JP5949249B2 - Thermosetting resin composition, prepreg, laminate and printed wiring board using the same - Google Patents

Description

  The present invention relates to a thermosetting resin composition suitable for semiconductor packages and printed wiring boards, and in particular, a thermosetting resin composition excellent in low thermal expansion and desmear resistance, and a prepreg and a laminate using the same. And a printed wiring board.

  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 excellent heat resistance and a low linear expansion coefficient.

As a laminated board for a printed wiring board, one obtained by curing and integrally molding a resin composition mainly composed of an epoxy resin and a glass woven fabric is generally used. In general, epoxy resin has a good balance of insulation, heat resistance, cost, etc. However, in order to respond to the demand for improved heat resistance due to the recent high density mounting of printed wiring boards and multi-layered construction, it is inevitably necessary. There is a limit to the increase in sex. Furthermore, since the thermal expansion coefficient is large, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring or by highly filling an inorganic filler such as silica (for example, see Patent Document 1).
However, increasing the inorganic filling amount with the resin composition for laminates causes a decrease in insulation reliability due to moisture absorption, insufficient adhesion of the resin-wiring layer, and poor press molding.
In addition, polybismaleimide resins widely used for high-density packaging and highly multilayered laminates are very excellent in heat resistance, but have high hygroscopicity and have difficulty in adhesion. Furthermore, there is a drawback in that productivity is poor because a high temperature and a long time are required compared with the epoxy resin during lamination.
That is, in general, the epoxy resin can be cured at a temperature of 180 ° C. or lower, but when a polybismaleimide resin is laminated, a high temperature of 220 ° C. or higher and a long-time treatment are required. Although the modified imide resin composition is improved in moisture resistance and adhesiveness (for example, see Patent Document 2), it is a low molecular weight compound containing a hydroxyl group and an epoxy group in order to ensure solubility in a general-purpose solvent such as methyl ethyl ketone. Since it is modified, the heat resistance of the resulting modified imide resin is significantly inferior to that of the polybismaleimide resin.

  In addition, in the process of manufacturing a multilayer printed circuit board, after forming a via hole by drilling or laser processing and desmearing with a desmear solution such as a permanganic acid solution, if the resin has low desmear resistance, There was a problem that the resin was shaved, the unevenness was increased, and defects such as plating soaking and plating peeling occurred.

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

  In view of the current situation, an object of the present invention is to provide a thermosetting resin composition that is particularly excellent in low thermal expansion and desmear resistance, and a prepreg, a laminate, and a printed wiring board using the same.

  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 a siloxane-modified polyimide having a specific structure, and have completed the present invention. . The present invention has been completed based on such knowledge.

［式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ独立にアルキル基、フェニル基又は置換フェニル基を示し、Ｒ⁷及びＲ⁸はそれぞれ独立に２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜５０の整数を示す。但し、ｍ及びｎは、１＜ｍ＋ｎ＜５０である。］

［式（２）中、Ｒ⁹は複数ある場合は各々独立に、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示し、Ｒ¹⁰は複数ある場合は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、ハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、ｘ＋ｙ＝５である。］
２．さらに、熱硬化性樹脂（Ｄ）を含有する上記１に記載の熱硬化性樹脂組成物。
３．上記１に記載の（Ａ）、（Ｂ）および（Ｃ）を反応させて得られる、分子構造中に酸性置換基を有するシロキサン変性ポリイミドを含有する上記１又は２に記載の熱硬化性樹脂組成物。
４．上記１に記載の（Ａ）、（Ｂ）および（Ｃ）と共に、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ただし、（Ｂ）の一般式（１）に示されるシロキサンジアミンを除く）（Ｅ）を配合することを特徴とする上記１又は２に記載の熱硬化性樹脂組成物。
５．分子構造中に酸性置換基を有するシロキサン変性ポリイミドが、さらに、１分子中に少なくとも２個の１級アミノ基を有するアミン化合物（ただし、（Ｂ）の一般式（１）に示されるシロキサンジアミンを除く）（Ｅ）を反応させて得られるものである上記３に記載の熱硬化性樹脂組成物。
６．前記熱硬化性樹脂（Ｄ）が分子構造中にエポキシ基またはシアネート基を有する樹脂である上記１〜５に記載の熱硬化性樹脂組成物。
７．さらに、無機充填材（Ｆ）を含有する上記１〜６に記載の熱硬化性樹脂組成物。
８．さらに、下記一般式（３）に示す変性イミダゾール化合物及び下記一般式（４）に示す変性イミダゾール化合物から選ばれた少なくとも一種の硬化促進剤（Ｇ）を含有する上記１〜７に記載の熱硬化性樹脂組成物。

