JP2011208150A - Modified cyanate ester based resin composition, resin film and multilayer printed wiring board using the same, and method for manufacturing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent moisture resistance, heat resistance, solvent resistance and chemical resistance, suited for a build-up lamination system, achieving low loss of a high-frequency circuit, and having excellent moldability such as a circuit filling property, and a resin film and a multilayer printed wiring board using the same.SOLUTION: The modified cyanate ester based resin composition includes (A) a cyanate ester compound, (B) phenols, (C) a polyphenylene oxide, (D) a metal compound catalyst, and (E) an epoxy resin, or (A') a modified cyanate ester based resin formed by modifying (A) with (B), (C), (D), and (E). The resin film and the multilayer printed wiring board use the resin. A method for manufacturing them is also disclosed.

Description

  The present invention relates to a modified cyanate ester resin composition used for forming an insulating layer in a printed wiring board, and also relates to a resin film and a multilayer printed wiring board obtained from the resin composition. Furthermore, this invention relates to the manufacturing method of those resin films and multilayer printed wiring boards.

  Along with the downsizing and high functionality of electronic devices, there has been a demand for a substrate material that can be used in printed wiring boards and that is thin, lightweight, and capable of high-density wiring. In recent years, a printed wiring board having a build-up laminate system having a small diameter and connecting only necessary layers with non-through holes has been developed and is rapidly spreading. The insulating layer of the build-up laminated printed wiring board is made of a heat-resistant resin that does not contain a substrate such as glass cloth, and the hole for IVH is formed by photolithography using a photosensitive resin or by heat. It is formed by a method such as thermally decomposing a curable resin with a laser processing machine.

  Furthermore, in recent years, in order to process a large amount of data at high speed, the frequency of signals has been increased in computers and information equipment terminals. As the frequency used increases, the transmission loss of electrical signals increases. In order to cope with this, there is a strong demand for the development of a printed wiring board having dielectric characteristics corresponding to higher frequencies.

  Transmission loss in high-frequency circuits is greatly affected by dielectric loss determined by the dielectric properties of the insulating layer (dielectric) around the wiring, and the dielectric constant and dielectric loss tangent (tanδ) of the printed wiring board substrate (especially insulating resin) are low. It is necessary to do. For example, in devices related to mobile communication, a substrate having a low dielectric loss tangent is strongly desired in order to reduce transmission loss in the quasi-microwave band (1 to 3 GHz) as the frequency of signals increases.

Furthermore, electronic information devices such as computers are equipped with high-speed microprocessors having an operating frequency exceeding 1 GHz, and delay of high-speed pulse signals on printed wiring boards has become a problem. In a printed wiring board, the signal delay time becomes longer in proportion to the square root of the dielectric constant ε _r of the insulator around the wiring. Therefore, a high-speed computer or the like requires a wiring board substrate having a low dielectric constant. .

  Furthermore, these wiring boards need to be resistant to the temperature and humidity of the environment in which they are used, that is, heat resistance and moisture resistance. With respect to these characteristics, a moisture resistance test using a constant temperature and humidity chamber of a pressure cooker test (PCT) and a heat resistance test of a test piece subjected to the moisture resistance test may be imposed.

  Corresponding to the above-mentioned technological trends in printed wiring boards, not only the dielectric constant and dielectric loss tangent in the high-frequency band are low, but also suitable for manufacturing the above-mentioned build-up laminated printed wiring boards, as well as heat resistance and moisture resistance. An excellent insulating film has become necessary.

  Conventionally, a polyphenylene oxide (PPO or PPE) resin, which is a heat-resistant thermoplastic resin (engineering plastic), is known as a film material having good dielectric properties. However, in order to apply to insulating materials for printed wiring boards, improvements in heat resistance that can withstand the solder connection process during mounting, solvent resistance and chemical resistance that can withstand printed wiring board manufacturing and other processes, etc. is necessary.

  Therefore, a method of modifying polyphenylene oxide with a thermosetting resin has been proposed as a method for improving heat resistance and solvent resistance. For example, as such a resin film, as disclosed in Japanese Patent Publication No. 1-53700, a curable resin composition in which polyphenylene oxide and a cyanate ester resin having the lowest dielectric constant among thermosetting resins are blended. There is a polyphenylene oxide film using a product.

  However, a film made of such a resin composition has a problem that the compatibility between the resins is poor, and a cyanate ester resin is used alone as the curable resin. Although the rate is relatively better than the other compositions described later, the dielectric loss tangent tends to be higher than the value of the dielectric constant, and the high-frequency characteristics (particularly, reduction of transmission loss) are insufficient.

  Similarly, as a resin composition using a cyanate ester-based modified resin, a resin composition of a bismaleimide / cyanate ester-modified resin and polyphenylene oxide disclosed in JP-B-63-33506, and JP-A-5-311071 are disclosed. And a resin composition of a modified phenolic resin / cyanate ester-based resin and polyphenylene oxide, which are disclosed in Japanese Laid-Open Patent Publication No. H11.

  However, the resin composition obtained by such a method is slightly compatible with polyphenylene oxide because the thermosetting resin for modifying polyphenylene oxide is a bismaleimide / cyanate ester modified resin or a modified phenol resin / cyanate ester resin. Although it becomes better, since it contains other thermosetting resin other than cyanate ester resin, the dielectric properties of the cured resin are worse than the resin modified with cyanate ester resin alone. Has further insufficient high-frequency characteristics.

  Moreover, as what improves thermostability and solvent resistance by imparting thermosetting property to a polyphenylene oxide resin which is a thermoplastic resin, it is disclosed in Japanese Patent Application Laid-Open No. 3-166225, which is crosslinked with polyphenylene oxide. A film obtained by casting a resin composition with a polymerizable polymer and / or a monomer, and a specific curable polyphenylene oxide having an unsaturated group disclosed in JP-A-7-188362 There are films that can be obtained.

  However, the method disclosed in Japanese Patent Application Laid-Open No. 3-166255 uses a crosslinkable polymer such as polytriallyl isocyanurate and styrene butadiene copolymer and / or a crosslinkable monomer such as triallyl isocyanurate. , By adding it to polyphenylene oxide, it gives thermosetting (radical polymerizability), but because the crosslinkable polymer and monomer to be blended are highly polar compounds, it is a small component that remains unreacted. Furthermore, the dielectric properties of the cured resin are poor.

