JP2017178991A - Thermosetting resin composition, prepreg using the same, film with resin, laminate, printed wiring board and semiconductor package, imide resin and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in copper foil adhesiveness, low thermal expansion property, low curing shrinkage property, heat resistance (solder heat resistance), elastic modulus and moldability.SOLUTION: There is provided a thermosetting resin composition containing an aromatic amine compound having at least 2 primary amino groups in one molecule (A), an aliphatic amine compound having at least 2 primary amino groups in one molecule (B), a siloxane compound having at least 2 primary amino groups at a molecular terminal (C), a maleimide compound having at least 2 N-substituted maleimide groups in one molecule (D).SELECTED DRAWING: None

Description

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

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

As a laminated board for printed wiring boards, a prepreg containing a resin composition mainly composed of an epoxy resin and glass cloth is cured and integrally formed.
Epoxy resin has an excellent balance of insulation, heat resistance, cost, etc., but further improvements are needed to meet the demand for higher heat resistance due to the recent high-density mounting of printed wiring boards and higher multi-layer configurations. It becomes.

  Further, particularly in recent years, with semiconductor package substrates, warping due to the difference in thermal expansion coefficient between the chip and the substrate has become a major issue at the time of component mounting and package assembly as the size and thickness are reduced. For this reason, a laminated board for use in a semiconductor package substrate is required to have good low thermal expansion. However, since an epoxy resin has a large coefficient of thermal expansion, an epoxy resin having an aromatic ring and an inorganic filler such as silica are used. The low thermal expansion property is achieved by increasing the filling of (see, for example, Patent Document 1). However, increasing the filling amount of the inorganic filler is known to cause a decrease in insulation reliability due to moisture absorption, insufficient adhesion between the resin and the wiring layer, poor press molding, etc. There was a limit to the reduction in thermal expansion due to the use of only.

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

Japanese Patent Laid-Open No. 5-148343 JP 2014-129521 A

However, although the siloxane-modified imide resin is excellent in low thermal expansibility, further improvement in adhesiveness is desired.
In view of the current situation, the present invention provides a thermosetting resin composition excellent in copper foil adhesion, low thermal expansion, low cure shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability, and a prepreg using the same. It is an object of the present invention to provide a film with resin, a laminate, a printed wiring board, a semiconductor package, an imide resin used in 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 an amine compound used in combination with a maleimide resin. As a result, the inventors have found that the above object can be achieved, and have completed the present invention.

  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 manufacturing method thereof.

[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 end A thermosetting resin composition comprising 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 [1], further including an amine compound (E) having an acidic substituent represented by the following general formula (I).

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

  According to the present invention, a thermosetting resin composition excellent in copper foil adhesiveness, low thermal expansion, low cure shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability, prepreg using the same, and with resin A film, a laminated board, a printed wiring board, a semiconductor package, an imide resin, and a manufacturing method thereof can be provided.

[Thermosetting resin composition]
The present invention discloses the following thermosetting resin compositions [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 end A thermosetting resin composition comprising 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, a structure derived from a siloxane compound (C) having at least two primary amino groups at the molecular terminals, and a structure derived from a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule; A thermosetting resin composition containing an imide resin containing
Hereinafter, the thermosetting resin composition of [1] is referred to as “first thermosetting resin composition”, and the thermosetting resin composition of [2] is referred to as “second thermosetting resin composition”. ".
In addition, when only calling it a "thermosetting resin composition", it shall refer to both a "first thermosetting resin composition" and a "second thermosetting resin composition".

<First thermosetting resin composition>
The first thermosetting resin composition comprises an aromatic amine compound (A) having at least two primary amino groups in one molecule (hereinafter referred to as “aromatic amine compound (A)” or “(A) component”). 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 “(B) component”), a molecule Siloxane compound (C) having at least two primary amino groups at its 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 “(D) component”).

(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).

^{(Wherein, A 11} is a group represented by the following general formula (1-1) or (1-2).)

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

(In the formula, R ¹² and R ¹³ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (1-3): q and r are each independently an integer of 0 to 4. .)

(Wherein R ¹⁴ and R ¹⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹³ is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s and t are each independently an integer 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. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among these, R ¹¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 2, from the viewpoint of availability. When p is an integer of 2 or more, the plurality of R ¹¹ may be the same or different.

