JP2017114964A - Thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed bord and semiconductor package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in heat resistance, adhesiveness, low thermal expansion property, elasticity, low curing shrinkage property and dielectric property in high frequency band (low dielectric constant and low dielectric loss tangent), a prepreg using the thermosetting resin composition, a film with a resin, a laminate, a multilayer printed board and a semiconductor package.SOLUTION: There are provided a thermosetting resin composition containing an amino modified siloxane compound (A) having a hydroxy group in a molecular structure and a maleimide compound (B) having a N-substituted maleimide group in a molecular structure, a prepreg using the thermosetting resin composition, a film with a resin, a laminate, a multilayer printed board and a semiconductor package.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition suitable for a semiconductor package and a printed wiring board, a prepreg using the thermosetting resin composition, a film with resin, a laminate, a multilayer printed wiring board, and a semiconductor package.

  In recent years, with the trend toward miniaturization and high performance of electronic devices, advancement of wiring density and high integration have progressed in printed wiring boards, and with this, laminated boards for printed wiring boards include: There is an increasing demand for improved reliability by improving heat resistance. In such applications, particularly semiconductor package substrate applications, it is required to have both excellent heat resistance and low thermal expansion.

As a laminated board for printed wiring boards, a prepreg containing a resin composition mainly composed of an epoxy resin and glass cloth is cured and integrally formed.
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 the 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 between the resin and the wiring layer, poor press molding, etc. There was a limit to the reduction in thermal expansion due to the use of only.
On the other hand, polybismaleimide resin widely used for high-density packaging and multilayered laminates 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 thermosetting resin composition has improved moisture resistance and adhesion, the imide resin is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group in order to ensure solubility in a general-purpose solvent such as methyl ethyl ketone. Therefore, there is a problem that the heat resistance of the resulting modified imide resin is significantly inferior to that of the polybismaleimide resin.
Further, particularly in recent years, in the semiconductor package substrate, due to the downsizing 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 expansibility, low cure shrinkage, and elastic modulus are required for a laminate for semiconductor package substrates.

In mobile communication devices such as mobile phones, base station devices, network infrastructure devices such as servers and routers, large computers, etc., the speed and capacity of signals used are increasing year by year. Along with this, printed wiring boards mounted on these electronic devices are required to cope with higher frequencies, and a low dielectric constant and low dielectric loss tangent substrate material capable of reducing transmission loss is required.
In recent years, in addition to the electronic devices described above, new systems that handle high-frequency radio signals in the field of ITS (Intelligent Transport Systems) (related to automobiles and transportation systems) and indoor short-range communication are available as applications that handle such high-frequency signals. Practical application and practical planning are progressing. Therefore, it is expected that a substrate material with a low transmission loss will be further required for printed wiring boards mounted on these devices in the future.

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

  In view of the current situation, the present invention has heat resistance, adhesiveness, low thermal expansion, elastic modulus, low curing shrinkage, and dielectric characteristics in a high frequency band (low dielectric constant and low dielectric loss tangent) [hereinafter referred to as “high frequency characteristics”. May be called. ], A prepreg using the thermosetting resin composition, a film with resin, a laminate, a multilayer printed wiring board, and a semiconductor package.

  As a result of intensive studies to solve the above problems, the present inventors have found that a thermosetting resin composition containing an amino-modified siloxane compound having a hydroxy group and a specific maleimide compound has heat resistance and adhesion. Have been found to be excellent in heat resistance, low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics, and have reached the present invention.

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] A thermosetting resin composition comprising an amino-modified siloxane compound (A) having a hydroxy group in the molecular structure and a maleimide compound (B) having an N-substituted maleimide group in the molecular structure.
[2] A structural unit derived from a siloxane compound (a) having an amino-modified siloxane compound (A) having a hydroxy group in the molecular structure and having at least two primary amino groups and a structural unit derived from an epoxy resin (b) The thermosetting resin composition according to the above [1], comprising:
[3] The thermosetting resin composition according to the above [1] or [2], wherein the amino-modified siloxane compound (A) having a hydroxy group in the molecular structure has an aromatic azomethine skeleton in the molecular structure.
[4] The amino-modified siloxane compound (A) having a hydroxy group in the molecular structure is a structural unit derived from a siloxane compound (a) having at least two primary amino groups and a structural unit derived from an epoxy resin (b) And the thermosetting resin composition according to any one of the above [1] to [3], comprising a structural unit derived from an aromatic azomethine compound (c) having at least one aldehyde group in one molecule.
[5] An aromatic azomethine compound (c) having at least one aldehyde group in one molecule is a structural unit derived from an aromatic amine compound (i) having at least two primary amino groups in one molecule; The thermosetting resin composition according to the above [4], comprising a structural unit derived from an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule.
[6] The thermosetting resin composition according to any one of the above [1] to [5], further comprising an amine compound (C) having an acidic substituent.
[7] The thermosetting resin composition according to any one of [1] to [6], further comprising a thermoplastic elastomer (D).
[8] The thermosetting resin composition according to any one of [1] to [7], further including a thermosetting resin (E).
[9] The thermosetting resin composition according to any one of the above [1] to [8], further comprising a curing accelerator (F).
[10] The thermosetting resin composition according to any one of [1] to [9], further including an inorganic filler (G).
[11] A prepreg comprising the thermosetting resin composition according to any one of [1] to [10].
[12] A film with a resin comprising the thermosetting resin composition according to any one of [1] to [10].
[13] A laminate comprising the cured product of the prepreg according to [11].
[14] A laminate including a cured product of the film with resin according to [12].
[15] A multilayer printed wiring board including the laminated board according to [13] or [14].
[16] A semiconductor package obtained by mounting a semiconductor on the multilayer printed wiring board according to [15].

  According to the present invention, a thermosetting resin composition excellent in heat resistance, adhesiveness, low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics, a prepreg using the thermosetting resin composition, and a film with a resin A laminated board, a multilayer printed wiring board, and a semiconductor package can be provided.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound (A) having a hydroxy group in the molecular structure and a maleimide compound (B) having an N-substituted maleimide group in the molecular structure. .
The thermosetting resin composition of the present invention has excellent heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics by adopting the above configuration. Become.
Hereinafter, each component will be described in order.

<Amino-modified siloxane compound (A) having a hydroxy group in the molecular structure>
The thermosetting resin composition of the present invention may be referred to as an amino-modified siloxane compound (A) having a hydroxy group in the molecular structure [hereinafter simply referred to as “modified siloxane compound (A)”. ] Is contained.
The modified siloxane compound (A) is not particularly limited as long as it is an amino-modified siloxane compound having a hydroxy group. For example, the siloxane compound (a) having at least two primary amino groups [hereinafter simply referred to as “siloxane compound ( a) ". ] And the structural unit derived from an epoxy resin (b) are preferably mentioned.
The modified siloxane compound (A) can be obtained, for example, by reacting the siloxane compound (a) with the epoxy resin (b). The modified siloxane compound (A) obtained by the reaction has a hydroxy group (OH group) generated when the epoxy group of the epoxy resin (b) reacts with the amino group of the siloxane compound (a). By containing the modified siloxane compound (A) obtained by reacting such a siloxane compound (a) and the epoxy resin (b), the adhesive strength can be improved without reducing the glass transition temperature.

(Siloxane compound (a) having at least two primary amino groups)
Although there is no restriction | limiting in particular as a siloxane compound (a), For example, it is preferable to have 1 or more primary amino groups in each molecular both ends, and it has one primary amino group in each molecular both ends. Is more preferable, and it is more preferable that each has only one primary amino group at both molecular ends.
The siloxane skeleton of the siloxane compound (a) may be either linear or branched, but is preferably linear from the viewpoint of compatibility with other resin components.
Preferred examples of the siloxane compound (a) include compounds represented by the following general formula (1).

In general formula (1), several R < ¹ > shows an alkyl group, a phenyl group, or a substituted phenyl group each independently, and may mutually be same or different. R ² and R ³ each independently represent a divalent organic group. n represents an integer of 2 to 50.

In general formula (1), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 or 2 carbon atoms. Further preferred. Specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Among these, a methyl group is preferable.
Examples of the substituent in the substituted phenyl group represented by R ¹ include an alkyl group, an alkenyl group, and an alkynyl group. Among these, an alkyl group is preferable. The alkyl group is preferably the same as described above.
Among the groups represented by R ¹ , a phenyl group or a methyl group is preferable and a methyl group is more preferable from the viewpoint of solubility with other resins.
Examples of the organic group represented by R ² or R ³ include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, or a divalent linking group in which these are combined. Among these, an alkylene group and an arylene group are preferable. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group. Examples of the arylene group include a phenylene group and a naphthylene group.