  In addition, the method disclosed in JP-A-7-188362 uses a polymer in which an unsaturated group such as an allyl group is introduced into polyphenylene oxide itself. Since the polymer is mainly composed of a derivative of polyphenylene oxide, which is a thermoplastic resin, it has a high melt viscosity and, in addition, utilizes radical polymerization of unsaturated groups. As curing proceeds, the minimum melt viscosity at the time of curing is high and the rate of increase in melt viscosity is also large. Therefore, the resin cannot be sufficiently fluidized during press molding. As a result, voids are generated, the circuit filling property becomes insufficient, and the control range of the press conditions in the multi-layer bonding process is narrowed, so that the moldability is poor.

  In order to solve such a situation, the present inventors previously used a method in which a specific cyanate ester resin is modified with a monohydric phenol as a resin composition for a printed wiring board (Japanese Patent Laid-Open No. Hei 10-2010). No. 273532, Japanese Patent Laid-Open Nos. 11-124453, and 11-124453 have been proposed. According to this method, by modifying a specific cyanate ester resin with a monohydric phenol, it is possible to obtain a resin composition having excellent dielectric characteristics in a high frequency (GHz) band and particularly having a low dielectric loss tangent. However, when these resin compositions are used as a multilayer wiring board material, peeling tends to occur in a moisture resistance test under a severe environment.

  The subject of the present invention is a build-up that has good heat resistance, moisture resistance, solvent resistance, and chemical resistance in response to the above situation, and is effective for reducing the thickness, weight and density of printed wiring boards. Forming an insulating film suitable for the lamination method, low dielectric constant and dielectric loss tangent in the high frequency band, low loss of high frequency circuits, and good moldability such as heat resistance, moisture resistance and circuit fillability Curable resin composition, resin film and multilayer printed wiring board using the same, and production method thereof

The present invention
(A) a cyanate ester compound having at least two cyanato groups in one molecule;
(B) phenols;
The present invention relates to a modified cyanate ester-based resin composition comprising (C) a thermoplastic resin; and (D) an epoxy resin. In particular,
(A) is represented by the general formula [1]:

(Wherein R ₁ is

And R ₂ and R ₃ may be the same or different and each represents hydrogen or a methyl group);
A modified cyanate ester-based resin composition which is a cyanate ester compound represented by:
(B) is represented by the general formula [2]:

(Wherein R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a methyl group; and n is 1 or 2)
A modified cyanate ester-based resin composition, which is a monohydric phenol represented by:
(C) relates to a modified cyanate ester-based resin composition, which is polyphenylene oxide.

  The present invention also provides (A) a modified cyanate ester resin cyanate ester compound obtained by reacting (A) a cyanate ester compound having at least two cyanato groups in one molecule and (B) a phenol. , (C), (D) and a modified cyanate ester-based resin composition to be included together with (E).

  Furthermore, this invention relates to the resin film and multilayer printed wiring board obtained using these modified cyanate ester-type resin compositions, and their manufacturing method.

  By using the resin composition of the present invention, it is possible to produce a resin film that can be handled alone. This resin film has excellent solvent resistance, and its cured product has a low dielectric constant and dielectric loss tangent in the high frequency band. Further, when used as a multilayer wiring board material, it has moisture resistance, moldability, and solder heat resistance. In addition, since the copper foil peel strength and the like are good, it is suitable for manufacturing a printed wiring board used for a device that handles high-speed digital signals and high-frequency signals related to wireless communication, particularly by a build-up lamination method. By using the resin film of the present invention, it becomes possible to easily produce a multilayer printed wiring board suitable for increasing the speed of computers and reducing the loss of high-frequency related equipment.

  The modified cyanate ester-based resin composition of the present invention includes (A) a cyanate ester compound having at least two cyanate groups in one molecule, preferably a cyanate ester compound represented by the general formula [1]; Phenols, preferably monohydric phenols represented by the above general formula [2]; (C) thermoplastic resin, preferably polyphenylene oxide; (D) metal compound catalyst; and (E) epoxy resin as essential components It is characterized by that.

  Another type of modified cyanate ester resin composition of the present invention comprises (A) a cyanate ester compound having at least two cyanate groups in one molecule, preferably a cyanate ester compound represented by the general formula [1] (B) a phenol, preferably a (A ′) modified cyanate ester resin cyanate ester compound obtained by reacting with a monohydric phenol represented by the general formula [2], (C), (D) and ( E), and in some cases, (B) a resin composition further containing phenols.

  The (A) cyanate ester compound used in the present invention has at least two cyanate groups in one molecule, and preferably has two cyanate groups in one molecule as shown by the general formula [1]. A cyanate ester compound having a specific structure. Examples of the compound represented by the formula [1] include bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, and bis (3,5-dimethyl-4-cyanatophenyl). ) Methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene And cyanate esterified products of phenol-added dicyclopentadiene polymers. Among them, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, etc. have a balance between the dielectric properties and curability of the cured product. It is particularly preferable because it is good. Examples of cyanate ester compounds other than those represented by the general formula [1] include trimers or pentamers in which the cyanate group of these cyanate ester compounds is cyclized to form a triazine ring, and tricyanate compounds having a novolak structure. be able to. These (A) cyanate ester compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  (B) used in the present invention is a phenol and has a function of reacting with an unreacted cyanato group derived from the component (A) to lower the dielectric constant and dielectric loss tangent. Examples of the phenols include monohydric phenols such as pt-butylphenol, pt-amylphenol, pt-octylphenol, and pt-nonylphenol; catechol, resorcinol, hydroquinone, bisphenol F, and bisphenol A. And polyhydric phenols having three or more phenolic hydroxyl groups such as pyrogallol are exemplified, but monohydric phenols are preferred from the effect of lowering dielectric constant and dielectric loss tangent, and cyanate group The monovalent compound represented by the general formula [2] is highly reactive, monofunctional and has a relatively low molecular weight, excellent compatibility with cyanate ester resins, and good heat resistance. More preferred are phenols. Examples of the compound represented by the general formula [2] include p-benzylphenol and p- (α-cumyl) phenol. Such (B) phenols may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The blended amount of (B) phenols in the present invention provides a cured product having sufficient dielectric properties, and a sufficiently low dielectric loss tangent can be obtained particularly in the high frequency band. Therefore, the amount of (A) cyanate ester compound is 100 parts by weight. The amount is preferably 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, and particularly preferably 5 to 25 parts by weight.

