JP2015224307A - Thermosetting resin composition, prepreg, film with resin, laminate sheet, multilayer printed circuit board and semiconductor package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that is excellent in low shrinkage property, low thermal expansion property and desmear resistance property, and to provide a prepreg, film with resin, laminate sheet, multilayer printed circuit board and semiconductor package using the same.SOLUTION: Provided is a thermosetting resin composition in which a maleimide compound represented by the general formula (1) (A), and an amino-modified siloxane compound having an aromatic azomethine group in the molecular structure (B) are formulated.

Description

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

As electronic devices have become smaller and higher performance in recent years, printed wiring boards have become increasingly dense and highly integrated, and as a result, reliability has been improved by improving the heat resistance of laminated boards for wiring. There is an increasing demand for improvement. In particular, in a semiconductor package substrate, warpage caused by a difference in coefficient of thermal expansion between the chip and the substrate is a major problem during component mounting or package assembly.
For these reasons, particularly in semiconductor packages, excellent heat resistance, low shrinkage, low thermal expansion, and high elastic modulus are required. Moreover, in order to cope with the increase in frequency of electric signals, high dielectric characteristics have been required.

  Epoxy resins are known to be excellent in dimensional stability, chemical resistance, moisture absorption resistance, and electrical insulation, and are used in wiring board materials, sealing materials, adhesives, paints, and the like. However, an epoxy resin has a large thermal expansion coefficient, and a low thermal expansion coefficient is achieved by selecting an epoxy resin having an aromatic ring or by increasing the filling of an inorganic filler such as silica (for example, see Patent Document 1). It is possible to further reduce the coefficient of thermal expansion by filling the inorganic filler at a high rate, but increasing the filling amount of the inorganic filler reduces the insulation reliability due to moisture absorption and the resin composition layer-wiring. It is known that the adhesion between layers is insufficient and press molding is poor.

  On the other hand, a polyimide resin has very excellent strength, heat resistance, and low thermal expansion compared to other polymer resin materials, and is excellent in electrical insulation, but has a problem of low adhesion. When the adhesiveness is low, there is a possibility that a problem such as disconnection of the wiring due to the warp generated during the mounting and disconnection may occur.

  In order to improve the adhesiveness of the polyimide resin, a thermosetting resin composition containing epoxy resin, phenol resin and modified imide resin as main components is known (for example, see Patent Document 2). However, although this thermosetting resin composition is improved in moisture resistance and adhesiveness, it is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group to ensure solubility in a general-purpose solvent such as methyl ethyl ketone. There is a problem that the desmear resistance of the resulting modified imide resin is significantly reduced as compared with the conventional polybismaleimide resin.

  In the process of manufacturing a multilayer printed circuit board, via holes are formed by drilling or laser processing, and smears adhering to the inside and outside of the holes are treated with a desmear solution containing a permanganate solution or the like. At this time, if the resin has low desmear resistance, the resin in the via hole is also shaved simultaneously, resulting in large irregularities, poor connection, and the need for more gold plating. It becomes. Therefore, the resin applied to the multilayer printed circuit board is required to have excellent desmear resistance.

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

  In view of the current situation, the object of the present invention is a thermosetting resin composition having excellent low shrinkage, low thermal expansion and desmear resistance, a prepreg using the same, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor. Is to provide a package.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a thermosetting resin composition comprising a specific maleimide compound (A) and a specific amino-modified siloxane compound (B). The present inventors have found that the above object is met and have reached the present invention.

That is, the present invention provides the following thermosetting resin composition, prepreg, resin-coated film, laminated board, multilayer printed wiring board, and semiconductor package.
[1] A thermosetting resin composition comprising a maleimide compound (A) represented by the following general formula (1) and an amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure.

[In General Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, and X represents an alkylene group, an arylene group, Or the following general formula (2)

(In General Formula (2), R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, and R ₅ , R ₆ , and R ₇ independently represents a single bond, an alkylene group, an amide group, or a carbonyl group, * represents a bond portion with an adjacent oxygen atom, and p and q each independently represents an integer of 0 to 4.)
The bivalent coupling group represented by these is shown. m and n each independently represents an integer of 0 to 4. ]

[2] X in the general formula (1) is a divalent linking group represented by the general formula (2), and R _{6 in the} general formula (2) is a single bond or an alkylene group. The thermosetting resin composition according to the above [1].
[3] The thermosetting resin composition according to the above [1] or [2], further comprising an amine compound (C) having an acidic substituent represented by the following general formula (3).

(In general formula (3), each R ₈ independently represents a hydroxyl group, carboxyl group or sulfone group which is an acidic substituent, and each R ₉ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. 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.)
[4] The thermosetting resin composition according to any one of [1] to [3], further comprising a curing agent (D).
[5] A maleimide compound (A) represented by the general formula (1), an amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure, and an amine compound (C) having an acidic substituent. The thermosetting resin composition according to the above [4], comprising an aromatic azomethine-containing modified imide resin (E) obtained by reacting with a curing agent (D).
[6] The amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure is composed of an aromatic azomethine compound (F) having at least one aldehyde group in one molecule and at least two at the molecular end. The thermosetting resin composition according to any one of the above [1] to [5], which is obtained by reacting with a siloxane compound (G) having a primary amino group.
[7] The aromatic azomethine compound (F) having at least one aldehyde group in one molecule includes the aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule and one molecule. The thermosetting resin composition according to the above [6], which is obtained by reacting the diamine compound (I) having at least two primary amino groups.
[8] The thermosetting resin composition according to any one of [1] to [7], further comprising a thermoplastic elastomer (J).
[9] The thermosetting resin composition according to any one of [1] to [8], further comprising an inorganic filler (K).
[10] The thermosetting resin composition according to any one of [1] to [9], further comprising a curing accelerator (L).
[11] A prepreg comprising the thermosetting resin composition according to any one of [1] to [10].
[12] A resin-coated film obtained by forming a layer on the support of the thermosetting resin composition according to any one of [1] to [10].
[13] A laminate obtained by laminate-molding the prepreg according to [11].
[14] A laminate obtained by laminating the film with resin according to [12].
[15] A multilayer printed wiring board produced using the laminated board according to [13] or [14].
[16] A semiconductor package obtained by mounting a semiconductor on the multilayer printed wiring board according to [15].

  According to the present invention, there are provided a thermosetting resin composition excellent in low shrinkage, low thermal expansion and desmear resistance, a prepreg using the same, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor package. Can do.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention (hereinafter also simply referred to as “resin composition”) has a maleimide compound (A) represented by the following general formula (1) and an aromatic azomethine group in the molecular structure. It is a thermosetting resin composition formed by blending an amino-modified siloxane compound (B).
Here, the aromatic azomethine group refers to a group in which at least one aromatic is bonded to a Schiff base (—N═CH—).