［式（３）中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は各々独立に水素原子、又は炭素数１〜５の脂肪族炭化水素基、フェニル基を示し、Ｂは存在しないか、又はアルキレン基、アルキリデン基、エーテル基、スルフォニル基のいずれかである］

［式（４）中、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸は各々独立に水素原子、又は炭素数１〜５の脂肪族炭化水素基、フェニル基を示し、Ｄはアルキレン基または芳香族炭化水素基のイソシアネート樹脂の残基である］
９．上記１〜８のいずれかに記載の熱硬化性樹脂組成物を用いたプリプレグ。
１０．上記９記載のプリプレグを用いて積層成形した得られた積層板。
１１．上記１０記載の積層板を用いて製造された多層プリント配線板。 That is, the present invention provides the following thermosetting resin composition, prepreg, laminate and printed wiring board.
1. (A) 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, (B) a siloxane diamine represented by the following general formula (1), (C) an acidic substituent represented by the following general formula (2) A thermosetting resin composition characterized by comprising an amine compound having a mixture.

[In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and R ⁷ and R ⁸ each independently represents 2 And m and n each independently represents an integer of 1 to 50. However, m and n are 1 <m + n <50. ]

[In Formula (2), when there are a plurality of R ^{9 s,} each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and when there are a plurality of R ^{10 s,} each independently represents a hydrogen atom or a carbon number of 1 An aliphatic hydrocarbon group of ˜5, a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and x + y = 5. ]
2. Furthermore, the thermosetting resin composition of said 1 containing a thermosetting resin (D).
3. 3. The thermosetting resin composition according to 1 or 2 above, comprising a siloxane-modified polyimide having an acidic substituent in the molecular structure obtained by reacting (A), (B) and (C) according to 1 above. object.
4). An amine compound having at least two primary amino groups in one molecule together with (A), (B) and (C) described in 1 above (provided that the siloxane represented by the general formula (1) of (B)) 3. The thermosetting resin composition as described in 1 or 2 above, which comprises (E) excluding diamine).
5. The siloxane-modified polyimide having an acidic substituent in the molecular structure is further converted into an amine compound having at least two primary amino groups in one molecule (provided that the siloxane diamine represented by the general formula (1) of (B) 3. The thermosetting resin composition as described in 3 above, which is obtained by reacting (E).
6). The thermosetting resin composition according to 1 to 5, wherein the thermosetting resin (D) is a resin having an epoxy group or a cyanate group in a molecular structure.
7). Furthermore, the thermosetting resin composition of said 1-6 containing an inorganic filler (F).
8). Furthermore, the thermosetting of said 1-7 containing at least 1 type of hardening accelerator (G) chosen from the modified imidazole compound shown to following General formula (3), and the modified imidazole compound shown to following General formula (4). Resin composition.

[In the formula (3), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and B is absent or Any of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group]

[In the formula (4), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, and D represents an alkylene group or an aromatic group. It is a residue of a hydrocarbon group isocyanate resin]
9. The prepreg using the thermosetting resin composition in any one of said 1-8.
10. A laminate obtained by laminating using the prepreg described in 9 above.
11. A multilayer printed wiring board produced using the laminate as described in 10 above.

  A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention and a laminate produced by laminating the prepreg are particularly excellent in low thermal expansion and desmear resistance. It is useful as a printed wiring board for equipment.

