JP2015086253A - Thermosetting resin composition, and prepreg, film with resin, laminate, printed wiring board and semiconductor package using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition exhibiting excellent low curing shrinkage, low thermal expansion, good dielectric characteristics, and high elasticity, and to provide a prepreg, a film with a resin, a laminate, a printed wiring board, and a semiconductor package using the above thermosetting resin composition.SOLUTION: The thermosetting resin composition comprises: an aromatic azomethine compound (A) having at least one aldehyde group in one molecule obtained by reacting an aromatic amine compound (i) having at least two primary amino groups in one molecule with an aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule; a siloxane compound (B) having at least two primary amino groups at a molecular end; and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. Also disclosed are a prepreg, a film with a resin, a laminate, a printed wiring board, and a semiconductor package using the above thermosetting resin composition.

Description

  The present invention relates to a thermosetting resin composition suitable for a semiconductor package or a printed wiring board, and a prepreg, a resin film, a laminate, a printed wiring board, and a semiconductor package using the same.

  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 respect, known liquid crystalline polymers such as polyester-based, polyamide-based, polycarbonate-based, polythiol-based, polyether-based, and polyazomethine-based 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.

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.
However, when the polyazomethine described in Patent Documents 1 to 7 is applied as a copper clad laminate or an interlayer insulating material, heat resistance and formability may be insufficient.
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.

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

  In view of the present situation, the object of the present invention is to provide a thermosetting resin composition that exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus, a prepreg using the same, and a resin-attached resin. It is to provide a film, a laminate, a printed wiring board, and a semiconductor package.

  As a result of intensive studies to achieve the above object, the present inventors have obtained an aromatic amine compound (i) having at least two primary amino groups in one molecule, and at least two aldehydes in one molecule. An aromatic azomethine compound (A) having at least one aldehyde group in one molecule obtained by reacting an aromatic aldehyde compound (ii) having a group, and at least two primary amino groups at the molecular end It has been found that the above object can be achieved by using a thermosetting resin composition containing a siloxane compound (B) and a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule. The present invention has been completed. The present invention has been completed based on such knowledge.

（式（１）中、Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ₂は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。）
４．芳香族アゾメチン化合物（Ａ）と、シロキサン化合物（Ｂ）と、マレイミド化合物（Ｃ）と、アミン化合物（Ｄ）を反応させて得られる、酸性置換基と芳香族アゾメチンを有する変性イミド樹脂を含有する、上記３の熱硬化性樹脂組成物。
５．さらに、熱可塑性エラストマー（Ｅ）を含有する上記１〜４いずれかの熱硬化性樹脂組成物。
６．さらに、エポキシ樹脂及びシアネート樹脂から選ばれる少なくとも一種の熱硬化性樹脂（Ｆ）を含有する上記１〜５いずれかの熱硬化性樹脂組成物。
７．さらに、無機充填材（Ｇ）を含有する上記１〜６いずれかの熱硬化性樹脂組成物。
８．さらに、硬化促進剤（Ｈ）を含有する上記１〜７いずれかの熱硬化性樹脂組成物。
９．上記１〜８のいずれかの熱硬化性樹脂組成物を基材に含浸してなるプリプレグ。
１０．上記１〜８のいずれかの熱硬化性樹脂組成物を支持体上に層形成してなる樹脂付フィルム。
１１．上記９のプリプレグを積層成形し得られる積層板。
１２．上記１０の樹脂付フィルムを積層成形して得られる積層板。
１３．上記１１又は１２の積層板を用いて製造されるプリント配線板。
１４．上記１３のプリント配線板に半導体素子を搭載してなる半導体パッケージ。 That is, this invention provides the following thermosetting resin compositions, a prepreg using the same, a film with resin, a laminated board, a printed wiring board, and a semiconductor package.
1. Obtained by reacting an aromatic amine compound (i) having at least two primary amino groups in the molecule and an aromatic aldehyde compound (ii) having at least two aldehyde groups in the molecule, An aromatic azomethine compound (A) having at least one aldehyde group in the molecule, a siloxane compound (B) having at least two primary amino groups at the molecular end, and at least two N-substituted in one molecule A thermosetting resin composition containing a maleimide compound (C) having a maleimide group.
2. The thermosetting resin composition according to 1 above, which contains a modified imide resin having an aromatic azomethine obtained by reacting an aromatic azomethine compound (A), a siloxane compound (B), and a maleimide compound (C).
3. Furthermore, the said thermosetting resin composition of 1 or 2 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.)
4). Contains a modified imide resin having an acidic substituent and an aromatic azomethine obtained by reacting an aromatic azomethine compound (A), a siloxane compound (B), a maleimide compound (C), and an amine compound (D) The thermosetting resin composition according to 3 above.
5. Furthermore, the thermosetting resin composition according to any one of the above 1 to 4, further comprising a thermoplastic elastomer (E).
6). Furthermore, the thermosetting resin composition in any one of said 1-5 containing at least 1 type of thermosetting resin (F) chosen from an epoxy resin and cyanate resin.
7). Furthermore, the thermosetting resin composition in any one of said 1-6 containing an inorganic filler (G).
8). Furthermore, the thermosetting resin composition in any one of said 1-7 containing a hardening accelerator (H).
9. A prepreg formed by impregnating a base material with the thermosetting resin composition according to any one of 1 to 8 above.
10. The film with a resin formed by layer-forming the thermosetting resin composition in any one of said 1-8 on a support body.
11. A laminate obtained by laminate-molding the prepreg described in 9 above.
12 A laminate obtained by laminating and forming the film with resin of 10 above.
13. A printed wiring board manufactured using the laminate of 11 or 12 above.
14 14. A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to the above 13.

