JP2016132738A - Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and dielectric characteristics (dielectric constant and dielectric loss tangent) in a high frequency band, and to provide a prepreg, a film with resin, a laminate, and a printed wiring board.SOLUTION: The thermosetting resin composition contains: an amino-modified siloxane compound (I) having an aromatic azomethine group, which is obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups; a maleimide compound (c) having at least two N-substituted maleimide groups; and an allyl compound (d) having two or more allyl groups.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition, a prepreg, a resin-coated film, a laminate, a multilayer printed wiring board, and a semiconductor package that are suitable for semiconductor packages and printed wiring boards.

  With recent downsizing and higher performance of electronic devices, printed wiring boards have advanced wiring density and higher integration, and as a result, printed wiring board laminates have excellent heat resistance and low thermal expansion. Sex is required.

As a laminate for a printed wiring board, a prepreg obtained by impregnating or coating a glass woven fabric with a resin composition containing an epoxy resin as a main ingredient is generally used.
Epoxy resin has an excellent balance of insulation, heat resistance, cost, etc., but further improvements are needed to meet the demand for higher heat resistance due to recent high-density mounting of printed wiring boards and higher multi-layer configurations. It becomes.
Moreover, since an epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring and increasing the filling of an inorganic filler such as silica (for example, see Patent Document 1). However, increasing the filling amount of the inorganic filler is known to cause a decrease in insulation reliability due to moisture absorption, insufficient adhesion with the copper foil, and molding defects during press working.
On the other hand, polybismaleimide resin widely used for printed wiring boards with high-density mounting and high multi-layers has a difficulty in adhesion to copper foil, and low thermal expansion is not sufficient.

Moreover, the thermosetting resin composition which has an epoxy resin, a phenol resin, and a modified imide resin as a main component is known (for example, refer patent document 2). Although this modified imide resin-containing composition is improved in moisture resistance and adhesiveness, it is obtained because it is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group in order to ensure solubility in general-purpose solvents such as methyl ethyl ketone. There is a problem that the heat resistance of the modified imide resin is significantly inferior to that of the polybismaleimide resin.
Furthermore, in recent years, in the package substrate for semiconductors, due to the miniaturization and thinning, due to the difference in thermal expansion coefficient between the chip and the substrate and the curing shrinkage rate and elastic modulus of the substrate during component mounting and package assembly. Warpage is a major issue. Therefore, good low thermal expansion, low cure shrinkage, and elastic modulus are required for a laminate used for a semiconductor package substrate.

  Further, in mobile communication devices typified by mobile phones, network infrastructure devices such as base station devices, servers and routers, or large computers, the speed of signals used and the increase in capacity are increasing year by year. Along with this, printed circuit board laminates mounted on these electronic devices are required to cope with high frequencies, and are required to have a low dielectric constant and a low dielectric loss tangent that can reduce transmission loss.

Japanese Patent Laid-Open No. 5-148343 JP-A-6-263843

  In view of the current situation, the problems of the present invention include heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage, and dielectric properties in a high frequency band (dielectric constant and An object of the present invention is to provide a resin composition, a prepreg, a resin-coated film, a laminated board, a multilayer printed wiring board, and a semiconductor package that are excellent in (dielectric loss tangent) (hereinafter sometimes referred to as high frequency characteristics).

  As a result of intensive studies to solve the above problems, the present inventors have found that a heat containing an amino-modified siloxane compound having an aromatic azomethine group, a specific maleimide compound, and an allyl compound having two or more allyl groups. Curable resin composition has heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and dielectric properties (dielectric constant and dielectric loss tangent) in high frequency band As a result, the present invention was reached.

That is, the present invention provides the following thermosetting resin composition, prepreg, resin-coated film, laminated board, multilayer printed wiring board, and semiconductor package.
[1] An aromatic azomethine group obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups An amino-modified siloxane compound (I) having
A maleimide compound (c) having at least two N-substituted maleimide groups, and an allyl compound (d) having two or more allyl groups
A thermosetting resin composition comprising:
[2] An aromatic azomethine group obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups A modified imide resin (J) having an aromatic azomethine group, obtained by reacting an amino-modified siloxane compound (I) having an aromatic group with a maleimide compound (c) having at least two N-substituted maleimide groups, and allyl Allyl compound (d) having two or more groups
A thermosetting resin composition comprising:
[3] An aromatic azomethine group obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups. An acidic substituent obtained by reacting an amino-modified siloxane compound (I) having an acid, a maleimide compound (c) having at least two N-substituted maleimide groups, and an amine compound (e) having an acidic substituent Modified imide resin (K) having aromatic azomethine group, and allyl compound (d) having two or more allyl groups
A thermosetting resin composition comprising:
[4] An aromatic azomethine compound (a) having at least one aldehyde group in one molecule comprises an aromatic amine compound (i) having at least two primary amino groups in one molecule and one molecule. The thermosetting resin composition according to any one of the above [1] to [3], which is obtained by reacting with an aromatic aldehyde compound (ii) having at least two aldehyde groups.
[5] The thermosetting resin composition according to any one of [1] to [4], further comprising an amine compound (e) having an acidic substituent.
[6] The thermosetting resin composition according to any one of [1] to [5], further comprising a thermoplastic elastomer (f).
[7] The thermosetting resin composition according to any one of [1] to [6], further comprising a thermosetting resin (g).
[8] The thermosetting resin composition according to any one of [1] to [7], further comprising a curing accelerator (h).
[9] The thermosetting resin composition according to any one of [1] to [8], further including an inorganic filler.
[10] A prepreg comprising the thermosetting resin composition according to any one of [1] to [9].
[11] A film with a resin comprising the thermosetting resin composition according to any one of [1] to [9].
[12] A laminate comprising the prepreg according to [10].
[13] A laminate comprising the resin-coated film according to [11].
[14] A multilayer printed wiring board using the laminated board according to [12] or [13].
[15] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to [14].

According to the present invention, a resin composition, a prepreg, a resin-coated film, a laminate and an excellent heat resistance, metal foil adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics A printed wiring board can be provided.
A prepreg comprising the thermosetting resin composition of the present invention, a film with a resin obtained by applying the thermosetting resin composition of the present invention to a support, and a laminate comprising the prepreg or the film with resin. The board and multilayer printed wiring board using the laminate are particularly excellent in heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion coefficient, elastic modulus, low curing shrinkage and high frequency characteristics. It is useful as a highly integrated semiconductor package or printed wiring board for electronic equipment.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention is
Amino modification having an aromatic azomethine group obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups Siloxane compound (I),
A maleimide compound (c) having at least two N-substituted maleimide groups, and an allyl compound (d) having two or more allyl groups
Is a thermosetting resin composition.
Hereinafter, each component will be described in order.

[Amino-modified siloxane compound having an aromatic azomethine group (I)]
The amino-modified siloxane compound (I) having an aromatic azomethine group includes an aromatic azomethine compound (a) having at least one aldehyde group in one molecule and a siloxane compound (b) having at least two primary amino groups. Obtained by reacting with.
Here, the aromatic azomethine group refers to a group in which at least one aromatic group (preferably an aromatic hydrocarbon group) is bonded to an azomethine group (—N═CH—).

(Aromatic azomethine compound (a) having at least one aldehyde group in one molecule)
The aromatic azomethine compound (a) having at least one aldehyde group in one molecule is, for example, an aromatic amine compound (i) having at least two primary amino groups in one molecule and at least in one molecule. It may be obtained by reacting an aromatic aldehyde compound (ii) having two aldehyde groups.

(Aromatic amine compound (i) having at least two primary amino groups in one molecule)
Aromatic amine compound (i) having at least two primary amino groups in one molecule [hereinafter sometimes abbreviated as aromatic amine compound (i). ] Is preferably an aromatic amine compound having 2 or 3 primary amino groups in one molecule, and more preferably an aromatic amine compound having 2 primary amino groups in one molecule.
The aromatic amine compound (i) has an aromatic hydrocarbon group, and as long as the aromatic amine compound (i) has an aliphatic hydrocarbon group. For example, the aromatic amine compound (i) also includes a structure having an aromatic hydrocarbon group-aliphatic hydrocarbon group-aromatic hydrocarbon group in the molecule.
The aromatic amine compound (i) is preferably represented by the following general formula (i).

(In the formula, A ¹ is a group represented by the following general formula (1) or (2).)

(In the formula, each R ¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P is an integer of 0 to 4.)

(In the formula, R ² and R ³ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond, or a group represented by the following general formula (3): q and r are each independently an integer of 0 to 4. )

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³ is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s and t are each independently an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. As this aliphatic hydrocarbon group, a C1-C3 aliphatic hydrocarbon group may be selected, and a methyl group may be selected. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among these, as R ¹ , an aliphatic hydrocarbon group having 1 to 5 carbon atoms can be selected.
p is an integer of 0 to 4, and an integer of 0 to 2 or 2 may be selected from the viewpoint of availability. When p is an integer of 2 or more, the plurality of R ¹ may be the same or different.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ² and R ³ are the same as those in the case of R ¹ . As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms may be selected, a methyl group or an ethyl group may be selected, and an ethyl group may be selected.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, and the like. Is mentioned. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is selected from the viewpoint of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. Or a methylene group may be selected.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ² include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group may be selected from the viewpoints of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
As A ² , among the above options, an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms may be selected. In addition, a group may be selected from the viewpoint of the aforementioned characteristics.
q and r are each independently an integer of 0 to 4, and from the viewpoint of easy availability, either an integer of 0 to 2 may be selected, or 0 or 2 may be selected. When q or r is an integer of 2 or more, a plurality of R ^{2 s} or R ^{3 s} may be the same or different.

Aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ⁴ and ^{R 5,} examples of the halogen atom include the same as those in of ^{R 2} and ^{R 3.}
Alkylene group having 1 to 5 carbon atoms represented by A ^3, alkylidene group having 2 to 5 carbon atoms, alkylene group having 1 to 5 carbon atoms represented by ^{A 2,} the same as the alkylidene group having 2 to 5 carbon atoms include It is done.
As A ³ , among the above options, an alkylidene group having 2 to 5 carbon atoms may be selected.
s and t are integers of 0 to 4, and from the viewpoint of availability, either an integer of 0 to 2 may be selected, 0 or 1 may be selected, or 0 may be selected. Good. When s or t is an integer greater than or equal to 2, several R < ⁴ > or R < ⁵ > may be same or different, respectively.
As the group represented by the general formula (3), a group represented by the following general formula (3 ′) may be selected.

(A ³ , R ⁴ , R ⁵ , s and t in the general formula (3 ′) are the same as those in the general formula (3).)

A ¹ is represented by the general formula (2) from the viewpoints of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. A group may be selected, or a group represented by the following general formula (2 ′) may be selected.

(A ² , R ² , R ³ , q and r in the general formula (2 ′) are the same as those in the general formula (2).)

A ¹ in the general formula (i) is any one of the following formulas from the viewpoints of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. May be selected.

  Examples of the aromatic amine compound (i) include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene. 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4 '-Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4, 4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) Propane), 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 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, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, etc. It is done. You may use these individually by 1 type or in mixture of 2 or more types.

  Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl, which has high reactivity at the time of reaction and can achieve higher heat resistance. -4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-amino Phenoxy) phenyl] propane or the like may be selected. From the viewpoint of being inexpensive and soluble in an organic solvent, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-3,3 ′ -Diethyl-diphenylmethane, bis [4- (4-aminophenoxy) phenyl] propane may be selected. From the viewpoint of low thermal expansibility and dielectric properties, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane may be selected. . From the viewpoint of increasing the elastic modulus, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene may be selected. .

(Aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule)
Aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule [hereinafter sometimes simply referred to as aromatic aldehyde compound (ii). ] Is preferably an aromatic aldehyde compound having 2 or 3 aldehyde groups in one molecule, more preferably an aromatic aldehyde compound having 2 aldehyde groups in one molecule.
The aromatic aldehyde compound (ii) has an aromatic hydrocarbon group, and as long as it has an aliphatic hydrocarbon group. For example, a case where the molecule has a structure of aromatic hydrocarbon group-aliphatic hydrocarbon group-aromatic hydrocarbon group is also included in the aromatic aldehyde compound (ii).
As the aromatic aldehyde compound (ii), a compound represented by the following general formula (ii) may be selected.

(In the formula, A ¹¹ is a group represented by the following general formula (11) or (12).)

(In the formula, each R ¹¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P1 is an integer of 0 to 4.)

(In the formula, R ¹² and R ¹³ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond, or a group represented by the following general formula (13): q1 and r1 are each independently an integer of 0 to 4. )

(Wherein R ¹⁴ and R ¹⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹³ is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s1 and t1 are each independently an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group represented by R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. As this aliphatic hydrocarbon group, a C1-C3 aliphatic hydrocarbon group may be selected, and a methyl group may be selected. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among the above, R ¹¹ may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p1 is an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 may be selected, 0 or 1 may be selected, or 0 may be selected. If p1 is an integer of 2 or more, among the plurality of R ¹¹ may be different even in the same.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ¹² and R ¹³ are the same as those in the case of R ¹¹ . As this aliphatic hydrocarbon group, a C1-C3 aliphatic hydrocarbon group may be selected, a methyl group, an ethyl group may be selected, and an ethyl group may be selected.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ¹² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Is mentioned. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is selected from the viewpoint of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. Or a methylene group may be selected.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ¹² include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group may be selected from the viewpoints of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
As A ¹² , among the above options, an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms may be selected.
q1 and r1 are each independently an integer of 0 to 4, and from the viewpoint of easy availability, either an integer of 0 to 2 or 0 or 2 may be selected. If q1 or r1 is an integer of 2 or more, plural R ¹² s or R ¹³ together may each be the same or different.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ¹⁴ and R ¹⁵ include the same as those for R ¹² and R ¹³ .
Alkylene group having 1 to 5 carbon atoms which A ¹³ represents, alkylidene group having 2 to 5 carbon ^atoms, alkylene group of 1 to 5 carbon atoms ^{which A 12} represents, the same as the alkylidene group having 2 to 5 carbon atoms include It is done.
As A ¹³ , among the above options, an alkylidene group having 2 to 5 carbon atoms may be selected.
s1 and t1 are integers of 0 to 4, and from the viewpoint of easy availability, either an integer of 0 to 2 may be selected, 0 or 1 may be selected, or 0 may be selected. Good. If s1 or t1 is an integer of 2 or more, plural R ¹⁴ s or R ¹⁵ together may each be the same or different.
As the group represented by the general formula (13), a group represented by the following general formula (13 ′) may be selected.

(A ¹³ , R ¹⁴ , R ¹⁵ , s1 and t1 in the general formula (13 ′) are the same as those in the general formula (13).)

As the A ^11, the heat resistance, the metal foil adhesion, expressed by the glass transition temperature (Tg), low thermal expansion, elastic modulus, from the viewpoint of low curing shrinkage and high frequency characteristics, the formula (11) A group may be selected, or a group represented by the following general formula (11 ′) may be selected.

(In General Formula (11 ′), R ¹¹ and p1 are the same as those in General Formula (11).)

  Examples of the aromatic aldehyde compound (ii) include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2'-bipyridine-4,4'-dicarboxaldehyde, and the like. Among these, for example, terephthalaldehyde that can be further reduced in thermal expansion, has high reactivity during the reaction, is excellent in solubility in an organic solvent, and is easily available commercially may be selected.

(Siloxane compound (b) having at least two primary amino groups)
Siloxane compound (b) having at least two primary amino groups [hereinafter sometimes referred to simply as siloxane compound (b). ] May be selected from those having one or more primary amino groups at both ends of the molecule, or those having one primary amino group at each of both ends of the molecule. Each having one primary amino group may be selected.
As the siloxane compound (b), one having a linear siloxane skeleton and a dimethylsilicone skeleton in the molecule may be selected.
The amino group equivalent of the siloxane compound (b) may be selected in the range of 200 to 7000, may be selected in the range of 300 to 6000, may be selected in the range of 400 to 4000, and 600 to 3000. You may select in the range.

A commercially available product may be used as the siloxane compound (b). Examples of commercially available products include “KF-8010” (amino group equivalent 430), “X-22-161A” (amino group equivalent 800), “X-22-161B” (amino group equivalent 1500), “KF— 8012 "(amino group equivalent 2200)," KF-8008 "(amino group equivalent 5700)," X-22-9409 "(amino group equivalent 700)," X-22-1660B-3 "(amino group equivalent 2200) (Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (amino group equivalent 460), “BY-16-853” (amino group equivalent 650), “BY-16-853B” (amino group equivalent) 2200) (made by Toray Dow Corning Co., Ltd.). You may use these individually by 1 type or in mixture of 2 or more types.
Among these, for example, from the viewpoint of reactivity during synthesis and low thermal expansion, X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, BY-16-853B X-22-161A and X-22-161B may be selected, or X-22-161B may be selected from the viewpoint of excellent compatibility and high modulus of elasticity. .

(Method for producing amino-modified siloxane compound (I) having an aromatic azomethine group)
As a method for producing an amino-modified siloxane compound (I) having an aromatic azomethine group, for example, first, an aromatic amine compound (i) having at least two primary amino groups in one molecule and one molecule The aromatic aldehyde compound (ii) having at least two aldehyde groups is subjected to a dehydration condensation reaction in an organic solvent [hereinafter referred to as dehydration condensation reaction 1]. ], An aromatic azomethine compound (a) having at least one aldehyde group in one molecule is obtained. Next, the compound and the siloxane compound (b) having at least two primary amino groups are subjected to a dehydration condensation reaction [hereinafter referred to as dehydration condensation reaction 2] in an organic solvent. ], It is possible to produce an amino-modified siloxane compound (I) having an aromatic azomethine group.
According to this reaction method, the molecular weight of the aromatic azomethine group in the molecule of the amino-modified siloxane compound (I) having an aromatic azomethine group can be easily controlled, and the resin composition containing this can have a high elastic modulus. It is particularly effective.

The organic solvent used for each dehydration condensation reaction is not particularly limited. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketone solvents such as cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atoms such as dimethylsulfoxide Containing solvent; ester solvents such as γ-butyrolactone. These can be used individually by 1 type or in mixture of 2 or more types.
Among these, from the viewpoint of solubility, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, and γ-butyrolactone may be selected. Moreover, you may select propylene glycol monomethyl ether and toluene from a viewpoint that it is highly volatile and it is hard to remain | survive in a prepreg and a film with resin.
Further, since the reaction is a dehydration condensation reaction, water is generated as a by-product. For the purpose of removing water as a by-product, it is preferable to react while removing water as a by-product by azeotropy with an aromatic solvent, for example.