［式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ独立にアルキル基、フェニル基又は置換フェニル基を示し、Ｒ⁷及びＲ⁸はそれぞれ独立に２価の有機基を示し、ｍ及びｎはそれぞれ独立に１〜５０の整数を示す。但し、ｍ及びｎは、１＜ｍ＋ｎ＜５０である。］

［式（２）中、Ｒ⁹は複数ある場合は各々独立に、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示し、Ｒ¹⁰は複数ある場合は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、ハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、ｘ＋ｙ＝５である。］ Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention comprises (A) 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, (B) a siloxane diamine represented by the following general formula (1), (C) An amine compound having an acidic substituent represented by the general formula (2) is blended.

[In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and R ⁷ and R ⁸ each independently represents 2 And m and n each independently represents an integer of 1 to 50. However, m and n are 1 <m + n <50. ]

[In Formula (2), when there are a plurality of R ^{9 s,} each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and when there are a plurality of R ^{10 s,} each independently represents a hydrogen atom or a carbon number of 1 An aliphatic hydrocarbon group of ˜5, a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and x + y = 5. ]

  By using 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane as the component (A) in the thermosetting resin composition of the present invention, solvent solubility and resin compatibility are improved. High desmear resistance can be obtained.

As the siloxane diamine represented by the general formula (1) of the component (B) in the thermosetting resin composition of the present invention, a commercially available product can be used. For example, “KF-8010” (amine equivalent 430), “X -22-161A "(amine equivalent 800)," X-22-161B "(amine equivalent 1500)," KF-8012 "(amine equivalent 2200)," KF-8008 "(amine equivalent 5700)," X-22 −9409 ”(amine equivalent 700),“ X-22-1660B-3 ”(amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.),“ BY-16-853U ”(amine equivalent 460),“ BY -16-853 "(amine equivalent 650)," BY-16-853B "(amine equivalent 2200) (above, manufactured by Toray Dow Corning Co., Ltd.) and the like. Or it may be used as a mixture of two or more.
Among these siloxane diamines, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and BY-16-853B are preferable in terms of low water absorption, and low heat X-22-161A, X-22-161B, and KF-8012 are particularly preferable from the viewpoint of expansibility.

  Examples of the amine compound having an acidic substituent of component (C) 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. Among these, solubility and synthesis From the viewpoint of yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and m-amino from the viewpoint of heat resistance. Phenol and p-aminophenol are more preferred.

  The thermosetting resin composition of the present invention is a mixture of the above (A), (B) and (C), and is obtained by pre-reacting (A), (B) and (C). It can also be used as a siloxane-modified polyimide having an acidic substituent. By performing such a pre-reaction, the molecular weight can be controlled, and the thermal expansion coefficient can be further lowered and the desmear resistance can be improved.

These reactions are preferably carried out in an organic solvent while being heated and heated to synthesize a siloxane-modified polyimide having an acidic substituent.
When the above components (A), (B) and (C) are reacted in an organic solvent, the reaction temperature is preferably 70 to 150 ° C, more preferably 100 to 130 ° C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
Here, the amount of the monoamine compound having the (B) siloxane diamine and the (C) acidic substituent is the relationship between the sum of the —NH ₂ group equivalents and the C═C group equivalent of the maleimide ring of (A). But,
0.1 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 10.0 is preferable. More preferably, this relationship is
1.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 9.0, particularly preferably
2.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 8.0
The range.
When the ratio is 0.1 or more, gelation and heat resistance do not decrease, and when it is 10.0 or less, solubility in organic solvents and heat resistance do not decrease.
While maintaining the relationship as described above, the amount of the component (A) used is preferably 50 to 3000 parts by mass, more preferably 100 to 1500 parts by mass with respect to 100 parts by mass of the component (B). When the amount is 50 parts by mass or more, the heat resistance does not decrease, and when the amount is 3000 parts by mass or less, the low thermal expansion can be kept good.

  Moreover, 1-1000 mass parts is preferable with respect to 100 mass parts of (B) component, and, as for the usage-amount of (C) component, 10-500 mass parts is more preferable. When the amount is 1 part by mass or more, the heat resistance does not decrease, and when the amount is 1000 parts by mass or less, the low thermal expansion can be kept good.

  The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Examples include sulfur atom-containing solvents such as dimethyl sulfoxide, and one or two or more of them can be used in combination.

  Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferred from the viewpoint of solubility, and cyclohexanone, propylene are preferred because of their low toxicity and high volatility that are difficult to remain as a residual solvent. Glycol monomethyl ether and dimethylacetamide are particularly preferred.

  The amount of the organic solvent used is preferably 25 to 1000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the sum of the components (A), (B) and (C). When the amount of the organic solvent used is 25 to 1000 parts by mass, there are no disadvantages such as insufficient solubility and a long time for synthesis, which is preferable.

Moreover, a reaction catalyst can be arbitrarily used for this reaction, and it is not specifically limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Can be used.
Furthermore, the thermosetting resin composition of the present invention also contains an amine compound (E) having at least two primary amino groups in one molecule together with the above (A), (B) and (C). be able to.

  The amine compound of the component (E) is not particularly limited as long as it is other than the siloxane diamine represented by the general formula (1) of (B). For example, m-phenylenediamine, p-phenylene Diamine, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4-diaminomesitylene, m-xylene -2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-bis (amino-t-butyl) toluene, 2,4 -Diaminoxylene, 2,4-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminodurene, 4,5 Diamino-6-hydroxy-2-mercaptopyrimidine, 3-bis (3-aminobenzyl) benzene, 4-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3- Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3-bis (3- (3-aminophenoxy) phenoxy) benzene 4-bis (4- (4-aminophenoxy) phenoxy) benzene, 3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene, 4-bis (4- (4- (4- (4- Aminophenoxy) phenoxy) phenoxy) benzene, 3-bis (α, α-dimethyl-3-aminobenzyl) benzene, 1,4-bis (α, α -Dimethyl-3-aminobenzyl) benzene, 3-bis (α, α-dimethyl-4-aminobenzyl) benzene, bis (4-methylaminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) Benzene, 1,4-bis (3-aminopropyldimethylsilyl) benzene, bis [(4-aminophenyl) -2-propyl] 1,4-benzene, 2,5-diaminobenzenesulfonic acid, 3,3′- Diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 '-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl, 5,5'-diethyl-4,4'-diaminodiphe Nylmethane, 4,4′-methylene-bis (2-chloroaniline), 3,3′-diaminodiphenylethane, 4,4′-diaminodiphenylethane, 2,2′-diaminodiphenylpropane, 3,3′-diamino Diphenylpropane, 4,4′-diaminodiphenylpropane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 3- (2 ′, 4′-diaminophenoxy) propanesulfonic acid, bis (4-aminophenyl) diethylsilane, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diamino Diphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-dia Nodiphenyl ether, bis (4-amino-t-butylphenyl) ether, 4,4′-diaminodiphenyl ether-2,2′-disulfonic acid, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, benzidine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl-6,6'-disulfonic acid, 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl 3,3′-dichloro-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 4,4′-diamino-3,3 ′ -Biphenyldiol, 1,5-diaminonaphthalene, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene, 9,9'-bis (4-aminophenyl) fluorene, 9,9'-bis (4-aminophenyl) ) Aromatic amines such as fluorene-2,7-disulfonic acid, 9,9′-bis (4-aminophenoxyphenyl) fluorene, diaminoanthraquinone, 3,7-diamino-2,8-dimethyldibenzothiophene sulfone, ethylenediamine , Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine , Octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4- Dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 2,5-diamino-1,3,4-oxadiazol , Aliphatic amines such as bis (4-aminocyclohexyl) methane, melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine 2,4-diamino-6-acryloyl Shiechiru -s- triazine, guanamine compound such as 2,4-diamino-6-methacryloyloxyethyl -s- triazine.

  (E) As an amine compound (except for the siloxane diamine represented by the general formula (1) of (B)), among these, m which is an aromatic amine having good reactivity and heat resistance -Phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'- Diethyl-4,4′-diaminodiphenylmethane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 3,3′- Diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone Preferred are benzidine, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 4,4′-diamino-3,3′-biphenyldiol and benzoguanamine which is a guanamine compound, and is inexpensive. P-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-dimethyl- 4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, and benzoguanamine are more preferable, and 3,3′-diaminodiphenylsulfone, 3,3 from the viewpoint of toxicity and solubility in solvents. Specially '-diethyl-4,4'-diaminodiphenylmethane Preferred. These may be used alone or in combination of two or more.

