WO2014084310A1

WO2014084310A1 - Amino-modified siloxane compound, modified imide resin, thermosetting resin composition, prepreg, resin-equipped film, laminated plate, multilayer printed circuit board, and semiconductor package

Info

Publication number: WO2014084310A1
Application number: PCT/JP2013/082054
Authority: WO
Inventors: 智彦小竹; 駿介長井; 慎太郎橋本; 慎一郎安部; 正人宮武; 高根沢　伸; 村井　曜
Original assignee: 日立化成株式会社
Priority date: 2012-11-28
Filing date: 2013-11-28
Publication date: 2014-06-05
Also published as: JP6747655B2; KR20150089017A; TW201434850A; JPWO2014084318A1; TW201428030A; JP6372071B2; TWI614286B; JPWO2014084310A1; JP6375951B2; CN106973490B; CN107254049A; JP2014129520A; KR102166235B1; TWI614262B; CN106973490A; CN104812805B; WO2014084318A1; CN104812805A

Abstract

Provided are: an amino-modified siloxane compound comprising an aromatic azomethine in a molecular structure obtained by reacting a siloxane compound (B) having at least two primary amino groups on the molecular end thereof with an aromatic azomethine compound (A) that has at least one aldehyde group per molecule and that is obtained by reacting an aromatic amine compound (i) having at least two primary amino groups per molecule with an aromatic aldehyde compound (ii) having at least two aldehyde groups per molecule; and a modified imide resin and a thermosetting resin composition using said amino-modified siloxane compound.

Description

Amino-modified siloxane compound, modified imide resin, thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board, and semiconductor package

The present invention relates to an amino-modified siloxane compound having an aromatic azomethine suitable for semiconductor packages and printed wiring boards, a modified imide resin using the same, a thermosetting resin composition, a prepreg, a film with a resin, a laminate, and a multilayer print The present invention relates to a wiring board and a semiconductor package.

In recent years, with the trend toward miniaturization and higher performance of electronic devices, the 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 such applications, particularly semiconductor packages, it is required to have both excellent heat resistance and low thermal expansion. In addition, dielectric characteristics corresponding to higher frequency of electric signals have been required.

In this regard, known liquid crystalline polymers such as polyesters, polyamides, polycarbonates, polythiols, polyethers, and polyazomethines are thermosetting resins that are excellent in low thermal expansion, dielectric properties, and heat resistance. However, there is a problem that workability and moldability are insufficient, and a problem that solubility in an organic solvent is insufficient and handling is difficult.

Among these liquid crystalline polymers, G.M. F. Since D'Aleio found polyazomethine, which is a liquid crystalline oligomer (see Non-Patent Document 1), many cases relating to resins using polyazomethine have been reported (see, for example, Patent Documents 1 to 7).

Patent Document 1 discloses various polyazomethines, and Patent Documents 2 to 7 disclose polyazomethines having specific structures. Patent Document 8 discloses thermosetting polyazomethine resins containing unsaturated groups, and describes that these resins exhibit high heat resistance.

JP 51-138800 A JP-A-60-181127 JP-A-60-101123 JP 2003-073470 A JP-A-63-193925 Japanese Patent Laid-Open No. 01-069631 Japanese Patent Laid-Open No. 01-079233 Japanese Patent Laid-Open No. 05-140067

However, the polyazomethines described in Patent Documents 1 to 7 may have insufficient heat resistance and formability when applied as a copper clad laminate or an interlayer insulating material. Further, the thermosetting polyazomethine resin described in Patent Document 8 still lacks improvement in heat resistance and toughness, and even when these are applied as a copper clad laminate or an interlayer insulating material, the heat resistance and reliability are also improved. , Workability and the like may be insufficient.

In view of the current situation, the object of the present invention is a modified imide resin or thermosetting which exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications. Amino-modified siloxane compound capable of realizing a functional resin composition, the modified imide resin and a thermosetting resin composition, a prepreg using the same, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor package It is.

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using an amino-modified siloxane compound having an aromatic azomethine. The present invention is based on such knowledge.

That is, the present invention provides an amino-modified siloxane compound having the following aromatic azomethine, a modified imide resin using the amino-modified siloxane compound, a thermosetting resin composition containing the amino-modified siloxane compound, a prepreg, and a film with a resin The present invention provides a laminated board, a multilayer printed wiring board, and a semiconductor package.

[1] Obtained by reacting an aromatic amine compound (i) having at least two primary amino groups in one molecule and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule, Aromatic azomethine compound (A) having at least one aldehyde group in one molecule and siloxane compound (B) having at least two primary amino groups at the molecular end can be reacted with an aromatic in the molecular structure. An amino-modified siloxane compound having azomethine.
[2] Obtained by reacting an amino-modified siloxane compound having an aromatic azomethine in the molecular structure according to [1] and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. A modified imide resin having an aromatic azomethine.

[3] The modified imide resin according to [2], further having an acidic substituent, wherein the acidic substituent is derived from the acidic substituent of the amine compound (D) represented by the following general formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ 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] A thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine according to [1] and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule.

[5] The thermosetting resin composition according to [4], further comprising an amine compound (D) having an acidic substituent represented by the following general formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ 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.)
[6] The thermosetting resin composition according to [4] or [5], further containing a thermoplastic elastomer (E).
[7] The thermosetting resin composition according to any one of [4] to [6], further containing at least one thermosetting resin (F) selected from an epoxy resin and a cyanate resin.
[8] The thermosetting resin composition according to any one of [4] to [7], further containing an inorganic filler (G).
[9] The thermosetting resin composition according to any one of [4] to [8], further comprising a curing accelerator (H).

