JP6604565B2 - Resin composition for printed wiring board, prepreg, metal-clad laminate and printed wiring board - Google Patents

Description

  The present invention relates to a resin composition for printed wiring boards, a prepreg, a metal-clad laminate, and a printed wiring board.

  Printed wiring boards are widely used in various fields such as electronic devices, communication devices, and computers. In recent years, especially in small portable devices such as portable communication terminals and notebook PCs, with the increase in the amount of information processing, the integration, multi-functionality, high performance, thinning and miniaturization of mounted semiconductor devices are rapidly increasing. Electronic components such as semiconductor packages mounted on such devices are also becoming thinner and smaller. Along with this, insulating materials such as printed wiring boards used to mount these electronic components have low dielectric constants and dielectric loss tangents in order to increase signal transmission speed and reduce loss during signal transmission. Is required. Furthermore, printed circuit boards are also required to have high performance such as miniaturization, multilayering, thinning, and mechanical properties of wiring patterns.

  In Patent Document 1, in order to achieve an excellent glass transition temperature (Tg) while maintaining the excellent dielectric properties of polyphenylene ether, at least a part of the hydroxyl groups of polyphenylene ether is reacted in advance with an epoxy group of an epoxy compound. The invention of the resin composition containing the made reaction product, the cyanate ester compound, and the organometallic salt is described.

  On the other hand, Patent Document 2 includes a thermosetting resin, silica, and a molybdenum compound for the purpose of achieving excellent electrical workability and low thermal expansibility with excellent drill workability, and the content of silica. Describes an invention of a thermosetting resin composition in which is 20 vol% or more and 60 vol% or less.

JP 2014-152283 A JP 2012-023248 A

  In a resin composition obtained by further adding silica and a molybdenum compound to a reaction product obtained by reacting at least a part of the hydroxyl group of polyphenylene ether with an epoxy group of an epoxy compound and a cyanate ester compound, a glass of the cured product is obtained. The transition temperature and dielectric loss tangent may be significantly reduced.

  The present invention has been made in view of the above points, and has a stable and excellent glass transition temperature and dielectric properties, and a resin composition for a printed wiring board that can realize good drill processability and moldability, An object is to provide a prepreg, a metal-clad laminate, and a printed wiring board.

  As a result of intensive investigations to solve the above problems, the inventors of the present application have obtained the following knowledge. That is, when new silica particles (dried silica particles) are used, the glass transition temperature and dielectric loss tangent of the cured product are excellent. On the other hand, depending on the storage state of the silica particles, when the hygroscopic silica particles are used, the glass transition temperature and the dielectric properties of the cured product are deteriorated with time. From this knowledge, the present invention has been completed.

The resin composition for a printed wiring board according to the present invention is:
(A) a preliminary reaction product obtained by reacting a polyphenylene ether and an epoxy compound having an epoxy group, and (b) a resin component containing a cyanate ester compound;
(C) Hydrophobic silica particles obtained by subjecting crushed silica having a specific surface area of 0.1 m ² / g to 15 m ² / g and surface treatment, and (d) the molybdenum on the surface of a support made of a material other than a molybdenum compound. Obtained by blending an inorganic filler containing molybdenum compound particles on which a compound is supported or coated,
Content of the said molybdenum compound particle (d) is 0.1 to 3.1 mass parts with respect to 100 mass parts of said resin components.
In the printed wiring board resin composition, the molybdenum compound is preferably one or more selected from the group consisting of zinc molybdate, calcium molybdate, and magnesium molybdate.

In the printed wiring board resin composition, the material other than the molybdenum compound is preferably talc .

  In the printed wiring board resin composition, the content of the hydrophobic silica particles is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the resin component.

Further, in the printed wiring board resin composition, the content of the previous SL crushing silica is preferably 150 parts by weight or less than 10 parts by mass relative to the resin component 100 parts by mass.

  The prepreg according to the present invention can be obtained by impregnating a base material with the resin composition for printed wiring board and semi-curing it.

  The metal-clad laminate according to the present invention can be obtained by superimposing a metal foil on the prepreg and then integrating them by heating and pressing.

  The printed wiring board according to the present invention is obtained by removing a part of the metal foil of the metal-clad laminate and forming a conductor pattern.

  According to the present invention, the glass transition temperature and the dielectric properties are stable and excellent, and good drillability and formability can be realized.

  Embodiments of the present invention will be described below.

The resin composition for a printed wiring board according to the present embodiment (hereinafter referred to as a resin composition) comprises a resin component including the following (a) and (b), and an inorganic filler including the following (c) and (d). It was obtained.
(A) Prereacted product obtained by reacting polyphenylene ether with an epoxy compound having an epoxy group (b) Cyanate ester compound (c) Hydrophobic silica particles obtained by subjecting silica particles to surface treatment (d) Molybdenum Molybdenum compound particles having at least a surface layer of the compound, that is, the resin composition is prepared by first compounding an epoxy compound and reacting a polyphenylene ether and an epoxy compound to form a pre-reacted material (a), and further cyanate ester It is obtained by blending compound (b), hydrophobic silica particles (c) and molybdenum compound particles (d). Thus, the cured product of the resin composition rather than the resin composition obtained without forming the preliminary reaction product by previously reacting the polyphenylene ether and the epoxy compound to form the preliminary reaction product (a). The glass transition temperature of (hereinafter, cured product) can be increased. Furthermore, since the cured product uses the resin component as a base resin, it is excellent in dielectric characteristics such as dielectric constant and dielectric loss tangent.