According to the present invention, a thermosetting resin composition that exhibits excellent low curing shrinkage, low thermal expansion, good dielectric properties, and high elastic modulus, a prepreg using the same, a film with resin, a laminate, A printed wiring board and a semiconductor package can be provided.
In particular, a prepreg obtained by impregnating a base material with the thermosetting resin composition of the present invention, a resin-coated film formed on a support, and the prepreg or the resin-coated film are produced by lamination molding. The laminated board has low curing shrinkage, low thermal expansion, excellent dielectric properties, and high elastic modulus, and is useful as a printed wiring board and a semiconductor package.

  Hereinafter, the present invention will be described in detail. The thermosetting resin composition of the present invention comprises an aromatic amine compound (i) having at least two primary amino groups in one molecule (hereinafter sometimes referred to as aromatic amine compound (i)), one molecule At least one aldehyde group in one molecule obtained by reacting aromatic aldehyde compound (ii) having at least two aldehyde groups therein (hereinafter sometimes referred to as aromatic aldehyde compound (ii)) An aromatic azomethine compound (A) (hereinafter sometimes referred to as an aromatic azomethine compound (A)) and a siloxane compound (B) having at least two primary amino groups at the molecular ends (hereinafter referred to as siloxane compound ( B)) and maleimide compound (C) having at least two N-substituted maleimide groups in one molecule (hereinafter referred to as maleimide compound (C)). A thermosetting resin composition.

The aromatic amine compound (i) having at least two primary amino groups in one molecule used in the present invention is preferably an aromatic amine compound having two primary amino groups in one molecule.
Examples of the aromatic amine compound (i) having at least two primary amino groups in one molecule used in the present invention include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1 , 4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diamino-diphenylmethane, 3,3′-diethyl- 4,4′-diamino-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'-di Droxybenzidine, 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) Examples include sulfone and 9,9-bis (4-aminophenyl) fluorene. These may be used alone or in combination of two or more. Among these, for example, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3 are highly reactive at the time of reaction and can be further improved in heat resistance. '-Dimethyl-4,4'-diamino-diphenylmethane, 3,3'-diethyl-4,4'-diamino-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4- Aminophenoxy) phenyl) propane is preferable and 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3 ′ from the viewpoint of low cost and solubility in a solvent. -Diethyl-4,4'-diamino-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are more preferred. From the viewpoint of low thermal expansion and dielectric properties, 3,3'-die Le-4,4'-diamino - diphenylmethane, bis (4- (4-aminophenoxy) phenyl) propane is particularly preferred. In addition, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene are also preferable from the viewpoint of increasing the elastic modulus.

The aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule used in the present invention is preferably an aromatic aldehyde compound having two aldehyde groups in one molecule.
Examples of the aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule used in the present invention include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2′-bipyridine-4,4. Examples include '-dicarboxaldehyde. These may be used alone or in combination of two or more. Among these, terephthalaldehyde, which can be further reduced in thermal expansion, has high reactivity during reaction, is excellent in solvent solubility, and is easily commercially available, is particularly preferable.

  In the present invention, the reaction for obtaining an aromatic azomethine compound (A) having at least one aldehyde group in one molecule is 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, by dehydration condensation reaction in an organic solvent, an aromatic azomethine compound having at least one aldehyde group in one molecule (A) can be obtained.

  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. These may be used alone or in combination of two or more. 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 preferable 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 optionally used as necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine and tributylamine, methylimidazole, Examples thereof include imidazoles such as phenylimidazole and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. In order to advance the dehydration condensation reaction efficiently, for example, an acidic catalyst such as p-toluenesulfonic acid is preferable.

  The amount of aromatic amine compound (i) having at least two primary amino groups in one molecule and aromatic aldehyde compound (ii) having at least two aldehyde groups in one molecule is, for example, aromatic amine The number of primary amino groups in compound (i) [amount of aromatic amine compound (i) used (g) / functional equivalent of primary amino group in aromatic amine compound (i) (g / mol)] is the aromatic aldehyde compound 0.1 times to 5.0 times the number of aldehyde groups (ii) [amount of use of aromatic aldehyde compound (ii) (g) / functional group equivalent of aldehyde group of aromatic aldehyde compound (ii) (g / mol)] It is preferable to use so that it may become the range of 2 times, 0.1 to 2.0 times is more preferable, and 0.1 to 0.9 times is especially preferable. By setting it to 0.1 times or more, a decrease in the molecular weight of the aromatic azomethine compound obtained by this reaction is suppressed, and by setting it to 5.0 times or less, a decrease in solubility in a solvent is suppressed. .