In general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, and X represents an alkylene group, an arylene group, or A divalent linking group represented by the following general formula (2) is shown. m and n each independently represents an integer of 0 to 4.

In General Formula (2), R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, and R ₅ , R ₆ , and R ₇ Each independently represents a single bond, an alkylene group, an amide group or a carbonyl group, and * represents a bond with an adjacent oxygen atom. p and q each independently represent an integer of 0 to 4.

(Maleimide compound (A))
The maleimide compound (A) used in the present invention is represented by the following general formula (1).

In general formula (1), R ₁ and R ₂ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, and have reactivity, solvent solubility, and availability. From the viewpoint, an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and an alkynyl group having 1 to 5 carbon atoms. Reactivity, solvent solubility From the viewpoint of availability, and an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.
In general formula (1), m and n are each independently an integer of 0 to 4, and are preferably an integer of 0 to 2, more preferably 0 or from the viewpoints of reactivity, solvent solubility, and availability. 1.

In general formula (1), X represents a single bond, an alkylene group, an arylene group, or a divalent linking group represented by the following general formula (2).
Although carbon number of an alkylene group is not specifically limited, Preferably it is 1-10, More preferably, it is 1-5, More preferably, it is 1-3. Examples of the alkylene group include linear or branched alkylene groups, and specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a pentylene group. Among these, a methylene group is preferable from the viewpoints of low shrinkage, low thermal expansion, and desmear resistance.
Although carbon number of an arylene group is not specifically limited, Preferably it is 6-20, More preferably, it is 6-16, More preferably, it is 6-14.
In the present specification, the arylene group means a divalent linking group obtained by removing two hydrogen atoms from an aromatic hydrocarbon which is a monocyclic and / or condensed ring, and is a monocyclic and / or condensed ring. It does not include those bonded to each other through a single bond or a bonding group.
Specific examples of the arylene group include a phenylene group, a naphthylene group, and an anthranylene group. The arylene group may have the same substituent as R ₃ and R ₄ .
X is preferably a divalent linking group represented by the following general formula (2) from the viewpoints of low shrinkage, low thermal expansion and desmear resistance.

In the general formula (2), R ₃ and R ₄ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, it is a preferred embodiment R ₁ and R _Same as ₂ .
In general formula (2), p and q are each independently an integer of 0 to 4, and are preferably an integer of 0 to 2, more preferably 0, from the viewpoints of reactivity, solvent solubility, and availability. Or it is 1.
In the general formula _{(2), R 5, R} 6, and R ₇ are each independently a single bond, an alkylene group, an amide group, or a carbonyl group.
R ₆ is preferably a single bond or an alkylene group, more preferably an alkylene group, from the viewpoints of low shrinkage, low thermal expansion, and desmear resistance.
R ₅ and R ₇ are preferably a single bond or an alkylene group, more preferably a single bond, from the viewpoints of low shrinkage, low thermal expansion, and desmear resistance.
Although carbon number of an alkylene group is not specifically limited, Preferably it is 1-10, More preferably, it is 1-5, More preferably, it is 1-3. Examples of the alkylene group include linear or branched alkylene groups, and specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a pentylene group. Among these, from the viewpoint of low shrinkage, low thermal expansion and desmear resistance, a methylene group or an isopropylene group is preferable, and an isopropylene group is more preferable.

  Specific examples of the maleimide compound (A) include 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, bis (2,2′-dimethylmaleimidophenoxy) methane, and bis (4- (4 -Maleimidophenoxy)) biphenyl, bis (4-maleimidophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 2,2'-bis [4,4'-(2 ", 2 '" -Maleimidophenoxyethylene) phenylene] propane, bis (4-maleimidophenoxy) -2,2'-dimethylbiphenyl and the like, and 2,2-bis (4- (4-maleimidophenoxy) in terms of elastic modulus and shrinkage ) Phenyl) propane, 2,2′-bis [4,4 ′-(2,2′-maleimidophenoxyethylene) phenylene] propane, bis (4-male) Midofenokishi) -2,2'-dimethyl-biphenyl is preferable, from the viewpoint of resistance to desmear resistance, 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane is preferable.

  In the thermosetting resin composition of the present invention, the blending amount of the maleimide compound (A) is preferably 30 to 99 parts by mass with respect to 100 parts by mass of the resin component total amount in the thermosetting resin composition. More preferably, it is 40-95 mass parts, More preferably, it is 60-93 mass parts. By setting it as the compounding quantity of this range, an elasticity modulus, low thermal expansibility, and desmear resistance can be improved.

(Amino-modified siloxane compound (B))
The amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure has an aromatic azomethine compound (F) having at least one aldehyde group in one molecule and at least two primary amino groups at the molecular end. What is obtained by making it react with the siloxane compound (G) which has is preferable.

<Aromatic azomethine compound (F) having at least one aldehyde group in one molecule>
The aromatic azomethine compound (F) having at least one aldehyde group in one molecule includes an aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule and at least two in one molecule. It is obtained by reacting with a diamine compound (I) having a primary amino group.

[Aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule]
Examples of the aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2′-bipyridine-4,4′-dicarboxaldehyde. Etc. Among these, for example, terephthalaldehyde, which can be further reduced in thermal expansion, has high reactivity during reaction, is excellent in solvent solubility, and is easily available commercially, is preferable.

[Diamine compound (I) having at least two primary amino groups in one molecule]
Examples of the diamine compound (I) having at least two primary amino groups in one molecule include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, 2 , 5-dimethyl-1,4-diaminobenzene, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl- Diphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ketone, benzidine, 3,3′-dimethyl-4,4 ′ -Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2, , 2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4 -Aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9, And 9-bis (4-aminophenyl) fluorene. You may use these individually or in mixture of 2 or more types.

  Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino, which has high reactivity during the reaction and can be further improved in heat resistance. -3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis (4- (4 -Aminophenoxy) phenyl) propane and the like are preferable, and 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4 is preferable from the viewpoint of low cost and solubility in a solvent. , 4′-diamino-3,3′-diethyl-diphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane are more preferred, and low thermal expansion and induction In terms of characteristics, 4,4'-diamino-3,3'-diethyl - diphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane is preferable. 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.

<Siloxane compound (G) having at least two primary amino groups at the molecular terminals>
As the siloxane compound (G) having at least two primary amino groups at the molecular terminals, commercially available products can be used. For example, “KF-8010” (amino group equivalent 430), “X-22-161A” ( Amino group equivalent 800), “X-22-161B” (amino group equivalent 1500), “KF-8012” (amino group equivalent 2200), “KF-8008” (amino group equivalent 5700), “X-22-9409” ”(Amino group equivalent 700),“ X-22-1660B-3 ”(amino group equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.),“ BY-16-853U ”(amino group equivalent 460),“ BY-16-853 "(amino group equivalent 650)," BY-16-853B "(amino group equivalent 2200) (above, manufactured by Toray Dow Corning Co., Ltd.) and the like. In Germany, or it may be used as a mixture of two or more.

