JP2003128784A - Flame-retardant thermosetting resin composition, prepreg, electrical insulation film, laminated board, resin-coated metallic foil and multilayer wiring board, and method for producing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant thermosetting resin composition including a flame-retardant cyanate resin with no concern such as deterioration in heat resistance and moldability and the contamination of liquid chemicals in a wiring board manufacturing process by flame retarding the corresponding cyanate resin with excellent dielectric properties without using any bromine-based flame retardant, and to provide electrical insulation films, resin-coated metallic foils and multilayer printed wiring boards each using the composition. SOLUTION: This flame-retardant thermosetting resin composition comprises (A) a bifunctional cyanate ester compound and (B) a reactive phosphorus compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant thermosetting resin composition, a prepreg, an insulating film, a laminate, a metal foil with resin, a multilayer wiring board, and a method for producing the same.

[0002]

2. Description of the Related Art In recent printed circuit boards, in order to shorten the signal propagation delay time and the dielectric loss,
There is a demand for a resin having a low dielectric constant. Due to these requirements, cyanate resins having excellent dielectric properties have been used as materials for printed wiring boards, and various companies have proposed methods of using cyanate resins as materials for printed wiring boards.

In order to use a cyanate resin as a material for printed wiring boards, it is necessary to impart flame retardancy, and normally a bromine compound having high flame retardancy is used. For example, in Japanese Patent Publication No. 4-24370, brominated bisphenol A
And a hydroxy ether of brominated bisphenol A,
JP-A-2-286723 discloses brominated phenol novolac glycidyl ether, and JP-A-5-339342 discloses brominated bisphenol A glycidyl ether.
In -207022, brominated maleimides, JP-A-2000-2000
In -95938, an addition type bromine compound having no reactivity with a cyanate ester compound is used. Although such a bromine compound has high flame retardancy, in recent years, a material made flame-retardant without using such a brominated flame retardant has been required as an environmental measure.

The flame retardants used in flame-retardant epoxy resins instead of bromine compounds include metal hydroxides such as aluminum hydroxide and magnesium hydroxide. However, the compounding of metal oxides has a potential problem of deterioration of dielectric properties, heat resistance, impact resistance and moldability as described above. Phosphorus compounds such as triphenyl phosphate and resorcinol bis (diphenyl phosphate) are also often added to epoxy resins as flame retardants replacing bromine compounds. However, if these phosphorus compounds are blended in a large amount, heat resistance,
In many cases, moisture resistance and water absorption are reduced. In addition, since the flame-retardant effect is often low with respect to the epoxy resin that is generally used as a multilayer wiring board material, it is difficult to make it flame-retardant only with a phosphorus compound. A method of using a metal hydroxide and a phosphorus compound in combination has been often used for flame retarding the composition.

[0005]

An object of the present invention is to make a cyanate resin having excellent dielectric properties flame-retardant without using a brominated flame retardant, and further reduce heat resistance and moldability, and a chemical liquid in a wiring board manufacturing process. (EN) Provided are a thermosetting resin composition containing a flame-retardant cyanate resin, which is free from concerns such as contamination, and an insulating film, a resin-coated metal foil and a multilayer printed wiring board using the composition.

[0006]

The present invention relates to the items described below. (1) A thermosetting resin composition comprising (A) a divalent cyanate ester compound and (B) a reactive phosphorus compound. (2) The divalent cyanate ester compound (A) has the general formula [1]:

[Chemical 7] (In the formula, R ₁ is

[Chemical 8] R ₂ and R _{3, which} may be the same or different, each represent a hydrogen atom or a methyl group. ] The thermosetting resin composition as described in (1) which is a cyanate ester compound shown by these. (3) The thermosetting resin composition according to (1) or (2), which contains a phosphorus compound having a phenolic hydroxyl group as the reactive phosphorus compound.

(4) The phosphorus compound having a phenolic hydroxyl group is represented by the formula [2] or the formula [3]:

[Chemical 9]

[Chemical 10] (In the formula, R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.) The thermosetting resin composition according to (3), which is a phosphorus compound. (5) The thermosetting resin composition according to (2) to (4), which contains a phosphorus-containing epoxy resin as the reactive phosphorus compound. (6) The thermosetting resin composition according to (5), wherein the phosphorus-containing epoxy resin is a phosphorus-containing epoxy resin obtained by reacting a phosphorus compound having a phenolic hydroxyl group with the epoxy resin.

(7) The phosphorus compound having a phenolic hydroxyl group is represented by the formula [2] or the formula [3]:

[Chemical 11]

[Chemical 12] (In the formula, R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.) The thermosetting resin composition according to (6), which is a phosphorus compound. (8) The thermosetting resin composition according to (6) or (7), wherein the epoxy resin reacted with the phosphorus compound to produce a phosphorus-containing epoxy resin is a polyfunctional epoxy resin.

(9) The thermosetting resin composition further comprises epoxy resin other than phosphorus-containing epoxy resin, phenol resin, alkyd resin, polyester resin, polyimide resin, polyurethane resin, silicone resin, bismaleimide resin, vinyl resin, benzo. The thermosetting resin composition according to any one of (8), which is a thermosetting resin composition containing a thermosetting resin selected from the group consisting of cyclobutene resins. (10) The thermosetting resin composition according to (9), wherein the thermosetting resin is an epoxy resin having a biphenyl skeleton. (11) A thermosetting resin composition in which the thermosetting resin composition further contains a thermoplastic resin selected from the group consisting of fluororesin, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyetherimide, polyetheretherketone, and polyarylate. It is a thing (1)
The thermosetting resin composition according to any one of to (10).