In the general formula (1-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ¹² and R ¹³ include the same as those in the case of R ¹¹ . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and still more preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by A ¹² include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of copper foil adhesion, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability. More preferred is a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by A ¹² include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoints of copper foil adhesion, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus, and moldability.
A ¹² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
q and r are each independently an integer of 0 to 4, and are each preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability. If q or r is an integer of 2 or more, plural R ¹² s or R ¹³ together may each be the same or different.

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

A ¹¹ in the general formula (1) is represented by any of the following formulas from the viewpoints of copper foil adhesion, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus, and moldability. More preferably, the group is

  Specific examples of the aromatic amine compound (A) include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, 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'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis (3-amino- -Hydroxyphenyl) propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- ( 4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4, 4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9,9-bis (4-aminophenyl) ) Fluorene and the like. These may be used alone or in combination of two or more.

  Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-, because of 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 preferred, and is inexpensive and has 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. Furthermore, 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are preferred from the viewpoint of low thermal expansion and dielectric properties. Further, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene capable of increasing the elastic modulus are also preferable.

(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)

R ₂₁ and the carbon number of the aliphatic hydrocarbon group having 1 to 5 _carbon atoms _{R 22} represents preferably 1 to 4, more preferably 1 to 3, 1 or 2 is more preferred.
As said C1-C5 aliphatic hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, etc. are mentioned, 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, and an n-pentyl group. 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 achieving low thermal expansion.

  Moreover, it is preferable that an aliphatic amine compound (B) is 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).)

  2-20 are preferable, as for carbon number of an aliphatic amine compound (B), 5-15 are more preferable, and 7-12 are more preferable.

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-oxadiazol, bis (4-aminocyclohexyl) me And the like. These may be used alone or in combination of two or more. Among these, hexamethylenediamine and 2,2,4-trimethylhexamethylenediamine are preferable from the viewpoint of obtaining better moldability.

(Siloxane compound (C) having at least two primary amino groups at the molecular terminals)
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 represents an alkyl group, a phenyl group or a substituted phenyl group, and m represents an integer of 2 to 100.)

The alkyl group represented by R ₃₁ and R ₃₂ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably an alkyl group having 1 or 2 carbon atoms.
Specific examples of the alkyl group represented by R ₃₁ and R ₃₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. Of these, a methyl group is preferred.
Examples of the substituent in the substituted phenyl group represented by R ₃₁ and R ₃₂ include an alkyl group, an alkenyl group, and an alkynyl group, and among these, an alkyl group is preferable. The alkyl group is preferably the same as described above.
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 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.

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

(Wherein R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and R ₃₅ and R ₃₆ each independently represents a divalent organic group. M 'represents an integer of 1 to 100.)

The alkyl group, phenyl group or substituted phenyl group represented by R _31, R ₃₂ , R ₃₃ and R ₃₄ is the same as 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, and a propylene group. Examples of the arylene group include a phenylene group and a naphthylene group.
m ′ is 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 terminals 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 ”(amino group functional group equivalent 700),“ X-22-1660B-3 ”(amino group functional group equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.),“ BY-16-853U ”( Functional group equivalent of amino group 460), “BY-16-853” (functional group equivalent of amino group 650), “BY-16-853B” (functional group equivalent of amino group 2200) (above, Toray Dow Corning “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) ( As mentioned above, Momentive Performance Materials Japan GK) etc. are mentioned (the unit of the functional group equivalent of an amino group is g / mol). These may be used alone or in combination of two or more.
Among these, for example, “X-22-161A”, “X-22-161B”, “KF-8012”, “X-22-1660B-” are high in reactivity at the time of synthesis and can be reduced in thermal expansion. 3 ”,“ XF42-C5379 ”,“ XF42-C6252 ”, and“ XF42-C5742 ”are preferable, and“ X-22-161A ”,“ X-22-161B ”are excellent in terms of compatibility and high elastic modulus. ”,“ XF42-C6252 ”, and“ XF42-C5742 ”are more preferable, and“ XF42-C6252 ”and“ XF42-C5742 ”are more 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 maleimide having two N-substituted maleimide groups in one molecule A compound is preferable, and a compound represented by the following general formula (4) is more preferable.

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

(In the formula, each R ⁴¹ is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P2 is an integer of 0 to 4.)

(In the formula, R ⁴² and R ⁴³ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ⁴² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (4-5): q2 and r2 are each independently an integer of 0 to 4. .)

(In the formula, R ⁴⁴ and R ⁴⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ⁴³ is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s2 and t2 are each independently an integer of 0 to 4.)

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

(Wherein 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. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among these, R ⁴¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p2 is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability. When p2 is an integer of 2 or more, the plurality of R ⁴¹ may be the same or different.