  Among these, for example, "X-22-161A", "X-22-161B", "KF-8012", "X-22-1660B-" are highly reactive at the time of synthesis and have low thermal expansion. 3 "and" BY-16-853B "are preferable, and" X-22-161A "and" X-22-161B ", which are excellent in compatibility and can increase the elastic modulus, are more preferable.

In the present invention, as a reaction for obtaining an amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure, first, a diamine compound (I) having at least two primary amino groups in one molecule. And an aromatic azomethine compound having at least one aldehyde group in one molecule by subjecting the aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule to dehydration condensation reaction in an organic solvent (F) is obtained. Next, the compound (F) and a siloxane compound (G) having at least two primary amino groups at the molecular ends are subjected to a dehydration condensation reaction in an organic solvent, whereby an amino group having an aromatic azomethine group in the molecular structure. A modified siloxane compound (B) can be obtained.
In addition, this reaction has a feature that the molecular weight control of the aromatic azomethine group in the molecule of the amino-modified siloxane compound (B) having an aromatic azomethine group used in the present invention is easy. This is particularly effective for increasing the elastic modulus of the resulting resin composition.

  Examples of the organic solvent used in the dehydration condensation 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, tetrahydrofuran, and the like. Ether solvents, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, sulfur atom-containing solvents such as dimethylsulfoxide, and ester systems such as γ-butyrolactone A solvent etc. are mentioned, 1 type (s) or 2 or more types can be mixed and used. Among these, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, γ-butyrolactone and the like are preferable from the viewpoint of solubility, and propylene glycol monomethyl which is highly volatile and hardly remains as a residual solvent at the time of manufacturing a prepreg. Ether and toluene are more preferable. Moreover, since this reaction is a dehydration condensation reaction, water is produced as a by-product. For the purpose of removing water as a by-product, it is desirable to react while removing water as a by-product by azeotropy with an aromatic solvent, for example.

  In the dehydration condensation reaction, a reaction catalyst can be used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine, and tributylamine, methylimidazole, and phenylimidazole. Examples thereof include phosphorus-based catalysts such as imidazoles such as triphenylphosphine, and the like, which can be used alone or in combination. From the viewpoint of allowing the dehydration condensation reaction to proceed efficiently, for example, an acidic catalyst such as p-toluenesulfonic acid is preferred.

First, a diamine compound (I) having at least two primary amino groups in one molecule and an aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule are dehydrated and condensed in an organic solvent. By reacting, an aromatic azomethine compound (F) having at least one aldehyde group in one molecule is obtained.
Here, blending of the diamine compound (I) having at least two primary amino groups in one molecule and the aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule in the dehydration condensation reaction For example, the number of primary amino groups of the diamine compound (I) [the amount of the diamine compound (I) / the primary amino group equivalent of the diamine compound (I)] is the number of aldehyde groups of the aromatic aldehyde compound (H) [aromatic The blending amount of the aldehyde compound (H) / the aldehyde group equivalent of the aromatic aldehyde compound (H) is preferably in the range of 0.1 to 5.0 times. By making it 0.1 times or more, it is possible to suppress a decrease in the molecular weight of the aromatic azomethine compound obtained by this reaction, and by making it 5.0 times or less, it is possible to reduce the solubility in a solvent. Can be suppressed.

  Moreover, the compounding quantity of the organic solvent is preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass with respect to 100 parts by mass of the total of the diamine compound (I) and the aromatic aldehyde compound (H). 40-500 mass parts is still more preferable. By setting the blending amount of the organic solvent to 25 parts by mass or more, the solubility does not become insufficient, and by setting it to 2000 parts by mass or less, the reaction does not take a long time.

The aromatic azomethine compound (F) is prepared by charging the above raw materials, organic solvent and, if necessary, a reaction catalyst in a reaction kettle and stirring for 0.1 to 10 hours while performing heating and thermal insulation as necessary to cause a dehydration condensation reaction. can get.
The reaction temperature is preferably 70 to 150 ° C., for example, and it is desirable to perform the reaction while removing water as a by-product, and therefore 100 to 130 ° C. is more preferable. By setting the temperature to 70 ° C. or higher, the reaction rate does not slow down, and by setting the temperature to 150 ° C. or lower, the reaction solvent does not require a high boiling point solvent, and the solvent remains when producing the prepreg. It is difficult to suppress a decrease in heat resistance.

Subsequently, the aromatic azomethine compound (F) obtained by the above reaction and the siloxane compound (G) having at least two primary amino groups at the molecular ends are subjected to a dehydration condensation reaction in an organic solvent, thereby obtaining a molecular structure. An amino-modified siloxane compound (B) having an aromatic azomethine group can be obtained.
Here, the blending amount of the aromatic azomethine compound (F) and the siloxane compound (G) is, for example, the number of primary amino groups of the siloxane compound (G) [the blending amount of the siloxane compound (G) / primary of the siloxane compound (G). The amino group equivalent] is 1.0 to 10.0 times the number of aldehyde groups of the aromatic azomethine compound (F) [the amount of the aromatic azomethine compound (F) / the aldehyde group equivalent of the aromatic azomethine compound (F)]. This range is desirable. Mixing the amino-modified siloxane compound (B) having an aromatic azomethine group by reducing the solubility in a solvent to 1.0 times or more without decreasing it to 10.0 times or less. It is possible to suppress a decrease in the elastic modulus of the thermosetting resin.

  Moreover, the compounding quantity of an organic solvent has preferable 25-2000 mass parts with respect to 100 mass parts of sum total of the resin component of an aromatic azomethine compound (F) and a siloxane compound (G), for example, and 40-1000 mass parts. More preferred is 40 to 500 parts by mass. By setting the blending amount of the organic solvent to 25 parts by mass or more, the solubility does not become insufficient, and by setting it to 2000 parts by mass or less, the reaction does not take a long time.

An amino acid having an aromatic azomethine group is prepared by, for example, stirring for 0.1 hour to 10 hours and carrying out a dehydration condensation reaction while charging the above raw materials, organic solvent, and if necessary, a reaction catalyst in a reaction kettle and heating and keeping warm as necessary. A modified siloxane compound (B) is obtained.
The reaction temperature is preferably 70 to 150 ° C., for example, and it is desirable to perform the reaction while removing water as a by-product, and therefore the reaction temperature is more preferably 100 to 130 ° C. By setting the temperature to 70 ° C. or higher, the reaction rate does not slow down, and by setting the temperature to 150 ° C. or lower, the reaction solvent does not require a high boiling point solvent, and the solvent remains when producing the prepreg. It is difficult to suppress a decrease in heat resistance.

