JP2014111696A - Thermosetting resin composition, prepreg using the same, laminate, and multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition particularly excellent in surface smoothness and warpage reduction, a prepreg using the same, a laminate, and a multilayer printed wiring board.SOLUTION: There are provided: the thermosetting resin composition containing (A) at least one thermosetting resin selected from an epoxy resin and a cyanate resin, (B) a maleimide compound having at least two N-substituted maleimide groups in one molecule, (C) an amine compound having at least two primary amino groups in one molecule, (D) a monoamine compound having an acidic substituent, and (E) a rheology control agent; the prepreg using the thermosetting resin composition; the laminate; and the multilayer printed wiring board.

Description

  The present invention relates to a thermosetting resin composition suitable for semiconductor packages and multilayer printed wiring boards, prepregs, laminates and multilayer printed wiring boards, and more particularly, thermosetting resin particularly excellent in surface smoothness and warpage reduction. The present invention relates to a composition, a prepreg using the same, a laminate, and a multilayer printed wiring board.

  With the trend toward smaller and higher performance electronic devices in recent years, printed wiring boards have become increasingly dense and highly integrated, and with this, 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 cured and integrally molded. In general, epoxy resins have a good balance of insulation, heat resistance, cost, etc. However, in order to meet the demand for high heat resistance due to the recent high-density mounting of printed wiring boards and multi-layered configurations, the heat resistance is unavoidable. There is a limit to the improvement of 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).

  Particularly in recent years, with the reduction in size and thickness of semiconductor package substrates, warpage due to the difference in thermal expansion coefficient between the chip and the substrate has become a major issue during component mounting and package assembly. In order to reduce the coefficient of thermal expansion, a reduction in the thermal expansion coefficient is required, but increasing the filling amount of the inorganic filler reduces the surface smoothness and appearance of the prepreg due to a decrease in fluidity, and the difference in thickness between the front and back surfaces of the prepreg surface layer resin. It is known that warpage after press molding due to the cause, deterioration of insulation reliability due to moisture absorption, insufficient adhesion of the resin-wiring layer, and poor press molding are caused.

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. 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.

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 excellent in surface smoothness and warpage reduction, a prepreg, a laminate and a multilayer printed wiring board using the same.

The present inventors have made intensive studies in order to achieve the object, at least one thermosetting resin that is selected from an epoxy resin and a cyanate resin, at least two N- substituted maleimide groups in a molecule It has been found that a resin composition containing a maleimide compound having an amine, an amine compound having at least two primary amino groups in a molecule, a monoamine compound having an acidic substituent and a rheology control agent meets the above-mentioned purpose. The present invention has been reached.

That is, the present invention provides the following thermosetting resin composition, prepreg, laminate, and multilayer printed wiring board.
1. (A) at least one thermosetting resin selected from an epoxy resin and a cyanate resin, (B) a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (C) at least two in one molecule. A thermosetting resin composition comprising: an amine compound having a primary amino group of: (D) a monoamine compound having an acidic substituent; and (E) a rheology control agent.
2. 2. The modified imide resin having an acidic substituent obtained by reacting the component (B), the component (C) and the component (D), as the component (B), (C), or (D). Thermosetting resin composition.
3. The thermosetting according to the above 1 or 2, wherein the (E) rheology control agent is at least one selected from the group consisting of polycarboxylic acid amide, urea-modified polyamide, urea-modified urethane, and polyaminoamide polycarboxylate. Resin composition.
4). Furthermore, (F) The thermosetting resin composition in any one of said 1-3 containing an inorganic filler.
5. The prepreg using the thermosetting resin composition in any one of said 1-4.
6). 6. A laminate obtained by laminating the prepreg as described in 5 above.
7). A multilayer printed wiring board produced by using the laminated board described in 6 above.

