JP6785422B2 - Thermosetting resin composition, prepreg, film with resin, laminated board, multilayer printed wiring board and semiconductor package - Google Patents

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 a resin, a laminated board, a multilayer printed wiring board and a semiconductor package.

With the recent trend toward miniaturization and higher performance of electronic devices, the wiring density and integration of printed wiring boards are increasing, and along with this, laminated boards for printed wiring boards are being used. 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 a printed wiring board, a prepreg containing a resin composition containing an epoxy resin as a main component and a glass cloth is generally cured and integrally molded.
Epoxy resin has an excellent balance of insulation, heat resistance, cost, etc., but further improvement is required to meet the recent demand for improved heat resistance due to high-density mounting of printed wiring boards and high-multilayer configurations. It becomes.
Further, since the 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 (see, for example, Patent Document 1). However, it is known that increasing the filling amount of the inorganic filler causes deterioration of insulation reliability due to moisture absorption, insufficient adhesion between the resin and the wiring layer, poor press molding, etc., and the filling of the inorganic filler is increased. There was a limit to the low thermal expansion by chisel.
On the other hand, polybismaleimide resin, which is widely used for high-density mounting and high-multilayer laminates, has a problem in adhesion to copper foil and does not have sufficient low thermal expansion.

Further, a thermosetting resin composition containing an epoxy resin, a phenol resin and a modified imide resin as main components is known (see, for example, Patent Document 2). Although this thermosetting resin composition has improved moisture resistance and adhesiveness, 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 obtained modified imide resin is significantly inferior to that of the polybismaleimide resin.
Furthermore, especially in recent years, semiconductor package substrates have been caused by the difference in the coefficient of thermal expansion between the chip and the substrate, and the curing shrinkage and elastic modulus of the substrate during component mounting and package assembly due to miniaturization and thinning. Warpage has become a major issue. Therefore, a laminated board for a semiconductor package substrate is required to have good low thermal expansion property, low curing shrinkage property, and elastic modulus.

Further, in mobile communication devices typified by mobile phones, their base station devices, servers, network infrastructure devices such as 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 need to be compatible with high frequencies, and low dielectric constant and low dielectric loss tangent substrate materials that can reduce transmission loss are required.
In recent years, as applications that handle such high-frequency signals, in addition to the above-mentioned electronic devices, new systems that handle high-frequency wireless signals in the ITS (Intelligent Transport Systems) field (automobiles, transportation systems) and indoor short-range communication fields have also been introduced. Practical application and practical plan are in progress. Therefore, in the future, it is expected that substrate materials having low transmission loss will be further required for printed wiring boards mounted on these devices.

Japanese Unexamined Patent Publication No. 5-148343 Japanese Unexamined Patent Publication No. 6-263843

In view of these circumstances, the present invention has heat resistance, adhesiveness, low thermal expansion, elastic modulus, low curing shrinkage, and dielectric properties in a high frequency band (low dielectric constant and low dielectric loss tangent) [hereinafter, "high frequency characteristics". It may be called. ], An object of the present invention is to provide a thermosetting resin composition, a prepreg using the thermosetting resin composition, a film with a resin, a laminated board, a multilayer printed wiring board, and a semiconductor package.

As a result of intensive studies to solve the above problems, the present inventors have obtained a thermosetting resin composition containing an amino-modified siloxane compound having a hydroxy group and a specific maleimide compound, which has heat resistance and adhesion. We have found that it is excellent in properties, low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics, and arrived at the present invention.

That is, the present invention provides the following thermosetting resin compositions, prepregs, films with resins, laminated boards, multilayer printed wiring boards, and semiconductor packages.
[1] A thermosetting resin composition containing an amino-modified siloxane compound (A) having a hydroxy group in its molecular structure and a maleimide compound (B) having an N-substituted maleimide group in its molecular structure.
[2] The amino-modified siloxane compound (A) having a hydroxy group in its molecular structure is 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 the above [1], which comprises.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the amino-modified siloxane compound (A) having a hydroxy group in its molecular structure has an aromatic azomethine skeleton in its molecular structure.
[4] The amino-modified siloxane compound (A) having a hydroxy group in its molecular structure is 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 any one of the above [1] to [3], which comprises and a structural unit derived from the aromatic azomethine compound (c) having at least one aldehyde group in one molecule.
[5] The aromatic azomethine compound (c) having at least one aldehyde group in one molecule is a structural unit derived from the aromatic amine compound (i) having at least two primary amino groups in one molecule. The thermosetting resin composition according to the above [4], which comprises 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], which further contains an amine compound (C) having an acidic substituent.
[7] The thermosetting resin composition according to any one of [1] to [6] above, which further contains a thermoplastic elastomer (D).
[8] The thermosetting resin composition according to any one of the above [1] to [7], which further contains a thermosetting resin (E).
[9] The thermosetting resin composition according to any one of the above [1] to [8], which further contains a curing accelerator (F).
[10] The thermosetting resin composition according to any one of the above [1] to [9], which further contains an inorganic filler (G).
[11] A prepreg containing the thermosetting resin composition according to any one of the above [1] to [10].
[12] A film with a resin containing the thermosetting resin composition according to any one of the above [1] to [10].
[13] A laminated board containing a cured product of the prepreg according to the above [11].
[14] A laminated board containing a cured product of the resin-containing film according to the above [12].
[15] A multilayer printed wiring board including the laminate according to the above [13] or [14].
[16] A semiconductor package in which a semiconductor is mounted on the multilayer printed wiring board according to the above [15].

According to the present invention, a thermosetting resin composition excellent in heat resistance, adhesiveness, low thermal expansion, elasticity, low curing shrinkage and high frequency characteristics, a prepreg using the thermosetting resin composition, and a film with a resin. , Laminated boards, multilayer printed wiring boards and semiconductor packages 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 its molecular structure and a maleimide compound (B) having an N-substituted maleimide group in its molecular structure. ..
The thermosetting resin composition of the present invention is excellent in heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics by adopting the above structure. Become.
Hereinafter, each component will be described in order.

<Amino-modified siloxane compound (A) having a hydroxy group in its molecular structure>
The thermosetting resin composition of the present invention has an amino-modified siloxane compound (A) having a hydroxy group in its molecular structure [hereinafter, may be 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, but for example, a siloxane compound (a) having at least two primary amino groups [hereinafter, simply "siloxane compound ( It may be referred to as "a)". ] Derived structural unit and those containing the epoxy resin (b) -derived structural unit 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 by reacting the epoxy group of the epoxy resin (b) with the amino group of the siloxane compound (a). By containing the modified siloxane compound (A) formed by reacting the siloxane compound (a) with the epoxy resin (b), the adhesive strength can be improved without lowering the glass transition temperature.

(Siloxane compound (a) having at least two primary amino groups)
The siloxane compound (a) is not particularly limited, but for example, it is preferable to have one or more primary amino groups at each end of the molecule, and each end of the molecule has one primary amino group. Is more preferable, and it is further preferable to have one primary amino group at each end of the molecule.
The siloxane skeleton of the siloxane compound (a) may be linear or branched, but is preferably linear from the viewpoint of compatibility with other resin components.
As the siloxane compound (a), for example, a compound represented by the following general formula (1) is preferably mentioned.

In the general formula (1), a plurality of R ¹ each independently represent an alkyl group, a phenyl group or substituted phenyl group, may be the same or different from each other. R ² and R ³ each independently represent a divalent organic group. n represents an integer of 2 to 50.

