JP6819062B2 - Thermosetting resin composition, prepreg using it, film with resin, laminated board, printed wiring board and semiconductor package, and imide resin and its manufacturing method. - 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 printed wiring board and a semiconductor package, and an imide resin. Regarding the manufacturing method.

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, particularly in recent years, with the miniaturization and thinning of semiconductor package substrates, warpage due to the difference in the coefficient of thermal expansion between the chip and the substrate has become a major problem at the time of component mounting and package assembly. For this reason, laminated plates for semiconductor package substrates are required to have good low thermal expansion properties, but since epoxy resins have a large coefficient of thermal expansion, selection of epoxy resins with aromatic rings and inorganic fillers such as silica are required. The thermal expansion is reduced by increasing the filling capacity of the resin (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.

Further, as a material having excellent heat resistance, polybismaleimide resin is widely used as a laminated board material for printed wiring boards. However, the polybismaleimide resin has a problem in adhesiveness such as copper foil adhesive strength, and low thermal expansion property is not sufficient.
A resin composition containing a modified imide resin modified with siloxane has been studied for the purpose of lowering the thermal expansion of the polybismaleimide resin (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 5-148343 Japanese Unexamined Patent Publication No. 2014-129521

However, although the siloxane-modified imide resin is excellent in low thermal expansion property, further improvement in adhesiveness is desired.
In view of these circumstances, the present invention provides a thermosetting resin composition having excellent copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elasticity and moldability, and a prepreg using the same. An object of the present invention is to provide a film with a resin, a laminated board, a printed wiring board and a semiconductor package, an imide resin used for these, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors use a specific siloxane compound having a primary amino group, an aromatic amine compound and an aliphatic amine compound as the amine compound to be used in combination with the maleimide resin. As a result, it has been found that the above object can be achieved, and the present invention has been completed.

That is, the present invention provides the following thermosetting resin composition, prepreg, resin-coated film, laminated board, printed wiring board, semiconductor package, imide resin, and a method for producing the same.

[1] An aromatic amine compound (A) having at least two primary amino groups in one molecule, an aliphatic amine compound (B) having at least two primary amino groups in one molecule, and a molecular terminal. A thermosetting resin composition containing a siloxane compound (C) having at least two primary amino groups and a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule.
[2] The thermosetting resin composition according to the above [1], which further contains an amine compound (E) having an acidic substituent represented by the following general formula (I).

(In the general formula (I), R ₁ independently represents a hydroxyl group, a carboxy group or a sulfonic acid group which are acidic substituents, and R ₂ independently represents a hydrogen atom and an aliphatic hydrocarbon having 1 to 5 carbon atoms. It represents a hydrogen group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)
[3] A structure derived from an aromatic amine compound (A) having at least two primary amino groups in one molecule, and an aliphatic amine compound (B) having at least two primary amino groups in one molecule. A structure derived from a siloxane compound (C) having at least two primary amino groups at the end of the molecule, and a structure derived from a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule. An imide resin containing.
[4] The imide resin according to the above [3], further containing a structure derived from the amine compound (E) having an acidic substituent represented by the general formula (I).
[5] An aromatic amine compound (A) having at least two primary amino groups in one molecule, an aliphatic amine compound (B) having at least two primary amino groups in one molecule, and a molecular terminal. A method for producing an imide resin, which comprises reacting a siloxane compound (C) having at least two primary amino groups with a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule.
[6] The amine compound (E) having the component (A), the component (B), the component (C), the component (D), and an acidic substituent represented by the general formula (I). ) And the above-mentioned method for producing an imide resin according to [5].
[7] A thermosetting resin composition containing the imide resin according to the above [3] or [4].
[8] The thermosetting resin composition according to any one of the above [1], [2] or [7], which further contains a thermoplastic elastomer (F).
[9] The thermosetting resin composition according to any one of the above [1], [2], [7] or [8], which further contains an epoxy resin.
[10] The thermosetting resin composition according to any one of the above [1], [2], and [7] to [9], which further contains an inorganic filler (H).
[11] The thermosetting resin composition according to any one of the above [1], [2], and [7] to [10], which further contains a curing accelerator (I).
[12] A prepreg containing the thermosetting resin composition according to any one of the above [1], [2], and [7] to [11].
[13] A film with a resin containing the thermosetting resin composition according to any one of the above [1], [2], and [7] to [11].
[14] A laminated board containing a cured product of the prepreg according to the above [12].
[15] A laminated board containing a cured product of the resin-attached film according to the above [13].
[16] A printed wiring board containing the laminated board according to the above [14] or [15].
[17] A semiconductor package containing the printed wiring board according to the above [16].

According to the present invention, a thermosetting resin composition having excellent copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elasticity and moldability, a prepreg using the same, and a resin are attached. A film, a laminated board, a printed wiring board and a semiconductor package, and an imide resin and a method for producing the same can be provided.

[Thermosetting resin composition]
The present invention discloses the thermosetting resin compositions of the following [1] and [2].
[1] An aromatic amine compound (A) having at least two primary amino groups in one molecule, an aliphatic amine compound (B) having at least two primary amino groups in one molecule, and a molecular terminal. A thermosetting resin composition containing a siloxane compound having at least two primary amino groups and a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule.
[2] A structure derived from an aromatic amine compound (A) having at least two primary amino groups in one molecule, and an aliphatic amine compound (B) having at least two primary amino groups in one molecule. A structure derived from a siloxane compound (C) having at least two primary amino groups at the end of the molecule, and a structure derived from a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule. A thermocurable resin composition containing an imide resin containing.
Hereinafter, the thermosetting resin composition of the above [1] will be referred to as a "first thermosetting resin composition", and the thermosetting resin composition of the above [2] will be referred to as a "second thermosetting resin composition". ".
In addition, when it is simply referred to as "thermosetting resin composition", it means both "first thermosetting resin composition" and "second thermosetting resin composition".

<First thermosetting resin composition>
The first thermosetting resin composition is an aromatic amine compound (A) having at least two primary amino groups in one molecule (hereinafter, “aromatic amine compound (A)” or “component (A)”. (Also also referred to as), an aliphatic amine compound (B) having at least two primary amino groups in one molecule (hereinafter, also referred to as “aliphatic amine compound (B)” or “component (B)”) and a molecule. A siloxane compound (C) having at least two primary amino groups at the terminal (hereinafter, also referred to as “siloxane compound (C)” or “component (C)”) and at least two N-substituted maleimides in one molecule. It is a thermosetting resin composition containing a maleimide compound (D) having a group (hereinafter, also referred to as “maleimide compound (D)” or “component (D)”).