The prepreg obtained by impregnating or coating the base material with the thermosetting resin composition of the present invention has a small difference in thickness between the front and back surfaces of the prepreg surface layer resin and is excellent in surface smoothness. The printed wiring board is excellent in resin-wiring layer adhesion and press formability.
In addition, a laminated board produced by laminating the prepreg, and a multilayer printed wiring board produced using the laminated board are excellent in glass transition temperature, coefficient of thermal expansion, warpage, and printed wiring board for electronic equipment. Useful as.

These are the figures which show the measurement location of evaluation of (1) evaluation of prepreg surface smoothness in an Example, and (2) 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, maleimide having (A) an epoxy resin and that is selected from cyanate resin of at least one thermosetting resin, (B) a at least two N- substituted maleimide groups in a molecule A compound, (C) an amine compound having at least two primary amino groups in one molecule, (D) a monoamine compound having an acidic substituent, and (E) a rheology control agent.

  Examples of the component (A) epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol. F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy Resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl esters of polycyclic aromatics such as anthracene Ether compounds and phosphorus-containing epoxy resin obtained by introducing a phosphorus compound mentioned in these epoxy resins may be used individually or in combination of two or more kinds. 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 component (A) cyanate resin include novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, tetramethylbisphenol F-type cyanate resin, and some of these are triazines. Can be used, and these can 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.

  Examples of maleimide compounds having at least two N-substituted maleimide groups in one molecule of component (B) include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, Bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2 -Bis (4- (4-maleimidophenoxy) phenyl) propane and the like can be mentioned, and these can be used alone or in admixture of two or more.

  Among these components (B), bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-, which has a high reaction rate and can have higher heat resistance. Diethyl-4,4′-diphenylmethane bismaleimide and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred, and 3,3′-dimethyl-5,5 from the viewpoint of solubility in a solvent. '-Diethyl-4,4'-diphenylmethane bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred because it is inexpensive.

  (C) As an amine compound which has at least 2 primary amino group in 1 molecule of a component, a commercial item can be used, for example, "KF-8010" (functional group equivalent 430), "X-22 -161A "(functional group equivalent 800)," X-22-161B "(functional group equivalent 1500)," KF-8012 "(functional group equivalent 2200)," KF-8008 "(functional group equivalent 5700)," X Amine modified silicones such as “-22-9409” (functional group equivalent 700), “X-22-1660B-3” (functional group equivalent 2200) [manufactured by Shin-Etsu Chemical Co., Ltd.], p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenylmeta 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5,5′-diethyl-4,4 ′ -Diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl Sulfone, benzidine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 1,4-diaminonaphthalene, etc. Aromatic amines, ethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptame Aliphatic amines such as range amine, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, melamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6 Guanamine compounds such as -allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, and the like. Or a mixture of two or more.

  Among these components (C), KF-8010, X-22-161A, X-22-161B, KF-8012, X-22-9409, X-22 from the viewpoint of low toxicity and solubility in a solvent. -1660B-3, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, and 4,4′-bis (4-aminophenoxy) biphenyl are preferred, and X has good reactivity and heat resistance. -22-161A, X-22-161B, KF-8012, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bi [4- (4-Aminophenoxy) phenyl] sulfone and 4,4′-bis (4-aminophenoxy) biphenyl are more preferable, and X-22-161A and X-22 having good chemical resistance and low thermal expansion. -161B, KF-8012, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane are particularly preferred.

  Examples of the monoamine compound having an acidic substituent of component (D) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzene sulfonic acid, m-aminobenzene sulfonic acid, p-aminobenzene sulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. may be mentioned. These may be used alone or in combination of two or more. Can be mixed and used. Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are used in terms of solubility and synthesis yield. Preferably, m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance, and p-aminophenol is particularly preferable from the viewpoint of low thermal expansion.

  Examples of the rheology control agent of component (E) include polycarboxylic acid amides, urea-modified polyamides, urea-modified urethanes, and polyaminoamide polycarboxylates, and these rheology control agents may be used alone. Two or more types may be mixed and used.