The amino-modified siloxane compound (B) having an aromatic azomethine group obtained by the above reaction can be confirmed by performing IR measurement. The IR measurement, to confirm that the peak of 1620 cm ^-1 attributable to the azomethine group (-N = CH-) appears, also, at 3,440 cm ^-1 due to the primary amino group, and there is a peak of 3370cm around ^-1 By confirming that the reaction is carried out, it can be confirmed that the reaction proceeds well and the desired compound is obtained. Moreover, 6,500-85,000 are preferable and, as for the weight average molecular weight (Mw) of an amino modified siloxane compound (B), 15,000-30,000 are more preferable. When the weight average molecular weight (Mw) is 6,500 or more, good low shrinkage and low thermal expansion tend to be obtained, and when it is 85,000 or less, good compatibility and elastic modulus tend to be obtained. It is in.

The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve produced using standard polystyrene. For example, it can be performed under the following conditions.
Examples of the measuring apparatus include an auto sampler (AS-8020 manufactured by Tosoh Corporation), a column oven (860-C0 manufactured by JASCO Corporation), an RI detector (830-RI manufactured by JASCO Corporation), UV / It is possible to use a VIS detector (870-UV manufactured by JASCO Corporation) or an HPLC pump (880-PU manufactured by JASCO Corporation).
As the column used, for example, TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation can be used. As measurement conditions, for example, measurement temperature: 40 ° C., flow rate: 0.5 ml / min, and the solvent is tetrahydrofuran. Is measurable.

(Amine compound having an acidic substituent (C))
The thermosetting resin composition of the present invention may contain an amine compound (C) having an acidic substituent represented by the following general formula (3).

(In general formula (3), each R ₈ independently represents a hydroxyl group, carboxyl group or sulfone group which is an acidic substituent, and each R ₉ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. 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.)

The amine compound (C) having an acidic substituent is, for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-amino. Benzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc., and among these, solubility and synthesis yield From the viewpoint, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and m-aminophenol and p are preferable from the viewpoint of heat resistance. -Aminophenol is more preferable, and p-aminophenol is particularly preferable from the viewpoint of low thermal expansion. These may be used alone or in admixture of two or more.
As a compounding quantity, 0.5-10 mass parts is preferable with respect to 100 mass parts of solid content conversion resin components total in a thermosetting resin composition, 1-8 mass parts is more preferable, 2-7 masses Part is more preferred. By setting the blending amount within this range, heat resistance and low thermal expansion can be improved.

  The thermosetting resin composition of this invention can improve heat resistance, adhesiveness, and mechanical strength by using a hardening | curing agent (D) and a radical initiator together as needed.

(Curing agent (D))
The thermosetting resin composition of the present invention may contain a curing agent (D).
Examples of the curing agent (D) include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine. Aromatic amines such as hexamethylene diamine, and aliphatic amines such as 2,5-dimethylhexamethylene diamine, and guanamine compounds such as melamine and benzoguanamine.
Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.
Examples of the radical initiator include organic peroxides such as acyl peroxides, hydroperoxides, ketone peroxides, organic peroxides having a t-butyl group, and peroxides having a cumyl group. Can be used. These may be used alone or in admixture of two or more.

(Aromatic azomethine-containing modified imide resin (E))
In the thermosetting resin composition of the present invention, the maleimide compound (A) represented by the general formula (1), the amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure, and optionally used. The amine compound (C) having an acidic substituent and the curing agent (D) may be pre-reacted before and / or after compounding.
That is, the thermosetting resin composition of the present invention comprises a maleimide compound (A) represented by the general formula (1), an amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure, and if desired. An aromatic azomethine-containing modified imide resin (E) obtained by pre-reacting an amine compound (C) having an acidic substituent and a curing agent (D) may be contained. By performing such a pre-reaction, the molecular weight can be controlled, and low shrinkage, low thermal expansion, and desmear resistance can be improved. Hereinafter, each aspect will be described.

<Aromatic azomethine-containing modified imide resin formed by reacting components (A) and (B)>
An aromatic azomethine-containing modified imide resin obtained by reacting components (A) and (B) (hereinafter also referred to as “modified imide resin (i)”) is heated and kept warm in an organic solvent while the components (A) and ( B) is preferably pre-reacted (hereinafter also referred to as “pre-reaction (1)”) for synthesis.
The reaction temperature of the pre-reaction (1) is preferably, for example, 70 to 150 ° C, 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.
In the pre-reaction (1), the blending amounts of the components (A) and (B) are, for example, the number of maleimide groups in the component (A) [the blending amount of the component (A) / the maleimide group equivalent of the component (A)] A range that is 2.0 to 10.0 times the number of primary amino groups of component (B) [the amount of component (B) / the primary amino group equivalent of component (B)] is desirable. When it is 2.0 times or more, gelation and heat resistance are not lowered, and when it is 10.0 times or less, solubility in an organic solvent and heat resistance are not lowered.
The blending amount of the component (A) in the pre-reaction is preferably 50 to 3000 parts by mass, and more preferably 100 to 1500 parts by mass with respect to 100 parts by mass of the component (B) while maintaining the above relationship. preferable. When the amount is 50 parts by mass or more, the heat resistance does not decrease, and when the amount is 3000 parts by mass or less, the low thermal expansion can be kept good.

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, and acetic acid. 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 Examples thereof include sulfur atom-containing solvents such as 1 type or a mixture of two or more types.
Among these organic solvents, for example, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable, because they have low toxicity and are highly volatile and hardly remain as residual solvents. Is preferably cyclohexanone, propylene glycol monomethyl ether, or dimethylacetamide.
The blending amount of the organic solvent is, for example, preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and 40 to 500 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Further preferred. By setting the blending amount of the organic solvent to 25 parts by mass or more, the solubility does not become insufficient, and by setting it to 2000 parts by mass or less, the reaction does not take a long time.

  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, and alkali metal amides such as lithium amide, sodium amide, and potassium amide. 1 type or 2 or more types can be mixed and used.

  The content of the modified imide resin (i) in the thermosetting resin composition of the present invention is, for example, 50 to 100 parts by mass per 100 parts by mass of the resin component total amount in the thermosetting resin composition. Preferably, 60-100 mass parts is more preferable. By setting the blending amount of the modified imide resin (i) to 50 parts by mass or more, low thermal expansibility and high elastic modulus can be obtained.