(Aromatic amine compound (A) having at least two primary amino groups in one molecule)
The aromatic amine compound (A) is not particularly limited as long as it is an aromatic amine compound having at least two primary amino groups in one molecule.
In the present specification, the aromatic amine compound means a compound having a primary amino group directly bonded to a carbon atom of an aromatic hydrocarbon group.
The aromatic amine compound (A) is preferably an aromatic amine compound having two primary amino groups in one molecule, and more preferably a compound represented by the following general formula (1).

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

(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 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 (1-3). Q and r are independently integers of 0 to 4. .)

(In the formula, R ¹⁴ and R ¹⁵ 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. S and t are independently integers of 0 to 4).

In the general formula (1-1), 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 (1-2), 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.
As the alkylene group having 1 to 5 carbon atoms which A ¹² represents, for example, methylene, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability. 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 copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability.
Among the above options, A ¹² 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 (1-3), 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 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 described above.
s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and 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 (1-3) is preferably represented by the following general formula (1-3').

(A ¹³ , R ¹⁴ , R ¹⁵ , s and t in the general formula (1-3') are the same as those in the general formula (1-3).)

Incidentally, in the general formula (1), the A ^11, the copper foil adhesion, low thermal expansion, low cure shrinkage, heat resistance (solder heat resistance), from the viewpoints of elastic modulus and moldability, the general formula ( It is preferably a group represented by 1-2), and more preferably a group represented by the following general formula (1-2').

(A ¹² , R ¹² , R ¹³ , q and r in the general formula (1-2') are the same as those in the general formula (1-2').)

Table A ¹¹ in the general formula (1), a copper foil adhesive property, low thermal expansion, low cure shrinkage, heat resistance (solder heat resistance), from the viewpoints of elastic modulus and moldability, by any of the following formulas It is more preferable that it is a group to be used.

Specific examples of the aromatic amine compound (A) include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diamino. Benzene, 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'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-dimethyl-5,5'-diethyl-4,4' −Diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1, 3-Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) Examples thereof include sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and 9,9-bis (4-aminophenyl) fluorene. Only one type of these may be used, or two or more types may be mixed and used.

Among these, for example, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl- because of its high reactivity and higher heat resistance. 4,4'-Diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] Propane is preferable, and because of its low cost and solubility in a solvent, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl -4,4'-diaminodiphenylmethane and bis [4- (4-aminophenoxy) phenyl] propane are preferred. Further, 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.

(Aliphatic amine compound (B) having at least two primary amino groups in one molecule)
The aliphatic amine compound (B) is not particularly limited as long as it is an aliphatic amine compound having at least two primary amino groups in one molecule.
In the present specification, the aliphatic amine compound means a compound having a primary amino group directly bonded to a carbon atom of an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched or cyclic.
The aliphatic amine compound (B) preferably contains a structure represented by the following general formula (2).

(In the formula, R ₂₁ and R ₂₂ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 1 to 20.)

The carbon number of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ₂₁ and R ₂₂ is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group and the like, and among these, an alkyl group is preferable. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. Among these, a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
n is an integer of 1 to 20 from the viewpoint of increasing the elastic modulus, preferably 2 to 10 from the viewpoint of low curing shrinkage, and more preferably 3 to 7 from the viewpoint of low thermal expansion.

The aliphatic amine compound (B) is preferably a compound represented by the following general formula (2-1).

(In the general formula (2-1), R ₂₁ , R ₂₂ and n are the same as those in the general formula (2).)

The aliphatic amine compound (B) preferably has 2 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and even more preferably 7 to 12 carbon atoms.

The aliphatic amine compound (B) is preferably an aliphatic amine compound having two primary amino groups in one molecule.
Specific examples of the aliphatic amine compound (B) include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, 2,2,4-trimethylhexamethylenediamine, octamethylenediamine, nonamethylenediamine, Decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine, 5-methylnona Methylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 2,5-diamino-1,3,4-oxadiazole, bis (4-aminocyclohexyl) methane And so on. Only one type of these may be used, or two or more types may be mixed and used. Among these, hexamethylenediamine and 2,2,4-trimethylhexamethylenediamine are preferable from the viewpoint of obtaining more excellent moldability.

(Siloxane compound (C) having at least two primary amino groups at the end of the molecule)
The siloxane compound (C) is not particularly limited as long as it is a siloxane compound having at least two primary amino groups at the molecular terminals, but preferably contains a structure represented by the following general formula (3).

(In the formula, R ₃₁ and R ₃₂ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 2 to 100.)

As the alkyl group represented by R ₃₁ and R ₃₂ , 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 further preferable.
Specific examples of the alkyl group represented by R ₃₁ and R ₃₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. Of these, a methyl group is preferable.
Examples of the substituent in the substituted phenyl group represented by R ₃₁ and R ₃₂ 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 group as described above is preferably mentioned.
Among the groups represented by R ₃₁ and R ₃₂ , a phenyl group or a methyl group is preferable, and a methyl group is more preferable, from the viewpoint of solubility with other resins.
m is preferably an integer of 1 to 100 from the viewpoint of low thermal expansion, and is preferably an integer of 2 to 50 from the viewpoint of compatibility and high elastic modulus.

Further, the siloxane compound (C) is more preferably a compound represented by the following general formula (3-1).

(In the formula, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and R ₃₅ and R ₃₆ each independently represent a divalent organic group. Indicates. M'indicates an integer from 1 to 100.)

The alkyl group, phenyl group or substituted phenyl group represented by R _31, R ₃₂ , R ₃₃ and R ₃₄ are the same as those of R ₃₁ and R ₃₂ in the general formula (3).
Examples of the divalent organic group represented by R ₃₅ or R ₃₆ 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.
m'is preferably an integer of 1 to 100 from the viewpoint of low thermal expansion, and is preferably an integer of 2 to 50 from the viewpoint of compatibility and high elastic modulus.