  In the present invention, (A) cyanate ester compound and (B) monohydric phenols or phenol resin can be used as (A ′) modified cyanate ester resin obtained by reacting both. That is, it is used as a modified resin to which (B) monohydric phenols are added together with (A) prepolymerization of a cyanate ester compound. This reaction may be performed in advance before preparing the resin composition of the present invention, or may be performed in a solution of the resin composition or in any step of curing the resin composition as described below. .

  (A) When the cyanate ester compound and (B) phenol are reacted, from the initial stage of the reaction, the whole amount of (B) phenol having the above-mentioned appropriate blending amount is added and reacted, and (A ′) modification Cyanate ester resin may be used, and at the beginning of the reaction, a part of the above-mentioned appropriate blending amount is reacted, and after cooling, the remaining (B) monohydric phenol or phenol resin is added to form a B stage or cure. (A ′) A modified cyanate ester resin may be formed by reacting at the step. The reaction conditions are usually a temperature of 40 to 140 ° C.

  In the present invention, (C) a thermoplastic resin, particularly polyphenylene oxide having a good dielectric property, is blended with a modified cyanate ester resin having a good dielectric property. Cyanate ester resin and polyphenylene oxide, which are difficult to obtain a uniform resin, are obtained by the method found by the present inventors, that is, (C) a thermoplastic resin, particularly in a solvent solution of polyphenylene oxide. A uniform resin varnish for a curable film is produced by a so-called “semi-IPN” method in which a compound and (B) a phenol are reacted. Further, it is cast on one side of a copper foil or a carrier film. The compatibilized resin film can be obtained by removing the solvent by heat drying.

  (C) used in the present invention is a thermoplastic resin, and examples thereof include polyphenylene oxide, polyphenylene sulfide, polyphenylene naphthalate, and polyetherimide. Polyphenylene oxide is preferable because of excellent dielectric properties. Here, polyphenylene oxide is a polymer in which a benzene ring which may have a substituent such as an alkyl group is bonded by an ether bond, and includes those modified by polystyrene, styrene-butadiene copolymer, ABS or the like. To do. As the substituent, a methyl group is preferable. Examples of the polyphenylene oxide include poly (2,6-dimethyl-1,4-phenylene) oxide, polymer alloy of poly (2,6-dimethyl-1,4-phenylene) oxide and polystyrene, and poly (2,6 A polymer alloy of dimethyl-1,4-phenylene) oxide and a styrene-butadiene copolymer, among which a polymer alloy of poly (2,6-dimethyl-1,4-phenylene) oxide and polystyrene, and poly (2, A polymer alloy of 2,6-dimethyl-1,4-phenylene) oxide and styrene-butadiene copolymer is more preferable. The amount of poly (2,6-dimethyl-1,4-phenylene) oxide in the polymer alloy is more preferably 50% by weight or more and 65% by weight or more because the dielectric properties of the cured product are good. It is particularly preferred that

  In the present invention, (C) a thermoplastic resin, in particular, polyphenylene oxide is blended in a cured product having sufficient dielectric properties and sufficient reactivity and curability of (A) cyanate ester resin, which is a thermosetting component. In particular, since a resin film excellent in heat resistance and solvent resistance can be obtained, 5 to 500 parts by weight is preferable with respect to 100 parts by weight of (A) cyanate ester compound, more preferably 10 to 300 parts by weight, 200 parts by weight are particularly preferred.

  The (D) epoxy resin used in the present invention is a low to high molecular weight compound having two or more epoxy groups in the molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy. Resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, salicylaldehyde novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type Examples thereof include epoxy resins, hydantoin type epoxy resins and isocyanurate type epoxy resins; hydrogenated products and halides thereof; and a mixture of two or more selected from the above resins. Examples of alicyclic epoxy resins include bis (dicyclopentadiene) type dicyclopentadiene type epoxy resins and cyclohexene oxide type epoxy resins. Among these, a resin cured product having excellent molecular skeleton symmetry and excellent dielectric properties can be obtained. Therefore, bis (dicyclopentadiene) type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S Type epoxy resin is preferred.

  The blending amount of the epoxy resin (D) in the present invention is such that a cured product excellent in moisture resistance can be obtained, and an increase in the dielectric properties of the cured product, particularly the dielectric loss tangent, is suppressed. The amount is preferably 10 to 600 parts by weight, more preferably 30 to 500 parts by weight with respect to parts by weight. In the present invention, the step (E) of blending the epoxy resin may be blended in a necessary amount as an additive when producing the modified cyanate resin composition, or the modified cyanate resin composition. It may be added after the modification reaction for producing is completed. In particular, excellent dielectric properties tend to be obtained by adding after the modification reaction is completed.

  In the present invention, a metal compound catalyst (E) can be used to promote the reaction between (A) a cyanate ester compound and (B) a phenol, particularly a monohydric phenol. The (E) metal compound catalyst may be used as a reaction catalyst in the production of a resin composition containing a modified cyanate resin, and the curing is accelerated when the resin film obtained from the resin composition is cured. It may be used as an agent. As the metal compound catalyst, organic compounds containing metal atoms such as manganese, iron, cobalt, nickel, copper, and zinc are used. Specifically, octanoate, 2-ethylhexanoate, naphthenate, and the like. And metal complexes having an organic ligand such as an acetylacetone complex. The reaction accelerator for producing the modified cyanate-based resin composition and the curing accelerator for producing the laminated plate may be the same metal compound catalyst alone, or two or more different types of each. It may be used.

  In the present invention, the compounding amount of the (E) metal compound catalyst is sufficient to obtain sufficient reactivity and an appropriate curing rate, and the reaction is easy to control, and the molding is caused by insufficient fluidity during molding and curing. 1-300 ppm by weight is preferable with respect to the (A) cyanate ester compound, and 1-200 ppm by weight is more preferable. Further, in the present invention, the step of blending the metal compound catalyst (E) may be performed by collectively blending the necessary amounts as a reaction accelerator and a curing accelerator when producing a modified cyanate resin composition, When the modified cyanate resin composition is produced, an amount necessary for promotion of the modification reaction may be used, and after the reaction, the same catalyst or another metal compound catalyst may be added as a curing accelerator.