(12) The thermosetting resin composition according to (11), wherein the thermoplastic resin is polyphenylene ether. (13) The equivalent ratio of the cyanato group to the phenolic hydroxyl group (phenolic hydroxyl group / cyanato group) in the thermosetting resin composition is 5/100 to 100/100, (1) to
The thermosetting resin composition as described in (12). (14) The equivalent ratio of the cyanato group to the epoxy group (epoxy resin / cyanate ester compound) in the thermosetting resin composition is 10/100 to 200/100, (1)
The thermosetting resin composition according to any one of to (13). (15) The thermosetting resin composition contains a cyanate ester compound and a polyphenylene ether, and the weight ratio of the cyanate ester compound and the polyphenylene ether (polyphenylene ether / cyanate ester compound) is 5 /.
The thermosetting resin composition according to any one of (1) to (14), which is 100 to 200/100.

(16) A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition according to any one of (1) to (15). (17) A laminated plate formed by laminating the prepreg according to (16). (18) An insulating film obtained by applying the thermosetting resin composition according to any one of (1) to (15) to a support film. (19) A resin-coated metal foil obtained by applying the thermosetting resin composition according to any one of (1) to (15) to a metal foil.

(20) A multilayer wiring board having an insulating layer made of the thermosetting resin composition according to any one of (1) to (15). (21) Manufacture of a multilayer wiring board, characterized in that the insulating film according to (18) is laminated and integrated on a circuit surface of an inner layer circuit board to form an insulating resin layer, and a circuit is formed on the insulating resin layer. Method. (22) A multilayer wiring board, characterized in that the metal foil with resin according to (19) is laminated and integrated on the circuit surface of the inner layer circuit board, and the metal layer derived from the metal foil with resin is subjected to circuit processing. Manufacturing method.

[0013]

According to the present invention, it is difficult to introduce a phosphorus atom into a resin skeleton by using a cyanate ester compound and a reactive phosphorus compound having a functional group such as a phenolic hydroxyl group and an epoxy group. A flammable cyanate resin can be obtained. This resin can be made flame-retardant without using a brominated flame retardant. Further, since the phosphorus atom is introduced into the resin skeleton, there is no concern about chemical contamination in the wiring board manufacturing process. In other words, when using an additive type phosphorus compound that does not have a reactive group, such as triphenyl phosphate or resorcinol bis (diphenyl phosphate), the phosphorus compound may be used as a chemical solution used during the wiring board manufacturing process. There is no need to consider problems such as pollution. Furthermore, in the flame-retardant cyanate resin of the present invention, a high flame retardancy is exhibited by the synergistic effect of the nitrogen atoms present in the cyanate resin in a large amount and the phosphorus atom introduced, so that it is necessary for the flame retardation of the cyanate resin. The amount of such phosphorus atoms may be smaller than that of the epoxy resin. Thereby, in the flame-retardant cyanate resin of the present invention, heat resistance by introducing a phosphorus atom in the resin skeleton, water absorption,
It is possible to minimize the deterioration of various characteristics such as insulation.
It is useful.

The divalent cyanate ester compound (A) used in the present invention has two cyanato groups in one molecule. For example, the compound represented by the above general formula [1] can be used. it can. Examples of the compound represented by the general formula [1] include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, and 2,2-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 the like. Among them,
2,2-bis (4-cyanatophenyl) propane is preferable because it has a particularly good balance between the dielectric properties and the curability of the cured product and is inexpensive in cost. The cyanate ester compounds may be used alone or in combination of two or more. Further, a part of the cyanate ester compound used here may be previously oligomerized to a trimer or a pentamer. A preferable blending ratio of the cyanate ester compound is in the range of 15 to 80% by weight, more preferable blending ratio is in the range of 20 to 60% by weight, and a particularly preferable blending ratio is based on the total solid content in the resin composition. It is 25 to 40% by weight. If the compounding ratio of the cyanate ester compound is less than 15% by weight,
The heat resistance and the solvent resistance decrease, and when the compounding ratio of the cyanate ester compound exceeds 80% by weight, the impact resistance of the cured product decreases.

In the present invention, the (B) reactive phosphorus compound is a temperature range assumed in a usual manufacturing process of a multilayer wiring board, that is, 60 to 300 ° C., preferably 100.
The phosphorus compound having a functional group that reacts with the cyanato group of the divalent cyanate ester compound (A) in the range of 180 ° C to 180 ° C. Examples of such a functional group that reacts with a cyanato group include a cyanato group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, an epoxy group, a maleimide group, and a carboxyl group. The reactive phosphorus compound (B) may include at least one of these functional groups in the compound. Among the functional groups that react with the cyanate ester compound, the phenolic hydroxyl group and the epoxy group are particularly preferable because they have high reactivity with the cyanate ester compound. As the phosphorus compound having such a phenolic hydroxyl group, H represented by the general formula [2] or [3] is used.
Since CA-HQ (manufactured by Sanko Chemical Co., Ltd.) is commercially available, it can be used. When a compound having a phenolic hydroxyl group is used, the ratio of cyanato group to phenolic hydroxyl group (cyanato group / phenolic hydroxyl group) is 5 /
By setting the ratio to 100 to 100/100, it is possible to obtain a resin having an excellent balance of flame retardancy and heat resistance. The phosphorus compound having a phenolic hydroxyl group is preferably mixed in a ratio of cyanato group to phenolic hydroxyl group (cyanato group / phenolic hydroxyl group) of 5/100 to 100.
/ 100 range, more preferably 20 /
It is in the range of 100 to 60/100, and a particularly preferable mixing ratio is 30/100 to 40/100. If the mixing ratio of the phenolic hydroxyl group and the cyanato group is less than 5/100, flame retardancy cannot be obtained. Further, if it exceeds 100/100, heat resistance and moisture resistance are deteriorated.

A phosphorus compound having an epoxy group is also useful because it has high reactivity with a cyanate ester compound. The phosphorus compound having an epoxy group is represented by the formula [2]
And a phosphorus-containing epoxy resin containing a phosphorus atom in the resin skeleton, which is obtained by previously reacting a phosphorus compound having a phenolic hydroxyl group shown in [3] with a polyfunctional epoxy resin. Among such phosphorus-containing epoxy resins, ZX-1548 (manufactured by Tohto Kasei Co., Ltd.) and the like are commercially available and may be used because they are easily available.