<Aromatic azomethine-containing modified imide resin formed by reacting components (A) to (C)>
The aromatic azomethine-containing modified imide resin (hereinafter also referred to as “modified imide resin (ii)”) obtained by reacting the components (A) to (C) is heated and kept warm in an organic solvent while the components (A) to ( C) is preferably pre-reacted (hereinafter also referred to as “pre-reaction (2)”) for synthesis.
The reaction temperature and reaction time of the pre-reaction (2) are the same as those of the pre-reaction (1), and the preferred embodiments are also the same.
In this pre-reaction, the blending amounts of components (A) to (C) are, for example, the number of maleimide groups in component (A) [the blending amount of component (A) / the maleimide group equivalent of component (A)] ) And (C) sum of primary amino groups [(component (B) blending amount / component (B) primary amino group equivalent) + (component (C) blending amount / component (C) primary amino group equivalent] )] Is desirably in the range of 2.0 to 10.0 times. When it is 2.0 times or more, gelation and heat resistance are not lowered, and when it is 10.0 times or less, solubility in an organic solvent and heat resistance are not lowered.
The compounding amount of the component (A) in the pre-reaction (2) is preferably, for example, 50 to 3000 parts by mass, and 100 to 1500 parts by mass with respect to 100 parts by mass of the component (B) while maintaining the above relationship. Is more preferable. When the amount is 50 parts by mass or more, the heat resistance does not decrease, and when the amount is 3000 parts by mass or less, the low thermal expansion can be kept good.
The organic solvent and reaction catalyst used in the pre-reaction (2) are the same as those in the pre-reaction (1), and the preferred embodiments are also the same.
The amount of the organic solvent used in the pre-reaction (2) is preferably, for example, 25 to 2000 parts by mass, and 40 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (C). More preferred is 40 to 500 parts by mass. By setting the blending amount of the organic solvent to 25 parts by mass or more, the solubility does not become insufficient, and by setting it to 2000 parts by mass or less, the reaction does not take a long time.
The content of the modified imide resin (ii) in the thermosetting resin composition of the present invention is, for example, from 52 to 100 parts by mass per 100 parts by mass of the resin component total amount in the thermosetting resin composition. Preferably, 62-100 mass parts is more preferable. By setting the blending amount of the modified imide resin (ii) to 52 parts by mass or more, low thermal expansibility and high elastic modulus can be obtained.

<Aromatic azomethine-containing modified imide resin formed by reacting components (A) to (D)>
An aromatic azomethine-containing modified imide resin (hereinafter also referred to as “modified imide resin (iii)”) obtained by reacting components (A) to (D) is heated and kept warm in an organic solvent while the components (A) to ( It is preferable to synthesize D) by pre-reaction (hereinafter also referred to as “pre-reaction (3)”).
The reaction temperature and reaction time of the pre-reaction (3) are the same as those of the pre-reaction (1), and the preferred embodiments are also the same.
The compounding amounts of the components (A) to (C) in the pre-reaction (3) are the same as in the pre-reaction (2), and the preferred embodiments are also the same.
The blending amount of the curing agent (D) is 2.0 to 10.0 times the number of maleimide groups in the curing agent (the blending amount of the component (A) / the maleimide group equivalent of the component (A)). The range that becomes is desirable. By setting it to 2.0 times or more, the adhesiveness and heat resistance do not decrease, and by setting it to 10.0 times or less, the solubility in organic solvents and the mechanical strength do not decrease.
The organic solvent and reaction catalyst used in the pre-reaction (3) are the same as those in the pre-reaction (1), and the preferred embodiments are also the same.
From the viewpoint of solubility, the blending amount of the organic solvent used in the pre-reaction (3) is preferably 25 to 1,000 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (D), and the reaction time. From the viewpoint, 40 to 700 parts by mass are more preferable.
The content of the modified imide resin (iii) in the thermosetting resin composition of the present invention is, for example, from 58 to 100 parts by mass per 100 parts by mass of the total amount of resin components in terms of solid content in the thermosetting resin composition. Preferably, 68-100 mass parts is more preferable. Low thermal expansion and high elastic modulus can be obtained by setting the amount of the modified imide resin (i) to 58 parts by mass or more.

  Among the above-mentioned modified imide resins (i) to (iii), the thermosetting resin composition of the present invention contains the modified imide resin (iii) from the viewpoints of low shrinkage, low thermal expansion and desmear resistance. Is preferred.

(Thermoplastic elastomer (J))
The thermosetting resin composition of the present invention can further contain a thermoplastic elastomer (J). Examples of the thermoplastic elastomer (J) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers and derivatives thereof. These are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These can be used individually by 1 type or in mixture of 2 or more types.

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

  Among these thermoplastic elastomers (J), for example, styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers, and silicone-based elastomers are preferable in terms of heat resistance and insulation reliability.

  Moreover, the reactive functional group which has in the molecular terminal or molecular chain of these thermoplastic elastomers (J) is an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an amide from the point of adhesiveness with metal foil, for example. Group is preferable, and from the viewpoint of heat resistance and insulation reliability, an epoxy group, a hydroxyl group, and an amino group are more preferable.

  The blending amount of the thermoplastic elastomer (J) component is, for example, from the viewpoint of effectively expressing the low shrinkage and low thermal expansibility of the cured product, and the total amount of resin components in terms of solid content in the thermosetting resin composition is 100 mass. 0.1-50 mass parts is preferable with respect to part, and 2-30 mass parts is more preferable.

(Cyanate resin)
The thermosetting resin composition of the present invention can further contain a cyanate resin.
Examples of the cyanate resin include bisphenol cyanate resins such as bisphenol A type cyanate resin, bisphenol E type cyanate resin, and tetramethylbisphenol F type cyanate resin, novolak type cyanate resins, and prepolymers in which these are partially triazine. be able to. Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.

  In the thermosetting resin composition containing these cyanate resins, a curing agent for cyanate resins can be used as necessary. Examples of curing agents for cyanate resins include, for example, polyfunctional phenolic compounds such as phenol novolac, cresol novolac, aminotriazine novolak resin, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride Examples thereof include acid anhydrides such as acid, maleic anhydride, and maleic anhydride copolymers, and one of these can be used alone or two or more of them can be used in combination.

  As a compounding quantity of cyanate resin, 0-50 mass parts is preferable with respect to 100 mass parts of solid content conversion resin components in a thermosetting resin composition from a heat resistant and chemical-resistant viewpoint, for example. 10-30 mass parts is more preferable.

(Inorganic filler (K))
An inorganic filler (K) can be further blended in the thermosetting resin composition of the present invention. Inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, and boron. Examples thereof include aluminum powder, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads. These 1 type (s) or 2 or more types can be mixed and used.

  As the inorganic filler, silica is preferable in terms of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused spherical silica. Among these, fused spherical silica is more preferable from the viewpoint of low thermal expansion and high fluidity when filled in a resin.

  When using fused spherical silica as the inorganic filler, the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles 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 based on the particle diameter is obtained with the total volume of the particles as 100%, and a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.

  The blending amount of the inorganic filler is preferably 20 to 300 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the total solid content converted resin component in the thermosetting resin composition. By making the compounding quantity of an inorganic filler into 20-300 mass parts, the moldability and low thermal expansibility of a prepreg can be kept favorable.

