JP2010090237A - Epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is suitable for forming an insulating layer of a multilayer printed wiring board or the like, wherein, when the insulating layer obtained by heat-curing the resin composition is formed, the insulating layer has a low thermal expansion, a roughened surface that has low roughness and is uniform can be formed on a surface of the insulating layer, and a conductor layer formed on the roughened surface has excellent adhesiveness. <P>SOLUTION: The resin composition contains: (A) an epoxy resin; (B) a cyanate ester resin; (C) an adduct body of an imidazole compound and the epoxy resin; and (D) a metallic curing catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition suitable for forming an insulating layer such as a multilayer printed wiring board.

  In recent years, electronic devices have been reduced in size and performance, and in multilayer printed wiring boards, conductor wiring has been miniaturized in order to improve the mounting density of electronic components. As a resin composition used for an insulating layer of a multilayer printed wiring board, for example, it is known that a resin composition containing a cyanate ester resin can 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 ester resin, an epoxy resin, and a phenoxy resin, and discloses an organometallic compound as a curing catalyst for the resin composition. .

  As a method for forming a high-density fine wiring on the insulating layer, an additive method in which a conductive layer is formed by electroless plating after the surface of the insulating layer is roughened, or a conductive layer is formed by electroless plating and electrolytic plating. The semi-additive method is known. In these methods, generally, a roughened surface is formed on the surface of the insulating layer through wet roughening with an oxidizing agent such as an alkaline permanganate solution, and a conductor layer is formed on the roughened surface by plating. This wet roughening step is a process of ensuring adhesion strength with a conductor layer formed thereon by forming a relatively large physical anchor on the surface of the insulating layer. However, in recent years, the formation of high-density fine wiring has been desired, and the roughness of the insulating layer surface is kept low (if the roughness is large, the plated portion that has entered the anchor is not removed by etching, and high-density wiring is formed. However, it is important to obtain a sufficient adhesion strength with the conductor layer. In addition, multilayer printed wiring boards with high-density wiring tend to cause problems such as cracking due to the difference in thermal expansion coefficient between copper wiring and insulating layer, so it is also necessary to keep the thermal expansion coefficient of insulating layer low. Is done.

  As a resin composition having a low coefficient of thermal expansion and a low roughness of the insulating layer surface and capable of forming a conductor layer having a high peel strength, an epoxy resin composition containing a specific naphthol type epoxy resin in Patent Document 2 is used. It is disclosed.

International Publication 2003/099952 Pamphlet International Publication No. 2008/044766 Pamphlet

  On the other hand, according to the knowledge of the present inventors, when a composition containing an epoxy resin, a cyanate ester resin and a metal-based curing catalyst as disclosed in Patent Document 2 is used for forming an insulating layer, an inner layer circuit board When an insulating layer is formed on the surface and the surface of the insulating layer is roughened, a conductor is formed on the surface of the insulating layer formed on the circuit conductor layer on the surface of the internal circuit board and the surface of the insulating layer formed on the base insulating layer. It has been found that the surface roughness of the insulating layer on the layer tends to be larger, and the uniformity of the roughness of the entire surface of the insulating layer is reduced. Thus, when the uniformity of the roughness of the surface of the insulating layer is low, a large difference also occurs in the peel strength of the conductor layer formed on the surface, which is disadvantageous for the formation of high-density fine wiring.

