JP2003128753A - Flame-retardant thermosetting resin composition, prepreg, laminate, insulating film, metal foil with resin and multilayered wiring board and method for producing the board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant thermosetting resin composition comprising a flame-retardant cyanate resin without a fear such as lowering of heat and moisture resistances and moldability and staining with a chemical fluid in a step of producing a wiring board while flame retarding a cyanate resin having excellent dielectric characteristics without using a bromine-based flame retardant and an insulating film, a metal foil with a resin and a multilayered printed wiring board using the composition. SOLUTION: This flame-retardant thermosetting resin composition comprises (A) a bivalent cyanate ester compound, (B) a phosphorus compound and (C) an epoxy resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant thermosetting resin composition, a prepreg, a laminate, an insulating film, a resin-coated metal foil, 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 resin as a material for a printed wiring board, it is necessary to impart flame retardancy, and usually a bromine compound having high flame retardancy is used. For example, JP-B-4-24370 discloses a brominated bisphenol A and a hydroxy ether of brominated bisphenol A.
286723, brominated phenol novolac glycidyl ether, JP-A-5-339342 discloses brominated bisphenol A glycidyl ether, JP-A-7-2070.
No. 22, brominated maleimides, JP-A-2000-9593.
In No. 8, an addition type bromine compound having no reactivity with the 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, moisture resistance and moldability, and manufacture a wiring board. To provide a flame-retardant thermosetting resin composition containing a flame-retardant cyanate resin, which is free from concerns such as chemical contamination in a process, 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 flame-retardant thermosetting resin composition comprising a divalent cyanate ester compound (A), a phosphorus compound (B) and an epoxy resin (C). (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 from each other, each represents a hydrogen atom or a methyl group), are cyanate ester compounds, and the flame-retardant thermosetting resin composition according to (1). . (3) The flame-retardant thermosetting resin composition according to (1) or (2), which contains a phosphorus compound having a phenolic hydroxyl group as the phosphorus compound (B).

(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 flame-retardant thermosetting resin composition according to (3), which is a phosphorus compound. (5) The flame-retardant thermosetting resin composition according to (2) to (4), which contains a phosphorus-containing epoxy resin as the (B) phosphorus compound. (6) The flame-retardant 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 an 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] The flame-retardant thermosetting resin composition according to claim 6, which is a phosphorus compound represented by the formula (R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group). (8) The flame-retardant 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 flame-retardant thermosetting resin composition according to (1) to (8), wherein the (C) epoxy resin is an epoxy resin having a biphenyl skeleton. (10) Flame-retardant thermosetting resin composition further contains a thermoplastic resin selected from the group consisting of fluororesin, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyetherimide, polyetheretherketone, and polyarylate. The flame-retardant thermosetting resin composition according to any one of (1) to (9), which is a thermosetting resin composition. (11) The flame-retardant thermosetting resin composition according to (10), wherein the thermoplastic resin is polyphenylene ether. (12) A prepreg obtained by impregnating or coating a base material with the flame-retardant thermosetting resin composition according to any one of (1) to (11). (13) A laminated plate formed by laminating the prepreg according to (12).

(14) An insulating film obtained by applying the flame-retardant thermosetting resin composition according to any one of (1) to (11) to a support film. (15) A resin-coated metal foil obtained by applying the flame-retardant thermosetting resin composition according to any one of (1) to (11) to a metal foil. (16) Manufacturing of a multilayer wiring board, characterized in that the insulating film according to (14) 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. (17) A multilayer wiring board, characterized in that the metal foil with resin according to (15) is laminated and integrated on the circuit surface of an inner layer circuit board, and the metal layer derived from the metal foil with resin is subjected to circuit processing. Manufacturing method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have found that the addition of a phosphorus compound is particularly effective for making a cyanate resin flame-retardant.
It has been found that a thermosetting resin composition having excellent dielectric properties can be obtained by this. Since the compounding amount of the phosphorus compound required for flame retardation may be smaller than that for the case of making the epoxy resin flame-retardant, the deterioration of physical properties as seen in the case of the epoxy resin is suppressed to a minimum. It is possible.
Further, flame retardation can be achieved without using metal hydroxide together, and thus a thermosetting resin composition having good dielectric properties, heat resistance, impact resistance, and moldability can be provided.
As described above, the reason why the phosphorus compound exerts a particularly high effect in making the cyanate resin flame-retardant is that the cyanate resin contains a nitrogen atom.

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.

As the phosphorus compound (B), an additive containing a phosphorus element such as a phosphoric acid ester compound may be used, or a reactive phosphorus compound having a reactive functional group in the molecule may be used. Good. Here, the reactive functional group means the temperature in the step of producing a laminate, that is, 60 to 300 ° C.,
It preferably refers to a functional group in which the reaction with the cyanato group of the cyanate compound proceeds in the range of 100 to 180 ° C., and specifically, a cyanato group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, an epoxy group, a maleimide group. , And a functional group that reacts with a cyanate ester compound such as a carboxyl group. At least one reactive functional group is present in the compound.
It is preferable that one or more pieces are contained. Among the functional groups that react with the cyanate ester compound, a phenolic hydroxyl group and an epoxy group are particularly preferable because they have high reactivity with the cyanate ester compound. As an example of the phosphorus compound having a phenolic hydroxyl group, a phosphorus compound represented by the formula [2] or the formula [3] is preferably used, and for example, HCA-HQ.
(Sanko Chemical Co., Ltd. product name) is commercially available, so it can be used as it is.