  Among these components (E), when a large amount of filler is filled, a smooth surface can be obtained without generating “streaks” on the prepreg surface, and the difference in thickness between the front and back of the resin can be suppressed. Polycarboxylic acid amide is particularly preferred. The “streaks” here refers to smears that occur when the resin is not uniformly applied. In the present invention, by adding the rheology control agent of the component (E), thixotropy is imparted and the varnish viscosity increases, so that dripping can be suppressed. In addition, the temperature dependency is small and the viscosity stability over time is high. This makes it possible to smooth the surface of the prepreg and suppress the difference in thickness between the front and back surfaces of the resin.

  The thermosetting resin composition of the present invention is a mixture of the above components (A), (B), (C), (D) and (E). First, (B), (C) The component (D) can be pre-reacted to be used as a modified imide resin 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.

In this pre-reaction, it is preferable to synthesize a modified imide resin having an acidic substituent by reacting the components (B), (C), and (D) while heating and keeping in an organic solvent.
The reaction temperature when the components (B), (C), and (D) are reacted in an organic solvent is preferably 70 to 150 ° C, and more preferably 100 to 130 ° C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

In this pre-reaction, the amount of the amine compound having at least two primary amino groups in one molecule of (C) and the monoamine compound having an acidic substituent of (D) is the sum of the equivalents of —NH ₂ group equivalents. The equivalent ratio of the maleimide ring of (B) to the C = C group equivalent is
0.1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 10.0
It is preferable that it is the range which is. This equivalence ratio is
1.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 9.0,
It is more preferable that the range is
2.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 8.0
It is particularly preferable that the range is
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.

The amount of the component (B) used in the pre-reaction 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 (C) while maintaining the above relationship. 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 (C) component, and, as for the usage-amount of (D) component in a pre reaction, 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 pre-reaction is not particularly limited. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone And sulfur atom-containing solvents such as dimethyl sulfoxide and the like, and one kind or a mixture of two or more kinds can be used.

  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 (B), (C), and (D). By using the organic solvent in an amount of 25 to 1000 parts by mass, there are no disadvantages such as insufficient solubility and a long time for synthesis, which is preferable.

  In addition, a reaction catalyst can be optionally used for this pre-reaction. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Can be mixed and used.

In the thermosetting resin composition of the present invention, the amount of the component (A) used is preferably 10 to 50 parts by mass per 100 parts by mass of the total of the resin components in view of copper foil adhesion and chemical resistance. In addition, a resin component is (A), (B), (C), (D) component (solid content conversion).
Moreover, the usage-amount of the modified imide resin which has an acidic substituent obtained by carrying out the pre-reaction of (B), (C), (D) component by the above is 50-90 mass per 100 mass parts of sum total of a resin component. Part, preferably 50 to 80 parts by mass. By setting the blending amount of the modified imide resin having an acidic substituent to 50 parts by mass or more, excellent heat resistance, low water absorption, and low thermal expansion can be obtained.

  When blending the components (B), (C), and (D) without performing the pre-reaction, 30 to 89 parts by mass of the component (B) and 100 parts by mass of the component (C) per 100 parts by mass of the total resin components. It is preferable that 0.5-30 mass parts and (D) component shall be 0.5-30 mass parts.

  Furthermore, it is preferable to use (E) component at 0.1-10 mass parts per 100 mass parts of sum total of a resin component. More preferably, it is 0.2-5 mass parts, Most preferably, it is 0.2-2 mass parts. If the component (E) is 0.1 part by mass or more, the blending effect of the rheology control agent can be sufficiently expressed. If the component is 10 parts by mass or less, the characteristics of the varnish are not deteriorated, and good characteristics are obtained. It is possible to obtain a prepreg, a laminated board, and a printed wiring board.

  In the thermosetting resin composition of the present invention, a curing agent and a curing accelerator can be used as necessary. Examples of curing agents include, for example, polyfunctional phenol compounds such as phenol novolak resin, cresol novolak resin, aminotriazine novolak resin, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, Examples thereof include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, and one or more of these may be used in combination.

