JP6107050B2 - Thermosetting resin composition, prepreg, laminate and printed wiring board - Google Patents

Description

  The present invention relates to a thermosetting resin composition, a prepreg, a laminated board, and a printed wiring board that are excellent in heat resistance, low thermal expansion, surface smoothness, and warpage reduction, and are used in electronic components and the like.

  Along with the trend toward miniaturization and higher performance of electronic devices in recent years, printed wiring boards have become increasingly dense and highly integrated, and as a result, reliability has been improved by improving the heat resistance of laminated boards for wiring. There is an increasing demand for improvement.

  As a prepreg used for a laminate for a printed wiring board, a resin composition mainly composed of an epoxy resin and a glass woven fabric are integrally formed. In general, epoxy resin has a good balance of insulation, heat resistance, cost, etc. However, in order to meet the demand for high heat resistance due to recent high-density mounting of printed wiring boards and multi-layered configurations, it is absolutely necessary to have heat resistance. There is a limit to the improvement of sex. Furthermore, since the commonly used epoxy resin has a large coefficient of thermal expansion, the selection of an epoxy resin having an aromatic ring with a specific structure, and the low thermal expansion is achieved by highly filling an inorganic filler such as silica (for example, Patent Document 1).

  Particularly in recent years, with semiconductor package substrates, along with miniaturization and thinning, warpage caused by the difference in thermal expansion coefficient between the chip and the substrate has become a major issue during component mounting or package assembly. Further, in order to reduce the warpage of the semiconductor package substrate, a low thermal expansion coefficient is required. However, increasing the filling amount of the inorganic filler reduces the surface smoothness and appearance of the prepreg due to a decrease in fluidity, causes warpage after press molding due to the difference between the front and back of the prepreg surface layer resin, and insulation reliability due to moisture absorption. It is known to cause a decrease in adhesion, insufficient adhesion between 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, compared with an epoxy resin, there exists a fault that high temperature and a long time are required for hardening, and productivity is bad.
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. Further, the modified imide resin composition has improved moisture resistance and adhesiveness (see, for example, Patent Document 2). However, since it is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group in order to ensure solubility in general-purpose solvents such as methyl ethyl ketone, the heat resistance of the resulting modified imide resin is significantly inferior to that of polybismaleimide resin.

JP 05-148343 A Japanese Patent Application Laid-Open No. 06-263843

  In view of the current situation, an object of the present invention is to provide a thermosetting resin composition, a prepreg, a laminate, and a printed wiring board that are excellent in heat resistance, low thermal expansion, surface smoothness, and warpage reduction. The heat resistance can be confirmed by the glass transition temperature.

As a result of intensive studies to achieve the above object, the present inventors have found that a resin composition containing a leveling agent comprising a maleimide compound, a silicone compound having a reactive organic group, and a nitrogen-containing polymer compound is obtained. It has been found that the above-mentioned purpose is met.
That is, the present invention provides the following thermosetting resin composition, prepreg, laminated board, and printed wiring board.

1. (A) a maleimide compound having at least two N-substituted maleimide groups in one molecular structure, (B) a silicone compound having at least one reactive organic group in one molecular structure, and (C) a nitrogen-containing polymer. A thermosetting resin composition comprising a leveling agent comprising a compound.
2. Further, (D) The thermosetting resin composition according to 1 above, which contains a thermosetting resin.
3. Furthermore, (E) The thermosetting resin composition according to 1 or 2, further comprising an amine compound having an acidic substituent represented by the following general formula (I).

(In the formula, when there are a plurality of R _{1 s,} each is independently a hydroxyl group, carboxyl group or sulfonic acid group which is an acidic substituent, and when there are a plurality of R _{2 s,} each is independently a hydrogen atom, an aliphatic having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and x + y = 5.)

