The organic solvent may be used alone or in combination of two or more.

[0367] Drying can be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, and the drying is carried out under the condition that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The drying conditions vary depending on the boiling point of the organic solvent in the resin varnish. For example, in the case of using a resin varnish containing 30% to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes.

[0368] The resin sheet can be stored in a roll. If the resin sheet has a protective film, it can be used by peeling off the protective film.

[0369] [Printed wiring board]

[0370] The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.

[0371] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet through a method including the following steps (I) and (II):

[0372] (I) laminating the resin sheet on the inner substrate so that the resin composition layer is bonded to the inner substrate;

[0373] (II) A step of thermally curing the resin composition layer to form an insulating layer.

[0374] The "inner substrate" used in step (I) refers to a component that becomes a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both sides of a substrate is also referred to as an "inner circuit substrate". In addition, an intermediate product that requires further formation of an insulating layer and / or a conductor layer when manufacturing a printed wiring board is also included in the "inner substrate" referred to in the present invention. In the case where the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

[0375] The lamination of the inner substrate and the resin sheet can be carried out, for example, by heat-pressing the resin sheet to the inner substrate from the support body side. As a component (hereinafter also referred to as "heat-pressing component") for heat-pressing the resin sheet to the inner substrate, for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) etc. can be cited. It should be noted that it is better not to press the heat-pressing component directly on the resin sheet, but to press it with an elastic material such as heat-resistant rubber so that the resin sheet fully conforms to the surface unevenness of the inner substrate.

[0376] The lamination of the inner substrate and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably implemented under reduced pressure conditions of 26.7hPa or less.

[0377] Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch vacuum pressure laminator.

[0378] After lamination, the laminated resin sheet can be smoothed by, for example, pressing the heating and pressing member from the support body side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0379] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0380] In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

[0381] For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, and the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and further preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

[0382] The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes) before the resin composition layer is thermally cured.

[0383] When manufacturing a printed wiring board, it is also possible to implement a process (III) of opening holes in the insulating layer, a process (IV) of roughening the insulating layer, and a process (V) of forming a conductor layer. These processes (III) to (V) can be implemented according to various methods known to those skilled in the art used in the manufacture of printed wiring boards. It should be noted that when the support body is removed after process (II), the removal of the support body can be implemented between process (II) and process (III), between process (III) and process (IV), or between process (IV) and process (V). In addition, the formation of the insulating layer and the conductor layer of processes (II) to (V) can be repeatedly implemented as needed to form a multilayer wiring board.

[0384] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes and vias in the insulating layer. Step (III) can be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

[0385] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), the smear is also removed. The steps and conditions of the roughening treatment are not particularly limited, and the known steps and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer is roughened by swelling treatment using a swelling liquid, roughening treatment using an oxidant, and neutralization treatment using a neutralizing liquid in sequence. The swelling liquid used in the roughening treatment is not particularly limited, and alkali solutions, surfactant solutions, etc. can be listed, preferably alkali solutions, and sodium hydroxide solutions and potassium hydroxide solutions are better as the alkali solution. As commercially available swelling liquids, for example, "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", "SwellingDip Securiganth P" and the like manufactured by ATOTECH JAPAN Co., Ltd. can be listed. The swelling treatment using the swelling liquid is not particularly limited, and can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. As the oxidant used in the roughening treatment, there is no particular limitation, and examples thereof include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidant such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidants, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. In addition, as the neutralizing solution used in the roughening treatment, an acidic aqueous solution is preferred, and commercially available products include, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment using the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 1 minute to 30 minutes. From the viewpoint of operability, etc., it is preferred to immerse the object subjected to the roughening treatment using the oxidizing agent in the neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes.

[0386] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably less than 300nm, more preferably less than 250nm, and further preferably less than 200nm. There is no particular limitation on the lower limit, but it is preferably more than 30nm, more preferably more than 40nm, and further preferably more than 50nm. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0387] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above metals (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be listed. Among them, from the perspective of versatility, cost, and ease of pattern formation of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single metal layer of copper is more preferred.