  The amino group equivalent of the siloxane compound (a) is preferably 200 to 7000 g / mol, more preferably 300 to 6000 g / mol, and still more preferably 400 to 4000 g / mol, from the viewpoint of low thermal expansion and compatibility with other resins. mol, particularly preferably 600 to 3000 g / mol.

A commercially available product can be used as the siloxane compound (a). Examples of the commercially available siloxane compound (a) include “KF-8010” (amino group equivalent: 430 g / mol), “X-22-161A” (amino group equivalent: 800 g / mol), “X-22-161B”. (Amino group equivalent 1500 g / mol), “KF-8012” (amino group equivalent 2200 g / mol), “KF-8008” (amino group equivalent 5700 g / mol), “X-22-9409” (amino group equivalent 700 g / mol) mol), "X-22-1660B-3" (amino group equivalent 2200 g / mol) (above, manufactured by Shin-Etsu Chemical Co., Ltd.), "BY-16-853U" (amino group equivalent 460 g / mol), "BY- 16-853 "(amino group equivalent 650 g / mol)," BY-16-853B "(amino group equivalent 2200 g / mol) (above, Toray Dowco Packaging Co., Ltd.), and the like. These can be used alone or in admixture of two or more.
Among these, for example, from the viewpoints of reactivity during synthesis and low thermal expansion, “X-22-161A”, “X-22-161B”, “KF-8012”, “X-22-1660B-3” And “BY-16-853B” are preferable, and “X-22-161A” and “X-22-161B” are more preferable from the viewpoint of excellent compatibility and high elastic modulus, and “X-22-161B”. Is more preferable.

(Epoxy resin (b))
Although there is no restriction | limiting in particular as an epoxy resin (b), For example, the epoxy resin which has a 2 or more epoxy group in 1 molecule is preferable. The epoxy resin (b) is classified into, for example, 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 is preferable.
The epoxy resin (b) is classified into various epoxy resins depending on the difference in the main skeleton. In each of the above types of epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy are further provided. Bisphenol type epoxy resin such as 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 Epoxy resin; phenol aralkyl type epoxy resin; stilbene type epoxy resin; dicyclopentadiene type epoxy resin; naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin Thalene skeleton-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; Pentadiene type epoxy resins; classified into phosphorus-containing epoxy resins in which a phosphorus compound is introduced. These can be used alone or in admixture of two or more.
Among these, from the viewpoints of heat resistance and flame retardancy, a biphenyl aralkyl type epoxy resin and a naphthalene skeleton-containing type epoxy resin are preferable.

  The epoxy equivalent of the epoxy resin (b) is preferably 100 to 500 g / mol, more preferably 150 to 400 g / mol, and still more preferably 200 to 350 g / mol from the viewpoints of heat resistance and flame retardancy.

The modified siloxane compound (A) preferably further has an aromatic azomethine skeleton in the molecular structure. Thereby, while being able to obtain hardened | cured material with high elasticity, in the reflow process performed after hardening, shrinkage | contraction rate can be made small enough.
Here, the aromatic azomethine refers to a compound in which at least one aromatic group (preferably an aromatic hydrocarbon group) is bonded to a Schiff base (—N═CH—).
In the present specification, an amino-modified siloxane compound (A) having an aromatic azomethine and a hydroxy group in the molecular structure is referred to as “amino-modified siloxane compound (H) having an aromatic azomethine and a hydroxy group in the molecular structure” or May be simply referred to as “modified siloxane compound (H) having an aromatic azomethine”.

[Amino-modified siloxane compound having aromatic azomethine and hydroxy group in molecular structure (H)]
The modified siloxane compound (H) having an aromatic azomethine is not particularly limited as long as it is an amino-modified siloxane compound having an aromatic azomethine and a hydroxy group in the molecular structure, but has, for example, at least two primary amino groups. A structural unit derived from the siloxane compound (a), a structural unit derived from the epoxy resin (b), and an aromatic azomethine compound (c) having at least one aldehyde group in one molecule [hereinafter simply referred to as “aromatic azomethine compound” (C) ". ] Containing the structural unit derived from] is mentioned preferably.

  A structural unit derived from the siloxane compound (a) contained in the modified siloxane compound (H) having an aromatic azomethine, a structural unit derived from the epoxy resin (b), and a structural unit derived from the aromatic azomethine compound (c) The total content is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more. There is no restriction | limiting in particular in an upper limit, 100 mass% or less may be sufficient.

  The modified siloxane compound (H) having an aromatic azomethine can be obtained, for example, by reacting a siloxane compound (a), an epoxy resin (b), and an aromatic azomethine compound (c).

<< Aromatic azomethine compound (c) having at least one aldehyde group in one molecule >>
The aromatic azomethine compound (c) is not particularly limited. For example, the aromatic amine compound (i) having at least two primary amino groups in one molecule [hereinafter simply referred to as “aromatic amine compound (i) ) ". ] And a structural unit derived from an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule [hereinafter sometimes referred to simply as “aromatic aldehyde compound (ii)”. ] Containing the structural unit derived from] is mentioned preferably.

  The total content of the structural unit derived from the aromatic amine compound (i) and the structural unit derived from the aromatic aldehyde compound (ii) contained in the aromatic azomethine compound (c) is preferably 80% by mass or more, more preferably It is 85 mass% or more, More preferably, it is 90 mass% or more. There is no restriction | limiting in particular in an upper limit, 100 mass% or less may be sufficient.

  The aromatic azomethine compound (c) can be obtained, for example, by reacting an aromatic amine compound (i) with an aromatic aldehyde compound (ii).

The aromatic amine compound (i) is preferably an aromatic amine compound having 2 or 3 primary amino groups in one molecule, and more preferably having 2 primary amino groups in one molecule. It is an aromatic amine compound.
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 has a structure of 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).

(Wherein, ^{A 1} is a group represented by the following general formula (i-1) or (i-2).)

(In the formula, each R ¹¹ 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 ¹² and R ¹³ 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 (i-3): q and r are each independently an integer of 0 to 4. .)

(In the formula, R ¹⁴ and R ¹⁵ 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.)

In the general formula (i-1), 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, and a t-butyl group. , N-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among these, R ¹¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 2, from the viewpoint of availability. When p is an integer of 2 or more, the plurality of R ¹¹ may be the same or different.

In the general formula (i-2), 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 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and still more preferably an ethyl group.
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, and a 1,5-pentamethylene group. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics. More preferred is a methylene group.
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 is preferable from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
A ² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
q and r are each independently an integer of 0 to 4, and are each preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability. If q or r is an integer of 2 or more, plural R ¹² s or R ¹³ together may each be the same or different.

In the general formula (i-3), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ¹⁴ and R ¹⁵ are the same as those in R ¹² and R ¹³ and are preferable. Is the same.
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 The preferred ones are the same.
A ³ is preferably an alkylidene group having 2 to 5 carbon atoms among the above options, and more preferably as described above.
s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0. When s or t is an integer of 2 or more, plural R ¹⁴ s or R ¹⁵ together may each be the same or different.
The general formula (i-3) is preferably represented by the following general formula (i-3 ′).

(A ³ , R ¹⁴ , R ¹⁵ , s and t in the general formula (i-3 ′) are the same as those in the general formula (i-3).)

Incidentally, in the formula (i), as the A ^1, heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, from the viewpoint of low curing shrinkage and high frequency characteristics, the formula ( It is preferably a group represented by i-2), and more preferably a group represented by the following general formula (i-2 ′).

(A ² , R ¹² , R ¹³ , q and r in the general formula (i-2 ′) are the same as those in the general formula (i-2).)

A ¹ in the general formula (i) is any one of the following formulas from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage, and high frequency characteristics. More preferably, it is a group represented.

  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- -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 and the like. These can be used alone or in admixture of two or more.

  Among these, for example, from the viewpoint of high reactivity and higher heat resistance, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl- 4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] propane and the like are preferred. From the viewpoint of low cost and solubility in a solvent, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′- Diaminodiphenylmethane and bis [4- (4-aminophenoxy) phenyl] propane are preferred. From the viewpoint of low thermal expansibility and dielectric properties, 3,3′-diethyl-4,4′-diaminodiphenylmethane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are preferred. Further, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene capable of increasing the elastic modulus are also preferable.