  Examples of the curing accelerator include zinc metal naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) and the like, imidazole And derivatives thereof, organic phosphorus compounds such as phosphines and phosphonium salts, secondary amines, tertiary amines, and quaternary ammonium salts. Can be used.

  Among these curing accelerators, imidazoles and derivatives thereof, organophosphorus compounds such as phosphines and phosphonium salts are preferable from the viewpoint of heat resistance, flame retardancy, copper foil adhesion, and the following general formula (1). A modified imidazole compound in which the imidazole group represented by the formula (2) is modified by an epoxy resin, or a modified imidazole compound in which the imidazole group represented by the following general formula (2) is modified by an isocyanate resin at a relatively low temperature of 200 ° C. or lower. It is more preferable because it is excellent in the curing moldability of varnish and aging of varnish and prepreg, and the compound represented by the following formula (3) or formula (4) may be used in a small amount, and is also commercially inexpensive. This is particularly preferable.

（式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は各々独立に水素原子、又は炭素数１〜２０の脂肪族炭化水素基又はフェニル基を示し、Ａは単結合、アルキレン基、アルキリデン基、エーテル基又はスルフォニル基を示す。）

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a phenyl group, and A represents a single bond or an alkylene group. Represents an alkylidene group, an ether group or a sulfonyl group.)

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸は各々独立に水素原子、又は炭素数１〜２０の脂肪族炭化水素基又はフェニル基であり、Ｂはアルキレン基又は芳香族炭化水素基である。）

(In the formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a phenyl group, and B is an alkylene group or aromatic. It is a hydrocarbon group.)

  The amount of the curing accelerator used is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 1 part by mass per 100 parts by mass of the total resin components. It is particularly preferable to use parts. Heat resistance, flame retardancy, copper foil adhesion, etc. are improved by setting the use amount of the curing accelerator 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 moldability does not fall.

  In the thermosetting resin composition of the present invention, (F) an inorganic filler can be optionally used in combination. As the inorganic filler (F) component, silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, carbonic acid Examples include calcium, barium sulfate, aluminum borate, potassium titanate, glass powder such as E glass, T glass, and D glass, and hollow glass beads. These can be used alone or in admixture of two or more.

  Among these inorganic fillers, 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, etc. , Crushed silica, fumed silica, and fused spherical silica. Among these silicas, 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 diameter is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.

The content of the inorganic filler is preferably 20 to 300 parts by mass and more preferably 50 to 200 parts by mass per 100 parts by mass of the total 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 addition, when an inorganic filler was included in the thermosetting resin composition, the inorganic filler was pretreated with a surface treatment agent such as a silane-based or titanate-based coupling agent or a silicone oligomer, or an integral blend treatment. A thing may be used.

  The thermosetting resin composition of the present invention includes any known thermoplastic resin, elastomer, organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, as long as it does not contradict its purpose. , Fluorescent whitening agents, adhesion improvers and the like can be blended.

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

  Examples of the 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, Examples thereof include 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 in the varnish 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.

  It is preferable that the thermosetting 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 thermosetting resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coating properties and obtain a prepreg having an appropriate resin composition adhesion amount.

  The prepreg of the present invention is produced by applying the thermosetting resin composition (varnish) to a substrate by a method such as impregnation or spraying and extrusion, and semi-curing (B-stage) by heating or the like. be able to.

  As the base material of the prepreg, well-known materials used for various laminates for electrical insulating materials can be used. As the material of the substrate, inorganic fibers such as E glass, D glass, S glass and Q glass, para-aramid, meta-aramid, ultrahigh molecular weight polyethylene, PBO, polyarylate, polyphenylene sulfide, polyimide, polytetrafluoroethylene And organic fibers such as these, 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 substrate is not particularly limited. For example, a substrate having a thickness of about 0.01 to 1.5 mm can be used, and the surface treatment with a silane coupling agent or the like, or mechanical opening treatment can be performed. What has been applied is preferable from the viewpoint of heat resistance, moisture resistance, and workability.