[0388] The conductor layer may be a single layer structure, or a multilayer structure in which two or more single metal layers or alloy layers formed of different types of metals or alloys are stacked. When the conductor layer is a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

[0389] The thickness of the conductor layer varies depending on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0390] In one embodiment, the conductor layer can be formed by plating. For example, the conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. From the perspective of manufacturing simplicity, it is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

[0391] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having a desired wiring pattern.

[0392] [Semiconductor devices]

[0393] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be produced using the printed wiring board of the present invention.

[0394] Examples of the semiconductor device include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, cars, trains, ships, and aircraft).

[0395] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conductive position of a printed wiring board. "Conductive position" refers to "a position in a printed wiring board where an electrical signal is conducted", and the position may be on the surface or embedded. In addition, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor.

[0396] The method for mounting semiconductor chips when manufacturing semiconductor devices is not particularly limited as long as the semiconductor chips can function effectively, and specific examples include wire bonding mounting methods, flip chip mounting methods, mounting methods based on built-in non-bump-less build-up layers (BBUL), mounting methods based on anisotropic conductive films (ACF), mounting methods based on non-conductive films (NCF), etc. Here, "mounting method based on built-in non-bump-less layers (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board."

[0397] Example

[0398] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In the following description, unless otherwise expressly stated, the "parts" and "%" indicating the amount respectively represent "parts by mass" and "% by mass". In addition, unless otherwise expressly stated, the operations described below are performed under normal temperature and pressure.

[0399] [Synthesis Example 1: Synthesis of high molecular weight component]

[0400] A varnish containing a polyimide resin as a high molecular weight component was prepared as follows;

[0401] A 500 mL separable flask equipped with a water quantitative receiver connected to a reflux condenser, a nitrogen inlet pipe, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to the flask, and stirred at 45°C for 2 hours under a nitrogen flow to react and obtain a reaction solution.

[0402] Next, the reaction solution was heated, and while being maintained at about 160°C, the condensation water was azeotropically removed together with toluene under a nitrogen gas flow. "A specified amount of water was accumulated in the water quantitative receiver" and "no water outflow was observed" were confirmed. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. It was then cooled to obtain a varnish containing 20% ​​by mass of a polyimide resin having a 1,1,3-trimethylindane skeleton (hereinafter also referred to as "the polyimide resin of Synthesis Example 1"). The polyimide resin of Synthesis Example 1 has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the polyimide resin of Synthesis Example 1 was measured by the same method as the weight average molecular weight of component (C), and the result was 12000.

[0403] [Chemical formula 29]

[0404]

[0405] [Chemical formula 30]

[0406]

[0407] [Example 1]

[0408] (Preparation of Resin Varnish A Containing Resin Composition)

[0409] 100 parts of biphenyl aralkyl type maleimide resin "MIR-3000-70MT" (maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution containing 70% of nonvolatile matter) (hereinafter also referred to as "maleimide compound A-containing solution") manufactured by Nippon Kayaku Co., Ltd. as a maleimide compound, 30 parts of the varnish containing 20% ​​by mass of the polyimide resin as a high molecular weight component obtained in Synthesis Example 1 (hereinafter also referred to as "high molecular weight component A-containing varnish"), 15 parts of toluene, 15 parts of methyl ethyl ketone (MEK), "ALP-d" (an allyl group-containing benzoxazine compound containing unsubstituted allyl groups) manufactured by Shikoku Chemical Industry Co., Ltd. as an allyl group-containing benzoxazine compound were uniformly dispersed in a high-speed rotary mixer. 4 parts of a 50% MEK solution containing benzoxazine compound (equivalent weight of groups participating in the ring-opening reaction: 257 g / eq., equivalent weight of allyl group: 257 g / eq.), 0.5 parts of "PERHEXYL (registered trademark) D" (hereinafter also referred to as "polymerization initiator A") manufactured by NOF Corporation as a polymerization initiator, and 135 parts of spherical silica "SO-C2" (hereinafter also referred to as "inorganic filler A") manufactured by Yaduma Co., Ltd., which was surface-treated with phenylaminosilane coupling agent "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. as an amine coupling agent, as an inorganic filler, to obtain a resin varnish A containing a resin composition;

[0410] The average particle size of the inorganic filler A measured by the above-mentioned measuring method was 0.5 μm, and the specific surface area measured by the above-mentioned measuring method was 5.9 m 2 / g.