  The amount of moisture carried into the resin composition is preferably less than 0.1%, more preferably 0.07% by mass or less, based on the total mass of the resin composition. When the amount of moisture brought into the resin composition is within the above range, the varnish gel time of the resin composition is hardly shortened. If the varnish gel time is short, when the resin composition is cured, heat cannot be sufficiently applied to the resin composition, and many volatile components remain in the cured product. Therefore, there exists a possibility that the glass transition temperature of hardened | cured material may fall large. In addition, when the surface treatment is not performed on the silica particles, the amount of moisture brought into the resin composition is mainly caused by the moisture absorbed by the silica particles not subjected to the surface treatment. Here, the amount of moisture brought into the resin composition is a value obtained in the same manner as in the methods described in Examples.

  The varnish gel time of the resin composition is greatly shortened by the amount of water brought into the resin composition because the pre-reacted product (a), the cyanate ester compound (b), the hydrophobic silica particles (c) and the molybdenum compound particles ( It is peculiar to the resin composition containing d). This is, for example, a resin obtained by polymerizing polyphenylene ether, epoxy compound, cyanate ester compound (b), hydrophobic silica particles (c) and molybdenum compound particles (d) without using the pre-reacted product (a). Not found in the composition.

  The reason why the varnish gel time is shortened when the amount of water brought into the resin composition is large is presumed to be because the trimerization reaction of the cyanate ester resulting from the cyanate ester compound (b) is promoted. That is, when the amount of moisture brought into the resin composition is large, the cyanate ester compound (b) and water are likely to react with each other, and carbamate is likely to be generated. The active hydrogen in the carbamate, together with the molybdenum compound, greatly promotes the trimerization reaction of the cyanate ester resulting from the cyanate ester compound (b), thereby generating a triazine ring. It is presumed that this triazine ring functions as a curing agent and the resin composition is easily gelled.

  The varnish gel time of the resin composition is 120 seconds or more, preferably 120 to 240 seconds, and more preferably 150 to 210 seconds. Here, the varnish gel time is a value measured in the same manner as described in the examples.

(Resin component)
The resin component includes a pre-reacted product (a) and a cyanate ester compound (b).

(Preliminary reaction product (a))
The preliminary reaction product (a) is obtained by reacting the polyphenylene ether (a-1) with the epoxy compound (a-2) having an epoxy group.

  The polyphenylene ether (a-1) preferably has an average of 1.5 to 2 hydroxyl groups in one molecule. Having an average of 1.5 to 2 hydroxyl groups in one molecule means that the average number of hydroxyl groups per molecule (average number of hydroxyl groups) is 1.5 to 2. If the average number of hydroxyl groups is 1.5 or more, the three-dimensional crosslinking is caused by reacting with the epoxy group of the epoxy compound (a-2), so that the adhesion at the time of curing can be improved. Further, when the average number of hydroxyl groups is 2 or less, it is considered that there is no possibility of gelation during the preliminary reaction.

  The average number of hydroxyl groups of polyphenylene ether (a-1) can be seen from the standard value of the polyphenylene ether product used. Examples of the average number of hydroxyl groups of polyphenylene ether (a-1) include the average value of hydroxyl groups per molecule of all the polyphenylene ethers present in 1 mol of polyphenylene ether.

  The number average molecular weight (Mn) of the polyphenylene ether (a-1) is preferably 800 or more and 2000 or less. When the number average molecular weight is 800 or more, dielectric properties, heat resistance, and a high glass transition temperature can be ensured. If the number average molecular weight is 2000 or less, even when a pre-reacted product reacted with a low epoxy group number epoxy resin is contained, it is possible to suppress resin flow and phase separation or deterioration of moldability. Can do.

  The polyphenylene ether having a number average molecular weight of 800 or more and 2000 or less, for example, may be obtained directly by a polymerization reaction, or a polyphenylene ether having a number average molecular weight of 2000 or more is mixed with a phenolic compound and radical initiation in a solvent. It may be obtained by redistribution reaction in the presence of an agent.

  The number average molecular weight (Mn) of the polyphenylene ether (a-1) can be measured using, for example, gel permeation chromatography.

  Examples of the polyphenylene ether (a-1) include polyphenylene ether and poly (2,6-dimethyl-1,4-phenylene) composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol. Oxides) and the like containing polyphenylene ether as a main component. Among these, polyphenylene ether composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol is preferable. Examples of the bifunctional phenol include tetramethylbisphenol A.

  The epoxy compound (a-2) preferably has an average of 2 to 2.3 epoxy groups in one molecule. When the average number of epoxy groups is within this range, a pre-reacted product with polyphenylene ether (a-1) can be favorably produced while maintaining the heat resistance of the cured product.

  Examples of the epoxy compound (a-2) include dicyclopentadiene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin. . These may be used alone or in combination of two or more. Among these, dicyclopentadiene type epoxy resins are particularly preferably used from the viewpoint of improving dielectric properties. Further, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferably used from the viewpoint of good compatibility with polyphenylene ether. In addition, although it is preferable not to contain a halogenated epoxy resin from a heat resistant viewpoint, you may mix | blend as needed if it is a range which does not impair the effect of this invention.

  The average number of epoxy groups of the epoxy compound (a-2) can be seen from the standard value of the epoxy resin product used. Specific examples of the number of epoxy groups in the epoxy resin include an average value of epoxy groups per molecule of all epoxy resins present in 1 mol of the epoxy resin.

  The epoxy compound (a-2) preferably has a solubility in toluene of 10% by mass or more at 25 ° C. Thereby, the heat resistance of hardened | cured material is fully improved, without inhibiting the outstanding dielectric property which polyphenylene ether (a-1) has. This is considered to be because the compatibility with the polyphenylene ether (a-1) is relatively high and, therefore, it easily reacts uniformly with the polyphenylene ether (a-1).