As the siloxane compound (C), a siloxane compound having two primary amino groups at the molecular terminal is preferable.
As the siloxane compound (C), commercially available products can be used, for example, "KF-8010" (functional group equivalent of amino group 430), "X-22-161A" (functional group equivalent of amino group 800), ". "X-22-161B" (functional group equivalent of amino group 1500), "KF-8012" (functional group equivalent of amino group 2200), "KF-8008" (functional group equivalent of amino group 5700), "X-22" -9409 "(functional group equivalent of amino group 700)," X-22-1660B-3 "(functional group equivalent of amino group 2200) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.)," BY-16-853U "( Amino group functional group equivalent 460), "BY-16-853" (amino group functional group equivalent 650), "BY-16-853B" (amino group functional group equivalent 2200) (above, Toray Dow Corning Co., Ltd.) (Manufactured by the company), "XF42-C5742" (functional group equivalent of amino group 1280), "XF42-C6252" (functional group equivalent of amino group 1255), "XF42-C5379" (functional group equivalent of amino group 745) (above , Momentive Performance Materials Japan GK), etc. (The unit of functional group equivalent of amino group is g / mol). Only one type of these may be used, or two or more types may be mixed and used.
Among these, for example, "X-22-161A", "X-22-161B", "KF-8012", "X-22-1660B-" because of their high reactivity during synthesis and low thermal expansion. "3", "XF42-C5379", "XF42-C6252", "XF42-C5742" are preferable, and "X-22-161A", "X-22-161B" are excellent in compatibility and high elastic modulus. , "XF42-C6252" and "XF42-C5742" are more preferable, and "XF42-C5422" and "XF42-C5742" are further preferable because they are inexpensive.

(Maleimide compound (D) having at least two N-substituted maleimide groups in one molecule)
The maleimide compound (D) is not particularly limited as long as it is a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule, but a maleimide having two N-substituted maleimide groups in one molecule. The compound is preferable, and the compound represented by the following general formula (4) is more preferable.

(In the formula, A ⁴¹ is a group represented by the following general formulas (4-1), (4-2), (4-3) or (4-4).)

(In the formula, R ⁴¹ 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 ⁴² and R ⁴³ are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A ⁴² 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 (4-5). Q2 and r2 are independently integers of 0 to 4, respectively. .)

(In the formula, R ⁴⁴ and R ⁴⁵ are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. A ⁴³ is an alkylene group having 1 to 5 carbon atoms and alkylidene having 2 to 5 carbon atoms. Group, ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond. S2 and t2 are independently integers from 0 to 4).

(In the formula, n2 is an integer of 1 to 10.)

(In the formula, R ⁴⁶ and R ⁴⁷ 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 (4-1), examples of the aliphatic hydrocarbon group represented by R ⁴¹ 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 ⁴¹ .
p2 is an integer of 0 to 4, and from the viewpoint of availability, it is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. When p2 is an integer of 2 or more, the plurality of R ^41s may be the same or different.

In the general formula (4-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ⁴² and R ⁴³ and the halogen atom are the same as those in the case of R ⁴¹ . 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 ⁴² 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 copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability. More preferably, it is a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ⁴² 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 copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability.
Among the above options, A ⁴² 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. If q2 or r2 is an integer of 2 or more, plural R ⁴² s or R ⁴³ together may each be the same or different.

In the general formula ^(4-5), an aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R 44} and ^{R 45} represent, as the halogen ^atom, the same thing can be mentioned in the case of ^{R 42} and ^{R 43,} preferred 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 ⁴³ include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by A ^42. And so is the preferred one.
Among the above options, A ⁴³ 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. If s2 or t2 is an integer of 2 or more, plural R ⁴⁴ s or R ⁴⁵ together may each be the same or different.
The general formula (4-5) is preferably represented by the following general formula (4-5').

(A ⁴³ , R ⁴⁴ , R ⁴⁵ , s2 and t2 in the general formula (4-5') are the same as those in the general formula (4-5).)

In the general formula (4-3), n2 is an integer of 1 to 10, preferably 1 to 5, and more preferably 1 to 3 from the viewpoint of availability.
In the general formula (4-4), the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ⁴⁶ and R ⁴⁷ and the halogen atom are the same as in the case of R ^{41 in} the general formula (4-1). The same is true for the preferred ones.
u2 is an integer of 1 to 8, preferably 1 to 3, and more preferably 1.

In the general formula (4), A ⁴¹ is the general formula (4) 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 a group represented by 4-2), and more preferably a group represented by the following general formula (4-2').

(A ⁴² , R ⁴² , R ⁴³ , q2 and r2 in the general formula (4-2') are the same as those in the general formula (4-2).)

The A ⁴¹ in the general formula (4) can be any of the following formulas from the viewpoints of copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability. It is preferably the group represented.

Specific examples of the maleimide compound (D) include bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl-. 5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) Examples include propane. Only one type of these may be used, or two or more types may be mixed and used.
Among these, for example, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, and 2,2-bis (4- (4-maleimide)) are high in reactivity and can be made more heat resistant. Phenoxy) phenyl) propane is preferable, and bis (4-maleimidephenyl) methane and 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane are more preferable from the viewpoint of solubility in a solvent.

(Content of each component in the first thermosetting resin composition)
The content of the aromatic amine compound (A) and the aliphatic amine compound (B) in the first thermosetting resin composition is, for example, 0.1 ≤ [aromatic amine compound from the viewpoint of copper foil adhesion. The number of moles of (A)] / [the number of moles of the aliphatic amine compound (B)] ≦ 10, preferably 0.15 ≦ [the number of moles of the aromatic amine compound (A)] / [the number of moles of the aromatic amine compound] Number of moles of (B)] ≦ 5 is preferable.
Further, the total content of the aromatic amine compound (A) and the aliphatic amine compound (B) in the first thermosetting resin composition maintains the above relationship from the viewpoint of copper foil adhesiveness and moldability. On the other hand, 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 3 to 10 parts by mass per 100 parts by mass of the total solid content-equivalent resin component of the thermosetting resin composition.
In the present specification, the "resin component" is mainly an aromatic amine compound (A), an aliphatic amine compound (B), a siloxane compound (C) and a maleimide compound (D), and is thermosetting. If the resin composition contains at least one of an amine compound (E) having an acidic substituent, a thermoplastic elastoma (F), a thermosetting resin (G), and other resin components, these are also included.
Further, the "solid content" is a non-volatile content excluding volatile substances such as water and a solvent, and the "total of solid content-equivalent resin components" is the resin component in the thermosetting resin composition. It is the amount obtained by converting the total amount into solid content.

The content of the siloxane compound (C) in the first thermosetting resin composition is 100 parts by mass in total of the solid content-equivalent resin components of the thermosetting resin composition from the viewpoint of copper foil adhesiveness and chemical resistance. It is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass.
The content of the maleimide compound (D) in the first thermosetting resin composition is per 100 parts by mass of the total solid content-equivalent resin component of the thermosetting resin composition from the viewpoint of low thermal expansion and high elastic modulus. , 30 to 99 parts by mass, more preferably 40 to 80 parts by mass.

