TW200831600A - Resin composition - Google Patents

Abstract

Disclosed is a resin composition having low thermal expansion, which enables to form a plated conductive layer with sufficient adhesion strength, while suppressing roughness of an insulating layer surface (namely, ensuring low surface roughness of an insulating layer) during a wet roughening process. Specifically disclosed is a resin composition characterized by containing a cyanate ester resin and a naphthol epoxy resin represented by the following formula (1). (In the formula, n represents a number having an average of 1-6; X represents a glycidyl group or a hydrocarbon group having 1-8 carbon atoms; and the ratio of hydrocarbon group/glycidyl group is within the range of 0.05-2.0.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for forming an insulating layer of a multilayer printed circuit board or the like. [Prior Art] In recent years, miniaturization and high performance of electronic devices have progressed, and multilayer printed circuit boards have been moving toward miniaturization of conductor circuits in order to increase the mounting density of electronic components. As the resin composition used for the insulating layer of the multilayer printed wiring board, for example, a resin composition containing a cyanate resin is known to form an insulating layer having excellent dielectric properties. For example, Patent Document 1 discloses a resin composition for a multilayer printed wiring board containing a cyanate resin, an epoxy resin, and a phenoxy resin. As a method of forming a high-density fine circuit on an insulating layer, an additive process for forming a conductor layer in nonelectrolytic plating after roughening the surface of the insulating layer, or a non-electrolytic plating is known. A semi-additive method (S emi - additivepr 〇 cess) for forming a conductor layer by electrolytic plating. In these techniques, the surface of the insulating layer is generally roughened by wet roughening with an oxidizing agent such as an alkaline permanganic acid solution, and the roughened surface is formed into a conductor layer by electroplating. This wet refining process is a process in which a large physical anchor is formed on the surface of the insulating layer to ensure adhesion strength to the conductor layer formed thereon. However, in recent years, the formation of a high-density micro-circuit is more desirable, and the thickness of the surface of the insulating layer is controlled to be low (the thickness is large, and the plated portion that is infiltrated in the holder is not removed due to the etch - 200831,600, In addition to the difficulty in forming a high-density circuit and the deterioration of the reliability of the subsequent insulation, it is still an important problem to obtain sufficient adhesion strength with the conductor layer. Further, since the multilayer printed circuit board of the high-density circuit is susceptible to cracking due to the difference in thermal expansion coefficient between the copper circuit and the insulating layer, it is required to control the thermal expansion rate of the insulating layer to be low. . [Patent Document 1] International Publication No. 03/099952 [Draft of the Invention] [Disclosure of the Invention] The present invention provides a resin composition containing a cyanate resin suitable for forming an insulating layer. In the wet roughening process, while controlling the thickness of the surface of the insulating layer to be low (low thickness) and forming an electroplated conductor layer having sufficient adhesion strength, the resin composition having excellent thermal expansion coefficient is OBJECTIVES OF THE INVENTION The inventors of the present invention have focused on the above problems and found an insulating layer formed by a resin composition containing a cyanate resin and a specific naphthoquinone type epoxy resin. In the wet roughening process, the surface of the insulating layer is low in thickness, and an electroplated conductor layer having sufficient adhesion strength can be formed, and the insulating layer can also have excellent thermal expansion rate, and can be suitable for a multilayer printed circuit board. The invention is manufactured and used to complete the present invention. -5- 200831600 That is, the present invention contains the following contents. Π] - a resin composition characterized by containing a cyanate resin and a naphthalene vinegar type epoxy resin of the following formula (1), [Chemical 1]

OX 0X