4). (B) The thermosetting resin according to any one of 1 to 3 above, wherein the reactive organic group of the component is at least one selected from an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group. Composition.
5. (B) The thermosetting resin composition in any one of said 1-4 which is a silicone compound in which a component contains the structure represented by the following general formula (II).
Wherein, R _3, R ₄ each independently represents an alkyl group, a phenyl group or substituted phenyl group, n is an integer of 1 to 100. ]

6). (B) The thermosetting resin composition according to any one of 1 to 5 above, wherein the component is a silicone compound having a reactive organic group at least at one end.
7). (B) The thermosetting resin composition according to any one of 1 to 5, wherein the component is a silicone compound having a reactive organic group in at least a part of the side chain.
8). (B) The thermosetting resin composition according to any one of 1 to 5, wherein the component is a silicone compound having at least two reactive organic groups in one molecular structure.
9. (B) The thermosetting resin composition according to 8 above, wherein the component is a silicone compound having a reactive organic group in at least two or more terminals.
10. (B) The thermosetting resin composition according to 8 above, wherein the component is a silicone compound having a side chain and a reactive organic group at at least one terminal.
11. (1) The above component (C), wherein the component is at least one nitrogen-containing polymer compound selected from amides of polycarboxylic acids, specially modified ureas, modified ureas, polymer urea derivatives, urea-modified urethanes, polyurethanes, urea-modified medium polar polyamides 10 thermosetting resin composition.
12 (D) The thermosetting resin composition according to any one of 2 to 11 above, wherein the component is a thermosetting resin having an epoxy group and / or a cyanate group in the molecular structure.

13. Furthermore, (F) The thermosetting resin composition according to any one of 1 to 12 above, which contains a curing accelerator represented by the following general formula (III) or (IV).
(Wherein R ₆ , R ₇ , R ₈ and R ₉ 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 hydrocarbon. Group.)

(Wherein R ₆ , R ₇ , R ₈ and R ₉ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, and B represents a single bond, an alkylene group or an alkylidene group) A group, an ether group, or a sulfonyl group.)

14 Furthermore, (G) The thermosetting resin composition according to any one of 1 to 13 above, which contains an inorganic filler.
15. A prepreg obtained by impregnating or coating a base material with any one of the above thermosetting resin compositions and semi-curing (B-stage).
16. The laminated board obtained by carrying out lamination molding using the prepreg in any one of said 1-14.
17. The printed wiring board manufactured using said 16 laminated board.

  The thermosetting resin composition of the present invention, a prepreg obtained therefrom, a laminate obtained by laminate molding using the prepreg, and a multilayer printed wiring board produced using the laminate are heat resistant, Since it has excellent low thermal expansibility, has a smooth surface in a prepreg state, and reduces the amount of warping when it is made into a laminate, wiring formability is particularly good.

It is a figure which shows the measurement location of (3) evaluation of prepreg surface smoothness in an Example, and (4) evaluation of the front-back thickness difference of prepreg surface layer resin.

Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention has (A) a maleimide compound having at least two N-substituted maleimide groups in one molecular structure, and (B) at least one reactive organic group in one molecular structure. It contains a leveling agent comprising a silicone compound and (C) a nitrogen-containing polymer compound.

  Examples of the maleimide compound having at least two N-substituted maleimide groups in one molecular structure of the component (A) in the thermosetting resin composition of the present invention include N, N′-ethylenebismaleimide, N, N '-Hexamethylene bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N '-[1,3- (2-methylphenylene)] bismaleimide, N, N'-[1, 3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3 , 3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimi Phenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4- Bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4 -(4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2 -Bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) ) Phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- ( 3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1, 3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3 -Maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] keto 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] Sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4 -Maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α , Α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α -Dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) −3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3- Bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimide (for example, trade name: BMI-2300 manufactured by Daiwa Kasei Co., Ltd.) ,these Maleimide compounds may be used as a mixture of two or more may be used alone.