In the general formula (1), as the alkyl group represented by R ¹ , an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 1 or 2 carbon atoms is preferable. More preferred. Specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and 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, an alkynyl group and the like, and among these, an alkyl group is preferable. As the alkyl group, the same ones as described above are preferably mentioned.
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, a propylene group and the like. 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 further preferably 400 to 4000 g / mol from the viewpoint of low thermal expansion and compatibility with other resins. It is mol, particularly preferably 600 to 3000 g / mol.

As the siloxane compound (a), a commercially available product can be used. 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), and "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) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), "BY-16-853U" (amino group equivalent 460 g / mol), "BY-" Examples thereof include "16-853" (amino group equivalent 650 g / mol) and "BY-16-853B" (amino group equivalent 2200 g / mol) (all manufactured by Toray Dow Corning Co., Ltd.). These can be used alone or in admixture of two or more.
Among these, for example, from the viewpoint of reactivity and low thermal expansion during synthesis, "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, and "X-22-161B" is more preferable from the viewpoint of excellent compatibility and high elastic modulus. Is even more preferable.

(Epoxy resin (b))
The epoxy resin (b) is not particularly limited, but for example, an epoxy resin having two or more epoxy groups in one 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 according to 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 classified. 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 novolak type epoxy resin, bisphenol F novolak type epoxy resin, etc. Epoxy resin; phenol aralkyl type epoxy resin; stillben type epoxy resin; dicyclopentadiene type epoxy resin; naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin and other naphthalene skeleton-containing epoxy resin; triazine skeleton-containing epoxy resin; fluorene skeleton-containing Epoxy resin; triphenol methane type epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylylene type epoxy resin; dihydroanthracene type epoxy resin; dicyclopentadiene type epoxy resin; phosphorus-containing epoxy resin in which a phosphorus compound is introduced. It is classified into such as. These can be used alone or in admixture of two or more.
Among these, a biphenyl aralkyl type epoxy resin and a naphthalene skeleton-containing epoxy resin are preferable from the viewpoint of heat resistance and flame retardancy.

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

The modified siloxane compound (A) preferably has an aromatic azomethine skeleton in its molecular structure. As a result, a highly elastic cured product can be obtained, and the shrinkage rate can be sufficiently reduced in the reflow step performed after curing.
Here, the aromatic azomethin refers to a Schiff base (−N = CH−) to which at least one aromatic group (preferably an aromatic hydrocarbon group) is bonded.
In the present specification, the amino-modified siloxane compound (A) having an aromatic azomethin and a hydroxy group in the molecular structure is referred to as "amino-modified siloxane compound (H) having an aromatic azomethin and a hydroxy group in the molecular structure" or. , It may be simply referred to as "modified siloxane compound (H) having aromatic azomethin".

[Amino-modified siloxane compound (H) having aromatic azomethine and a hydroxy group in its molecular structure]
The modified siloxane compound (H) having an aromatic azomethin is not particularly limited as long as it is an amino-modified siloxane compound having an aromatic azomethin and a hydroxy group in the molecular structure, and has, for example, at least two primary amino groups. Aromatic azomethine compound (c) having a structural unit derived from the siloxane compound (a), a structural unit derived from the epoxy resin (b), and at least one aldehyde group in one molecule [hereinafter, simply "aromatic azomethine compound" It may be referred to as "(c)". ] Derived structural units are preferably included.

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, still more preferably 90% by mass or more. The upper limit value is not particularly limited and may be 100% by mass or less.

The modified siloxane compound (H) having an aromatic azomethin can be obtained, for example, by reacting the siloxane compound (a) with the epoxy resin (b) and the 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, but for example, an aromatic amine compound (i) having at least two primary amino groups in one molecule [hereinafter, simply "aromatic amine compound (i)". ) ”. ] Derived structural unit and aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule [hereinafter, may be simply referred to as “aromatic aldehyde compound (ii)”. ] Derived structural units are preferably included.

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% by mass or more, more preferably 90% by mass or more. The upper limit value is not particularly limited and may be 100% by mass or less.

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 two or three primary amino groups in one molecule, and more preferably has two primary amino groups in one molecule. It is an aromatic amine compound.
The aromatic amine compound (i) has an aromatic hydrocarbon group, and may also have an aliphatic hydrocarbon group as long as it has an aromatic hydrocarbon group. For example, the aromatic amine compound (i) also includes a structure having an aromatic hydrocarbon group-an aliphatic hydrocarbon group-an aromatic hydrocarbon group in the molecule.
The aromatic amine compound (i) is preferably represented by the following general formula (i).

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

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

(In the formula, R ¹² and R ¹³ are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A ² is an alkylene group having 1 to 5 carbon atoms and 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 independently integers of 0 to 4. .)

^{(Wherein, R 14} and ^{R 15} are each independently an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms .A ³ represents an alkylene group having 1 to 5 carbon atoms, alkylidene of 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. S and t are independently integers 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. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, as R ¹¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 2 from the viewpoint of availability. If p is an integer of 2 or more, among the plurality of R ¹¹ may be different even in the same.

In the general formula (i-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ¹² and R ¹³ and the halogen atom 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 further 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, a 1,5-pentamethylene group and the like. Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics. More preferably, it 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.
Among the above options, A ² is preferably an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
q and r 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. When q or r is an integer of 2 or more, the plurality of R ^12s or R ^13s may be the same or different from each other.

In the general formula (i-3), examples of 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 the case of R ¹² and R ¹³ , which are preferable. Is the same.
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ³ include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ^2. The same is true for the preferred ones.
The A ^3, among the above-mentioned alternatives, preferably an alkylidene group having 2 to 5 carbon atoms, more preferred are as defined 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 even more preferably 0. When s or t is an integer of 2 or more, the plurality of R ^14s or R ^15s may be the same or different from each other.
The general formula (i-3) is preferably represented by the following general formula (i-3').

(Formula (i-3 ') in ^{A 3, R 14, R 15} , s and t are the same as 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 ( The group represented by i-2) is preferable, and the group represented by the following general formula (i-2') is more preferable.

(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).)

The A ¹ of the In formula (i), heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, from the viewpoint of low curing shrinkage and high frequency characteristics, by any of the following formulas It is more preferably the 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 ′ -Diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylketone, benzene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4, 4'-diaminobiphenyl, 3,3'-dihydroxybenzene, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone , Bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene 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 or the like is preferable. From the viewpoint of low cost and solubility in 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 expansion and dielectric properties, 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are preferable. Further, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene, which can increase the elastic modulus, are also preferable.

The aromatic aldehyde compound (ii) is preferably an aromatic aldehyde compound having two or three aldehyde groups in one molecule, and more preferably an aromatic aldehyde compound having two aldehyde groups in one molecule. It is a compound.
The aromatic aldehyde compound (ii) has an aromatic hydrocarbon group, and may also have an aliphatic hydrocarbon group as long as it has an aromatic hydrocarbon group. For example, an aromatic aldehyde compound (ii) also includes a structure having an 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, R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. P1 is an integer of 0 to 4.)

(In the formula, R ²² and R ²³ are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A ¹² is an alkylene group having 1 to 5 carbon atoms and 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 independently integers of 0 to 4, respectively. .)