  In addition to the above essential components, the modified cyanate resin composition of the present invention may contain a flame retardant, an inorganic and organic filler, a curing accelerator, and other additives as necessary. Examples of flame retardants include brominated phenol compounds such as tribromophenol and tetrabromobisphenol A; polybromodiphenyl ethers typified by decabromodiphenyl ether; 1,2-dibromo-4- (1,2-dibromoethyl) Brominated hydrocarbons such as cyclohexane, tetrabromocyclohexane and hexabromocyclododecane; Brominated epoxy resins such as tetrabromobisphenol A type epoxy resin and brominated novolak type epoxy resin; such as brominated polystyrene and brominated polycarbonate Brominated thermoplastic resin; Brominated triphenyl cyanurate such as 2,4,6-tris (tribromophenoxy) -1,3,5-triazine and the like. Among them, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane and 2,4,6-tris (tribromophenoxy) -1,3,5- A flame retardant such as triazine is preferable because it has no reactivity with the cyanate ester compound, and thus the obtained cured product has good dielectric properties.

  The blending amount of the flame retardant in the present invention is such that a cured product having sufficient flame resistance and heat resistance is obtained, so that (A) a cyanate ester compound, (B) a monohydric phenol or phenol resin, and (C) polyphenylene oxide. 5 to 300% by weight is preferable and 5 to 200% by weight is more preferable.

  As the inorganic filler, silica, alumina, aluminum hydroxide, titanium oxide, clay, talc, silicon nitride, boron nitride, calcium carbonate, barium titanate, lead titanate, strontium titanate and the like can be used. As the organic filler, silicone resin, acrylic rubber, butadiene rubber, polybutadiene type core shell rubber, pulp, and the like can be used. The blending amount of the filler is preferably 300% by weight or less based on the total amount of the resin composition of the present invention in order to obtain a molding material having uniform and good handling properties, particularly a curable film.

  An imidazole compound, an organic phosphorus compound, a tertiary amine, a quaternary ammonium salt, or the like can be used as an epoxy resin curing accelerator.

  The blending amount of the curing accelerator exhibits a sufficient curing accelerating action and is easy to control the reaction. For example, an appropriate curing rate can be obtained, and fluidity is sufficient and good moldability can be obtained. Therefore, the range of 0.01 to 25% by weight is preferable with respect to the epoxy resin, and the range of 0.01 to 20% by weight is more preferable.

  The resin composition of the present invention can be prepared by mixing the above-mentioned components by a usual method. Each component is preferably prepared in the form of a varnish by dissolving or dispersing it in an organic solvent. Further, after each component of the resin composition of the present invention is dissolved or dispersed in a solvent to obtain a resin varnish having an active ingredient content of 10 to 70% by weight, it is applied to one side of the carrier film using a bar coater or a roll coater. The solvent is removed by heat drying and the resin film is semi-cured or usually heated to 150 to 250 ° C. to form a curable resin film (film formation).

  Examples of the solvent used in producing the above resin varnish include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as trichloroethylene and chlorobenzene; N, N-dimethylformamide, Amides such as N, N-dimethylacetamide; nitrogen-containing solvents such as N-methylpyrrolidone are used. In particular, aromatic hydrocarbons such as benzene, toluene and xylene are preferred. These solvents may be used alone or in combination of two or more. The blending amount in the case of using aromatic hydrocarbons as a solvent is preferably 25 to 900% by weight, more preferably 40 to 600% by weight, and particularly preferably 40 to 400% by weight with respect to the total amount of the resin composition.

  Moreover, when a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone is used in combination with the above aromatic hydrocarbon solvent, the varnish becomes a suspension solution, but a higher concentration solution is obtained. There are advantages. However, if the amount of the ketone solvent is too large, the resin composition may be separated and settled. Therefore, the amount of the ketone solvent is preferably 250% by weight or less based on the aromatic hydrocarbon solvent.

  The carrier film used for forming the resin film may be a metal foil such as copper or aluminum; a resin film such as polyester or polyimide; or a surface of these carrier films coated with a release agent. it can. It is preferable to perform a release agent treatment on the carrier film in order to improve workability when peeling the curable film from the carrier film or peeling the carrier film after laminating the film with the carrier on the substrate.

  Hereinafter, a copper foil is described as an example of a metal foil, and a copper-clad laminate is described as an example of a metal-clad laminate. These descriptions also apply when a metal other than copper, for example, aluminum is used.

  As for the curable film in which the insulating resin layer is formed on one side of the carrier film as described above, for example, a sheet-like resin from which the carrier film is removed is used or a plurality of sheets are laminated, and copper foil is formed on the upper and lower sides thereof. By laminating and press-molding, a copper-clad laminate for printed wiring boards can be produced. The press molding conditions are usually a temperature of 150 to 250 ° C., a pressure of 0.1 to 5 MPa, and a time of 0.5 to 5 hours.

  Moreover, after apply | coating resin varnish to the single side | surface of copper foil using a bar coater, a roll coater, etc., a solvent is removed by heat drying and it can also be set as the resin film with copper foil. The thickness of the resin layer is usually 1 to 300 μm. The resin film with copper foil has an advantage that the copper foil can be used as a circuit conductor as it is when a circuit is formed on the insulating layer.

  A copper foil for printed wiring boards is formed by, for example, laminating a resin film with a copper foil so as to match the resin layers, and if necessary, interposing one or more resin films from which the carrier film has been removed. A tension laminate can be manufactured.

  Also, after forming a circuit on a conventional glass cloth base copper clad laminate or the above copper clad laminate, one or more resin films from which the carrier film has been removed are laminated, and a copper foil or copper foil is further laminated thereon. A substrate for a multilayer wiring board can be manufactured by arranging a press-attached resin film and press-molding, or placing a resin film with a copper foil and press-molding.

  In addition, after forming a circuit on a conventional copper-clad laminate of glass cloth base or the above-mentioned copper-clad laminate, the resin varnish is applied and heated and dried, and then a copper foil is placed thereon and press molded. By doing so, a substrate for a multilayer wiring board can also be manufactured. Furthermore, after forming a circuit on a conventional copper-clad laminate of glass cloth substrate or the above-mentioned copper-clad laminate, one or more of the above resin films are laminated and plated to provide a multilayer wiring board. The substrate can also be manufactured.

  Note that a conventional method can be applied to the formation of the circuit. For example, through holes or non-through holes are drilled on a copper-clad laminate or multilayer wiring board substrate as necessary, then electroless plating or electroplating is applied to make the inner walls of the holes conductive, and then the conduction hole portions are protected, A circuit can be formed by a process such as formation of an etching resist and removal of copper in a non-wiring portion by etching.