  In each dehydration condensation reaction, a reaction catalyst can be optionally used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. These can be used individually by 1 type or in mixture of 2 or more types. From the viewpoint of allowing the dehydration condensation reaction to proceed efficiently, an acidic catalyst may be selected, or p-toluenesulfonic acid may be selected.

(Dehydration condensation reaction 1)
First, an aromatic amine compound (i) and an aromatic aldehyde compound (ii) are subjected to a dehydration condensation reaction in an organic solvent, thereby producing an aromatic azomethine compound (a) having at least one aldehyde group in one molecule [ Hereinafter, it may be simply referred to as an aromatic azomethine compound (a). ] Is obtained.
Here, the amount of aromatic amine compound (i) and aromatic aldehyde compound (ii) used is, for example, the number of aldehyde groups of aromatic aldehyde compound (ii) [the amount of aromatic aldehyde compound (ii) used / aromatic aldehyde The aldehyde group equivalent of compound (ii)] is the number of primary amino groups of aromatic amine compound (i) [amount of aromatic amine compound (i) used / primary amino group equivalent of aromatic amine compound (i)]. You may use it so that it may become 1-5 times, you may use it so that it may become 1.5-5 times, and you may use it so that it may become 2-4 times. When the ratio is 1.1 times or more, the reaction proceeds sufficiently and the product comes to have an aldehyde group, and when it is 5 times or less, it is necessary to express characteristics such as elastic modulus. A large number of aromatic azomethine groups.

  Moreover, the usage-amount of the organic solvent in the dehydration condensation reaction 1 is 25-2000 mass parts with respect to 100 mass parts of sum total of the resin component of aromatic amine compound (i) and aromatic aldehyde compound (ii), for example. It is good also as 40-1000 mass parts, and good also as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, good solubility tends to be obtained, and when it is 2000 parts by mass or less, the reaction hardly takes a long time.

The aromatic azomethine compound (a) is obtained by charging the above raw materials, organic solvent and, if necessary, a reaction catalyst into a reactor, and stirring and dehydrating and condensing for 0.1 to 10 hours while heating or keeping warm as necessary.
The reaction temperature may be, for example, 70 to 150 ° C or 100 to 130 ° C. Moreover, you may make it react, removing the water which is a by-product. By setting the reaction temperature to 70 ° C. or higher, the reaction rate does not become too slow, and by setting the reaction temperature to 150 ° C. or lower, it is not necessary to use a high-boiling organic solvent as the reaction solvent. In addition, the organic solvent hardly remains, and the heat resistance tends to be suppressed from decreasing.

(Dehydration condensation reaction 2)
Next, an aromatic azomethine group (a) obtained by the dehydration condensation reaction 1 and a siloxane compound (b) having at least two amino groups are subjected to a dehydration condensation reaction in an organic solvent, thereby producing an aromatic azomethine group. An amino-modified siloxane compound (I) having the following can be obtained.
Here, the amount of the aromatic azomethine compound (a) and the siloxane compound (b) used is, for example, the number of primary amino groups of the siloxane compound (b) [the amount of the siloxane compound (b) used / the primary amino group of the siloxane compound (b). Group equivalent] is in the range of 1 to 10 times the number of aldehyde groups of aromatic azomethine compound (a) [amount of aromatic azomethine compound (a) / aldehyde group equivalent of aromatic azomethine compound (a)]. May be used. By setting the number of primary amino groups of the siloxane compound (b) to 1 or more times the number of aldehyde groups of the aromatic azomethine compound (a), good solubility in a solvent tends to be obtained. Moreover, by setting it as 10 times or less, it exists in the tendency for the fall of the elasticity modulus of the thermosetting resin containing amino modified siloxane compound (I) which has an aromatic azomethine group to be suppressed.

  Moreover, the usage-amount of the organic solvent in the dehydration condensation reaction 2 is good also as 25-2000 mass parts with respect to 100 mass parts of sum totals of an aromatic azomethine compound (a) and a siloxane compound (b), for example, 40-1000. The mass may be 40 parts by mass or 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, good solubility tends to be obtained, and when it is 2000 parts by mass or less, the reaction hardly takes a long time.

An amino-modified siloxane compound having an aromatic azomethine group is prepared by charging the above raw materials, an organic solvent, and if necessary, a reaction catalyst into a reactor and stirring and dehydrating and condensing for 0.1 to 10 hours while heating or keeping warm as necessary. I) is obtained.
The reaction temperature may be, for example, 70 to 150 ° C or 100 to 130 ° C. Moreover, you may make it react, removing the water which is a by-product. By setting the reaction temperature to 70 ° C. or higher, the reaction rate does not become too slow, and by setting it to 150 ° C. or lower, it is not necessary to use a high boiling point organic solvent as a reaction solvent. In addition, the organic solvent hardly remains, and good heat resistance tends to be obtained.

The amino-modified siloxane compound (I) having an aromatic azomethine group obtained through the dehydration condensation reactions 1 and 2 can be confirmed by performing IR measurement. The IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, there is a peak around at 3,440 cm ^-1 and 3370cm ^-1 due to primary amino groups By confirming this, it can be confirmed that the reaction proceeds well and the desired compound is obtained.

The weight average molecular weight (Mw) of the amino-modified siloxane compound (I) having an aromatic azomethine group is not particularly limited, but may be, for example, 1000 to 300,000, 6000 to 150,000, or 6000. It may be ˜50000. If the weight average molecular weight (Mw) is 1000 or more, low curing shrinkage and low thermal expansion tend to be suppressed, and if it is 300,000 or less, compatibility and elastic modulus tend to be suppressed. is there. In the present specification, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene. For example, the following conditions are used. Can do.
As a measuring device, for example, an auto sampler (AS-8020, manufactured by Tosoh Corporation), a column oven (860-C0, manufactured by JASCO Corporation), an RI detector (830-RI, manufactured by JASCO Corporation), UV / It is possible to use a VIS detector (870-UV, JASCO Corporation) and an HPLC pump (880-PU, JASCO Corporation).
In addition, as the column used, for example, TSKgel SuperHZ2000 and 2300 manufactured by Tosoh Corporation can be used, and the measurement conditions include, for example, a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent as tetrahydrofuran. Is possible.

[Maleimide compound (c) having at least two N-substituted maleimide groups]
The thermosetting resin composition of the present invention further has a maleimide compound (c) having at least two N-substituted maleimide groups [hereinafter sometimes simply referred to as a maleimide compound (c). ] Is contained.
As the maleimide compound (c), a maleimide compound represented by the following general formula (c) may be selected.

(In the formula, A ³¹ is a group represented by the following general formula (31), (32), (34) or (35).)

(In the formula, each R ³¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P2 is an integer of 0 to 4.)

(In the formula, R ³² and R ³³ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond, or a group represented by the following general formula (33): q2 and r2 are each independently an integer of 0 to 4. )

(In the formula, R ³⁴ and R ³⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³³ is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s2 and t2 are each independently an integer of 0 to 4.)

(In the formula, n2 is an integer of 0 to 10.)

(In the formula, R ³⁶ and R ³⁷ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U2 is an integer of 1 to 8.)

Examples of the aliphatic hydrocarbon group represented by R ³¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. As this aliphatic hydrocarbon group, a C1-C3 aliphatic hydrocarbon group may be selected, and a methyl group may be selected. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among the above, R ³¹ may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p2 is an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 may be selected, 0 or 1 may be selected, or 0 may be selected. When p2 is an integer of 2 or more, the plurality of R ³¹ may be the same or different.

Aliphatic hydrocarbon group of 1 to 5 carbon atoms which R ³² and ^{R 33} represent, as the halogen atom ^include the same ones as for ^{R 31.} The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, and still more preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ³² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Is mentioned. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is selected from the viewpoint of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. Or a methylene group may be selected.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ³² include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group may be selected from the viewpoints of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
As A ³² , among the above options, an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms may be selected. In addition, a methylene group may be selected from the viewpoint of the aforementioned characteristics.
q2 and r2 are each independently an integer of 0 to 4, and from the viewpoint of availability, either an integer of 0 to 2 may be selected, or 0 or 2 may be selected. If q2 or r2 is an integer of 2 or more, among the plurality of R ³² s or R ³³ may each be the same or different.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³⁴ and R ³⁵ include the same as those for R ³² and R ³³ .
Alkylene group having 1 to 5 carbon atoms which A ³³ represents, alkylidene group having 2 to 5 carbon ^atoms, alkylene group of 1 to 5 carbon atoms ^{which A 32} represents, the same as the alkylidene group having 2 to 5 carbon atoms include It is done.
The A ^33, among the above-mentioned alternatives may select an alkylidene group having 2 to 5 carbon atoms. In addition, a propylidene group may be selected from the viewpoint of the aforementioned characteristics.
s2 and t2 are integers of 0 to 4, and from the viewpoint of easy availability, either an integer of 0 to 2 may be selected, 0 or 1 may be selected, or 0 may be selected. Good. When s2 or t2 is an integer of 2 or more, the plurality of R ³⁴ or R ³⁵ may be the same or different from each other.
As the group represented by the general formula (33), a group represented by the following general formula (33 ′) may be selected.