(In the formula, R ²⁴ and R ²⁵ are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A ¹³ is an alkylene group having 1 to 5 carbon atoms and 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. S1 and t1 are independently integers 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. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable as R ²¹ .
p1 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of availability. When p1 is an integer of 2 or more, the plurality of R ^21s 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 are 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 or an ethyl group, and further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ¹² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics. More preferably, it 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.
The A ^12, among the above options, an alkylene group having 1 to 5 carbon atoms, alkylidene group having 2 to 5 carbon atoms preferred. 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 are the same as those in the case of R ²² and R ²³ , which are preferable. Is the same.
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ¹³ include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ^12. And so is the preferred one.
The A ^13, among the above-mentioned alternatives, preferably an alkylidene group having 2 to 5 carbon atoms, more preferred are as defined above.
s1 and t1 are integers of 0 to 4, and from the viewpoint of availability, both are preferably an integer 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 ^24s or R ^25s 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 ( The group represented by ii-1) is preferable, and the group represented by the following general formula (ii-1') is more preferable.

(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'-dicarboxyaldehyde and the like. Among these, for example, terephthalaldehyde is preferable from the viewpoint of being capable of lower thermal expansion, having high reactivity, having excellent solvent solubility, and being easily commercially available.

(Method for producing amino-modified siloxane compound (A) having a hydroxy group)
The modified siloxane compound (A) can be obtained, for example, by subjecting a siloxane compound (a) having at least two amino groups and an 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 of the siloxane compound (a). The base equivalent] is preferably used so as to be in the range of 4 to 30 times the number of epoxy groups of the epoxy resin (b) [amount of the epoxy resin (b) used / epoxy group equivalent of the epoxy resin (b)]. When the value is 4 times or more, the adhesiveness of the thermosetting resin composition containing the modified siloxane compound (A) becomes excellent, and when the value is 30 times or less, excellent resin compatibility can be obtained. Be done.
That is, the ratio of the structural unit derived from the siloxane compound (a) contained in the modified siloxane compound (A) to the structural unit derived from the epoxy resin (b) is the use of the above-mentioned siloxane compound (a) and epoxy resin (b). It is preferably a ratio converted from the amount.

The ring-opening addition reaction is preferably carried out in an organic solvent. The amount of the organic solvent that can be used in the ring-opening addition reaction is preferably 60 to 500 parts by mass, preferably 100 to 500 parts by mass, based on 100 parts by mass of the total of the siloxane compound (a) and the epoxy resin (b). It is more preferably 400 parts by mass, and further preferably 140 to 300 parts by mass. When the amount of the organic solvent used is 60 parts by mass or more, good solubility can be obtained, and when it is 500 parts by mass or less, a sufficient reaction rate can be obtained.

A modified siloxane compound (a), an epoxy resin (b), and if necessary, an organic solvent, a reaction catalyst, or the like are charged into the reactor, and if necessary, the mixture is stirred while being heated or kept warm 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 and the like.
The reaction time can be, for example, in the range of 0.1 to 10 hours. The reaction temperature can be, for example, in the range of 100 to 150 ° C., preferably 110 to 150 ° C. 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 solvent having a high boiling point is not required for the reaction solvent, so that the solvent is less likely to remain in the cured product. , The obtained prepreg, resin-coated film, etc. 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 You can confirm that you are there. Further, by confirming that all the peaks caused by the raw material epoxy resin (b) disappear by GPC measurement, it can be confirmed that the reaction proceeds satisfactorily and the desired compound is obtained. ..
The measurement by GPC of this measurement can be performed under the following conditions, for example.
Examples of the measuring device include an auto sampler (AS-8020, manufactured by Tosoh Corporation), a column oven (860-C0, manufactured by JASCO Corporation), an RI detector (830-RI, manufactured by JASCO Corporation), and UV. / VIS detector (870-UV, manufactured by JASCO Corporation) and HPLC pump (880-PU, manufactured by JASCO Corporation) can be used.
Further, as the column to be used, for example, TSKgel SuperHZ2000 and 2300 manufactured by Tosoh Corporation can be used, and as the measurement conditions, for example, the measurement temperature is 40 ° C., the flow rate is 0.5 ml / min, and tetrahydrofuran is used as the solvent. Can be done.

The weight average molecular weight (Mw) of the amino-modified siloxane compound (A) is not particularly limited, but is preferably 4,000 to 450,000, more preferably 7,000 to 150,000, and 10,000 to 100, for example. 000 is more preferable. When the weight average molecular weight (Mw) is 4,000 or more, excellent low curing shrinkage and low thermal expansion are obtained, and when 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 an amino-modified siloxane compound (H) having an aromatic azomethin and a hydroxy group in its molecular structure)
In producing the modified siloxane compound (H) having an aromatic azomethin, for example, first, an aromatic amine compound (i) having at least two primary amino groups in one molecule and at least an aromatic amine compound (i) in one molecule are produced. The aromatic aldehyde compound (ii) having two aldehyde groups may be referred to as a dehydration condensation reaction [hereinafter, “dehydration condensation reaction 1”. ], The aromatic azomethine compound (c) having at least one aldehyde group in one molecule is obtained.
Next, 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 [hereinafter]. , May be referred to as "dehydration condensation reaction 2". ], A modified siloxane compound (H) having an aromatic azomethin can be obtained.
According to the reaction method, it is easy to control the molecular weight of the aromatic azomethin in the molecule of the modified siloxane compound (H) having the aromatic azomethin, and the thermosetting resin composition containing the molecular weight can be easily increased in elastic modulus. Especially effective for high adhesiveness.

Each dehydration condensation reaction and ring-opening addition reaction are preferably carried out 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 mesitylen; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide; ester solvents such as γ-butyrolactone and the like can be mentioned. .. 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 they are highly volatile and do not easily remain as a residual solvent during the production of preprene and resin-coated films. Propylene glycol monomethyl ether and toluene are more preferred.
Further, since the reaction is a dehydration condensation reaction, water is produced as a by-product. For the purpose of removing water, which is a by-product, it is preferable to react while removing water, which is a by-product, by azeotrope with an aromatic solvent, for example.

A reaction catalyst can be used for each dehydration condensation reaction and ring-opening addition reaction, if necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine. These can be used alone or in admixture of two or more. From the viewpoint of efficiently advancing the dehydration condensation reaction, an acidic catalyst is preferable, and p-toluenesulfonic acid is more preferable.

[Dehydration condensation reaction 1]
The 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 the aromatic amine compound (i) and the aromatic aldehyde compound (ii) used is, for example, the number of aldehyde groups of the aromatic aldehyde compound (ii) [the amount of the aromatic aldehyde compound (ii) used / aromatic aldehyde. The aldehyde group equivalent of compound (ii)] is the primary amino group number of the aromatic amine compound (i) [the amount of the aromatic amine compound (i) used / the primary amino group equivalent of the aromatic amine compound (i)]. It is preferably used so as to be 1 to 5 times, more preferably 1.5 to 5 times, and further preferably 2 to 4 times. By setting it to 1 times or more, the reaction can proceed sufficiently, and the product has a formyl group, and by setting it to 5 times or less, characteristics such as elastic modulus can be exhibited. 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 above-mentioned aromatic amine compound (i). It is preferable that the ratio is converted from the amount of the aromatic aldehyde compound (ii) used.

The dehydration condensation reaction 1 is preferably carried out 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, preferably 25 to 2000 parts by mass, based on 100 parts by mass of the total of the aromatic amine compound (i) and the aromatic aldehyde compound (ii). The amount is more preferably ~ 1000 parts by mass, and particularly preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, good solubility can be obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate can be obtained.