  Accordingly, the present invention provides a resin composition suitable for forming an insulating layer such as a multilayer printed wiring board, and when the insulating layer obtained by thermosetting the resin composition is formed, the insulating layer has a low thermal expansion. An object of the present invention is to provide a resin composition that can form a uniform roughened surface with a low roughness on the surface of the insulating layer, and that is excellent in the adhesion of the conductor layer formed on the roughened surface.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an insulating layer formed of an epoxy resin, a cyanate ester resin, an adduct of a guanidine compound and an epoxy resin, and a resin composition containing a metal curing catalyst. However, it has been found that the resin composition has a low coefficient of thermal expansion, a uniform roughened surface is formed in roughening the surface of the insulating layer, and high adhesion between the insulating layer and the conductor layer can be maintained even at low roughness. The present invention has been completed. That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a cyanate ester resin, (C) an adduct of a guanidine compound and an epoxy resin, and (D) a metal-based curing catalyst.
[2] When the nonvolatile content of the resin composition is 100% by mass, the content of the component (A) is 5 to 60% by mass, the content of the component (B) is 5 to 50% by mass, and the component (C) The content of the adduct of the guanidine compound and the epoxy resin is 0.1 to 5% by mass, and the metal content based on the metal-based curing catalyst (D) is 25 to 500 ppm, and the cyanate ester group and the epoxy group The epoxy resin composition according to the above [1], wherein the ratio is 1: 0.4 to 1: 2.
[3] The above [1] or [2], wherein the metal-based curing catalyst is an organometallic complex or an organometallic salt of one or more metals selected from cobalt, copper, zinc, iron, nickel, manganese, and tin. The resin composition as described.
[4] The resin composition according to any one of [1] to [3], wherein the guanidine compound is dicyandiamide.
[5] Further selected from polyvinyl acetal resin, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin Resin composition in any one of said [1]-[4] containing 1 or more types of polymer resin.
[6] The resin composition according to the above [5], wherein the content of the polymer resin is 1 to 20% by mass with respect to the resin composition (nonvolatile content: 100% by mass).
[7] The resin composition according to any one of [1] to [6], further including an inorganic filler.
[8] The resin composition according to the above [7], wherein the content of the inorganic filler is 10 to 70% by mass with respect to the resin composition (nonvolatile content: 100% by mass).
[9] The resin composition according to the above [7] or [8], wherein the inorganic filler is silica.
[10] An adhesive film in which the resin composition according to any one of [1] to [9] is layered on a support.
[11] A prepreg obtained by impregnating the resin composition according to any one of [1] to [9] into a sheet-like reinforcing base material made of fibers.
[12] A multilayer printed wiring board in which an insulating layer is formed from a cured product of the resin composition according to any one of [1] to [9].

  According to the present invention, a resin composition suitable for forming an insulating layer of a multilayer printed wiring board, the insulating layer formed of the resin composition has a low coefficient of thermal expansion, and a uniform roughened surface can be formed. Provided is a resin composition capable of maintaining high adhesion between an insulating layer and a conductor layer even at low roughness.

  The epoxy resin used in the present invention is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy Resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthol type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, epoxidized product of phenol and aromatic aldehyde having phenolic hydroxyl group, biphenyl Examples thereof include aralkyl type epoxy resins, fluorene type epoxy resins, xanthene type epoxy resins, triglycidyl isocyanurate and the like. Two or more epoxy resins may be used in combination. Epoxy resins include bisphenol A type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and epoxy resins having a butadiene structure from the viewpoint of heat resistance, insulation reliability, and adhesion to metal films. preferable. As the epoxy resin, a naphthol type epoxy resin represented by the following general formula (1) is particularly preferable.

(N shows the number of 1-6 as an average value, X shows a glycidyl group or a C1-C8 hydrocarbon group, and the ratio of a hydrocarbon group / glycidyl group is 0.05-2.0. )
The ratio of the hydrocarbon group and glycidyl group as an average value in the epoxy resin is in the range of hydrocarbon group / glycidyl group = 0.05 to 2.0, preferably in the range of 0.1 to 1.0. . Examples of the hydrocarbon group when X represents a hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, propargyl group, butyl group, n-pentyl group, sec -Pentyl group, tert-pentyl group, cyclohexyl group, phenyl group, benzyl group and the like can be mentioned, and a methyl group is particularly preferable. The naphthol epoxy resin represented by the formula (1) is a known resin described in JP-A-2006-160868, and can be produced according to the production method described in the publication.

  Examples of commercially available epoxy resins include “jER828EL” (liquid bisphenol A type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., “HP4032”, “HP4032D” (Naphthalene type 2) manufactured by Dainippon Ink & Chemicals, Inc. Functional epoxy resin), "HP4700" (naphthalene type tetrafunctional epoxy resin) manufactured by Dainippon Ink & Chemicals, Ltd., "ESN-475V" (naphthol type epoxy resin) manufactured by Toto Kasei Co., Ltd., Daicel Chemical Industries, Ltd. “PB-3600” (epoxy resin having a butadiene structure) manufactured by Nippon Kayaku Co., Ltd., “NC3000H”, “NC3000L” (biphenyl type epoxy resin), “YX4000” (biphenyl type epoxy) manufactured by Japan Epoxy Resin Co., Ltd. Resin), "YX8800" manufactured by Japan Epoxy Resin Co., Ltd. (Anthracene skeleton-containing epoxy resin), (naphthol type epoxy resin represented by the general formula (1)) by Nippon Steel Chemical Co., Ltd. "ESN-475V", and the like.