The aromatic aldehyde compound (ii) is preferably an aromatic aldehyde compound having 2 or 3 aldehyde groups in one molecule, more preferably an aromatic aldehyde having 2 aldehyde groups in one molecule. A compound.
The aromatic aldehyde compound (ii) has an aromatic hydrocarbon group, and as long as it has an aliphatic hydrocarbon group. For example, the aromatic aldehyde compound (ii) also has a structure of aromatic hydrocarbon group-aliphatic hydrocarbon group-aromatic hydrocarbon group in the molecule.
The aromatic aldehyde compound (ii) is preferably represented by the following general formula (ii).

(In the formula, A ¹¹ is a group represented by the following general formula (ii-1) or (ii-2).)

(In the formula, each R ²¹ independently represents 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 ²² and R ²³ 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 (ii-3): q1 and r1 are each independently an integer of 0 to 4. .)

(In the formula, R ²⁴ and R ²⁵ 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.)

In the general formula (ii-1), examples of the aliphatic hydrocarbon group represented by R ²¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. , N-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among these, R ²¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p1 is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability. When p1 is an integer of 2 or more, the plurality of R ²¹ may be the same or different.

In the general formula (ii-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ²² and R ²³ include the same as those in the case of R ²¹ . 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 ¹² include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics. More preferred is a methylene group.
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 is preferable from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
A ¹² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
q1 and r1 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 2. If q1 or r1 is an integer of 2 or more, among the plurality of R ²² s or R ²³ may each be the same or different.

In the general formula (ii-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ²⁴ and R ²⁵ include the same as those in R ²² and R ²³ , and are preferable. Is the same.
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 The preferred ones are the same.
A ¹³ is preferably an alkylidene group having 2 to 5 carbon atoms among the above options, and more preferably as described above.
s1 and t1 are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s1 or t1 is an integer of 2 or more, the plurality of R ²⁴ or R ²⁵ may be the same or different from each other.
The general formula (ii-3) is preferably represented by the following general formula (ii-3 ′).

(A ¹³ , R ²⁴ , R ²⁵ , s1 and t1 in the general formula (ii-3 ′) are the same as those in the general formula (ii-3).)

Incidentally, in the above general formula (ii), there may as is A ^11, heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, from the viewpoint of low curing shrinkage and high frequency characteristics, the formula ( It is preferable that it is group represented by ii-1), and it is more preferable that it is group represented by the following general formula (ii-1 ').

(In the general formula (ii-1 ′), R ²¹ and p1 are the same as those in the general formula (ii-1).)

  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 is preferable from the viewpoint of lower thermal expansion, high reactivity, excellent solvent solubility, and easy commercial availability.

(Method for producing amino-modified siloxane compound (A) having a hydroxy group)
The modified siloxane compound (A) can be obtained, for example, by subjecting the siloxane compound (a) having at least two amino groups and the epoxy resin (b) to a ring-opening addition reaction.
Here, the amount of the siloxane compound (a) and the epoxy resin (b) used is, for example, the number of primary amino groups of the siloxane compound (a) [the amount of the siloxane compound (a) used / the primary amino group of the siloxane compound (a). The group equivalent] is preferably 4 to 30 times the number of epoxy groups of the epoxy resin (b) [the amount of the epoxy resin (b) used / the epoxy group equivalent of the epoxy resin (b)]. By making it 4 times or more, the adhesiveness of the thermosetting resin composition containing the modified siloxane compound (A) becomes excellent, and by making it 30 times or less, excellent resin compatibility is obtained. It is done.
That is, the ratio between the structural unit derived from the siloxane compound (a) and the structural unit derived from the epoxy resin (b) contained in the modified siloxane compound (A) is the use of the above siloxane compound (a) and the epoxy resin (b). The ratio is preferably converted from the amount.

  The ring-opening addition reaction is preferably performed in an organic solvent. The amount of the organic solvent that can be used for the ring-opening addition reaction is preferably 60 to 500 parts by mass with respect to 100 parts by mass of the total of the siloxane compound (a) and the epoxy resin (b), for example, It is more preferable to set it as 400 mass parts, and it is still more preferable to set it as 140-300 mass parts. When the amount of the organic solvent used is 60 parts by mass or more, good solubility is obtained, and when the amount is 500 parts by mass or less, a sufficient reaction rate is obtained.

The modified siloxane compound (a), the epoxy resin (b), and, if necessary, an organic solvent, a reaction catalyst, etc. are charged into the reactor, and stirred while being heated or kept warm if necessary to cause a ring-opening addition reaction. A) is obtained.
The reaction conditions are not particularly limited, and may be appropriately determined according to the type of raw material.
The reaction time can be, for example, in the range of 0.1 to 10 hours. Moreover, reaction temperature can be made into the range of 100-150 degreeC, for example, and 110-150 degreeC is preferable. By setting the reaction temperature to 100 ° C. or higher, a sufficient reaction rate can be obtained, and by setting the reaction temperature to 150 ° C. or lower, a high boiling point solvent is not required for the reaction solvent, so that the solvent hardly remains in the cured product. The obtained prepreg, resin-coated film and the like have excellent heat resistance.

The presence of the modified siloxane compound (A) obtained by the above reaction can be confirmed by performing infrared spectroscopy (IR) measurement and gel permeation chromatography (GPC) measurement. Specifically, by IR measurement, by peak around at 3,440 cm ^-1 and 3370cm ^-1 due to primary amino groups to make sure that the decrease and better reaction proceeds, the desired compound is obtained Can be confirmed. Further, by confirming that all the peaks due to the raw material epoxy resin (b) disappear by GPC measurement, it is possible to confirm that the reaction proceeds well and that the desired compound is obtained. .
The measurement by GPC of this measurement can be performed on the following conditions, for example.
Examples of the measuring apparatus include an autosampler (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, and the like. / VIS detector (870-UV, manufactured by JASCO Corporation), HPLC pump (880-PU, manufactured by JASCO Corporation) can be used.
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, measurement temperature of 40 ° C., flow rate of 0.5 ml / min, and measurement using tetrahydrofuran as a solvent. Can do.

  Although the weight average molecular weight (Mw) of an amino modified siloxane compound (A) is not specifically limited, For example, 4,000-450,000 are preferable, 7,000-150,000 are more preferable, 10,000-100,000 are preferable. 000 is more preferable. If the weight average molecular weight (Mw) is 4,000 or more, excellent low curing shrinkage and low thermal expansion are obtained, and if it is 450,000 or less, excellent compatibility and elastic modulus are obtained. The weight average molecular weight (Mw) can be measured by the method described above.

(Method for producing amino-modified siloxane compound (H) having aromatic azomethine and hydroxy group in molecular structure)
In producing the modified siloxane compound (H) having an aromatic azomethine, for example, first, an aromatic amine compound (i) having at least two primary amino groups in one molecule and at least in one molecule The aromatic aldehyde compound (ii) having two aldehyde groups may be referred to as dehydration condensation reaction [hereinafter referred to as “dehydration condensation reaction 1”. ], An aromatic azomethine compound (c) having at least one aldehyde group in one molecule is obtained.
Subsequently, the siloxane compound (a) having at least two primary amino groups, the epoxy resin (b), and the aromatic azomethine compound (c) obtained above are subjected to a ring-opening addition reaction and a dehydration condensation reaction [below] , Sometimes referred to as “dehydration condensation reaction 2”. ], The modified siloxane compound (H) having an aromatic azomethine can be obtained.
According to this reaction method, it is easy to control the molecular weight of the aromatic azomethine in the molecule of the modified siloxane compound (H) having an aromatic azomethine, and the thermosetting resin composition containing the aromatic azomethine has a high elastic modulus. It is particularly effective for high adhesion.

Each dehydration condensation reaction and ring-opening addition reaction is preferably performed in an organic solvent. Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; ester solvents such as γ-butyrolactone . These can be used alone or in admixture of two or more.
Among these, for example, from the viewpoint of solubility, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, and γ-butyrolactone are preferable, and are highly volatile and hardly remain as a residual solvent when producing a prepreg and a resin-coated film. More preferred are propylene glycol monomethyl ether and toluene.
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.

  A reaction catalyst can be used if necessary for each dehydration condensation reaction and ring-opening addition reaction. 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 alone or in admixture of two or more. From the viewpoint of efficiently proceeding with the dehydration condensation reaction, an acidic catalyst is preferable, and p-toluenesulfonic acid is more preferable.

[Dehydration condensation reaction 1]
Dehydration condensation reaction 1 is a reaction for obtaining an aromatic azomethine compound (c) by subjecting an aromatic amine compound (i) and an aromatic aldehyde compound (ii) to a dehydration condensation reaction.
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)]. It is preferable to use 1 to 5 times, more preferably 1.5 to 5 times, and even more preferably 2 to 4 times. By setting it to 1 or more times, the reaction can proceed sufficiently, and the product comes to have a formyl group, and by setting it to 5 times or less, characteristics such as elastic modulus can be expressed. The required number of azomethine groups can be secured.
That is, the ratio of the structural unit derived from the aromatic amine compound (i) contained in the aromatic azomethine compound (c) to the structural unit derived from the aromatic aldehyde compound (ii) is the same as that of the aromatic amine compound (i) described above. The ratio is preferably converted from the amount of aromatic aldehyde compound (ii) used.