[10] A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of [4] to [9].
[11] A film with a resin obtained by forming a layer of the thermosetting resin composition according to any one of [4] to [9] on a support.
[12] A laminate obtained by laminate-molding the prepreg according to [10].
[13] A laminate obtained by laminating the film with resin according to [11].
[14] A multilayer printed wiring board produced using the laminated board according to [12] or [13].
[15] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to [14].

According to the present invention, a modified imide resin or thermosetting resin composition that exhibits excellent low curing shrinkage and low thermal expansion, good dielectric properties, and high elastic modulus when applied to various applications. An amino-modified siloxane compound, a modified imide resin and a thermosetting resin composition that can be realized, a prepreg, a film with a resin, a laminate, a multilayer printed wiring board, and a semiconductor package using the same can be provided.

In particular, a modified imide resin or a thermosetting resin composition using an amino-modified siloxane compound having an aromatic azomethine of the present invention is obtained by impregnating and coating a base material and a support. A laminated film produced by laminating and forming a film with resin and the prepreg, in particular, has low curing shrinkage, low thermal expansion, excellent dielectric properties, and high elastic modulus, and is used as a multilayer printed wiring board and semiconductor package. Useful.

Hereinafter, the present invention will be described in detail.
(Amino-modified siloxane compound)
The amino-modified siloxane compound having an aromatic azomethine of the present invention is an aromatic amine compound (i) having at least two primary amino groups in one molecule, and an aromatic aldehyde having at least two aldehyde groups in one molecule. An aromatic azomethine compound (A) having at least one aldehyde group in one molecule and a siloxane compound (B) having at least two primary amino groups at the molecular ends obtained by reacting compound (ii) It can be obtained by reaction.
Here, the aromatic azomethine means a compound in which at least one aromatic is bonded to a Schiff base (—N═CH—).

Examples of the aromatic amine compound (i) having at least two primary amino groups in one molecule of the present invention (hereinafter sometimes referred to as component (i)) include p-phenylenediamine and 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'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4 ' -Diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-dia Nobiphenyl, 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-amino) Phenoxy) 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 admixture of two or more.

Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4 has high reactivity at the time of reaction and can achieve higher heat resistance. '-Diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4- Aminophenoxy) phenyl) propane is preferred. Furthermore, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-3,3 ′ are inexpensive and have solubility in solvents. -Diethyl-diphenylmethane, bis (4- (4-aminophenoxy) phenyl) propane is more preferred. Furthermore, 4,4′-diamino-3,3′-diethyl-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are particularly 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.

Examples of the aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule of the present invention (hereinafter sometimes referred to as component (ii)) include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde. 2,2′-bipyridine-4,4′-dicarboxaldehyde and the like. Among these, for example, terephthalaldehyde is particularly preferable because it can be further reduced in thermal expansion, has high reactivity during the reaction, is excellent in solvent solubility, and is easily available commercially.

The siloxane compound (B) (hereinafter sometimes referred to as component (B)) having at least two primary amino groups at the molecular ends of the present invention includes the following general formula (2).

[Wherein, R ₃ and R ₄ each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100. ]
In the general formula (2), n is an integer of 1 to 100, more preferably an integer of 2 to 50.

Moreover, a commercial item can be used as a component (B). Examples of commercially available products include “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) (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.). These may be used alone or in admixture of two or more.
Among these, from the viewpoint of high reactivity during synthesis and low thermal expansion, for example, X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, BY-16- 853B is preferable, and X-22-161A and X-22-161B, which have excellent compatibility and can increase the elastic modulus, are more preferable.

In the present invention, as a reaction for obtaining an amino-modified siloxane compound having an aromatic azomethine in the molecular structure, first, an aromatic amine compound (i) having at least two primary amino groups in one molecule; Aromatic azomethine compound (A) having at least one aldehyde group in one molecule by subjecting aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule to dehydration condensation reaction in an organic solvent (Hereinafter sometimes referred to as component (A)). Next, an amino-modified siloxane compound having an aromatic azomethine is obtained by subjecting the component (A) and a siloxane compound (B) having at least two primary amino groups at the molecular ends to a dehydration condensation reaction in an organic solvent. Can do.
In addition, this reaction has a feature that the molecular weight of the aromatic azomethine can be easily controlled in the molecule of the amino-modified siloxane compound having the aromatic azomethine of the present invention, and the resin composition containing this has a high elastic modulus. Is particularly effective.

In the present invention, examples of the organic solvent used when the component (i) and the component (ii) are subjected to a dehydration condensation reaction include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether. , Including ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples thereof include solvents, sulfur atom-containing solvents such as dimethyl sulfoxide, and ester solvents such as γ-butyrolactone. These may be used alone or in admixture of two or more. Among these, from the viewpoint of solubility, for example, propylene glycol monomethyl ether, cyclohexanone, toluene, dimethylformamide, dimethylacetamide, γ-butyrolactone and the like are preferable. Furthermore, propylene glycol monomethyl ether and toluene are more preferable because they are highly volatile and hardly remain as a residual solvent during the production of the prepreg.
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 of component (i) and component (ii), a reaction catalyst can be optionally used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. . These may be used alone or in admixture of two or more. In order to allow the dehydration condensation reaction to proceed efficiently, for example, an acidic catalyst such as p-toluenesulfonic acid is preferred.