(Amine compound (E) having an acidic substituent)
The first thermosetting resin composition preferably further contains an amine compound (E) having an acidic substituent represented by the following general formula (I).

(In the general formula (I), R ₁ independently represents a hydroxyl group, a carboxy group or a sulfonic acid group which are acidic substituents, and R ₂ independently represents a hydrogen atom and an aliphatic hydrocarbon having 1 to 5 carbon atoms. It represents a hydrogen group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

Specific examples of the amine compound (E) having an acidic substituent include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o. -Aminobenzene sulfonic acid, m-aminobenzene sulfonic acid, p-aminobenzene sulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. Only one type of these may be used, or two or more types may be mixed and used. Among these, for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline in terms of solubility and synthetic yield. Is preferable, and m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance.

When the first thermosetting resin composition contains an amine compound (E) having an acidic substituent, the content thereof is a solid content-equivalent resin component of the thermosetting resin composition from the viewpoint of low thermal expansion. Of the total of 100 parts by mass, 0.5 to 30 parts by mass is preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.

<Second thermosetting resin composition>
Next, the second thermosetting resin composition of the present invention will be described.
The second thermosetting resin composition has a structure derived from the aromatic amine compound (A) having at least two primary amino groups in one molecule and a fat having at least two primary amino groups in one molecule. A maleimide compound having a structure derived from a group amine compound (B), a structure derived from a siloxane compound (C) having at least two primary amino groups at the molecular terminals, and at least two N-substituted maleimide groups in one molecule. It is a thermosetting resin composition containing the structure derived from (D) and an imide resin containing (hereinafter, also simply referred to as "modified imide resin (J)").

(Modified imide resin (J))
The modified imide resin (J) contains a structure derived from the component (A), a structure derived from the component (B), a structure derived from the component (C), and a structure derived from the component (D). Is what you do.

The content of the structure derived from the aromatic amine compound (A) and the structure derived from the aliphatic amine compound (B) in the modified imide resin (J) is, for example, 0.1 ≤ [fragrance] from the viewpoint of copper foil adhesion. The number of moles of the structure derived from the group amine compound (A)] / [the number of moles of the structure derived from the aliphatic amine compound (B)] ≤ 10.0, preferably 0.15 ≤ [aromatic amine compound (A). ) / [Number of moles of structure derived from the aliphatic amine compound (B)] ≤ 5.
The total content of the structure derived from the aromatic amine compound (A) and the structure derived from the aliphatic amine compound (B) in the modified imide resin (J) has the above relationship from the viewpoint of copper foil adhesiveness and moldability. 1 to 40% by mass is preferable, 3 to 25% by mass is more preferable, and 4 to 15% by mass is more preferable.
The content of the structure derived from the siloxane compound (C) in the modified imide resin (J) is preferably 1 to 40% by mass, more preferably 6 to 25% by mass, from the viewpoint of copper foil adhesiveness and chemical resistance.
The content of the structure derived from the maleimide compound (D) in the modified imide resin (J) is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, from the viewpoint of low thermal expansion and high elastic modulus.

Further, the modified imide resin (J) preferably further contains a structure derived from the amine compound (E) having an acidic substituent represented by the general formula (I).
That is, the modified imide resin (J) has a structure derived from the component (A), a structure derived from the component (B), a structure derived from the component (C), and a structure derived from the component (D). It is preferable that the structure is derived from the amine compound (E) component having an acidic substituent.

When the modified imide resin (J) contains a structure derived from the amine compound (E) having an acidic substituent, the content thereof is 0.5 to 0.5 to 0.5 in the modified imide resin (J) from the viewpoint of low thermal expansion. It is preferably 40% by mass, more preferably 1 to 15% by mass, still more preferably 1.5 to 4% by mass.

The content of the modified imide resin (J) in the second thermosetting resin composition is preferably 50 to 100 parts by mass, preferably 60 parts by mass, per 100 parts by mass of the total solid content-equivalent resin component of the thermosetting resin composition. ~ 90 parts by mass is more preferable, and 70 to 85 parts by mass is further preferable. By setting the content of the modified imide resin (J) to 50 parts by mass or more, excellent copper foil adhesiveness, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability can be obtained. Be done.

Further, based on the mass of the second thermosetting resin composition, the structure derived from the aromatic amine compound (A) contained in the second thermosetting resin composition and the structure derived from the aliphatic amine compound (B) are derived. The preferable contents of the structure, the structure derived from the siloxane compound (C), the structure derived from the maleimide compound (D), and the structure derived from the amine compound (E) having an acidic substituent are as follows.
In the second thermosetting resin composition, the total content of the structure derived from the aromatic amine compound (A) and the structure derived from the aliphatic amine compound (B) is determined from the viewpoint of copper foil adhesiveness and moldability. It is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, still more preferably 3 to 10 parts by mass, based on 100 parts by mass of the total solid content-equivalent resin component of the curable resin composition.
The content of the structure derived from the siloxane compound (C) in the second thermosetting resin composition is the sum of the solid content-converted resin components of the thermosetting resin composition from the viewpoint of copper foil adhesiveness and chemical resistance. 1 to 30 parts by mass is preferable, and 5 to 20 parts by mass is more preferable, per 100 parts by mass.
In the second thermosetting resin composition, the content of the structure derived from the maleimide compound (D) is a total of 100 solid content-equivalent resin components of the thermosetting resin composition from the viewpoint of low thermal expansion and high elastic modulus. It is preferably 30 to 99 parts by mass, more preferably 40 to 80 parts by mass, per part by mass.
When the second thermosetting resin composition contains a structure derived from the amine compound (E) having an acidic substituent, the content of the structure derived from the amine compound (E) having an acidic substituent is low thermal expansion. From this point of view, 0.5 to 30 parts by mass is preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable, per 100 parts by mass of the total solid content-equivalent resin component of the thermosetting resin composition. ..

Next, a method for producing the modified imide resin (J) will be described.

(Manufacturing method of modified imide resin (J))
The modified imide resin (J) contains an aromatic amine compound (A), an aliphatic amine compound (B), a siloxane compound (C), a maleimide compound (D), and an amine compound (E) having an acidic substituent, if necessary. It can be produced by reacting (hereinafter, the reaction is also simply referred to as "pre-reaction"). By this pre-reaction, the molecular weight of the modified imide resin (J) can be controlled, and low curing shrinkage and low thermal expansion can be improved.
The conditions of the pre-reaction will be described below.