(A ³³ , R ³⁴ , R ³⁵ , s2 and t2 in the general formula (33 ′) are the same as those in the general formula (33).)

As the A ^31, the heat resistance, the metal foil adhesion, glass transition temperature (Tg), represented by a low thermal expansion, elastic modulus, from the viewpoint of low curing shrinkage and high frequency characteristics, the formula (32) A group may be selected, or a group represented by the following general formula (32 ′) may be selected.

(A ³² , R ³² , R ³³ , q2 and r2 in the general formula (32 ′) are the same as those in the general formula (32).)

In the general formula (34), n2 may be selected in the range of 0 to 5 or in the range of 0 to 3 from the viewpoint of availability.
In the general formula (35), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³⁶ and R ³⁷ include the same as those in the case of R ¹ .
u2 is an integer of 1 to 8, an integer of 1 to 3 may be selected, or 1 may be selected.

As A ³¹ in the group represented by the general formula (c), from the viewpoint of heat resistance, metal foil adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. May be a group represented by any of the following formulae.

  Examples of the maleimide compound (c) include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5, 5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, etc. It is done. These can be used individually by 1 type or in mixture of 2 or more types.

Among these, from the viewpoint of high reaction rate and higher heat resistance, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4 , 4-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane may be selected, and from the viewpoint of solubility in organic solvents, 3,3-dimethyl-5, 5-Diethyl-4,4-diphenylmethane bismaleimide and bis (4-maleimidophenyl) methane may be selected, and bis (4-maleimidophenyl) methane may be selected from the viewpoint of being inexpensive.
As content of the maleimide compound (c) in the thermosetting resin composition of this invention, with respect to 100 mass parts of total of solid content (however, except an inorganic filler) of a thermosetting resin composition, 30-80 mass parts may be sufficient and 35-65 mass parts may be sufficient. If it is this range, it exists in the tendency for a favorable elastic modulus and low thermal expansibility to be acquired.

[Allyl compound having two or more allyl groups (d)]
The thermosetting resin composition of the present invention may further be referred to as an allyl compound (d) having two or more allyl groups [hereinafter simply referred to as an allyl compound (d). ] Is contained. By the allyl compound (d), the crosslinking density is improved and the curing is sufficiently advanced, so that the heat resistance, the adhesiveness between the resin and the metal, and the high frequency characteristics can be improved while maintaining the low thermal expansion. .
The allyl compound (d) may be an allyl compound having 2 to 4 allyl groups, or may be an allyl compound having 2 or 3 allyl groups. The “allyl group” herein includes those having a substituent, for example, a methallyl group, a crotyl group, and the like are also included in the allyl group.
The allyl compound (d) is not particularly limited. For example, an allyl compound having an aryl group such as a phenyl group, a benzyl group or a naphthyl group, or an allyl compound having a heterocyclic ring such as a triazine ring or an isocyanurate ring. Etc. Specific examples include triallyl isocyanurate and diallyl bisphenol A.
You may use an allyl compound (d) individually by 1 type or in mixture of 2 or more types.
As an allyl compound (d), for example, a compound represented by the following general formula (d ′) or (d ″) may be used.

(In the formula, R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, An ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond.)

Examples of the alkyl group having 1 to 5 carbon atoms of R ⁴¹ and R ⁴² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Etc. Among these, a C1-C3 alkyl group may be selected and a methyl group may be selected.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Can be mentioned. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is selected from the viewpoint of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics. Or a methylene group may be selected.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group may be selected from the viewpoints of heat resistance, metal foil adhesion, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
Among the above, as X, an alkylidene group having 2 to 5 carbon atoms may be selected, and a propylidene group may be selected from the viewpoint of the above-described properties.

  As content of the allyl compound (d) in the thermosetting resin composition of this invention, with respect to 100 mass parts of total of solid content (however, except an inorganic filler) in a thermosetting resin composition. 1-10 mass parts may be sufficient, and 2-8 mass parts may be sufficient. By setting it as this range, it exists in the tendency for favorable heat resistance, adhesiveness with resin and metal foil, and a high frequency characteristic to be acquired, maintaining low thermal expansibility.

[Other ingredients]
(Amine compound having an acidic substituent (e))
The thermosetting resin composition of the present invention may further contain an amine compound (e) having an acidic substituent. The number of acidic substituents possessed by the amine compound (e) may be one, two, or one.
Here, as an acidic substituent, a hydroxyl group, a carboxyl group, a sulfonic acid group etc. are mentioned, for example. The amine compound (e) having an acidic substituent may have at least one selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group.
Examples of the amine compound (e) having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o- Aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline from the viewpoint of solubility and synthesis yield. M-aminophenol and p-aminophenol may be used from the viewpoint of heat resistance, and p-aminophenol may be used from the viewpoint of low thermal expansion.
The amine compound (e) having an acidic substituent can be used alone or in combination of two or more.

  When the thermosetting resin composition of the present invention contains an amine compound (e) having an acidic substituent, the content thereof is a solid content in the thermosetting resin composition (however, an inorganic filler is used). 0.5 to 20 parts by mass, or 0.7 to 15 parts by mass with respect to 100 parts by mass of the total. By setting it as this range, it exists in the tendency for heat resistance and low thermal expansibility to improve.

  The amino-modified siloxane compound (I) having an aromatic azomethine group, the maleimide compound (c), and the amine compound (e) having an acidic substituent may be contained in the thermosetting resin composition as they are. For example, at least a part of each component may be reacted by heating (hereinafter sometimes referred to as pre-reaction).

That is, as one aspect of the thermosetting resin composition of the present invention, an aromatic azomethine group obtained by reacting an amino-modified siloxane compound (I) having an aromatic azomethine group with a maleimide compound (c) is used. Modified imide resin (J) [hereinafter referred to as modified imide resin (J) having an aromatic azomethine group] and an allyl compound (d) having two or more allyl groups It may be. As described above, when the amino-modified siloxane compound (I) having an aromatic azomethine group is pre-reacted with the maleimide compound (c), the molecular weight is easy to control, and therefore, good low curing shrinkage and low thermal expansion are obtained. It tends to be obtained.
Moreover, the weight average molecular weight (Mw) of the modified imide resin (J) having an aromatic azomethine group is not particularly limited, but may be, for example, 1000 to 300000, 1000 to 30000, 2000 to 2000 It may be 10,000. If the weight average molecular weight (Mw) is 1000 or more, low curing shrinkage and low thermal expansion tend to be suppressed, and if it is 300,000 or less, compatibility and elastic modulus tend to be suppressed. is there.

As an embodiment of this pre-reaction, an amino-modified siloxane compound (I) having an aromatic azomethine group and a maleimide compound (c) may be reacted in an organic solvent.
The reaction conditions for reacting the amino-modified siloxane compound (I) having an aromatic azomethine group and the maleimide compound (c) in an organic solvent are not particularly limited. For example, the reaction temperature is 70-150 degreeC may be sufficient and 100-130 degreeC may be sufficient. The reaction time may be, for example, 0.1 to 10 hours or 1 to 6 hours.

  In this pre-reaction, the amount of the amino-modified siloxane compound (I) having an aromatic azomethine group and the maleimide compound (c) is, for example, the number of maleimide groups of the maleimide compound (c) [the amount of maleimide compound (c) used / maleimide] The maleimide group equivalent of the compound (c) is the number of primary amino groups of the amino-modified siloxane compound (I) having an aromatic azomethine group [Amount of amino-modified siloxane compound (I) having an aromatic azomethine group / aromatic azomethine group It may be in a range of 2 to 10 times the primary amino group equivalent of the amino-modified siloxane compound (I) having By setting it to 2 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10 times or less.

  The amount of the maleimide compound (c) used in this pre-reaction is, for example, 50 to 3000 parts by mass with respect to 100 parts by mass of the amino-modified siloxane compound (I) having an aromatic azomethine group while maintaining the above relationship. It may be 100 to 1500 parts by mass. When the amount is 50 parts by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.

Examples of the organic solvent used in this pre-reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as ethyl ester and γ-butyrolactone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; dimethyl sulfoxide And a sulfur atom-containing solvent. These can be used alone or in combination of two or more.
Among these organic solvents, for example, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone may be used. Cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide may be used from the viewpoint that they do not easily remain.

  The amount of the organic solvent used may be, for example, 25 to 2000 parts by mass with respect to 100 parts by mass of the total of the amino-modified siloxane compound (I) having an aromatic azomethine group and the maleimide compound (c). -1000 mass parts may be sufficient, and 40-500 mass parts may be sufficient. If the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility is suppressed, and if it is 2000 parts by mass or less, the reaction time is appropriate.

  In addition, a reaction catalyst can be optionally used for this pre-reaction. The reaction catalyst is not particularly limited. For example, amines such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; phosphorus-based catalysts such as triphenylphosphine; alkalis such as lithium amide, sodium amide, and potassium amide And metal amides. These can be used alone or in combination of two or more.