  Further, in the curable resin film of the present invention, drilling or laser processing can be employed as a method for forming a through hole or a non-through hole. In the case of laser processing, laser drilling can be performed by a direct imaging method in which holes are formed directly by laser shot, or a conformal mask method using a metal mask or the like. An example of a curable film obtained in the present invention, a metal foil with a resin using a copper foil as a carrier film, using as a mask a copper foil in which a place where a through hole or a non-through hole is to be formed is removed in advance by etching. Laser drilling can be performed.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by these examples. A film-forming varnish was prepared from the raw materials and blending amounts shown in Table 1, semi-cured resin films were prepared, and each evaluation was performed.

Example 1
A four-necked separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 270 g of toluene and 70 g of polyphenylene oxide (Nonyl PKN4752, a trade name of GE Plastics, Inc.) and heated to 80 ° C. while stirring. Dissolved. Next, 140 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, trade name of Asahi Ciba Co., Ltd.) and 8 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) were added. After dissolution, 0.4 g of a solution obtained by diluting manganese naphthenate (Mn content 6% by weight, trade name, Nippon Chemical Industry Co., Ltd.) with toluene to a Mn content of 0.6% by weight is added, and the reaction is performed at reflux temperature for 3 hours. I let you. Then, it cools to room temperature, 140 g of dicyclopentadiene type epoxy resins (HP-7200H, Dainippon Ink Chemical Co., Ltd. trade name) and imidazole curing accelerators (Curesol 2MZ-CNS, trade name of Shikoku Kasei Co., Ltd.) 6 g was added and stirred for 1 hour to prepare a resin varnish for film formation (solid content concentration 45% by weight).

  This resin varnish is applied to a polyethylene terephthalate (PET) film (Purex A-63, Teijin product name) with a release agent of 50 μm in thickness using a comma coater (manufactured by Hirano Techseed Co., Ltd.) which is a type of bar coater. It was applied and dried (140 ° C.) to prepare a resin film with a carrier film having a resin layer thickness of 30 to 33 μm. The obtained resin film was excellent in handleability because it did not crack or fall off even when cut with a cutter knife.

Example 2
A four-neck separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 300 g of toluene and 70 g of polyphenylene oxide (Nonyl PKN4752, a trade name of Nippon GE Plastics Co., Ltd.) and heated to 80 ° C. while stirring. Dissolved. Next, 230 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, trade name of Asahi Ciba Co., Ltd.) and 5 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) were added. After dissolution, 0.5 g of a solution obtained by diluting manganese naphthenate (Mn content: 6% by weight, trade name, Nippon Chemical Industry Co., Ltd.) with toluene to a Mn content of 0.6% by weight is added, and the reaction is performed at reflux temperature for 6 hours. I let you. After further cooling to room temperature, 21 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) and 230 g of polyfunctional epoxy resin (Epicoat 1031, trade name of Yuka Shell Epoxy Co., Ltd.) are added and dissolved. Thus, a resin varnish for film molding (solid content concentration: 36% by weight) was prepared.

  Using this varnish, a resin film with a carrier film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. The obtained resin film was excellent in handleability because it did not crack or fall off even when cut with a cutter knife.

Example 3
A four-necked separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 400 g of toluene and 100 g of polyphenylene oxide (Nonyl PKN4752, a trade name of Nippon GE Plastics Co., Ltd.) and heated to 80 ° C. while stirring. Dissolved. Next, 67 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, trade name of Asahi Ciba Co., Ltd.) and 8 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) were added. After dissolution, 0.3 g of a solution obtained by diluting cobalt naphthenate (Co content: 8% by weight, trade name of Nippon Chemical Industry Co., Ltd.) with toluene to 0.8% by weight of Co is added and reacted at reflux temperature for 2 hours. I let you. After cooling the reaction solution to room temperature, 60 g of o-cresol novolac type epoxy resin (ESCN-190-3, trade name of Sumitomo Chemical Co., Ltd.) is added, and the mixture is stirred and dissolved to obtain a resin varnish for film molding ( A solid content concentration of 37% by weight) was prepared.

  Using this varnish, a resin film with a carrier film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. The obtained resin film was excellent in handleability because it did not crack or fall off even when cut with a cutter knife.

Example 4
A four-necked separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 230 g of toluene and 75 g of polyphenylene oxide (Nonyl PKN4752, a trade name of Nippon GE Plastics Co., Ltd.) and heated to 80 ° C. while stirring. Dissolved. Next, 75 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, trade name of Asahi Ciba Co., Ltd.) and 5 g of p- (α-cumyl) phenol (manufactured by Sun Techno Chemical Co., Ltd.) are added and dissolved. After that, 0.2 g of a solution obtained by diluting manganese naphthenate (Mn content: 6% by weight, trade name, Nippon Chemical Industry Co., Ltd.) with toluene to a Mn content of 0.6% by weight was added and reacted at reflux temperature for 6 hours. It was. After further cooling to room temperature, 200 g of toluene, 3 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.), 80 g of dicyclopentadiene type epoxy resin (HP-7200, trade name of Dainippon Ink & Chemicals, Inc.) Then, 4 g of an imidazole-based curing catalyst was added and dissolved to prepare a resin varnish for film forming (solid content concentration: 40% by weight).

  Using this varnish, a resin film with a carrier film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. The obtained resin film was excellent in handleability because it did not crack or fall off even when cut with a cutter knife.

Example 5
A four-necked separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 200 g of toluene and 30 g of polyphenylene oxide (Nonyl PKN4752, a trade name of Nippon GE Plastics Co., Ltd.), and heated to 80 ° C. while stirring. Dissolved. Next, 100 g of bis (3,5-dimethyl-4-cyanatophenyl) methane (Arocy M-10, trade name of Asahi Ciba Co., Ltd.) and 2 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) are added. After dissolution, 0.2 g of a solution obtained by diluting manganese naphthenate (Mn content: 6% by weight, trade name, Nippon Chemical Industry Co., Ltd.) with toluene to a Mn content of 0.6% by weight was added, and the mixture was refluxed at 5%. Reacted for hours. Subsequently, the reaction solution was cooled, and when the internal temperature reached 90 ° C., 100 g of methyl ethyl ketone (MEK) was added and suspended while stirring. After cooling the reaction solution to room temperature, 2 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.), cobalt naphthenate (Co content 8 wt%, trade name of Nippon Chemical Industry Co., Ltd.), toluene and Co content. By adding 0.2 g of a solution diluted to 0.8% by weight, and then adding 110 g of salicylaldehyde novolak type epoxy resin (EPPN502, Nippon Kayaku Co., Ltd., trade name) and 1 g of imidazole, and stirring to dissolve, A film-forming resin varnish (solid content concentration: 45% by weight) was prepared.