When the resin composition of the present invention is used, in the cured resin, the reaction between the divalent cyanate ester compound (A) and the reactive phosphorus compound (B) results in
A phosphorus atom is introduced into the cyanate resin skeleton. This reaction may be performed in solution. Further, it may be carried out when the mixture is applied to a film or a metal foil, or may be carried out during thermosetting after the mixture is laminated on a substrate. The reaction is usually performed in the range of 60 to 180. When preliminarily reacting in a solution, the solvent is mainly benzene,
Aromatic hydrocarbon solvents such as toluene, xylene, and trimethylbenzene are used, but are not limited thereto. When adjusting the viscosity of the reaction system or when improving the solubility of the thermoplastic resin to be dissolved in advance, a reaction such as a ketone solvent, an ether solvent, an alcohol solvent, an ether alcohol solvent or an amide solvent. An inert solvent may be used together therewith. The reaction time can be appropriately adjusted depending on the concentration of the reaction system, the amount of catalyst and the like. In the case of reacting in a solution, the conversion rate (progress of the reaction in the cyanate compound) is used to prevent the viscosity of the solution from increasing and making it difficult to handle.
Is preferably controlled. To control the conversion rate, the monomer conversion rate ( _TM ) obtained from the change in the monomer concentration or the functional group conversion rate ( _TF ) obtained from the change in the functional group concentration can be used as an index. The monomer conversion rate (T _M ) is obtained from GC, GPC, etc., and in the present invention, it is preferable that 0 ≦ T _M ≦ 60%. The monomer conversion rate ( _TM ) when measured by GPC
Is expressed by the following equation.

## EQU1 ## T _M = 100 × (S ₀ −S _t ) / S ₀ S ₀ : Peak area derived from monomer before reaction S _t : Peak area derived from monomer at the time of measurement (time t)

The conversion rate (T _F ) of the functional group is IR, N
Calculated from MR, DSC, etc., and in the present invention, 0 ≦
It is preferable that T _F ≦ 40%. The monomer conversion rate (T _F ) when measured by IR is represented by the following equation.

## EQU2 ## T _F = 100 × (A ₀ −A _t ) / A ₀ A ₀ : Cyanato group-derived absorbance before reaction A _t : Cyanato group-derived absorbance at the time of measurement (time t)

Further, the thermosetting composition containing the flame-retardant cyanate resin having a phosphorus atom in the resin skeleton may further contain one or more kinds of the thermosetting resin (C). Examples of the thermosetting resin include epoxy resin, phenol resin, alkyd resin, polyester resin, polyimide resin, polyurethane resin, silicone resin, bismaleimide resin, vinyl resin and benzocyclobutene resin.

Particularly, when an epoxy resin is mixed, the moisture resistance of the cured product is greatly improved, which is preferable. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and phenol novolac type epoxy resin. Resin, alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, epoxy resin having dicyclopentadiene skeleton, epoxidized product of condensation product of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanurate The alicyclic epoxy resin, the phosphorus-containing epoxy resin having a phosphorus atom in the resin skeleton and the like can be used alone or in combination of two or more kinds. When an epoxy resin is blended, the dielectric properties, flame retardancy, and physical properties such as Tg tend to deteriorate, but when an epoxy resin having a biphenyl skeleton such as YX4000H (trade name of Japan Epoxy Resin Co., Ltd.) is used, It is preferable because the deterioration of physical properties as described above can be suppressed. Further, it is possible to further improve the flame retardancy by using a phosphorus-containing epoxy resin containing a phosphorus atom in the resin skeleton. As such a phosphorus-containing epoxy resin, a phosphorus compound having a phenolic hydroxyl group represented by the formula [2] is previously reacted with a polyfunctional epoxy resin,
Examples thereof include phosphorus-containing epoxy resins containing a phosphorus atom in the resin skeleton. Among these, ZX-1548 (manufactured by Tohto Kasei Co., Ltd.) and the like are commercially available and can be easily obtained, and thus may be used. A preferable blending ratio of the epoxy compound is such that the ratio of epoxy group to cyanato group (epoxy group / cyanato group) is in the range of 10/100 to 200/100, and more preferable blending ratio is 30/100 to 1
It is in the range of 00/100, and a particularly preferable mixing ratio is 6
It is 0/100 to 80/100. Moisture resistance cannot be obtained when the mixing ratio of the epoxy group and the cyanato group is less than 10/100. If it exceeds 200/100, the dielectric characteristics,
A decrease in Tg and flame retardance is seen.

The thermosetting resin composition of the present invention may further contain one or more thermoplastic resins. Examples of the thermoplastic resin include fluororesin, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polycarbonate, polyetherimide, polyetheretherketone, and polyarylate. Among them, it is more preferable to blend the polyphenylene ether and the modified polyphenylene ether because the dielectric properties of the cured product and the impact resistance of the cured product are improved.
Examples of the polyphenylene ether and modified polyphenylene ether include poly (2,6-dimethyl-1,
4-phenylene) ether, poly (2,6-dimethyl-
Alloyed polymer of 1,4-phenylene) ether and polystyrene, Alloyed polymer of poly (2,6-dimethyl-1,4-phenylene) ether and styrene-butadiene copolymer, poly (2,6-dimethyl-1,4) Alloyed polymers of phenylene) ether and styrene-maleic anhydride copolymer, alloyed polymers of poly (2,6-dimethyl-1,4-phenylene) ether and polyamide, poly (2,6-dimethyl-1,4-) Examples include alloyed polymers of phenylene) ether and styrene-butadiene-acrylonitrile copolymer. When polyphenylene ether is used, the compounding amount of the polyphenylene ether / cyanate compound is from 5/100 to 200/1 because a resin having a good balance of dielectric properties and heat resistance can be obtained.
It is preferably set to 00. A preferable blending ratio of the polyphenylene ether and the modified polyphenylene ether is such that the weight ratio (polyphenylene ether / cyanate compound) of the polyphenylene ether and the modified polyphenylene ether to the cyanate ester compound is 5 /.
It is in the range of 100 to 200/100, more preferably in the range of 10/100 to 100/100,
A particularly preferable mixing ratio is 30/100 to 70/100. If the weight ratio of the polyphenylene ether and the modified polyphenylene ether to the cyanate ester compound is less than 5/100, the impact resistance and the dielectric properties are deteriorated. Further, when it exceeds 200/100, heat resistance is deteriorated.