Here, the amount of component (i) and component (ii) used is, for example, the number of primary amino groups of component (i) [the amount of component (i) used / the primary amino group equivalent of component (i)] It is desirable to use it in a range of 0.1 to 5.0 times the number of aldehyde groups in ii) [amount of component (ii) used / aldehyde group equivalent of component (ii)]. By setting it to 0.1 times or more, a decrease in the molecular weight of the aromatic azomethine compound obtained by this reaction tends to be suppressed. Moreover, it exists in the tendency for the fall of the solubility to a solvent to be suppressed by setting it as 5.0 times or less.

The amount of the organic solvent used is preferably 25 to 2000 parts by mass, for example, 40 to 1000 parts by mass with respect to 100 parts by mass of the total of the resin components of component (i) and component (ii). More preferably, the amount is 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. Further, when the amount is 2000 parts by mass or less, there is a tendency that a long time is required for the reaction.

Component (A) is obtained 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, if necessary, while heating and keeping warm to cause a dehydration condensation reaction.
The reaction temperature at this time is preferably 70 to 150 ° C., for example, and more preferably 100 to 130. Moreover, it is preferable to react, removing the water which is a by-product. By setting the reaction temperature to 70 ° C. or higher, the reaction rate tends to be low. In addition, by setting the reaction temperature to 150 ° C. or lower, a high-boiling solvent is not required as the reaction solvent, and when the prepreg is produced, the residual solvent hardly remains and the heat resistance tends to be reduced.

Next, an amino-modified siloxane having an aromatic azomethine is obtained by subjecting the component (A) obtained by the above reaction and a siloxane compound (B) having at least two amino groups at the molecular ends to a dehydration condensation reaction in an organic solvent. A compound can be obtained.

Here, the amount of component (A) and component (B) used is, for example, the number of primary amino groups in component (B) [the amount of component (B) used / the primary amino group equivalent of component (B)] It is desirable that the number of aldehyde groups in A) is 1.0 to 10.0 times the number of aldehyde groups [amount of component (A) used / aldehyde equivalent of component (A)]. By setting it to 1.0 times or more, a decrease in solubility in a solvent tends to be suppressed. Moreover, a favorable elastic modulus is obtained in the thermosetting resin containing the amino modified siloxane compound which has aromatic azomethine by setting it as 10.0 times or less.

The amount of the organic solvent used is preferably 25 to 2000 parts by weight, for example, 40 to 1000 parts by weight with respect to 100 parts by weight of the total of the resin components of component (A) and component (B). More preferably, the amount is 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the lack of solubility tends to be small. Moreover, by setting it as 2000 mass parts or less, reaction does not require a long time.

An amino-modified siloxane compound having an aromatic azomethine is prepared by charging the above raw materials, an organic solvent, and if necessary, a reaction catalyst in a reaction kettle and stirring and dehydrating and condensing for 0.1 to 10 hours while heating and holding as necessary. can get.
The reaction temperature is, for example, preferably 70 to 150 ° C., more preferably 100 to 130. Moreover, it is preferable to react, removing the water which is a by-product. By setting the reaction temperature to 70 ° C. or higher, the reaction rate tends not to be too slow. Moreover, when the reaction temperature is set to 150 ° C. or lower, a high-boiling solvent is not required for the reaction solvent, and when the prepreg is produced, the residual solvent hardly remains and good heat resistance tends to be obtained.

The amino-modified siloxane compound having an aromatic azomethine 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. The weight average molecular weight (Mw) is not particularly limited, but is preferably 1000 to 300000, and more preferably 6000 to 150,000, for example. When the weight average molecular weight (Mw) is 1000 or more, good low curing shrinkage and low thermal expansion tend to be obtained. Moreover, it exists in the tendency for favorable compatibility and an elasticity modulus to be obtained as it is 300,000 or less. 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.
As a measuring device, 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), a UV / VIS detector (Japan) Spectroscopic industry 870-UV), HPLC pump (JASCO Corporation 880-PU) is used.
In addition, TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation is used as the column used, and measurement is possible by using a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent of tetrahydrofuran.

(Modified imide resin)
The modified imide resin of the present invention is obtained by reacting the aforementioned amino-modified siloxane compound of the present invention with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. .

Furthermore, the modified imide resin preferably has an acidic substituent, and the acidic substituent is derived from the acidic substituent of the amine compound (D) represented by the following general formula (1). The acidic substituent can be introduced by reacting the amine compound (D). By having such an acidic substituent, good low thermal expansibility can be obtained.

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ 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.)
Further details of the amine compound (D) will be described later. The term “derived from the acidic substituent of the amine compound (D)” refers to the acidic substituent itself of the amine compound (D) and the one containing the acidic substituent.

The modified imide resin can be produced in a “pre-reaction” when producing a thermosetting resin composition described later.

(Thermosetting resin composition)
The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. is there.

Examples of maleimide compounds (C) having at least two N-substituted maleimide groups in one molecule (hereinafter sometimes referred to as component (C)) include bis (4-maleimidophenyl) methane and polyphenylmethane. Maleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebis And maleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, and the like. A component (C) may be used independently, or 2 or more types may be mixed and used for it.

Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 2,2-bis (4- (4- (4- Maleimidophenoxy) phenyl) propane is preferred, and bis (4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferred and inexpensive from the viewpoint of solubility in solvents. Bis (4-maleimidophenyl) methane is particularly preferred from a certain point.

In the thermosetting resin composition of the present invention, the amount of the amino-modified siloxane compound having an aromatic azomethine is preferably, for example, 1 to 30 parts by mass per 100 parts by mass of the total resin components. It is more preferable to set it as a mass part from the point of copper foil adhesiveness and chemical resistance.
The amount of component (C) used is, for example, preferably from 30 to 99 parts by weight, and preferably from 40 to 95 parts by weight per 100 parts by weight of the sum of the resin components in terms of low thermal expansion and high elastic modulus. More preferred

The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. . Moreover, it can also be used as modified imide resin which has the said compound pre-reacted and has aromatic azomethine. By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.