  Using this varnish, a resin film with a carrier layer thickness of 30 to 33 μm was prepared in the same manner as in Example 1. The obtained resin film was excellent in handleability because it did not crack or fall off even when cut with a cutter knife.

Comparative Example 1
A four-necked separable flask equipped with a thermometer, a condenser, and a stirrer is charged with 360 g of toluene and 120 g of polyphenylene oxide (Nonyl PKN4752, a trade name of GE Plastics, Inc.) and heated to 80 ° C. while stirring. It melt | dissolved and the resin varnish for film forming (solid content concentration of 25 weight%) was prepared. Using this varnish, a resin film with a carrier film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. The obtained resin film was excellent in handleability because it did not crack or fall off even when cut with a cutter knife.

Comparative Example 2
In a four-necked separable flask equipped with a thermometer, a condenser, and a stirrer, 240 g of methyl ethyl ketone, 120 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, Asahi Ciba Co., Ltd. trade name) and p -(Α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) 2 g was charged and dissolved by stirring, and then cobalt naphthenate (Co content 8% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd.) with toluene was allowed to have a Co content of 0. 1.2 g of a solution diluted to 8% by weight was added and reacted at reflux temperature for 2 hours. After cooling to room temperature, 10 g of dicyclopentadiene type epoxy resin (HP-7200, trade name of Dainippon Ink and Chemicals, Inc.) and 1 g of imidazole-based curing catalyst are added and dissolved by stirring to form a film-forming resin. A varnish (solid concentration: 36% by weight) was prepared. Using this varnish, a resin film with a carrier film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. When the obtained resin film was cut with a cutter knife, resin cracking and powder falling occurred, and when the carrier film was peeled off, the resin film could not be handled alone.

Comparative Example 3
A four-neck separable flask equipped with a thermometer, a condenser, and a stirrer was charged with 300 g of toluene and 70 g of polyphenylene oxide (Nonyl PKN4752, a trade name of Nippon GE Plastics Co., Ltd.) and heated to 80 ° C. while stirring. Dissolved. Next, 230 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, trade name of Asahi Ciba Co., Ltd.) and 5 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) were added. After dissolution, 0.5 g of a solution obtained by diluting manganese naphthenate (Mn content: 6% by weight, trade name, Nippon Kagaku Sangyo Co., Ltd.) with toluene to a Mn content of 0.6 parts by weight was added and reacted at reflux temperature for 6 hours. It was. After further cooling to room temperature, 21 g of p- (α-cumyl) phenol (trade name of Sun Techno Chemical Co., Ltd.) and cobalt naphthenate (Co content 8 wt%, trade name of Nippon Chemical Industry Co., Ltd.) with toluene are used as Co components. A resin varnish for forming a film (solid content concentration = 35% by weight) was prepared by adding and dissolving 1.2 g of a solution diluted to 0.8% by weight and 300 g of toluene. Using this varnish, a resin film with a carrier film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. The obtained resin film was excellent in handleability because it did not crack or fall off even when cut with a cutter knife.

Comparative Example 4
In a 4-neck separable flask equipped with a thermometer, a condenser, and a stirrer, 100 g of toluene, 400 g of dicyclopentadiene type epoxy resin (HP-7200, trade name of Dainippon Ink and Chemicals) and 5 g of imidazole-based curing catalyst Was heated and dissolved at 80 ° C. with stirring to prepare a resin varnish for film forming (solid content concentration 80% by weight). Using this varnish, a resin film with a carrier film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. When the obtained resin film was cut with a cutter knife, resin cracking and powder falling occurred, and when the carrier film was peeled off, the resin film could not be handled alone.

  Table 1 summarizes the raw materials used in Examples 1 to 5 and Comparative Examples 1 to 4.

The contents of the raw materials indicated by abbreviations in Table 1 are as follows.
(A) B-10: 2,2-bis (4-cyanatophenyl) propane (trade name of Asahi Ciba Co., Ltd.);
M-10: Bis (3,5-dimethyl-4-cyanatophenyl) methane (trade name of Asahi Ciba Co., Ltd.);
B-30: 2,2-bis (4-cyanatophenyl) propane oligomer (trade name of Asahi Ciba Co., Ltd.);
(B) PCP: p- (α-cumyl) phenol (manufactured by Sun Techno Chemical Co., Ltd.) (trade name of Asahi Ciba Co., Ltd.);
(C) PPO: polyphenylene oxide (nonyl PKN4752, trade name of GE Plastics, Inc.);
(D) HP: dicyclopentadiene type epoxy resin (HP-7200, trade name of Dainippon Ink & Chemicals, Inc.);
HP-H: dicyclopentadiene type epoxy resin (HP-7200H, trade name of Dainippon Ink & Chemicals, Inc.);
1031: polyfunctional epoxy resin (Epicoat 1031, trade name of Yuka Shell Epoxy Co., Ltd.);
ESCN: o-cresol novolac type epoxy resin (ESCN-190-3, trade name of Sumitomo Chemical Co., Ltd.);
502: Salicylaldehyde novolak type epoxy resin (EPPN502, Nippon Kayaku Co., Ltd. trade name);
(E) Co: Cobalt naphthenate (Co content: 8% by weight, trade name of Nippon Chemical Industry Co., Ltd.) is used as a toluene diluted solution having a Co content of 0.8% by weight;
Mn: Manganese naphthenate (Mn content: 6% by weight, trade name of Nippon Chemical Industry Co., Ltd.) was used as a toluene diluted solution with a Mn content of 0.6% by weight.

  Next, for the resin films with a carrier film of Examples 1 to 5, the handling property of the resin film alone and the solvent resistance of the cured film were evaluated.

Evaluation of handleability Each carrier film was peeled from each of the resin films with a carrier film obtained in Examples 1 to 5, and 12 sheets of the obtained resin films were stacked. And then press-molded at 200 ° C. and 1.5 MPa for 1 hour to produce a cured resin film having a thickness of about 0.4 mm.