In the general formula (4-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁴² and R ⁴³ include 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 still more preferably an ethyl group.
As the alkylene group having 1 to 5 carbon atoms which A ⁴² represents, for example, methylene, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of copper foil adhesion, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability. More preferred is a methylene group.
The alkylidene group having 2 to 5 carbon atoms which A ⁴² represents, for example, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, an isopropylidene group is preferable from the viewpoints of copper foil adhesion, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus, and moldability.
The A ^42, among the above options, an alkylene group having 1 to 5 carbon atoms, alkylidene group having 2 to 5 carbon atoms preferred. More preferred are as described above.
q2 and r2 are each independently an integer of 0 to 4, and are each preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability. If q2 or r2 is an integer of 2 or more, plural R ⁴² s or R ⁴³ together may each be the same or different.

In the general formula (4-5), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁴⁴ and R ⁴⁵ include the same as those in the case of R ⁴² and R ^43. Is the same.
Alkylene group having 1 to 5 carbon atoms which A ⁴³ represents, alkylidene group having 2 to 5 carbon ^atoms, alkylene group of 1 to 5 carbon atoms ^{which A 42} represents, include the same ones as the alkylidene group having 2 to 5 carbon atoms The preferred ones are the same.
A ⁴³ is preferably an alkylidene group having 2 to 5 carbon atoms among the above options, and more preferred is as described above.
s2 and t2 are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. 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, and preferably 1 to 5, 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 and the halogen atom represented by R ⁴⁶ and R ⁴⁷ are the same as in the case of R ^{41 in} the general formula (4-1). And preferred ones are the same.
u2 is an integer of 1 to 8, preferably 1 to 3, and more preferably 1.

Incidentally, in the general formula (4), the A ^41, the heat resistance, adhesiveness, glass transition temperature (Tg), low thermal expansion, elastic modulus, from the viewpoint of low curing shrinkage and high frequency characteristics, the formula ( It is preferable that it is group represented by 4-2), and it is more preferable that it is 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).)

A ⁴¹ in the general formula (4) is any one of the following formulas from the viewpoint of copper foil adhesion, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus, and moldability. It is preferable that it is group represented.

Specific examples of the maleimide compound (D) include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl- 5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) Examples include propane. These may be used alone or in combination of two or more.
Among these, for example, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, and 2,2-bis (4- (4-maleimide) are highly reactive and can have higher heat resistance. Phenoxy) phenyl) propane is preferred, and bis (4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferred 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 adhesiveness. The number of moles of (A)] / [number of moles of aliphatic amine compound (B)] ≦ 10, preferably 0.15 ≦ [number of moles of aromatic amine compound (A)] / [aliphatic amine compound] It is preferable that the number of moles of (B)] ≦ 5.
In the first thermosetting resin composition, the total content of the aromatic amine compound (A) and the aliphatic amine compound (B) maintains the above relationship from the viewpoint of copper foil adhesiveness and moldability. Meanwhile, 1 to 30 parts by mass is preferable, 2 to 20 parts by mass is more preferable, and 3 to 10 parts by mass is more preferable per 100 parts by mass of the total solid 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. When the resin composition contains at least one of an amine compound (E) having an acidic substituent, a thermoplastic elastomer (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 resin components in terms of solid content” is the resin component in the thermosetting resin composition. This is the total amount converted to solid content.

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

(Amine compound having an acidic substituent (E))
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), each R ₁ independently represents a hydroxyl group, a carboxy group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom, an aliphatic carbon atom having 1 to 5 carbon atoms. 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 -Aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like. These may be used alone or in combination of two or more. Among these, for example, from the viewpoint of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline. 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 is a resin component in terms of solid content of the thermosetting resin composition from the viewpoint of low thermal expansion. Is preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1 to 5 parts by weight per 100 parts by weight of the total.

<Second thermosetting resin composition>
Next, the 2nd thermosetting resin composition of this invention is demonstrated.
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 structure derived from an aromatic amine compound (B), a structure derived from a siloxane compound (C) having at least two primary amino groups at the molecular ends, and a maleimide compound having at least two N-substituted maleimide groups in one molecule (D) is a thermosetting resin composition containing an imide resin (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). To 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 adhesiveness. The number of moles of the structure derived from the aromatic amine compound (A)] / [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] / [number of moles of structure derived from aliphatic amine compound (B)] ≦ 5.
Moreover, 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) is the above relation from the viewpoint of copper foil adhesiveness and moldability. 1-40 mass% is preferable, 3-25 mass% is more preferable, and 4-15 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 and 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 and more preferably 50 to 85% by mass from the viewpoint of low thermal expansion and high elastic modulus.