This pre-reaction is performed by reacting an amino-modified siloxane compound having aromatic azomethine with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule while heating and keeping in an organic solvent. It is preferable to synthesize an imide resin.
The reaction temperature when reacting an amino-modified siloxane compound having an aromatic azomethine in an organic solvent with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule is, for example, 70 to 150. ° C is preferable, and 100 to 130 ° C is more preferable. The reaction time is, for example, preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

In this pre-reaction, the amount of the amino-modified siloxane compound having component (C) and aromatic azomethine is, for example, the number of maleimide groups of component (C) [the amount of component (C) used / maleimide group equivalent of component (C) ] Of the primary amino group number of amino-modified siloxane compound having aromatic azomethine [the amount of amino-modified siloxane compound having aromatic azomethine used / primary amino group equivalent of amino-modified siloxane compound having aromatic azomethine] A range that is 10.0 times larger is preferable. By setting it to 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10.0 times or less.

The amount of component (C) used in the pre-reaction is, for example, preferably 50 to 3000 parts by weight, and 100 to 1500 parts by weight with respect to 100 parts by weight of the resin component of the amino-modified siloxane compound while maintaining the above relationship. Is more preferable. When the amount is 50 parts by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.

Examples of the organic solvent used in this 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 And sulfur atom-containing solvents such as These organic solvents can 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 particularly preferable.

The amount of the organic solvent used is, for example, 100 parts by mass of the total resin component of the modified siloxane compound having aromatic azomethine and the maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, and particularly preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. In addition, when the amount is 2000 parts by mass or less, the reaction does not take a long time.

In addition, a reaction catalyst can be optionally used for this 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. Etc. These reaction catalysts can be used alone or in combination of two or more.

The amount of the modified imide resin having an aromatic azomethine obtained from the pre-reaction is preferably 50 to 100 parts by mass, for example, 100 to 100 parts by mass per 100 parts by mass of the total resin components. More preferably. By setting the blending amount of the modified imide resin having aromatic azomethine to 50 parts by mass or more, good low thermal expansibility and high elastic modulus can be obtained.

A thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine of the present invention and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule, and The modified imide resin having an aromatic azomethine obtained by the reaction alone has good thermosetting reactivity, but if necessary, a curing agent and a radical initiator can be used in combination. By using a curing agent and a radical initiator, heat resistance, adhesiveness, and mechanical strength can be improved.
Examples of the curing agent used in combination include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine. Aromatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine. These may be used alone or in admixture of two or more.

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. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.

Furthermore, the thermosetting resin composition of the present invention can contain an amine compound (D) having an acidic substituent represented by the following general formula (1).

(In formula (1), each R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R ₂ 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.)

Examples of the amine compound (D) having an acidic substituent (hereinafter sometimes referred to as component (D)) 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, etc. . Among these, for example, in terms of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5- Dihydroxyaniline is preferred. From the viewpoint of heat resistance, m-aminophenol and p-aminophenol are more preferable.

The amount of component (D) used is, for example, preferably from 0.5 to 30 parts by weight, and more preferably from 1 to 20 parts by weight per 100 parts by weight of the total of the resin components, from the viewpoint of low thermal expansion. preferable.

The thermosetting resin composition of the present invention comprises an amino-modified siloxane compound having an aromatic azomethine, a maleimide compound (C) having at least two N-substituted maleimide groups in a molecule, and an amine compound having an acidic substituent ( D) may be contained. Alternatively, the compound can be pre-reacted and used as a modified imide resin having an acidic substituent and an aromatic azomethine. By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.

This pre-reaction involves synthesizing a modified imide resin having an acidic substituent by reacting an amino-modified siloxane compound having an aromatic azomethine, component (C), and component (D) while keeping the temperature in an organic solvent. Is preferred.
The reaction temperature at the time of reacting the amino-modified siloxane compound having aromatic azomethine, component (C), and component (D) in an organic solvent is preferably, for example, 70 to 150 ° C., and preferably 100 to 130 ° C. More preferably. The reaction time is, for example, preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

In this pre-reaction, the amount of amino-modified siloxane compound having aromatic azomethine, component (C), and component (D) is, for example, the number of maleimide groups in component (C) [the amount of component (C) used / component ( C) maleimide group equivalent] is an amino-modified siloxane compound having an aromatic azomethine and the number of primary amino groups in component (D) [amount of amino-modified siloxane compound having an aromatic azomethine / amino-modified siloxane compound having an aromatic azomethine The primary amino group equivalent + the amount of component (D) used / the primary amino group equivalent of component (D)] is desirably in a range of 2.0 to 10.0 times. By setting it to 2.0 times or more, gelation and a decrease in heat resistance tend to be suppressed. Moreover, it exists in the tendency for the solubility to an organic solvent and the fall of heat resistance to be suppressed by setting it as 10.0 times or less.

The amount of the component (C) used in the pre-reaction is preferably 50 to 3000 parts by weight with respect to 100 parts by weight of the resin component of the amino-modified siloxane compound having an aromatic azomethine while maintaining the above relationship, 100 to 1500 parts by mass is more preferable. When the amount is 50 parts by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 3000 mass parts or less.
The amount of component (D) used in the pre-reaction is, for example, preferably from 1 to 1000 parts by weight, more preferably from 5 to 500 parts by weight, based on 100 parts by weight of the resin component of the amino-modified siloxane compound. When the content is 1 part by mass or more, a decrease in heat resistance tends to be suppressed. Moreover, low thermal expansibility can be kept favorable by setting it as 1000 mass parts or less.