  The preliminary reaction product (a) can be obtained, for example, by reacting as follows. First, the polyphenylene ether (a-1) and the epoxy compound (a-2) are mixed for about 10 to 60 minutes so that the polyphenylene ether (a-1) and the epoxy compound (a-2) have a predetermined ratio. The mixture is stirred and mixed in an organic solvent having a solid content concentration of about 50 to 70%. And after mixing polyphenylene ether (a-1) and an epoxy compound (a-2), it is made to heat at 80-110 degreeC for 2 to 12 hours, and polyphenylene ether (a-1) and an epoxy compound (a- 2) is reacted. Thereby, a preliminary reaction product (a) is obtained. The organic solvent is not particularly limited as long as it dissolves polyphenylene ether (a-1), epoxy compound (a-2) and the like and does not inhibit these reactions, and examples thereof include toluene.

  The ratio of the polyphenylene ether (a-1) to the epoxy compound (a-2) is the molar ratio of the hydroxyl group of the polyphenylene ether (a-1) to the epoxy group of the epoxy compound (a-2). Is preferably 3 to 6, more preferably about 3.5 to 5.5. If the molar ratio is in the above range, both ends of the polyphenylene ether (a-1) can be efficiently capped. Furthermore, it is thought that the viscosity of the resin varnish and prepreg described later can be lowered and the manufacturability is improved by lowering the viscosity of the preliminary reaction product (a).

  When the polyphenylene ether (a-1) and the epoxy compound (a-2) are reacted, a catalyst may be mixed with the mixture of the polyphenylene ether (a-1) and the epoxy compound (a-2). The catalyst is not particularly limited as long as it can accelerate the reaction between the hydroxyl group of polyphenylene ether (a-1) and the epoxy group of epoxy compound (a-2). For example, octanoic acid, stearic acid , Organic metal salts such as Zn, Cu, and Fe of organic acids such as acetylacetonate, naphthenic acid, and salicylic acid; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), triethylamine, and triethylamine Tertiary amines such as ethanolamine; imidazoles such as 2-ethyl-4-imidazole (2E4MZ) and 4-methylimidazole; organic phosphines such as triphenylphosphine (TPP), tributylphosphine, tetraphenylphosphonium and tetraphenylborate And the like. These may be used alone or in combination of two or more. Among these, imidazoles, particularly 2-ethyl-4-imidazole, is particularly preferably used because it can shorten the reaction time and further suppress polymerization between epoxy resins (self-polymerization of epoxy resins). It is done. Moreover, the content of the catalyst is preferably 0.05 to 1 part by mass with respect to 100 parts by mass in total of the polyphenylene ether (a-1) and the epoxy compound (a-2). If the content of the catalyst is within the above range, the reaction between the hydroxyl group of the polyphenylene ether (a-1) and the epoxy group of the epoxy compound (a-2) does not take time, and the reaction is easily controlled. , Difficult to gel.

  In consideration of reaction efficiency and viscosity (manufacturability), the solid content concentration during the reaction is preferably about 50 to 70%.

(Cyanate ester compound (b))
The cyanate ester compound (b) is preferably a compound having an average number of cyanate groups per molecule (average cyanate group number) of 2 or more. Thereby, the heat resistance of hardened | cured material can be improved. Here, the average number of cyanate groups is an average value of cyanate groups per molecule of all cyanate resins present in 1 mol of cyanate resin. The average number of cyanate groups can be determined from the standard value of the product of the cyanate resin used.

  Examples of the cyanate ester compound (b) include 2,2-bis (4-cyanatephenyl) propane (bisphenol A type cyanate resin), bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2- Examples thereof include aromatic cyanate ester compounds such as bis (4-cyanatephenyl) ethane and derivatives thereof. These may be used alone or in combination of two or more.

  The resin composition preferably further contains an epoxy compound (e). As with the epoxy compound (a-2), the epoxy compound (e) preferably has an average of 2 to 2.3 epoxy groups in one molecule. Examples of the epoxy compound (e) include dicyclopentadiene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and the like. These may be used alone or in combination of two or more. In this case, the epoxy compound (e) may be the same as or different from the epoxy compound (a-2). From the viewpoint of improving the dielectric properties, a dicyclopentadiene type epoxy resin is preferably used. In addition, as the epoxy compound (e), in addition to an epoxy compound having an average of 2 to 2.3 epoxy groups in one molecule, a polyfunctional type such as a cresol novolac type epoxy resin (an average of 2.3 in one molecule). Those having more than one epoxy group) Epoxy compounds can also be used.

  When a dicyclopentadiene type epoxy resin is included as the epoxy compound (a-2) and / or the epoxy compound (e), the dicyclopentadiene type is used with respect to the total mass of the epoxy compound (a-2) and the epoxy compound (e). It is preferable to contain so that the epoxy compound may be 50 mass% or more. Thereby, an insulating material having better dielectric properties can be obtained.

  The blending ratio of the resin component is, for example, 100 parts by mass of the polyphenylene ether (a-1), the epoxy compound (a-2), the cyanate ester compound (b) and the epoxy compound (e) (the epoxy compound) 10 to 40 parts by mass of the polyphenylene ether (a-1) and 20 to 60 parts by mass (including the epoxy compound (a-2) and the epoxy compound (e)). When the compounding of the epoxy compound (e) is 0, it is preferable that the epoxy compound (a-2) is 20 to 60 parts by mass) and the cyanate ester compound (b) is 20 to 40 parts by mass. Thereby, it is thought that the outstanding dielectric property, heat resistance, and adhesiveness (adhesiveness) can be made compatible.

  The resin composition may further contain a halogen flame retardant or a non-halogen flame retardant. Thereby, a flame retardance can be improved. When a halogen-based flame retardant is used, flame retardancy can be imparted, the glass transition temperature of the cured product is unlikely to decrease, and a significant decrease in heat resistance is unlikely to occur. When a halogen-based flame retardant is used, flame retardancy can be easily imparted even when a dicyclopentadiene type epoxy resin that is difficult to impart flame retardancy is used.