Moreover, it is preferable that modified imide resin (J) contains the structure derived from the amine compound (E) which has an acidic substituent further represented by the said 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), a structure derived from the component (D), And a structure derived from the amine compound (E) component having the acidic substituent.

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

  The content of the modified imide resin (J) in the second thermosetting resin composition is preferably 50 to 100 parts by mass per 100 parts by mass of the total solid resin component of the thermosetting resin composition. -90 mass parts is more preferable, and 70-85 mass parts is further more preferable. By setting the content of the modified imide resin (J) to 50 parts by mass or more, excellent copper foil adhesion, low thermal expansion, low curing shrinkage, heat resistance (solder heat resistance), elastic modulus and moldability are obtained. It is 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, derived from the aliphatic amine compound (B) The preferred 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 heat from the viewpoint of copper foil adhesiveness and moldability. 1 to 30 parts by mass is preferable, 2 to 20 parts by mass is more preferable, and 3 to 10 parts by mass is even more preferable per 100 parts by mass of the total solid resin component of the curable resin composition.
In the second thermosetting resin composition, the content of the structure derived from the siloxane compound (C) is the sum of the resin components in terms of solid content of the thermosetting resin composition from the viewpoint of copper foil adhesion and chemical resistance. 1-100 mass parts is preferable per 100 mass parts, and 5-20 mass parts is more preferable.
In the second thermosetting resin composition, the content of the structure derived from the maleimide compound (D) is a total of 100 resin components in terms of solid content of the thermosetting resin composition from the viewpoint of low thermal expansion and high elastic modulus. 30-99 mass parts is preferable per mass part, and 40-80 mass parts is more preferable.
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 the above point, 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 more preferable per 100 parts by mass of the total solid resin component of the thermosetting resin composition. .

  Next, the manufacturing method of modified imide resin (J) is demonstrated.

(Method for producing modified imide resin (J))
The modified imide resin (J) comprises an aromatic amine compound (A), an aliphatic amine compound (B), a siloxane compound (C), a maleimide compound (D), and, if necessary, an amine compound (E) having an acidic substituent. 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 the low curing shrinkage and the low thermal expansion can be improved.
Hereinafter, various conditions for the pre-reaction will be described.

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

  Furthermore, 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 preferred. The heat resistance which was excellent by setting it as 50 mass parts or more is acquired, and low thermal expansion property can be kept favorable by setting it as 3000 mass parts or less.

  When the modified imide resin (J) contains a structure derived from an amine compound (E) having an acidic substituent, the amount of each component used in the pre-reaction is the number of maleimide groups in the maleimide compound (D) [(D ) Component use amount / (D) component maleimide group equivalent] 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 [(Amount of component (A) / Primary amine equivalent of component (A)) + (Amount of component (B) / Primary amine equivalent of component (B)) + ((C) of component Use amount / (primary amino group equivalent of (C) component) + (use amount of (E) component / primary amine equivalent of (E) component)] is preferably in the range of 2.0 to 10.0 times. . By making it 2.0 times or more, gelation and heat resistance can be suppressed, and by making it 10.0 times or less, solubility in organic solvents and 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 is maintained at 100 parts by mass of the siloxane compound (C) while maintaining the above-described relationship. On the other hand, 1-100 mass parts is preferable and 3-30 mass parts is more preferable. By setting it to 1 part by mass or more, good heat resistance can be obtained, and by setting it to 100 parts by mass or less, low thermal expansion can be kept good.

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

Examples of the organic solvent used in the pre-reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as ethyl ester and γ-butyrolactone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; dimethyl sulfoxide And sulfur atom-containing solvents such as These may be used alone or in combination of two or more.
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 has low toxicity and is highly volatile and hardly remains 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, and still more preferably 40 to 500 parts by mass with respect to 100 parts by mass of the total of the raw material components of the pre-reaction. . When the amount of the organic solvent used is 25 parts by mass or more, good solubility is obtained, and when it is 2000 parts by mass or less, a sufficient reaction rate is obtained.

  A 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-based catalysts such as triphenylphosphine; alkali metal amides such as lithium amide, sodium amide, and potassium amide Etc. These may be used alone or in combination of two or more.