  The thermosetting resin composition of the present invention is one in which the above (A), (B) and (C) are blended, and (A), (B), (C) and (E) are pre-treated. It can also be used as a siloxane-modified polyimide having an acidic substituent obtained by reaction. By performing such a pre-reaction, the molecular weight can be controlled, and the thermal expansion coefficient can be further lowered and the desmear resistance can be improved.

These reactions are preferably carried out in an organic solvent while being heated and heated to synthesize a siloxane-modified polyimide having an acidic substituent.
When the above components (A), (B), (C) and (E) are reacted in an organic solvent, the reaction temperature is preferably 70 to 150 ° C, more preferably 100 to 130 ° C. . The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

Here, (B) siloxane diamine, (C) a monoamine compound having an acidic substituent, and (E) an amine compound having at least two primary amino groups in one molecule (provided that (B) The amount used with the exception of the siloxane diamine represented by the general formula (1) is the relationship between the sum of —NH ₂ group equivalents and the C═C group equivalents of the maleimide ring of (A),
0.1 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 10.0 is preferable. More preferably, this relationship is
1.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 9.0, particularly preferably
2.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 8.0
The range.
When the ratio is 0.1 or more, gelation and heat resistance are not reduced, and when it is 10.0 or less, solubility in organic solvents and heat resistance are not reduced. ,preferable.

  (E) As for the usage-amount of a component, 50-3000 mass parts is preferable with respect to 100 mass parts of (B) component, maintaining the said relationship, and 100-1500 mass parts is more preferable. When the amount is 50 parts by mass or more, the heat resistance does not decrease, and when the amount is 3000 parts by mass or less, the low thermal expansion can be kept good.

When the components (A), (B), (C) and (E) are reacted, the same organic solvent or reaction catalyst as that used when the components (A), (B) and (C) are reacted is used. used.
The amount of the organic solvent used is preferably 25 to 1000 parts by mass, more preferably 50 to 500 parts by mass per 100 parts by mass of the sum of (A), (B), (C) and (E). preferable. When the amount of the organic solvent used is 25 to 1000 parts by mass, there are no disadvantages such as insufficient solubility and a long time for synthesis, which is preferable.

The thermosetting resin composition of the present invention has good thermosetting reactivity by itself, but if necessary, it can be used in combination with other thermosetting resin (D) to improve heat resistance, adhesiveness, and mechanical strength. Can be improved.
The thermosetting resin (D) used in combination is not particularly limited. For example, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, Examples include allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, and the like. These may be used alone or in admixture of two or more. Among these, epoxy resins and cyanate resins are preferable from the viewpoint of moldability and electrical insulation.

  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 And these phosphorus-containing epoxy resin obtained by introducing a phosphorus compound are mentioned, these alone, or two or more kinds may be used in admixture. Among these, biphenylaralkyl type epoxy resins and naphthalene type epoxy resins are preferred 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. These may be used alone or in admixture of two or more. Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy.

  As a usage-amount of a thermosetting resin (D), it is preferable to set it as 20-50 mass parts from a copper foil adhesiveness and a chemical-resistant point with respect to 100 mass parts of total of a resin component.

  Moreover, a curing agent and a curing accelerator can be used in combination with these thermosetting resin compositions as necessary. Examples of curing agents 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 Acid anhydrides, such as an acid and a maleic anhydride copolymer, etc. are mentioned, These 1 type (s) or 2 or more types can be mixed and used.

  Examples of the curing accelerator include, for example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III). , Imidazoles and derivatives thereof, organophosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, quaternary ammonium salts, etc., and one or more of these Can be used in combination.