  The halogen-based flame retardant is preferably one that does not dissolve and disperses in the resin varnish described below. Examples of the halogen flame retardant include ethylene dipentabromobenzene, ethylene bistetrabromoimide, decabromodiphenyl oxide, tetradecabromodiphenoxybenzene having a melting point of 300 ° C. or higher. By using such a halogen-based flame retardant, it is considered that elimination of halogen at high temperatures can be suppressed, and a decrease in heat resistance can be suppressed.

  The blending ratio of the halogen-based flame retardant is preferably from the viewpoint of flame retardancy and heat resistance so that the halogen concentration is contained in the resin component of the total amount at a ratio of about 5 to 30% by mass.

<Inorganic filler>
(Hydrophobic silica particles (c))
Hydrophobic silica particles (c) are obtained by subjecting silica particles to surface treatment. Thereby, silica particles become difficult to absorb moisture even in a high temperature or high humidity environment. Therefore, even if hydrophobic silica particles that are left (stored) at room temperature for a long time are used as the material of the resin composition, it is difficult for moisture to be brought into the resin composition, and the varnish gel time equivalent to that of the dried silica particles is obtained. Can be maintained. As a result, depending on the storage state of the silica particles, the glass transition temperature and dielectric properties of the cured product are unlikely to deteriorate with time, and the glass transition temperature and dielectric properties are stable and excellent. Here, the dry silica particles refer to silica particles having a water content measured by the Karl Fischer method of less than 0.1%.

  Examples of the surface treatment agent applied to the hydrophobic silica particles (c) include β-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and hexamethyldisilane. Silane coupling agents such as silazane and dimethyldichlorosilane, and known processing agents such as silicone oil can be used. The surface-treated hydrophobic silica particles are available as a commercial product, and examples thereof include “Megasil 525RCS” manufactured by Sibelco Japan Co., Ltd.

Examples of the silica particles constituting the hydrophobic silica particles (c) include spherical silica and crushed silica. Among these, spherical silica or crushed silica having a specific surface area of 0.1 m ² / g or more and 15 m ² / g or less is preferable from the viewpoint of further improving the drillability of the cured product, and the specific surface area is 0 from an economical point of view. .1m ² / g or more ^{15 m} 2 / g or less of the crushed silica is more preferable. The specific surface area can be measured by the BET method.

The crushed silica is obtained, for example, by pulverizing fused silica or pulverizing crystalline silica mined as ore. When the specific surface area of the crushed silica is 0.1 m ² / g or more, when a laminated board such as a metal-clad laminated board is manufactured using the resin composition, the drillability of the laminated board should be good. Can do. That is, it is conventionally considered that drilling workability is significantly reduced when crushed silica is used, compared to the case where spherical silica is used, such as drill blades are easily worn when drilling a laminated plate or the like. By using crushed silica having a specific surface area of 0.1 m ² / g or more together with the molybdenum compound particles (d), the wear of the drill blade is greatly improved. On the other hand, the crushed silica has a specific surface area of 15 m ² / g or less, so that the thickening of the varnish of the resin composition is suppressed, and the increase in the melt viscosity at the time of thermoforming is also suppressed. Thus, the moldability at the time of producing the laminate is improved. As a result, it is possible to prevent the prepreg from being difficult to manufacture and to prevent voids (cavities) from remaining in the insulating layer of the laminate.

  The content of the hydrophobic silica particles (c) is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 150 parts by mass or less, further preferably 30 parts by mass with respect to 100 parts by mass of the resin component. The amount is 100 parts by mass or less. When the content of the hydrophobic silica particles (c) is within the above range, the thermal linear expansion coefficient of the cured product can be reduced.

  When the silica particles constituting the hydrophobic silica particles (c) are crushed silica, the content of the hydrophobic silica particles (c) is preferably 10 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the resin component. Part or less, more preferably 20 parts by mass or more and 100 parts by mass or less. If the content of crushed silica is within the above range, the degree to which crushed silica contributes to lowering the thermal expansion coefficient becomes too small, and other inorganic fillings such as spherical silica are required to achieve a sufficiently low thermal linear expansion coefficient. There is a need to add a large amount of material, and the significance of including crushed silica is not substantially lost. There is no need to use a large amount of the molybdenum compound particles (d) in order to sufficiently improve the drill workability, and there is no fear of reducing the heat resistance, and the drill workability can be sufficiently improved.

The combination is not limited as long as the specific surface area and content of the crushed silica are within the above-mentioned range, but when the specific surface area of crushed silica is 9 to 15 m ² / g, the content of the crushed silica is the resin component 100. It is preferable that it is 10-100 mass parts with respect to a mass part. That is, if the specific surface area of the crushed silica increases, the molten clay of the resin composition at the time of molding tends to increase. Therefore, by suppressing the content of crushed silica, the fluidity of the resin composition is ensured and good molding is achieved. It is because sex is obtained.

(Molybdenum compound particles (d))
The molybdenum compound particles (d) are inorganic particles having at least a molybdenum compound in the surface layer portion. When the molybdenum compound particles (d) are used together with crushed silica, the molybdenum compound functions as a lubricant, so that wear of the drill due to the crushed silica is suppressed and drill workability can be improved. The molybdenum compound particle (d) is a particle having a form in which a molybdenum compound is supported or coated on the surface of an inorganic filler made of another material as a carrier, even if the entire particle is composed of the molybdenum compound. May be. In addition, it is thought that the molybdenum compound which exists in the surface layer part of molybdenum compound particle | grains (d) acts mainly on suppression of wear of a drill. Therefore, in order to obtain the effect of improving the drilling workability with a small amount of the molybdenum compound, it is preferable to use in the form of particles having a molybdenum compound on the surface of an inorganic filler made of another material, as in the latter. In general, a molybdenum compound has a specific gravity larger than that of an inorganic filler such as silica and has a large specific gravity difference from a resin component. Therefore, also from the viewpoint of dispersibility in the resin composition, like the latter, it is preferable to use in the form of particles having a molybdenum compound on the surface of an inorganic filler made of another material. As the inorganic filler used as the carrier, talc, aluminum hydroxide, boehmite, magnesium hydroxide, silica, etc., which are usually used as inorganic fillers for laminates, can be suitably used. The average particle size of the carrier is preferably 0.05 μm or more. Such molybdenum compound particles are available as commercial products, such as Chem Card manufactured by Sherwin Williams.