  Moreover, it is preferable that the usage-amount of an organic solvent shall be 25-2000 mass parts with respect to 100 mass parts of total of the resin component of an aromatic amine compound (i) and aromatic aldehyde compound (ii), for example, It is more preferable to set it as -1000 mass parts, and it is especially preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, sufficient solubility is obtained, and when it is 2000 parts by mass or less, the reaction does not take a long time.

The aromatic azomethine compound (A) is obtained by charging the above raw materials, 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 keeping warm as necessary. .
For example, the reaction temperature is preferably 70 to 150 ° C, and more preferably 100 to 130 ° C. By setting the temperature to 70 ° C. or higher, the reaction rate is sufficiently high, and by setting the temperature to 150 ° C. or lower, the reaction solvent does not require a high boiling point solvent, and when the prepreg is produced, the residual solvent hardly remains. , A decrease in heat resistance is suppressed. Moreover, it is preferable to react, removing the water which is a product.

The aromatic azomethine compound (A) having at least one aldehyde group in one molecule obtained by the above reaction can be confirmed by performing IR measurement. By IR measurement, it can be confirmed that a peak at 1620 cm ⁻¹ due to the azomethine group (—N═CH—) appears, and it can be confirmed that a peak at 1690 cm ⁻¹ due to the aldehyde group exists. Also, if the primary amino groups are present in the molecule can be confirmed that the peak around at 3,440 cm ^-1, and 3370cm ^-1 due to the primary amino groups are present.
Moreover, although a weight average molecular weight (Mw) is not specifically limited, For example, 1000-5000 are preferable and 1000-3000 are especially preferable. When the weight average molecular weight (Mw) is 1000 or more, good low curing shrinkage and low thermal expansion tend to be obtained, and when it is 5000 or less, good solvent solubility tends to be obtained. The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve produced using standard polystyrene.
The weight average molecular weight (Mw) can be measured, for example, 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) and HPLC pump (JASCO Corporation 880-PU) can be used.
In addition, TSKgel SuperHZ2000, 2300 manufactured by Tosoh Corporation can be used as the column used, and measurement can be performed by using a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent of tetrahydrofuran.

The siloxane compound (B) having at least two primary amino groups at the molecular ends of the present invention is preferably a siloxane compound having two primary amino groups at the molecular ends.
As the siloxane compound (B) having at least two primary amino groups at the molecular terminals of the present invention, commercially available products can be used. For example, “KF-8010” (functional group equivalent of amino group 430), “X -22-161A "(amino group functional equivalent 800)," X-22-161B "(amino functional equivalent 1500)," KF-8012 "(amino functional equivalent 2200)," KF- 8008 ”(functional group equivalent of amino group 5700),“ X-22-9409 ”(functional group equivalent of amino group 700),“ X-22-1660B-3 ”(functional group equivalent of amino group 2200) (above, Manufactured by Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (functional group equivalent of amino group 460), “BY-16-853” (functional group equivalent of amino group 650), “BY-16-853B” Amino equivalent 2200) (all include Dow Corning Toray Co., Ltd.). These may be used alone or in combination of two or more. The unit of functional group equivalent is g / mol.
Among these, for example, X-22-161A, X-22-161B, KF-8012, X-22-1660B-3, BY-16-853B are highly reactive at the time of synthesis and have low thermal expansion. X-22-161A and X-22-161B, which are excellent in compatibility and can increase the elastic modulus, are particularly preferable.

The maleimide compound (C) having at least two N-substituted maleimide groups in one molecule used in the present invention is preferably a maleimide compound having two N-substituted maleimide groups in one molecule.
Examples of the maleimide compound (C) having at least two N-substituted maleimide groups in one molecule used in the present invention include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, and bis (4-maleimidophenyl). ) Ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane and the like can be mentioned. These may be used alone or in combination of two or more.

  Among these, for example, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, and 2,2-bis (4- (4-maleimidophenoxy), which have high reactivity and can have higher heat resistance. Phenyl) propane is preferable, and from the viewpoint of solubility in a solvent, bis (4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are more preferable and inexpensive. Bis (4-maleimidophenyl) methane is particularly preferred.

In the thermosetting resin composition of the present invention, the amount of the aromatic azomethine compound (A) used is preferably, for example, 1 to 30 parts by mass, and 5 to 20 parts by mass per 100 parts by mass of the total resin components. It is more preferable from the viewpoint of low curing shrinkage and copper foil adhesiveness.
The amount of the siloxane compound (B) used is, for example, preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass per 100 parts by mass of the total of the resin components. From the point of view, it is more preferable.
The amount of maleimide compound (C) used is preferably, for example, 30 to 99 parts by mass, and 40 to 80 parts by mass per 100 parts by mass of the total resin components. It is more preferable from the point.