Aromatic amine compound (i), aromatic aldehyde compound (ii), and if necessary, an organic solvent, a reaction catalyst, etc. are charged into the reactor, and if necessary, the reactor is stirred while being heated or kept warm to cause a dehydration condensation reaction. The 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 and the like.
The reaction time can be, for example, in the range of 0.1 to 10 hours. The reaction temperature can be, for example, in the range of 70 to 150 ° C., and the reaction is preferably carried out while removing water as a by-product, more preferably 100 to 130 ° C. When the temperature is 70 ° C. or higher, a sufficient reaction rate can be obtained, and when the temperature is 150 ° C. or lower, a solvent having a high boiling point is not required for the reaction solvent, so that the solvent is less likely to remain in the cured product and can be obtained. The heat resistance of the prepreg, the film with resin, etc. is excellent.

[Ring-opening addition reaction and dehydration condensation reaction 2]
Then, the ring-opening addition reaction and the dehydration condensation reaction 2 are carried out. In the ring-opening addition reaction and the dehydration condensation reaction 2, the siloxane compound (a), the epoxy resin (b), and the aromatic azomethine compound (c) obtained by the dehydration condensation reaction 1 are subjected to the ring-opening addition reaction and dehydration. This is a reaction for obtaining a modified siloxane compound (H) having aromatic azomethine by subjecting it to a condensation reaction.
Here, the amount of the aromatic azomethine compound (c) and the siloxane compound (a) used is, for example, the number of primary amino groups of the siloxane compound (a) [the amount of the siloxane compound (a) used / 1 of the siloxane compound (a)). The secondary amino group equivalent] is in the range of 2 to 10 times the number of aldehyde groups of the aromatic azomethin compound (c) [the amount of the aromatic azomethin compound (c) used / the aldehyde group equivalent of the aromatic azomethin compound (c)]. It is preferable to use it as such. A thermosetting resin composition containing a modified siloxane compound (H) having an aromatic azomethin, with a value of 2 times or more, good solubility in a solvent, and a value of 10 times or less. 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 aromatic azomethin to the structural unit derived from the aromatic azomethin compound (c) is the same as that of the above-mentioned siloxane compound (a). It is preferable that the ratio is converted from the amount of the aromatic azomethin 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 the siloxane compound (a) used / the primary amino group of the siloxane compound (a). The equivalent] is preferably used so as to be in the range of 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)]. When the value is 4 times or more, the adhesiveness of the thermosetting resin composition containing the modified siloxane compound (H) having an aromatic azomethin is excellent, and when the value is 30 times or less, a good resin is used. Compatibility is obtained.
That is, the ratio of the structural unit derived from the siloxane compound (a) contained in the modified siloxane compound (H) having aromatic azomethine to the structural unit derived from the epoxy resin (b) is the ratio of the above-mentioned 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 the dehydration condensation reaction 2 are preferably carried out in an organic solvent. The amount of the organic solvent used in the ring-opening addition reaction and the 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 preferably parts by mass, more preferably 40 to 1000 parts by mass, and even more preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, good solubility can be obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate can be 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 the reactor, and if necessary, the reaction mixture is stirred while being heated or kept warm, and the ring-opening addition reaction and dehydration are performed. By the condensation reaction, a modified siloxane compound (H) having an aromatic azomethin is obtained.
The reaction conditions are not particularly limited and may be appropriately determined according to the type of raw material and the like.
The reaction time can be, for example, in the range of 0.1 to 10 hours. The reaction temperature can be, for example, in the range of 70 to 150 ° C., and the reaction is preferably carried out while removing water as a by-product, more preferably 100 to 130 ° C. When the temperature is 70 ° C. or higher, a sufficient reaction rate can be obtained, and when the temperature is 150 ° C. or lower, a solvent having a high boiling point is not required for the reaction solvent, so that the solvent is less likely to remain in the cured product and can be obtained. The heat resistance of the prepreg, the film with resin, etc. is excellent.

The presence of the modified siloxane compound (H) having an aromatic azomethin 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 peak in the vicinity, it can be confirmed that the reaction proceeds satisfactorily and the desired compound is obtained.
Further, by confirming that all the peaks caused by the raw material epoxy resin disappear by GPC measurement, it can be confirmed that the reaction proceeds satisfactorily and the desired compound is 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 azomethin is not particularly limited, but is preferably 5,000 to 500,000, more preferably 8,000 to 200,000, for example. More preferably, 20,000 to 100,000. When the weight average molecular weight (Mw) is 5,000 or more, excellent low curing shrinkage and low thermal expansion are obtained, and when 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 100 parts by mass based on the total solid content (excluding the inorganic filler) of the thermosetting resin composition. , Preferably 3 to 50 parts by mass, more preferably 7 to 40 parts by mass. This range is preferable because the elastic modulus and low thermal expansion property are improved.

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

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

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

(In the formula, R ³² and R ³³ are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A ³² is an alkylene group having 1 to 5 carbon atoms and 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 independently integers of 0 to 4, respectively. .)

(In the formula, R ³⁴ and R ³⁵ are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A ³³ is an alkylene group having 1 to 5 carbon atoms and 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. S2 and t2 are independently integers of 0 to 4).

(In the formula, n2 is an integer from 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. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable as R ³¹ .
p2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of availability. If p2 is an integer of 2 or more, among the plurality of R ³¹ may be different even in the same.

In the general formula (B-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³² and R ³³ are the same as those in the case of 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 further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ³² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics. More preferably, it 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 and 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 from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 2. When q2 or r2 is an integer of 2 or more, the plurality of R ^32s or R ^33s may be the same or different from each other.

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 are the same as those in the case of R ³² and R ³³ , which are preferable. Is the same.
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ³³ include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ^32. The same is true for the preferred ones.
Among the above options, A ³³ is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferable one is as described above.
s2 and t2 are integers of 0 to 4, and from the viewpoint of availability, both are preferably an integer 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 ^34s or R ^35s 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 represented by R ³⁶ and R ³⁷ and the halogen atom are the same as in the case of R ^{11 in} the general formula (i-1). The same is true for the preferred ones.
u2 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

In the general formula (B), A ³¹ is the general formula (B) from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics. The group represented by B-2) is preferable, and the group represented by the following general formula (B-2') is more preferable.

(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) may be any of the following formulas from the viewpoints of heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, low curing shrinkage and high frequency characteristics. It is preferably the group represented.

Examples of the maleimide compound (B) include bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, and 3,3'-dimethyl-5. , 5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane And so on. These can be used alone or in admixture of two or more.
Among these, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, which has a high reaction rate and can be made more heat resistant, 3,3'-dimethyl-5,5'-diethyl-4,4 '-Diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane are preferred, and from the viewpoint of solvent solubility, 3,3'-dimethyl-5,5'-diethyl-4. , 4'-Diphenylmethane Bismaleimide, Bis (4-maleimidephenyl) methane is more preferable, and bis (4-maleimidephenyl) methane is further preferable from the viewpoint of low cost.

The content of the maleimide compound (B) in the thermosetting resin composition of the present invention is 100 parts by mass based on the total solid content (excluding the inorganic filler) of the thermosetting resin composition. It is preferably 30 to 95 parts by mass, more preferably 35 to 65 parts by mass. This range is preferable because the elastic modulus and low thermal expansion property are improved.

<Amine compound (C) having an acidic substituent>
The thermosetting resin composition of the present invention is further referred to as an amine compound (C) having an acidic substituent [hereinafter, simply referred to as "amine compound (C)". ] May be contained. The number of acidic substituents contained in the amine compound (C) is preferably one or two, and more preferably one.
Here, examples of the acidic substituent include a hydroxyl group, a carboxy group, a sulfonic acid group and the like. 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, and the like. Examples thereof include m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline and 3,5-dicarboxyaniline. 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 synthetic 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 further preferable.