  Among these maleimide compounds, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, N, N ′, which have a high reaction rate and can increase the heat resistance of the formed laminate and printed wiring board. -(1,3-phenylene) bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, and polyphenylmethanemaleimide are preferable. From the viewpoint of solubility in a solvent, bis (4-maleimide) Phenyl) methane is particularly preferred.

  As the reactive organic functional group in the silicone compound having at least one reactive organic group in one molecular structure of the component (B), epoxy group, amino group, hydroxyl group, methacryl group, mercapto group, carboxyl group, alkoxy group Is mentioned. In addition, when there are a plurality of reactive organic functional groups, each reactive organic functional group may be the same or different.

Examples of the silicone compound having at least one reactive organic group in the molecular structure of the component (B) include silicone compounds having a structure represented by the following general formula (II).
Wherein, R _3, R ₄ each independently represents an alkyl group, a phenyl group or substituted phenyl group, n is an integer of 1 to 100. ]

  Examples of the silicone compound having the structure as described above include a silicone compound having a reactive organic group at at least a part of the terminal and a silicone compound having a reactive organic group at least at a part of the side chain. Further, as the component (B), a silicone compound having at least two reactive organic groups in one molecular structure is preferably used, and a silicone having a reactive organic group at at least two parts of the terminal of the silicone structure A compound and a silicone compound having a side chain and a reactive organic group at at least one terminal are used. In the present application, “terminal” refers to the case where they are bonded to the left and right of the general formula (II), and “side chain” refers to the case where they are bonded to the upper and lower positions of the general formula (II).

As the silicone compound having an epoxy group in the molecular structure, a commercially available product can be used. For example, “X-22-163” (functional group equivalent 200) having an epoxy group at both ends, “KF-105” ( Functional group equivalent 490), "X-22-163A" (functional group equivalent 1000), "X-22-163B" (functional group equivalent 1750), "X-22-163C" (functional group equivalent 2700), both ends "X-22-169AS" having a cycloaliphatic epoxy group (functional group equivalent 500), "X-22-169B" (functional group equivalent 1700), "X-22-1730X having an epoxy group at one end" (Functional group equivalent 4500), side chain and "X-22-9002" having an epoxy group at both ends (functional group equivalent 5000), "X-22-343" (functional) having an epoxy group on the side chain Equivalent 525), “KF-101” (functional group equivalent 350), “KF-1001” (functional group equivalent 3500), “X-22-2000” (functional group equivalent 620), “X-22-4741” ( Functional group equivalent 2500), “KF-1002” (functional group equivalent 4300), “X-22-2046” (functional group equivalent 600) having an alicyclic epoxy group in the side chain, “KF-102” (functional group) Equivalent, 3600 or more, manufactured by Shin-Etsu Chemical Co., Ltd.), which can be used alone or in combination of two or more and further mixed with various epoxy resins.
Among these silicone compounds having an epoxy group in the molecular structure, "X-22-163A", "X-22-163B", from the viewpoint of the heat resistance of the formed laminate and the heat resistance of the printed wiring board, “X-22-343”, “X-22-9002” and “KF-101” are preferable, “X-22-163A” and “X-22-163B” are more preferable. X-22-163B "is particularly preferred.

A commercially available product can be used as the silicone compound having an amino group in the molecular structure. For example, “KF-8010” (functional group equivalent 430), “X-22-161A” (functional group equivalent 800), “X-22-161B” (functional group equivalent 1500) having amino groups at both ends, “ "KF-8012" (functional group equivalent 2200), "KF-8008" (functional group equivalent 5700), "X-22-9409" (functional group equivalent 700), "X-22-1660B-3" (functional group equivalent) 2200) (Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (functional group equivalent 460) “BY-16-853” (functional group equivalent 650), “BY-16-853B” (functional) Group equivalent 2200) (manufactured by Toray Dow Corning Co., Ltd.), “KF-868” (functional group equivalent 8800) having an amino group in the side chain, “KF-865” (functional group equivalent 5000), “KF— 864 "(Government Group equivalent 3800), "KF-880" (functional group equivalent 1800), "KF-8004" (functional group equivalent 1500) (or, Shin-Etsu Chemical Co., Ltd.) and the like. These may be used alone or in admixture of two or more.
Among these silicone compounds having an amino group in the molecular structure, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3 from the viewpoint of low water absorption. BY-16-853B is preferable, and X-22-161A, X-22-161B, and KF-8012 are particularly preferable from the viewpoint of a low thermal expansion coefficient.