  The thermosetting resin composition of the present invention comprises 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. Including those containing a modified imide resin having an aromatic azomethine obtained by reacting a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule (hereinafter referred to as pre-reaction) Sometimes called). By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.

In this pre-reaction, it is preferable to synthesize a modified imide resin by reacting the aromatic azomethine compound (A), the siloxane compound (B), and the maleimide compound (C) while heating and keeping in an organic solvent.
The reaction temperature when the aromatic azomethine compound (A), the siloxane compound (B), and the maleimide compound (C) are reacted in an organic solvent is, for example, preferably 70 to 150 ° C, and preferably 100 to 130 ° C. It is more preferable. For example, the reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

  In this pre-reaction, the amount of the aromatic azomethine compound (A) and the siloxane compound (B) used is, for example, the number of primary amino groups of the siloxane compound (B) [the amount of siloxane compound (B) used (g) / siloxane compound ( B) functional group equivalent of primary amino group (g / mol)] is the number of aldehyde groups of aromatic azomethine compound (A) [amount of use of aromatic azomethine compound (A) (g) / aromatic azomethine compound (A) The functional group equivalent (g / mol) of the aldehyde group is preferably 1.0 to 10.0 times, more preferably 1.5 to 5.0 times. By setting it as 1.0 times or more, the fall of the solubility to a solvent is suppressed, and the fall of an elasticity modulus is suppressed by setting it as 10.0 times or less.

  The amount of siloxane compound (B) and maleimide compound (C) used is, for example, the number of maleimide groups in maleimide compound (C) [the amount of maleimide compound (C) used (g) / maleimide group in maleimide compound (C) Functional group equivalent (g / mol)] is the number of primary amino groups of siloxane compound (C) [Amount of use of siloxane compound (C) (g) / Functional group equivalent of primary amino group of siloxane compound (C) (g / mol) )] Is preferably in the range of 2.0 to 50.0 times, more preferably 5.0 to 40.0 times. By making it 2.0 times or more, gelation and a decrease in heat resistance are suppressed, and by making it 50.0 times or less, solubility in an organic solvent and heat resistance are suppressed.

  The amount of the maleimide compound (C) used in the pre-reaction is, for example, 10 with respect to 100 parts by mass of the total resin components of the aromatic azomethine compound (A) and the siloxane compound (B) while maintaining the above relationship. -3000 mass parts is preferable, 30-1500 mass parts is more preferable, and 60-800 mass parts is more preferable. By setting it as 10 mass parts or more, a heat resistant fall is suppressed, and by setting it as 3000 mass parts or less, low thermal expansibility can be kept favorable.

  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 may be used alone or in combination of two or more.

  Among these organic solvents, for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent. , Propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.

  The amount of the organic solvent used is preferably 25 to 2000 parts by mass with respect to 100 parts by mass of the total resin components of the aromatic azomethine compound (A), siloxane compound (B), and maleimide compound (C), for example. 40 to 1000 parts by mass, more preferably 40 to 500 parts by mass. When the amount of the organic solvent used is 25 parts by mass or more, the solubility does not become insufficient, and when it 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 thereof 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. These may be used alone or in combination of two or more.

  Moreover, it is preferable that the usage-amount of the modified imide resin which has the aromatic azomethine obtained from the said pre reaction shall be 50-100 mass parts per 100 mass parts of sum total of a resin component, for example, and 60-80 mass parts. More preferably. Low thermal expansion and high elastic modulus can be obtained by setting the blended amount of the modified imide resin having aromatic azomethine to 50 parts by mass or more.

An aromatic azomethine compound (A) having at least one aldehyde group in one molecule of the present invention, a siloxane compound (B) having at least two primary amino groups at the molecular ends, and at least two in one molecule A thermosetting resin composition containing a maleimide compound (C) having an N-substituted maleimide group and a modified imide resin having an aromatic azomethine obtained by pre-reacting the compound are excellent thermosetting alone. Although it has reactivity, if necessary, heat resistance, adhesiveness, and mechanical strength can be improved by using a curing agent and a radical initiator in combination.
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 hexamethylene diamine, and aliphatic amines such as 2,5-dimethylhexamethylene diamine, and guanamine compounds such as melamine and benzoguanamine. These may be used alone or in combination 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.

（式（１）中、Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を、Ｒ₂は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。） 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 include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o- Aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. These may be used alone or in combination of two or more. 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, and m-aminophenol and p-aminophenol are more preferred from the viewpoint of heat resistance.

  The amount of the amine compound (D) having an acidic substituent is preferably 0.5 to 30 parts by mass, and preferably 1 to 20 parts by mass per 100 parts by mass of the total resin components. More preferable from the viewpoint of expansibility.