Examples of the molybdenum compound constituting the molybdenum compound particles (d) include molybdenum oxides such as molybdenum trioxide; zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, barium molybdate, sodium molybdate, molybdenum. Molybdate compounds such as potassium acid, phosphomolybdic acid, and ammonium phosphomolybdate; and molybdenum compounds such as molybdenum boride, molybdenum disilicide, molybdenum nitride, and molybdenum carbide. These may be used alone or in combination of two or more. Among these, one or more selected from the group consisting of zinc molybdate (ZnMoO ₄ ), calcium molybdate (CaMoO ₄ ), and magnesium molybdate (MgMoO ₄ ) from the viewpoints of chemical stability, moisture resistance, and insulation. Are preferred. Only one of these may be used, two may be used in combination, or all three may be used.

  The content of the molybdenum compound particles (d) is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 7 parts by mass or less, further preferably 100 parts by mass of the resin component. It is 0.1 mass part or more and 5 mass parts or less. If the content of the molybdenum compound particles (d) is within the above range, it can sufficiently function as a lubricant and improve the drillability of the laminate. Furthermore, the influence on the heat resistance of a laminated board and copper foil peel strength can be suppressed. Further, since the molybdenum compound has low oil absorption, it does not have a practical adverse effect on the resin fluidity during molding or the like.

  The molybdenum compound particles (d) contain a molybdenum compound. The total content of the molybdenum compound in the resin composition is preferably in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the resin component. If the content of the molybdenum compound in the resin composition is within the above range, a sufficient effect of improving drillability can be obtained. Furthermore, the heat resistance of the laminate can be maintained.

  The resin composition may further contain a catalyst. Thereby, the curing reaction (crosslinking reaction) between the preliminary reaction product (a) and the cyanate ester compound (b) can be promoted. That is, the catalyst acts as a curing accelerator. Therefore, the high glass transition temperature, heat resistance, and adhesion of the cured product can be ensured.

  As the catalyst, for example, what is generally called a metal soap can be used, for example, an organic acid such as octylic acid, naphthenic acid, stearic acid, lauric acid and ricinoleic acid, acetyl acetate, zinc, copper, cobalt, etc. And organic metal salts composed of metals such as lithium, magnesium, calcium and barium. Among these, copper naphthenate is preferably used because it has a low cyanate ester trimerization activity and has a relatively good pot life of varnish and prepreg (while maintaining heat resistance). A catalyst may be used independently or may be used in combination of 2 or more type.

  The blending amount of the catalyst is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the preliminary reaction product (a) and the cyanate ester compound (b). If the blending amount of the catalyst is within the above range, the curing accelerating effect can be enhanced, the high heat resistance and glass transition temperature of the cured product can be secured, and a prepreg having no problem in moldability can be easily produced.

  The inorganic filler may contain other fillers different from these in addition to the hydrophobic silica particles (c) and the molybdenum compound particles (d). That is, by adding other fillers, in addition to the effect of reducing the thermal expansion coefficient by the hydrophobic silica particles (c), it is possible to further reduce the thermal expansion coefficient, and the hydrophobic silica particles (c ) Alone, it is possible to impart properties such as flame retardancy and thermal conductivity that cannot be sufficiently obtained. Other fillers can be appropriately selected from known fillers according to the purpose and are not limited, but those having relatively low hardness that are difficult to reduce drill workability are preferred, specifically , Aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, talc, clay, mica and the like.

  The resin composition may further contain, for example, additives such as a heat stabilizer, an antistatic agent, an ultraviolet absorber, a dye, a pigment, and a lubricant as long as the effects of the present invention are not impaired. .

  The resin composition can be prepared and used in a varnish (resin varnish) by mixing predetermined amounts of the various components described above in a solvent. The solvent is not particularly limited as long as it can dissolve the resin components such as the preliminary reaction product (a), the cyanate ester compound (b), and the epoxy compound (e) and does not inhibit the curing reaction. Organic solvents such as toluene, cyclohexanone, methyl ethyl ketone, and propylene glycol monomethyl ether acetate.

  In preparing this resin varnish, for the purpose of promoting dissolution / dispersion of the solid component, the resin component may be heated in a temperature range where the resin component does not cause a curing reaction, if necessary. Furthermore, when an inorganic filler or a halogen-based flame retardant is added as necessary, the varnish may be agitated using a ball mill, a bead mill, a planetary mixer, a roll mill, or the like until a good dispersion state is obtained.

  A prepreg according to an embodiment of the present invention will be described. The prepreg impregnates the resin varnish obtained as described above into a base material such as glass cloth, and heat-drys it at 110 to 140 ° C., removes the solvent in the resin varnish, and removes the resin composition by half. It can be manufactured by curing. At this time, the resin content (content of the resin composition) of the prepreg is preferably adjusted in a range of 30 to 80% by mass with respect to the total amount of the prepreg.

  A metal-clad laminate according to an embodiment of the present invention will be described. The metal-clad laminate can be produced by stacking a metal foil such as a copper foil on the prepreg obtained as described above and then heating and pressing. For example, a metal-clad laminate such as a copper-clad laminate is manufactured by laminating a metal foil such as copper foil on one or both sides of one prepreg or a plurality of prepregs, and laminating them by heating and pressing. can do. In the metal-clad laminate, the cured prepreg forms an insulating layer. The conditions of heating and pressing are, for example, 140 to 200 ° C., 0.5 to 5.0 MPa, and 40 to 240 minutes.