  In the thermosetting resin composition, the content of the modified imide resin (J) having an aromatic azomethine group obtained by the pre-reaction is, for example, the solid content of the thermosetting resin composition (however, inorganic filling) 50 to 100 parts by mass or 60 to 100 parts by mass may be per 100 parts by mass of the total. When the content of the modified imide resin (J) having an aromatic azomethine group is 50 parts by mass or more, low thermal expansibility and high elastic modulus tend to be obtained.

Moreover, as one aspect | mode of the thermosetting resin composition of this invention, the amino modified siloxane compound (I) which has an aromatic azomethine group, the maleimide compound (c), and the amine compound (e) which has an acidic substituent, A modified imide resin (K) having an acidic substituent and an aromatic azomethine group (hereinafter referred to as a modified imide resin (K) having an acidic substituent and an aromatic azomethine group) obtained by reacting It may be a thermosetting resin composition containing an allyl compound (d) having two or more. Thus, when the amino-modified siloxane compound (I) having an aromatic azomethine group, the maleimide compound (c), and the amine compound (e) having an acidic substituent are pre-reacted, the molecular weight can be easily controlled, Good low cure shrinkage and low thermal expansion tend to be obtained.
Moreover, the weight average molecular weight (Mw) of the modified imide resin (K) having an acidic substituent and an aromatic azomethine group is not particularly limited, but may be, for example, 1000 to 300000, or 1000 to 30000. It may be 2000-8000. If the weight average molecular weight (Mw) is 1000 or more, low curing shrinkage and low thermal expansion tend to be suppressed, and if it is 300,000 or less, compatibility and elastic modulus tend to be suppressed. is there.

As an embodiment of this pre-reaction, an amino-modified siloxane compound (I) having an aromatic azomethine group, a maleimide compound (c), and an amine compound (e) having an acidic substituent are reacted in an organic solvent. It may be.
The reaction conditions for reacting the amino-modified siloxane compound (I) having an aromatic azomethine group, the maleimide compound (c) and the amine compound (e) having an acidic substituent in an organic solvent are particularly limited. Although it is not a thing, 70-150 degreeC may be sufficient as reaction temperature, for example, and 100-130 degreeC may be sufficient as it. The reaction time may be, for example, 0.1 to 10 hours or 1 to 6 hours.

  In this pre-reaction, the amount of amino-modified siloxane compound (I) having an aromatic azomethine group, maleimide compound (c), and amine compound (e) having an acidic substituent is, for example, maleimide of maleimide compound (c) The number of groups [the amount of maleimide compound (c) used / maleimide group equivalent of maleimide compound (c)] is the primary amino of amino-modified siloxane compound (I) having an aromatic azomethine group and amine compound (e) having an acidic substituent. Number of groups [(Amount of amino-modified siloxane compound (I) having aromatic azomethine group / primary amino group equivalent of amino-modified siloxane compound (I) having aromatic azomethine group) + (amine compound having acidic substituent (e ) Usage amount / primary amino group equivalent of amine compound (e) having acidic substituents]] 2 to 10 times It may be in the range to be. By setting it to 2 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10 times or less.

The amount of the maleimide compound (c) used in this pre-reaction is, for example, 50 to 3000 parts by mass with respect to 100 parts by mass of the amino-modified siloxane compound (I) having an aromatic azomethine group while maintaining the above relationship. It may be 100 to 1500 parts by mass. By setting it to 50 parts by mass or more, a decrease in heat resistance can be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.
Moreover, the usage-amount of the amine compound (e) which has an acidic substituent in this pre reaction is 1-1000 mass parts with respect to 100 mass parts of solid content of the amino modification siloxane compound (I) which has an aromatic azomethine group, for example. It may be 5 to 500 parts by mass. By setting it as 1 mass part or more, a heat resistant fall can be suppressed, and low thermal expansion can be kept favorable by setting it as 1000 mass parts or less.

  The organic solvent used in this pre-reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents; ester solvents such as ethyl acetate and γ-butyrolactone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Contains solvent; Sulfur atom containing solvents such as dimethyl sulfoxide. These can be used alone or in combination of two or more.

  Among these organic solvents, for example, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone may be used. Cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide may be used from the viewpoint that they do not easily remain.

  The amount of the organic solvent used is, for example, 25 with respect to 100 parts by mass of the total of the amino-modified siloxane compound (I) having an aromatic azomethine group, the maleimide compound (c), and the amine compound (e) having an acidic substituent. -2000 mass parts may be sufficient, 40-1000 mass parts may be sufficient, and 40-500 mass parts may be sufficient. If the amount of the organic solvent used is 25 parts by mass or more, the lack of solubility tends to be suppressed. Moreover, if it is 2000 mass parts or less, reaction time will become suitable.

  In this pre-reaction, a reaction catalyst can be optionally used. The reaction catalyst is not particularly limited. For example, amines such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; phosphorus-based catalysts such as triphenylphosphine; alkalis such as lithium amide, sodium amide, and potassium amide And metal amides. These can be used alone or in combination of two or more.

  In the thermosetting resin composition, the content of the modified imide resin (K) having an acidic substituent and an aromatic azomethine group obtained by the pre-reaction is, for example, the solid content of the thermosetting resin composition ( However, it is preferably 50 to 100 parts by mass and more preferably 60 to 100 parts by mass per 100 parts by mass of the total of the inorganic filler. When the content of the modified imide resin having an acidic substituent and an aromatic azomethine group is 50 parts by mass or more, low thermal expansibility and high elastic modulus can be obtained.

(Thermoplastic elastomer (f))
The thermosetting resin composition of the present invention may further contain a thermoplastic elastomer (f).
Examples of the thermoplastic elastomer (f) include styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, acrylic-based thermoplastic elastomers, and silicone-based heat. Examples thereof include plastic elastomers and derivatives thereof. These have a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These can be used individually by 1 type or in mixture of 2 or more types.
Among these, in terms of heat resistance and insulation reliability, styrene thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, and silicone thermoplastic elastomers are preferable, and even styrene thermoplastic elastomers may be used. Good.
The styrene-based thermoplastic elastomer is not particularly limited as long as it is a thermoplastic elastomer having a structural unit derived from styrene (see below).

Examples of the structural unit other than the structural unit derived from styrene in the styrene-based thermoplastic elastomer include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, and a structural unit derived from maleic anhydride. Styrenic thermoplastic elastomers may be used alone or in combination of two or more.
The structural unit derived from butadiene and the structural unit derived from isoprene are preferably hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
The styrene-based thermoplastic elastomer includes a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) from the viewpoints of heat resistance, adhesion to a conductor, glass transition temperature, thermal expansion coefficient, elastic modulus, and high frequency characteristics. , SBBS), and a hydrogenated styrene-isoprene-styrene block copolymer (SEPS), a hydrogenated styrene-butadiene-styrene block copolymer (SEBS, SBBS).
The hydrogenated styrene-butadiene-styrene block copolymer includes SEBS in which the hydrogenation rate of carbon-carbon double bonds is usually 90% or more (preferably 95% or more), and 1 in the butadiene block. , SBBS in which the carbon-carbon double bonds at the 2-bonding sites are partially hydrogenated (the hydrogenation rate with respect to the total carbon-carbon double bonds is approximately 60 to 85%). Among these, SEBS may be selected.

Moreover, as a thermoplastic elastomer (f), what has a reactive functional group in a molecular terminal or a molecular chain can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryl group, a methacryl group, and a vinyl group. By having these reactive functional groups in the molecular terminal or molecular chain, compatibility with the resin is improved, and internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. As a result, it is possible to significantly reduce the warpage of the substrate.
Moreover, the reactive functional group possessed in the molecular terminal or molecular chain may be an epoxy group, a hydroxyl group, a carboxyl group, an amino group, or an amide group from the viewpoint of adhesion to the metal foil, and it has heat resistance, insulation. From the viewpoint of reliability, it may be an epoxy group, a hydroxyl group or an amino group.

  When the thermosetting resin composition contains the thermoplastic elastomer (f), the content is good in compatibility with the resin, and can effectively express the low curing shrinkage and low thermal expansion of the cured product. From a viewpoint, 0.1-50 mass parts may be sufficient with respect to 100 mass parts of total of solid content (however, except an inorganic filler) of a thermosetting resin composition, and it is 2-30 mass parts. There may be 5-30 mass parts.

(Thermosetting resin (g))
The thermosetting resin composition of the present invention may further contain a thermosetting resin (g). Examples of the thermosetting resin (g) include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene. Resins, silicone resins, triazine resins, melamine resins and the like can be mentioned. These may be used alone or in combination of two or more. Among these, an epoxy resin and a cyanate resin may be used from the viewpoints of moldability and electrical insulation.

As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable. Here, the epoxy resin is classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among these, a glycidyl ether type epoxy resin may be used.
Epoxy resins are classified into various epoxy resins depending on the difference in the main skeleton, and in each of the above types of epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc. Bisphenol type epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, etc. Phenolic aralkyl type epoxy resin; Stilbene type epoxy resin; Dicyclopentadiene type epoxy resin; Naphthalene such as naphthol novolac type epoxy resin and naphthol aralkyl type epoxy resin Skeletal-containing epoxy resin; Triazine skeleton-containing epoxy resin; Fluorene skeleton-containing epoxy resin; Triphenolmethane-type epoxy resin; Biphenyl-type epoxy resin; Biphenyl aralkyl-type epoxy resin; Xylylene-type epoxy resin; Type epoxy resins; classified into phosphorus-containing epoxy resins in which a phosphorus compound is introduced. These may be used alone or in combination of two or more.
The epoxy resin may be a biphenyl aralkyl type epoxy resin or a naphthalene skeleton-containing type epoxy resin from the viewpoint of heat resistance and flame retardancy.