  A commercially available product can be used as the silicone compound having a hydroxyl group in the molecular structure. For example, “KF-6001” (functional group equivalent 900), “KF-6002” (functional group equivalent 1600) having hydroxyl groups at both ends, “X-22-1821” (functional group) having phenolic hydroxyl groups at both ends Equivalent 1470) (above, manufactured by Shin-Etsu Chemical Co., Ltd.), “BY-16-752A” (functional group equivalent 1500) (above, manufactured by Toray Dow Corning Co., Ltd.), “X- having a hydroxyl group at one end” 22-170BX "(functional group equivalent 2800)," X-22-170DX "(functional group equivalent 4670)," X-22-4039 "having a hydroxyl group in the side chain (functional group equivalent 970)" X-22-4015 " "(Functional group equivalent 1870) (above, manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in admixture of two or more.

  As the silicone compound having a methacryl group in the molecular structure, a commercially available product can be used. For example, “X-22-164A” (functional group equivalent 860) having a methacrylic group at both ends, “X-22-164B” (functional group equivalent 1630) “X-22-174DX having a methacrylic group at one end” "(Functional group equivalent 4600) (the above, manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in admixture of two or more.

  A commercial item can be used for the silicone compound which has a mercapto group in molecular structure. For example, “X-22-167B” (functional group equivalent 1670) having a mercapto group at both ends, “KF-2001” (functional group equivalent 1900), “KF-2004” (functional group) having a mercapto group in the side chain Equivalent 30000) (manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in admixture of two or more.

  A commercially available product can be used as the silicone compound having a carboxyl group in the molecular structure. For example, “X-22-162C” having a carboxyl group at both ends (functional group equivalent 2300), “X-22-3710” having a carboxyl group at one end (functional group equivalent 1450), and a carboxyl group at the side chain And "X-22-3701E" (functional group equivalent 4000) (manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in admixture of two or more.

  A commercial item can be used for the silicone compound which has an alkoxy group in molecular structure. For example, “FZ-3704” (functional group equivalent 150) having an alkoxy group in the side chain (manufactured by Toray Dow Corning Co., Ltd.) can be mentioned. These may be used alone or in admixture of two or more.

  (B) As for the usage-amount of a component, 1-100 mass parts is preferable with respect to 100 mass parts of (A) component, and 5-80 mass parts is more preferable. By setting it to 1 part by mass or more, a low thermal expansion coefficient can be achieved. The copper foil adhesiveness and moldability of the laminated board and printed wiring board formed by setting it as 100 mass parts or less can be ensured.

Examples of the nitrogen-containing polymer compound used as the leveling agent for component (C) include polycarboxylic acid amides, specially modified ureas, modified ureas, polymer urea derivatives, urea-modified urethanes, polyurethanes, and urea-modified medium polar polyamides. Can be used.
Of these, amides of polycarboxylic acid and modified urea are particularly preferable. Polycarboxylic acid amides and modified ureas, when filled with a large amount of filler, are capable of obtaining a smooth surface without causing "streaks" on the surface of the prepreg, and in that the difference between the front and back of the resin can be suppressed. Useful. The “streaks” here refers to smears that occur when the resin is not uniformly applied.
By adding a leveling agent composed of a nitrogen-containing polymer compound, the viscosity of the varnish obtained from the thermosetting resin increases, so that dripping is suppressed, and thereby a uniform prepreg appearance can be obtained. The term “liquid sag” as used herein refers to a trace of varnish flow that occurs when the varnish viscosity is low. In addition, the temperature dependency is small, the surface of the prepreg can be smoothed, and the difference in thickness between the front and back surfaces of the surface resin of the prepreg can be reduced.