  In addition to the modified imide resin (J), the second thermosetting resin composition further includes an aromatic amine compound (A), an aliphatic amine compound (B), a siloxane compound (C), a maleimide compound (D), and You may contain 1 or more types chosen from the group which consists of an amine compound (E) which has 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 the first thermosetting resin composition and the second thermosetting resin composition of the present invention can contain as necessary 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, radical polymerization initiators are preferable, and organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group are preferred. An oxide etc. are mentioned. These may be used alone or in combination of two or more.

(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 elastomers, siloxane-based elastomers, and derivatives thereof. These are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These may be used alone or in combination of two or more. Among these, for example, a styrene elastomer, an olefin elastomer, a polyamide elastomer, and a siloxane elastomer are preferable from the viewpoint of heat resistance and insulation reliability, and a styrene elastomer and an olefin elastomer are more preferable from the viewpoint of dielectric characteristics. .

  As the thermoplastic elastomer (F), one having a reactive functional group at the molecular end or molecular chain can be used. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amide group, an isocyanato group, an acryl group, a methacryl group, and a vinyl group. By having these reactive functional groups in the molecular terminals or molecular chains, the compatibility with the resin is improved, and the internal stress generated during curing of the thermosetting resin composition of the present invention is more effectively reduced. be able to.

  When the thermosetting resin composition of the present invention contains a thermoplastic elastomer (F), the content of the thermoplastic elastomer (F) is 100 parts by mass of the total resin component in terms of solid content of the thermosetting resin composition. 0.1-50 mass parts is preferable, and 2-30 mass parts is more preferable. By setting the content of the thermoplastic elastomer (F) within the above range, it is excellent in moldability and can effectively exhibit 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)”). It 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 novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, Triphenol phenol methane type epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Naphthol type epoxy Of polycyclic aromatics such as resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polyfunctional phenols and anthracene And phosphorus-containing epoxy resin glycidyl ether compounds and these were introduced phosphorus compounds. These may be used alone or in combination of two or more. 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 novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, bisphenol-type cyanate resin such as tetramethylbisphenol F-type cyanate resin, and prepolymers in which these are partially triazine. It is done. These may be used alone or in combination of two or more. Among these, a novolac type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.

  When the thermosetting resin composition of the present invention contains the 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 is preferable, and 8 to 30 parts by mass is more preferable per 100 parts by mass of the total solid resin component.

When the thermosetting resin composition of this invention contains a thermosetting resin (G), the thermosetting resin composition of this invention contains the hardening | curing agent of a thermosetting resin (G) as needed. It may be.
Examples of the curing agent include polyfunctional phenol compounds such as phenol novolak, cresol novolak, and aminotriazine novolak resin; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride, maleic anhydride, Examples thereof include acid anhydrides such as maleic anhydride copolymers. These may be used alone or in combination of two or more.

(Inorganic filler (H))
The thermosetting resin composition of the present invention may further contain an inorganic filler (H).
As inorganic filler (H), silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, sulfuric acid Examples include barium, aluminum borate, potassium titanate, glass powder, and hollow glass beads. Preferred examples of the glass include E glass, T glass, and D glass. These may be used alone or in combination of two or more.
Among these, for example, silica is preferable in terms of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica further include crushed silica, fumed silica, fused silica (fused spherical silica) and the like depending on the production method. Among these, spherical silica is preferable and fused spherical silica is more preferable because of low thermal expansion and high fluidity when filled in a resin.

  When silica is used as the inorganic filler (H), the average particle diameter is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By making the average particle diameter of silica 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by making it 10 μm or less, the mixing probability of coarse particles is reduced, resulting in coarse particles The occurrence of defects can be suppressed. Here, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve according to the particle diameter is obtained with the total volume of the particles being 100%, and a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.

  When the thermosetting resin composition of 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 resin component of the thermosetting resin composition. Is preferable, and 50-250 mass parts is more preferable. By making content of an inorganic filler (H) into the said range, the moldability and low thermal expansibility of a thermosetting resin composition can be kept favorable.

  In addition, when the inorganic filler (H) is added to the thermosetting resin composition, for example, the inorganic filler (H) is treated with a coupling agent such as silane or titanate, or a surface treatment agent such as silicone oligomer. Pretreatment or integral blend treatment is also preferred.

(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 include imidazoles and derivatives thereof; organophosphorus compounds such as phosphines and phosphonium salts; secondary amines, tertiary amines, quaternary ammonium salts, and the like. These may be used alone or in combination of two or more. Among these, for example, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of curing acceleration effect and storage stability.