［式（３）中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は各々独立に水素原子、又は炭素数１〜５の脂肪族炭化水素基、フェニル基を示し、Ｂは存在しないか、又はアルキレン基、アルキリデン基、エーテル基、スルフォニル基のいずれかである］

［式（４）中、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸は各々独立に水素原子、又は炭素数１〜５の脂肪族炭化水素基、フェニル基を示し、Ｄはアルキレン基または芳香族炭化水素基のイソシアネート樹脂の残基である］
下記一般式（５）又は（６）で表される化合物が少量の配合使用でよく、また商業的にも安価であることから特に好ましい。

Among them, imidazoles and derivatives thereof are preferable in terms of heat resistance, flame retardancy, copper foil adhesion, and the like, and further represented by the following general formula (3), a modified imidazole compound in which an imidazole group is modified with an epoxy resin, The modified imidazole compound represented by the following general formula (4), in which the imidazole group is modified with an isocyanate resin, is excellent in curing moldability at a relatively low temperature at 200 ° C. or lower and aging stability of varnish and prepreg. More preferred,

[In the formula (3), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and B is absent or Any of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group]

[In the formula (4), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, and D represents an alkylene group or an aromatic group. It is a residue of a hydrocarbon group isocyanate resin]
The compound represented by the following general formula (5) or (6) may be used in a small amount and is particularly preferable because it is commercially inexpensive.

  The amount of the curing accelerator used is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight per 100 parts by weight of the total resin components. It is particularly preferably 0.1 parts by weight or more and 1 part by weight or less. If the amount of the curing accelerator used is small, the heat resistance, flame retardancy, copper foil adhesiveness, etc. are insufficient, and if it exceeds 10 parts by weight, the heat resistance, aging stability and press formability are lowered.

  In the thermosetting resin composition of the present invention, the amount of the siloxane-modified polyimide having an acidic substituent is preferably 20 to 100 parts by mass, and 50 to 90 parts by mass per 100 parts by mass of the total resin components. More preferably. By setting the blending amount of the siloxane-modified polyimide having an acidic substituent to 20 parts by mass or more, excellent heat resistance, low water absorption, and low thermal expansion can be obtained.

  An inorganic filler (F) can be optionally used in combination with the thermosetting resin composition of the present invention. Inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, and boron. Examples include aluminum oxide, 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.

  Among these inorganic fillers, silica is particularly preferable from the viewpoints of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused spherical silica. Among these, fused spherical silica is 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, 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 size is a particle size at a point corresponding to a volume of just 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.

  The content of the inorganic filler is preferably 20 to 300 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the total resin components. By making content of an inorganic filler into 20-300 mass parts per 100 mass parts of sum total of a resin component, the moldability and low thermal expansibility of a resin composition can be kept favorable.

  In the present invention, any known thermoplastic resin, elastomer, organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, and adhesiveness may be used without departing from the object. An improver or the like can be used.

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

  Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.

  Organic fillers include resin fillers of uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., acrylate ester resins, methacrylate ester resins, conjugated diene resins, etc. And a core-shell resin filler having 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.

  As flame retardants, halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphorous flame retardants such as red phosphorus, guanidine sulfamate, Nitrogen flame retardants such as 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 of the present invention is used for a prepreg, it is preferable that each component is finally in a varnish state in which each component is dissolved or dispersed in an organic solvent.
Examples of the organic solvent 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, 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 Examples thereof include sulfur atom-containing solvents such as 1 type or a mixture of two or more types. Among these, 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.

  In addition, when blended in the resin composition, it is also preferable that the inorganic filler is pretreated with a silane or titanate coupling agent, or a surface treatment agent such as a silicone oligomer, or an integral blend treatment.

  It is preferable that the resin composition in the varnish finally obtained is 40 to 90 mass% of the whole varnish, and it is more preferable that it is 50 to 80 mass%. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coatability and obtain a prepreg having an appropriate resin composition adhesion amount.

  The prepreg of the present invention is obtained by coating the above-described resin composition of the present invention on a base material, or applying the base material to the base material by a method such as impregnation or spraying or extrusion. Hereinafter, the prepreg of the present invention will be described in detail.

  The prepreg of the present invention can be produced by impregnating or coating the base material with the thermosetting resin composition of the present invention and semi-curing (B-stage) by heating or the like. As the base material of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass and Q glass, or glass films thereof, organic fibers such as polyimide, polyester and tetrafluoroethylene, and mixtures thereof.

  These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined. The thickness of the base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.

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

  The laminate of the present invention can be formed by laminate molding using the prepreg of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.

  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. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a laminated board.