[0411] (Production of Resin Sheet A)

[0412] A support having a release layer was prepared by subjecting one surface of a polyethylene terephthalate film ("LUMIRROR R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130° C.) to a release treatment using an alkyd resin release agent ("AL-5" manufactured by Lintec Corporation).

[0413] The resin varnish A is evenly applied to the release layer of the support using a die coater in such a manner that the thickness of the resin composition layer after drying becomes 40 μm. Then, the resin varnish A is dried at 70°C to 105°C for 3 minutes. Thus, a resin sheet comprising a support and a resin composition layer containing a resin composition disposed on the support is obtained. Next, the rough surface of a polypropylene film ("ALPHAN MA-411" manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is attached to the surface of the resin composition layer that is not bonded to the support. Thus, a resin sheet A having a support, a resin composition layer and a protective film in sequence is obtained.

[0414] (Evaluation of Cured Product of Resin Composition)

[0415] Using the resin composition layer of the obtained resin sheet A, a cured product of the resin composition was evaluated from the viewpoints of dielectric loss tangent value, brittleness, and adhesion according to the evaluation method described later.

[0416] [Example 2]

[0417] While stirring, 70 parts of polyphenylmethane maleimide "BMI-2300" (maleimide group equivalent 186 g / eq.) (hereinafter also referred to as "maleimide compound B") manufactured by Yamato Chemical Industry Co., Ltd. as a maleimide compound and 6 parts of polycarbonate resin "FPC2136" (weight average molecular weight 30,000, number average molecular weight 20,895) (hereinafter also referred to as "high molecular weight component B") manufactured by Mitsubishi Gas Chemical Co., Ltd. as a high molecular weight component were heated and dissolved in 40 parts of toluene and 40 parts of MEK. After the obtained solution was cooled to room temperature, 4 parts of a solution containing "benzoxazine compound A containing an allyl group", 0.5 parts of a polymerization initiator A, and 135 parts of spherical silica "SO-C2" (hereinafter also referred to as "inorganic filler B") manufactured by Yaduma Co., Ltd., which was surface-treated with a methacrylic coupling agent "KBM503" manufactured by Shin-Etsu Chemical Co., Ltd. as a (meth)acrylic coupling agent, were uniformly dispersed in the solution using a high-speed rotary mixer to obtain a resin varnish A containing a resin composition.

[0418] The average particle size of the inorganic filler B measured by the above-mentioned measuring method was 0.5 μm, and the specific surface area measured by the above-mentioned measuring method was 5.9 m 2 / g;

[0419] Next, the resin varnish A was used and the same procedure as in Example 1 was carried out to obtain a resin sheet A. The resin composition layer of the resin sheet A was evaluated in the same manner as in Example 1.

[0420] [Example 3]

[0421] 3 parts of high molecular weight component B were heated and dissolved in 20 parts of toluene and 20 parts of MEK under stirring. After the obtained solution was cooled to room temperature, 100 parts of a solution containing maleimide compound A, 15 parts of liquid bismaleimide "BMI-689" (maleimide group equivalent 345 g / eq.) (hereinafter also referred to as "maleimide compound C") manufactured by Artificial Molecular Co., Ltd. as a maleimide compound, 4 parts of a solution containing "benzoxazine compound A containing an allyl group", 0.5 parts of polymerization initiator A, and 235 parts of inorganic filler A were uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Next, using the resin varnish A, the same operation as in Example 1 was performed to obtain a resin sheet A. The resin composition layer of the resin sheet A was subjected to evaluation in the same manner as in Example 1.