  When the thermosetting resin composition of this invention contains hardening accelerator (I), the content is 0.01-3 per 100 mass parts of sum total of the solid content conversion resin component of a thermosetting resin composition. 0.0 parts by mass is preferable, and 0.05 to 1.5 parts by mass is more preferable. By making content of hardening accelerator (I) into the said range, a hardening acceleration effect and storage stability can be kept favorable.

  The thermosetting resin composition of the present invention can be arbitrarily selected from known thermoplastic resins, organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescence enhancers, as long as they do not contradict its purpose. You may contain a whitening agent, an adhesive improvement agent, etc.

  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 a resin filler made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, and the like; an acrylic ester resin, a methacrylic ester resin, a conjugated diene resin, and the like. Examples thereof include a resin filler having a core-shell structure having a rubbery core layer and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.

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

  As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned, for example. Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants. Examples of the photopolymerization initiator include benzophenone, benzyl ketal, and thioxanthone photopolymerization initiators. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative. Examples of the adhesion improver include urea compounds such as urea silane; coupling agents such as silane, titanate, and aluminate.

(Organic solvent)
The thermosetting resin composition of the present invention is preferably made into a varnish state by containing an organic solvent from the viewpoint of facilitating handling and easy manufacture of a prepreg or a resin-coated film 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; 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 mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; And sulfur atom-containing solvents such as dimethyl sulfoxide. These may be used alone or in combination of two or more.
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-mentioned range, it is possible to obtain a prepreg and a resin-attached film in which an appropriate amount of the thermosetting resin composition is adhered while maintaining good coating properties. it can.

[Prepreg]
The prepreg of the present invention contains the thermosetting resin composition of the present invention.
The prepreg of the present invention can be obtained, for example, by impregnating the thermosetting resin composition of the present invention into a base material, or by impregnating or spraying the base material and then applying it by a method such as extrusion [hereinafter, these The method may be collectively referred to as “impregnation or coating”. ] Can be manufactured. Specifically, after impregnating or coating the thermosetting resin composition of the present invention on a base material, for example, by semi-curing (B-stage) by heating or the like, the base material and the semi-cured (B-stage) The prepreg of the present invention containing the thermosetting resin composition thus obtained 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 spraying method. . Among these, the method of immersing the base material in the varnish is preferable from the viewpoint of impregnation.

As a base material used for the prepreg of this invention, the well-known thing used for the laminated board for various electrical insulation materials can be used, for example. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. In other applications, for example, carbon fibers can be used for fiber reinforced substrates.
These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, a surfacing mat, for example. What is necessary is just to select the material and shape of a base material with the use and performance of the target molded object, and if necessary, it can combine individually or two or more types of materials and shapes.
A substrate that is surface-treated with a silane coupling agent or the like or that has been mechanically subjected to a fiber opening treatment is suitable from the viewpoint of heat resistance, moisture resistance, and workability.
The thickness of a base material can be made into the range of about 0.03-0.5 mm, for example.

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

[Film with resin]
The film with a resin of the present invention contains the thermosetting resin composition of the present invention.
The film with resin of the present invention is formed, for example, by layering the thermosetting resin composition of the present invention on a support.
The method for forming the layer is not particularly limited. For example, after the thermosetting resin composition obtained in the present invention is in a varnish state, it is 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) from the thermosetting resin composition of the present invention on the support. It can manufacture by forming the resin composition layer which becomes.
The film with resin of the present invention thus obtained has a support and a semi-cured resin composition layer formed from the thermosetting resin composition of the present invention on one surface of the support. Is. However, this semi-cured state is a state in which the adhesive force between the thermosetting resin composition and the circuit pattern substrate is ensured when the thermosetting resin composition is cured, and the embedding property of the circuit pattern substrate is also ensured. It is desirable that the (fluidity) is ensured.

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

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

Examples of the support in the resin-coated film of the present invention include films such as polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter also referred to as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, and polyimide; Pattern paper; metal foil such as copper foil and aluminum foil. These supports and protective films described later may be subjected to mat treatment, corona treatment, mold release treatment, and the like.
The thickness of the support is, for example, preferably 10 to 150 μm, and more preferably 25 to 50 μm.
A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. By laminating the protective film, foreign matter can be prevented from being mixed. The thickness of the protective film is, for example, 1 to 40 μm.
The film with resin can also be wound and stored in a roll shape.

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

As a method of forming a laminated board using the film with resin of this invention, the method of laminating the film with resin of this invention on the single side | surface or both surfaces of a circuit board using a vacuum laminator is mentioned, for example.
Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means the thing in which the conductor layer (circuit) patterned by the one side or both surfaces of the above boards was formed. Further, in a laminated board obtained 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 surfaces of the outermost layer of the printed wiring board are patterned. The circuit board referred to here is also included. Note that the surface of the conductor layer may be previously roughened by blackening or the like.