(η as an average 値 represents a number of 1 to 6, X represents an epoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and the ratio of a hydrocarbon group to an epoxy group is 〇.〇5 to 2.0). [2] The resin composition according to the above [1], wherein the content of the cyanate resin is 5 to 60% by mass based on the resin composition (100% by mass of the nonvolatile matter) [3] as described above [1] In the resin composition according to the above [2], the content of the naphthol type epoxy resin represented by the formula (1) is from 1 to 50% by mass based on the resin composition (nonvolatile content φ% by mass). [4] The resin composition according to any one of [1] to [3] which further comprises a phenoxy resin, a polyimine resin, a polyamidimide resin, a polyether quinone imide resin, One or more polymer resins selected from the group consisting of polybenzazole resin, polyether oxime resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin. [5] The resin composition according to the above [4], wherein the content of the polymer resin is 1 to 6 〇 mass% with respect to the resin composition (nonvolatile content: 1% by mass) 200831600 [6] such as [4] The resin composition according to [5], wherein the polymer resin has a weight average molecular weight of 5,000 to 20,000. [7] The resin composition according to any one of the above [4] to [6] wherein the high molecular weight resin is a phenoxy resin. [8] The resin composition according to any one of the above [1] to [7] which further comprises an inorganic entangled material. [9] The resin composition according to the above [8], wherein the content of the inorganic filler is 50% by mass or less based on the resin composition (100% by mass of the nonvolatile matter). [10] The resin composition according to the above [8] or [9] wherein the inorganic cerium material is cerium oxide. An adhesive film according to any one of the above [1] to [10], wherein the resin composition layer is formed on a support film. [12] A prepreg according to any one of [1] to [1], wherein the resin composition is immersed in a sheet-like reinforcing substrate made of fibers. [13] A multilayer printed circuit board comprising an insulating layer formed of a cured product of the resin composition according to any one of the above [1] to [10]. [Effect of the Invention] According to the present invention, a resin composition suitable for forming an insulating layer of a multilayer printed circuit board can be provided, and an insulating layer formed after thermal curing has a low thermal expansion coefficient and a low thickness of the insulating layer surface. A resin composition of an electroplated conductor layer having sufficient adhesion strength can be formed. 200831600 [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The cyanate resin to be used in the present invention is not particularly limited, and examples thereof include a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate resin, bisphenol type (bisphenol A type, Bisphenol F type, bisphenol S type, etc.) Cyanate resin and such a part of Sanxiaohua prepolymer. These may be used singly or in combination of two or more. The weight average molecular weight of the cyanate resin is not particularly limited, but is preferably from 500 to 4,500, more preferably from 600 to 3,000. Specific examples of the cyanate resin include, for example, bisphenol A. Cyanate ester, polyphenol cyanate (oligo(3-methylene-1,5-phenylene), 4,4,-methylenebis(2,6-dimethylphenyl cyanide) Acid ester), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-dicyanate) phenylpropane, 1,1 - bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1·( 2-functional cyanate resin such as benzyl, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether, phenol novolac, cresol novolac A polyfunctional cyanate resin derived from the same, a partially pre-polymerized triazineated resin such as the cyanate resin, etc. As a commercially available cyanate resin, a phenol novolak represented by the following formula (2) A varnish-type polyfunctional cyanate resin (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and the following formula (3) A dicyanate ester of one part or all of the triazine, of the prepolymer from the trimer (Lonza Japan (shares) system, BA230, cyanate equivalent 232) or the like. 200831600

[In the formula, η represents an arbitrary number as an average 値. 〕 【化3】

The content of the cyanate resin in the OCN resin composition is not particularly limited, but is preferably 5 to 60% by mass, more preferably 20 to 4%, based on the resin composition (100% by mass of the nonvolatile matter). 0% by mass. When the content of the cyanate resin is too small, the heat resistance is lowered and the coefficient of thermal expansion tends to increase. When the content of the cyanate resin is too large, the adhesion strength of the plated conductor layer tends to decrease. The naphthol type epoxy resin used in the present invention is represented by the following formula (1). 【化4】