[0422] [Example 4]

[0423] 70 parts of maleimide compound B were heated and dissolved in 40 parts of toluene and 40 parts of MEK under stirring. After the obtained solution was cooled to room temperature, 15 parts of liquid bismaleimide "BMI-1500" (maleimide group equivalent 750 g / eq.) (hereinafter also referred to as "maleimide compound D") manufactured by Artificial Molecular Co., Ltd. as a maleimide compound, 10 parts of phenoxy resin "YX7553BH30" (weight average molecular weight 35000, 1:1 solution of MEK and cyclohexanone with 30% by mass of non-volatile components) (hereinafter also referred to as "solution containing high molecular weight component C") manufactured by Mitsubishi Chemical Corporation as a high molecular weight component, 4 parts of a solution containing "benzoxazine compound A containing an allyl group", 0.5 parts of polymerization initiator A, and 235 parts of inorganic filler A were uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Next, the resin varnish A was used and the same procedure as in Example 1 was carried out to obtain a resin sheet A. The resin composition layer of the resin sheet A was evaluated in the same manner as in Example 1.

[0424] [Example 5]

[0425] 100 parts of a solution containing maleimide compound A, 20 parts of toluene, 20 parts of MEK, 15 parts of maleimide compound C, 15 parts of a varnish containing a high molecular weight component A, 20 parts of a solution containing an "allyl group-containing benzoxazine compound A", 0.5 parts of a polymerization initiator A, and 235 parts of an inorganic filler B were uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Next, using the resin varnish A, the same operation as in Example 1 was performed to obtain a resin sheet A. The resin composition layer of the resin sheet A was evaluated in the same manner as in Example 1.

[0426] [Example 6]

[0427] 100 parts of a solution containing maleimide compound A, 15 parts of maleimide compound D, 20 parts of toluene, 20 parts of MEK, 15 parts of a varnish containing a high molecular weight component A, 30 parts of a solution containing an "allyl group-containing benzoxazine compound A", 0.5 parts of a polymerization initiator A, and 235 parts of an inorganic filler A were uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Next, using the resin varnish A, the same operation as in Example 1 was performed to obtain a resin sheet A. The resin composition layer of the resin sheet A was evaluated in the same manner as in Example 1.

[0428] [Example 7]

[0429] 100 parts of a solution containing maleimide compound A, 15 parts of maleimide compound C, 20 parts of toluene, 20 parts of MEK, 10 parts of a solution containing high molecular weight component C, 4 parts of a solution containing "allyl group-containing benzoxazine compound A", 0.5 parts of a polymerization initiator A, and 100 parts of a solution containing maleimide compound A are uniformly dispersed in a high-speed rotary mixer. 235 parts of naphthalene epoxy resin "HP4032SS" (epoxy equivalent of about 144 g / eq.) manufactured by DIC Corporation as a thermosetting resin, 8 parts of active ester curing agent "HPC-8000-65T" (active group equivalent of about 223 g / eq., toluene solution with a non-volatile content of 65% by mass) manufactured by DIC Corporation as a thermosetting resin, and 1 part of 1-benzyl-2-phenylimidazole (1B2PZ) (MEK solution with a non-volatile content of 20% by mass) as a thermosetting resin were prepared to obtain a resin varnish A containing a resin composition. Next, using the resin varnish A, the same operation as in Example 1 was performed to obtain a resin sheet A. The resin composition layer of the resin sheet A was subjected to evaluation in the same manner as in Example 1.

[0430] [Example 8]

[0431] 100 parts of a solution containing maleimide compound A, 15 parts of maleimide compound C, 20 parts of toluene, 20 parts of MEK, 15 parts of a varnish containing a high molecular weight component A, 4 parts of a solution containing an "allyl group-containing benzoxazine compound A", 0.5 parts of a polymerization initiator A, 235 parts of an inorganic filler B, and 50 parts of a radical polymerizable compound "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. (a toluene solution having a number average molecular weight of 1200 and a nonvolatile content of 65% by mass) as a thermosetting resin were uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Next, using the resin varnish A, a resin sheet A was obtained in the same manner as in Example 1. The resin composition layer of the resin sheet A was subjected to evaluation in the same manner as in Example 1.