  The dehydration condensation reaction 1 is preferably performed in an organic solvent. The amount of the organic solvent used in the dehydration condensation reaction 1 is preferably 25 to 2000 parts by mass with respect to 100 parts by mass of the total of the aromatic amine compound (i) and the aromatic aldehyde compound (ii), for example. It is more preferable to set it as -1000 mass parts, and it is especially preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, good solubility is obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate is obtained.

Aromatic amine compound (i), aromatic aldehyde compound (ii), and if necessary, an organic solvent, a reaction catalyst, etc. are charged into a reactor, and if necessary, stirred while being heated or kept warm for dehydration condensation reaction. A group azomethine compound (c) is obtained.
The reaction conditions are not particularly limited, and may be appropriately determined according to the type of raw material.
The reaction time can be, for example, in the range of 0.1 to 10 hours. Moreover, reaction temperature can be made into the range of 70-150 degreeC, for example, it is preferable to react, removing the water which is a by-product, and 100-130 degreeC is more preferable. By setting the temperature to 70 ° C. or higher, a sufficient reaction rate can be obtained, and by setting the temperature to 150 ° C. or lower, a high boiling point solvent is not required as the reaction solvent. The heat resistance of a prepreg, a film with resin, etc. is excellent.

[Ring-opening addition reaction and dehydration condensation reaction 2]
Subsequently, ring-opening addition reaction and dehydration condensation reaction 2 are performed. The ring-opening addition reaction and dehydration condensation reaction 2 consist of the ring-opening addition reaction and dehydration of the siloxane compound (a), the epoxy resin (b), and the aromatic azomethine compound (c) obtained by the dehydration condensation reaction 1. This is a reaction for obtaining a modified siloxane compound (H) having an aromatic azomethine by a condensation reaction.
Here, the usage amount of the aromatic azomethine compound (c) and the siloxane compound (a) is, for example, the number of primary amino groups of the siloxane compound (a) [the usage amount of the siloxane compound (a) / 1 of the siloxane compound (a). Secondary amino group equivalent] ranges from 2 to 10 times the number of aldehyde groups of aromatic azomethine compound (c) [amount of aromatic azomethine compound (c) / aldehyde group equivalent of aromatic azomethine compound (c)]. Are preferably used. By making it 2 times or more, good solubility in a solvent can be obtained, and by making it 10 times or less, the thermosetting resin composition containing the modified siloxane compound (H) having an aromatic azomethine can be obtained. The elastic modulus is excellent.
That is, the ratio of the structural unit derived from the siloxane compound (a) contained in the modified siloxane compound (H) having an aromatic azomethine and the structural unit derived from the aromatic azomethine compound (c) is the same as that of the siloxane compound (a) described above. The ratio is preferably converted from the amount of the aromatic azomethine compound (c) used.

The amount of the siloxane compound (a) and the epoxy resin (b) used is, for example, the number of primary amino groups of the siloxane compound (a) [the amount of siloxane compound (a) used / the primary amino group of the siloxane compound (a). [Equivalent]] is preferably 4 to 30 times the number of epoxy groups of epoxy resin (b) [the amount of epoxy resin (b) used / epoxy group equivalent of epoxy resin (b)]. By making it 4 times or more, the adhesiveness of the thermosetting resin composition containing the modified siloxane compound (H) having an aromatic azomethine becomes excellent, and by making it 30 times or less, a good resin The compatibility of is obtained.
That is, the ratio of the structural unit derived from the siloxane compound (a) contained in the modified siloxane compound (H) having an aromatic azomethine and the structural unit derived from the epoxy resin (b) is the same as that of the above siloxane compound (a) and the epoxy resin. It is preferable that the ratio is converted from the amount used in (b).

  The ring-opening addition reaction and dehydration condensation reaction 2 are preferably performed in an organic solvent. The amount of the organic solvent used in the ring-opening addition reaction and dehydration condensation reaction 2 is, for example, 25 to 2000 with respect to 100 parts by mass of the total of the siloxane compound (a), the epoxy resin (b), and the aromatic azomethine compound (c). It is preferable to set it as a mass part, It is more preferable to set it as 40-1000 mass parts, It is more preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, good solubility is obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate is obtained.

A siloxane compound (a), an epoxy resin (b), an aromatic azomethine compound (c), and if necessary, an organic solvent and a reaction catalyst are charged into a reactor, and if necessary, stirred while heating or keeping warm, ring-opening addition reaction and dehydration By carrying out the condensation reaction, a modified siloxane compound (H) having an aromatic azomethine is obtained.
The reaction conditions are not particularly limited, and may be appropriately determined according to the type of raw material.
The reaction time can be, for example, in the range of 0.1 to 10 hours. Moreover, reaction temperature can be made into the range of 70-150 degreeC, for example, it is preferable to react, removing the water which is a by-product, and 100-130 degreeC is more preferable. By setting the temperature to 70 ° C. or higher, a sufficient reaction rate can be obtained, and by setting the temperature to 150 ° C. or lower, a high boiling point solvent is not required as the reaction solvent. The heat resistance of a prepreg, a film with resin, etc. is excellent.

The presence of the modified siloxane compound (H) having an aromatic azomethine obtained by the above reaction can be confirmed by performing IR measurement and GPC measurement. Specifically, by IR measurement, at 3,440 cm ^-1 and 3370cm ^-1 peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) Make sure that the appearance and also due to the primary amino groups By confirming the presence of a nearby peak, it can be confirmed that the reaction proceeds well and the desired compound is obtained.
Further, by confirming that all the peaks attributed to the raw material epoxy resin disappear by GPC measurement, it is possible to confirm that the reaction has proceeded well and the desired compound has been obtained. The measurement conditions for GPC are the same as those described in the section of the method for producing the modified siloxane compound (A).

  The weight average molecular weight (Mw) of the modified siloxane compound (H) having an aromatic azomethine is not particularly limited, but is preferably 5,000 to 500,000, more preferably 8,000 to 200,000, More preferably, it is 20,000-100,000. If the weight average molecular weight (Mw) is 5,000 or more, excellent low curing shrinkage and low thermal expansion are obtained, and if it is 500,000 or less, excellent compatibility and elastic modulus are obtained. The measurement conditions for GPC are the same as those described in the section of the method for producing the modified siloxane compound (A).

  The content of the modified siloxane compound (A) in the thermosetting resin composition of the present invention is based on 100 parts by mass of the total solid content of the thermosetting resin composition (excluding inorganic fillers). , Preferably it is 3-50 mass parts, More preferably, it is 7-40 mass parts. If it is this range, since an elasticity modulus and low thermal expansibility improve, it is preferable.

<Maleimide compound (B) having N-substituted maleimide group in molecular structure>
The thermosetting resin composition of the present invention may further be referred to as a maleimide compound (B) having an N-substituted maleimide group in the molecular structure [hereinafter simply referred to as “maleimide compound (B)”. ] Is contained.
The maleimide compound (B) preferably has at least two N-substituted maleimide groups, and preferred examples include maleimide compounds represented by the following general formula (B).

(In the formula, A ³¹ is a group represented by the following general formula (B-1), (B-2), (B-3) or (B-4)).

(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 (B-5): 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.)

In the general formula (B-1), 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, and a t-butyl group. , N-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among these, R ³¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p2 is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability. When p2 is an integer of 2 or more, the plurality of R ³¹ may be the same or different.

In the general formula ^(B-2), an 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 and 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, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage and high frequency characteristics. More preferred is a methylene group.
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 is preferable from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage, and high frequency characteristics.
Among the above options, A ³² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
q2 and r2 are each independently an integer of 0 to 4, and are each preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability. 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.

In the general formula (B-5), 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 in R ³² and R ³³ , and are preferable. Is the same.
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 The preferred ones are the same.
A ³³ is preferably an alkylidene group having 2 to 5 carbon atoms among the above options, and more preferably as described above.
s2 and t2 are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. 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.
The general formula (B-5) is preferably represented by the following general formula (B-5 ′).

(A ³³ , R ³⁴ , R ³⁵ , s2 and t2 in the general formula (B-5 ′) are the same as those in the general formula (B-5).)