  The printed wiring board according to the present invention is manufactured by forming a circuit on the surface of the laminated board. That is, the conductor layer of the laminated board according to the present invention is subjected to wiring processing by a normal etching method, and a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated and subjected to hot press processing to be multilayered at once. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
In addition, the glass transition temperature, the coefficient of thermal expansion, the copper foil adhesiveness, and the desmear resistance were measured and evaluated by the following methods using the copper clad laminates obtained in the examples and comparative examples.

(1) 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 (manufactured by DuPont, TMA2940) was used. The thermomechanical analysis was performed 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.

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

(3) Evaluation of copper foil adhesiveness (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 adhesiveness (90 ° peel strength) of the foil was measured.

(4) Evaluation of desmear resistance A 40 mm × 40 mm evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was subjected to a desmear treatment by the steps shown in Table 1 below. A chemical manufactured by Atotech was used. For evaluation of desmear resistance, the weight loss was calculated from the difference in dry weight before and after desmear treatment at 130 ° C.

Production Example 1: Production of Siloxane-Modified Polyimide (P-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, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] propane: 162.3 g, KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 430): 48.6 g, p-aminophenol: 3.9 g, and Dimethylacetamide: 300.0 g was added and reacted at 100 ° C. for 3 hours to obtain a siloxane-modified polyimide (P-1) -containing solution having an acidic substituent in the molecular structure.

Production Example 2: Production of Siloxane-Modified Polyimide (P-2) In a reaction vessel having a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, which can be heated and cooled, a 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] propane: 162.3 g, X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 800): 24.3 g, and p-aminophenol: 3.9 g And 300.0 g of propylene glycol monomethyl ether were allowed to react at 115 ° C. for 3 hours to obtain a siloxane-modified polyimide (P-2) -containing solution having an acidic substituent in the molecular structure.

Production Example 3 Production of Siloxane-Modified Polyimide (P-3) In a reaction vessel having a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, a 2-liter [2-liter [ 4- (4-maleimidophenoxy) phenyl] propane: 162.3 g, X-22-1660B-3 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 2200): 24.3 g, m-aminophenol: 3 .9 g and propylene glycol monomethyl ether: 300.0 g were added and reacted at 115 ° C. for 3 hours to obtain a siloxane-modified polyimide (P-3) -containing solution having an acidic substituent in the molecular structure.

Production Example 4: Production of Siloxane-Modified Polyimide (P-4) 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, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] propane: 159.1 g and X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 800): 28.3 g, 3,3′-diethyl-4, 4'-diaminodiphenylmethane: 8.8 g, p-aminophenol: 3.8 g, and propylene glycol monomethyl ether: 300.0 g are added and reacted at 115 ° C. for 3 hours to have an acidic substituent in the molecular structure. A siloxane-modified polyimide (P-4) -containing solution was obtained.

Production Example 5 Production of Siloxane-Modified Polyimide (P-5) 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, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] propane: 159.1 g, X-22-161B (trade name, amine equivalent 1500, manufactured by Shin-Etsu Chemical Co., Ltd.): 24.3 g, 2,2′-bis [4 -(4-Aminophenoxy) phenyl] propane: 9.7 g, p-aminophenol: 3.8 g, and propylene glycol monomethyl ether: 300.0 g were added and reacted at 115 ° C. for 3 hours. A siloxane-modified polyimide (P-5) -containing solution having an acidic substituent was obtained.

Production Comparative Example 1: Production of Siloxane-modified Polyimide (P-6) Bis (4-maleimidophenyl) methane: 164 in a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters .3 g, X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 800): 99.2 g, m-aminophenol: 4.5 g, and dimethylacetamide: 250.0 g, The reaction was carried out at 100 ° C. for 3 hours to obtain a siloxane-modified polyimide (P-6) -containing solution having an acidic substituent in the molecular structure.

Production Comparative Example 2: Production of Siloxane-Modified Polyimide (P-7) Bis (4-maleimidophenyl) was added to 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. ) Methane: 143.0 g, KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 2200): 88.0 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane: 14.0 g , P-aminophenol: 5.5 g and propylene glycol monomethyl ether: 250.0 g, reacted at 115 ° C. for 3 hours, and a siloxane-modified polyimide (P-7) -containing solution having an acidic substituent in the molecular structure Got.