  When the leveling agent of (C) component obtains a prepreg, it is preferable to contain 1-20 mass parts with respect to 100 mass parts of total amounts of the resin component of a thermosetting resin composition. More preferably, it is 2-15 mass parts, Most preferably, it is 2-10 mass parts. If the amount is 1 part by mass or more, the above-described effect can be more sufficiently exhibited. If the amount is 20 parts by mass or less, the characteristics of the thermosetting resin are not deteriorated, and prepregs, laminates, and printed wirings having better characteristics. It is possible to obtain a board.

  The thermosetting resin composition of the present invention preferably further contains (D) a thermosetting resin. The thermosetting resin of component (D) 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 , Allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, and melamine resin. 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, Triphenolmethane type epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene type Epoxy resins, cycloaliphatic epoxy resins, polyfunctional phenols, anthracene polycyclic aromatic diglycidyl ether compounds, and these Phosphorus-containing epoxy resin obtained by introducing a phosphorus compounds in epoxy resin. These may be used alone or in admixture of two or more. Among these, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferred from the viewpoint of heat resistance and flame retardancy of the laminate and printed wiring board to be formed.

  Examples of cyanate resins include novolak-type cyanate resins, bisphenol A-type cyanate resins, bisphenol E-type cyanate resins, and bisphenol-type cyanate resins such as tetramethylbisphenol F-type cyanate resins, and some of these cyanate resins are triazines. Can be mentioned. These may be used alone or in admixture of two or more. Among these, a novolak cyanate resin is preferred from the viewpoint of heat resistance and flame retardancy of the laminate and printed wiring board formed.

  (D) As for content of a component, 10-200 mass parts is preferable with respect to 100 mass parts of (A) component, and 20-150 mass parts is more preferable. By setting it as 10 mass parts or more, the outstanding moisture absorption characteristic and copper foil adhesiveness are obtained. By setting it to 200 parts by mass or less, heat resistance can be secured and a low thermal expansion coefficient can be achieved.

The thermosetting resin composition of the present invention preferably further contains an amine compound having an acidic substituent represented by the following general formula (I) as the component (E).
(In the formula, when there are a plurality of R _{1 s,} each is independently a hydroxyl group, carboxyl group or sulfonic acid group which is an acidic substituent, and when there are a plurality of R _{2 s,} each is independently a hydrogen atom, an aliphatic having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and x + y = 5.)

  Examples of the amine compound of component (E) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfone. Examples include acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline. Of these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferred from the viewpoint of solubility and synthesis yield. M-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance of the laminated board and printed wiring board to be formed.

  As for content of (E) component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, and 1-15 mass parts is more preferable. The heat resistance and copper foil adhesiveness which were excellent by using 0.1 mass part or more are obtained. Heat resistance can be ensured by setting it as 20 mass parts or less.

  The component (E) is preferably reacted with the component (A) in advance. The organic solvent used for this reaction is not particularly limited. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ether solvents such as tetrahydrofuran, toluene, xylene, mesitylene, etc. And aromatic solvents such as, a nitrogen atom-containing solvent such as methylformamide, dimethylacetamide, and N-methylpyrrolidone, and a sulfur atom-containing solvent such as dimethylsulfoxide. These may be used alone or in admixture of two or more. Among these, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferable from the viewpoint of solubility. Moreover, cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity. Furthermore, propylene glycol monomethyl ether, which is highly volatile and hardly remains as a residual solvent during the production of the prepreg, is particularly preferable.

  In addition, a reaction catalyst can be optionally used for the reaction, if necessary, and is not particularly 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. These may be used alone or in combination of two or more. May be used in combination.