  Although content of the epoxy resin in a resin composition is not specifically limited, Preferably it is 5-60 mass% with respect to a resin composition (nonvolatile content 100 mass%), More preferably, 10-50 % By mass. If the epoxy resin content is too small, roughening unevenness tends to occur, and if the epoxy resin content is too large, the cyanate ester resin content is relatively reduced, so the coefficient of thermal expansion. Tend to increase.

  The cyanate ester resin used in the present invention is not particularly limited, and examples thereof include novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester resin, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S). Examples thereof include cyanate ester resins and prepolymers in which these are partially triazine. Although the weight average molecular weight of cyanate ester resin is not specifically limited, Preferably it is 500-4500, More preferably, it is 600-3000.

  Specific examples of the cyanate ester resin include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol Novolac, cle Examples thereof include polyfunctional cyanate resins derived from urenovolak, dicyclopentadiene structure-containing phenol resins, etc., prepolymers in which these cyanate resins are partially triazines, etc. Cyanate ester resins may be used in combination of two or more. .

  As a commercially available cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin represented by the following formula (2) (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), represented by the following formula (3): Bisphenol A dicyanate, part or all of which is a tripolymerized prepolymer (Lonza Japan KK, BA230, cyanate equivalent 232), dicyclopentadiene structure-containing cyanate ester resin (Lonza Japan KK) Manufactured, DT-7000) and the like.

  Although content of the cyanate ester resin in a resin composition is not specifically limited, Preferably it is 5-50 mass% with respect to a resin composition (nonvolatile content 100 mass%), More preferably, 20- 40% by mass. When there is too little content of cyanate ester resin, it exists in the tendency for heat resistance to fall and for a coefficient of thermal expansion to increase. When there is too much content of cyanate ester resin, it exists in the tendency for the adhesive strength of a plating conductor layer to fall.

  The ratio of the cyanate equivalent of the cyanate ester resin to the epoxy equivalent of the epoxy resin is preferably 1: 0.4 to 1: 2, more preferably 1: 0.5 to 1: 1.5. If the equivalent ratio is out of the above range, it tends to be difficult to achieve both low roughness of the insulating layer surface and adhesion strength of the plated conductor layer.

  The adduct of a guanidine compound and an epoxy resin used in the present invention is a known compound as an adduct of an amine compound and an epoxy resin. For example, as described in JP-A-6-65356, a guanidine compound And an epoxy resin can be obtained by heating reaction. The adduct body of the guanidine compound and the epoxy resin in the present invention functions as a curing catalyst or a curing accelerator, like the metal-based curing catalyst. Examples of the starting guanidine compound include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and tetramethyl. Guanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca 5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl Biguanide, 1-phenylbiguanide, 1- (o- Lil) biguanides, and the like. Preferred guanidine compounds include dicyandiamide, 1- (o-tolyl) biguanide and the like, and dicyandiamide is particularly preferable. As commercially available guanidine compounds, “JER Cure DICY-7” (Dicyandiamide) manufactured by Japan Epoxy Resin Co., Ltd., “Noxeller BG” (1- (o-tolyl) biguanide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. Etc. Examples of the epoxy resin used as a raw material include the epoxy resins described above and phenyl glycidyl ether. Two or more adducts of a guanidine compound and an epoxy resin may be used in combination.

  The content of the adduct body of the guanidine compound and the epoxy resin is 0.1 to 5% by mass, more preferably 0.2 to 2% by mass with respect to the resin composition (nonvolatile content 100% by mass). Is preferred. When the content is less than 0.1% by mass, the uniformity of the roughening of the surface of the insulating layer tends to be reduced.

  Examples of the metal-based curing catalyst used in the present invention include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. As metal-based curing catalysts, from the viewpoint of curability and solvent solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) acetyl Acetonate is preferable, and cobalt (II) acetylacetonate and zinc naphthenate are particularly preferable. Two or more metal-based curing catalysts may be used in combination.

  The addition amount of the metal-based curing catalyst is such that the metal content based on the metal-based curing catalyst is 25 to 500 ppm, more preferably 40 to 200 ppm with respect to the resin composition (non-volatile content 100% by mass). Is preferred. If it is less than 25 ppm, it tends to be difficult to form a conductor layer having excellent adhesion to the surface of the low-roughness insulating layer, and if it exceeds 500 ppm, the storage stability and insulation of the resin composition tend to decrease. It becomes.