A curing catalyst or a curing accelerator may be added to accelerate the curing reaction. As the curing catalyst, metals such as manganese, iron, cobalt, nickel, copper and zinc are used, and specifically, organic metal salts such as 2-ethylhexanoate, naphthenate and octylate and acetylacetone. It is used as an organometallic complex such as a complex. These may be used alone or in combination of two or more. Phenols are preferably used as the curing accelerator, monofunctional phenols such as nonylphenol and paracumylphenol, bifunctional phenols such as bisphenol A, bisphenol F and bisphenol S, or polyfunctional phenols such as phenol novolac and cresol novolac. Etc. can be used. These may be used alone or in combination of two or more.

Further, an inorganic filler may be mixed with the thermosetting resin composition of the present invention. As the inorganic filler, alumina, aluminum hydroxide, magnesium hydroxide, clay, talc, antimony trioxide, antimony pentoxide,
Examples thereof include zinc oxide, fused silica, glass powder, quartz powder, and shirasu balloon. These inorganic fillers may be used alone or in combination of two or more.

In order to use the thermosetting resin composition of the present invention as a resin varnish, an organic solvent may be added. As the organic solvent, usually an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or trimethylbenzene is mainly used. When adjusting the viscosity of the varnish or when improving the solubility of the thermoplastic resin to be dissolved in advance, if necessary, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ether solvent such as tetrahydrofuran Solvent; alcohol solvent such as isopropanol and butanol; ether alcohol solvent such as 2-methoxyethanol and 2-butoxyethanol; N-methylpyrrolidone, N,
An amide-based solvent such as N-dimethylformamide or N, N-dimethylacetamide may be appropriately used in combination. The solvent amount in the varnish when producing the prepreg is preferably in the range of 20 to 80% by weight, and the viscosity of the varnish is preferably in the range of 50 to 300 cP. When a resin film and a resin-coated copper foil are prepared, the amount of solvent in the varnish is preferably in the range of 20 to 80% by weight, and the viscosity of the varnish is 100 to 500.
It is preferably in the range of cP.

The resin composition of the present invention and the prepreg, laminated board, resin film and copper foil with resin using the composition are particularly useful as materials for printed wiring boards. For the prepreg using the thermosetting resin composition of the present invention, the manufacturing method which has been conventionally generally used can be applied as it is. That is, the prepreg of the present invention is obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention, and as the base material, a well-known material used for various electrically insulating material laminates is known. Things can be used. Examples of the material of the base material include inorganic fibers such as E glass, D glass, S glass or Q glass, organic fibers such as polyimide, polyester or tetrafluoroethylene, and a mixture thereof. These base materials have shapes such as woven cloth, non-woven cloth, robink, chopped strand mat, surfacing mat, and the like, and the material and shape are selected depending on the intended use and performance of the molded product, and may be used alone or as needed. It is possible to use materials and shapes of more than one type. The thickness of the base material is not particularly limited, but is usually 0.03 to
Those having a surface treatment with a silane coupling agent or the like or those subjected to mechanical fiber opening treatment using a material having a thickness of about 0.5 mm are suitable in terms of heat resistance, moisture resistance, and workability. Normal,
After the base material is impregnated or coated so that the amount of the resin composition adhered to the base material is 20 to 90% by weight in terms of the resin content of the prepreg after drying, the temperature is usually 1 to 1 Heat dried for 30 minutes, semi-cured state (B stage state)
Get the prepreg of.

A laminated board can be produced by laminating and molding using the above-mentioned prepreg of the present invention. A general method can be applied as it is to the lamination molding. For example, 1 to 20 sheets of the prepreg of the present invention are usually laminated, and a metal foil such as copper or aluminum is arranged on one side or both sides of the prepreg to form by heating and pressing. By doing so, a metal-clad laminate can be obtained. The metal foil is not particularly limited as long as it is used for wiring board material applications. As a molding condition, a usual method for a laminated plate and a multilayer plate for electric insulating materials can be applied. For example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and a temperature of 10
Molding is performed at 0 to 250 ° C., pressure of 2 to 100 kg / cm 2, and heating time of 0.1 to 5 hours.

The resin film using the thermosetting resin composition of the present invention can be manufactured by directly applying the manufacturing method generally used in the past. For example, the thermosetting resin composition of the present invention can be applied to a support film to form a resin film. As the support film, known ones used for various resin films can be used, and examples thereof include polyolefin films such as polyethylene and polyvinyl chloride, and polyester films such as polyethylene terephthalate. The resin film can be obtained by applying a resin varnish to a support film and then heating and drying it. The heating and drying conditions are preferably 100 to 200 ° C. and 1 to 30 minutes. These support films have a matte treatment,
Surface treatment such as corona treatment and release treatment may be applied. Usually, the thickness of the supporting film is 10 to 150 μm.
Is common. The thickness of the resin composition is 10 to 15
0 μm is common. The amount of residual solvent in the resin composition after heating and drying is appropriately about 0.2 to 10%. The resin film obtained as described above is laminated on a substrate by laminating or pressing under pressure and heating conditions, and after peeling the supporting film, it is heat-cured. Then, a multilayer printed wiring board is manufactured through the multilayer printed wiring board manufacturing process described below.