Regarding the amount of each component used in the pre-reaction, for example, the number of maleimide groups of the maleimide compound (D) [the amount of the component (D) used / the equivalent of the maleimide group of the component (D)] is the aromatic amine compound (A) and the fat. Total number of primary amino groups of group amine compound (B) and siloxane compound (C) [(Amount of component (A) used / primary amine equivalent of component (A)) + (amount of component (B) used / (B)) The range is preferably 2.0 to 10.0 times the primary amine equivalent of the component) + (the amount of the component (C) used / the primary amino group equivalent of the component (C))]. When it is 2.0 times or more, excellent heat resistance is obtained without gelation, and when it is 10.0 times or less, excellent solubility in an organic solvent and heat resistance can be obtained.

Further, the amount of the maleimide compound (D) used in the pre-reaction is preferably 50 to 3000 parts by mass and 100 to 1500 parts by mass with respect to 100 parts by mass of the siloxane compound (C) while maintaining the above relationship. Part is more preferable. When the amount is 50 parts by mass or more, excellent heat resistance can be obtained, and when the amount is 3000 parts by mass or less, low thermal expansion property can be kept good.

When the modified imide resin (J) contains a structure derived from the amine compound (E) having an acidic substituent, the amount of each component used in the prereaction is the number of maleimide groups of the maleimide compound (D) [(D). ) Component usage amount / Maleimide group equivalent of component (D)] of the aromatic amine compound (A), aliphatic amine compound (B), siloxane compound (C) and amine compound (E) having an acidic substituent. Total number of primary amino groups [((A) component used / (A) component primary amine equivalent) + ((B) component used / (B) component primary amine equivalent) + ((C) component Amount used / primary amino group equivalent of component (C)) + (amount used of component (E) / primary amine equivalent of component (E))] is preferably in the range of 2.0 to 10.0 times. .. When it is 2.0 times or more, gelation and deterioration of heat resistance can be suppressed, and when it is 10.0 times or less, solubility in an organic solvent and deterioration of heat resistance can be suppressed. ..

When the modified imide resin (J) contains a structure derived from the amine compound (E) having an acidic substituent, the content thereof is 100 parts by mass of the siloxane compound (C) while maintaining the above relationship. On the other hand, 1 to 100 parts by mass is preferable, and 3 to 30 parts by mass is more preferable. Good heat resistance can be obtained by setting the amount to 1 part by mass or more, and low thermal expansion property can be kept good by setting the amount to 100 parts by mass or less.

The pre-reaction is preferably carried out while being heated and kept warm in an organic solvent.
The reaction temperature is, for example, preferably 70 to 150 ° C, more preferably 100 to 130 ° C. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours, for example.

The organic solvent used in the pre-reaction is, for example, an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; acetic acid. Ester-based solvents such as ethyl ester and γ-butyrolactone; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; dimethylsulfoxide Such as sulfur atom-containing solvent and the like. Only one type of these may be used, or two or more types may be mixed and used.
Among these organic solvents, for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone is low in toxicity and is highly volatile and does not easily remain as a residual solvent. , Propylene glycol monomethyl ether and dimethylacetamide are preferred.

The amount of the organic solvent used is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, still more preferably 40 to 500 parts by mass, based on 100 parts by mass of the total of each raw material component of the pre-reaction. .. 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 reaction catalyst can be optionally used for the pre-reaction. Examples of the reaction catalyst include amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; phosphorus catalysts such as triphenylphosphine; alkali metal amides such as lithium amide, sodium amide and potassium amide. And so on. Only one type of these may be used, or two or more types may be mixed and used.

In addition to the modified imide resin (J), the second thermosetting resin composition further comprises an aromatic amine compound (A), an aliphatic amine compound (B), a siloxane compound (C), a maleimide compound (D), and the like. It may contain one or more selected from the group consisting of the amine compound (E) having an acidic substituent. In this case, the total content of each component and the structural unit derived from each component may be within the range of the content of the structural unit derived from each component based on the mass of the second thermosetting resin composition. preferable.

Next, other components that can be contained in the first thermosetting resin composition and the second thermosetting resin composition of the present invention will be described.

<Other ingredients>
The thermosetting resin composition of the present invention has good thermosetting reactivity, but if necessary, it contains a curing agent and / or a polymerization initiator to further improve heat resistance, adhesiveness and mechanical strength. be able to.

(Polymerization initiator)
As the polymerization initiator, a radical polymerization initiator is preferable, and organic peroxides such as acyl peroxide, hydroperoxide, ketone peroxide, organic peroxide having a t-butyl group, and peroxide having a cumyl group are used. Examples include oxides. Only one type of these may be used, or two or more types may be mixed and used.

(Thermoplastic elastomer (F))
The thermosetting resin composition of the present invention may further contain a thermoplastic elastomer (F).
Examples of the thermoplastic elastomer (F) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, siloxane-based elastomers, and derivatives thereof. These consist of a hard segment component and a soft segment component, and the former generally contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. Only one type of these may be used, or two or more types may be mixed and used. Among these, for example, styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers and siloxane-based elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene-based elastomers and olefin-based elastomers are more preferable from the viewpoint of dielectric properties. ..

As the thermoplastic elastomer (F), one having a reactive functional group at the molecular terminal 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.

When the thermosetting resin composition of the present invention contains a thermoplastic elastomer (F), the content of the thermoplastic elastomer (F) is per 100 parts by mass of the total solid content-equivalent resin component of the thermosetting resin composition. , 0.1 to 50 parts by mass, more preferably 2 to 30 parts by mass. By setting the content of the thermoplastic elastomer (F) within the above range, it is possible to effectively exhibit excellent moldability, low curing shrinkage, low thermal expansion, and excellent dielectric properties of the cured product.

(At least one thermosetting resin (G) selected from epoxy resin and cyanate resin)
The thermosetting resin composition of the present invention further contains at least one thermosetting resin (G) selected from an epoxy resin and a cyanate resin (hereinafter, also simply referred to as "thermosetting resin (G)"). May be.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol F novolac type epoxy resin. , Stilben type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy Examples thereof include resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracene, and phosphorus-containing epoxy resins in which a phosphorus compound is introduced therein. Only one type of these may be used, or two or more types may be mixed and used. Among these, naphthol type epoxy resin, biphenyl aralkyl type epoxy resin and naphthalene type epoxy resin are preferable from the viewpoint of heat resistance and flame retardancy.
Examples of the cyanate resin include bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and prepolymers in which these are partially triazined. Be done. Only one type of these may be used, or two or more types may be mixed and used. Among these, novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.