  The resin composition of the present invention can further improve the film molding ability when used in the form of a mechanical strength of the cured product or an adhesive film by further containing a specific polymer compound. Examples of such a polymer compound include polyvinyl acetal resin, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester. Resins can be mentioned. Two or more polymer compounds may be used in combination. As the polymer compound, polyvinyl acetal resin and phenoxy resin are particularly preferable.

  As the polyvinyl acetal resin, a polyvinyl butyral resin is particularly preferable. Specific examples of the polyvinyl acetal resin include those manufactured by Denki Kagaku Kogyo Co., Ltd., electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP, and Sekisui Chemical Co., Ltd., ESREC BH series, BX series, and KS. Series, BL series, BM series and the like. Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Toto Kasei Co., Ltd., YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213, YL7290, and the like manufactured by Japan Epoxy Resin Co., Ltd. The polyvinyl acetal resin having a glass transition temperature of 80 ° C. or higher is particularly preferable. The “glass transition temperature” here is determined according to the method described in JIS K7197. When the glass transition temperature is higher than the decomposition temperature and the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention. The decomposition temperature is defined as the temperature at which the mass reduction rate is 5% when measured according to the method described in JIS K 7120.

  The weight average molecular weight of the polymer compound is preferably in the range of 5,000 to 200,000. If it is smaller than this range, the effect of improving the film forming ability and mechanical strength tends to be insufficient. If it is larger than this range, the compatibility with the cyanate ester resin and the epoxy resin is lowered, and the surface of the insulating layer is roughened. Later roughness tends to increase.

  In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Although content of the high molecular compound in a resin composition is not specifically limited, Preferably it is 1-20 mass% with respect to a resin composition (nonvolatile content 100 mass%), More preferably, it is 2- 15% by mass. If the content of the thermoplastic resin is too small, the effect of improving the film forming ability and the mechanical strength tends to be hardly exhibited, and if too large, the roughness of the surface of the insulating layer after the roughening process tends to increase.

  An inorganic filler may be added to the resin composition of the present invention in order to further reduce the thermal expansion coefficient of the insulating layer obtained from the resin composition. Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, and synthetic silica Particularly preferred. The silica is preferably spherical. Two or more inorganic fillers may be used in combination. The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 0.7 μm or less from the viewpoint of forming fine wiring on the insulating layer. If the average particle size of the inorganic filler is too small, when the epoxy resin composition is used as a resin varnish, the viscosity of the varnish tends to increase and the handleability tends to decrease. It is preferable that it is 05 μm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

  The inorganic filler is preferably one that has been surface treated with a surface treatment agent such as an epoxy silane coupling agent, an amino silane coupling agent, or a titanate coupling agent to improve its moisture resistance. The addition amount of the inorganic filler is usually 10 to 70% by mass, preferably 20 to 55% by mass with respect to the resin composition (non-volatile content 100% by mass). When there is too much content of an inorganic filler, it exists in the tendency for hardened | cured material to become weak and for the peel strength to fall.

  From the viewpoint of plating adhesion, rubber particles may be further added to the resin composition of the present invention. The rubber particles that can be used in the present invention are, for example, those that do not dissolve in the organic solvent used when preparing the varnish of the resin composition, and are incompatible with the essential components such as cyanate ester resin and epoxy resin. is there. Accordingly, the rubber particles exist 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 a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  Preferable examples of rubber particles that can be used in the present invention include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is formed of a glassy polymer and an inner core layer is formed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Two or more rubber particles may be used in combination. Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade name, manufactured by Ganz Kasei Co., Ltd.), and Metabrene 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 size: 0.5 μm, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Methbrene W300A (average particle size 0.1 μm) and W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

  The average particle diameter of the rubber particles to be blended 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 using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.

  The content of the rubber particles is preferably 1 to 10% by mass and more preferably 2 to 5% by mass with respect to the resin composition (nonvolatile content 100% by mass).