When the thermosetting resin composition of the present invention contains the amine compound (C), the content thereof is the total of the solid content (excluding the inorganic filler) in the thermosetting resin composition. It is preferably 0.5 to 20 parts by mass, and more preferably 0.7 to 15 parts by mass with respect to 100 parts by mass. Within this range, heat resistance and low thermal expansion 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, or may be pre-reacted if necessary. It may be contained in. In this case, for example, at least a part of each of the above components may be reacted by heating or heat retention before use, or 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, the reaction product obtained by reacting the modified siloxane compound (A) with the maleimide compound (B) is referred to as "modified imide resin (I) having a hydroxy group in the molecular structure". In some cases, the 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 "an acidic substituent in the molecular structure". It may be referred to as "modified imide resin (J) having a hydroxy group".

When the modified siloxane compound (H) having aromatic azomethine is used as the modified siloxane compound (A), the content of the maleimide compound (B) in the thermosetting resin composition is such that gelation prevention and heat resistance From the above viewpoint, it is preferable that the equivalent of the maleimide group of the maleimide compound (B) exceeds the equivalent of the primary amino group of the modified siloxane compound (H) having aromatic azomethine and the amine compound (C). The content of the modified siloxane compound (H) having an aromatic azomethin is preferably about 7 to 35 times the content of the amine compound (C) from the viewpoint of heat resistance.
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 carried out in an organic solvent. The organic solvent that can be used in the pre-reaction is not particularly limited, and is, for example, an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone. Etc. Ketone solvents; Ester solvents such as ethyl acetate, γ-butyrolactone; Ether solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene, mesitylen; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Nitrogen atom-containing solvent; Examples thereof include a sulfur atom-containing solvent such as dimethyl sulfoxide. These can be used alone or in admixture of two or more.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve and γ-butyrolactone are preferable from the viewpoint of solubility, and they are said to have low toxicity and high volatility and are unlikely to remain as a residual solvent during the production of 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 shall be 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 viewpoint of solubility and reaction time. Is preferable, and 40 to 700 parts by mass is more preferable.

<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 styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, acrylic-based thermoplastic elastomers, and silicone-based thermoplastics. Examples thereof include thermoplastic elastomers and derivatives thereof. These are composed of a hard segment component and a soft segment component, and generally 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 viewpoint 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 styrene-based 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 styrene-derived structural unit contained in the styrene-based thermoplastic elastomer include a butadiene-derived structural unit, an isoprene-derived structural unit, a maleic acid-derived structural unit, and a maleic anhydride-derived structural unit. These may be contained 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.
Styrene-based thermoplastic elastomers include hydrogenated styrene-butadiene-styrene block copolymers and styrene from the viewpoints of heat resistance, adhesion to conductors, glass transition temperature, thermal expansion coefficient, elastic coefficient and high frequency characteristics. It is preferably at least one selected from the hydrogenated additives (SEPS; styrene-ethylene-propylene-styrene block copolymer) of the −isoprene-styrene block copolymer, and the styrene-butadiene-styrene block copolymer. Hydrogenated additives are more preferred.
As the hydrogenated additive of the styrene-butadiene-styrene block copolymer, SEBS (styrene-ethylene-butylene-) in which the hydrogenation rate of the carbon-carbon double bond is usually 90% or more (preferably 95% or more). Styrene block copolymer) and SBBS (styrene-butadiene-butylene-styrene block copolymer) (overall) in which the carbon-carbon double bond at the 1,2-bond site in the butadiene block is partially hydrogenated. The hydrogenation rate for carbon-carbon double bonds is approximately 60-85%). Among these, SEBS is more preferable.

Further, as the thermoplastic elastomer (D), one having a reactive functional group at the molecular end or in the 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 acrylic group, a methacryl group and a vinyl group. By having these reactive functional groups at the molecular ends or in the molecular chain, 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, the warpage of the substrate can be significantly reduced.
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 a metal foil, and an epoxy group, a hydroxyl group and an amide group are preferable from the viewpoint of heat resistance and insulation reliability. Amino groups are more preferred.

When the thermosetting resin composition of the present invention contains a thermoplastic elastomer (D), the content thereof is good in compatibility with the resin, and the low curing shrinkage and low thermal expansion of the cured product are effectively achieved. 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 (excluding the inorganic filler) of the thermosetting resin composition. More preferably, 5 to 30 parts by mass is further preferable.

<Thermosetting resin (E)>
The thermosetting resin composition of the present invention may further contain a thermosetting resin (E) other than the above-mentioned components. Examples of the thermosetting resin (E) include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, and dicyclopentadiene. Examples thereof include resins, silicone resins, triazine resins, and melamine resins. These can be used alone or in admixture of two or more. Among these, epoxy resins and cyanate resins are preferable, and epoxy resins are more preferable, from the viewpoint of moldability and electrical insulation.
Examples of the epoxy resin include those similar to the epoxy resin (b), and among these, a naphthalene skeleton-containing epoxy resin and a biphenyl aralkyl type epoxy resin are preferable from the viewpoint 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. With respect to 100 parts by mass of the total, 1 to 50 parts by mass is preferable, 1 to 30 parts by mass is more preferable, and 1 to 20 parts by mass is further 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, imidazoles are preferable from the viewpoint of reactivity, and an adduct of hexamethylene diisocyanate represented by the following general formula (3) and 2-ethyl-4-methylimidazole is more preferable. The compound represented by the following general formula (3) is available as, for example, "G-8009L" (trade name) manufactured by Dai-ichi 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 the solid content in the thermosetting resin composition (however, the inorganic filler). It 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 setting the content of the curing accelerator (F) within the above range, low shrinkage, low thermal expansion and excellent dielectric properties of the cured product can be more effectively exhibited.

<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, beryria, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, and silicate. Aluminum oxide, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, aluminum borate, silicon carbide, short glass fiber, glass fine powder, hollow glass, etc. Can be mentioned. As the glass, E glass, T glass, D glass and the like are preferably mentioned. 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 further preferable, from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy. Examples of silica include precipitated silica produced by a wet method and having a high water content, and dry silica produced by a dry method and containing almost no bound water or the like. Further, examples of the dry method silica include crushed silica, fumed silica, molten silica (molten spherical silica), explosive silica (spherical silica obtained by utilizing the explosive phenomenon of metal powder), and the like, depending on the manufacturing 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 thereof 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. Particularly preferably, it is 0.2 to 1 μm. By setting the average particle size of the molten silica to 0.1 μm or more, the fluidity at the time of high filling can be kept good, and by setting it to 10 μm or less, the probability of mixing coarse particles is reduced and the coarse particles are coarse particles. It is possible to suppress the occurrence of defects caused by. Here, the average particle size is the particle size of a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with the particle size distribution measuring device or the like.

When the thermosetting resin composition of the present invention contains an inorganic filler (G), the content thereof is the total solid content in the thermosetting resin composition (however, the inorganic filler is excluded). It is preferably 10 to 300 parts by mass, more preferably 50 to 270 parts by mass, still more preferably 100 to 250 parts by mass, and particularly preferably 150 to 230 parts by mass with respect to 100 parts by mass. By setting the content of the inorganic filler (G) in this range, the moldability and low thermal expansion of the prepreg and the film with resin can be kept good.