(1) 200831600 (η as an average 値 represents a number of 1 to 6, X represents an epoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and a ratio of a hydrocarbon group to an epoxy group is 0.05 to 2.0). The range of the hydrocarbon group of the average oxime in the epoxy resin and the ratio of the epoxy group-based hydrocarbon group / epoxy propyl group = 0. 05 to 2.0 is preferably in the range of 0.1 to 1.0. X is a hydrocarbon group in the case of a hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, an η-propyl group, an isopropyl group, an allyl group, a propargyl group, a butyl group, an η-pentyl group, and a sec-pentyl group. A base, a tert-pentyl group, a cyclohexyl group, a phenyl group, a benzyl group and the like are preferred, and a methyl group is preferred. The naphthol epoxy resin represented by the formula (1) is a well-known resin described in JP-A-2006-16058, and can be produced by following the method described in the publication. The content of the naphthol type epoxy resin in the resin composition is not particularly limited, but is preferably from 1 to 50% by mass, more preferably from 5 to 5% by mass based on the resin composition (nonvolatile content: 100% by mass). 40% by mass. When the content of the naphthoquinone type epoxy resin is too small, it is difficult to make the surface of the insulating layer in the wet roughening process low in thickness and the adhesion strength of the plated conductor layer. Further, when the content of the naphthol type epoxy resin is too large, the amount of the cyanate resin is relatively decreased, and the coefficient of thermal expansion tends to increase. The resin composition of the present invention may be used in the range in which the effects of the present invention can be exerted. The naphthol type epoxy resin represented by the formula (1) may be used in combination with another epoxy resin. Examples of such an epoxy resin include a double-type A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol s-type epoxy resin, a phenol novolac type epoxy resin, and an alkylphenol novolac type epoxy resin. Resin, bisphenol type epoxy resin, alkyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, epoxy with condensate of aromatic aldehyde having phenol and phenolic hydroxyl group Compound, bisphenol aralkyl type epoxy resin, fluorene type epoxy resin, xanthene-10-200831600 type epoxy resin, triepoxypropyl isomeric cyanurate, and the like. These epoxy resins may be used singly or in combination of two or more. The ratio of the cyanate equivalent of the cyanate resin to the epoxy equivalent of the naphthol type epoxy resin is preferably 1: 〇 3 to 1: 3, more preferably 1: 〇 5 to 1: 1. When the amount is outside the above range, it is difficult to make the surface of the insulating layer in the wet roughening process low in thickness and the adhesion strength of the plated conductor layer. Further, when the resin composition contains a compound having an epoxy group other than the naphthol type epoxy resin represented by the formula (1), the ratio of the cyanate equivalent to the epoxy equivalent is also included in the above range. It is better. Since the resin composition of the present invention contains a specific polymer compound, it can improve the film forming ability when used in the mechanical strength of the cured product or the form of the adhesive film. Examples of such a polymer compound include a phenoxy resin, a polyimine resin, a polyamidimide resin, a polyether quinone resin, a polyfluorene resin, a polyether oxime resin, a polyphenylene ether resin, and a polycarbonate. Ester resin, polyether ether ketone resin, polyester resin. These polymer compounds may be used singly or in combination of two or more. The weight average molecular weight of the polymer compound is preferably in the range of from 5,000 to 200,000. If it is smaller than this range, the effect of improving the film forming ability or mechanical strength may not be sufficiently exhibited, and if it is larger than this range, the compatibility between the cyanate resin and the naphthol type epoxy resin may be insufficient, and after hardening, The surface unevenness is increased, and it is difficult to form a high-density fine circuit. Further, the weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). By the weight average molecular weight of the GPC method, specifically, the LC-9A/RID-6A manufactured by Shimadzu Corporation is used as the measuring device; the column is made by Showa Denko Co., Ltd. -11 - 200831600

Shodex K-800P / K-804L / K-804L; mobile phase using chloroform, etc., measured at a column temperature of 40 ° C, using a standard polystyrene calibration line can be calculated. The content of the polymer compound in the resin composition is not particularly limited, but is preferably 1 to 60% by mass, and more preferably 2 to 20% by mass based on the resin composition (100% by mass of the nonvolatile matter). When the content of the thermoplastic resin is too small, the effect of improving the film forming ability or mechanical strength cannot be exhibited, and if the content is too large, the thickness of the surface of the insulating layer after the wet roughening process tends to increase. In the resin composition of the present invention, an inorganic chelating material may be added in order to further reduce the thermal expansion coefficient of the insulating layer obtained from the resin composition. Examples of the inorganic chelating material include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, and