  When (A) component and (E) component are made to react in an organic solvent, it is preferable that reaction temperature is 70-150 degreeC, and it is more preferable that it is 100-130 degreeC. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

In the thermosetting resin composition of the present invention, it is desirable to use (F) a curing accelerator in order to improve heat resistance, flame retardancy, copper foil adhesion, and the like. Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts.
Among them, imidazoles and derivatives thereof are preferable from the viewpoints of heat resistance, flame retardancy, copper foil adhesion, and the like. Further, a compound in which the imidazole group represented by the following general formula (III) is masked with an isocyanate resin and a compound in which the imidazole group represented by the following general formula (IV) is masked by an epoxy resin are compared at 200 ° C. or lower. It is more preferable because it is excellent in curing moldability at low temperatures and aging stability of varnish and prepreg. Specifically, the compound represented by the following formula (V) or formula (VI) may be used in a small amount, and is particularly preferable because it is commercially inexpensive.

(Wherein R ₆ , R ₇ , R ₈ and R ₉ 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 hydrocarbon. Group.)

(Wherein R ₆ , R ₇ , R ₈ and R ₉ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, and B represents a single bond, an alkylene group or an alkylidene group) A group, an ether group, or a sulfonyl group.)

(F) The content of the curing accelerator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of resin components in terms of solid content. The content is preferably 0.1 to 1 part by mass. Excellent heat resistance, flame retardancy, and copper foil adhesion can be obtained by setting the amount of the curing accelerator used to 0.1 parts by mass or more, and heat resistance and aging stability by setting it to 10 parts by mass or less. And press formability does not deteriorate.
In addition, in this invention, a resin component is (A) component, (B) component, (D) component, and (E) component.

  The (G) inorganic filler 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 thereof include glass powders such as aluminum oxide, potassium titanate, 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 of component (G), 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 or the like. Examples of the dry process silica include crushed silica, fumed silica, and fused spherical silica 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, the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle size of the fused spherical silica to 0.1 μm or more, it is possible to maintain good fluidity when the resin is highly filled. On the other hand, by setting the average particle diameter of the fused spherical silica to 10 μm or less, the mixing probability of coarse particles can be reduced and the occurrence 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.

  (G) The content of the inorganic filler is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, per 100 parts by mass of the total amount of resin components in terms of solid content. By making content of an inorganic filler into 10-300 mass parts per 100 mass parts of total amounts of a resin component, the moldability and low thermal expansibility of a resin composition can be kept favorable.

The thermosetting resin composition of the present invention can optionally contain a known thermoplastic resin, elastomer, organic filler and the like .
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.
Examples of the organic filler include organic powders such as silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  The thermosetting resin composition of the present invention can optionally contain an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.

  The thermosetting resin composition of the present invention is used as a varnish when producing a prepreg. As the solvent used for the varnish, the same organic solvent as that used for the reaction of the component (A) and the component (E) is used. The varnish is preferably used as a solid content concentration of 50 to 75% by mass.

The prepreg of the present invention is obtained by impregnating or coating the base material with the thermosetting resin composition of the present invention to form a B-stage. Hereinafter, the prepreg of the present invention will be described.
The prepreg of the present invention can be produced by impregnating and coating the above thermosetting resin composition on a sheet-like reinforcing base material and semi-curing (B-stage) by heating or the like.
As the base material of the prepreg, well-known materials used for various 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, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and a mixture of these inorganic fibers and organic fibers.

  These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, and a surfacing mat, for example. The material and shape of the substrate are selected depending on the intended use and performance of the molded article, and if necessary, two or more kinds of materials and shapes can be combined. The thickness in particular of a base material is not restrict | limited, For example, about 0.03-0.5 mm can be used. A substrate that is surface-treated with a silane coupling agent or the like or that has been mechanically subjected to a fiber opening treatment is suitable from the viewpoint of heat resistance, moisture resistance, and workability.