  The epoxy resin composition of the present invention may contain a flame retardant as long as the effects of the present invention are not impaired. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Examples of organophosphorus flame retardants include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Fine Techno. Reefos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ manufactured by Hokuko Chemical Co., Ltd., Clariant Phosphorus ester compounds such as OP930 manufactured by Daihachi Chemical Co., Ltd., PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 manufactured by Toto Kasei Co., Ltd., and FX310, and phosphorus-containing phenoxy such as ERF001 manufactured by Toto Kasei Co., Ltd. Examples thereof include resins. Examples of organic nitrogen-containing phosphorus compounds include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Seisakusho Co., Ltd. Examples thereof include phosphazene compounds. As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20.

  In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include, for example, organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, and imidazole-based materials. Examples thereof include adhesion imparting agents such as thiazole, triazole, and silane coupling agents, and coloring agents such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are mixed using a rotary mixer or the like, if necessary, by adding a solvent or the like.

  The resin composition of the present invention can be suitably used for forming an insulating layer in the production of a multilayer printed wiring board. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

  The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. Is done. Those skilled in the art can appropriately set suitable drying conditions through simple experiments.

  The thickness of the resin composition layer formed in the adhesive film is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  Although the thickness of a support body is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is 25-50 micrometers.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

  Next, an example of a method for producing a multilayer printed wiring board using the adhesive film produced as described above will be described.

  First, an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107). 9.9 × 10 ⁴ N / m ² ), and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll.

  The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature, and when the support is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 200 ° C. It is selected in the range of 30 to 120 minutes at ° C.

  If the support is not peeled off after the insulating layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured resin composition layer (insulating layer) is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / Roughening treatment is performed with an oxidizing agent such as sulfuric acid or nitric acid to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

  The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material made of fibers by a hot melt method or a solvent method, and heating and semi-curing. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like reinforcement base material which consists of fibers. As the sheet-like reinforcing substrate made of fibers, for example, those made of fibers that are commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.

  In the hot melt method, the resin is once coated on a coated paper having good releasability from the resin without dissolving it in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or the resin is used in an organic solvent. This is a method for producing a prepreg by directly coating a sheet-like reinforcing substrate with a die coater without dissolving it. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying.

Next, an example of a method for producing a multilayer printed wiring board using the prepreg produced as described above will be described. One or several prepregs of the present invention are stacked on a circuit board, sandwiched between metal plates through a release film, and press-laminated under pressure and heating conditions. The pressurizing / heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Similarly to the adhesive film, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd.), 30 parts by mass of methyl ethyl ketone (hereinafter abbreviated as MEK) solution having a cyanate equivalent of about 232 and a nonvolatile content of 75% by mass, a phenol novolac type polyfunctional cyanate ester resin ( "PT30" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 124) was mixed with 10 parts by mass and 10 parts of MEK and mixed with "ESN-475V" manufactured by Tohto Kasei Co., Ltd. as a naphthol type epoxy resin (the following general formula (1) 40 parts by mass of a MEK solution having a nonvolatile content of 65% by mass with an epoxy equivalent of about 340 represented by the following: 8 parts by mass of a liquid bisphenol A type epoxy resin (“jER828EL” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of about 185) Phenoxy resin solution (Japan Epoxy "YX-6554" manufactured by Gin Co., Ltd., 20 parts by mass of a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass, adduct of guanidine compound and epoxy resin (15 parts by mass of dicyandiamide (Japan Epoxy Resin Co., Ltd.) “JERcure DICY7”) and 30 parts by mass of bisphenol A type epoxy resin (“jER 828US” manufactured by Japan Epoxy Resin Co., Ltd.) were reacted at 100 ° C. for 2 hours in 55 parts by mass of 1-methoxypropanol solution. 3 parts by mass of a solution (by mass%), 4 parts by mass of a 1% by mass N, N-dimethylformamide (DMF) solution of cobalt (II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.), and spherical silica ( ) Admatex "SOC2" surface-treated with aminosilane, average particle size 0.5μ ) 50 parts by mass were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a varnish of a thermosetting resin composition.
In the nonvolatile content of the resin composition, 27% by mass of epoxy resin, 26% by mass of cyanate ester resin, 1.1% by mass of adduct of imidazole compound and epoxy resin, 58 ppm of metal (cobalt) added as an organometallic catalyst, high The molecular resin is 5% by mass and the inorganic filler is 41% by mass.
Next, such a resin composition varnish is uniformly applied on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as PET film) with a die coater so that the thickness of the resin composition layer after drying is 40 μm, It dried for 6 minutes at 80-120 degreeC (average 100 degreeC) (residual solvent amount in a resin composition layer: about 1.5 mass%). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition layer. The roll-like adhesive film was slit to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 × 336 mm.