  The thermosetting resin composition of the present invention comprises 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. It has an acidic substituent and an aromatic azomethine obtained by reacting a maleimide compound (C) having at least two N-substituted maleimide groups in one molecule with an amine compound (D) further having an acidic substituent. Including those containing a modified imide resin (hereinafter, this reaction may be referred to as pre-reaction). By performing such a pre-reaction, the molecular weight can be controlled, and further low curing shrinkage and low thermal expansion can be improved.

In this pre-reaction, an aromatic azomethine compound (A), a siloxane compound (B), a maleimide compound (C), and an amine compound (D) having an acidic substituent are reacted while being heated and kept in an organic solvent. It is preferable to synthesize a modified imide resin having an aromatic azomethine.
The reaction temperature when the aromatic azomethine compound (A), the siloxane compound (B), the maleimide compound (C), and the amine compound (D) having an acidic substituent are reacted in an organic solvent is, for example, 70 to 150 ° C. It is preferable that the temperature is 100 to 130 ° C. For example, the reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

In this pre-reaction, the amount of the aromatic azomethine compound (A), the siloxane compound (B) and the amine compound (D) having an acidic substituent is, for example, the siloxane compound (B) and an amine compound having an acidic substituent ( D) Number of primary amino groups [amount of use of siloxane compound (B) (g) / functional equivalent (g / mol) of primary amino group of siloxane compound (B) + use of amine compound (D) having an acidic substituent Amount (g) / functional group equivalent (g / mol) of primary amino group of amine compound (D) having acidic substituent is the number of aldehyde groups of aromatic azomethine compound (A) [of aromatic azomethine compound (A) Use amount (g) / functional equivalent of aldehyde group (g / mol) of aromatic azomethine compound (A)] is preferably used in a range of 1.0 to 10.0 times. , 1.5 to 8.0 times is more preferable. By setting it as 1.0 times or more, the fall of the solubility to a solvent is suppressed, and the fall of an elasticity modulus is suppressed by setting it as 10.0 times or less.
The amount of maleimide compound (C), siloxane compound (B), and amine compound (D) having an acidic substituent is, for example, the number of maleimide groups in maleimide compound (C) [the amount of maleimide compound (C) used (g ) / Functional group equivalent (g / mol) of the maleimide group of the maleimide compound (C)] is the number of primary amino groups of the amine compound (D) having an acidic substituent and the siloxane compound (B) [use of the siloxane compound (B) Amount (g) / functional amount of primary amino group of siloxane compound (B) (g / mol) + amount of amine compound (D) having acidic substituent (g) / amine compound having acidic substituent (D The functional group equivalent (g / mol) of the primary amino group is preferably in the range of 2.0 to 20.0 times. By setting it to 2.0 times or more, gelation and a decrease in heat resistance are suppressed, and by setting it to 20.0 times or less, solubility in an organic solvent and a decrease in heat resistance are suppressed.

The amount of the maleimide compound (C) used in the pre-reaction is, for example, that of the aromatic azomethine compound (A), the siloxane compound (B), and the amine compound (D) having an acidic substituent while maintaining the above relationship. 10-3000 mass parts is preferable with respect to 100 mass parts of sum total of a resin component, 30-1500 mass parts is more preferable, and 50-700 mass parts is more preferable. By setting it as 10 mass parts or more, a heat resistant fall is suppressed, and by setting it as 3000 mass parts or less, low thermal expansibility can be kept favorable.
Moreover, the usage-amount of the amine compound (D) which has an acidic substituent in a pre-reaction is 1-500 mass with respect to 100 mass parts of resin components of a siloxane compound (B), for example, maintaining the above relationships. Part is preferable, and 1 to 300 parts by mass is more preferable. By setting it to 1 part by mass or more, good heat resistance can be obtained, and by setting it to 500 parts by mass or less, low thermal expansion can be kept good.

  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 may be used alone or in combination of two or more.

  Among these organic solvents, for example, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone has low toxicity and is highly volatile and hardly remains as a residual solvent. , Propylene glycol monomethyl ether, and dimethylacetamide are particularly preferable.

  The amount of the organic solvent used is, for example, 100 parts by mass of the total resin component of the aromatic azomethine compound (A), the siloxane compound (B), the maleimide compound (C), and the amine compound (D) having an acidic substituent. It is preferable to set it as 25-2000 mass parts, It is more preferable to set it as 40-1000 mass parts, It is especially preferable to set it as 40-500 mass parts. When the amount of the organic solvent used is 25 parts by mass or more, the solubility does not become insufficient, and when it 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. Reaction catalysts include, for example, amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, alkali metal amides such as lithium amide, sodium amide and potassium amide Is mentioned. These may be used alone or in combination of two or more.

  Moreover, it is preferable that the usage-amount of the modified imide resin which has the acidic substituent obtained from the said pre reaction and aromatic azomethine is 50-100 mass parts per 100 mass parts of sum total of a resin component, for example. More preferred is 80 parts by mass. By setting the blending amount of the modified imide resin having an acidic substituent and aromatic azomethine to 50 parts by mass or more, low thermal expansibility and high elastic modulus can be obtained.