Examples of the cyanate resin include novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, and bisphenol-type cyanate resins such as tetramethylbisphenol F-type cyanate resin and prepolymers in which these are partially triazine. Can be mentioned. As the cyanate resin, a novolac type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These may be used alone or in combination of two or more.
When a thermosetting resin composition contains a thermosetting resin (g), the content is 100 mass of the sum total of solid content (however, except an inorganic filler) in a thermosetting resin composition. 1-50 mass parts is preferable with respect to part, 1-30 mass parts is more preferable, and 1-20 mass parts is further more preferable.

(Curing accelerator (h))
The thermosetting resin composition of the present invention may further contain a curing accelerator (h).
Examples of the curing accelerator (h) include imidazoles and derivatives thereof; phosphines and phosphonium salts; organophosphorus compounds such as adducts of tertiary phosphines and quinones; secondary amines and tertiary amines. And quaternary ammonium salts. One of these can be used alone or two or more of them can be used together.
The curing accelerator (h) may be, for example, an organic phosphorus compound such as an imidazole derivative, a phosphonium salt, or an adduct of a tertiary phosphine and a quinone from the viewpoint of an acceleration effect and storage stability. A commercially available product may be used as the curing accelerator (h). Commercially available products include, for example, isocyanate mask imidazole (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: G-8809L), tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical Co., Ltd., trade name: TPP-MK). ), Triphenylphosphine triphenylborane [made by Hokuko Chemical Co., Ltd., trade name: TPP-S] and the like.

  The blending amount of the curing accelerator (h) is, for example, from the viewpoint of the acceleration effect and storage stability, with respect to 100 parts by mass of the total solid content of the thermosetting resin composition (excluding inorganic fillers). 0.01-3 mass parts may be sufficient and 0.05-1.5 mass parts may be sufficient.

(Inorganic filler)
The thermosetting resin composition of the present invention may further contain an inorganic filler. Examples of inorganic fillers include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, Examples include calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, aluminum borate, silicon carbide, short glass fiber, fine glass powder, hollow glass, and the like. . Preferred examples of the glass include E glass, T glass, and D glass. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
Among these, silica, alumina, mica, talc, silica, alumina, or silica may be used from the viewpoints of thermal expansion coefficient, elastic modulus, heat resistance, and flame retardancy. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica include crushed silica, fumed silica, and fused silica (fused spherical silica) depending on the production method. The silica used for the inorganic filler may be fused silica from the viewpoint of low thermal expansibility and high fluidity when filled in a resin.

  When fused silica is used as the inorganic filler, the average particle size is not particularly limited, but may be in the range of 0.1 to 10 μm, in the range of 0.1 to 5 μm, It may be ˜2 μm or 0.2 to 1 μm. By making the average particle diameter of the fused silica 0.1 μm or more, the fluidity at the time of high filling can be kept good, and by making it 10 μm or less, the mixing probability of coarse particles is reduced and coarse particles It is possible to suppress the occurrence of defects due to. Here, the average particle size is a particle size at a point corresponding to a volume of just 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.

  The compounding amount of the inorganic filler may be 1 to 300 parts by mass with respect to 100 parts by mass of the total solid content (excluding the inorganic filler) in the thermosetting resin composition, and 50 to 50 270 mass parts may be sufficient, 100-250 mass parts may be sufficient, and 150-230 mass parts may be sufficient. By making the compounding quantity of an inorganic filler into this range, the moldability and low thermal expansion property of a prepreg and a film with a resin can be kept favorable.

  The thermosetting resin composition of the present invention has a thermoplastic resin, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, to the extent that the thermosetting property is not impaired as the resin composition. You may contain a fluorescent whitening agent, an adhesive improvement agent, etc. You may use these individually by 1 type or in mixture of 2 or more types.

  Examples of thermoplastic resins include, for example, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin. , Polyetheretherketone resin, polyetherimide resin, silicone resin, tetrafluoroethylene resin and the like.

  Examples of the organic filler include, for example, a resin filler having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene. A resin having a core-shell structure having a rubber-like core layer made of an acrylic resin and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like A filler etc. are mentioned.

  Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine; phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, red phosphorus; sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; and inorganic flame retardants such as antimony trioxide.

As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned, for example. Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants. Examples of the photopolymerization initiator include benzophenone-based, benzyl ketal-based, and thioxanthone-based photopolymerization initiators. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative. Examples of the adhesion improver include urea compounds such as urea silane; coupling agents such as silane, titanate, and aluminate.
Further, at the time of blending, it is also preferable that the inorganic filler is pretreated with an silane-based or titanate-based coupling agent or a surface-treating agent such as a silicone oligomer, or an integral blend treatment.

[Resin varnish]
From the viewpoint of facilitating handling by diluting the thermosetting resin composition of the present invention and from the viewpoint of facilitating the production of a prepreg or a film with a resin described later, the thermosetting resin composition is made into a varnish state by containing an organic solvent. Good. In the present specification, the varnish may be referred to as a resin varnish.
Examples of the organic solvent include, but are not limited to, alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents including amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; Sulfur atom-containing solvent containing: ester solvent containing lactone solvent such as γ-butyrolactone.
One organic solvent may be used alone, or two or more organic solvents may be used in combination.
Among these, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether may be used from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether may be used from the viewpoint of low toxicity. It may be.
The solid (nonvolatile content) concentration of the varnish finally obtained is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass of the entire varnish. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to obtain a prepreg and a resin-coated film in which an appropriate amount of the thermosetting resin composition is adhered while maintaining good coating properties.

[Prepreg]
The prepreg of the present invention is formed using the thermosetting resin composition of the present invention.
The prepreg of the present invention can be produced, for example, by impregnating a base material with the above-described thermosetting resin composition of the present invention and semi-curing (B-stage) by heating or the like. Although it does not specifically limit as a method to make a base material impregnate the thermosetting resin composition of this invention, For example, the method of immersing a base material in a resin varnish, the method of apply | coating with various coaters, the method of spraying, etc. are mentioned. The method of impregnating the base material with the thermosetting resin composition of the present invention may be a method of immersing the base material in a resin varnish from the viewpoint of impregnation of the thermosetting resin composition with respect to the base material. The base material used for the prepreg of the present invention is not particularly limited, and for example, well-known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. In other applications, for example, carbon fibers can be used for fiber reinforced substrates.

  These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, or a surfacing mat, for example. The material and shape are selected depending on the intended use and performance of the molded product, and if necessary, two or more kinds of materials and shapes can be combined. As the thickness of the substrate, for example, about 0.02 to 0.5 mm can be used. Further, from the viewpoint of heat resistance, moisture resistance, and processability, a substrate that has been surface-treated with a silane coupling agent or the like or a substrate that has been mechanically subjected to fiber opening treatment may be used.

  The prepreg of the present invention, for example, after impregnating the base material so that the adhesion amount of the thermosetting resin composition to the base material is 20 to 90% by mass with the resin content of the prepreg after drying, It can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

[Film with resin]
The film with a resin of the present invention is formed using the thermosetting resin composition of the present invention. The film with resin is obtained, for example, by applying a thermosetting resin composition to a support. Specifically, in the film with resin of the present invention, a semi-cured film of the thermosetting resin composition of the present invention is formed on the support surface. The resin-coated film is a resin composition layer in which the thermosetting resin composition or resin varnish of the present invention is applied to a support film and dried to volatilize an organic solvent and to be semi-cured (B-staged). It is obtained by forming a layer (later C-stage to be an insulating resin layer). However, this semi-cured state is a state in which when the resin composition layer of the resin-coated film and the circuit board are laminated and cured, the adhesive force between the resin composition layer and the circuit board is secured, and the circuit It is preferable that the embedding property (fluidity) in the substrate is ensured. In this specification, a circuit board is a conductive layer (such as a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board) patterned on one side or both sides of a board. Circuit) is formed. Further, in a laminated board formed by laminating a plurality of patterned conductor layers (circuits) and insulating resin layers and a multilayer printed wiring board manufactured from the laminated board, one or both sides of the outermost layer of the multilayer printed wiring board What is a conductor layer (circuit) that has been patterned is also included in the circuit board. The surface of the conductor layer may be previously roughened by a blackening process or the like.
As a coating method (coating machine), a die coater, a comma coater, a bar coater, a kiss coater, a roll coater or the like can be used, and it is appropriately used depending on the thickness of the insulating resin layer. As a drying method, heating, hot air blowing, or the like can be used.

  The drying condition after applying the thermosetting resin composition or the resin varnish to the support may be, for example, dried so that the content of the organic solvent in the resin composition layer to be formed is 10% by mass or less. You may make it dry so that it may become 5 mass% or less. Depending on the amount of organic solvent in the resin varnish and the boiling point of the organic solvent, for example, if it is a resin varnish containing 30 to 60% by mass of an organic solvent, by drying at 50 to 150 ° C. for about 3 to 10 minutes, A resin composition layer having an organic solvent content within the above range is formed. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  The thickness of the resin composition layer formed on the resin-coated film is equal to or greater than the thickness of the conductor layer of the circuit board. The thickness of the conductor layer may be, for example, 5 to 70 μm, and may be 5 to 50 μm or 5 to 30 μm in order to reduce the thickness of the multilayer printed wiring board.