When the thermosetting resin composition of the present invention contains a thermosetting resin (G), the content of the thermosetting resin (G) is the thermosetting resin composition from the viewpoint of heat resistance and chemical resistance. 1 to 50 parts by mass, more preferably 8 to 30 parts by mass, per 100 parts by mass of the total solid content-equivalent resin component.

When the thermosetting resin composition of the present invention contains a thermosetting resin (G), the thermosetting resin composition of the present invention contains a curing agent of the thermosetting resin (G), if necessary. May be.
Examples of the curing agent include polyfunctional phenol compounds such as phenol novolac, cresol novolac, and aminotriazine novolac resin; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride, maleic anhydride, and the like. Examples thereof include acid anhydrides such as maleic anhydride copolymers. Only one type of these may be used, or two or more types may be mixed and used.

(Inorganic filler (H))
The thermosetting resin composition of the present invention may further contain an inorganic filler (H).
Examples of the inorganic filler (H) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, and sulfuric acid. Examples thereof include barium, aluminum borate, potassium titanate, glass powder, hollow glass beads and the like. As the glass, E glass, T glass, D glass and the like are preferably mentioned. Only one type of these may be used, or two or more types may be mixed and used.
Among these, for example, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. 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, as the dry method silica, crushed silica, fumed silica, molten silica (molten spherical silica) and the like can be mentioned depending on the difference in the manufacturing method. Among these, spherical silica is preferable, and molten spherical silica is more preferable because of its low thermal expansion property and high fluidity when filled in a resin.

When silica is used as the inorganic filler (H), its average particle size is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm. By setting the average particle size of silica to 0.1 μm or more, it is possible to maintain good fluidity when the resin is highly filled, and by further setting it to 10 μm or less, the probability of mixing coarse particles is reduced and it is caused by coarse particles. It is possible to suppress the occurrence of defects. 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 (H), the content thereof is 20 to 300 parts by mass per 100 parts by mass of the total solid content-equivalent resin component of the thermosetting resin composition. Is preferable, and 50 to 250 parts by mass is more preferable. By setting the content of the inorganic filler (H) within the above range, the moldability and low thermal expansion property of the thermosetting resin composition can be kept good.

When the inorganic filler (H) is blended with the thermosetting resin composition, for example, the inorganic filler (H) is used as a coupling agent such as a silane type or a titanate type, or a surface treatment agent such as a silicone oligomer. Pretreatment or integral blending treatment is also preferable.

(Curing accelerator (I))
The thermosetting resin composition of the present invention may further contain a curing accelerator (I).
Examples of the curing accelerator (I) include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III); Examples thereof include imidazoles and derivatives thereof; organic phosphorus compounds such as phosphines and phosphonium salts; secondary amines, tertiary amines, quaternary ammonium salts and the like. Only one type of these may be used, or two or more types may be mixed and used. Among these, for example, zinc naphthenate, an imidazole derivative, and a phosphonium salt are preferable from the viewpoint of curing promoting effect and storage stability.

When the thermosetting resin composition of the present invention contains a curing accelerator (I), the content thereof is 0.01 to 3 per 100 parts by mass of the total solid content-equivalent resin component of the thermosetting resin composition. .0 parts by mass is preferable, and 0.05 to 1.5 parts by mass is more preferable. By setting the content of the curing accelerator (I) within the above range, the curing promoting effect and storage stability can be kept good.

The thermosetting resin composition of the present invention is optionally known as a thermoplastic resin, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, and an optical brightener within a range not contrary to the object thereof. It may contain a whitening agent, an adhesiveness improver and the like.

Examples of the thermoplastic resin include polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin silicone resin and the like.

Examples of the organic filler include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin and the like; acrylic acid ester resin, methacrylic acid ester resin, conjugated diene resin and the like. Examples thereof include a resin filler having a core-shell structure having a core layer in a rubber state and a shell layer in a glass state made of an acrylic acid ester resin, a methacrylate ester resin, an aromatic vinyl resin, a vinyl cyanide resin and the like.

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

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.

(Organic solvent)
The thermosetting resin composition of the present invention preferably contains 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.
Examples of the organic solvent used for producing the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylen; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Examples thereof include a sulfur atom-containing solvent such as dimethyl sulfoxide. Only one type of these may be used, or two or more types may be mixed and used.
Among these, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity. preferable.
The solid content of the thermosetting resin composition in the varnish is, for example, preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the entire varnish. By setting the solid content of the thermosetting resin composition in the varnish within the above range, it is possible to maintain good coatability and obtain a prepreg and a film with a resin to which an appropriate amount of the thermosetting resin composition is attached. it can.

[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. The prepreg of the present invention containing the thermosetting resin composition can be produced.

The method of impregnating the base material with the thermosetting resin composition of the present invention is not particularly limited, and examples thereof include a method of immersing the base material in the varnish, a method of applying with various coaters, and a method of spraying with a spray. .. Among these, the method of immersing the base material in the varnish is preferable from the viewpoint of impregnation property.

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.
The base material is preferably surface-treated with a silane coupling agent or the like or mechanically opened, from the viewpoint of heat resistance, moisture resistance and processability.
The thickness of the base material can be, for example, in the range of about 0.03 to 0.5 mm.

In the prepreg of the present invention, for example, the amount of solid content of the thermosetting resin composition attached to the substrate is preferably 20 to 90% by mass in terms of the content of the thermosetting resin composition to the prepreg after drying.
The prepreg of the present invention is, for example, after impregnating or coating a base material with the thermosetting resin composition of the present invention so that the amount of solid 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 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

[Film with resin]
The film with resin of the present invention contains the thermosetting resin composition of the present invention.
The resin-attached film of the present invention is, for example, formed by forming a layer of the thermosetting resin composition of the present invention on a support.
The method for forming the layer is not particularly limited, but for example, the thermosetting resin composition obtained in the present invention is made into a varnish, applied to a film as a support using various coaters, and further heated. The organic solvent in the varnish is volatilized by drying by blowing hot air or the like, and the thermosetting resin composition is semi-cured (B-staged), and the thermosetting resin composition of the present invention is placed on the support. It can be produced by forming a resin composition layer.
The resin-attached 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.