A thermosetting resin composition comprising the aromatic azomethine compound (A), siloxane compound (B), maleimide compound (C), amine compound (D) having an acidic substituent of the present invention, and the above compound are pre-reacted The modified imide resin having an acidic substituent and aromatic azomethine obtained by itself has good thermosetting reactivity alone, but if necessary, heat resistance and adhesiveness can be obtained by using a curing agent and a radical initiator in combination. , 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 hexamethylene diamine, and aliphatic amines such as 2,5-dimethylhexamethylene diamine, and guanamine compounds such as melamine and benzoguanamine. These may be used alone or in combination 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 combination 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) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers and derivatives thereof. These have a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. These may be used alone or in combination of two or more.

  Moreover, as these elastomers, those having a reactive functional group at the molecular terminal 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. As a result, it is possible to significantly reduce the warpage of the substrate.

  Among these elastomers, for example, styrene elastomers, olefin elastomers, polyamide elastomers, and silicone elastomers are preferable in terms of heat resistance and insulation reliability, and styrene elastomers and olefins are preferable in terms of dielectric properties. Elastomers are particularly preferred.

  Further, the reactive functional group possessed in the molecular terminal or molecular chain of these elastomers 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. From the viewpoint of insulation reliability, an epoxy group, a hydroxyl group, and an amino group are particularly preferable.

  The amount of the thermoplastic elastomer (E) component used is, for example, preferably 0.1 to 50 parts by mass, and 2 to 30 parts by mass with respect to 100 parts by mass of the total resin components. It is more preferable because it has good compatibility and can effectively exhibit low curing shrinkage, low thermal expansion and excellent dielectric properties of the cured product.

Furthermore, the thermosetting resin composition of the present invention can contain at least one thermosetting resin (F) selected from an epoxy resin and a cyanate resin.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, 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 ether compounds of polycyclic aromatics such as anthracene Beauty These phosphorus-containing epoxy resin obtained by introducing a phosphorus compound is mentioned. These may be used alone or in combination 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 include novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, and bisphenol-type cyanate resin such as tetramethylbisphenol F-type cyanate resin, and prepolymers in which these are partially triazine. Can be mentioned. These may be used alone or in combination 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 thermosetting resins (F) as necessary. Examples of curing agents include, for example, polyfunctional phenolic compounds such as phenol novolac, cresol novolac, aminotriazine novolac 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 may be used alone or in combination of two or more.

  As a usage-amount of a thermosetting resin (F), it is preferable to set it as 1-50 mass parts per 100 mass parts of sum total of a resin component, for example, and 10-30 mass parts from the point of heat resistance and chemical resistance. It is more preferable that

  The thermosetting resin composition of the present invention can contain an inorganic filler (G). Examples of 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, and barium sulfate. , Aluminum borate, potassium titanate, glass powder such as E glass, T glass, D glass, and hollow glass beads. These may be used alone or in combination of two or more.

  Among these inorganic fillers, for example, silica is particularly preferable from the viewpoint 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 fused spherical silica is used as the inorganic filler, 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 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 content of the inorganic filler is, for example, preferably 20 to 300 parts by mass, and more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the total resin components. By making content of an inorganic filler into such a range, the moldability and low thermal expansibility of a resin composition can be kept favorable.
In addition, when an inorganic filler is blended in the resin composition, for example, the inorganic filler is pretreated with a silane or titanate coupling agent, a surface treatment agent such as a silicone oligomer, or an integral blend treatment. It is also preferable.

  The thermosetting resin composition of the present invention can contain a curing accelerator (H). Examples of the curing accelerator include zinc metal naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) and the like, imidazoles and Examples thereof include organic phosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more. Among these, for example, zinc naphthenate, imidazole derivatives, and phosphonium salts are preferable from the viewpoint of the promoting effect and the storage stability.

  The content of the curing accelerator is, for example, preferably 0.01 to 3.0 parts by mass and more preferably 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the total resin components. . By making the content of the curing accelerator 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 as long as they do not contradict its purpose. Etc. can be used.

  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; phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, 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.

  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 organic solvents used here include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 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 may be used alone or in combination of two or more. Among these, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.

The resin component in the finally obtained varnish is, for example, preferably 40 to 90% by mass and more preferably 50 to 80% by mass with respect to the entire varnish. By setting the content of the resin component 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.
In the present specification, the resin component is mainly an aromatic azomethine compound (A), a siloxane compound (B) and a maleimide compound (C), an amine compound (D), a thermoplastic elastomer (E), When at least one of the thermosetting resin (F), the inorganic filler (G), and the curing accelerator (H) is blended, these blends are also included.

The prepreg of the present invention is obtained by impregnating a base material with the above-described 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 a base material with the thermosetting resin composition of the present invention and semi-curing (B-stage) by heating or the like. Although it does not specifically limit as a method of impregnating the base material with the resin composition obtained by 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 fibers can be used for fiber reinforced substrates.