[0432] [Comparative Example 1]

[0433] In Example 1, 4 parts of the solution containing the "benzoxazine compound A containing an allyl group" was replaced with 4 parts of a MEK solution containing 50% of a non-volatile component of "Pd" (a benzoxazine compound having no functional group reactive with a maleimide group, ring-opening reaction participating group equivalent: 217 g / eq., allyl group equivalent: 0 g / eq.) manufactured by Shikoku Chemical Industry Co., Ltd. as the (B') component;

[0434] Except for the above matters, the resin varnish A containing the comparative resin composition was obtained in the same manner as in Example 1. Next, the resin varnish A was used to obtain a resin sheet A in the same manner as in Example 1. In the same manner as in Example 1, the resin composition layer of the resin sheet A was evaluated.

[0435] [Comparative Example 2]

[0436] In Example 1, 4 parts of the solution containing the "allyl group-containing benzoxazine compound A" were replaced with 2 parts of diallyl phthalate "DAISO DAP (registered trademark) monomer" (molecular weight 246, allyl group equivalent: 123 g / eq.) manufactured by Osaka Soda Co., Ltd. as the component (B");

[0437] Except for the above matters, the resin varnish A containing the comparative resin composition was obtained in the same manner as in Example 1. Next, the resin varnish A was used to obtain a resin sheet A in the same manner as in Example 1. In the same manner as in Example 1, the resin composition layer of the resin sheet A was evaluated.

[0438] [Comparative Example 3]

[0439] In Example 1, 4 parts of the solution containing the "allyl group-containing benzoxazine compound A" were replaced with 2 parts of a 50% non-volatile MEK solution of "Pd" manufactured by Shikoku Chemical Industry Co., Ltd. and 1 part of diallyl phthalate "DAISO DAP (registered trademark) monomer" (molecular weight 246) manufactured by Osaka Soda Co., Ltd. as the (B') component;

[0440] Except for the above matters, the resin varnish A containing the comparative resin composition was obtained in the same manner as in Example 1. Next, the resin varnish A was used to obtain a resin sheet A in the same manner as in Example 1. In the same manner as in Example 1, the resin composition layer of the resin sheet A was evaluated.

[0441] [Comparative Example 4]

[0442] In Example 1, 20 parts of the varnish containing the high molecular weight component A was not used;

[0443] Except for the above matters, the same operation as in Example 1 was carried out to obtain a resin varnish A containing a comparative resin composition. Next, the same operation as in Example 1 was carried out using the resin varnish A to obtain a resin sheet A. The resin composition layer of the resin sheet A was evaluated in the same manner as in Example 1. However, for Comparative Example 4, the value of dielectric loss tangent and brittleness could not be evaluated.

[0444] [Evaluation method]

[0445] The cured products of the resin composition layers using the resin sheets A obtained in the above-mentioned Examples and Comparative Examples were evaluated from the viewpoints of dielectric loss tangent value, brittleness and adhesion according to the following methods.

[0446] <Evaluation of Adhesion>

[0447] The evaluation of adhesion was carried out by measuring the copper foil peel strength according to the following procedure;

[0448] <<Production of evaluation substrate>>

[0449] (1) Base treatment of copper foil

[0450] The shiny surface of 3EC-III (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining and Co., Ltd. was etched 1 μm with "CZ-8101" manufactured by MEC Corporation to roughen the copper surface, and then subjected to rust prevention treatment (CL8300). This copper foil is called CZ copper foil. Furthermore, it was heated in an oven at 130°C for 30 minutes. Thus, an inner layer substrate was obtained.