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

The laminate of the present invention can be formed by laminate molding using the 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.
As the molding conditions for producing the laminate, the method of laminate for electrical insulating material and multilayer plate can be applied, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., and a temperature of 100 to 250 ° C. And 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 multilayer printed wiring board of 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 of the present invention is processed by wiring by a normal etching method, a plurality of laminated boards processed by wiring through the above-described prepreg are stacked, and heated and pressed to form a multilayer. 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 description of these Examples.
In addition, about the surface smoothness in the prepreg obtained by each Example and the comparative example, the front-back thickness difference of surface layer resin, and the glass transition temperature (Tg) in a copper clad laminated board, a thermal expansion coefficient, and a curvature characteristic by the following methods. Measured and evaluated.

(1) 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 measurement locations of the prepreg were confirmed at the front and back portions at three positions A, B, and C shown in FIG. 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).

(2) Evaluation of thickness difference between front and back surfaces of prepreg surface resin
The difference in thickness between the front and back surfaces of the resin on the prepreg surface was evaluated by a beta ray backscattering method using a Fisherscope MMS manufactured by Fisher Instruments Co., Ltd. The measurement locations of the prepreg were the thicknesses of the front and back at each of the three positions A, B, and C shown in FIG. 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 in thickness (μm) between the front and back surfaces of the resin on the prepreg surface was calculated by the following (Formula 2).

(3) Measurement of glass transition temperature (Tg) A 5-mm square evaluation board | substrate which removed the copper foil was produced by immersing a copper clad laminated board in copper etching liquid, and TMA test apparatus (TA Instruments company make, Q400). ) Was used for the thermomechanical analysis by the compression method. After mounting the evaluation substrate on the apparatus in the Z direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined, and the heat resistance was evaluated.

(4) Measurement of coefficient of thermal expansion A 5 mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (TA Instruments, Q400) was used. The thermomechanical analysis was performed by the compression method. After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The average coefficient of thermal expansion from 30 ° C. to 100 ° C. in the second measurement was calculated and used as the value of the coefficient of thermal expansion.

(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.

Production Example 1: Production of Modified Imide Resin (P-1) Having Acid Substituent In a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, X- 22-161A: 30.7 g, bis (4-maleimidophenyl) methane: 194.2 g, p-aminophenol: 25.1 g, and propylene glycol monomethyl ether: 250.0 g were added and reacted at 115 ° C. for 4 hours. Thus, a modified imide resin (P-1) -containing solution having an acidic substituent was obtained.

Production Example 2: Production of Modified Imide Resin (P-2) Having Acidic Substituent In a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD AA]: 28.4 g, bis (4-maleimidophenyl) methane: 213.5 g, p -Aminophenol: 8.1g and propylene glycol monomethyl ether: 250.0g were put, and it was made to react at 115 degreeC for 4 hours, and the modified imide resin (P-2) containing solution which has an acidic substituent was obtained.

Production Example 3: Production of Modified Imide Resin (P-3) Having Acidic Substituent KAYAHARD A was added to a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. -A: 20.3 g, X-22-161A: 30.38 g, bis (4-maleimidophenyl) methane: 192.0 g, p-aminophenol: 7.3 g, and propylene glycol monomethyl ether: 250.0 g And reacted at 115 ° C. for 4 hours to obtain a modified imide resin (P-3) -containing solution having an acidic substituent.

Examples 1-12, Comparative Examples 1-6
The blending ratios shown in Tables 1 to 3 using the components (A) to (G), the modified imide resin having an acidic substituent, the curing agent, the curing accelerator, and the dilution solvent using methyl ethyl ketone ( To obtain a uniform varnish having a resin content of 65% by mass.

The varnish thus prepared 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% by 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 230 ° C. for 60 minutes to obtain a copper-clad laminate.
The measurement and evaluation results of the obtained prepreg and copper clad laminate are shown in Tables 1 to 3.