Examples 1-12, Comparative Examples 1-3
The siloxane-modified polyimide-containing solution obtained in Production Examples 1 to 5 or the siloxane-modified polyimide-containing solution obtained in Production Comparative Examples 1 and 2, and the thermosetting resin, inorganic filler, curing accelerator, and Methyl ethyl ketone was used as a diluent solvent and mixed at a blending ratio (parts by mass) shown in Tables 2 to 4 to obtain a uniform varnish having a resin content of 65% by mass.

(Thermosetting resin)
PT-30: Novolac-type cyanate resin [Lonza Japan Co., Ltd., trade name]
BA230: Bisphenol A dicyanate prepolymer [Lonza Japan Co., Ltd., trade name]
NC-3000-H, biphenyl aralkyl type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name]
NC-7000L, α-naphthol / cresol novolac type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.)
(Inorganic filler)
SC2050-KNK: fused silica [manufactured by Admatech Co., Ltd., trade name]
(Curing accelerator)
G-8809L: Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name]

Next, 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 resin content of 48 mass%.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate.
The measurement and evaluation results of the obtained copper-clad laminate are shown in Tables 2 to 4.

  As is apparent from Tables 2 to 4, the examples of the present invention are excellent in the coefficient of thermal expansion and resistance to desmear. On the other hand, the comparative example is inferior in a thermal expansion coefficient and desmear resistance compared with an Example.

  A multilayer printed wiring board produced using a laminate obtained by laminating a prepreg obtained from the thermosetting resin composition of the present invention is excellent in glass transition temperature, thermal expansion coefficient, copper foil adhesiveness, desmear resistance, It is useful as a highly integrated semiconductor package or printed wiring board for electronic equipment.

Claims (11)

(A) 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, (B) a siloxane diamine represented by the following general formula (1), (C) an acidic substituent represented by the following general formula (2) A thermosetting resin composition characterized by comprising an amine compound having a mixture.

[In formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and R ⁷ and R ⁸ each independently represents 2 And m and n each independently represents an integer of 1 to 50. However, m and n are 1 <m + n <50. ]

[In formula (2), when there are a plurality of R ^{9 s,} each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and when there are a plurality of R ^{10 s,} each independently represents a hydrogen atom or a carbon number of 1 An aliphatic hydrocarbon group of ˜5, a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and x + y = 5. ]   Furthermore, the thermosetting resin composition of Claim 1 containing a thermosetting resin (D).   The thermosetting property of Claim 1 or 2 containing the siloxane modified polyimide which has an acidic substituent in the molecular structure obtained by making (A), (B) and (C) of Claim 1 react. Resin composition.   An amine compound having at least two primary amino groups in one molecule together with (A), (B) and (C) according to claim 1 (provided by the general formula (1) of (B)) The thermosetting resin composition according to claim 1, wherein (E) is blended (excluding siloxane diamine).   The siloxane-modified polyimide having an acidic substituent in the molecular structure is further converted into an amine compound having at least two primary amino groups in one molecule (provided that the siloxane diamine represented by the general formula (1) of (B) The thermosetting resin composition according to claim 3, which is obtained by reacting (E). The thermosetting resin composition according to any one of claims 2 to 5 , wherein the thermosetting resin (D) is a resin having an epoxy group or a cyanate group in a molecular structure. Furthermore, the thermosetting resin composition in any one of Claims 1-6 containing an inorganic filler (F). Furthermore, in any one of Claims 1-7 containing the at least 1 type of hardening accelerator (G) chosen from the modified imidazole compound shown to following General formula (3), and the modified imidazole compound shown to following General formula (4). The thermosetting resin composition as described.

[In the formula (3), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and B is absent or Any of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group]

[In the formula (4), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and D represents an alkylene group or an aromatic group. It is a residue of a hydrocarbon group isocyanate resin]   The prepreg using the thermosetting resin composition in any one of Claims 1-8. Laminate obtained by laminating molding using a prepreg of claim 9, wherein.   The multilayer printed wiring board manufactured using the laminated board of Claim 10.