For the resin-coated metal foil for a multilayer printed wiring board according to the present invention, a manufacturing method which has been conventionally generally used can be applied as it is. That is, the metal foil with resin of the present invention is obtained by coating the metal foil with the thermosetting resin composition of the present invention. As the metal foil, well-known ones used for various resin-coated metal foils can be used, for example, copper foil, aluminum foil, nickel foil, ultrathin metal foil capable of removing supporting metal foil by etching or peeling, and the like. It is illustrated. The resin-coated metal foil can be obtained by applying a resin varnish to the metal foil and then heating and drying it. The heating and drying conditions are 100 to 200 ° C.
Appropriately 30 minutes. Generally, the thickness of the metal foil is generally 10 to 50 μm, but when an ultrathin metal foil is used, a resin-coated metal foil having a metal foil thickness of 1 to 10 μm can be obtained. The thickness of the resin composition is generally 10 to 150 μm. The amount of residual solvent in the resin composition after heating and drying is appropriately about 0.2 to 10%. The resin-coated product obtained as described above is laminated on a substrate by laminating or pressing under pressure and heating conditions and heat-cured. Then, a multilayer printed wiring board is manufactured through the multilayer printed wiring board manufacturing process described below.

Next, a method for producing a multilayer printed wiring board using the thermosetting resin composition of the present invention and a resin film obtained from the composition will be described. First, the thermosetting resin composition of the present invention is laminated on a patterned inner layer circuit board. The method is to apply an organic solvent varnish of the present resin composition to an inner layer circuit board, and after drying and curing by heating, or using a resin film made of the resin composition of the present invention, pressurization, the substrate under heating conditions. The support film is laminated or pressed on the top, and the support film is peeled off, followed by heat curing. As the inner layer circuit board, a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting PPE board, or the like can be used, and the circuit surface may be preliminarily roughened. . The conditions for heat curing are 120 ° C. or higher, preferably 170 to 220 ° C., and usually 15 to 300 minutes, preferably 60 to 150 minutes are sufficient. After laminating and curing the resin composition of the present invention on the substrate as described above, drilling and / or laser drilling is performed to form through holes and via holes. A carbon dioxide laser, a YAG laser, an excimer laser, etc. can be used for a laser drilling machine. After that, sandblasting, plasma treatment, chemical treatment using an oxidizing agent such as permanganate or dichromate is performed to roughen the surface. In this step, resin residues generated during drilling and laser drilling are also removed at the same time. After obtaining electrical continuity between the inner layer and the outer layer using a technique such as electroless copper plating, metal deposition, sputtering, or ion plating, the layers are laminated using the circuit forming method for a normal build-up wiring board. A circuit is formed on the surface of the thermosetting resin composition of the invention.

When the resin-coated metal foil of the present invention is used, a multilayer printed wiring board is manufactured through the following steps. First, a resin-coated metal foil is laminated or pressed on a substrate under pressure and heating conditions and cured by heating. After that, when the metal foil used is thin, the metal foil and the resin can be punched at the same time. In this case, the surface of the metal foil may be roughened. When the metal foil used is thick, laser drilling is performed after forming a window hole using the conformal mask method or the large window method. After drilling, the resin residue is removed as described above to obtain electrical continuity between the inner layer and the outer layer, and then the heat-cured layer of the present invention is laminated using the circuit forming method in a normal build-up wiring board. A circuit is formed on the surface of the resin composition.

[0031]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 100 g of toluene and 2,2-bis (4-cyanatophenyl) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a condenser and a stirrer.
Propane (Arocy B-10, product name of Asahi Ciba Co., Ltd.) 100 g, 9,10-dihydro-9 of general formula [2]
-Oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, Sanko Chemical Co., Ltd.) 18.8
After adding g, 0.1 g of a 17% toluene dilute solution of manganese naphthenate (Mn content = 6% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added and polymerized at 105 ° C. for 4 hours to give a resin skeleton of the present invention. A cyanate resin having a phosphorus atom was obtained. Before the polymerization, HCA-HQ was not dissolved in the solvent and the solution was cloudy, but the solution after the polymerization was transparent. From this, it can be inferred that HCA-HQ and the cyanate ester compound have reacted to introduce a phosphorus atom into the resin skeleton. The obtained resin composition is applied to a copper foil (GTS-12, manufactured by Furukawa Circuit Foil Co., Ltd.) and dried at 155 ° C. for 10 minutes, and then the resin surfaces are laminated and pressed at 200 ° C. for 90 minutes to cure the resin. The thing was made. After etching the copper foil, the cured resin (what sample it became) 1
The relative permittivity and the dielectric loss tangent at GHz were measured with an impedance-material analyzer HP4291B manufactured by Hewlett-Packard Co., and the relative permittivity was 2.
93, the dielectric loss tangent was 0.0057.

(Example 2) In a 1 liter 4-neck separable flask equipped with a thermometer, a condenser and a stirrer, 183 g of toluene and polyphenylene ether resin (PKN4) were used.
752, trade name of Nippon GE Plastics Co., Ltd.) (50 g) was added, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) propane (A
rocyB-10, product name manufactured by Asahi Ciba Co., Ltd.) 100
g, 9,10-dihydro-9-oxa-of the general formula [2]
10-phosphaphenanthrene-10-oxide (H
CA-HQ, manufactured by Sanko Chemical Co., Ltd.) 18.8 g, and then a 17% toluene diluted solution of manganese naphthenate (Mn content = 6 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.1
g was added and polymerized at 105 ° C. for 4 hours. HC before polymerization
A-HQ was not dissolved in the solvent and the solution was cloudy, but the solution after polymerization was transparent. From this, HCA
It can be inferred that —HQ and the cyanate ester compound react to introduce a phosphorus atom into the resin skeleton. Example 1
The relative permittivity at 1 GHz of the resin cured product measured in the same manner as above was 2.49, and the dielectric loss tangent was 0.0035.

(Example 3) In a 1 liter 4-neck separable flask equipped with a thermometer, a condenser and a stirrer, 183 g of toluene and polyphenylene ether resin (PKN4) were used.
752, trade name of Nippon GE Plastics Co., Ltd.) (50 g) was added, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) propane (A
rocyB-10, product name manufactured by Asahi Ciba Co., Ltd.) 100
g, 9,10-dihydro-9-oxa-of the general formula [2]
10-phosphaphenanthrene-10-oxide (H
CA-HQ, manufactured by Sanko Chemical Co., Ltd.) 18.8 g, and then a 17% toluene diluted solution of manganese naphthenate (Mn content = 6 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.1
g was added and polymerized at 105 ° C. for 4 hours. HC before polymerization
A-HQ was not dissolved in the solvent and the solution was cloudy, but the solution after polymerization was transparent. From this, HCA
It can be inferred that —HQ and the cyanate ester compound react to introduce a phosphorus atom into the resin skeleton. The solution is cooled to room temperature and an epoxy resin having a biphenyl skeleton (YX4000H, manufactured by Epoxy Shell Resin Co., Ltd.)
93.4 g was added to obtain a thermosetting resin composition containing a phosphorus atom in the resin skeleton of the present invention. The relative permittivity at 1 GHz of the resin cured product measured in the same manner as in Example 1 was 2.6.
5, the dielectric loss tangent was 0.0068.