  A resin molded film was produced from the resin film with a carrier film obtained in Comparative Example 1 in the same manner as the resin films with a carrier film in Examples 1 to 5. Similarly, the resin films of Comparative Examples 2 to 4 were press-molded to produce respective cured resin films. However, since the resin film with the carrier film of Comparative Example 2 is a film of the cyanate ester resin alone, when the carrier film is peeled off, the resin film itself is fragile and cracks, and the film is handled alone. I could not. As a result, a cured resin film could not be produced. Moreover, since the resin film layer of the resin film with a carrier film of the comparative example 4 is a film made of an epoxy resin alone, the resin film itself is also fragile and cracks, and the resin cured film cannot be handled alone. It could not be produced.

Evaluation of solvent resistance The cured resin film obtained as described above was cut into 50 mm squares, immersed in toluene, and allowed to stand at room temperature for 60 minutes. In the cured resin films of Examples 1 to 5, neither swelling nor appearance change was observed. Moreover, although the surface of the resin cured film of Examples 1-5 prepared separately was rubbed several times with the cloth containing toluene or methyl ethyl ketone, the presence or absence of abnormality of the film surface was observed. No surface abnormality was observed. From the above, it was confirmed that the cured resin films of Examples 1 to 5 had good solvent resistance.

  However, the resin molded film of Comparative Example 1 was cut into 50 mm squares, immersed in toluene, and allowed to stand at room temperature for 60 minutes. As a result, the resin molded film of polyphenylene oxide alone swelled and partly dissolved. Oops. Further, when the surface of another resin molded film was rubbed several times with a cloth containing toluene, the surface of the film melted and stickiness was generated. Moreover, when the surface of another resin molded film was rubbed several times with a cloth containing methyl ethyl ketone, the film was cracked (cracked), and finally it was perforated and cut.

  From the above results, it was confirmed that the polyphenylene oxide-modified cyanate ester resin film of the present invention can be handled alone as a film and has good solvent resistance.

Evaluation of Dielectric Properties, Glass Transition Temperature, and Tensile Elastic Modulus Next, for cured products of resin films using the resin varnishes for curable films obtained in Examples 1 to 5 and Comparative Example 3, dielectric properties in the gigahertz band The glass transition temperature and the tensile modulus were evaluated.

  The cured resin from which the copper foil was completely removed by chemical etching was measured for dielectric constant and dielectric loss tangent at 1 GHz using an RF impedance / material analyzer (manufactured by Agilent Technologies, HP 4291B). Further, a test piece was cut out from a cured resin obtained by completely removing the copper foil by chemical etching, and using a wide area viscoelasticity measuring device (DVE manufactured by Rheology Co., Ltd.), a tensile mode (frequency: 10 Hz, temperature increase: 5 The glass transition temperature (Tg) and the tensile modulus at 40 ° C. were measured at (° C./min). The results are shown in Table 2.

  From Table 2, since the resin film using the modified cyanate ester resin of the present invention is reacted with specific monohydric phenols, the cyanate ester has a low dielectric property, particularly a dielectric loss tangent. It could be confirmed.

Preparation and Evaluation of Multilayer Wiring Board Next, using each of the resin varnishes obtained in Examples 1 to 5 and Comparative Example 3, a resin film with a copper foil was prepared, and the characteristics as a multilayer material for printed wiring boards were evaluated. did.

  The resin varnishes obtained in Examples 1 to 5 and Comparative Example 3 were coated on a roughened surface of an electrolytic copper foil having a thickness of 18 μm using a comma coater (manufactured by Hirano Techseed Co., Ltd.) which is a kind of bar coater. The resin film with a copper foil having a resin layer thickness of 60 to 70 μm was prepared by drying at 2 ° C. for 2 minutes. None of the obtained resin films were excellent in handleability because they did not crack or fall off even when cut with a cutter knife.

  Subsequently, the resin film with copper foil is formed on both surfaces of the inner layer circuit board (base material thickness: 0.1 mm) of the glass cloth base material on which the surface-treated conductor circuit (copper foil thickness for circuit; 18 μm) is formed. Were stacked so that the resin layer was in contact with the inner layer circuit, and press molded at 200 ° C. and 2.5 MPa for 60 minutes to produce a four-layer wiring board.

The four-layer printed wiring board thus obtained was evaluated for moisture resistance, solder heat resistance, and copper foil peel strength by the following methods. The results are shown in Table 3.
<Characteristic evaluation method>
Moldability: The outer layer copper of the four-layer wiring board was completely removed by chemical etching, and the resin filling property (the presence or absence of voids or creaking) of the inner layer circuit was visually determined.
-Moisture resistance: The copper foil of the outer layer of the four-layer wiring board is completely removed by chemical etching, and the cured resin product after 192 hours has been loaded into a pressure cooker tester at 121 ° C and 2.1 atm. And the adhesiveness between the inner layer copper foil surfaces were observed.
Solder heat resistance: A 25 mm square four-layer plate with an outer layer copper foil was floated on 260 ° C. molten solder, and the time until blistering was measured.
Copper foil peel strength: measured in accordance with JIS C6481.

  As shown in Table 3, the four-layer wiring board using the resin film with copper foil obtained from the resin varnishes of Examples 1 to 5 had high moisture resistance without causing peeling by the pressure cooker test. On the other hand, the wiring board using the resin film obtained from the resin varnish of Comparative Example 3 was found to be peeled off in the pressure cooker test and was inferior in moisture resistance. As a result, it was confirmed that the resin film with copper foil of the present invention had high moisture resistance when used as a wiring board. Further, these resin films had good moldability as a multilayer wiring board material. Furthermore, the 4-layer wiring board using the resin film with copper foil of the present invention obtained by curing the cyanate ester resin with a specific monohydric phenol compound by the resin composition of the present invention reacts with It was confirmed that the heat resistance of the solder was good and that it had the same characteristics as those of the prepreg for bonding using a conventional glass cloth as a base material.

  The dielectric properties of polymer materials and the like are greatly influenced by the orientation polarization of the dipole. Therefore, the dielectric constant can be lowered by reducing the polar groups in the molecule, and the dielectric loss tangent can be lowered by suppressing the mobility of the polar groups. Cyanate ester resin has a highly polar cyanate group, but generates a symmetric and rigid triazine structure upon curing. Therefore, the cured product has the lowest dielectric constant and dielectric loss tangent as a thermosetting resin. Is obtained.

  However, in the actual curing reaction, it is impossible for all cyanate groups in the cyanate ester resin to react to form a triazine structure, and as the curing reaction proceeds, the reaction system loses fluidity. , It remains in the system as an unreacted cyanato group. As a result, with the conventional cyanate ester resins, only cured products having a higher dielectric constant and dielectric loss tangent than the properties that the original cured product should exhibit were obtained.