In the general formula (B-3), n2 is preferably 0 to 5, more preferably 0 to 3, from the viewpoint of availability.
In the general formula (B-4), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³⁶ and R ³⁷ are the same as in the case of R ^{11 in} the general formula (i-1). And preferred ones are the same.
u2 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

Incidentally, in the foregoing formula (B), as the A ^31, the heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, from the viewpoint of low curing shrinkage and high frequency characteristics, the formula ( A group represented by B-2) is preferred, and a group represented by the following general formula (B-2 ′) is more preferred.

(A ³² , R ³² , R ³³ , q2 and r2 in the general formula (B-2 ′) are the same as those in the general formula (B-2).)

A ³¹ in the general formula (B) is any one of the following formulas from the viewpoint of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansibility, elastic modulus, low curing shrinkage, and high frequency characteristics. It is preferable that it is group represented.

Examples of the maleimide compound (B) include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, and 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. These can be used alone or in admixture of two or more.
Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4 having a high reaction rate and higher heat resistance can be obtained. '-Diphenylmethane bismaleimide and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane are preferred. From the viewpoint of solubility in a solvent, 3,3'-dimethyl-5,5'-diethyl-4 , 4′-diphenylmethane bismaleimide and bis (4-maleimidophenyl) methane are more preferable, and bis (4-maleimidophenyl) methane is more preferable from the viewpoint of being inexpensive.

  As content of the maleimide compound (B) 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, Preferably it is 30-95 mass parts, More preferably, it is 35-65 mass parts. If it is this range, since an elasticity modulus and low thermal expansibility improve, it is preferable.

<Amine compound having an acidic substituent (C)>
The thermosetting resin composition of the present invention may be further referred to as an amine compound (C) having an acidic substituent [hereinafter simply referred to as “amine compound (C)”. ] May be included. The number of acidic substituents possessed by the amine compound (C) is preferably one or two, more preferably one.
Here, as an acidic substituent, a hydroxyl group, a carboxy group, a sulfonic acid group etc. are mentioned, for example. The amine compound (C) having an acidic substituent preferably has at least one selected from a hydroxyl group, a carboxy group, and a sulfonic acid group.
Examples of the amine compound (C) 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. These can be used alone or in admixture of two or more.
Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and synthesis yield. From the viewpoint of heat resistance, m-aminophenol and p-aminophenol are more preferable, and from the viewpoint of low thermal expansion, p-aminophenol is more preferable.

  When the thermosetting resin composition of the present invention contains an amine compound (C), the content thereof is the sum of solids (excluding inorganic fillers) in the thermosetting resin composition. Preferably it is 0.5-20 mass parts with respect to 100 mass parts, More preferably, it is 0.7-15 mass parts. By setting it as this range, heat resistance and low thermal expansion property are improved.

The above-mentioned modified siloxane compound (A), maleimide compound (B) and amine compound (C) may be contained in the thermosetting resin composition as they are, respectively, or in a pre-reacted state as necessary. It may be contained. In this case, for example, it may be used after reacting at least a part of each of the above components by heating or keeping warm, and further, if necessary after being contained in the thermosetting resin composition together with other components. For example, at least a part of each component may be reacted by heating or keeping warm.
Here, in the present specification, a reaction product obtained by reacting the modified siloxane compound (A) and the maleimide compound (B) is referred to as “modified imide resin (I) having a hydroxy group in the molecular structure”. In addition, a reaction product obtained by reacting the modified siloxane compound (A), the maleimide compound (B), and the amine compound (C) having an acidic substituent is referred to as “acidic substituent in the molecular structure and It may be referred to as “modified imide resin (J) having a hydroxy group”.

When the modified siloxane compound (H) having an aromatic azomethine is used as the modified siloxane compound (A), the content of the maleimide compound (B) in the thermosetting resin composition can prevent gelation and heat resistance. From the above viewpoint, it is preferable that the maleimide group equivalent of the maleimide compound (B) exceeds the equivalent of the primary amino group of the modified siloxane compound (H) and amine compound (C) having an aromatic azomethine. In addition, it is preferable from a heat resistant viewpoint that content of the modification | denaturation siloxane compound (H) which has aromatic azomethine is about 7 to 35 times of content of an amine compound (C).
When heating, the temperature is preferably 70 to 200 ° C., and the reaction time is preferably 0.5 to 10 hours.

The pre-reaction may be performed in an organic solvent. The organic solvent that can be used in the pre-reaction is not particularly limited, and examples thereof include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents such as ethyl acetate and γ-butyrolactone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Nitrogen atom-containing solvents; sulfur atom-containing solvents such as dimethyl sulfoxide. These can be used alone or in admixture of two or more.
Among these, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable, and are low in toxicity and highly volatile, and hardly remain as a residual solvent when producing a prepreg or resin-coated film. From the viewpoint, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are more preferable.
The amount of the organic solvent used is 25 to 1000 parts by mass per 100 parts by mass of the total amount of the modified siloxane compound (A), maleimide compound (B) and amine compound (C) from the viewpoints of solubility and reaction time. Is preferable, and it is more preferable to set it as 40-700 mass parts.

<Thermoplastic elastomer (D)>
The thermosetting resin composition of the present invention may further contain a thermoplastic elastomer (D).
Examples of the thermoplastic elastomer (D) include a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, a urethane thermoplastic elastomer, a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, an acrylic thermoplastic elastomer, and a silicone heat. Examples thereof include plastic elastomers and derivatives thereof. These are composed of 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 alone or in admixture of two or more. Among these, from the viewpoints of heat resistance and insulation reliability, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and silicone-based thermoplastic elastomers are preferable, and styrene-based thermoplastic elastomers are more preferable.
The styrenic thermoplastic elastomer is preferably a thermoplastic elastomer having a structural unit derived from styrene represented by the following general formula (2).

Examples of the structural unit other than the structural unit derived from styrene that the styrene thermoplastic elastomer has 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. These 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.
Styrenic thermoplastic elastomers include a hydrogenated styrene-butadiene-styrene block copolymer and styrene from the viewpoints of heat resistance, adhesion to conductors, glass transition temperature, thermal expansion coefficient, elastic modulus, and high frequency characteristics. -It is preferably at least one selected from hydrogenated product of isoprene-styrene block copolymer (SEPS; styrene-ethylene-propylene-styrene block copolymer), of styrene-butadiene-styrene block copolymer A hydrogenated product is more preferable.
As the hydrogenated product of styrene-butadiene-styrene block copolymer, SEBS (styrene-ethylene-butylene-) having a hydrogenation rate of carbon-carbon double bonds of usually 90% or more (preferably 95% or more) is used. Styrene block copolymer) and SBBS (styrene-butadiene-butylene-styrene block copolymer) in which carbon-carbon double bonds at the 1,2-bonding sites in the butadiene block are partially hydrogenated (total The hydrogenation rate with respect to the carbon-carbon double bond is approximately 60 to 85%. Among these, SEBS is more preferable.

Moreover, as a thermoplastic elastomer (D), 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 carboxy 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 terminals or molecular chains, the compatibility with the resin is improved, and the internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. be able to. As a result, it is possible to significantly reduce the warpage of the substrate.
Among these reactive functional groups, an epoxy group, a hydroxyl group, a carboxy group, an amino group, and an amide group are preferable from the viewpoint of adhesion to the metal foil, and from the viewpoint of heat resistance and insulation reliability, an epoxy group, a hydroxyl group, and An amino group is more preferable.

  When the thermosetting resin composition of the present invention contains the thermoplastic elastomer (D), the content thereof is good in compatibility with the resin, and effectively reduces the low curing shrinkage and low thermal expansion of the cured product. From the viewpoint that it can be expressed, 0.1 to 50 parts by mass is preferable and 2 to 30 parts by mass is preferable with respect to 100 parts by mass of the total solid content of the thermosetting resin composition (excluding inorganic fillers). More preferred is 5 to 30 parts by mass.

<Thermosetting resin (E)>
The thermosetting resin composition of the present invention may further contain a thermosetting resin (E) other than the above components. Examples of the thermosetting resin (E) include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene. Resins, silicone resins, triazine resins, melamine resins and the like can be mentioned. These can be used alone or in admixture of two or more. Among these, from the viewpoints of moldability and electrical insulation, epoxy resins and cyanate resins are preferable, and epoxy resins are more preferable.
Examples of the epoxy resin include those similar to the epoxy resin (b), and among these, a naphthalene skeleton-containing epoxy resin and a biphenylaralkyl epoxy resin are preferable from the viewpoints of moldability and electrical insulation.