aluminum borate. Barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium chromate, calcium citrate, etc., especially cerium oxide, especially spherical cerium oxide is preferred. The average particle diameter of the inorganic entangled material is not particularly limited, but is preferably 5 μm or less from the viewpoint of formation of a fine circuit of the insulating layer. The average particle diameter ' of the above inorganic filler material can be measured by the laser folding back and scattering method according to the (Mie) scattering theory. Specifically, the particle size distribution of the inorganic entangled material is prepared on a volume basis by a laser-folding type particle size distribution measuring apparatus, and the diameter can be measured as an average particle diameter. For the measurement of the sample, it is preferred to use an inorganic entangled material which is ultrasonically dispersed in water. As the laser-refractive-type particle size distribution measuring device, -12-200831600 LA-5 00, manufactured by Co., Ltd., Ltd., can be used. The inorganic filler material is surface-treated with a surface treatment agent such as a decane coupling agent to improve the moisture resistance. The amount of the inorganic filler to be added is generally in the range of 50% by mass or less, preferably 20% to 40% by mass based on the resin composition (100% by mass of the nonvolatile matter). When the content of the inorganic filler is too large, the cured product tends to be brittle and the peel strength tends to decrease. The resin composition of the present invention may be added with an organometallic compound which is used as a curing catalyst for the purpose of shortening the hardening time by using a conventional epoxy resin composition and a cyanate compound. Examples of the organometallic compound include organic copper compounds such as copper (II) acetamidine acetone, organic zinc compounds such as zinc (II) acetamidine acetone, and organic compounds such as cobalt (II) acetamidine acetone and cobalt (III) acetyl acetonide. Cobalt compounds, etc. The amount of the organometallic compound to be added is usually in the range of 10 to 500 ppm, preferably 25 to 200 ppm, based on the cyanate resin. In the resin composition of the present invention, rubber particles may be added from the viewpoint of plating adhesion. The rubber particles which can be used in the present invention, for example, are not dissolved in the organic solvent used for preparing the varnish of the resin composition, and the cyanate resin of the essential component or the naphthalene represented by the formula (1) Phenolic epoxy resins and the like are also incompatible. Therefore, the rubber particles are present in a dispersed state in the varnish of the resin composition of the present invention. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to such an extent that it is not dissolved in an organic solvent or a resin. Preferred examples of the rubber particles which can be used in the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked phenylethylene-13-200831600 olefinic rubber particles, and propylene groups. Rubber particles, etc. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and for example, the shell layer of the outer layer is composed of a glassy polymer, and the core layer of the inner layer is a two-layer structure composed of a rubber-like polymer. The shell layer of the outer layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate or the like, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3 832, AC3816N (trade name, manufactured by GANZ Chemical Co., Ltd.), and METABLEN KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile-butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the propylene-based rubber particles include METABLEN W3 00A (average particle diameter Ο.ΐμπχ) and W450A (average particle diameter 0·2μπι) (manufactured by Mitsubishi Rayon Co., Ltd.). The average particle diameter of the blended rubber particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured by a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber particles is prepared on a mass basis using a thick particle size Analyzer (FPAR-1 000; manufactured by Otsuka Electronics Co., Ltd.). The measurement can be carried out by using the diameter as the average particle diameter. The content of the rubber particles is preferably from 1 to 10% by mass, more preferably from 2 to 5% by mass, based on the resin composition (nonvolatile matter: 00 -14 to 200831,600% by mass). In the resin composition of the present invention, other components may be blended as needed within a range not inhibiting the effects of the present invention. Examples of the other component include an organic phosphorus-based flame retardant, a phosphorus compound containing an organic nitrogen, a nitrogen compound, a polysulfonium-based flame retardant, and a metal hydroxide, and the like; a tantalum powder, a nylon powder, and the like. An organic chelating