Example 4 In a 1-liter four-necked separable flask equipped with a thermometer, a cooling tube, and a stirrer, 183 g of toluene and polyphenylene ether resin (PKN4) were used.
752, trade name of Nippon GE Plastics Co., Ltd.) (50 g) was added, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) propane (A
rocyB-10, product name manufactured by Asahi Ciba Co., Ltd.) 100
g, 9,10-dihydro-9-oxa-of the general formula [2]
10-phosphaphenanthrene-10-oxide (H
CA-HQ, manufactured by Sanko Chemical Co., Ltd.) 18.8 g, and then a 17% toluene diluted solution of manganese naphthenate (Mn content = 6 wt%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.1
g was added and polymerized at 105 ° C. for 4 hours. HC before polymerization
A-HQ was not dissolved in the solvent and the solution was cloudy, but the solution after polymerization was transparent. From this, HCA
It can be inferred that —HQ and the cyanate ester compound react to introduce a phosphorus atom into the resin skeleton. The solution is cooled to room temperature and an epoxy resin having a biphenyl skeleton (YX4000H, manufactured by Epoxy Shell Resin Co., Ltd.)
69.7 g, phosphorus-containing epoxy resin (ZX-1548-
4 manufactured by Tohto Kasei Co., Ltd.) to obtain a thermosetting resin composition containing phosphorus atoms in the resin skeleton of the present invention. 1GH of a cured resin product measured in the same manner as in Example 1.
The relative permittivity in z is 2.61, and the dielectric loss tangent is 0.006.
It was 3.

COMPARATIVE EXAMPLE 1 100 g of toluene and 2,2-bis (4-glycidylphenyl) propane (DER331L, Dow Chemical Co., Ltd.) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a cooling tube, and a stirrer. (Manufactured by Japan Ltd.) 100 g, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- of the general formula [2].
Oxide (HCA-HQ, Sanko Chemical Co., Ltd.) 1
After adding 8.8 g, manganese naphthenate (Mn content =
6% by weight, manufactured by Nippon Kagaku Sangyo Co., Ltd.) and added with 0.1 g of a 17% toluene diluted solution, and polymerized at 105 ° C. for 4 hours,
A cyanate resin having a phosphorus atom in the resin skeleton of the present invention was obtained. Before the polymerization, HCA-HQ was not dissolved in the solvent and the solution was cloudy, but the solution after the polymerization was transparent.
From this, HCA-HQ and epoxy resin react,
It can be assumed that a phosphorus atom is introduced into the resin skeleton.
The resin cured product measured in the same manner as in Example 1 had a relative dielectric constant at 1 GHz of 3.74 and a dielectric loss tangent of 0.0190.

Example 5 An E glass cloth having a thickness of 0.1 mm was impregnated and coated with the resin composition obtained in Example 1, and 1
It was heated and dried at 55 ° C. for 10 minutes to obtain a prepreg having a resin content of 55%. Next, 4 sheets of this prepreg were stacked and copper foil (GTS-12, manufactured by Furukawa Circuit Foil Co., Ltd.)
Placed at the top and bottom, and pressure at 2.0MP for 90 minutes at 200MP
Pressing was carried out at a to obtain a laminated plate. After etching the copper foil, the relative dielectric constant and dielectric loss tangent at 1 GHz of the resin cured product containing glass cloth were measured by Hewlett-Packard Co. Impedance-Material Analyzer HP429.
When measured by 1B, the relative dielectric constant was 3.62 and the dielectric loss tangent was 0.0064. For the flame resistance test, a copper foil on the surface was used for etching, and the test conditions were based on UL-94. As a result, the maximum combustion time was 7.2 seconds, the average combustion time was 3.4 seconds, and V-0 was achieved. Moreover, when the laminated plate was cut into 5 cm squares and the solder heat resistance at 288 ° C. was evaluated by the float method (n = 8), the average was 205.
Blistering occurred in seconds.

Example 6 The resin composition obtained in Example 2 was made into a prepreg by the same method as in Example 5 and then made into a laminated plate. When the dielectric properties at 1 GHz of the resin cured product containing the glass cloth were evaluated in the same manner as in Example 5, the relative dielectric constant was 3.28 and the dielectric loss tangent was 0.0044. When a flame resistance test was conducted in the same manner as in Example 5, the maximum burning time was 8.6 seconds and the average burning time was 4.6 seconds.
Achieved -0. Moreover, when the solder heat resistance was evaluated in the same manner as in Example 5, swelling occurred on average in 195 seconds.

(Example 7) The resin composition obtained in Example 3 was made into a prepreg by the same method as in Example 5, and then a laminate. When the dielectric characteristics at 1 GHz of the resin cured product containing the glass cloth were evaluated in the same manner as in Example 5, the relative dielectric constant was 3.44 and the dielectric loss tangent was 0.0074. When a flame resistance test was conducted in the same manner as in Example 5, the maximum burning time was 12.5 seconds and the average burning time was 6.5 seconds.
Achieved V-1. Further, when the solder heat resistance was evaluated in the same manner as in Example 5, no blistering was observed for 300 seconds or longer.