The support in the film with resin is, for example, polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyester such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyimide film; release paper; metal foil such as copper foil and aluminum foil, etc. Is mentioned. The support may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
The thickness of the support may be, for example, 10 to 150 μm or 25 to 50 μm.

Moreover, a protective film can be further laminated | stacked on the surface in which the support body of a resin composition layer is not provided. The thickness of the protective film is, for example, 1 to 40 μm. Although a protective film is not specifically limited, What is used for the above-mentioned support body can be used. By laminating the protective film, foreign matter can be prevented from being mixed. Note that the protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
The film with resin can also be wound and stored in a roll shape.

[Laminated board]
One aspect of the laminated board of the present invention is formed using the film with resin of the present invention. The laminate of the present invention can be produced, for example, by laminating and molding the resin composition layer of the resin-coated film of the present invention on one side or both sides of a circuit board, prepreg or base material. For example, the film with resin can be produced by laminating on one or both sides of a circuit board, prepreg, base material, etc. using a laminator, and curing by heating as necessary. Examples of the substrate used for the circuit substrate 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. The prepreg and the base material are as described above.

  In the laminate, when the resin-coated film has a protective film, after removing the protective film, the resin-coated film and the circuit board are preheated as necessary, and the resin-coated film is pressurized and heated. While crimping to the circuit board. In the film with resin of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method can be adopted. Lamination conditions can be selected, for example, from a pressure bonding temperature (lamination temperature) in the range of 70 to 140 ° C., a pressure bonding pressure in the range of 0.1 to 1.1 MPa, and an air pressure of 20 mmHg (26.7 hPa) or less. Lamination can be done under reduced pressure. The lamination method may be a batch method or a continuous method using a roll.

  After laminating the resin-coated film on the circuit board, the film is cooled to around room temperature, and then the support is peeled off as necessary, followed by thermosetting to form an insulating resin layer on the circuit board. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but may be selected, for example, at 150 ° C. to 220 ° C. for 20 minutes to 180 minutes. The temperature may be selected from 160 ° C. to 200 ° C. for 30 minutes to 120 minutes.

  If the support is not peeled off after the insulating resin layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating resin layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

Next, a conductor layer is formed on the insulating resin layer by dry plating or wet plating.
As the dry plating, a known method such as a vapor deposition method, a sputtering method, or an ion plating method can be used.
In the case of wet plating, first, the surface of the cured insulating resin layer is roughened with an oxidizing agent to form uneven anchors. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. Among these, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate can be selected as the oxidizing agent. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.

Another aspect of the laminate of the present invention is the one using the aforementioned prepreg of the present invention. The laminate of the present invention can be produced by laminating the prepreg of the present invention. For example, it can be manufactured by using one prepreg of the present invention or by stacking 2 to 20 sheets and laminating and forming with a configuration in which a metal foil such as copper or aluminum is arranged on one or both sides.
As the molding conditions for manufacturing the laminate, for example, a technique used for a laminate for an electrical insulating material and a multilayer plate can be adopted. For example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., it can shape | mold in the range of the temperature of 100-250 degreeC, the pressure of 0.2-10 MPa, and the heating time of 0.1-5 hours. Moreover, the prepreg of the present invention and a circuit board can be combined and laminated to produce a laminated board.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention is formed using the laminated board of the present invention. For example, it can be manufactured by forming a circuit on the surface of the laminate of the present invention.
Specifically, the following manufacturing method can be adopted. The conductor layer of the laminated board according to the present invention can be processed by ordinary etching to obtain a circuit board. Then, a plurality of laminated boards processed by wiring through the above-described prepreg are laminated and subjected to hot press processing to be multi-layered at once. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.

[Semiconductor package]
The semiconductor package of the present invention is obtained by mounting a semiconductor element on the multilayer printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the multilayer printed wiring board.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
In addition, each performance was measured or evaluated by the following method using the resin board and copper clad laminated board obtained by each following Example or comparative example.

(1) Curing shrinkage rate of resin plate The resin plate obtained in each example was cut out to produce a resin plate having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 1 mm (Z direction). Thermomechanical analysis was performed by a compression method using TA Instruments, Q400). After mounting the resin plate in the X direction or Y direction on the device, the load is 5 g, the heating rate is 45 ° C./min, 20 ° C. (5 min hold) to 260 ° C. (2 min hold) to 20 ° C. (5 min hold) The temperature profile was measured. Based on the 20 ° C. dimension before the temperature increase, the curing shrinkage rate (%) of the resin plate was evaluated from the dimensional change at 20 ° C. before and after the temperature increase.
Specifically, the curing shrinkage rate of the resin plate was calculated using the following formula.
Curing shrinkage rate (%) = {(20 ° C. before temperature rise (mm) −20 ° C. after temperature rise (mm)) / 20 ° C. before temperature rise (mm)} × 100

(2) High frequency characteristics (dielectric constant and dielectric loss tangent)
The copper clad laminate obtained in each example was immersed in a 10% by mass solution of ammonium persulfate (Mitsubishi Gas Chemical Co., Ltd.) to remove the copper foil by etching, and then cut into a size of 60 mm long × 2 mm wide, and the atmosphere At a temperature of 25 ° C., a dielectric constant (Dk) and a dielectric loss tangent (Df) at 10 GHz were calculated from a resonance frequency obtained by a cavity resonator method and an unloaded Q value. The measurement was performed using Vector Network Analyzer E8364B manufactured by Agilent Technologies, Inc., CP531 (10 GHz resonator) and CPMA-V2 (program) manufactured by Kanto Electronics Application Development Co., Ltd., respectively.

(3) Evaluation of heat resistance (solder heat resistance with copper) An evaluation board of 25 mm square was prepared from the copper clad laminate obtained in each example, and the evaluation board was floated in a solder bath at a temperature of 288 ° C. for 120 minutes to give an appearance. By visually observing, the solder heat resistance with copper was evaluated according to the following evaluation criteria.
A: No swelling C: With swelling

(4) Metal foil adhesion (copper foil adhesion)
The copper-clad laminate obtained in each example is immersed in a copper etching solution to form a copper foil having a width of 3 mm to produce an evaluation substrate, and the adhesion of the copper foil (90 ° peel strength) using a tensile tester Was measured.
The wiring board preferably has a peel strength of 0.7 KN / m or more.

(5) Glass transition temperature (Tg)
By immersing the copper clad laminate obtained in each example in a copper etching solution, an evaluation board of 5 mm in length (X direction), 5 mm in width (Y direction), and thickness direction (Z direction) was prepared. Thermomechanical analysis was performed by a compression method using a TMA test apparatus (TA Instruments, Q400). After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined.

(6) Low thermal expansion (thermal expansion coefficient)
By immersing the copper clad laminate obtained in each example in a copper etching solution, an evaluation board having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness direction (Z direction) was prepared. Then, thermomechanical analysis was performed by a compression method using a TMA test apparatus (Q400, manufactured by TA Instruments). After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated, and this was used as the value of the coefficient of thermal expansion (linear expansion coefficient), which was used as an index of low thermal expansion. The smaller the value, the better the low thermal expansion.

(7) Elastic modulus (flexural modulus)
A copper-clad laminate obtained in each example was immersed in a copper etching solution to produce a 50 mm × 25 mm evaluation board from which the copper foil was removed, and a 5-ton tensilon manufactured by Orientec Co., Ltd. was used. The measurement was performed at a min and span distance of 20 mm.
In addition, as a wiring board, the bending elastic modulus of 28 GPa or more is preferable.

  In each example, the compounds (I-1) to (I-2), (J-1) and (K-1) produced in the following production examples were used.

Production Example 1: Production of amino-modified siloxane compound (I-1) having an aromatic azomethine group In a reaction vessel having a volume of 2 L capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 3,3′-diethyl-4,4′-diaminodiphenylmethane (i-1) “KAYAHARD A-A” (Nippon Kayaku Co., Ltd., trade name) 12.9 g, terephthalaldehyde (ii) “TPAL” (Toray・ Fine Chemical Co., Ltd., trade name) 17.1 g and propylene glycol monomethyl ether 45.0 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by atmospheric concentration, aromatic azomethine compound The containing solution (solid content concentration: 60 mass%) was obtained.
Next, 325.5 g of siloxane compound (b) “X-22-161B” (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amino group equivalent 1500) and 513.3 g of propylene glycol monomethyl ether are added to the above solution. After reacting at 4 ° C. for 4 hours, the mixture was heated to 130 ° C. and dehydrated by normal pressure concentration, and the solution containing an amino-modified siloxane compound (I-1) having an aromatic azomethine group (Mw: 30000, solid content concentration: 90 mass) %).
Note that, by IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, the peak around at 3,440 cm ^-1 and 3370cm ^-1 due to primary amino groups Confirmed that it exists.