  The 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 is obtained by laminate molding using the above-described prepreg of the present invention. For example, it can be manufactured by stacking 1 to 20 prepregs and laminate-molding them with a configuration in which a metal foil such as copper and aluminum is disposed 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 can be applied to a laminate for an electrical insulating material and a multilayer board, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., at a temperature of 100 to 250 ° C., a pressure of 0.2 to It can be molded in a range of 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 multilayer board.

  The printed wiring board of the present invention is manufactured by forming a circuit on the surface of the laminate. That is, the conductor layer of the laminated board of the present invention is subjected to wiring processing by a normal etching method, a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated, and then multilayered by heating press processing. 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.

EXAMPLES Next, although an Example demonstrates this invention in more detail, this invention is not limited to these description.
In addition, using the prepreg and copper-clad laminate obtained in each Example and Comparative Example, the glass transition temperature (Tg) of the copper-clad laminate, the coefficient of thermal expansion, the surface smoothness of the prepreg, the front and back thickness of the prepreg surface layer resin The difference and warpage amount were measured and evaluated by the following methods.

(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 a compression method 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 prepreg surface smoothness
Resin smoothness on the surface of the prepreg was evaluated by a beta ray back-scattering formula using a Fisherscope MMS manufactured by Fisher Instruments Co., Ltd.
The prepreg was measured at three positions A, B, and C shown in FIG. 1, and the surface smoothness at each of the three positions was confirmed. A and C are prepreg end portions at the time of coating, and B is the center side of the prepreg at the time of coating. The sample sizes of A, B, and C were 100 mm × 100 mm, and the measurement time was 20 seconds. From the measurement results, the surface smoothness of the resin on the prepreg surface was confirmed by the dispersion σ ^{2 according} to the following (Formula 1).

(4) Evaluation of thickness difference between front and back surfaces of prepreg surface resin
Using a Fischer Scope MMS manufactured by Fisher Instruments Co., Ltd., the difference in thickness between the front and back surfaces of the resin on the prepreg surface was evaluated by a beta ray backscattering equation. The prepreg was measured at three positions A, B, and C shown in FIG. 1, and the difference in thickness between the front and back surfaces was measured for each position. A and C are prepreg end portions at the time of coating, and B is the center side of the prepreg at the time of coating. The sample sizes of A, B, and C were 100 mm × 100 mm, and the measurement time was 20 seconds. From the measurement results, the difference between the front and back surfaces (μm) of the resin on the prepreg surface was calculated by the following (Formula 2).

(5) Evaluation of warpage amount The warpage amount of the copper clad laminated board was evaluated using Thermoray PS200 shadow moire analysis manufactured by AKROMETRIX. The sample size of the substrate was 40 mm × 40 mm, and the measurement area was 36 mm × 36 mm. The amount of warpage when heated from room temperature to 260 ° C. and then cooled to 50 ° C. was measured.

Examples 1-5, Comparative Examples 1-3
Methyl ethyl ketone was used for the following components (A) to (G) and the diluent solvent, and mixed at a blending ratio (parts by mass) shown in Table 1 to obtain a uniform varnish having a resin content of 65% by mass.
Next, the varnish was 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 50 mass%.
Four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 230 ° C. for 90 minutes to obtain a copper-clad laminate.
The measurement evaluation results of the obtained copper-clad laminate are shown in Tables 1 and 2.