The drying conditions after applying the thermosetting resin composition of the present invention to the support are, for example, a condition that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. can do. The drying conditions vary depending on the amount of the organic solvent in the varnish, the boiling point of the organic solvent, etc., but 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 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-attached 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 making the printed wiring board lighter, thinner, shorter, and smaller. Therefore, the thickness of the resin composition layer can be, for example, 5 μm or more, and is, for example, 80 μm or less, preferably in the range of 60 μm or less, more preferably 40 μm or less from the viewpoint of thinning. , The thickness may be greater than or equal to the thickness of the conductor layer.

The support in the resin-attached film of the present invention includes a film made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter also referred to as "PET"), polyester such as polyethylene naphthalate, polycarbonate and polyimide; Pattern: Examples include metal foils such as copper foil and 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 can be further 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-attached 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-coated film of the present invention.
Hereinafter, the method for producing the laminated board of the present invention will be described in detail. In the laminated board of the present invention, a layer made of a cured product of the prepreg of the present invention or a cured product of a resin-coated film may be referred to as an "insulating resin layer".

Examples of the method for forming a laminated plate 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 printed wiring board manufactured from the laminated board, a conductor layer (circuit) in which one or both sides of the outermost layer of the printed wiring board is patterned. ) 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 film with resin 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-attached film on the circuit board, cooling it to around room temperature, peeling the support, and then heat-curing the support. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition layer of the resin-coated film, and are selected, for example, in the range of 20 to 180 minutes at 150 to 220 ° C. , Preferably selected in the range of 30 to 120 minutes at 160 to 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 by, for example, a drill, a laser, a plasma, or a combination method thereof. 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.
The laminated board of the present invention can be produced by laminating and molding the prepreg of the present invention. In this case, the laminated board of the present invention contains an insulating resin layer obtained by curing the prepreg of the present invention.
For example, a laminated board can be manufactured by laminating 1 to 20 sheets of the prepreg of the present invention and laminating and molding a metal foil such as copper or 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 electrically insulating material and a multilayer plate can be applied, and a temperature of 100 to 250 ° C. and a pressure of 0.2 are used by using a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, or the like. It can be molded under the conditions of 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.

[Printed circuit board]
The printed wiring board of the present invention contains the laminated board of the present invention.
The printed wiring board of the present invention can be manufactured by circuit-processing a conductor layer (metal leaf) 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 printed wiring board of the present invention can be manufactured through the formation of through holes or blind via holes by drilling or laser processing 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 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 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.
Using the copper-clad laminates obtained in each example, the glass transition temperature, coefficient of thermal expansion, copper foil adhesiveness, heat resistance of solder with copper, flexural modulus and moldability were measured and evaluated by the following methods. did.

(1) 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 was obtained. The product was prepared and subjected to thermomechanical analysis by a compression method using a TMA test device (manufactured by TA Instruments, trade name: Q400). The thermomechanical analysis is performed twice in succession under the conditions of a load of 5 g and a heating rate of 10 ° C./min after mounting the evaluation substrate on the apparatus in the X direction, and is indicated by the intersection of different tangents of the second thermal expansion curve. The glass transition temperature (Tg) was determined.

(2) 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) (Direction) evaluation substrate was prepared, and thermomechanical analysis was performed by a compression method using a TMA test device (manufactured by TA Instruments, trade name: Q400). The thermomechanical analysis is performed twice continuously under the conditions of a load of 5 g and a heating rate of 10 ° C./min after mounting the evaluation substrate on the apparatus in the X direction, and the average from 30 ° C. to 100 ° C. in the second analysis. The coefficient of thermal expansion was calculated and used as the value of the coefficient of thermal expansion (linear expansion rate).

(3) Copper foil adhesiveness (copper foil peel strength)
The copper-clad laminates obtained in each example are formed with a resist having a width of 3 mm on the outer layer copper foil, and then immersed in a copper etching solution to obtain an evaluation substrate having an outer layer copper foil having a width of 3 mm as a peel strength measuring unit. Made. Peel off one end of the copper foil of the adhesive strength measuring part at the interface between the copper foil and the substrate, grasp it with a gripper, and use a tensile tester (manufactured by Shimadzu Corporation, product name: Autograph S-100) to make it vertical. The pulling speed in the direction was 50 mm / min, and the load when peeled off at room temperature was measured.

(4) 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 10 minutes to visually check the appearance of the evaluation substrate. The heat resistance of the solder with copper was evaluated.

(5) Bending elastic modulus A 25 mm × 50 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.

(6) Moldability Two prepregs obtained in each example are stacked, copper foils having a thickness of 12 μm are placed on both sides thereof, and pressed for 85 minutes at a pressure of 3.0 MPa and a temperature of 250 ° C. using a multi-stage vacuum press. As a result, a copper-clad laminate was produced. The copper foil of the obtained copper-clad laminate was removed by etching, and the appearance of the cured prepreg was visually observed to evaluate the moldability.

[Manufacturing of modified imide resin]
Manufacturing Example 1
(Manufacture of Modified Imide Resin 1)
3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.,) in a reaction vessel with a volume of 1 liter that can be heated and cooled with a thermometer, agitator, and a water content meter with a reflux cooling tube. Product name: KAYAHARD A-A) 16.23 g, 2,2,4-trimethylhexamethylenediamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 1.44 g, both-terminal amino-modified siloxane (Momentive Performance Materials Japan GK) , Amino group functional group equivalent 1280 g / mol, trade name: XF42-C5742) 47.9 g, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane 248.39 g (manufactured by Daiwa Kasei Kogyo Co., Ltd.) , Trade name: BMI-4000), p-aminophenol (manufactured by Kanto Chemical Co., Ltd.) 5.94 g, propylene glycol monomethyl ether 459.43 g were added, reacted at 115 ° C. for 4 hours, and then heated to 130 ° C. The mixture was concentrated at atmospheric pressure to obtain a modified imide resin 1-containing solution (resin component content: 60% by mass).

Production Examples 2 to 6, Production Comparative Examples 1 to 2
(Manufacture of Modified Imide Resins 2-8)
In Production Example 1, a modified imide resin 2-8-containing solution (resin component content: 60% by mass) was obtained in the same manner as in Production Example 1 except that the amount of each raw material used was changed as shown in Table 1. ) Was obtained respectively.