（ｎは平均値として１〜６の数を示し、Ｘはグリシジル基又は炭素数１〜８の炭化水素基を示し、炭化水素基／グリシジル基の比率は０．０５〜２．０である。）

(N shows the number of 1-6 as an average value, X shows a glycidyl group or a C1-C8 hydrocarbon group, and the ratio of a hydrocarbon group / glycidyl group is 0.05-2.0. )

<Example 2>
3 parts by mass of an adduct of the guanidine compound and the epoxy resin of Example 1 were mixed with 20 parts by mass of (1-o-tolylbiguanide (“Noxeller BG” manufactured by Ouchi Shinsei Chemical Co., Ltd.)) and 20 parts by mass of phenylglycidyl ether. Example 1 except that a varnish of a thermosetting resin composition changed to 5 parts by mass) was used. An adhesive film was obtained in the same manner as in 1.

<Comparative Example 1>
In Example 1, an adhesive film was obtained in exactly the same manner as in Example 1 except that a varnish of a thermosetting resin composition without adding an adduct of a guanidine compound and an epoxy resin was used.

<Comparative example 2>
In Example 1, an adhesive film was obtained in exactly the same manner as in Example 1, except that a varnish of a thermosetting resin composition to which no cobalt (II) acetylacetonate solution was added was used.

<Comparative Example 3>
In Example 1, instead of 3 parts by mass of an adduct of a guanidine compound and an epoxy resin, 5 parts by mass of dicyandiamide (10% by mass N, N-dimethylformamide solution of “JERcure DICY7” manufactured by Japan Epoxy Resin Co., Ltd.) When the varnish of the thermosetting resin composition changed to 1 was prepared, the dicyandiamide crystals were precipitated at a time exceeding 2 hours at room temperature. Could not be done.

<Comparative example 4>
In Example 1, instead of 3 parts by mass of an adduct of a guanidine compound and an epoxy resin, 1-o-tolylbiguanide (10% by mass N, N-dimethyl of “Noxeller BG” manufactured by Ouchi Shinsei Chemical Co., Ltd.) Formamide solution) When a varnish of a thermosetting resin composition changed to 10 parts by mass was produced, a gel-like material was generated when the temperature exceeded 2 hours at room temperature, and an adhesive film could not be produced.

<Preparation of samples for measuring peel strength and surface roughness>
(1) Substrate treatment of laminate board Both sides of glass cloth base epoxy resin double-sided copper-clad laminate [copper foil thickness 18μm, substrate thickness 0.3mm, Matsushita Electric Works R5715ES] on which inner layer circuit was formed The copper surface was roughened by immersing in CZ8100 manufactured by Co., Ltd.
(2) Lamination of adhesive film The adhesive films prepared in Examples and Comparative Examples were laminated on both surfaces of a laminate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
(3) Curing of resin composition The PET film was peeled from the laminated adhesive film, and the resin composition was cured under curing conditions of 100 ° C for 30 minutes and 180 ° C for 30 minutes.
(4) Roughening treatment The laminate is dipped in a swelling dip securigand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, and then the outlet of Atotech Japan Co., Ltd. as a roughening liquid. Immerse in rate compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution), and finally as a neutralizing solution, immerse in Atotech Japan Co., Ltd. Reduction Sholysin Securigant P at 40 ° C for 5 minutes did. Roughening conditions: immersed in a swelling liquid at 80 ° C. for 10 minutes and immersed in a roughening liquid at 80 ° C. for 20 minutes. About the laminated board after this roughening process, the surface roughness was measured.
(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the laminate was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing for 30 minutes at 150 ° C., an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 ± 5 μm. Next, annealing was performed at 180 ° C. for 60 minutes. About this laminated board, the peel strength of the plated copper was measured.

<Measurement of peel strength (peel strength) of plated conductor layer>
When the conductor layer of the laminate is cut into a 10 mm wide and 100 mm long part, this end is peeled off and gripped with a gripping tool, and 35 mm is peeled off vertically at a speed of 50 mm / min at room temperature. The load of was measured.
In order to verify roughening unevenness, both the peel strength on the resin composition laminated on the entire surface conductor of the inner layer circuit and the peel strength on the resin composition laminated on the entire surface substrate of the inner layer circuit were measured. It was measured.