  When the thermosetting resin composition of the present invention contains the thermosetting resin (E), the content thereof is the solid content (excluding the inorganic filler) in the thermosetting resin composition. 1-50 mass parts is preferable with respect to 100 mass parts of total, 1-30 mass parts is more preferable, and 1-20 mass parts is more preferable.

<Curing accelerator (F)>
The thermosetting resin composition of the present invention may further contain a curing accelerator (F). By containing the curing accelerator (F), the shrinkage rate and the amount of warpage can be further reduced.
Examples of the curing accelerator (F) include imidazoles and derivatives thereof, organophosphorus compounds, secondary or tertiary amines, quaternary ammonium salts, and the like. These can be used alone or in admixture of two or more. Among these, from the viewpoint of reactivity, imidazoles are preferable, and an adduct of hexamethylene diisocyanate and 2-ethyl-4-methylimidazole represented by the following general formula (3) is more preferable. The compound represented by the following general formula (3) is available, for example, as “G-8809L” (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

  When the thermosetting resin composition of the present invention contains a curing accelerator (F), the content of the curing accelerator (F) is a solid content in the thermosetting resin composition (however, an inorganic filler) Is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the total. By making content of a hardening accelerator (F) into the said range, the low shrinkage of a hardened | cured material, low thermal expansibility, and the outstanding dielectric characteristic can be expressed more effectively.

<Inorganic filler (G)>
The thermosetting resin composition of the present invention may further contain an inorganic filler (G). Examples of the inorganic filler (G) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, and silica. Clay such as aluminum oxide, 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, etc. Is mentioned. Preferred examples of the glass include E glass, T glass, and D glass. These can be used alone or in admixture of two or more.
Among these, silica, alumina, mica and talc are preferable, silica and alumina are more preferable, and silica is more preferable 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 silica include crushed silica, fumed silica, fused silica (fused spherical silica), deflagration silica (spherical silica obtained by utilizing the deflagration phenomenon of metal powder), and the like depending on the production method. Among these, spherical silica is preferable, and fused silica is particularly preferable from the viewpoint of low thermal expansion and high fluidity when filled in a resin.

  When fused silica is used as the inorganic filler (G), the average particle size is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, still more preferably 0.1 to 2 μm, Especially preferably, it is 0.2-1 micrometer. 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 diameter is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles being 100%, and a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.

  When the thermosetting resin composition of this invention contains an inorganic filler (G), the content is the sum total of the solid content in a thermosetting resin composition (however, except an inorganic filler). Preferably it is 10-300 mass parts with respect to 100 mass parts, More preferably, it is 50-270 mass parts, More preferably, it is 100-250 mass parts, Most preferably, it is 150-230 mass parts. By making content of an inorganic filler (G) into this range, the moldability and low thermal expansibility of a prepreg and a film with a resin can be kept favorable.

<Other ingredients>
The thermosetting resin composition of the present invention is a thermoplastic resin, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, as long as the effects of the present invention are not impaired. An adhesion improver or the like may be contained. These can be used alone or in admixture of two or more.

(Thermoplastic resin)
Examples of the thermoplastic resin include 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, poly Examples include ether ether ketone resins, polyether imide resins, silicone resins, and tetrafluoroethylene resins.

(Organic filler)
Examples of the organic filler include 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, and conjugated diene resin. Etc. and a core-shell structure resin filler having a glassy shell layer made of an acrylic ester resin, methacrylic ester resin, aromatic vinyl resin, vinyl cyanide resin, etc. Is mentioned.

(Flame retardants)
Examples of the flame retardant include phosphorus flame retardant, metal hydrate, halogen flame retardant and the like. Among these, phosphorus flame retardants and metal hydrates are preferable from the viewpoint of environmental problems. The halogen-based flame retardant is usually limited to use for electronic components that are not discarded or burnt.
Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides Phosphoric acid; phosphine oxide and the like.
Examples of organic phosphorus flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, disubstituted phosphinic acid metal salts, organic nitrogenous phosphorus compounds, and cyclic organic phosphorus compounds. Is mentioned.
Examples of metal hydrates include aluminum hydroxide hydrate, magnesium hydroxide hydrate, and the like.
Examples of the halogen flame retardant include a chlorine flame retardant and a bromine flame retardant.

(UV absorber, etc.)
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, benzyl ketal, and thioxanthone 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 (G) is pretreated or integral blended with a surface treatment agent such as a silane or titanate coupling agent or a silicone oligomer.

(Organic solvent)
The thermosetting resin composition of the present invention may be made into a varnish state by adding an organic solvent from the viewpoint of facilitating handling and easy manufacture of a prepreg or a resin-coated film described later. It is preferable to be in a state.
Although it does not restrict | limit especially as an organic solvent used for preparation of a varnish, For example, 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; 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; dimethyl sulfoxide, etc. Examples thereof include a sulfur atom-containing solvent including a sulfoxide solvent; an ester solvent including a lactone solvent such as γ-butyrolactone. These can be used alone or in admixture of two or more.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents and nitrogen atom-containing solvents are preferable, ketone solvents are more preferable, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are further preferable, and methyl ethyl ketone is particularly preferable.
The content of the thermosetting resin composition in the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, based on the entire varnish. By setting the content of the thermosetting resin composition within the above range, it is possible to obtain a prepreg and a resin-attached 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 contains the thermosetting resin composition of the present invention.
The prepreg of the present invention can be obtained, for example, by impregnating the thermosetting resin composition of the present invention into a base material, or by impregnating or spraying the base material and then applying it by a method such as extrusion [hereinafter, these The method may be collectively referred to as “impregnation or coating”. ] Can be manufactured. Specifically, after impregnating or coating the thermosetting resin composition of the present invention on a base material, for example, by semi-curing (B-stage) by heating or the like, the base material and the semi-cured (B-stage) The prepreg of the present invention comprising the thermosetting resin composition obtained by the above-mentioned method can be produced.

As a base material used for the prepreg of this invention, the well-known thing used for the laminated board for various electrical insulation materials can be used, for example. 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, a surfacing mat, for example. What is necessary is just to select the material and shape of a base material with the use and performance of the target molded object, and if necessary, it can combine individually or two or more types of materials and shapes.
Moreover, as a base material, the thing surface-treated with the silane coupling agent etc. or the thing which performed the fiber opening process is suitable from the surface of heat resistance, moisture resistance, and workability.
The thickness in particular of a base material is not restrict | limited, For example, it can be set as the range of about 0.02-0.5 mm.

The content (adhesion amount) of the thermosetting resin composition in the prepreg of the present invention is preferably 20 to 90% by mass in terms of the content of the thermosetting resin composition in the dried prepreg.
The prepreg of the present invention is obtained by, for example, impregnating or coating the base material with the thermosetting resin composition of the present invention so that the content of the thermosetting resin composition in the prepreg falls within the above range, then 100 It can be manufactured by heating and drying at a temperature of ˜200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

[Film with resin]
The film with a resin of the present invention contains the thermosetting resin composition of the present invention.
The film with resin of the present invention can be obtained, for example, by applying the thermosetting resin composition of the present invention to a support. Specifically, the organic solvent in the varnish is volatilized by applying a varnish containing the thermosetting resin composition of the present invention to a support and drying, and the thermosetting resin composition is semi-cured (B stage). And a resin composition layer formed by layering the thermosetting resin composition of the present invention on a support can be produced.
The resin-coated film of the present invention thus obtained has a support and a semi-cured resin composition layer formed from the thermosetting resin composition of the present invention on one surface of the support. Is. However, this semi-cured state is a state in which the adhesive force between the thermosetting resin composition and the circuit pattern substrate is ensured when the thermosetting resin composition is cured, and the embedding property of the circuit pattern substrate is also ensured. It is desirable that the (fluidity) is ensured.

  As a method (coating machine) for applying the thermosetting resin composition to the support, for example, a die coater, comma coater, bar coater, kiss coater, roll coater or the like can be used. These coating machines can be appropriately selected depending on the desired thickness of the resin composition layer.

As a drying method after applying the thermosetting resin composition to the support, methods such as heating and hot air blowing can be applied.
As drying conditions, for example, the content of the organic solvent in the resin composition layer after formation can be 10% by mass or less, preferably 5% by mass or less. The drying conditions vary depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent. For example, by drying a varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes, A composition layer can be formed. Moreover, it is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  In general, the thickness of the resin composition layer in the film with resin is preferably equal to or greater than the thickness of the conductor layer of the circuit board. The thickness of the conductor layer is, for example, 5 to 70 μm, and is preferably 5 to 50 μm and more preferably 5 to 30 μm from the viewpoint of reducing the thickness and thickness of the multilayer printed wiring board. Therefore, the thickness of the resin composition layer can be, for example, 5 μm or more, and is, for example, in the range of 80 μm or less, preferably 60 μm or less, more preferably 40 μm or less. The thickness can be selected.