[0451] (2) Preparation of inner substrate:

[0452] Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) with an inner layer circuit formed thereon were etched by 1 μm using "CZ8101" manufactured by MEC Corporation to roughen the copper surface. Thus, a CZ copper foil having a treated surface was obtained.

[0453] (3) Lamination of resin composition layers

[0454] The protective film is peeled off from the resin sheet A prepared in the examples and comparative examples to expose the resin composition layer. A batch vacuum pressurized laminator (manufactured by Nikko-Materials Co., Ltd., 2-stage laminating laminator "CVP700") is used to laminate the resin composition layer on both sides of the inner substrate in such a manner that the resin composition layer is in contact with the above-mentioned inner substrate. The lamination is carried out as follows: After the air pressure is adjusted to below 13 hPa by reducing the pressure for 30 seconds, it is pressed at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing is performed at 100°C and a pressure of 0.5 MPa for 60 seconds. Then, the support is peeled off to expose the resin composition layer.

[0455] (4) Lamination of copper foil and curing of resin composition layer The treated surface of CZ copper foil was laminated on the exposed resin composition layer under the same conditions as above. Then, the resin composition layer was cured at 200°C for 90 minutes to form a cured product (insulating layer). Thus, an evaluation substrate A with CZ copper foil laminated on both sides was obtained.

[0456] <<Measurement of copper foil peel strength before HAST>>

[0457] The prepared evaluation substrate A was cut into small pieces of 150 mm × 30 mm. A cutter was used to cut a 10 mm wide and 100 mm long cut on the copper foil portion of the small piece, one end was peeled off and clamped with the clamp of the tensile tester described later, and the load [kgf / cm] when 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature (normal temperature) was measured. The load value obtained from the measurement result was used as the "copper foil peeling strength before HAST". A tensile tester (AUTOCOM universal testing machine "AC-50C-SL" manufactured by TSE Co., Ltd.) was used in the measurement. The measurement was carried out in accordance with Japanese Industrial Standard JIS C6481. The results are shown in Table 1.

[0458] <<Measurement of copper foil peel strength after HAST>>

[0459] For the evaluation substrate A prepared, a highly accelerated life tester ("PM422" manufactured by Kusumoto Chemicals Co., Ltd.) was used to carry out an accelerated environmental test for 100 hours at high temperature and high humidity conditions of 130°C and 85%RH. Then, a cut was made on the evaluation substrate A after HAST in the same manner as described above, and one end of the cut was peeled off and clamped with the clamp of the above-mentioned tensile tester in the same manner as the above-mentioned measurement, and the load [kgf / cm] when peeling 35mm in the vertical direction at a speed of 50mm / min at room temperature (normal temperature) was measured. The load value obtained from the measurement result is taken as the "copper foil peel strength after HAST". The measurement was carried out in accordance with Japanese Industrial Standard JIS C6481. The results are shown in Table 1.

[0460] <Evaluation of dielectric loss tangent>

[0461] The dielectric loss tangent is evaluated by measuring its value according to the following steps;

[0462] <<Preparation of cured product for evaluation>>

[0463] The protective film was peeled off from the resin sheet A prepared in the examples and comparative examples, and the resin composition layer was thermally cured by heating at 200°C for 90 minutes, and then the support was peeled off to obtain a cured film formed of a cured product of the resin composition. No cured film was obtained in Comparative Example 4. The cured film was cut into a 2 mm wide and 80 mm long piece to obtain a cured product A for evaluation.

[0464] <<Measurement>>

[0465] The dielectric loss tangent value (Df value) of each evaluation cured product A was measured by the cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using “HP8362B” manufactured by Agilent Technologies Inc. The measurement was performed on three test pieces, and the average value was calculated. The results are shown in Table 1.

[0466] <Evaluation of brittleness>

[0467] The evaluation of brittleness was carried out by measuring the elongation at break according to the following procedure;

[0468] The evaluation cured product A was subjected to a tensile test using a Tensilon universal testing machine (RTC-1250A manufactured by Orientec Corporation) in accordance with Japanese Industrial Standards JIS K7127 to measure the elongation at break [%). The results are shown in Table 1.