Example 8 The resin composition obtained in Example 4 was made into a prepreg by the same method as in Example 5, and then a laminated plate. When the dielectric properties at 1 GHz of the resin cured product containing the glass cloth were evaluated in the same manner as in Example 5, the relative dielectric constant was 3.42 and the dielectric loss tangent was 0.0076. When a flame resistance test was conducted in the same manner as in Example 5, the maximum burning time was 6.3 seconds, the average burning time was 2.4 seconds, and V
Achieved -0. Further, when the solder heat resistance was evaluated in the same manner as in Example 5, no blistering was observed for 300 seconds or longer.

Comparative Example 2 The resin composition obtained in Comparative Example 1 was made into a prepreg by the same method as in Example 5, and then made into a laminated plate. When the dielectric properties at 1 GHz of the resin cured product containing the glass cloth were evaluated in the same manner as in Example 5, the relative dielectric constant was 4.12 and the dielectric loss tangent was 0.0182. When a flame resistance test was conducted in the same manner as in Example 5, the maximum burning time was 14.3 seconds and the average burning time was 8.2 seconds.
Achieved V-1. Further, when the solder heat resistance was evaluated in the same manner as in Example 5, no blistering was observed for 300 seconds or longer.

Example 9 The resin composition obtained in Example 1 was applied to a copper foil (GTS-12, manufactured by Furukawa Circuit Foil Co., Ltd.) and dried at 155 ° C. for 10 minutes to give a resin-coated copper foil. . The thickness of the resin was about 80 μm. Halogen-free laminate (MCL-RO-
(67G, manufactured by Hitachi Chemical Co., Ltd.) was used by laminating a resin-coated copper foil on an etched copper foil on the surface and then etching copper on the surface. Test conditions are UL-9
4 was complied with. As a result, the maximum burning time was 8.1 seconds, the average burning time was 3.2 seconds, and V-0 was achieved. For solder heat resistance test, halogen-free laminated board (MCL-R
O-67G, manufactured by Hitachi Chemical Co., Ltd.) was used, which was obtained by laminating a resin-coated copper foil on a copper foil on the surface of which oxidation-reduction treatment was performed. When this sample was cut into 5 cm squares and the solder heat resistance at 288 ° C. was evaluated by the float method (n = 8), swelling occurred on average in 215 seconds. After etching the copper foil of this sample, Hirayama Seisakusho Co., Ltd.
PCT (Presure Cooker Test)
PCT resistance (test conditions 121 ° C, 2 atm,
When the relative humidity was 100%), it was visually confirmed that swelling had occurred on the substrate surface after the treatment for about 2 hours.

(Example 10) The resin composition obtained in Example 2 was used as a resin-coated copper foil in the same manner as in Example 9. When a flame resistance test was conducted in the same manner as in Example 9, the maximum combustion time was 7.6 seconds, the average combustion time was 3.6 seconds, and V-0.
Was achieved. Further, when the solder heat resistance was evaluated in the same manner as in Example 9, swelling occurred in 220 seconds on average.
Further, when the PCT resistance was evaluated in the same manner as in Example 9, it was visually confirmed that swelling had occurred on the substrate surface after the treatment for about 2 hours.

(Example 11) The resin composition obtained in Example 3 was used as a resin-coated copper foil in the same manner as in Example 9. When a flame resistance test was conducted in the same manner as in Example 9, the maximum burning time was 14.8 seconds, the average burning time was 7.2 seconds, and V-
Achieved 1. When the solder heat resistance was evaluated in the same manner as in Example 9, no blistering occurred for 300 seconds or longer. Furthermore, when the PCT resistance was evaluated in the same manner as in Example 9, no blistering occurred even after the treatment for 300 hours or longer.

Example 12 The resin composition obtained in Example 4 was used as a resin-coated copper foil in the same manner as in Example 9. When a flame resistance test was conducted in the same manner as in Example 9, the maximum combustion time was 5.4 seconds, the average combustion time was 2.2 seconds, and V-0.
Was achieved. When the solder heat resistance was evaluated in the same manner as in Example 9, no blistering occurred for 300 seconds or longer. Furthermore, when the PCT resistance was evaluated in the same manner as in Example 9, no blistering occurred even after the treatment for 300 hours or longer.

Comparative Example 3 The resin composition obtained in Comparative Example 1 was used as a resin-coated copper foil in the same manner as in Example 9. When a flame resistance test was conducted in the same manner as in Example 9, the maximum combustion time was 18.3 seconds, the average combustion time was 7.5 seconds, and V-1
Was achieved. When the solder heat resistance was evaluated in the same manner as in Example 9, no blistering occurred for 300 seconds or longer. Furthermore, when the PCT resistance was evaluated in the same manner as in Example 9, no blistering occurred even after the treatment for 300 hours or longer.

Table 1 shows the compositions of the resin compositions obtained in Examples 1 to 4 and Comparative Example 1 and the dielectric properties of the cured products. Table 2 shows the evaluation results in the case of producing a laminated board using the resin compositions obtained in Examples 1 to 4 and Comparative Example 1. Table 3 shows the evaluation results when resin-coated copper foils were produced using the resin compositions obtained in Examples 1 to 4 and Comparative Example 1.

The resin composition having phosphorus atoms introduced into the epoxy resin skeleton as in Comparative Example 1 has a large relative permittivity and dielectric loss tangent, and, as shown in Comparative Examples 2 and 3, wiring boards. The flame retardancy when used as a material is also insufficient.
On the other hand, the resin composition obtained by introducing a phosphorus atom into the cyanate resin skeleton as in Example 1 exhibits excellent dielectric properties, and when used as a wiring board material as in Examples 5 and 9, It can be seen that it exhibits good flame retardancy. From this, it was shown that the resin composition according to the present invention is very useful. In Example 2, the polyphenylene ether resin was added to the resin composition having a phosphorus atom introduced into the cyanate resin skeleton. In this case, the relative dielectric constant was 2.49 and the dielectric loss tangent was 0.0035, and it is possible to obtain a resin composition having more excellent dielectric properties, and further, Example 6 and Example 10
It was confirmed that the flame retardancy as a wiring board material was also ensured. Example 3 is a thermosetting resin composition containing an epoxy resin, which has the problems of solder heat resistance and PCT, which have been problems in Examples 5, 6, 6, and 10. It was invented for the purpose of improving the sex. In this case, as shown in Example 7 and Example 11,
Although the dielectric properties and flame retardancy are slightly reduced,
It has improved PCT resistance and solder heat resistance and is suitable as a wiring board material. In the thermosetting resin composition in which the phosphorus-containing epoxy resin and the biphenyl type epoxy resin are used together as the epoxy resin as in Example 4, Example 8 and Example 1 are used.
As shown in FIG. 2, the flame retardance is improved, and various properties such as dielectric properties, solder heat resistance, and PCT resistance are good.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