The amount of the organic solvent used is, for example, 25 to 2000 parts by mass with respect to 100 parts by mass of the total of the amino-modified siloxane compound having aromatic azomethine, the component (C), and the resin component of component (D). The amount is preferably 40 to 1000 parts by weight, more preferably 40 to 500 parts by weight. When the amount of the organic solvent used is 25 parts by mass or more, insufficient solubility tends to be suppressed. In addition, when the amount is 2000 parts by mass or less, the reaction does not take a long time.

In addition, a reaction catalyst can be optionally used for this 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. Etc. These can be used alone or in combination of two or more.

The amount of the modified imide resin having an acidic substituent and an aromatic azomethine obtained by the pre-reaction is preferably 50 to 100 parts by mass, for example, per 100 parts by mass of the total resin components, and preferably 60 to More preferably, it is 90 parts by mass. When the blending amount of the modified imide resin having an acidic substituent and an aromatic azomethine is 50 parts by mass or more, good low thermal expansibility and high elastic modulus tend to be obtained.

An amino-modified siloxane compound having an aromatic azomethine of the present invention, comprising a maleimide compound (C) having at least two N-substituted maleimide groups in a molecule, and an amine compound (D) having an acidic substituent. A thermosetting resin composition and a modified imide resin having an aromatic substituent and an aromatic azomethine obtained by pre-reacting the above compound alone have good thermosetting reactivity, but if necessary, a curing agent and radical initiation An agent may be used. By using a curing agent and a radical initiator in combination, heat resistance, adhesiveness, and mechanical strength can be improved.
Examples of the curing agent used in combination include dicyandiamide, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenylsulfone, phenylenediamine, and xylenediamine. Aromatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine.
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. Among these, for example, aromatic amines are preferable from the viewpoint of good reactivity and heat resistance.

Furthermore, the thermosetting resin composition of the present invention can contain a thermoplastic elastomer (E).
Examples of the thermoplastic elastomer (E) (hereinafter sometimes referred to as the component (E)) include, for example, a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer. Examples thereof include elastomers and derivatives thereof. These include 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.

Further, as the component (E), 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 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. Can do. Therefore, as a result, it is possible to significantly reduce the warpage of the substrate.

Among these components (E), for example, styrene elastomers, olefin elastomers, polyamide elastomers, and silicone elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene elastomers from the viewpoint of dielectric properties. And olefin-based elastomers are particularly preferred.

Further, the reactive functional group possessed in the molecular terminal or molecular chain of these components (E) is preferably, for example, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an amide group in terms of adhesion to the metal foil. In view of heat resistance and insulation reliability, an epoxy group, a hydroxyl group, and an amino group are particularly preferable.

The amount of component (E) used is, for example, preferably from 0.1 to 50 parts by weight, and more preferably from 2 to 30 parts by weight, based on 100 parts by weight of the total resin components. It is more preferable because the compatibility of the resin is good, and the cured product has low curing shrinkage, low thermal expansion, and excellent dielectric properties.

Furthermore, the thermosetting resin composition of the present invention may contain at least one thermosetting resin (F) (hereinafter sometimes referred to as component (F)) selected from epoxy resins and cyanate resins. it can.
Examples of the component (F) epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol. F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy Resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl esters of polycyclic aromatics such as anthracene And Tel compounds and phosphorus-containing epoxy resin obtained by introducing a phosphorus compound thereof. These may be used alone or in admixture of two or more. Among these, for example, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy.

Examples of the cyanate resin of component (F) include, for example, bisphenol type cyanate resins such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and some of these. Examples include triazine prepolymers. These may be used alone or in admixture of two or more. Among these, for example, a novolac type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.

A curing agent can be used for these components (F) as necessary. Examples of the curing agent include, for example, polyfunctional phenol compounds such as phenol novolak, cresol novolak, aminotriazine novolak resin, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, maleic anhydride Examples thereof include acid anhydrides such as acid and maleic anhydride copolymers. These 1 type can be used individually or in mixture of 2 or more types.

The amount of component (F) used is, for example, preferably 1 to 50 parts by mass per 100 parts by mass of the total resin components, and 3 to 35 parts by mass from the viewpoint of heat resistance and chemical resistance. Is more preferable.

The thermosetting resin composition of the present invention can contain an inorganic filler (G).
Examples of the inorganic filler (G) (hereinafter sometimes referred to as component (G)) include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, and stannic acid. Examples thereof include zinc, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads. These may be used alone or in admixture of two or more.

As the component (G), for example, silica is particularly 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. Further, examples of the dry process silica include crushed silica, fumed silica, fused spherical silica and the like depending on the production method. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.

When using fused spherical silica as the component (G), for example, the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle size of the fused spherical silica to 0.1 μm or more, it is possible to maintain good fluidity when the resin is highly filled. Moreover, by setting it as 10 micrometers or less, the mixing probability of a coarse particle can be reduced and generation | occurrence | production of the defect resulting from a coarse particle can be suppressed. Here, the average particle diameter is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.

The content of the component (G) is, for example, preferably 20 to 500 parts by mass, more preferably 50 to 350 parts by mass with respect to 100 parts by mass of the total resin components. By setting the content of component (G) to 20 to 500 parts by mass with respect to 100 parts by mass of the total of the resin components, the moldability and low thermal expansibility of the resin composition can be kept good.
In addition, when the component (G) is blended into the resin composition, for example, the component (G) is pretreated with a silane or titanate coupling agent, a surface treatment agent such as a silicone oligomer, or an integral blend treatment. May be.