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

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

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

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

Next, the manufacturing method of the laminated board of this invention using the prepreg of this invention is demonstrated.
The laminate of the present invention can be produced by laminating the prepreg of the present invention. In this case, the laminated board of this invention contains the insulating resin layer formed by hardening | curing the prepreg of this invention.
For example, a laminate can be produced by laminating 1 to 20 prepregs of the present invention and laminating and forming one or both surfaces thereof with a metal foil such as copper or aluminum. A metal foil will not be restrict | limited especially if it is used with the laminated board for electrical insulation materials.
As the molding conditions, for example, the method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. Using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., a temperature of 100 to 250 ° C., a pressure of 0.2 It can be molded under the conditions of 10 to 10 MPa and heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce the laminated board of the present invention.

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

[Semiconductor package]
The semiconductor package of the present invention is obtained by mounting a semiconductor 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 of 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.
In addition, using the copper-clad laminate obtained in each example, the glass transition temperature, the thermal expansion coefficient, the copper foil adhesiveness, the solder heat resistance with copper, the bending elastic modulus and the formability are measured by the following methods and evaluated. did.

(1) Glass transition temperature (Tg)
An evaluation board having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 0.4 mm (Z direction) obtained by immersing the copper clad laminate obtained in each example in a copper etching solution is removed. It produced and the thermomechanical analysis was performed by the compression method using the TMA test apparatus (TA Instruments company make, brand name: Q400). The thermomechanical analysis is performed twice in succession under the conditions of a load of 5 g and a temperature increase rate of 10 ° C./min after mounting the evaluation board in the X direction on the apparatus, and is indicated by the intersection of tangents of the second thermal expansion curve. The glass transition temperature (Tg) was determined.

(2) Coefficient of thermal expansion 5 mm in length (X direction), 5 mm in width (Y direction), 0.4 mm in thickness (Z) from which the copper foil was removed by immersing the copper clad laminate obtained in each example in a copper etching solution Direction) and a thermomechanical analysis was performed by a compression method using a TMA test apparatus (TA Instruments, trade name: Q400). Thermomechanical analysis was performed twice in succession under conditions of a load of 5 g and a heating rate of 10 ° C./min after mounting the evaluation substrate in the X direction on the apparatus, and the average from 30 ° C. to 100 ° C. in the second analysis The thermal expansion coefficient was calculated and used as the value of the thermal expansion coefficient (linear expansion coefficient).

(3) Copper foil adhesion (copper foil peel strength)
After forming a 3 mm wide resist on the copper clad laminate obtained in each example on an outer layer copper foil, an evaluation board having an outer layer copper foil of 3 mm width as a peel strength measurement part is immersed in a copper etching solution. Produced. One end of the copper foil of the adhesive strength measuring part is peeled off at the interface between the copper foil and the substrate, and is gripped with a gripper, and vertically using a tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph S-100). The load when it was peeled off at room temperature at a pulling speed of 50 mm / min in the direction was measured.

(4) Solder heat resistance with copper A 25 mm square evaluation board is prepared from the copper clad laminate obtained in each example, the evaluation board is floated in a solder bath at a temperature of 288 ° C. for 10 minutes, and the appearance of the evaluation board is visually observed. Were observed to evaluate the heat resistance of the solder with copper.

(5) Flexural modulus A copper-clad laminate obtained in each example was immersed in a copper etching solution to produce a 25 mm × 50 mm evaluation board from which copper foil was removed, and 5 ton tensilon manufactured by Orientec Co., Ltd. was used. The measurement was performed at a crosshead speed of 1 mm / min and a span distance of 20 mm.

(6) Formability Two prepregs obtained in each example are stacked, a copper foil having a thickness of 12 μm is arranged on both surfaces, and pressed for 85 minutes under conditions of a pressure of 3.0 MPa and a temperature of 250 ° C. using a multistage vacuum press. Thus, a copper-clad laminate was produced. The copper foil of the obtained copper-clad laminate was removed by etching, and the appearance of the prepreg after curing was visually observed to evaluate the moldability.