(A) Thermosetting resin:
Novolac-type cyanate resin [Lonza Japan Co., Ltd., trade name: PT-30]
α-Naphthol / cresol novolac type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L]
(B) Maleimide compound:
Bis (4-maleimidophenyl) methane [manufactured by Kei-I Kasei Co., Ltd., trade name: BMI]
2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane [manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000]
(C) Amine compound:
Amine-modified silicone [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A]
3,3′-diethyl-4,4′-diaminodiphenylmethane [manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A]
(D) Monoamine compound having an acidic substituent:
p-aminophenol [manufactured by Kanto Chemical Co., Inc.]
(E) Rheology control agent:
Polycarboxylic acid amide [BIC Chemie Japan Co., Ltd., trade name: BYK-405]
Urea-modified polyamide [BIC Chemie Japan Co., Ltd., trade name: BYK-431]
Urea-modified urethane [BIC Chemie Japan Co., Ltd., trade name: BYK-410]
Polycarboxylate of polyaminoamide [BIC Chemie Japan Co., Ltd., trade name: ANTI-TERRA-205]
(F) Inorganic filler:
Fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KNK]
Zinc molybdate [manufactured by Sherwin Williams, trade name: KEMGARD1100]
-Modified imide resin having an acidic substituent:
Modified imide resins having acidic substituents obtained in Production Examples 1 to 3 (P-1, P-2, P-3)
・ Curing agent:
Cresol novolak resin [manufactured by DIC Corporation, trade name: KA-1165]
・ Curing accelerator:
Zinc naphthenate (II) 8% mineral spirit solution [manufactured by Tokyo Chemical Industry Co., Ltd.]
Isocyanate mask imidazole [Daiichi Kogyo Seiyaku Co., Ltd., trade name: G-8809L]
Tetraphenylphosphonium tetra-p-tolylborate [Hokuko Chemical Co., Ltd., trade name: TPP-MK]

As is apparent from Tables 1 and 2, in the examples of the present invention, the surface smoothness of the prepreg is excellent, and the difference in thickness between the front and back surfaces of the surface layer resin is small. Moreover, also in the characteristic of a laminated board, it is excellent in the glass transition temperature, a thermal expansion coefficient, and a curvature characteristic.
On the other hand, as is apparent from Table 3, the comparative example is inferior in the surface smoothness of the prepreg, and the front and back thickness difference of the surface layer resin is large. Further, the characteristics of the laminated plate are inferior to any of the characteristics of the glass transition temperature, the coefficient of thermal expansion, and the warp characteristics as compared with the examples.

The prepreg obtained from the thermosetting resin composition of the present invention has a particularly small difference in thickness between the front and back surfaces of the prepreg surface layer resin, excellent surface smoothness, and excellent resin-wiring layer adhesion and press moldability. Therefore, an integrated laminated board or multilayer printed wiring board can be advantageously manufactured.
In addition, a multilayer printed wiring board manufactured using a laminated board produced by laminating the prepreg of the present invention is a highly integrated semiconductor having excellent glass transition temperature, thermal expansion coefficient, and warpage characteristics. It is useful as a printed wiring board for packages and electronic devices.

Claims (7)

(A) at least one thermosetting resin selected from epoxy resins and cyanate resins;
(B) a maleimide compound having at least two N-substituted maleimide groups in one molecule, (C) an amine compound having at least two primary amino groups in one molecule, and (D) a monoamine having an acidic substituent. A thermosetting resin composition comprising a compound and (E) a rheology control agent.   The modified imide resin having an acidic substituent obtained by reacting the component (B), the component (C) and the component (D) is used as the component (B), (C) or (D). Thermosetting resin composition.   The heat according to claim 1 or 2, wherein the (E) rheology control agent is at least one selected from the group consisting of polycarboxylic acid amides, urea-modified polyamides, urea-modified urethanes, and polyaminoamide polycarboxylates. Curable resin composition.   Furthermore, the thermosetting resin composition in any one of Claims 1-3 containing (F) inorganic filler.   The prepreg using the thermosetting resin composition in any one of Claims 1-4.   A laminate obtained by laminating the prepreg according to claim 5.   The multilayer printed wiring board manufactured using the laminated board of Claim 6.

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