  A printed wiring board according to an embodiment of the present invention will be described. The printed wiring board can be manufactured by using a subtractive method or the like to remove a part of the metal foil of the metal-clad laminate obtained as described above by etching to form a conductor pattern. . In this case, drilling is performed to form a through hole or a blind via hole for connecting different layers on which the conductor pattern is formed. At this time, since the insulating layer in which the hole is made is a cured product of the prepreg (resin composition), the drilling workability is good and the wear of the drill can be suppressed. In addition, the metal-clad laminate and the printed wiring board obtained by processing the metal-clad laminate have an insulating layer formed of a cured product of prepreg, so that the moldability is good, the rust is not easily generated, and the heat resistance is high and low. It also has a coefficient of thermal expansion.

  A multilayer printed wiring board can be manufactured by preparing a printed wiring board as a core material (inner layer material) and laminating the printed wiring board using a prepreg thereon. That is, the conductor pattern (inner layer pattern) of the core material is roughened by black oxidation or the like, and then a metal foil is stacked on the surface of the core material via a prepreg, and this is heated and pressed to be laminated. The heating and pressing conditions at this time are, for example, 140 to 200 ° C., 0.5 to 5.0 MPa, and 40 to 240 minutes. The core material may be manufactured using a prepreg. Next, drilling and desmearing are performed. Then, a multilayer printed wiring board can be manufactured by forming a conductor pattern (outer layer pattern) using a subtractive method and plating the inner wall of the hole to form a through hole or a blind via hole. . The number of layers of the printed wiring board is not particularly limited.

  Hereinafter, the present invention will be specifically described by way of examples.

[Preparation of preliminary reaction product (a)]
The following materials were used as materials for preparing the preliminary reaction product (a).
(Polyphenylene ether)
PPE: “SA90” manufactured by SABIC Innovative Plastics (number average molecular weight: 1500, hydroxyl group: 1.9)
(Epoxy compound)
DCPD type epoxy resin: “HP7200” manufactured by DIC Corporation (dicyclopentadiene type epoxy compound, 2.3 average functional groups in one molecule)
(Catalyst during pre-act)
Imidazole: “2E4MZ” (2-ethyl-4-imidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.
After adding each component to toluene so that it may become the mixture ratio of Table 1, it was made to stir at 100 degreeC for 6 hours. That is, the pre-reaction product (a) was prepared by reacting (prereacting) polyphenylene ether and an epoxy resin in advance. The preliminary reaction product (a) thus obtained was prepared so that the solid concentration was 60%.

<Examples 1 to 6, 8, Comparative Examples 1 to 9, 16, 17>
The following were used as each material for preparing the resin composition.

(Resin component)
Pre-reaction PPE (a): Pre-reaction product prepared above (a)
Cyanate ester compound (b): 2,2-bis (4-cyanatephenyl) propane (“BADCy” manufactured by Lonza Japan)
(catalyst)
Metal soap: Zinc octoate (Zn-OCTOATE) manufactured by DIC Corporation
(Silica particles)
Crushing silica 1 (c): “Megasil 525RCS” manufactured by Siberco Japan Co., Ltd. (melted crushing silica particles, average particle size 1.6 μm, epoxysilane surface treatment)
・ Fractured silica 2 (c): Fractured silica particles subjected to a treatment (moisture absorption treatment) for leaving crushed silica 1 in a 35 ° C. and 90% environment for 7 days (168 hours) ・ Fractured silica 3: Sibelco Japan Co., Ltd. “Megasil 525” (melt-crushed silica particles, average particle size: 1.6 μm)
Crushed silica 4: Crushed silica particles obtained by subjecting the crushed silica 3 to the above moisture absorption treatment. Spherical silica 1 (c): “SC2500-SEJ” (spherical silica particles, average particle diameter: 0.8 μm) manufactured by Admatechs Co., Ltd. , Specific gravity: 2.2 g / cm ³ , epoxysilane surface treatment)
Spherical silica 2 (c): crushed silica particles obtained by subjecting spherical silica 1 to the above moisture absorption treatment. Spherical silica 3: “SO-25R” (spherical silica particles, average particle size: 0.6 μm) manufactured by Admatechs Co., Ltd. )
Spherical silica 4: Crushed silica particles (molybdenum compound particles) obtained by subjecting spherical silica 3 to the above moisture absorption treatment
Calcium molybdate (d): “KEMGARD 911A” manufactured by Sherwin Williams (calcium zinc molybdate, molybdate content: 10% by mass, specific gravity: 3.0 g / cm ³ , average particle size: 2. 7μm)
Zinc molybdate (d) (talc carrier): “KEMGARD 911C” manufactured by Sherwin Williams Co., Ltd. (zinc molybdate-treated talc, zinc molybdate content: 17% by mass, specific gravity: 2.8 g / cm ³ , (Average particle size: 3.0 μm)
The pre-reacted PPE (a) solution was heated to 30 to 35 ° C. so that the blending ratio shown in Table 4 was obtained, and the cyanate ester compound (b) and the catalyst were added thereto. Then, it was completely dissolved by stirring for 30 minutes. Further, silica particles and molybdenum compound particles were added and dispersed with a bead mill to obtain a varnish-like resin composition (resin varnish).

<Example 7, Comparative Examples 10 and 11>
As the resin component for preparing the resin composition, the same materials as in Example 1 were used except that the following materials were used.