[0469] [result]

[0470] The results of the above-mentioned Examples and Comparative Examples are shown in Table 1 below. In Table 1 below, the amount of each component represents the amount converted to non-volatile components. The content of the (C) component and the content of the (D) component in Table 1 represent the percentage [mass %] when the non-volatile components in the resin composition are set to 100 mass %.

[0471] [Table 1]

[0472]

[0473] <Discussion>

[0474] As can be seen from Table 1, by comparing the examples with the comparative examples, it can be seen that in the examples, a resin composition can be provided that can obtain a cured product having a small dielectric loss tangent value, excellent adhesion to a conductive material after an environmental resistance test, and improved brittleness. In addition, it can be seen that the resin composition described in the examples and a cured product of the resin composition, a resin sheet containing the resin composition, a printed wiring board containing an insulating layer formed using the cured product of the resin composition, and a semiconductor device can also be provided.

[0475] It should be noted that, in Examples 1 to 8, even when the components (D) to (F) were not contained, the same results as those of the above-described Examples were obtained, although the extent was different. In addition, it was also confirmed that, in Examples 1 to 8, even when one or both of the components (B') and (B") were contained in an amount that did not impair the desired effect of the present invention, the same results as those of the above-described Examples were obtained, although the extent was different.

Claims

1. A resin composition comprising: (A) maleimide compounds, (B) a benzoxazine compound containing an allyl group, and (C) high molecular weight components, The component (B) comprises at least one selected from the group consisting of a first type of allyl group-containing benzoxazine compound represented by the following general formula (B1-1) and a second type of allyl group-containing benzoxazine compound represented by the following general formula (B2-1), The weight average molecular weight or number average molecular weight of the component (C) is 5,000 or more and 100,000 or less, The mass ratio of the component (B) to the component (A) [component (B) / component (A)] is 0.01 or more and 0.20 or less, When the nonvolatile component in the resin composition is 100 mass %, the content of the component (C) is 0.1 mass % or more and 10 mass % or less, In formula (B1-1), R 20 and R 21 each independently represents a substituted or unsubstituted allyl group, R 22 represents a q-valent group, q represents an integer from 1 to 10, p1 each independently represents an integer from 0 to 4, p2 each independently represents an integer from 0 to 2; In formula (B2-1), R 20a , R 21a and R 22a each independently represents a substituted or unsubstituted allyl group, R 22’ represents a q'-valent group bonded to a carbon atom possessed by the benzoxazine ring, wherein the q'-valent group is at least one selected from a group in which one or more arylene groups are bonded to one or more oxygen atoms, an arylene-alkylene-arylene structure, a group in which one or more alkylene groups are bonded to one or more oxygen atoms, and a group in which one or more arylene groups, one or more alkylene groups, and one or more oxygen atoms are bonded to each other, q' represents an integer from 1 to 10, p1a each independently represents an integer from 0 to 4, p2a each independently represents an integer from 0 to 2, About R 22’ The maximum value of the sum of p1a and p2a for each combined benzoxazine ring is 5.

2. The resin composition according to claim 1, wherein (A) component is selected from Maleimide compounds having a biphenyl structure, and A maleimide compound containing at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms One or more of the following.

3. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (A) is 10 mass % or more and 40 mass % or less.

4. The resin composition according to claim 3, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (A) is 20 mass % or more.

5. The resin composition according to claim 3, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 35% by mass or less.

6. The resin composition according to claim 1, wherein When the nonvolatile component in the resin composition is 100 mass %, the content of the component (B) is 0.01 mass % or more and 15 mass % or less.

7. The resin composition according to claim 6, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 0.02% by mass or more.

8. The resin composition according to claim 6, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 10% by mass or less.

9. The resin composition according to claim 1, wherein [(B) component / (A) component] is 0.02 or more.

10. The resin composition according to claim 1, wherein [(B) component / (A) component] is 0.19 or less.

11. The resin composition according to claim 1, wherein The component (C) is a thermoplastic resin.

12. The resin composition according to claim 11, wherein The thermoplastic resin is at least one selected from polyimide resin, polycarbonate resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polystyrene resin, and polyester resin.