(A) Maleimide compound bis (4-maleimidophenyl) methane 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide

(B) Silicone compound X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., both terminal amino-modified, functional group equivalent 800)
X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd., both terminal amino-modified, functional group equivalent 1500)
KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., both terminal amino-modified, functional group equivalent 2200)

(C) Leveling agent Amide of polycarboxylic acid (BYK-405 manufactured by BYK)
Modified urea (BYK-411 BYK)

(D) Thermosetting resin Biphenyl aralkyl type epoxy resin (Nippon Kayaku NC-3000)
Bisphenol A type cyanate resin (Lonza Japan B10)

(E) Amine compound m-aminophenol p-aminophenol

(E) Curing accelerator G-809L (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole, which is a compound represented by the above formula (V).)
(G) Inorganic filler: fused silica (SO-C2 manufactured by Admatechs)

  As is apparent from Tables 1 and 2, in the examples of the present invention, heat resistance (glass transition temperature), thermal expansion coefficient, warpage characteristics, surface smoothness, and prepreg surface layer resin are excellent in thickness difference. ing. On the other hand, the comparative example is inferior to any of the characteristics in terms of warpage characteristics, surface smoothness, and difference in thickness between the front and back surfaces of the prepreg surface resin.

  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 heat resistance and thermal expansion coefficient, and has a smooth surface in a prepreg state. A printed wiring board having good surface smoothness and wiring formability in the case of a laminated board can be provided. In addition, since the difference in thickness between the front and back surfaces of the resin in the prepreg state is small, it is possible to provide a printed wiring board with high reliability when a laminated board is used.

Claims (16)

(A) a maleimide compound having at least two N-substituted maleimide groups in one molecular structure, (B) a silicone compound having at least one reactive organic group in one molecular structure , (C) a nitrogen-containing polymer A thermosetting resin composition comprising a leveling agent comprising a compound and (G) an inorganic filler (excluding fumed silica) .   Furthermore, the thermosetting resin composition of Claim 1 containing (D) thermosetting resin. Furthermore, (E) The thermosetting resin composition of Claim 1 or 2 containing the amine compound which has an acidic substituent represented by the following general formula (I).
(Wherein, each independently when R ₁ is located more hydroxyl acidic substituent, a carboxyl group or a sulfonic acid group, R ₂ each independently represent a hydrogen atom if there are multiple, aliphatic of 1 to 5 carbon atoms A hydrocarbon group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and x + y = 5.)   The heat according to any one of claims 1 to 3, wherein the reactive organic group of component (B) is at least one selected from an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group. Curable resin composition. The thermosetting resin composition according to claim 1, wherein the component (B) is a silicone compound including a structure represented by the following general formula (II).
_Wherein, R 3, _{R 4} represents each independently an alkyl group, a phenyl group or substituted phenyl group, n is an integer of 1 to 100. ]   The thermosetting resin composition according to claim 1, wherein the component (B) is a silicone compound having a reactive organic group at least at a part of the terminals.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the component (B) is a silicone compound having a reactive organic group in at least a part of the side chain.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the component (B) is a silicone compound having at least two reactive organic groups in one molecular structure.   The thermosetting resin composition according to claim 8, wherein the component (B) is a silicone compound having a reactive organic group in at least two or more terminals.   The thermosetting resin composition according to claim 8, wherein the component (B) is a silicone compound having a side chain and a reactive organic group at at least one terminal.   The component (C) is at least one nitrogen-containing polymer compound selected from amides of polycarboxylic acids, specially modified ureas, modified ureas, polymer urea derivatives, urea-modified urethanes, polyurethanes, urea-modified medium polar polyamides. The thermosetting resin composition in any one of 1-10. Further, (F) the following general formula (III) or thermosetting resin composition according to any one of claims 1 to 11, contains a curing accelerator represented by (IV).
(Wherein R ₆ , R ₇ , R ₈ and R ₉ 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 hydrocarbon group. .)
(In the formula, R ₆ , R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, and B represents a single bond or an alkylene group, an alkylidene group, Either an ether group or a sulfonyl group.) (G) The thermosetting resin composition according to any one of claims 1 to 12, wherein the inorganic filler is fused spherical silica. A prepreg obtained by impregnating or coating the thermosetting resin composition according to any one of claims 1 to 13 on a substrate and semi-curing (B-stage). A laminate obtained by laminate molding using the prepreg according to claim 14 . The printed wiring board manufactured using the laminated board of Claim 15 .