(Resin component)
-Pre-reaction PPE: Pre-reaction product prepared above-Cyanate ester compound: 2,2-bis (4-cyanatephenyl) propane ("BADCy" manufactured by Lonza Japan)
DCPD type epoxy resin: “EPICRON HP7200” manufactured by DIC Corporation (dicyclopentadiene type epoxy compound, 2.3 average functional groups in one molecule)
The pre-reacted PPE (a) solution was heated to 30 to 35 ° C. so that the blending ratios shown in Table 4 were obtained, and the DCPD type epoxy resin, cyanate ester compound (b) and catalyst were added thereto. Otherwise, a varnish-like resin composition (resin varnish) was obtained in the same manner as in Example 1.

<Comparative Examples 12-15>
The same materials as in Example 1 were used as the resin component and catalyst for preparing the resin composition, except that the following materials were used.

(Resin component)
PPE: “SA90” (number average molecular weight 1500, hydroxyl group: 1.9) manufactured by SABIC Innovative Plastics
Cyanate ester compound (b): 2,2-bis (4-cyanatephenyl) propane (“BADCy” manufactured by Lonza Japan)
Dicyclopentadiene type epoxy resin: “EPICRON HP7200” manufactured by DIC Corporation (dicyclopentadiene type epoxy compound, 2.3 average functional groups in one molecule)
・ Phenol novolac type epoxy resin: “EPICRON N-770” manufactured by DIC Corporation
-Phenol novolak: "TD-2090" (novolak type phenolic resin) manufactured by DIC Corporation
(catalyst)
Imidazole: “2E4MZ” (2-ethyl-4-imidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.
Metal soap: Zinc octoate (Zn-OCTOATE) manufactured by DIC Corporation
After adding each component to toluene so that it may become a mixture ratio of Table 4, it was made to stir at 30-35 degreeC for 60 minutes. Further, silica particles and molybdenum compound particles were added and dispersed with a bead mill to obtain a varnish-like resin composition (resin varnish).

<Examples 9 and 10, Comparative Examples 18 and 19>
The same materials as in Example 7 were used as materials for preparing the varnish-like resin composition. The pre-reacted PPE (a) solution is heated to 30 to 35 ° C. so that the blending ratios shown in Table 2 and Table 6 are obtained, and the cyanate ester compound (b), DCPD type epoxy resin, PPE And metal soap was added. Then, it was completely dissolved by stirring for 30 minutes. Further, silica particles and molybdenum compound particles were added and dispersed with a bead mill to obtain a varnish-like resin composition (resin varnish).

<Comparative Example 20>
After adding each component shown in Table 3 to toluene so that it may become the mixture ratio of Table 3 and Table 6, it was made to stir at 30-35 degreeC for 60 minutes. Further, silica particles and molybdenum compound particles were added and dispersed with a bead mill to obtain a varnish-like resin composition (resin varnish).

(Prepreg)
A substrate manufactured by Nitto Boseki Co., Ltd. (counter: WEA116ES136, thickness: 0.1 μm) was used. After impregnating the obtained resin varnish on the substrate at room temperature, it was dried by heating at 150 to 160 ° C. Thereby, the solvent in the resin varnish was removed, and the prepreg was produced by semi-curing the resin composition. The resin content (resin amount) of the prepreg was 57% by mass.

(Laminated board)
Six prepregs (300 mm × 450 mm) are stacked, and copper foil (made by Mitsui Mining & Smelting Co., Ltd., thickness: 35 μm) is stacked as metal foil on both sides, and heated for 90 minutes at 200 ° C. and 3 MPa. The laminated board for evaluation (thickness: 0.8 mm) was manufactured by pressure forming.

(Glass-transition temperature)
The glass transition temperature of the laminate for evaluation was measured by a DSC measurement method based on IPC-TM-650-2.4.25 under a temperature increase rate of 20 ° C./min.

(Dielectric loss tangent)
The dielectric loss tangent of the laminate for evaluation at 1 GHz was measured by a method based on IPC-TM-650-2.5.5.9. Specifically, the dielectric loss tangent of the evaluation laminated board at 1 GHz was measured using an impedance analyzer (RF impedance analyzer HP4291B manufactured by Agilent Technologies).

(Drill wear rate)
4 layers of 0.8mm thick laminates are stacked, 0.15mm aluminum plate is used as the entry board, 0.15mm bake plate is used as the backup board, and 5000h drilling is performed with a φ0.3mm drill. A hole was formed. The drill wear rate after drilling was measured. As a drill, “NHU L020W” manufactured by Union Tool Co., Ltd. was used. The rotation speed of the drill at the time of drilling was 160000 rpm / min, and the feed rate of the drill was 3.2 m / min.

(Varnish gel time)
The varnish gel time is a value obtained by measuring the time until 2.5 ml of the obtained resin composition (resin varnish) gels on a cure plate at 200 ° C.

(Adsorption moisture content of silica particles)
The amount of water adsorbed on the silica particles was measured by the Karl Fischer method (JIS K0113: 2005, coulometric titration method).

(Moisture amount brought into the resin composition)
Amount of water brought in the resin composition was thus calculated by the following equation.
Moisture amount brought into resin composition = (water amount contained in silica (Karl Fischer measurement value%) × silica addition amount / total amount of resin composition) × 100

  In Examples 1 to 10, since hydrophobic silica particles obtained by subjecting silica particles to surface treatment were used, the glass transition temperature was high and the dielectric loss tangent was low. Further, comparing Example 1 (without moisture absorption), Example 2 (with moisture absorption), Example 5 (without moisture absorption) and Example 6 (with moisture absorption), the glass transition temperature and dielectric loss tangent are respectively It was equivalent. That is, it was confirmed that the glass transition temperature and the dielectric properties were stable and excellent. Furthermore, since the resin composition contains hydrophobic silica particles and molybdenum compound particles, the drill wear rate was low. That is, it was confirmed that drilling workability and formability were good.