Production Example 2: Production of amino-modified siloxane compound (I-2) having an aromatic azomethine group In a reaction vessel having a volume of 2 L capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 2,5-dimethyl-1,4-diaminobenzene (i-2) “BAPP” (trade name), 8.7 g, manufactured by Wakayama Seika Kogyo Co., Ltd., terephthalaldehyde (ii) “TPAL” (Toray Fine Chemical Co., Ltd.) Product, trade name) 21.3 g and propylene glycol monomethyl ether 45.0 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by normal pressure concentration, and an aromatic azomethine compound-containing solution (solid (Min. Concentration: 60% by mass).
Next, 413.8 g of siloxane compound (b) “X-22-161B” (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amino group equivalent 1500) and 645.7 g of propylene glycol monomethyl ether are added to the above solution. After reacting at 4 ° C. for 4 hours, the temperature was raised to 130 ° C. and dehydrated by atmospheric concentration, and a solution containing an amino-modified siloxane compound (I-2) having an aromatic azomethine group (Mw: 32000, solid content concentration: 90 mass) %).
Note that, by IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, the peak around at 3,440 cm ^-1 and 3370cm ^-1 due to primary amino groups Confirmed that it exists.

Production Example 3 Production of Modified Imide Resin (J-1) Having Aromatic Azomethine Group A reaction vessel having a volume of 2 L, which can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, Modified siloxane compound (I-1) -containing solution having an aromatic azomethine group (solid content concentration: 90% by mass), 77.8 g, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (c-2) Contains 246.9 g and 425.3 g of propylene glycol monomethyl ether, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure, containing modified imide resin (J-1) having an aromatic azomethine group A solution (Mw: 6000, solid content concentration: 60% by mass) was obtained.
The modified imide resin (J-1) corresponds to a pre-reacted amino-modified siloxane compound (I) having an aromatic azomethine group and a maleimide compound (c).

Production Example 4 Production of Modified Imide Resin (K-1) Having Acid Substituent and Aromatic Azomethine Group Reaction of 2 L in Volume that can be Heated and Cooled with Thermometer, Stirrer, and Moisture Quantifier with Reflux Cooling Tube In a container, 94.7 g of a modified siloxane compound (I-1) -containing solution having an aromatic azomethine group (solid content concentration: 90% by mass), 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane ( c-2) 225.6 g, p-aminophenol 2.3 g, and propylene glycol monomethyl ether 427.4 g were added, reacted at 115 ° C. for 4 hours, then heated up to 130 ° C. and concentrated at normal pressure, acidic substituents And a modified imide resin (K-1) -containing solution having an aromatic azomethine group (Mw: 4000, solid content concentration: 60% by mass).
The modified imide resin (K-1) includes an amino-modified siloxane compound (I) having an aromatic azomethine group, a maleimide compound (c) having at least two N-substituted maleimide groups, and an acidic substituent. This corresponds to a product obtained by pre-reaction with the amine compound (e).

Here, in the said manufacture example, the weight average molecular weight (Mw) was converted from the calibration curve using a standard polystyrene by the gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name]) and approximated by a cubic equation. The GPC conditions are shown below.
Apparatus: (Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]),
(Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]),
(Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation])
Column; TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (all manufactured by Tosoh Corporation, trade name)
Column size: 6.0 × 40 mm (guard column), 7.8 × 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 20mg / 5mL
Injection volume: 10 μL
Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

Examples 1-19, Comparative Examples 1-6
Each component is mixed at a blending ratio shown in Tables 1 to 4 (parts by mass: in the case of a solution, it is a solid content conversion value), and the solid content (nonvolatile content) concentration is 65% by mass using methyl ethyl ketone as a solvent. A resin varnish was prepared. Next, this resin varnish was impregnated into an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.
The varnish is applied to a 16 μm polyethylene terephthalate film using a film applicator (trade name: PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the resin thickness after drying is 35 μm. Heat drying for 10 minutes to obtain a semi-cured resin powder.
This resin powder is put into a Teflon sheet form (length: 4 cm, width: 3 cm), the glossy surface of 12 μm electrolytic copper foil is placed up and down, and pressed at a pressure of 2.0 MPa and a temperature of 240 ° C. for 60 minutes. After that, the electrolytic copper foil was removed to obtain a resin plate having a thickness of 1 mm.
The result of having tested or evaluated using the obtained copper clad laminated board and the resin board is shown to Tables 1-4.

Hereinafter, each component in Tables 1 to 4 will be described.
Maleimide compound (c)
(C-1) Bis (4-maleimidophenyl) methane [manufactured by Kay Kasei Co., Ltd .; trade name: BMI]
(C-2) 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane [manufactured by Daiwa Kasei Kogyo Co., Ltd .; trade name: BMI-4000]

Allyl compound (d)
(D-1) TAIC (registered trademark) [manufactured by Nippon Kasei Co., Ltd .; name: triallyl isocyanurate, see structure below]

(D-2) TMAIC (registered trademark) [manufactured by Nippon Kasei Co., Ltd .; name: trimethallyl isocyanurate, see structure below]

(D-3) DABPA [manufactured by Daiwa Kasei Kogyo Co., Ltd .; name: 2,2′-diallylbisphenol A, see structure below]

Amine compound having acidic substituent (e)
p-aminophenol (manufactured by Kanto Chemical Co., Inc.)

Thermoplastic elastomer (f)
(F-1) Tuftec (registered trademark) H1043: Hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Corporation)
(F-2) Epofriend (registered trademark) CT-310: Epoxy-modified styrene-butadiene copolymer resin [manufactured by Daicel Corporation]
(F-3) Tuftec (registered trademark) M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Corporation)

Thermosetting resin (g)
(G-1) Naphthalene skeleton-containing epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; trade name: NC-7000L, more specifically, α-naphthol / cresol novolac type epoxy resin]
(G-2) Biphenyl aralkyl type epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; trade name: NC-3000H]

Curing accelerator (h)
(H-1): Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G-8809L]
(H-2): Triphenylphosphine triphenylborane [made by Hokuko Chemical Co., Ltd., trade name: TPP-S]

Inorganic filler: fused silica (manufactured by Admatechs Co., Ltd .: trade name: SC2050-KNK, average particle size: 0.5 μm, surface treatment: vinylsilane coupling agent (1% by mass / solid content), dispersion medium: methyl isobutyl ketone , Solid concentration 70 mass%, density 2.2 g / cm ³ )

As is clear from Tables 1 to 4, the thermosetting resin compositions of the examples are excellent in heat resistance, metal foil adhesiveness, glass transition temperature, low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics. Yes.
On the other hand, the thermosetting resin composition of the comparative example has a large curing shrinkage rate. Moreover, compared with the result of an Example about heat resistance, metal foil adhesiveness, glass transition temperature, low thermal expansibility, elastic modulus, and a high frequency characteristic, it is inferior to any characteristic.

  The prepreg using the thermosetting resin composition of the present invention, the film with resin, and the laminate using the prepreg are particularly heat resistant, metal foil adhesiveness, glass transition temperature, low thermal expansion, elasticity. It has excellent rate, low cure shrinkage and high frequency characteristics, and is useful as a highly integrated semiconductor package and multilayer printed wiring board for electronic equipment.

Claims (15)

Amino having an aromatic azomethine group obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups Modified siloxane compound (I),
A maleimide compound (c) having at least two N-substituted maleimide groups, and an allyl compound (d) having two or more allyl groups
A thermosetting resin composition comprising: Amino having an aromatic azomethine group obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups A modified imide resin (J) having an aromatic azomethine group obtained by reacting a modified siloxane compound (I) with a maleimide compound (c) having at least two N-substituted maleimide groups; Allyl compounds having at least two (d)
A thermosetting resin composition comprising: Amino having an aromatic azomethine group obtained by reacting an aromatic azomethine compound (a) having at least one aldehyde group in one molecule with a siloxane compound (b) having at least two primary amino groups An acidic substituent and an aromatic obtained by reacting the modified siloxane compound (I), a maleimide compound (c) having at least two N-substituted maleimide groups, and an amine compound (e) having an acidic substituent. Modified imide resin (K) having azomethine group, and allyl compound (d) having two or more allyl groups
A thermosetting resin composition comprising:   An aromatic azomethine compound (a) having at least one aldehyde group in one molecule is an aromatic amine compound (i) having at least two primary amino groups in one molecule and at least two in one molecule. The thermosetting resin composition according to any one of claims 1 to 3, obtained by reacting the aromatic aldehyde compound (ii) having an aldehyde group.   Furthermore, the thermosetting resin composition of any one of Claims 1-4 formed by containing the amine compound (e) which has an acidic substituent.   Furthermore, the thermosetting resin composition of any one of Claims 1-5 formed by containing a thermoplastic elastomer (f).   Furthermore, the thermosetting resin composition of any one of Claims 1-6 formed by containing a thermosetting resin (g).   Furthermore, the thermosetting resin composition of any one of Claims 1-7 formed by containing a hardening accelerator (h).   Furthermore, the thermosetting resin composition of any one of Claims 1-8 formed by containing an inorganic filler.   A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 9.   The film with resin which uses the thermosetting resin composition of any one of Claims 1-9.   A laminate comprising the prepreg according to claim 10.   A laminate comprising the resin-coated film according to claim 11.   A multilayer printed wiring board using the laminated board according to claim 12 or 13.   The semiconductor package which mounts a semiconductor element on the multilayer printed wiring board of Claim 14.