[Production of modified imide resin]
Production Example 1
(Production of modified imide resin 1)
To a reaction vessel with a volume of 1 liter that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Product name: KAYAHARD A-A) 16.23 g, 2,2,4-trimethylhexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.44 g, both-end amino-modified siloxane (Momentive Performance Materials Japan GK) Product, functional group equivalent of 1280 g / mol of amino group, trade name: XF42-C5742) 47.9 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane 248.39 g (manufactured by Daiwa Kasei Kogyo Co., Ltd.) , Trade name: BMI-4000), p-aminophenol (manufactured by Kanto Chemical Co., Inc.) 5.94 g, propi And then reacting at 115 ° C. for 4 hours, raising the temperature to 130 ° C. and concentrating at normal pressure to obtain a modified imide resin 1-containing solution (resin component content: 60 mass%). Obtained.

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

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

Examples 1-6, Comparative Examples 1-3
(Manufacture of copper-clad laminate)
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 a 0.1 mm thick S glass cloth and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a thermosetting resin composition having a solid content of 45% by mass. Next, 4 sheets of this prepreg were stacked, and an electrolytic copper foil having a thickness of 12 μm was placed up and down, 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 AA: 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.]
Elastomer 1000P: di-p-aminobenzoic acid polytetramethylene oxide [trade name, manufactured by Ihara Chemical Co., Ltd.]

Siloxane compound (C)
-XF42-C5742: Both-end amine-modified siloxane [Momentive Performance Materials Japan Limited, trade name]

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

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

Thermoplastic elastomer (F)
Tuftec M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin [trade name, manufactured by Asahi Kasei Chemicals Corporation]

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

Inorganic filler (H)
SC2050-KNK: fused spherical silica [manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, product name]
・ KEMGARD2200: zinc molybdate [manufactured by Sherwin Williams, trade name]

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

  As is apparent 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, a copper foil adhesiveness, a soldering heat resistance with copper, an elastic modulus, and a moldability. Is excellent for all. On the other hand, Comparative Examples 1 and 3 did not satisfy all of the glass transition temperature, the thermal expansion coefficient, the copper foil adhesiveness, the solder heat resistance with copper, the elastic modulus, and the moldability, and were inferior in any of the characteristics. In Comparative Example 2, an evaluation substrate could not be produced due to poor molding, and the glass transition temperature, the thermal expansion coefficient, the solder heat resistance with copper, and the elastic modulus could not be measured.

  The laminate comprising the thermosetting resin composition of the present invention and the prepreg containing the thermosetting resin composition and the cured product of the resin-coated film have excellent copper foil adhesion, low thermal expansion, and low curing shrinkage. It has heat resistance (solder heat resistance), elastic modulus and moldability, and is useful as a highly integrated semiconductor package and printed circuit board for electronic equipment.

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 molecular terminals 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. Furthermore, the thermosetting resin composition of Claim 1 containing the amine compound (E) which has an acidic substituent represented by the following general formula (I).
(In the general formula (I), each R ₁ independently represents a hydroxyl group, a carboxy group or a sulfonic acid group which is an acidic substituent, and each R ₂ independently represents a hydrogen atom, an aliphatic carbon atom having 1 to 5 carbon atoms. 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; A structure derived from a siloxane compound (C) having at least two primary amino groups at a molecular end and a structure derived from a maleimide compound (D) having at least two N-substituted maleimide groups in one molecule Imide resin.   Furthermore, the imide resin of Claim 3 containing the structure derived from the amine compound (E) which has an acidic substituent represented by the said general formula (I).   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 molecular terminals 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.   The component (A), the component (B), the component (C), the component (D), and the amine compound (E) having an acidic substituent represented by the general formula (I); The manufacturing method of the imide resin of Claim 5 made to react.   The thermosetting resin composition containing the imide resin of Claim 3 or 4.   Furthermore, the thermosetting resin composition of any one of Claim 1, 2, or 7 containing a thermoplastic elastomer (F).   Furthermore, the thermosetting resin composition of any one of Claim 1, 2, 7, or 8 containing an epoxy resin.   Furthermore, the thermosetting resin composition of any one of Claim 1, 2, 7-9 containing an inorganic filler (H).   Furthermore, the thermosetting resin composition of any one of Claims 1, 2, 7-10 containing hardening accelerator (I).   A prepreg containing the thermosetting resin composition according to any one of claims 1, 2, and 7 to 11.   The film with a resin containing the thermosetting resin composition of any one of Claims 1, 2, 7-11.   A laminate containing a cured product of the prepreg according to claim 12.   The laminated board containing the hardened | cured material of the film with a resin of Claim 13.   The printed wiring board containing the laminated board of Claim 14 or 15.   A semiconductor package containing the printed wiring board according to claim 16.