  On the other hand, in Comparative Examples 1 to 17, a prereacted product (a) of polyphenylene ether and an epoxy compound, a cyanate ester compound (b), a hydrophobic silica particle (c) and a molybdenum compound particle (d) are blended. Since it is not a resin composition obtained in this way, except for Comparative Examples 1, 4 and 16 using new silica particles (silica particles in a dry state), it has excellent glass transition temperature and dielectric properties, and good drillability. And moldability could not be realized.

  Comparative Example 1 (no moisture absorption treatment), Comparative Example 2 (moisture absorption treatment completed), Comparative Example 4 (no moisture absorption treatment) and Comparative Example 5 (moisture absorption treatment completed), Comparative Example 16 (no moisture absorption treatment) and Comparative Example 17 (moisture absorption treatment) When the silica particles that have not been subjected to moisture absorption treatment are used, when the silica particles that have been subjected to moisture absorption treatment are used, the glass transition temperature decreases and the dielectric loss tangent increases. Varnish gel time was significantly shortened. That is, it was confirmed that the glass transition temperature and the dielectric properties were not stable and excellent. It was the same even if the content of silica particles in the resin composition was reduced (Comparative Example 3).

  In Comparative Examples 6 to 10, since the molybdenum compound particles were not blended, the drill wear rate was high. That is, it was confirmed that drill workability and formability were not good. Further, when Comparative Example 6 (no moisture absorption treatment), Comparative Example 7 (moisture absorption treatment completed), Comparative Example 8 (no moisture absorption treatment) and Comparative Example 9 (moisture absorption treatment completed) are compared, the varnish gel time is the same as that of the example. there were. From this result and the results of Comparative Examples 4 and 5, it is presumed that the molybdenum compound particles promote the reduction of the varnish gel time.

  In Comparative Examples 12 and 13, since the pre-reaction PPE (a) was not used, the glass transition temperature was low. When Comparative Example 12 (no moisture absorption treatment) and Comparative Example 13 (moisture treatment completed) were compared, the varnish gel times were the same and were longer than the Examples.

  In Comparative Examples 14 and 15, since the base resin did not contain polyphenylene ether, the glass transition temperature was low and the dielectric loss tangent was high. On the other hand, when Comparative Example 14 (no moisture absorption treatment) and Comparative Example 15 (moisture absorption treatment completed) were compared, the varnish gel times were equivalent and longer than the Examples. From this result and the results of Comparative Examples 12 and 13, silica particles absorbed in a resin composition containing a pre-reaction product (a) of polyphenylene ether and an epoxy compound, a cyanate ester compound (b) and molybdenum compound particles (d) It was confirmed that the varnish gel time was abnormally shortened when using.

  In Examples 9 and 10, since hydrophobic silica particles obtained by subjecting silica particles to surface treatment were used, the glass transition temperature was high and the dielectric loss tangent was low. Furthermore, when Example 9 (without moisture absorption treatment) and Example 10 (with moisture absorption treatment) were compared, the glass transition temperature and dielectric loss tangent were the same. That is, it was confirmed that the glass transition temperature and the dielectric properties were stable and excellent.

  On the other hand, in Comparative Examples 18 to 20, a prereacted product (a) of polyphenylene ether and an epoxy compound, a cyanate ester compound (b), a hydrophobic silica particle (c) and a den compound particle (d) are blended. Since the resin composition was not obtained, excellent glass transition temperature and dielectric properties could not be realized.

  In Comparative Example 18 (no moisture absorption treatment), unlike Comparative Examples 1, 4 and 16, since new silica particles are not used, that is, silica particles having a high adsorbed moisture amount of silica particles are used, varnish gel time is It was short.

  Comparing Comparative Example 18 (without moisture absorption treatment) and Comparative Example 19 (with moisture absorption treatment), when using silica particles that have been subjected to moisture absorption treatment, compared to the case where silica particles that have not been subjected to moisture absorption treatment are used, The glass transition temperature decreased, the dielectric loss tangent increased, and the varnish gel time was significantly shortened. That is, it was confirmed that the glass transition temperature and the dielectric properties were not stable and excellent.

  In Comparative Example 20 (no moisture absorption treatment), the prereaction PPE was not used, so the glass transition temperature was low.

Claims (8)

(A) a preliminary reaction product obtained by reacting a polyphenylene ether and an epoxy compound having an epoxy group, and (b) a resin component containing a cyanate ester compound;
(C) Hydrophobic silica particles obtained by subjecting crushed silica having a specific surface area of 0.1 m ² / g to 15 m ² / g and surface treatment, and (d) the molybdenum on the surface of a support made of a material other than a molybdenum compound. Obtained by blending an inorganic filler containing molybdenum compound particles on which a compound is supported or coated,
Content of the said molybdenum compound particle (d) is 0.1 to 3.1 mass parts with respect to 100 mass parts of said resin components The resin composition for printed wiring boards. The resin composition for printed wiring boards according to claim 1, wherein the molybdenum compound is one or more selected from the group consisting of zinc molybdate, calcium molybdate, and magnesium molybdate. The resin composition for printed wiring boards according to claim 1 or 2, wherein the material other than the molybdenum compound is talc. The resin composition for a printed wiring board according to any one of claims 1 to 3, wherein a content of the hydrophobic silica particles is 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the resin component. . The resin composition for a printed wiring board according to any one of claims 1 to 4, wherein a content of the hydrophobic silica particles is 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin component.   A prepreg obtained by impregnating a substrate with the resin composition for a printed wiring board according to any one of claims 1 to 5.   A metal-clad laminate in which a metal foil is laminated on the prepreg according to claim 6 and integrated by heating and pressing.   A printed wiring board in which a conductor pattern is formed by removing a part of the metal foil of the metal-clad laminate according to claim 7.