<Other ingredients>
The thermosetting resin composition of the present invention comprises 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. It may contain an adhesiveness improver or the like. 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, and poly. Examples thereof include ether ether ketone resin, polyetherimide resin, silicone resin, tetrafluoroethylene resin and the like.

(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 and the like, an acrylic acid ester resin, a methacrylic acid ester resin, and a conjugated diene resin. A resin filler having a core-shell structure having a rubber-like core layer made of, etc., and a glass-like shell layer made of acrylic acid ester resin, methacrylic acid ester resin, aromatic vinyl resin, vinyl cyanide resin, etc. Can be mentioned.

(Flame retardants)
Examples of the flame retardant include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants and the like. Among these, phosphorus-based flame retardants and metal hydrates are preferable from the viewpoint of environmental problems. Halogen-based flame retardants are generally limited to use in electronic component applications that are not discarded or burned.
Examples of the inorganic phosphorus-based flame retardant include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. ; Phosphoric acid; phosphine oxide and the like.
Examples of the organic phosphorus-based flame retardant include aromatic phosphoric acid ester, mono-substituted phosphonic acid diester, 2-substituted phosphinic acid ester, metal salt of 2-substituted phosphinic acid, organic nitrogen-containing phosphorus compound, and cyclic organic phosphorus compound. Can be mentioned.
Examples of the metal hydrate include aluminum hydroxide hydrate and magnesium hydroxide hydrate.
Examples of the halogen-based flame retardant include chlorine-based flame retardants and brominated flame retardants.

(UV absorber, etc.)
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers. Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants. Examples of the photopolymerization initiator include benzophenone-based, benzylketal-based and thioxanthone-based photopolymerization initiators. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative. Examples of the adhesiveness improving agent include urea compounds such as ureasilane; and coupling agents such as silane-based, titanate-based, and aluminate-based.
It is also preferable that the inorganic filler (G) is pretreated or integral blended with a silane-based or titanate-based coupling agent or a surface treatment agent such as a silicone oligomer at the time of blending.

(Organic solvent)
The thermosetting resin composition of the present invention may contain an organic solvent to form a varnish from the viewpoint of facilitating handling and the production of a prepreg or a film with a resin, which will be described later, or the varnish. It is preferable to put it in a state.
The organic solvent used for producing the varnish is not particularly limited, and for example, alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone-based solvent; ether-based solvent such as tetrahydrofuran; aromatic solvent such as toluene, xylene, mesitylene; nitrogen atom-containing solvent containing amide-based solvent such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Sulfur atom-containing solvent containing a sulfoxide solvent; an ester solvent containing a lactone solvent such as γ-butyrolactone and the like can be mentioned. These can be used alone or in admixture of two or more.
Among these, from the viewpoint of solubility, an alcohol solvent, a ketone solvent and a nitrogen atom-containing solvent are preferable, a ketone solvent is 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 of 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 film with a resin to which an appropriate amount of the thermosetting resin composition is attached while maintaining good coatability.

[Prepreg]
The prepreg of the present invention contains the thermosetting resin composition of the present invention.
The prepreg of the present invention is, for example, a method of impregnating a base material with the thermosetting resin composition of the present invention, or a method of impregnating or spraying a base material and then applying a method such as extrusion [hereinafter, these The methods may be collectively referred to as "impregnation or coating". ] Can be manufactured. Specifically, after impregnating or coating the base material with the thermosetting resin composition of the present invention, the base material and the base material are semi-cured (B stage) by, for example, semi-curing (B stage) by heating or the like. It is possible to produce the prepreg of the present invention containing the thermosetting resin composition.

As the base material used for the prepreg of the present invention, for example, well-known materials used for various laminated plates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass and Q glass; organic fibers such as polyimide, polyester and tetrafluoroethylene, and mixtures thereof. In other applications, for example, carbon fiber can be used as long as it is a fiber reinforced base material.
These substrates have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats. The material and shape of the base material may be selected according to the intended use and performance of the molded product, and may be used alone or in combination of two or more types, if necessary.
Further, as the base material, those surface-treated with a silane coupling agent or the like or those subjected to a mechanical opening treatment are suitable from the viewpoint of heat resistance, moisture resistance and processability.
The thickness of the base material is not particularly limited and can be, for example, in the range of about 0.02 to 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 prepreg after drying.
The prepreg of the present invention is, for example, 100 after impregnating or coating a base material with the thermosetting resin composition of the present invention so that the content of the thermosetting resin composition in the prepreg is within the above range. It can be produced by heating and drying at a temperature of about 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

[Film with resin]
The resin-containing film of the present invention contains the thermosetting resin composition of the present invention.
The resin-containing film of the present invention can be obtained, for example, by applying the thermosetting resin composition of the present invention to a support. Specifically, a varnish containing the thermosetting resin composition of the present invention is applied to a support and dried to volatilize the organic solvent in the varnish, and the thermosetting resin composition is semi-cured (B stage). It can be produced by forming a resin composition layer formed by forming a layer of the thermosetting resin composition of the present invention on a support.
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. It is a thing. 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 circuit pattern substrate can be embedded. It is desirable that (fluidity) is ensured.

As a method (coating machine) for applying the thermosetting resin composition to the support, for example, a die coater, a comma coater, a bar coater, a kiss coater, a 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, a method such as heating or hot air blowing can be applied.
The drying conditions can be, for example, a condition in which the content of the organic solvent in the resin composition layer after formation is 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 the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes, the resin A composition layer can be formed. Further, it is preferable that the drying conditions are appropriately set in advance by a simple experiment.

The thickness of the resin composition layer in the resin-containing film is usually preferably equal to or larger 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, more preferably 5 to 30 μm, from the viewpoint of lightness, thinness, shortness, and miniaturization of the multilayer printed wiring board. Therefore, the thickness of the resin composition layer can be, for example, 5 μm or more, and for example, 80 μm or less, preferably 60 μm or less, more preferably 40 μm or less, and more than the thickness of the conductor layer. You can choose the thickness.

The support in the resin-coated film of the present invention is, for example, a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, or polyethylene terephthalate [hereinafter, may be referred to as "PET". ], A film made of polyester such as polyethylene naphthalate, polycarbonate, polyimide or the like; a release paper; a metal foil such as a copper foil or an aluminum foil. These supports and the protective film described later may be subjected to a matte treatment, a corona treatment, a mold release treatment, or the like.
The thickness of the support is, for example, preferably 10 to 150 μm, more preferably 25 to 50 μm.
A protective film similar to the support may be laminated on the surface of the resin composition layer where the support is not in close contact. By laminating a protective film, it is possible to prevent foreign matter from entering. The thickness of the protective film is, for example, 1 to 40 μm. The resin-coated film can also be rolled up and stored.

[Laminate board]
The laminated board of the present invention contains a cured product of the prepreg of the present invention and / or a cured product of the resin-containing film of the present invention.
Hereinafter, the method for producing the laminated board of the present invention will be described in detail. The layer made of the prepreg of the present invention or the cured product of the resin-coated film of the present invention contained in the laminated board of the present invention may be referred to as an "insulating resin layer".

Examples of the method of forming a laminated board using the resin-coated film of the present invention include a method of laminating the resin-coated film of the present invention on one side or both sides of a circuit board using a vacuum laminator.
Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. The circuit board means a circuit board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. Further, in a laminated board formed by alternately laminating conductor layers and insulating layers and a multilayer printed wiring board manufactured from the laminated board, a conductor layer in which one or both sides of the outermost layer of the multilayer printed wiring board is patterned. What is (circuit) is also included in the circuit board referred to here. The surface of the conductor layer may be roughened in advance by a blackening treatment or the like.