The support in the film with a resin of the present invention is, for example, polyolefin such as polyethylene, polypropylene, polyvinyl chloride, or polyethylene terephthalate [hereinafter sometimes referred to as “PET”. ], A film made of polyester such as polyethylene naphthalate, polycarbonate, polyimide or the like; release paper; metal foil such as copper foil or aluminum foil. These supports and protective films described later may be subjected to mat treatment, corona treatment, mold release treatment, and the like.
The thickness of the support is, for example, preferably 10 to 150 μm, and more preferably 25 to 50 μm.
You may laminate | stack the protective film according to a support body on the surface where the support body of the resin composition layer is not closely_contact | adhering. By laminating the protective film, foreign matter can be prevented from being mixed. The thickness of the protective film is, for example, 1 to 40 μm. The film with resin can also be wound and stored in a roll.

[Laminated board]
The laminated board of this invention contains the hardened | cured material of the cured product of the prepreg of this invention, and / or the film with a resin of this invention.
Hereinafter, the manufacturing method of the laminated board of this invention is explained in full detail. In addition, the layer which consists of the hardened | cured material of the prepreg of this invention or the film with resin of this invention contained in the laminated board of this invention may be called an "insulating resin layer."

As a method of forming a laminated board using the film with resin of this invention, the method of laminating the film with resin of this invention on the single side | surface or both surfaces of a circuit board using a vacuum laminator is mentioned, for example.
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. In addition, a circuit board means the thing in which the conductor layer (circuit) patterned by the one side or both surfaces of the above boards was formed. Moreover, in the laminated board which laminates | stacks a conductor layer and an insulating layer alternately, and the multilayer printed wiring board manufactured from this laminated board, the conductor layer by which the one or both surfaces of the outermost layer of this multilayer printed wiring board were patterned What is (circuit) is also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.

In the above laminate, if the film with resin has a protective film, after removing the protective film, preheat the film with resin and the circuit board as necessary, while pressing and heating the film with resin Crimp to 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 is suitably used. The laminating conditions are, for example, that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of air pressure 20 mmHg (26.7 hPa) or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the resin-coated film on the circuit board, after cooling to around room temperature, when the support is peeled off, the insulating resin layer can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type, content, etc. of the resin component in the resin composition layer. For example, the thermosetting conditions are selected at 150 to 220 ° C. for 20 to 180 minutes, preferably 160. It is selected in the range of 30 to 120 minutes at ~ 200 ° C.

When the support was not peeled off before the resin composition layer was cured, it was peeled off after the formation of the insulating resin layer, and then, if necessary, the insulating resin layer formed on the circuit board was perforated, A via hole, a through hole, or the like may be formed.
Drilling can be performed, for example, by a drill, laser, plasma, or a combination of these. Among these, drilling with a laser such as a carbon dioxide laser or a YAG laser is a common method.

  Next, a conductor layer may be formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin layer is made of permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. Roughening treatment is performed with an oxidizing agent to form uneven anchors. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. 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. As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.

Next, the manufacturing method of the laminated board of this invention using the prepreg of this invention is demonstrated.
Examples of the method for forming a laminate using the prepreg of the present invention include a method of producing the prepreg of the present invention by lamination molding. Specifically, a laminated board can be manufactured by laminating 1 to 20 sheets of the prepreg of the present invention and laminating and forming a metal foil such as copper or aluminum on one or both sides thereof. A metal foil will not be restrict | limited especially if it is used with the laminated board for electrical insulation materials.
As the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. For example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., a temperature of 100 to 250 ° C., a pressure of 0 It can be molded in a range of 2 to 10 MPa and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce the laminated board of the present invention.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention includes the laminated board of the present invention.
The multilayer printed wiring board of the present invention can be produced, for example, by subjecting a conductor layer (metal foil) disposed on one side or both sides of the insulating resin layer in the laminated board of the present invention to circuit processing.
Specifically, first, the conductor layer of the laminate of the present invention is subjected to wiring processing by a normal etching method, and then, a plurality of laminates that have been subjected to wiring processing via the prepreg of the present invention are laminated and subjected to hot press processing. Multi-layered at once. Then, the multilayer printed wiring board of the present invention can be manufactured through formation of through holes or blind via holes by drilling, laser processing, etc., and formation of interlayer wiring by plating or conductive paste.

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

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, the resin board and copper clad laminated board obtained by the Example and the comparative example measured and evaluated the performance with the following method.

(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 a product (trade name: TMA2940, manufactured by DuPont). After mounting the resin plate in the X direction, load 5g, temperature increase rate 45 ° C / min, temperature profile from 20 ° C (5 minutes hold) to 260 ° C (2 minutes hold) to 20 ° C (5 minutes hold) Measured with The curing shrinkage of the resin plate was calculated from the dimension at 20 ° C. before starting the temperature increase of the resin plate and the size at 20 ° C. after the temperature increase 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)
After removing the copper-clad laminate obtained in each example by etching, the copper-clad laminate was cut into a size of 60 mm long × 2 mm wide, and the dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz at an ambient temperature of 25 ° C. It was calculated from the resonance frequency obtained by the instrument method and the 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 solder heat resistance with copper A 25 mm square evaluation board was produced 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. By visually observing the appearance of the evaluation substrate, the solder heat resistance with copper was evaluated according to the following evaluation criteria.
A: No swelling C: With swelling

(4) Copper foil adhesion (copper foil peel strength)
By immersing the copper-clad laminate obtained in each example in a copper etching solution, an outer layer copper foil is formed to a width of 3 mm to prepare an evaluation substrate, and the adhesion of copper foil (90 ° peel) using a tensile tester. Strength) was measured. Note that the wiring board preferably has a peel strength of 0.7 kN / m or more.

(5) Glass transition temperature (Tg)
An evaluation board having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 0.4 mm (Z direction) obtained by immersing the copper clad laminate obtained in each example in a copper etching solution is removed. It produced and the thermomechanical analysis was performed by the compression method using the TMA test apparatus (The Du Pont company make, brand name: TMA2940). 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, and the heat resistance was evaluated.

(6) Coefficient of thermal expansion The copper-clad laminate obtained in each example was immersed in a copper etching solution to remove the copper foil, 5 mm long (X direction), 5 mm wide (Y direction), and 0.4 mm thick (Z Direction) was prepared, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). 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 used as the value of the coefficient of thermal expansion (linear expansion coefficient).

(7) 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 copper foil was removed, and 5 ton tensilon manufactured by Orientec Co., Ltd. was used. The measurement was performed at a crosshead speed of 1 mm / min and a span distance of 20 mm. The wiring board preferably has a flexural modulus of 28 GPa or more.

  In each example, the compounds produced in the following production examples were used.

[Production of Amino-Modified Siloxane Compound (H) Having Aromatic Azomethine and Hydroxy Group in Molecular Structure]
Production Example 1 Production of Amino-Modified Siloxane Compound (H-1) Having Aromatic Azomethine and Hydroxy Group in Molecular Structure Heatable and Coolable Volume 2L with Thermometer, Stirrer, Moisture Quantifier with Reflux Cooling Tube In the reaction vessel, 12.9 g of 3,3′-diethyl-4,4′-diaminodiphenylmethane [component (i)] (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A), terephthalaldehyde [(ii ) Ingredient] (Toray Fine Chemical Co., Ltd., trade name: TPAL) 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 concentrated at normal pressure. Dehydration gave an aromatic azomethine compound-containing solution (solid content concentration: 60% by mass).
Next, in the reaction solution, a siloxane compound having a primary amino group at both ends [component (a)] (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B, amino group equivalent 1500 g / mol) 325 .5 g, naphthalene skeleton-containing epoxy resin [component (b)] (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L, epoxy equivalent 231 g / mol), 7.9 g, propylene glycol monomethyl ether 513.3 g, After reacting at 115 ° C. for 4 hours, the mixture was heated to 130 ° C. and dehydrated by normal pressure concentration, and a solution containing an amino-modified siloxane compound (H-1) having an aromatic azomethine and hydroxy group in the molecular structure (Mw: 80 , 000, solid content concentration: 90% by 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 Was confirmed to exist. Further, it was confirmed by GPC measurement that all peaks due to the raw material epoxy resin disappeared, and it was confirmed that the desired compound was obtained.