The thermosetting resin composition of the present invention can contain a curing accelerator (H).
Examples of the curing accelerator (H) (hereinafter sometimes referred to as component (H)) include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and tris. Organometallic salts such as acetylacetonate cobalt (III), imidazoles and derivatives thereof, organophosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts Is mentioned. These 1 type can be used individually or in mixture of 2 or more types.
Among these, for example, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of the promoting effect and the storage stability.

The content of the component (H) is, for example, preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the total resin components. preferable. By setting the content of the component (H) to 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the total of the resin components, the acceleration effect and the storage stability can be kept good.

In the present invention, any known thermoplastic resin, organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, and adhesion improver may be used without departing from the object. Etc. can be used. These may be used alone or in combination of two or more.

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

Examples of the organic filler include a resin filler made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, 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 the flame retardant 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.

In addition, 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 etc. are mentioned.

Since the thermosetting resin composition containing the amino-modified siloxane compound having an aromatic azomethine of the present invention is used in a prepreg, finally, the varnish state in which each component is dissolved or dispersed in an organic solvent and It is preferable to do.

Examples of the organic solvent used here include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butyl acetate. Ester solvents such as 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, dimethyl sulfoxide And a sulfur atom-containing solvent. These can be used individually by 1 type or in mixture of 2 or more types.
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.

The final 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 content of the thermosetting resin composition in the varnish to 40 to 90% by mass, it is possible to obtain a prepreg having an appropriate resin composition adhesion amount while maintaining good coating properties.

Here, in this specification, “resin component” means an amino-modified siloxane compound, a modified imide resin (having an acidic substituent derived from the acidic substituent of the amine compound (D) represented by the general formula (1) described above). Modified imide resin), maleimide compound (C), amine compound (D) having an acidic substituent, thermoplastic elastomer (E), thermosetting resin (F), and reaction products thereof. The “thermosetting resin composition” refers to a resin component containing an inorganic filler and a curing accelerator.

(Prepreg)
The prepreg of the present invention is obtained by impregnating a base material with 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 to make a base material impregnate 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, 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 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 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 can be, 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 and It is suitable in terms of moisture resistance and processability.

The prepreg of the present invention has, for example, a base so that the amount of the thermosetting resin composition attached to the substrate is 20 to 90% by mass in terms of the content of the thermosetting resin composition of the prepreg after drying. After impregnating or coating the material, it can usually be obtained by drying by heating 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.
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, such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. dry. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, the resin composition layer can be obtained 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. It is formed. 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 even 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, polyolefin such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester 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. Note that the support and the protective film described later may be subjected to a release treatment in addition to the mat treatment and the corona treatment.

The thickness of the support is, for example, preferably 10 to 150 μm, more preferably 25 to 50 μm. A protective film can be further laminated on the surface of the resin composition layer on which the support is not provided. The protective film may be the same as or different from the material of the support. 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, and the resin-coated film can be wound into a roll and stored.

(Laminated 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.

When laminating as described above, 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, Crimp to circuit board while pressing and heating. 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 air pressure 20 mmHg (26.7 hPa) or less. Is preferred. The laminating method may be a batch method or a continuous method using a roll.

After laminating the resin-coated film on the circuit board, after cooling to around room temperature and then peeling the support, the resin composition layer is heat-cured after peeling the support (hereinafter, after heat-curing) The resin composition layer may be referred to as an insulating layer). The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 to 220 ° C. for 20 to 180 minutes, more preferably 160 to 200 ° C. It is selected in the range of 30 to 120 minutes at ° C. Moreover, you may peel a support body, after thermosetting a resin composition layer.

Next, if necessary, holes are made in the insulating 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 layer by dry plating or wet plating. As the dry plating, for example, 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 composition layer is permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid. Roughening treatment is performed with an oxidizing agent such as to form an uneven anchor. 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 structure in which a metal foil such as copper or aluminum is disposed on one or both sides.
The molding conditions for laminating the laminate can be, for example, the method of a laminate for an electrical insulating material and a multilayer plate, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. Molding can be performed in a range of up to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a laminated board.

(Multilayer printed wiring 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 through holes or blind via holes by drilling, laser processing, etc., and formation of interlayer wiring by plating or conductive paste.

(Semiconductor package)
The semiconductor package of the present invention is obtained by mounting a semiconductor element on the multilayer printed wiring board. The semiconductor package of the present invention is manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the printed wiring board.

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, it measured by the following method about the shrinkage | contraction rate using the resin board obtained by each Example and the comparative example, and evaluated. Furthermore, using a copper-clad laminate, the glass transition temperature, the coefficient of thermal expansion, the copper foil adhesion, the solder heat resistance with copper, the bending elastic modulus, and the dielectric properties were measured and evaluated by the following methods.