In the above lamination, when the resin-attached film has a protective film, after removing the protective film, the resin-attached film and the circuit board are preheated as necessary, and the resin-attached film is pressurized and heated. Crimped to the circuit board.
In the resin-coated film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating conditions are, for example, a crimping temperature (lamination temperature) preferably 70 to 140 ° C., a crimping pressure preferably 0.1 to 1.1 MPa, and laminating under a reduced pressure of 20 mmHg (26.7 hPa) or less. preferable. Further, the laminating method may be a batch method or a continuous method using a roll.

An insulating resin layer can be formed on the circuit board by laminating the resin-containing film on the circuit board, cooling it to around room temperature, peeling the support, and then thermosetting the support. The thermosetting conditions may be appropriately selected according to the type, content, etc. of the resin component in the resin composition layer, and are selected, for example, 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.

If the support is not peeled off before the resin composition layer is cured, the support is peeled off after the insulating resin layer is formed, and then, if necessary, the insulating resin layer formed on the circuit board is perforated. Via holes, through holes and the like may be formed.
Drilling can be performed, for example, by drilling, laser, plasma, or a combination of these. Among these, drilling with a laser such as a carbon dioxide gas laser or a YAG laser is a general method.

Then, the conductor layer may be formed on the insulating resin layer by dry plating or wet plating. As the dry plating, known methods such as thin film deposition, sputtering, and ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin layer is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. It is roughened with an oxidizing agent to form an uneven anchor. As the oxidizing agent, an aqueous solution of sodium hydroxide (aqueous solution of alkaline permanganate) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, the conductor layer is formed by a method that combines electroless plating and electrolytic plating. It is also possible to form a plating resist having a pattern opposite to that of the conductor layer, and to form the conductor layer only by electroless plating. As a method for subsequent pattern formation, for example, a known subtractive method, semi-additive method, or the like can be used.

Next, a method for manufacturing the laminated board of the present invention using the prepreg of the present invention will be described.
Examples of the method for forming a laminated plate using the prepreg of the present invention include a method of laminating and molding the prepreg of the present invention. Specifically, a laminated board can be manufactured by laminating and molding, for example, 1 to 20 sheets of the prepreg of the present invention and arranging metal foils such as copper and aluminum on one side or both sides thereof. The metal foil is not particularly limited as long as it is used in a laminated board for an electrically insulating material.
As the molding conditions, for example, the method of a laminated plate for an electric insulating material and a multilayer plate can be applied. For example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. It can be molded in the range of 2 to 10 MPa and a heating time of 0.1 to 5 hours. Further, the laminated board of the present invention can also be manufactured by combining the prepreg of the present invention and the wiring board for the inner layer and laminating and molding.

[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 manufactured, for example, by circuit-processing a conductor layer (metal foil) arranged on one side or both sides of the insulating resin layer in the laminated board of the present invention.
Specifically, first, the conductor layer of the laminated plate of the present invention is wired by an ordinary etching method, and then a plurality of laminated plates wired via the prepreg of the present invention are laminated and heat-pressed. Multi-layered collectively by. After that, the multilayer printed wiring board of the present invention can be manufactured through the formation of through holes or blind via holes by drilling, laser processing, etc., and the formation of interlayer wiring by plating or conductive paste.

[Semiconductor package]
The semiconductor package of the present invention comprises 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 on 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.
The performance of the resin plate and the copper-clad laminate obtained in Examples and Comparative Examples was measured and evaluated by the following methods.

(1) Curing Shrinkage Rate of Resin Plate The resin plate obtained in each example is cut out to prepare 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 (DuPont, trade name: TMA2940). After mounting the resin plate on the device in the X direction, the load is 5 g, the heating rate is 45 ° C./min, and the temperature profile is 20 ° C. (holding for 5 minutes) to 260 ° C. (holding for 2 minutes) to 20 ° C. (holding for 5 minutes). Measured at. From the dimensions of the resin plate at 20 ° C. before the start of temperature rise and the dimensions at 20 ° C. after the temperature rise, the curing shrinkage rate of the resin plate was calculated using the following formula.
Curing shrinkage rate (%) = {(dimensions at 20 ° C before temperature rise (mm) −dimensions at 20 ° C after temperature rise (mm)) / dimensions at 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, it is cut into a size of 60 mm in length × 2 mm in width, and the dielectric constant (Dk) and dielectric loss tangent (Df) at an atmospheric temperature of 25 ° C. It was calculated from the resonance frequency and the no-load Q value obtained by the instrument method. As the measuring instrument, a vector type network analyzer E8364B manufactured by Agilent Technologies Co., Ltd., CP531 (10 GHz resonator) and CPMA-V2 (program) manufactured by Kanto Electronics Applied Development Co., Ltd. were used.

(3) Evaluation of Heat Resistance of Solder with Copper A 25 mm square evaluation substrate was prepared from the copper-clad laminates obtained in each example, and the evaluation substrate 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 heat resistance of the solder with copper was evaluated according to the following evaluation criteria.
A: No swelling C: With swelling

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

(5) Glass transition temperature (Tg)
An evaluation substrate having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 0.4 mm (Z direction) from which the copper foil was removed by immersing the copper-clad laminate obtained in each example in a copper etching solution The product was prepared and subjected to thermomechanical analysis by a compression method using a TMA test apparatus (manufactured by DuPont, trade name: TMA2940). After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was carried out twice in succession 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 the tangents having different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.

(6) Coefficient of thermal expansion The copper foil was removed by immersing the copper-clad laminate obtained in each example in a copper etching solution. Length 5 mm (X direction), width 5 mm (Y direction), thickness 0.4 mm (Z) An evaluation substrate of (direction) was prepared, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (TMA2940, manufactured by DuPont). After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was carried out twice in succession 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 rate).

(7) Bending Elastic Modulus A 50 mm × 25 mm evaluation substrate from which the copper foil was removed was prepared by immersing the copper-clad laminate obtained in each example in a copper etching solution, and 5 ton tencilon manufactured by Orientec Co., Ltd. was used. , The cross head speed was 1 mm / min, and the distance between spans was 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 its molecular structure]
Production Example 1: Production of an amino-modified siloxane compound (H-1) having an aromatic azomethin and a hydroxy group in its molecular structure A volume 2 L that can be heated and cooled with a thermometer, a stirrer, and a water content meter with a reflux cooling tube. In the reaction vessel of 3,3'-diethyl-4,4'-diaminodiphenylmethane [(i) component] (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A) 12.9 g, terephthalaldehyde [(ii) ) Ingredients] (manufactured by Toray Fine Chemicals Co., Ltd., trade name: TCAL) 17.1 g and 45.0 g of propylene glycol monomethyl ether were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at atmospheric pressure. It was dehydrated to obtain an aromatic azomethin compound-containing solution (solid content concentration: 60% by mass).
Next, in the above reaction solution, a siloxane compound having a primary amino group at both ends [(a) component] (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name: X-22-161B, amino group equivalent 1500 g / mol) 325 .5 g, naphthalene skeleton-containing epoxy resin [(b) component] (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 temperature is raised to 130 ° C. and dehydrated by atmospheric concentration concentration, and the solution containing an amino-modified siloxane compound (H-1) having an aromatic azomethin and a hydroxy group in the molecular structure (Mw: 80). 000, solid content concentration: 90% by mass) was obtained.
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. In addition, it was confirmed by GPC measurement that all the peaks caused by the raw material epoxy resin disappeared, and it was confirmed that the desired compound was obtained.