  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 substrate 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.

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

  The film with a resin of the present invention is formed by layering the above-described 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. It can apply | coat to the film which is a support body, and also it can be dried by heating or hot air spraying etc., and a resin composition layer can be formed. 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 drying condition after applying the thermosetting resin composition of the present invention to the support is, for example, 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. To dry. 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 in the resin-coated film is usually not less than the thickness of the conductor layer that the circuit board has. 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 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. 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 on which the support is not in close contact. 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 shape.

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 a circuit board or the like, the substrate is cooled to around room temperature, and when the support is peeled off, the insulating resin layer can be formed on the circuit board or the like by peeling and thermosetting. The conditions for thermosetting 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.

  The printed wiring board of the present invention is manufactured using a laminated board obtained by laminating the above resin-coated film. For example, after forming an insulating resin layer on a circuit board or the like by the above-described method, if necessary, holes are formed in the insulating resin layer formed on the circuit board or the like to form via holes, through holes, or the like. 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. If the support is not peeled before the above-mentioned thermosetting, it can be peeled either before or after drilling.

  Subsequently, a printed wiring board can be manufactured by forming a conductor layer on an insulating resin layer by dry plating or wet plating and forming a circuit pattern. 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, the conductor layer can be 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 circuit pattern formation method, for example, a known subtractive method, semi-additive method, or the like 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 printed wiring board of the present invention is manufactured using a laminate obtained by laminating the above-described prepreg. For example, a printed wiring board can be obtained by forming a circuit pattern on a conductive layer of a laminated board obtained by laminating the above-described prepreg by an ordinary etching method. In addition, a plurality of circuit boards are stacked through the above-described prepreg, and are multilayered by heating and pressing. Thereafter, a 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.

  The semiconductor package of the present invention is obtained by mounting a semiconductor element on the printed wiring board of the present invention. 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, curing shrinkage using the resin plate obtained in each Example and Comparative Example, and using copper-clad laminate, glass transition temperature, coefficient of thermal expansion, copper foil adhesiveness, solder heat resistance with copper, bending The elastic modulus and 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, load 5g, temperature increase rate 45 ° C / min, temperature profile from 20 ° C (5 min hold) to 260 ° C (2 min hold) to 20 ° C (5 min hold) Measured with The curing shrinkage rate (%) of the resin plate was evaluated from the dimensional change at 20 ° C. before starting the temperature increase of the resin plate and at 20 ° C. after the temperature increase.
Specifically, the curing shrinkage rate of the resin plate was calculated using the following formula.
Curing shrinkage rate (%) = [(20 ° C. before starting temperature rise (mm) −20 ° C. after temperature raising (mm)) / 20 ° C. before temperature rising (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) Flexural modulus A copper-clad laminate was immersed in a copper etching solution to produce a 25 mm × 50 mm evaluation board from which the copper foil was removed, using a 5-ton tensilon manufactured by Orientec Co., Ltd., and a crosshead speed of 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 the copper foil was removed by immersing the copper clad laminate in a copper etching solution was prepared, and a dielectric constant at a frequency of 1 GHz was obtained using a cavity resonator device (manufactured by Kanto Electronics Development Co., Ltd.). The rate and dielectric loss tangent were measured.

Production Example 1 Production of Aromatic Azomethine Compound (A-1) In a reaction vessel with 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, then heated to 130 ° C. and normal pressure Dehydration was performed by concentration to obtain an aromatic azomethine compound (A-1) -containing solution (resin component: 60% by mass, weight average molecular weight (Mw): 1500).

Production Example 2 Production of Aromatic Azomethine Compound (A-2) 2,5-dimethyl was added to a reaction vessel with 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. -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. and concentrated at normal pressure. Dehydration gave an aromatic azomethine compound (A-2) -containing solution (resin component: 60 mass%, weight average molecular weight (Mw): 1200).

Production Example 3 Production of Modified Imide Resin (I-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 quantifier with a reflux condenser. Group azomethine compound-containing solution (A-1, resin component: 60% by mass): 5.8 g, X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amino group functional group equivalent 1500, both terminal amino acids Modified siloxane): 37.5 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 259.1 g, propylene glycol monomethyl ether: 447.7 g, and reacted at 115 ° C. for 4 hours, The temperature was raised to 130 ° C. and the solution was concentrated at normal pressure to obtain a modified imide resin (I-1) -containing solution (resin component: 60% by mass) having aromatic azomethine.

Production Example 4 Production of Modified Imide Resin (I-2) Having Aromatic Azomethine In 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, Group azomethine compound (A-2) -containing solution (resin component: 60% by mass): 4.5 g, X-22-161B: 37.6 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) Propane: 259.7 g and propylene glycol monomethyl ether: 448.2 g were added, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at normal pressure, and modified imide resin having aromatic azomethine (I-2 ) -Containing solution (resin component: 60% by mass) was obtained.