(1) Measurement of cure shrinkage rate of resin plate A 5 mm square resin plate (thickness 1 mm) was prepared, and thermomechanical analysis was performed by a compression method using a TMA test apparatus (TA Instruments, Q400). . After mounting the resin plate in the Z direction on the device, the temperature profile is 20 ° C (5 minutes hold) to 260 ° C (2 minutes hold) to 20 ° C (5 minutes hold) with a load of 5 g and a heating rate of 45 ° C / min. Measured with The cure shrinkage rate of the resin plate was evaluated from the initial dimension of the resin plate and the dimensional change at 20 ° C. before starting the temperature increase and 20 ° C. after the temperature increase.
Specifically, the curing shrinkage rate of the resin plate was calculated using the following formula.
Curing shrinkage (%) = [(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) Measurement of glass transition temperature (Tg) A 5-mm square evaluation board from which copper foil was removed by immersing a copper-clad laminate in a copper etching solution was prepared, and a TMA test apparatus (TA Instruments, Q400) was prepared. ) Was used for thermomechanical analysis by the compression method. After mounting the evaluation substrate on the apparatus in the Z 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) Measurement of coefficient of thermal expansion A 5-mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (TA Instruments, Q400) was used. The thermomechanical analysis was performed by the compression method. 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) Evaluation of copper foil adhesion (copper foil peel strength) A copper-clad laminate is immersed in a copper etching solution to form a copper foil having a width of 3 mm to produce an evaluation substrate, and copper is tested using a tensile tester. The adhesion (peel strength) of the foil was measured.

(5) Evaluation of solder heat resistance with copper Solder heat resistance with copper by preparing a 25 mm square evaluation board from a copper clad laminate, floating the evaluation board in a solder bath at a temperature of 288 ° C. for 120 minutes, and observing the appearance Sex was evaluated.

(6) A bending elastic modulus copper-clad laminate was immersed in a copper etching solution to prepare a 25 mm × 50 mm evaluation board from which the copper foil was removed, and a 5-ton tensilon manufactured by Orientec Co., Ltd. was used, and the crosshead speed was 1 mm / min. Measured at a span distance of 20 mm.

(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 used, and a cavity resonator device (manufactured by Kanto Electronics Application Development Co., Ltd.) was used to obtain a ratio at a frequency of 1 GHz. The dielectric constant and dielectric loss tangent were measured.

Production Example 1: Production of amino-modified siloxane compound (I-1) having aromatic azomethine In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 3,3′-diethyl-4,4′-diaminodiphenylmethane: 12.9 g, terephthalaldehyde: 17.1 g, propylene glycol monomethyl ether: 45.0 g were added, reacted at 115 ° C. for 4 hours, and then raised to 130 ° C. The mixture was dehydrated by warming and concentration under atmospheric pressure to obtain an aromatic azomethine compound-containing solution having at least one aldehyde group in one molecule (resin component: 60% by mass).
Next, in the reaction solution, siloxane compound X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) having at least two primary amino groups at the molecular terminals: 325.5 g, propylene glycol monomethyl ether: 513. 3 g was added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and dehydrated by atmospheric concentration, and a modified siloxane compound (I-1) -containing solution having an aromatic azomethine in the molecular structure (Mw: 30000) , Resin component: 90% by mass).

Production Example 2: Production of amino-modified siloxane compound (I-2) having aromatic azomethine In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 2,8.7-dimethyl-1,4-diaminobenzene: 8.7 g, terephthalaldehyde: 21.3 g, propylene glycol monomethyl ether: 45.0 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. The solution was dehydrated by normal pressure concentration to obtain an aromatic azomethine compound-containing solution (resin component: 60% by mass).
Next, X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd., trade name): 413.8 g and propylene glycol monomethyl ether: 645.7 g were added to the reaction solution, reacted at 115 ° C. for 4 hours, The mixture was heated up to 0 ° C. and dehydrated by atmospheric concentration to obtain a modified siloxane compound (I-2) -containing solution (Mw: 25000, resin component: 90% by mass) having an aromatic azomethine.

Production Example 3 Production of Modified Imide Resin (J-1) Having Aromatic Azomethine Into a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, Modified siloxane compound (I-1) -containing solution having a group azomethine (resin component: 90% by mass): 62.4 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 243.9 g, propylene 443.8 g of glycol monomethyl ether was added, reacted at 115 ° C. for 4 hours, heated to 130 ° C. and concentrated at normal pressure, and a modified imide resin (J-1) -containing solution having aromatic azomethine (Mw: 8000) , Resin component: 60% by mass).

Production Example 4 Production of Modified Imide Resin (K-1) Having Acid Substituent and Aromatic Azomethine Reaction of 2 liters in volume capable of heating and cooling with thermometer, stirrer, moisture meter with reflux condenser In a container, a modified siloxane compound (I-1) -containing solution having an aromatic azomethine (resin component: 90% by mass): 62.5 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 238 0.1 g, p-aminophenol: 5.7 g, propylene glycol monomethyl ether: 443.8 g, reacted at 115 ° C. for 4 hours, heated to 130 ° C. and concentrated at normal pressure, acid substituent and aromatic A modified imide resin (K-1) -containing solution having azomethine (Mw: 6500, resin component: 60% by mass) was obtained.

Examples 1 to 18 and Comparative Examples 1 to 6
Amino-modified siloxane compound-containing solution (I-1, I-2) having an aromatic azomethine obtained in Production Examples 1 and 2 and a modified imide resin-containing solution having an aromatic azomethine obtained in Production Example 3 ( J-1) and a modified imide resin-containing solution (K-1) having an acidic substituent and an aromatic azomethine obtained in Production Example 4, an aromatic amine compound (i) and an aromatic aldehyde compound ( ii), siloxane compound (B), maleimide compound (C), amine compound (D) having an acidic substituent, thermoplastic elastomer (E), thermosetting resin (F), inorganic filler (G), curing acceleration Using agent (H) and methyl ethyl ketone as a diluent solvent, mixing was carried out at the blending ratio (parts by mass) shown in Tables 1 to 4 to obtain a varnish having a resin content of 65% by mass.
Next, the varnish was applied to a 16 μm polyethylene terephthalate film with a film applicator (PI-1210, manufactured by Tester Sangyo Co., Ltd.) 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 powder. There is no restriction | limiting in particular as a support body, A general purpose thing can be used, Moreover, there is no restriction | limiting in particular also as the application | coating method, What is necessary is just to apply | coat using a normal desktop coating machine.
This resin powder was put into a mold of a Teflon (registered trademark) sheet, the glossy surface of 12 μm electrolytic copper foil was placed up and down, and pressed at a pressure of 2.0 MPa and a temperature of 240 ° C. for 60 minutes. The foil was removed to obtain a resin plate.
Further, the varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a thermosetting resin composition content of 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 3.0 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.
Tables 1 to 4 show the measurement and evaluation results of the obtained resin plates and copper-clad laminates.