(Curing accelerator (L))
A curing accelerator (L) can be further blended in the thermosetting resin composition of the present invention.
Examples of the curing accelerator (L) include imidazoles and derivatives thereof, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more, and imidazoles are preferred from the viewpoint of reactivity. Addition of hexamethylene diisocyanate and 2-ethyl-4-methylimidazole represented by the following general formula (L-1) More preferred.

  The blending amount of the curing accelerator (L) is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 5 parts by mass per 100 parts by mass of the resin component total in terms of solid content in the thermosetting resin composition. . By making the compounding quantity of a hardening accelerator into 0.01-10 mass parts, the moldability and low thermal expansibility of a prepreg can be kept favorable.

(Other ingredients)
The thermosetting resin composition of the present invention includes a thermoplastic resin, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, and a photopolymerization initiator as long as the thermosetting properties of the resin composition are not impaired. In addition, fluorescent brighteners and adhesion improvers can be used.

  Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, poly Examples include ether ether ketone resins, polyether imide resins, silicone resins, and tetrafluoroethylene resins.

  Examples of organic fillers include resin fillers of uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene resin And a core-shell structure resin filler having a rubber-like core layer and a glass-like shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like. Can be mentioned. Polyethylene, polypropylene, polystyrene, polyphenylene ether resin, and silicone resin can also be used as thermoplastic resins.

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

Other examples of UV absorbers include benzotriazole UV absorbers, examples of antioxidants include hindered phenols and hindered amines, and examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthone. Examples of photopolymerization initiators and fluorescent brighteners include stilbene derivative fluorescent brighteners, and adhesion improvers such as urea compounds such as urea silane and silane, titanate and aluminate cups. A ring agent is mentioned.
Further, at the time of blending, it is also preferable that the inorganic filler is pretreated with an silane-based or titanate-based coupling agent or a surface-treating agent such as a silicone oligomer, or an integral blend treatment.

[varnish]
The thermosetting resin composition of the present invention is usually used as a varnish using an organic solvent as a diluting solvent. The organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene. A system solvent etc. are mentioned, 1 type (s) or 2 or more types can be mixed and used.
40-90 mass% of the whole varnish is preferable, and, as for the resin composition in the varnish finally obtained, 50-80 mass% is more preferable. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coatability and obtain a prepreg having an appropriate resin composition adhesion amount.

[Prepreg]
The prepreg of the present invention is formed using the above-described thermosetting resin composition of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention can be produced by impregnating the thermosetting resin composition of the present invention into a substrate and semi-curing (B-stage) by heating or the like. Although it does not specifically limit as a method of impregnating a base material with the thermosetting resin composition of this invention, For example, the method of immersing a base material in a resin varnish, the method of apply | coating with various coaters, the method of spraying by a spray etc. are mentioned. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved.
As a base material, 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 fiber or the like can be used in the case of a fiber reinforced base material.

  These base materials have, for example, the shapes of woven fabric, non-woven fabric, robink, chopped strand mat and surfacing mat, and the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, can be used alone. Alternatively, two or more kinds of materials and shapes can be combined. The thickness of the base material is, for example, about 0.03 to 0.5 mm, and the surface treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment has heat resistance, moisture resistance, and It is suitable from the viewpoint of workability.

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

[Film with resin]
The film with a resin of the present invention is obtained by forming a layer of the thermosetting resin composition of the present invention on a support.
Although it does not specifically limit as a method of carrying out layer formation of the thermosetting resin composition obtained by this invention on a support body, For example, the thermosetting resin composition obtained by this invention is made into a varnish state, and various coaters are used. The resin composition layer can be formed by applying to a support and further drying by heating or blowing hot air. Thus, the resin-coated film of the present invention can be produced by being semi-cured (B-staged) by heating or the like. This semi-cured state is a state in which the adhesive force between the resin composition layer of the resin-coated film and the circuit board is secured when the film with resin and the circuit board are laminated and cured, and embedded in the circuit board. It is preferable that the property (fluidity) is ensured.
Here, the resin composition layer refers to a layer in which the thermosetting resin composition is formed in a semi-cured state on a support, and the insulating resin layer is formed by thermosetting the resin composition layer. Layer.

  The coater used when the thermosetting resin composition of the present invention is applied on a support is not particularly limited, and for example, a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, etc. can be used. . These can be appropriately selected depending on the thickness of the resin composition layer. As a drying method, heating, hot air blowing, or the like can be used.

  The drying conditions after applying the thermosetting resin composition to the support are, for example, dried so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. . Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. Is done. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  The thickness of the resin composition layer formed on the support is usually not less than the thickness of the conductor layer of the circuit board. The thickness of the conductor layer is preferably, for example, 5 to 70 μm, more preferably 5 to 50 μm, and more preferably 5 to 30 μm in order to reduce the thickness of the multilayer printed wiring board.

  The support in the film with resin is made of, for example, polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like. Examples of the film include metal foil such as release paper, copper foil, and aluminum foil. In addition, you may give a mold release process to a support body and the protective film mentioned later other than a mat | matte process and a corona treatment.

For example, the thickness of the support is preferably 10 to 150 μm, 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 where the support is not provided. The thickness of the protective film is, for example, 1 to 40 μm. By laminating the protective film, foreign matter can be prevented from being mixed.
The film with resin can also be wound and stored in a roll.

[Laminated board, multilayer printed wiring board]
The laminated board of the present invention is obtained by laminating the above-mentioned resin-coated film. For example, it can be manufactured by laminating a film with resin on one side or both sides of a circuit board, a prepreg, a base material and the like using a vacuum laminator and curing by heating as necessary.
Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the circuit pattern was formed in the one or both surfaces of the above boards. In addition, a printed wiring board in which a plurality of conductor layers and insulating layers are alternately laminated and having a circuit pattern formed on one side or both sides of the outermost layer of the printed wiring board is also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.

In the above laminate, if the film with resin has a protective film, after removing the protective film, preheat the film with resin and the circuit board as necessary, while pressing and heating the film with resin Crimp to circuit board.
In the film with resin of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination 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 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 conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the thermosetting resin composition, but are preferably 150 to 220 ° C. for 20 to 180 minutes, more preferably 160. It is selected within a range of 30 to 120 minutes at a temperature of from 200C to 200C.

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

  Next, a conductor layer is formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as 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.

The laminate of the present invention is obtained by laminating the above-described prepreg of the present invention. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating with a configuration in which a metal foil such as copper or aluminum is arranged on one or both sides thereof.
The molding conditions for producing the laminate can be applied, for example, to the method of laminates for electrical insulation materials and multilayer plates, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. Molding can be performed at 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Moreover, the prepreg of the present invention and a circuit board can be combined and laminated to produce a laminated board.