agent such as fluorine powder; a tackifier such as Oruben or bentonite; a defoaming agent or a coating agent for polyfluorene, fluorine or polymer; imidazole, thiazole, triazole An adhesion imparting agent such as a phthalic acid coupling agent; a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, DIS AZO yellow, or carbon black. The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a cyanate resin and a naphthol epoxy resin represented by the formula (1), and a mixed polymer compound is optionally used in a rotary mixer. , inorganic filler materials, hardening catalysts, rubber particles or other ingredients. The resin composition of the present invention can be suitably used for forming an insulating layer in the manufacture of a multilayer printed wiring board. The resin composition of the present invention may be applied to a circuit board to form an insulating layer in a varnish state, but it is generally used in the form of a sheet-like laminate such as a film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of lamination property of the sheet-like laminate. The adhesive film of the present invention can be prepared by a method known in the art, for example, a resin varnish in which a resin composition is dissolved in an organic solvent, and the resin varnish is applied to a support film of a support using a mold coater or the like. The organic solvent is dried by heating or by blowing hot air or the like, and is produced by forming a resin composition layer of -15-200831600. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol. Acetate such as acetate; cellulolytic agent, carbitol such as butyl carbitol; aromatic hydrocarbon such as toluene or xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. The organic solvent may be used in combination of two or more kinds. The drying conditions are not particularly limited, and the content of the organic solvent in the resin composition layer is usually 10% by mass or less, and preferably dried at 5% by mass or less. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, a varnish containing 30 to 60% by mass of an organic solvent can be dried by drying at 50 to 150 ° C for about 3 to 10 minutes to form a resin. Composition layer. For the industry, suitable and suitable drying conditions can be set by simple experiments. The thickness of the resin composition layer formed in the adhesive film is generally above the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is generally in the range of 5 to 70 μm, so that the resin composition preferably has a thickness of 10 to 100 μm. Examples of the support film of the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene terephthalate, and the like. Polyester; a film made of polycarbonate, polyimide, or the like, and a metal foil such as a release paper, a copper foil, or an aluminum foil. Further, the support film and the protective film described later may be subjected to a mold release treatment or a corona treatment, and may be subjected to a mold release treatment. The thickness of the support film is not particularly limited, but is generally from 10 to 150 μm, preferably from 25 to 50 μm. On the side of the resin composition layer where the support film is not attached, it is also possible to support the film-size protective film. The thickness of the protective film is not particularly limited, and is, for example, 1 to 40 μm. By laminating the protective film, adhesion or scratches to dust or the like on the surface of the resin composition layer can be prevented. The adhesive film can also be taken up in roll form for storage. Next, as described above, an example of a method of manufacturing a multilayer printed wiring board using the produced adhesive film will be described. First, an adhesive film is laminated on one or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a silicone resin substrate, and a thermosetting polyphenylene ether substrate. Further, the circuit board as used herein refers to a pattern formed by forming a conductor layer (circuit) on one or both sides of the substrate. Further, in a multilayer printed circuit board in which a staggered conductor layer and an insulating layer are laminated, one or both of the outermost layers of the multilayer printed circuit board are patterned conductor layers (circuits), and are also referred to herein. The circuit board. Further, on the surface of the conductor layer, roughening treatment may be performed in advance by blackening treatment. In the above lamination, when the protective film is removed by the protective film, the adhesive film and the circuit substrate are preheated as needed, and the film is pressurized. Adhesive film and heat are applied to the circuit substrate. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is suitable for use. The conditions for the lamination are not particularly limited, and for example, the pressure-adhesive temperature (lamination temperature) -17-200831600 is preferably 70 to 140 ° C, and the pressure-adhesive pressure is preferably 1 to llkSf/cm 2 (9.8 χ 104 ～ 107 · 9 χ 104 N). /m2) ' It is preferable to carry out lamination under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the method of laminating may be a batch type or a continuous type of rolls. Vacuum lamination can be carried out using a commercially available vacuum laminator. For example, a Vacuum Applicator manufactured by Nichig〇-Morton Co., Ltd., a vacuum pressure laminator manufactured by Nihon Seiki Co., Ltd., a Dry Coater manufactured by Hitachi Industries, and a Hitachi AIC. (Stock) vacuum laminator, etc. After laminating the adhesive film on the circuit board and cooling to room temperature to peel off the support film, an insulating layer can be formed on the circuit board by peeling and heat curing. The heat curing condition is preferably selected depending on the kind and content of the resin component in the resin composition, and is preferably selected from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably 160 ° C to 200 ° °C is carried out in the range of 30 minutes to 120 minutes. After the formation of the insulating layer, peeling of the support film before the hardening is performed, and peeling is performed here. Then, as needed, the insulating layer formed on the circuit substrate is perforated to form a via hole and a through hole. The perforation is performed by a well-known method such as drilling, laser, plasma, or the like, and may be combined as needed. The perforation of lasers such as carbon dioxide lasers and YAG lasers is the most common. method. Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. For dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In wet plating, the first hardened resin composition layer (insulating layer) -18- 200831600 surface is permanganate (potassium permanganate, sodium permanganate, etc.) dichromate, ozone, hydrogen peroxide An oxidizing agent such as sulfuric acid or nitric acid is subjected to roughening treatment to form a holder for unevenness. As the oxidizing agent, an aqueous sodium hydroxide solution (aqueous alkaline acid solution) such as potassium permanganate or sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a combination of non-electrolyte plating and electrolytic plating. Further, the conductor layer means a plating resist which forms an inverse pattern, and only a non-electrolyte plating can form a conductor layer. For the method of pattern formation thereafter, for example, a subtractive process, a semi-additive method, or the like which is well known among the industry can be used. The prepreg of the present invention is obtained by immersing the resin composition of the present invention in a sheet-like reinforcing substrate made of a fiber by a hot melt method or a solvent method, and heating it to be semi-hardened. That is, the resin composition of the present invention can be immersed in a sheet-like reinforcing substrate made of fibers to form a prepreg. As the sheet-like reinforcing base material made of the fiber, for example, a fiber which is usually used as a fiber for prepreg such as glass cloth or aramid fiber can be used. The hot-melt method is one in which the resin is not dissolved in an organic solvent, and is applied once on a coated paper having good peelability to the resin, and then laminated on a sheet-like reinforcing substrate; or insoluble in a resin in an organic solvent. Further, a method of producing a prepreg by directly applying to a sheet-like reinforcing substrate or the like by a die coater. Further, the solvent method is carried out in the same manner as the adhesive film, and the resin is immersed in an organic solvent to prepare a resin varnish. The varnish is immersed in a sheet-like reinforcing substrate, and the resin varnish is immersed in a sheet-like reinforcing substrate, and then dried. method. Next, an example of a method of manufacturing a multilayer printed wiring board using the manufactured prepreg will be described as described above. Laminated one on the circuit board. 19-200831600 The prepreg of the invention is overlapped as needed, and the release film is held by a metal plate and extruded under pressure and heating. The pressure and heating conditions are preferably 5 to 40 kgf/cm2 (49 χ 104 〜 3 92 &gt;&lt; 104 N/m2), and the temperature is 120 to 200 ° C for 20 to 100 minutes. Further, as in the case of the adhesive film, the prepreg is laminated on the circuit board by a vacuum lamination method, and then heat-hardened. Thereafter, the surface of the prepreg which has been hardened is roughened by the method described above, and then a conductor layer is formed by electroplating to produce a multilayer printed circuit board. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples. [Example 1] A prepolymer of bisphenol A dicyanate ("BA23 0 S75" manufactured by Lonza Japan Co., Ltd., a cyanate equivalent of about 2 3 2, and a nonvolatile content of 5% by mass of methyl group B) 30 parts by mass of a ketone ketone (hereinafter referred to as MEK) solution, a phenol novolac type polyfunctional cyanate resin ("PT30" manufactured by Lonza Japan Co., Ltd., cyanate equivalent: about 1 24) 10 parts by mass, general formula ( 1) 40% by mass of "ESN-475V" (MEK solution of a non-volatile epoxy group of about 340) having a naphthol type epoxy resin as shown in the above-mentioned naphthol type epoxy resin, and further liquid double Phenolic A-type epoxy resin ("828EL" manufactured by Nippon Epoxy Resin Co., Ltd., epoxy equivalent: 185) 5 parts by mass, phenoxy resin solution ("γρ-70" manufactured by Tohto Kasei Co., Ltd., nonvolatile content 40 Mass% of MEK and cyclohexanone mixed solution) 20 mass-20- 200831600 parts, hardening catalyst cobalt (II) acetamidine acetone (manufactured by Tokyo Chemical Industry Co., Ltd.) 1% by mass of N, N-II 4 parts by mass of methylformamide (DMF) solution, and spherical cerium oxide ("SOC2" manufactured by Admatechs, average particle size) treated with an amino decane surface Diameter 0.5μιη) 40 parts by mass, at a high speed rotary machine mixing uniformly dispersed to prepare a thermosetting resin composition varnish. Then, the resin composition varnish described above is uniformly applied to a polyethylene terephthalate film (thickness: 38 μm, hereinafter abbreviated as PET film) by a die coater to dry the resin composition. The thickness of the layer was 40 μm, and it was dried at 80 to 120 ° C (average 10 ° C) for 6 minutes (the amount of residual solvent in the resin composition layer: about 1% by mass). Subsequently, the surface of the resin composition layer was rolled into a roll shape while being laminated with a polypropylene film of 15 μm. The adhesive film having a roll-like shape was torn to a width of 507 mm to obtain a sheet-like adhesive film of 5 07 x 3 3 6 mm in size. <Comparative Example 1> The bisphenol aralkyl type epoxy resin represented by the formula (4) in which the naphthol type epoxy resin "ESN-475V" was converted into the same mass parts in terms of solid content was prepared. The adhesive film was obtained in the same manner as in Example 1 except that "NC-3 000H" (epoxy equivalent weight: about 290). 【化5】

-21 - 200831600 <Comparative Example 2> The new day of the β-naphthol type epoxy resin represented by the formula (5) in which the naphthol type epoxy resin "ESN-475V" is converted into the same mass fraction in terms of solid content. The adhesive film was obtained in the same manner as in the first example except for the "ESN-185V" (epoxy equivalent of about 280).

【化6】

(In the formula (5), η is an average 値 indicating the number of 1 to 6.) <Evaluation of thermal expansion coefficient> The adhesive films obtained in Example 1 and Comparative Examples 1 and 2 were thermally cured at 180 ° C for 90 minutes. And the sheet of hardened matter. A test piece having a cured product of about 5 mm in width and about 15 mm in length was cut, and a thermomechanical analysis was carried out by a tensile weighting method using a Rigakii thermomechanical analyzer (Thermo Plus TMA8 310). After the test piece was attached to the apparatus, the measurement was continuously performed twice under the measurement conditions of a load of 1 g and a temperature rise rate of 5 ° C /min. The average linear thermal expansion rate at 25 ° C to 150 ° C under the visual observation twice was calculated. The results obtained are shown in Table 1. <Measurement of the thickness of the surface of the insulating layer after the wet roughening process, and evaluation of the adhesion strength of the layer of the plated conductor-22-200831600> (1) Lamination of the adhesive film The glass cloth substrate epoxy layer with the inner layer circuit The adhesive film produced in Example 1 and Comparative Examples was applied to both sides of the laminate "thickness of copper foil 18 μηι, substrate thickness 0.8 mm, and R5715ES manufactured by Matsushita Electric Co., Ltd.", and a batch type vacuum pressure laminator MVLP- was used. 500 (product name, famous machine (stock) system) is laminated. The lamination was performed under reduced pressure for 30 seconds to bring the gas pressure to 13 hPa or less, followed by extrusion at 110 ° C for 30 seconds at a pressure of 74 74 °. The PET film was peeled off from the laminated adhesive film, and the resin composition was cured at 180 ° C for 30 minutes to form an insulating layer. (2) Wet roughening treatment and conductor layer plating The circuit substrate was immersed in Swelling Dip·Securiganth P of Atotech Japan (shares) of the swelling liquid at 80 ° C for 5 minutes. Subsequently, it was immersed in a crude solution of Atotech Japan (Concentrate· Compact P (KMn〇4: 60 g/L, NaOH: 40 g/L aqueous solution) at 80 ° C for 10 minutes. Finally, it was immersed in Atotech Japan's Reduction Solution·Securiganth P at 40 ° C for 5 minutes, and then roughened. Subsequently, after drying at 90 ° C for 30 minutes, Ra (10-point average roughness) of the surface of the insulating layer was determined using a non-contact surface roughness meter (WYKO NT33 0 0 manufactured by Veeco