[Production of Modified Imide Resin (I) Having Hydroxy Group in Molecular Structure]
Production Example 3: Production of Modified Imide Resin (I-1) Having Aromatic Azomethine and Hydroxy Group in Molecular Structure Heating and Cooling Volume 2L with Thermometer, Stirrer, Moisture Meter with Reflux Cooling Tube In a reaction vessel, a solution containing an amino-modified siloxane compound (H-1) having an aromatic azomethine and hydroxy group in the molecular structure obtained in Production Example 1 (solid content concentration: 90% by mass), 77.8 g, 2, 2 -Bis [4- (4-maleimidophenoxy) phenyl] propane [component (B)] (Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 246.9 g, propylene glycol monomethyl ether 425.3 g, 115 After reacting at 4 ° C. for 4 hours, the mixture was heated to 130 ° C. and concentrated at normal pressure, and the modified imide resin (I-1) having aromatic azomethine and hydroxy group in the molecular structure A containing solution (Mw: 7000, solid content concentration: 60% by mass) was obtained.
The modified imide resin (I-1) includes an amino-modified siloxane compound (H) having an aromatic azomethine and a hydroxy group in the molecular structure, and a maleimide compound (B) having an N-substituted maleimide group in the molecular structure. Is equivalent to a product obtained by previously reacting and.

[Production of modified imide resin (J) having acidic substituent and hydroxy group in molecular structure]
Production Example 4: Production of a modified imide resin (J-1) having an acidic substituent, aromatic azomethine and hydroxy group in the molecular structure. Heating and cooling with a thermometer, a stirrer and a moisture meter with a reflux condenser are possible. 94.7 g of a solution containing an amino-modified siloxane compound (H-1) having an aromatic azomethine and hydroxy group in the molecular structure obtained in Production Example 1 (solid content concentration: 90% by mass) in a reaction vessel having a volume of 2 L , 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane [(B) component] (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000), 225.6 g, p-aminophenol [(C ) Ingredients] 2.3 g and 427.4 g of propylene glycol monomethyl ether were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure, and placed in the molecular structure. A modified imide resin (J-1) -containing solution (Mw: 5,000, solid content concentration: 60% by mass) having a substituent, an aromatic azomethine, and a hydroxy group was obtained.
The modified imide resin (J-1) comprises an amino-modified siloxane compound (H) having an aromatic azomethine and a hydroxy group in the molecular structure, and a maleimide compound (B) having an N-substituted maleimide group in the molecular structure. And an amine compound (C) having an acidic substituent in advance.

Here, in the said manufacture example, the weight average molecular weight (Mw) was converted from the analytical curve using standard polystyrene by 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, The product name] was used to approximate the 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 varnish was prepared. Next, this varnish was impregnated and applied to 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 thermosetting resin composition 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 (PI-1210, manufactured by Tester Sangyo Co., Ltd.) so that the resin thickness after drying is 35 μm, and heated at 160 ° C. for 10 minutes. The semi-cured resin plate obtained by drying was crushed to obtain a semi-cured resin powder.
This resin powder was put into a Teflon (registered trademark) sheet form (length: 4 cm, width: 3 cm), and the glossy surface of 12 μm electrolytic copper foil was placed up and down at a pressure of 2.0 MPa and a temperature of 240 ° C. After pressing for a minute, the electrolytic copper foils on both sides were removed by etching 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.

[Amino-modified siloxane compound having aromatic azomethine and hydroxy group in molecular structure (H)]
H-1: Modified siloxane compound (H-1) having an aromatic azomethine obtained in Production Example 1
H-2: Modified siloxane compound having aromatic azomethine obtained in Production Example 2 (H-2)

[Modified imide resin (I) having aromatic azomethine and hydroxy group in the molecular structure]
I-1: Modified imide resin (I-1) having a hydroxy group in the molecular structure obtained in Production Example 3

[Modified imide resin (J) having an acidic substituent, aromatic azomethine and hydroxy group in the molecular structure]
J-1: Modified imide resin (J-1) having an acidic substituent and a hydroxy group in the molecular structure obtained in Production Example 4

[Maleimide compound (B) having N-substituted maleimide group in molecular structure]
BMI: Bis (4-maleimidophenyl) methane [manufactured by Kei-I Kasei Co., Ltd .; trade name]
BMI-4000: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (manufactured by Daiwa Kasei Kogyo Co., Ltd .; trade name)

[Amine compound having an acidic substituent (C)]
p-aminophenol (manufactured by Kanto Chemical Co., Inc.)

[Thermoplastic elastomer (D)]
Tuftec (registered trademark) H1043: hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Corporation; trade name)
Epofriend (registered trademark) CT-310: epoxy-modified styrene-butadiene copolymer resin [manufactured by Daicel Corporation; trade name]
Tuftec (registered trademark) M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (trade name, manufactured by Asahi Kasei Chemicals Corporation)

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

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

[Inorganic filler (G)]
SC2050-KNK: spherical silica (fused spherical silica) surface-treated with an aminosilane coupling agent (1% by mass / solid content) (manufactured by Admatechs Co., Ltd .; trade name, average particle size: 0.5 μm, dispersion medium: methyl isobutyl) Ketone, solid concentration 70 mass%, density 2.2 g / cm ³ )

[Aromatic amine compound (i)]
BAPP: 2,5-dimethyl-1,4-diaminobenzene (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name)

[Siloxane compound (a) having at least two primary amino groups]
X-22-161B: Siloxane compound having a primary amino group at both ends (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name, amino group equivalent 1500 g / mol)

From Tables 1-4, the resin board obtained from the thermosetting resin composition of Examples 1-19 has a small cure shrinkage rate, and in the characteristic of a laminated board, heat resistance, a thermal expansion coefficient, and copper foil adhesion | attachment It can be seen that it has excellent properties, elastic modulus and high frequency characteristics.
On the other hand, the resin plates obtained from the thermosetting resin compositions of Comparative Examples 1 to 6 have a large curing shrinkage rate, and also in the characteristics of the laminated plate, the thermal expansion coefficient, the copper foil adhesiveness, the elastic modulus, and the high frequency Inferior to any of the characteristics.

  The laminate obtained using the thermosetting resin composition, the resin-coated film and the prepreg of the present invention is particularly high in heat resistance, low curing shrinkage, high adhesion, high glass transition temperature, low thermal expansion, high It has an elastic modulus and excellent high frequency characteristics, and is useful as a highly integrated semiconductor package, a multilayer printed wiring board for electronic devices, and the like.

Claims (16)

  A thermosetting resin composition comprising an amino-modified siloxane compound (A) having a hydroxy group in the molecular structure and a maleimide compound (B) having an N-substituted maleimide group in the molecular structure.   The amino-modified siloxane compound (A) having a hydroxy group in the molecular structure includes a structural unit derived from the siloxane compound (a) having at least two primary amino groups and a structural unit derived from the epoxy resin (b). The thermosetting resin composition according to claim 1.   The thermosetting resin composition according to claim 1 or 2, wherein the amino-modified siloxane compound (A) having a hydroxy group in the molecular structure has an aromatic azomethine skeleton in the molecular structure.   The amino-modified siloxane compound (A) having a hydroxy group in the molecular structure is a structural unit derived from a siloxane compound (a) having at least two primary amino groups, a structural unit derived from an epoxy resin (b), and 1 The thermosetting resin composition according to any one of claims 1 to 3, comprising a structural unit derived from an aromatic azomethine compound (c) having at least one aldehyde group in the molecule.   An aromatic azomethine compound (c) having at least one aldehyde group in one molecule is a structural unit derived from an aromatic amine compound (i) having at least two primary amino groups in one molecule, and one molecule The thermosetting resin composition according to claim 4, comprising a structural unit derived from an aromatic aldehyde compound (ii) having at least two aldehyde groups therein.   Furthermore, the thermosetting resin composition of any one of Claims 1-5 formed by containing the amine compound (C) which has an acidic substituent.   Furthermore, the thermosetting resin composition of any one of Claims 1-6 formed by containing a thermoplastic elastomer (D).   Furthermore, the thermosetting resin composition of any one of Claims 1-7 formed by containing a thermosetting resin (E).   Furthermore, the thermosetting resin composition of any one of Claims 1-8 formed by containing a hardening accelerator (F).   Furthermore, the thermosetting resin composition of any one of Claims 1-9 formed by containing an inorganic filler (G).   The prepreg containing the thermosetting resin composition of any one of Claims 1-10.   The film with resin containing the thermosetting resin composition of any one of Claims 1-10.   A laminate comprising a cured product of the prepreg according to claim 11.   The laminated board containing the hardened | cured material of the film with a resin of Claim 12.   The multilayer printed wiring board containing the laminated board of Claim 13 or 14.   A semiconductor package obtained by mounting a semiconductor on the multilayer printed wiring board according to claim 15.