  The multilayer printed wiring board of this invention is manufactured using the said laminated board. For example, the circuit board can be obtained by wiring processing the conductor layer of the laminate of the present invention by an ordinary etching method. Then, a plurality of laminated boards processed by wiring through the above-described prepreg are laminated and subjected to hot press processing to be multi-layered at once. Thereafter, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing, and formation of an interlayer wiring by plating or conductive paste.

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

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

(1) Shrinkage rate of resin plate A resin plate having a length of 5 mm (X direction), a width of 5 mm (Y direction), and a thickness of 1.5 mm ± 0.5 mm (Z direction) was prepared, and a TMA test apparatus (TA instrument) Thermomechanical analysis was performed by the compression method using Q400). After mounting the resin plate in the X direction or Y direction on the device, the load is 5 g, the heating rate is 45 ° C./min, 20 ° C. (5 min hold) to 260 ° C. (2 min hold) to 20 ° C. (5 min hold) The temperature profile was measured. The shrinkage rate (%) of the resin plate was evaluated from the dimensional change at 20 ° C. before starting the temperature increase and at 20 ° C. after the temperature increase.
Specifically, the shrinkage ratio of the resin plate was calculated using the following formula.
Shrinkage rate (%) = {(dimension at 20 ° C. before starting temperature rise (mm) −dimension at 20 ° C. after temperature rise (mm)) / dimension at 20 ° C. before temperature rise (mm)} × 100

(2) Glass transition temperature (Tg)
A 5 mm square evaluation board from which the copper foil was removed was prepared by immersing the copper clad laminate in a copper etching solution, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.

(3) Coefficient of thermal expansion A 5 mm square evaluation substrate from which the copper foil has been removed by immersing a copper clad laminate in a copper etching solution is prepared, and heat is applied by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). Mechanical analysis was performed. After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion.

(4) Copper foil adhesion (copper foil peel strength)
A copper foil having a width of 3 mm was formed by immersing the copper-clad laminate in a copper etching solution to produce an evaluation substrate, and the adhesiveness (90 ° peel strength) of the copper foil was measured using a tensile tester.

(5) Evaluation of desmear resistance A 40 mm × 40 mm evaluation substrate from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was subjected to a desmear treatment by the steps shown in Table 1. A chemical manufactured by Atotech was used. In the evaluation of desmear resistance, the desmear weight reduction amount was calculated from the difference in dry weight before desmear treatment at 80 ° C. and after desmear treatment. The smaller the weight loss, the better the desmear resistance.

(6) Solder heat resistance test with copper A 2.5 mm × 2.5 mm copper clad laminate (n = 5) was prepared and floated in a solder bath at 288 ° C., and the time until copper bulge occurred was maximized. For 120 minutes.

(7) Dielectric properties (dielectric constant and dielectric loss tangent)
A 100 mm × 2 mm evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a cavity resonator device (manufactured by Kanto Electronics Application Development Co., Ltd.) was used at a frequency of 1 GHz. The relative dielectric constant and dielectric loss tangent were measured.

Examples 1-10, Comparative Examples 1-7
Each component shown below was mixed at a blending ratio (parts by mass) shown in Table 2, and a uniform varnish having a resin content of 65% by mass was produced using propylene glycol monomethyl ether (PGM) as a solvent. Next, this varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 130 ° C. for 3 minutes and a half to obtain a prepreg having a resin content of 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.

Further, the varnish was applied to a 16 μm polyethylene terephthalate film using a film applicator (Tester Sangyo Co., Ltd., PI-1210) so that the resin thickness after drying was 35 μm, and then at 160 ° C. for 10 minutes. Heat drying was performed to obtain a semi-cured resin plate.
This resin plate is put into a Teflon sheet form, the glossy surface of 12 μm electrolytic copper foil is placed up and down, pressed at a pressure of 2.0 MPa and a temperature of 240 ° C. for 60 minutes, and then the electrolytic copper foil is removed. A resin plate was obtained. Table 2 shows the test and evaluation results of the obtained copper-clad laminate and resin plate.

  The raw materials used in the examples and comparative examples are described below.

Component (A): Maleimide compound represented by general formula (1) (A-1): 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane represented by the following formula (4) [Yamato Product name: BMI-4000, manufactured by Kasei Kogyo Co., Ltd.

（Ａ−２）：下記式（５）で表されるビス（４−（４−マレイミドフェノキシ））ビフェニル（ＢＭＩ−ＢＰ）［下記製造例１で製造］

(A-2): Bis (4- (4-maleimidophenoxy)) biphenyl (BMI-BP) represented by the following formula (5) [produced in Production Example 1 below]

Resin for comparison 1: Bis (4-maleimidophenyl) methane [manufactured by Kay Kasei Co., Ltd .; trade name: BMI]

Component (B): Amino-modified siloxane compound having an aromatic azomethine group in the molecular structure AZS: Compound obtained by Production Example 2 below

Comparative resin 2: diamine-modified siloxane at both ends [manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-161B]

Component (C): amine compound having an acidic substituent p-aminophenol [manufactured by Kanto Chemical Co., Ltd.] (hereinafter also referred to as “PAP”)

Component (D): 4,4'-diamino-3,3'-diethyl-diphenylmethane [manufactured by Nippon Kayaku Co., Ltd .; trade name: KAYAHARD A-A] (hereinafter also referred to as "KH-A")

Component (E): Aromatic azomethine-containing modified imide resin (E-1): Compound obtained in Production Example 3 below (E-2): Compound obtained in Production Example 4 below

Comparative resin 3: Compound obtained in Production Example 5 below

Epoxy resin: α-naphthol / cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd .; trade name: NC-7000L]

Component (J): Thermoplastic elastomer-Epoxidized styrene-butadiene block copolymer [manufactured by Daicel Corporation; trade name: Epofriend CT-310] (hereinafter also referred to as "CT-310")

Ingredient (K): Inorganic filler-Fused silica [manufactured by Admatechs; trade name: SC-2050KNK]

Component (L): Curing accelerator-Addition product of hexamethylene diisocyanate and 2-ethyl-4-methylimidazole represented by the following general formula (L-1) [Daiichi Kogyo Seiyaku Co., Ltd .; trade name: G -8009L]

Production Example 1: Production of bis (4- (4-maleimidophenoxy)) biphenyl (BMI-BP) A reaction vessel having a volume of 5 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 4,4′-bis (4-aminophenoxy) biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.): 736.8 g, maleic anhydride: 392.0 g, cyclohexanone: 1670.6 g, toluene: 167.0 g The mixture was heated to 90 ° C. and dissolved uniformly. Next, the temperature was raised to the reflux temperature, and the reaction was carried out for 5 hours while removing the generated condensed water to obtain bis (4- (4-maleimidophenoxy)) biphenyl (BMI-BP).