Instruments Co., Ltd.). Next, the laminate was subjected to non-electrolyte plating, and then heated at 15 ° C for 30 minutes to be annealed, and copper layer was electrolytically plated by copper sulfate to a thickness of 25 ± 10 μm. Finally, at 1800 ° C for 3 〇 -23 - 200831600 fire treatment. On the electroplated copper layer of the obtained laminate, a rectangular notch having a width of 100 mm and a length of 100 mm was cut, and the end of one side of the longitudinal direction of the slit was peeled off, and the holder was grasped at room temperature at 50 mm. The speed of /min was measured at a load of 35 mm peeling in the vertical direction. The results of the peel strength (peel strength) of the electroplated conductor layer are shown in Table 1. [Table 1] Example 1 Comparative Example 1 Comparative Example 2 Average thermal expansion coefficient (ppm) 45 50 43 Surface roughness Ra (nm) after wet roughening 180 600 220 Conductive layer peel strength (kgf/cm) 0.7 0.6 0.4 As is apparent from Table 1, the insulating layer formed by the adhesive film obtained in Example 1 exhibited excellent characteristics in terms of the average thermal expansion coefficient, the surface roughness, and the peeling strength of the conductor layer. On the other hand, although the peeling strength of the insulating layer-based conductor layer formed by the adhesive film obtained in Comparative Example 1 was excellent, the surface roughness was large, which was disadvantageous in forming a high-density fine circuit. Further, the average coefficient of thermal expansion is also higher than that of Example 1. Further, the insulating layer formed by the adhesive film obtained in Comparative Example 2 was excellent in average thermal expansion coefficient and surface roughness, but the conductor layer peeling strength was lowered. [Industrial Applicability] The cured product of the resin composition of the present invention has a low coefficient of thermal expansion, and when the insulating layer is formed, the surface of the insulating layer is low in thickness and can be formed to have sufficient -24 - 200831600

The adhesion strength of the plated conductor layer is suitable for use in the manufacture of multilayer printed circuit boards. The present application is based on Japanese Patent Application No. 2006_27973, the entire disclosure of which is incorporated herein. -25-

Claims (1)

200831600 X. Patent application scope 1. A resin composition characterized by containing a cyanate resin and a naphthol type epoxy resin represented by the following formula (1), [Chemical 1] OX 0X (η as an average 値 represents a number of 1 to 6, and X represents an epoxy group or a hydrocarbon group having 1 to 8 carbon atoms, and the ratio of the hydrocarbon group to the epoxy group is 0.05 to 2·0). 2. The resin composition according to the first aspect of the invention, wherein the content of the cyanate resin is from 5 to 60% by mass based on the resin composition (nonvolatile content: 1% by mass). 3. The resin composition according to claim 1 or 2, wherein the content of the naphthol type epoxy resin represented by the formula (1) is 1 to 50 with respect to the resin composition (100% by mass of the nonvolatile matter) quality%. 4. The resin composition according to any one of claims 1 to 3, which further comprises a phenoxy resin, a polyimine resin, a polyamidimide resin, a polyether phthalimide resin, a polyfluorene One or more polymer resins selected from the group consisting of a resin, a polyether oxime resin, a polyphenylene ether resin, a polycarbonate resin, a polyether ether ketone resin, and a polyester resin. 5. The resin composition of claim 4, wherein the content of the polymer resin is from 1 to 60% by mass based on the resin composition (100% by mass of the nonvolatile matter). -26- 200831600 6. The resin composition of claim 4 or 5, wherein the high molecular weight resin has a weight average molecular weight of from 5,000 to 200,000. 7. The resin composition according to any one of claims 4 to 6, wherein the polymer resin is a phenoxy resin. 8. The resin composition according to any one of claims 1 to 7, which further comprises an inorganic chelating material. 9. The resin composition of claim 8, wherein the content of the inorganic ruthenium material is 50% by mass or less based on the resin composition (nonvolatile content: 100% by mass). 1 0. The resin composition according to claim 8 or 9, wherein the inorganic chelating material is oxidized chopping. An adhesive film formed by forming a resin composition layer according to any one of claims 1 to 10 on a support film. A prepreg obtained by immersing a resin composition according to any one of claims 1 to 10 in a sheet-like reinforcing substrate made of fibers. 1 3 - A multilayer printed circuit board formed by forming a heat-insulating layer of a resin composition according to any one of claims 1 to 1 -27-200831600 4 Peak VII, designated representative diagram (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -3-