Production Example 5 Production of Modified Imide Resin (J-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, aromatic azomethine compound (A-1) -containing solution (resin component: 60% by mass): 5.8 g, X-22-161B: 37.5 g, 2,2-bis (4- (4-maleimide) Phenoxy) phenyl) propane: 253.0 g, p-aminophenol: 6.1 g, propylene glycol monomethyl ether: 447.7 g, reacted at 115 ° C. for 4 hours, heated to 130 ° C. and concentrated at normal pressure. The modified imide resin (J-1) containing solution (resin component: 60 mass%) which has an acidic substituent and aromatic azomethine was obtained.

Production Example 6: Production of Modified Imide Resin (J-2) 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, aromatic azomethine compound (A-2) -containing solution (resin component: 60% by mass): 4.5 g, X-22-161B: 37.6 g, 2,2-bis (4- (4-maleimide) Phenoxy) phenyl) propane: 253.6 g, p-aminophenol: 6.1 g, propylene glycol monomethyl ether: 448.2 g, reacted at 115 ° C. for 4 hours, then heated to 130 ° C. and concentrated at atmospheric pressure. The modified imide resin (J-2) containing solution (resin component: 60 mass%) which has an acidic substituent and aromatic azomethine was obtained.

Examples 1-18 and Comparative Examples 1-6
Aromatic azomethine compound (A-1, A-2) -containing solution obtained in Production Examples 1 and 2, modified imide resin-containing solution (I-1) having aromatic azomethine obtained in Production Examples 3 and 4 I-2) and modified imide resin-containing solutions (J-1, J-2) having an acidic substituent and an aromatic azomethine obtained in Production Examples 5 and 6, and a siloxane compound (B) shown below , Maleimide compound (C), amine compound (D) having acidic substituent, thermoplastic elastomer (E), thermosetting resin (F), inorganic filler (G), curing accelerator (H), and diluent solvent In addition, methyl ethyl ketone was used and mixed at a 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 using 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-dried. The over-dried varnish was peeled off from the film and pulverized using a mortar to obtain a semi-cured resin powder.
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.
The varnish was impregnated with 0.1 mm thick E glass cloth and dried by heating at 160 ° C. for 10 minutes 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 3.0 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.
The measurement and evaluation results of the obtained resin plate and copper clad laminate are shown in Tables 1 to 4.

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

Maleimide compound (C)
-BMI: Bis (4-maleimidophenyl) methane (trade name, manufactured by Kay Kasei Corporation)
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 (manufactured by Kanto Chemical Co., Inc.)

Thermoplastic elastomer (E)
・ Tuftec H1043: Hydrogenated styrene-butadiene copolymer resin (trade name, manufactured by Asahi Kasei Chemicals Corporation)
・ Epofriend CT-310: Epoxy-modified styrene-butadiene copolymer resin (trade 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 (product name, manufactured by Nippon Kayaku Co., Ltd.)

Inorganic filler (G)
SC2050-KNK: fused spherical silica [manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, 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 [made by Hokuko Chemical Co., Ltd., trade name]

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, and 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 a base material with the thermosetting resin composition of the present invention, a film with a resin formed on a support, and a laminate produced by laminating the prepreg or the resin-coated film. The board has low curing shrinkage, low thermal expansion, copper foil adhesion, high elastic modulus, and excellent dielectric properties, and is useful as a highly integrated semiconductor package and printed wiring board for electronic equipment.

Claims (14)

  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 An aromatic azomethine compound (A) having at least one aldehyde group, a siloxane compound (B) having at least two primary amino groups at the molecular ends, and at least two N-substituted maleimide groups in one molecule The thermosetting resin composition containing the maleimide compound (C) which has this.   The thermosetting resin according to claim 1, comprising a modified imide resin having an aromatic azomethine obtained by reacting an aromatic azomethine compound (A), a siloxane compound (B), and a maleimide compound (C). Composition. Furthermore, the thermosetting resin composition of Claim 1 or 2 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.)   Contains a modified imide resin having an acidic substituent and an aromatic azomethine obtained by reacting an aromatic azomethine compound (A), a siloxane compound (B), a maleimide compound (C), and an amine compound (D) The thermosetting resin composition according to claim 3.   Furthermore, the thermosetting resin composition of any one of Claims 1-4 containing a thermoplastic elastomer (E).   Furthermore, the thermosetting resin composition of any one of Claims 1-5 containing the at least 1 type of thermosetting resin (F) chosen from an epoxy resin and cyanate resin.   Furthermore, the thermosetting resin composition of any one of Claims 1-6 containing an inorganic filler (G).   Furthermore, the thermosetting resin composition of any one of Claims 1-7 containing a hardening accelerator (H).   A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of claims 1 to 8.   The film with a resin formed by layer-forming the thermosetting resin composition of any one of Claims 1-8 on a support body.   A laminate obtained by laminating the prepreg according to claim 9.   A laminate obtained by laminating the film with resin according to claim 10.   The printed wiring board manufactured using the laminated board of Claim 11 or 12.   A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to claim 13.