[Production of modified imide resin (I) having a hydroxy group in its molecular structure]
Production Example 2 : Production of a modified imide resin (I-1) having an aromatic azomethin and a hydroxy group in its molecular structure. A heating and cooling volume of 2 L equipped with a thermometer, a stirrer, and a water content meter with a reflux cooling tube. A solution containing an amino-modified siloxane compound (H-1) having an aromatic azomethin and a hydroxy group in the molecular structure obtained in Production Example 1 (solid content concentration: 90% by mass) 77.8 g, 2,2 in a reaction vessel. -Bis [4- (4-maleimidephenoxy) phenyl] propane [(B) component] (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 246.9 g, propylene glycol monomethyl ether 425.3 g, 115 After reacting at ° C. for 4 hours, the temperature is raised to 130 ° C. and concentrated at atmospheric pressure, and a modified imide resin (I-1) -containing solution (Mw: 7000, solid content concentration) having an aromatic azomethin and a hydroxy group in the molecular structure is used. : 60% by mass) was obtained.
The modified imide resin (I-1) is an amino-modified siloxane compound (H) having an aromatic azomethin and a hydroxy group in its molecular structure, and a maleimide compound (B) having an N-substituted maleimide group in its molecular structure. Corresponds to the reaction of and in advance.

[Production of modified imide resin (J) having an acidic substituent and a hydroxy group in its molecular structure]
Production Example 3 : Production of a modified imide resin (J-1) having an acidic substituent, an aromatic azomethine, and a hydroxy group in the molecular structure. Heating and cooling possible with a thermometer, a stirrer, and a water content meter with a reflux cooling tube. A solution containing an amino-modified siloxane compound (H-1) having an aromatic azomethine and a hydroxy group in the molecular structure obtained in Production Example 1 (solid content concentration: 90% by mass) 94.7 g in a reaction vessel having a large volume of 2 L. , 2,2-Bis [4- (4-maleimidephenoxy) 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 atmospheric pressure to add acidic substituents and aromatic azomethine in the molecular structure. A modified imide resin (J-1) -containing solution having a hydroxy group (Mw: 5,000, solid content concentration: 60% by mass) was obtained.
The modified imide resin (J-1) is an amino-modified siloxane compound (H) having an aromatic azomethin and a hydroxy group in its molecular structure, and a maleimide compound (B) having an N-substituted maleimide group in its molecular structure. And the amine compound (C) having an acidic substituent are reacted in advance.

Here, in the above production example, the weight average molecular weight (Mw) was converted by GPC from the calibration curve using standard polystyrene. The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name] was used for approximation by a cubic equation. The conditions for GPC are shown below.
Equipment: (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, product name)
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: tetrahydrofuran Sample concentration: 20 mg / 5 mL
Injection volume: 10 μL
Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

Examples 1 to 17 , Comparative Examples 1 to 6
Each component is mixed at the 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 methyl ethyl ketone is used as a solvent to have a solid content (nonvolatile content) concentration of 65% by mass. A varnish was prepared. Next, this varnish was impregnated and coated on 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% by mass.
Four of these 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.
Further, the above varnish is applied to a 16 μm polyethylene terephthalate film using a film applicator (manufactured by Tester Sangyo Co., Ltd., PI-1210) so that the resin thickness after drying becomes 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 is put into a mold (length: 4 cm, width: 3 cm) of a Teflon (registered trademark) sheet, and glossy surfaces of a 12 μm electrolytic copper foil are arranged one above the other, and 60 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.
Tables 1 to 4 show the results of tests or evaluations using the obtained copper-clad laminates and resin plates.

Hereinafter, each component in Tables 1 to 4 will be described.

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

[Modified imide resin (I) having aromatic azomethine and hydroxy group in its molecular structure]
I-1: Modified imide resin (I-1) having a hydroxy group in the molecular structure obtained in Production Example 2.

[Modified imide resin (J) having an acidic substituent, aromatic azomethine and hydroxy group in its 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 3.

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

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

[Thermoplastic elastomer (D)]
Tough Tech (registered trademark) H1043: Hydrogenated styrene-butadiene copolymer resin [manufactured by Asahi Kasei Chemicals Co., Ltd .; trade name]
Epofriend (registered trademark) CT-310: Epoxy-modified styrene-butadiene copolymer resin [manufactured by Daicel Corporation; trade name]
Tough Tech (registered trademark) M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin [manufactured by Asahi Kasei Chemicals Co., Ltd .; trade name]

[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-8009L: Isocyanate mask imidazole [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; trade name]
TPP-S: Triphenylphosphine Triphenylborane [manufactured by Hokuko Chemical Co., Ltd .; trade name]

[Inorganic filler (G)]
SC2050-KNK: Spherical silica (molten spherical silica) surface-treated with an aminosilane coupling agent (1% by mass / solid content) (manufactured by Admatex Co., Ltd .; trade name, average particle size: 0.5 μm, dispersion medium: methyl isobutyl Ketone, solid content concentration 70% by 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 Shinetsu Chemical Industry Co., Ltd .; trade name, amino group equivalent 1500 g / mol)

From Tables 1 to 4, the resin plates obtained from the thermosetting resin compositions of Examples 1 to 17 have a small curing shrinkage rate, and the characteristics of the laminated board are heat resistance, thermal expansion rate, and copper foil adhesion. It can be seen that it is excellent in 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 terms of the characteristics of the laminated board, the coefficient of thermal expansion, copper foil adhesiveness, elastic modulus and high frequency. It is inferior to any of the characteristics.

The laminated board obtained by using the thermosetting resin composition of the present invention, the film with resin, and the prepreg has particularly high heat resistance, low curing shrinkage, high adhesiveness, high glass transition temperature, low thermal expansion, and high. It has 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 (13)

Amino-modified siloxane compound having a hydroxy group in its molecular structure and (A), Ri greens contain a maleimide compound having the N- substituted maleimide group in a molecular structure (B),
The amino-modified siloxane compound (A) having a hydroxy group in the molecular structure comprises 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). A thermosetting resin composition containing a structural unit derived from the aromatic azomethin compound (c) having at least one aldehyde group in one molecule . The aromatic azomethine compound (c) having at least one aldehyde group in one molecule is a structural unit derived from the aromatic amine compound (i) having at least two primary amino groups in one molecule, and one molecule. The thermosetting resin composition according to claim 1 , further comprising a structural unit derived from an aromatic aldehyde compound (ii) having at least two aldehyde groups therein. The thermosetting resin composition according to claim 1 or 2 , further comprising an amine compound (C) having an acidic substituent. The thermosetting resin composition according to any one of claims 1 to 3 , further comprising a thermoplastic elastomer (D). The thermosetting resin composition according to any one of claims 1 to 4 , further comprising a thermosetting resin (E). The thermosetting resin composition according to any one of claims 1 to 5 , further comprising a curing accelerator (F). The thermosetting resin composition according to any one of claims 1 to 6 , further comprising an inorganic filler (G). A prepreg containing the thermosetting resin composition according to any one of claims 1 to 7 . A film with a resin containing the thermosetting resin composition according to any one of claims 1 to 7 . A laminated board containing a cured product of the prepreg according to claim 8 . A laminated board containing a cured product of the film with resin according to claim 9 . A multilayer printed wiring board including the laminate according to claim 10 or 11 . A semiconductor package in which a semiconductor is mounted on the multilayer printed wiring board according to claim 12 .