Production Example 2: Production of amino-modified siloxane (B) having an aromatic azomethine group In a reaction vessel having a thermometer, a stirrer, a moisture meter with a reflux condenser and a capacity of 300 ml capable of heating and cooling, terephthalaldehyde ( Toray Fine Chemical Co., Ltd .: Component (H)): 22.75 g, 4,4′-diamino-3,3′-diethyl-diphenylmethane (Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A: Component (I)): 17.25 g, propylene glycol monomethyl ether (PGM): 60.0 g was added, and the mixture was refluxed for 2 hours to contain an aromatic azomethine compound-containing solution (component (F)) (hereinafter also referred to as “LCA”). Got.
Next, in a reaction vessel having a thermometer, a stirrer, a water quantifier with a reflux condenser, and a capacity of 500 ml capable of being cooled and cooled, the LCA obtained above: 22.15 g, both-end diamine-modified siloxane (Shin-Etsu Chemical) Product name: X-22-161B: Component (G)): 96.14 g, PGM: 144.21 g were added and refluxed for 2 hours, and then heated to 130 ° C. and concentrated at normal pressure. And an amino-modified siloxane (B) (weight average molecular weight Mw: 20,000) (hereinafter also referred to as “AZS”)-containing solution (resin component: 70 mass%) having an aromatic azomethine group in the molecular structure was obtained. .

Production Example 3 Production of Aromatic Azomethine-Containing Modified Imide Resin (E-1) In a reaction vessel having a volume of 5 liters, which can be heated and cooled, equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser, -Bis (4- (4-maleimidophenoxy) phenyl) propane (component (A)): 791.82 g, AZS (component (B)) obtained above: 101.22 g, p-aminophenol (component (C) ): 18.93 g, 4,4′-diamino-3,3′-diethyl-diphenylmethane (component (D)): 63.4 g, PGM: 1387.13 g, and after reacting at 115 ° C. for 4 hours, The temperature was raised to 130 ° C. and concentration was performed at normal pressure to obtain an aromatic azomethine-containing modified imide resin (E-1) -containing solution (resin component: 63% by mass).

Production Example 4: Production of Aromatic Azomethine-Containing Modified Imide Resin (E-2) Obtained above in a reaction vessel with a volume of 5 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. BMI-BP (component (A)): 753.72 g, AZS (component (B)) obtained above: 101.22 g, p-aminophenol (component (C)): 18.5 g, 4, 4 ′ -Diamino-3,3'-diethyl-diphenylmethane (component (D)): 61.9 g, PGM: 1387.13 g were added, reacted for 4 hours at 115 ° C, then heated to 130 ° C and concentrated at atmospheric pressure Then, an aromatic azomethine-containing modified imide resin (E-2) -containing solution (resin component: 63% by mass) was obtained.

Production Example 5: Production of Comparative Resin 3 In a reaction vessel having a volume of 5 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, BMI (Comparative Resin 1): 748.92 g AZS (component (B)) obtained above: 101.22 g, p-aminophenol (component (C)): 28.47 g, 4,4′-diamino-3,3′-diethyl-diphenylmethane (component ( D)): 96.76 g and PGM: 1387 g were added and reacted at 115 ° C. for 4 hours, and then heated to 130 ° C. and concentrated at normal pressure to give an aromatic azomethine-containing modified imide resin (Comparative Resin 3). A containing solution (resin component: 63% by mass) was obtained.

  As is apparent from Table 2, in the examples of the present invention, the shrinkage rate and desmear resistance are excellent, and the thermal expansion coefficient and electrical characteristics are also good. On the other hand, in the comparative example, the shrinkage rate and desmear resistance are not satisfactory. Therefore, the thermosetting resin composition of the present invention provides a laminate having excellent low shrinkage, low thermal expansion and desmear resistance.

  Since the thermosetting resin composition of the present invention can obtain a laminated board having particularly excellent shrinkage and desmear resistance, a printed wiring board having a high density and a high number of layers can be produced. Is suitably used for a wiring board for electronic equipment such as computers and information equipment terminals.

Claims (16)

A thermosetting resin composition comprising a maleimide compound (A) represented by the following general formula (1) and an amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure.

[In General Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, and X represents an alkylene group, an arylene group, Or the following general formula (2)

(In General Formula (2), R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a sulfone group, and R ₅ , R ₆ , and R ₇ independently represents a single bond, an alkylene group, an amide group, or a carbonyl group, * represents a bond portion with an adjacent oxygen atom, and p and q each independently represents an integer of 0 to 4.)
The bivalent coupling group represented by these is shown. m and n each independently represents an integer of 0 to 4. ] X in the general formula (1) is a divalent linking group represented by the general formula (2), and R _{6 in the} general formula (2) is a single bond or an alkylene group. The thermosetting resin composition described in 1. Furthermore, the thermosetting resin composition of Claim 1 or 2 formed by mix | blending the amine compound (C) which has an acidic substituent represented by following General formula (3).

(In general formula (3), each R ₈ independently represents a hydroxyl group, carboxyl group or sulfone group which is an acidic substituent, and each R ₉ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. 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.)   Furthermore, the thermosetting resin composition of any one of Claims 1-3 formed by mix | blending a hardening | curing agent (D).   A maleimide compound (A) represented by the general formula (1), an amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure, an amine compound (C) having an acidic substituent, and a curing agent The thermosetting resin composition of Claim 4 containing the aromatic azomethine containing modified imide resin (E) formed by reacting (D).   The amino-modified siloxane compound (B) having an aromatic azomethine group in the molecular structure is an aromatic azomethine compound (F) having at least one aldehyde group in one molecule and at least two primary amino groups at the molecular end. The thermosetting resin composition of any one of Claims 1-5 obtained by making it react with the siloxane compound (G) which has this.   The aromatic azomethine compound (F) having at least one aldehyde group in one molecule is an aromatic aldehyde compound (H) having at least two aldehyde groups in one molecule and at least two in one molecule. The thermosetting resin composition according to claim 6, which is obtained by reacting the diamine compound (I) having a primary amino group.   Furthermore, the thermosetting resin composition of any one of Claims 1-7 formed by mix | blending a thermoplastic elastomer (J).   Furthermore, the thermosetting resin composition of any one of Claims 1-8 formed by mix | blending an inorganic filler (K).   Furthermore, the thermosetting resin composition of any one of Claims 1-9 formed by mix | blending a hardening accelerator (L).   A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 10.   The film with a resin formed by layer-forming the thermosetting resin composition of any one of Claims 1-10 on a support body.   A laminate obtained by laminating the prepreg according to claim 11.   A laminate obtained by laminating the film with resin according to claim 12.   The multilayer printed wiring board manufactured using the laminated board of Claim 13 or 14.   A semiconductor package obtained by mounting a semiconductor on the multilayer printed wiring board according to claim 15.