Aromatic amine compounds (i)
KAYAHARD AA: 3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name]

Aromatic aldehyde compounds (ii)
・ TPAL: terephthalaldehyde (trade name, manufactured by Toray Fine Chemical Co., Ltd.)

Siloxane compound (B)
X-22-161B: terminal amino-modified siloxane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

Maleimide compound (C)
・ BMI: Bis (4-maleimidophenyl) methane (trade name, manufactured by Kay Kasei Co., Ltd.)
BMI-4000: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

Amine compound having acidic substituent (D)
・ P-Aminophenol (trade name, manufactured by Kanto Chemical Co., Inc.)

Thermoplastic elastomer (E)
・ Tuftec H1043: Hydrogenated styrene-butadiene copolymer resin [Asahi Kasei Chemicals Corporation, trade name:]
・ Epofriend CT-310: Epoxy-modified styrene-butadiene copolymer resin (product name: manufactured by Daicel Corporation)

Thermosetting resin (F)
PT-30: Novolac-type cyanate resin (Lonza Japan Co., Ltd., trade name)
NC-7000L: α-naphthol / cresol novolac type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)

Inorganic filler (G)
SC2050-KNK: fused silica [manufactured by Admatechs Co., Ltd., trade name]
・ Zinc molybdate [manufactured by Sherwin Williams, trade name: KEMGARD1100]

Curing accelerator (H)
・ Zinc (II) naphthenate 8% mineral spirit solution [Tokyo Chemical Industry Co., Ltd., trade name]
G-8809L: Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name]
・ TPP-MK: Tetraphenylphosphonium tetra-p-tolylborate (trade name, manufactured by Hokuko Chemical Co., Ltd.)

Hereinafter, amino-modified siloxane compound-containing solutions (I-1) and (I-2) having aromatic azomethines in Tables 1 to 4, modified imide resin-containing solutions (J-1) having aromatic azomethines, and acidic substituents The amount (parts by mass) of the modified imide resin-containing solution having azomethine and aromatic azomethine indicates a value in terms of solid content of the resin component.

As is apparent from Tables 1 to 4, in the examples of the present invention, the curing shrinkage rate of the resin plate is small and excellent in low cure shrinkage. Also in the characteristics of the laminated plate, the thermal expansion rate, the copper foil Excellent adhesion, elastic modulus and dielectric properties.
On the other hand, the comparative example has a large curing shrinkage rate of the resin plate, and also in the characteristics of the laminated plate, the thermal expansion coefficient, the copper foil adhesiveness, the elastic modulus, and the dielectric characteristics are any of the characteristics. Inferior.

A prepreg obtained by impregnating or coating a base material with a polyimide using an amino-modified siloxane compound having an aromatic azomethine of the present invention, or a thermosetting resin composition containing an amino-modified siloxane compound is applied to a support. The film with resin obtained by coating and the laminate produced by laminating the prepreg have particularly low cure shrinkage, low thermal expansion, copper foil adhesion, high elastic modulus, and excellent dielectric properties. It is useful as a highly integrated semiconductor package and multilayer printed wiring board for electronic devices.

Claims

In one molecule obtained by reacting an aromatic amine compound (i) having at least two primary amino groups in one molecule and an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule Having an aromatic azomethine in the molecular structure obtained by reacting an aromatic azomethine compound (A) having at least one aldehyde group with a siloxane compound (B) having at least two primary amino groups at the molecular ends. Amino-modified siloxane compound.
A modified imide resin having an aromatic azomethine obtained by reacting the amino-modified siloxane compound according to claim 1 with a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule.
The modified imide resin according to claim 2, further comprising an acidic substituent, wherein the acidic substituent is derived from the acidic substituent of the amine compound (D) represented by the following general formula (1).

(In formula (1), each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R 2 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.)
A thermosetting resin composition comprising the amino-modified siloxane compound having an aromatic azomethine according to claim 1 and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule.
Furthermore, the thermosetting resin composition of Claim 4 containing the amine compound (D) which has an acidic substituent shown to following General formula (1).

(In formula (1), each R 1 independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and each R 2 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 Claim 4 or 5 containing a thermoplastic elastomer (E).
The thermosetting resin composition according to any one of claims 4 to 6, further comprising at least one thermosetting resin (F) selected from an epoxy resin and a cyanate resin.
The thermosetting resin composition according to any one of claims 4 to 7, further comprising an inorganic filler (G).
The thermosetting resin composition according to any one of claims 4 to 8, further comprising a curing accelerator (H).
A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of claims 4 to 9.
A film with a resin obtained by forming a layer of the thermosetting resin composition according to any one of claims 4 to 9 on a support.
A laminate obtained by laminating the prepreg according to claim 10.
A laminate obtained by laminating the film with resin according to claim 11.
A multilayer printed wiring board manufactured using the laminated board according to claim 12 or 13.
A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 14.