By using the resin composition of the present invention and a prepreg, a laminated plate, an insulating film and a metal foil with a resin using the composition, it is suitable for increasing the speed of a computer and reducing the loss of high frequency related equipment. It becomes possible to manufacture a multilayer printed wiring board without using a brominated flame retardant.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 79/04 C08L 79/04 Z 5E346 101/00 101/00 H05K 3/46 H05K 3/46 TF term (reference) 4F072 AD03 AD07 AD11 AD23 AD33 AD37 AD41 AD42 AD43 AD45 AD46 AD47 AE07 AG03 AG17 AL13 4F100 AB01A AB33A AH02B AH02H AH06H AH07B AK02 AK17B AK31B AK33B AK43B AK44B AK45B AK49B AK51B AK52B AK53B AK54B AK56B AK57B AL05B BA02 BA10A BA10B CA08B GB43 JG05 JJ03 JJ07 JL01 YY00B 4J002 BD12Z BH02Y BK00Y CC03Y CD00Y CD11X CF03Y CF16Z CF28Y CG00Z CH07Z CK02Y CM02W CM04Y CM04Z CN02Z CP03Y GQ00 GQ01 4J036 CC32A12 CA32C12A12 CA12 CC25 CC02 JA08 JA11 4J043 PA32.

Claims (22)

[Claims] 1. A flame-retardant thermosetting resin composition comprising (A) a divalent cyanate ester compound and (B) a reactive phosphorus compound. 2. A divalent cyanate ester compound (A) is represented by the general formula [1]: (In the formula, R ₁ is R ₂ and R _{3, which} may be the same or different, each represent a hydrogen atom or a methyl group. The thermosetting resin composition according to claim 1, which is a cyanate ester compound represented by the formula (1). 3. The thermosetting resin composition according to claim 1, which contains a phosphorus compound having a phenolic hydroxyl group as the reactive phosphorus compound. 4. A phosphorus compound having a phenolic hydroxyl group is represented by the formula [2] or the formula [3]: [Chemical 4] The thermosetting resin composition according to claim 3, which is a phosphorus compound represented by the formula (wherein R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group). 5. The thermosetting resin composition according to claim 2, which contains a phosphorus-containing epoxy resin as the reactive phosphorus compound. 6. The thermosetting resin composition according to claim 5, wherein the phosphorus-containing epoxy resin is a phosphorus-containing epoxy resin obtained by reacting a phosphorus compound having a phenolic hydroxyl group with the epoxy resin. 7. A phosphorus compound having a phenolic hydroxyl group is represented by the formula [2] or the formula [3]: [Chemical 6] The thermosetting resin composition according to claim 6, which is a phosphorus compound represented by the formula (wherein R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group). 8. The thermosetting resin composition according to claim 6, wherein the epoxy resin reacted with the phosphorus compound to produce the phosphorus-containing epoxy resin is a polyfunctional epoxy resin. 9. The thermosetting resin composition further comprises epoxy resin other than phosphorus-containing epoxy resin, phenol resin, alkyd resin, polyester resin, polyimide resin, polyurethane resin, silicone resin, bismaleimide resin,
The thermosetting resin composition according to claim 8, which is a thermosetting resin composition containing a thermosetting resin selected from the group consisting of vinyl resins and benzocyclobutene resins. 10. The thermosetting resin composition according to claim 9, wherein the thermosetting resin is an epoxy resin having a biphenyl skeleton. 11. A thermosetting resin composition, wherein the thermosetting resin composition further contains a thermoplastic resin selected from the group consisting of fluororesin, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyetherimide, polyether ether ketone, and polyarylate. The thermosetting resin composition according to any one of claims 1 to 10, which is a resin composition. 12. The thermosetting resin composition according to claim 11, wherein the thermoplastic resin is polyphenylene ether. 13. The heat according to claim 1, wherein the equivalent ratio of the cyanato group to the phenolic hydroxyl group (phenolic hydroxyl group / cyanato group) in the thermosetting resin composition is 5/100 to 100/100. Curable resin composition. 14. The equivalent ratio of the cyanato group and the epoxy group (epoxy resin / cyanate ester compound) in the thermosetting resin composition is 10/100 to 200/100.
The thermosetting resin composition according to any one of claims 1 to 13. 15. The thermosetting resin composition contains a cyanate ester compound and a polyphenylene ether, and the weight ratio of the cyanate ester compound and the polyphenylene ether (polyphenylene ether / cyanate ester compound) is 5/100 to 200/100. Claim 1
The thermosetting resin composition according to any one of 1 to 14. 16. A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition according to any one of (1) to (15). 17. A laminated plate formed by laminating using the prepreg according to claim 16. 18. An insulating film obtained by applying the thermosetting resin composition according to any one of claims 1 to 15 to a support film. 19. A resin-coated metal foil obtained by applying the thermosetting resin composition according to any one of claims 1 to 15 to a metal foil. 20. A multilayer wiring board having an insulating layer made of the thermosetting resin composition according to any one of claims 1 to 15. 21. A multilayer wiring board, characterized in that the insulating film according to claim 18 is laminated and integrated on a circuit surface of an inner layer circuit board to form an insulating resin layer, and a circuit is formed on the insulating resin layer. Manufacturing method. 22. A multilayer comprising a resin-coated metal foil according to claim 19 laminated and integrated on a circuit surface of an inner layer circuit board, and a metal layer derived from the resin-coated metal foil is subjected to circuit processing. Wiring board manufacturing method.