<Measurement of surface roughness after roughening>
Using a non-contact type surface roughness meter (WYKO NT3300 manufactured by BEIKO INSTRUMENTS Co., Ltd.), an arithmetic average roughness (Ra value) was obtained from numerical values obtained by measuring the measurement range to 121 μm × 92 μm with a VSI contact mode and a 50 × lens. Moreover, it measured by calculating | requiring the average roughness of 10 points | pieces. In order to verify the uniformity of the surface roughness, the surface roughness of the insulating layer formed on the conductor layer on the surface of the inner circuit board where the entire surface is a conductor layer, and the front surface is an insulating layer. Both the surface roughness of the insulating layer formed on the underlying insulating layer on the inner layer circuit board surface were measured.

<Evaluation of linear thermal expansion coefficient>
The adhesive films obtained in Examples 1 and 2 and Comparative Examples 1, 2, and 3 were thermally cured at 190 ° C. for 90 minutes to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient from 25 ° C. to 150 ° C. in the second measurement was calculated.

The results are shown in Table 1.

From the results of Table 1, the insulating layer formed by the adhesive films obtained in Examples 1 and 2 has a low coefficient of linear thermal expansion of 40 ppm or less, and a surface roughness with a Ra value of 260 nm or less and a low roughness. It can also be seen that the conductor layer peel strength is as high as 0.6 kgf / cm or more, and the difference in roughness between the surface of the insulating layer on the conductor layer and the underlying insulating layer is small.
On the other hand, Comparative Example 1 which does not include an adduct of a guanidine compound and an epoxy resin and the curing accelerator is only a metal-based curing catalyst has a roughness between the insulating layer surface on the conductor layer and the insulating layer surface on the base insulating layer. This is a disadvantage in the formation of high-density fine wiring because the difference between the two is large and the peel strength of the conductor layer is also large. Further, in Comparative Example 2 that does not include a metal-based curing catalyst and the curing accelerator is only an adduct of a guanidine compound and an epoxy resin, both the surface of the insulating layer on the conductor layer and the base insulating layer have a large roughness. The peel strength was slightly lower. On the other hand, as in Comparative Examples 3 and 4, and when the guanidine compound itself is used instead of the adduct of the guanidine compound and the epoxy resin, an adhesive film can be produced due to poor crystallinity and storage stability. There wasn't.

Claims (12)

  A resin composition comprising (A) an epoxy resin, (B) a cyanate ester resin, (C) an adduct of a guanidine compound and an epoxy resin, and (D) a metal-based curing catalyst.   When the nonvolatile content of the resin composition is 100 mass%, the content of the component (A) is 5 to 60 mass%, the content of the component (B) is 5 to 50 mass, and the guanidine compound of the component (C) The content of the adduct body with the epoxy resin is 0.1 to 5% by mass, and the metal content based on the metal-based curing catalyst (D) is 25 to 500 ppm, and the ratio of the cyanate ester group to the epoxy group is 1 The epoxy resin composition according to claim 1, wherein the ratio is 0.4 to 1: 2.   The resin composition according to claim 1 or 2, wherein the metal-based curing catalyst is an organometallic complex or an organometallic salt of one or more metals selected from cobalt, copper, zinc, iron, nickel, manganese and tin.   The resin composition according to any one of claims 1 to 3, wherein the guanidine compound is dicyandiamide.   Further, one or more selected from polyvinyl acetal resin, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin The resin composition of any one of Claims 1-4 containing the high molecular resin.   The resin composition according to claim 5, wherein the content of the polymer resin is 1 to 20% by mass relative to the resin composition (nonvolatile content: 100% by mass).   Furthermore, the resin composition of any one of Claims 1-6 containing an inorganic filler.   The resin composition of Claim 7 whose content of an inorganic filler is 10-70 mass% with respect to a resin composition (non-volatile content 100 mass%).   The resin composition according to claim 7 or 8, wherein the inorganic filler is silica.   The adhesive film formed by carrying out the layer formation of the resin composition of any one of Claims 1-9 on a support body.   A prepreg formed by impregnating a sheet-like reinforcing base material made of fibers with the resin composition according to claim 1.   The multilayer printed wiring board by which an insulating layer is formed with the hardened | cured material of the resin composition of any one of Claims 1-9.