  On the other hand, in the resin composition of the present invention, (B) phenols, in particular, monohydric phenols represented by the general formula [2] are blended in an appropriate amount with respect to (A) cyanate ester resin. It was possible to reduce the dielectric constant and dielectric loss tangent of the cured product to their original values by converting the unreacted remaining cyanate group to imide carbonate and reducing its polarity.

  Conventionally, phenol compounds such as nonylphenol are sometimes used in an amount of about 1 to 2 parts by weight per 100 parts by weight of cyanate ester as a cocatalyst for the trimerization reaction of cyanate ester (generation of triazine ring). However, since the blending amount was a catalyst amount, the effect of reacting with the unreacted cyanato group as described above to lower the polarity was not recognized. On the other hand, as a result of studying the blending amount of the phenolic compound by the present inventors, when the phenolic compound is blended in a larger amount than the conventional catalyst amount, it is recognized that the dielectric constant and the dielectric loss tangent of the cured product are reduced, And when specific monohydric phenols were used, it discovered that the fall of the heat resistance by the compounding quantity increase could also be suppressed. Therefore, according to the method of the present invention, conventional cured products of cyanate ester resins alone, as well as conventional epoxy resins and polyhydric phenols (since some of these hydroxyl groups tend to remain as unreacted groups, the dielectric properties Or a cured product having a lower dielectric constant and dielectric loss tangent than a cured product of a resin blended with bismaleimide or the like.

  By the way, the insulating material for wiring boards is desired to have a low water absorption rate of the resin material, and it is necessary to maintain the adhesive force even after humidification. This is a characteristic that takes into account the manufacturing process and use environment of electronic equipment, and high humidity resistance is required as represented by an accelerated test using a constant temperature and constant temperature layer such as a pressure cooker as a moisture resistance test. . In the present invention, it is possible to provide a novel resin composition having high moisture resistance and low dielectric constant and dielectric loss tangent by adding an epoxy resin to the modified cyanate ester resin. This can be cast coated on one side of a copper foil or carrier film, and the solvent can be removed by heat drying to obtain a compatible resin film.

  Since the film obtained from the modified cyanate ester-based curable resin composition of the present invention is particularly excellent in high-frequency characteristics, printing such as high-speed computers equipped with wireless communication-related terminal devices, antennas, and high clock frequency microprocessors, etc. Suitable for manufacturing for wiring boards.

  Furthermore, by not including a substrate such as glass cloth in the wiring board from the film of the present invention, the printed wiring board can be made thinner and lighter, and IVH (interstitial via) can be formed by a build-up lamination method. Provided are a heat-resistant insulating varnish and a film that can be easily formed with a connection hole having a (hole) structure and are effective in increasing the density of wiring.

Claims (19)

(A) a cyanate ester compound having at least two cyanato groups in one molecule;
(B) phenols;
(C) a thermoplastic resin; and (D) a modified cyanate ester-based resin composition comprising an epoxy resin. (A) is represented by the general formula [1]:

(Wherein R ₁ is

And R ₂ and R ₃ may be the same or different and each represents hydrogen or a methyl group);
The resin composition of Claim 1 which is a cyanate ester compound shown by these. (B) is represented by the general formula [2]:

(Wherein R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a methyl group; and n is 1 or 2)
The resin composition of Claim 1 or 2 which is monohydric phenol shown by these.   The resin composition according to any one of claims 1 to 3, wherein (C) is polyphenylene oxide.   (A) The resin composition of any one of Claims 1-4 whose quantity of (B) phenols is 4-30 weight part with respect to 100 weight part of cyanate ester compounds.   (A) The cyanate ester compound is any one of 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, or a mixture thereof. The resin composition according to any one of claims 1 to 5, wherein (A ′) a modified cyanate ester resin obtained by reacting a cyanate ester compound having at least two cyanato groups in one molecule with phenols;
A modified cyanate ester-based resin composition comprising (C) a thermoplastic resin; and (D) an epoxy resin, and optionally (B) a phenol.   (B) The resin composition of any one of Claims 1-7 whose phenols are p-((alpha) -cumyl) phenol.   (C) Polyphenylene oxide is a polymer alloy containing poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene or styrene-butadiene copolymer, of which poly (2,6-dimethyl-1,4 The resin composition according to any one of claims 1 to 8, wherein -phenylene) ether is 50% by weight or more.   (D) The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, salicylaldehyde novolak type epoxy resin. Bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, dicyclopentadiene type epoxy resin, hydantoin type epoxy resin and isocyanurate type epoxy resin; and hydrogenation thereof The resin composition of any one of Claims 1-9 which is 1 type, or 2 or more types chosen from the group which consists of a thing and a halide.   Furthermore, the resin composition of any one of Claims 1-10 containing (E) metal compound catalyst.   (E) The metal compound catalyst is one or more selected from octanoate, 2-ethylhexanoate, naphthenate and acetylacetone complex of manganese, iron, cobalt, nickel, copper and zinc, Item 11. The resin composition according to Item 11.   (A) The resin composition of any one of Claims 1-11 whose quantity of (D) epoxy resin is 10-600 weight part with respect to 100 weight part of cyanate ester compounds.   A modified cyanate ester-based resin film obtained by semi-curing or curing an insulating varnish containing the resin composition according to claim 1.   The resin film with metal foil produced by the method including the process of carrying out the cast application of the varnish containing the resin composition of any one of Claims 1-13 on the single side | surface of metal foil.   The resin film according to claim 14 or the resin film with metal foil according to claim 15 is laminated with a wiring board on which an inner layer circuit has been formed in advance, and then a circuit is formed on the outer layer surface to electrically connect the circuit and the inner layer circuit. Multi-layer printed wiring board made by conducting to.   A method for producing a resin film, comprising forming a varnish containing the resin composition according to any one of claims 1 to 13 by a method comprising a step of casting and applying the varnish to one side of a carrier film.   A method for producing a resin film, comprising forming a varnish containing the resin composition according to any one of claims 1 to 13 by a method including a step of casting and applying the varnish to one side of a metal foil.   A varnish containing the resin composition according to any one of claims 1 to 13 is formed and cured by a method including a step of applying the varnish to a wiring board on which an inner layer circuit has been formed in advance to form a circuit on the outer layer surface. A method for producing a multilayer printed wiring board, comprising electrically connecting the circuit to an inner layer circuit.