Manufacturing Comparative Example 3
(Manufacturing of modified imide resin 9)
In Production Example 1, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A) was not used, and 2,2,4-trimethyl-hexa was used. Di-p-aminobenzoic acid polytetramethylene oxide (manufactured by Ihara Chemical Co., Ltd., trade name: Erasmer 1000P) was used instead of methylenediamine, except that the amount of each raw material used was changed as shown in Table 1. A modified imide resin 9-containing solution (resin component content: 60% by mass) was obtained in the same manner as in Production Example 1.

Examples 1-6, Comparative Examples 1-3
(Manufacturing of copper-clad laminates)
Each component shown in Table 2 and methyl ethyl ketone were mixed to obtain a varnish having a solid content of 65% by mass.
The varnish was impregnated and coated on an S 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 solid content of 45% by mass in the thermosetting resin composition. Next, four of these prepregs were stacked, electrolytic copper foils having a thickness of 12 μm were arranged one above the other, and pressed at a pressure of 3.0 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate. Table 2 shows the evaluation results of the obtained copper-clad laminate.

The raw materials used in each example are as follows.

Aromatic amine compound (A)
-KAYAHARD A-A: 3,3'-diethyl-4,4'-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name]

Aliphatic amine compound (B)
・ 2,2,4-trimethylhexamethylenediamine [manufactured by Tokyo Chemical Industry Co., Ltd.]
-Erasmer 1000P: Polytetramethylene oxide of di-p-aminobenzoate [manufactured by Ihara Chemical Industry, trade name]

Siloxane compound (C)
-XF42-C5742: Amine-modified siloxane at both ends [Momentive Performance Materials Japan, Inc., trade name]

Maleimide compound (D)
-BMI-4000: 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane [manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name]

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

Thermoplastic elastomer (F)
-Tough Tech M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin [manufactured by Asahi Kasei Chemicals Co., Ltd., trade name]

Thermosetting resin (G)
-HP-9540-P02: Naftor type epoxy resin [manufactured by DIC Corporation, trade name]

Inorganic filler (H)
-SC2050-KNK: Fused spherical silica [manufactured by Admatex Co., Ltd., average particle size 0.5 μm, trade name]
-KEMGARD2200: Zinc molybdate [manufactured by Sherwin Williams, trade name]

Curing accelerator (I)
-TBP2: Addition reaction product of p-benzoquinone and tri-n-butylphosphine [manufactured by Kurokin Kasei Co., Ltd., trade name]

As is clear from Table 2, the copper-clad laminates obtained in Examples 1 to 6 of the present invention have a glass transition temperature, a coefficient of thermal expansion, copper foil adhesiveness, heat resistance to copper solder, elastic modulus and moldability. Excellent in all of. On the other hand, Comparative Examples 1 and 3 did not satisfy all of the glass transition temperature, the coefficient of thermal expansion, the copper foil adhesiveness, the heat resistance of the solder with copper, the elastic modulus, and the moldability, and were inferior in any of the characteristics. Further, in Comparative Example 2, the evaluation substrate could not be produced due to the molding defect, and the glass transition temperature, the coefficient of thermal expansion, the heat resistance of the solder with copper, and the elastic modulus could not be measured.

The thermosetting resin composition of the present invention and the laminated board containing the cured product of the prepreg and the resin-attached film containing the thermosetting resin composition have excellent copper foil adhesiveness, low thermal expansion, and low curing shrinkage. It has heat resistance (solder heat resistance), elasticity and moldability, and is useful as a highly integrated semiconductor package and printed wiring board for electronic devices.

Claims (17)

An aromatic amine compound (A) having at least two primary amino groups in one molecule, an aliphatic amine compound (B) having at least two primary amino groups in one molecule, and at least two at the end of the molecule. A thermosetting resin composition containing a siloxane compound (C) having a primary amino group and a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule. The thermosetting resin composition according to claim 1, further comprising an amine compound (E) having an acidic substituent represented by the following general formula (I).

(In the general formula (I), R ₁ independently represents a hydroxyl group, a carboxy group or a sulfonic acid group which are acidic substituents, and R ₂ independently represents a hydrogen atom and an aliphatic hydrocarbon having 1 to 5 carbon atoms. It represents a hydrogen group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.) A structure derived from an aromatic amine compound (A) having at least two primary amino groups in one molecule, and a structure derived from an aliphatic amine compound (B) having at least two primary amino groups in one molecule. It contains a structure derived from a siloxane compound (C) having at least two primary amino groups at the end of a molecule and a structure derived from a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule. Iimide resin. Further contains a structure derived from the amine compound (E) having an acidic substituent represented by the following formula (I), the imide resin according to claim 3.

(In the general formula (I), R ₁ independently represents a hydroxyl group, a carboxy group or a sulfonic acid group which are acidic substituents, and R ₂ independently represents a hydrogen atom and an aliphatic hydrocarbon having 1 to 5 carbon atoms. It represents a hydrogen group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.) An aromatic amine compound (A) having at least two primary amino groups in one molecule, an aliphatic amine compound (B) having at least two primary amino groups in one molecule, and at least two at the end of the molecule. A method for producing an imide resin, in which a siloxane compound (C) having a primary amino group and a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule are reacted. Wherein the component (A), wherein the component (B), wherein the component (C), wherein the component (D), an amine compound having an acidic substituent represented by the following general formula (I) and (E), The method for producing an imide resin according to claim 5, wherein the imide resin is reacted.

(In the general formula (I), R ₁ independently represents a hydroxyl group, a carboxy group or a sulfonic acid group which are acidic substituents, and R ₂ independently represents a hydrogen atom and an aliphatic hydrocarbon having 1 to 5 carbon atoms. It represents a hydrogen group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.) A thermosetting resin composition containing the imide resin according to claim 3 or 4. The thermosetting resin composition according to claim 7 , further comprising a thermoplastic elastomer (F). The thermosetting resin composition according to claim 7 or 8 , further comprising an epoxy resin. The thermosetting resin composition according to any one of claims 7 to 9, further comprising an inorganic filler (H). The thermosetting resin composition according to any one of claims 7 to 10, further comprising a curing accelerator (I). A prepreg containing the thermosetting resin composition according to any one of claims 7 to 11. A film with a resin containing the thermosetting resin composition according to any one of claims 7 to 11. A laminated board containing a cured product of the prepreg according to claim 12. A laminated board containing a cured product of the film with resin according to claim 13. A printed wiring board containing the laminated board according to claim 14 or 15. A semiconductor package containing the printed wiring board according to claim 16.