13. The resin composition according to claim 11, wherein The thermoplastic resin is at least one selected from the group consisting of polyimide resin, polycarbonate resin and phenoxy resin.

14. The resin composition according to claim 1, wherein The weight average molecular weight or number average molecular weight of the component (C) is 8,000 or more.

15. The resin composition according to claim 1, wherein The weight average molecular weight or number average molecular weight of the component (C) is 80,000 or less.

16. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 0.5% by mass or more.

17. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 8% by mass or less. 18 . The resin composition according to claim 1 , further comprising (D) an inorganic filler.

19. The resin composition according to claim 18, wherein The component (D) is surface-treated with at least one selected from an amine coupling agent, a (meth)acrylic coupling agent, and a vinyl coupling agent.

20. The resin composition according to claim 18, wherein The component (D) is surface-treated with an amine coupling agent or a (meth)acrylic coupling agent.

21. The resin composition according to claim 18, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (D) is 50 mass % or more.

22. The resin composition according to claim 21, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (D) is 55 mass % or more.

23. The resin composition according to claim 21, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (D) is 60 mass % or more.

24. The resin composition according to claim 18, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (D) is 95 mass % or less.

25. The resin composition according to claim 24, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 90% by mass or less. 26 . The resin composition according to claim 1 , further comprising (E) a polymerization initiator.

27. The resin composition according to claim 26, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (E) is 0.01 mass % or more and 1 mass % or less.

28. The resin composition according to claim 27, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (E) is 0.1 mass % or more.

29. The resin composition according to claim 27, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (E) is 0.3 mass % or less. 30 . The resin composition according to claim 1 , further comprising (F) a thermosetting resin.

31. The resin composition according to claim 30, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (F) is 0.1 mass % or more and 15 mass % or less.

32. The resin composition according to claim 31, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (F) is 0.5 mass % or more.

33. The resin composition according to claim 31, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (F) is 10% by mass or less.

34. The resin composition according to claim 1, wherein The resin composition was heat treated at 200° C. for 90 minutes to obtain a cured product. When the cured product was measured by a resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C., the dielectric loss tangent of the cured product was not more than 0.

005.

35. The resin composition according to claim 1, wherein The resin composition was heat treated at 200° C. for 90 minutes to obtain a cured product. When the cured product was measured by a resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C., the dielectric loss tangent of the cured product was 0.0049 or less.

36. The resin composition according to claim 1, wherein The resin composition was heat-treated at 200° C. for 90 minutes to obtain a cured product. When the cured product was measured in accordance with Japanese Industrial Standard JIS K7127, the elongation at break of the cured product exceeded 0.6%.

37. The resin composition according to claim 1, wherein The resin composition was heat-treated at 200° C. for 90 minutes to obtain a cured product. When the cured product was measured in accordance with Japanese Industrial Standard JIS K7127, the elongation at break of the cured product was 0.7% or more.

38. The resin composition according to claim 1, wherein The resin composition was heat-treated at 200° C. for 90 minutes to obtain a cured product. When the cured product was measured in accordance with Japanese Industrial Standard JIS K7127, the elongation at break of the cured product was 1.0% or more. The resin composition according to claim 1 , which is used for forming an insulating layer.

40. The resin composition according to claim 1, which is used to form an insulating layer, and the insulating layer is used to form a conductor layer.

41. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 40.

42. A resin sheet comprising: Support body, and A resin composition layer provided on the support and comprising the resin composition according to any one of claims 1 to 40. 43 . A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 1 .

44. A printed wiring board comprising an insulating layer formed from the cured product according to claim 41.

45. A semiconductor device comprising the printed wiring board according to claim 43.

46. ​​A semiconductor device comprising the printed wiring board according to claim 44.

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