When a phosphorus compound having a phenolic hydroxyl group is used, the flame retardancy and heat resistance can be improved by adjusting the ratio of cyanato group to phenolic hydroxyl group (cyanato group / phenolic hydroxyl group) from 5/100 to 100/100. It is possible to obtain a resin excellent in balance. A preferred blending ratio of the phosphorus compound having the phenolic hydroxyl group is:
Ratio of cyanato group and phenolic hydroxyl group (cyanato group /
(Phenolic hydroxyl group) is in the range of 5/100 to 100/100, and a more preferable mixing ratio is 20/100 to 6
It is in the range of 0/100, 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.

As described above, the phosphorus compound having an epoxy group is also useful because it has high reactivity with the cyanate ester compound. As the phosphorus compound having an epoxy group,
It is preferable to use a phosphorus-containing epoxy resin containing a phosphorus atom in the resin skeleton, such as a resin obtained by reacting an epoxy resin with a phosphorus compound having a phenolic hydroxyl group represented by Formula [2] or Formula [3]. it can. A polyfunctional epoxy resin is preferably used as the epoxy resin for reacting with the phosphorus compound. Commercially available phosphorus-containing epoxy resins include ZX-1548 (trade name manufactured by Tohto Kasei Co., Ltd.) and the like, and these may be used because they are easily available.

The thermosetting composition of the present invention further comprises
(C) Epoxy resin is an essential component. The epoxy resin has a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin, an alkylphenol novolac type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, and a dicyclopentadiene skeleton. Epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, triglycidyl isocyanurate, alicyclic epoxy resins, phosphorus-containing epoxy resins having a phosphorus atom in the resin skeleton They can be used alone or in combination of two or more. When an epoxy resin is blended, the dielectric properties, flame retardancy, Tg, etc. may decrease, but when an epoxy resin having a biphenyl skeleton is used, such a decrease in physical properties can be suppressed to a particularly small level, which is preferable. As the epoxy resin having a biphenyl skeleton, for example, YX4000H (trade name of Japan Epoxy Resin Co., Ltd.) and the like are commercially available, and this can be used as it is. 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 as shown in Formula [2] or Formula [3] is reacted with a polyfunctional epoxy resin in advance, and a phosphorus atom is contained in the resin skeleton. Examples thereof include phosphorus-containing epoxy resin. As the phosphorus-containing epoxy resin, ZX-1548 (trade name, manufactured by Tohto Kasei Co., Ltd.) and the like are commercially available and may be used because they are easily available. A preferable blending ratio of the epoxy compound is such that the ratio of the epoxy group to the cyanato group (epoxy group / cyanato group) is in the range of 10/100 to 200/100, and the more preferable blending ratio is 30/100 to 10.
It is in the range of 0/100, and a particularly preferable mixing ratio is 60.
/ 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 property, T
g, the flame retardance is decreased.

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 flame-retardant thermosetting resin composition of the present invention in an amount that does not adversely affect various properties. As the inorganic filler, alumina,
Examples thereof include aluminum hydroxide, magnesium hydroxide, clay, talc, antimony trioxide, antimony pentoxide, zinc oxide, fused silica, glass powder, quartz powder, and shirasu balloon. These inorganic fillers may be used alone or as a mixture of two or more kinds, but not limited thereto.

An organic solvent may be added in order to use the thermosetting resin composition of the present invention as a resin varnish. 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.

When the cyanate ester compound and the reactive phosphorus compound are reacted, this reaction may be carried out in a varnish stage solution. Further, it may be carried out when the mixture is formed on a film or applied to a metal foil, or may be carried out during thermosetting after the mixture is laminated on a substrate. The reaction usually proceeds in the range of 60 to 300 ° C. 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.
When the reaction is carried out in a solution, it is preferable to control the conversion rate (progress of reaction in the cyanate compound) in order to prevent the solution from becoming too viscous and difficult to handle. 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%. In addition,
The monomer conversion rate ( _TM ) measured by GPC is represented 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)

The resin composition of the present invention and the prepreg, laminated board, resin film and resin-coated copper foil 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 prepreg of the present invention described above. 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 of the present invention, the manufacturing method generally used in the past 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 the 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.

[0029]

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 4-neck separable flask equipped with a thermometer, a cooling tube 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 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. 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 four-necked separable flask equipped with a thermometer, a cooling tube, and a stirrer, 183 g of toluene and polyphenylene ether resin (PKN4)
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 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.)
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 4-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 to obtain 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 laminated plate. 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 obtain 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, a wiring board. 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.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

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.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/24 CEZ C08J 5/24 CEZ 5G305 C08L 63/00 C08L 63/00 Z H01B 3/30 H01B 3/30 Q H05K 3/46 H05K 3/46 TF Term (Reference) 4F072 AB04 AB05 AB07 AB09 AB28 AB29 AC02 AC15 AD07 AD13 AD15 AD28 AD37 AD41 AD42 AD45 AD46 AE02 AF25 AF30 AG03 AH25 AH31 AJ04 AK02 AK14 AL12 AL13 4F100 AB17 AB33BH17AK01H33AH02H01H01H AK53K AK54C AL05C AL06C AT00A BA03 BA07 BA10A BA10C CA08C GB43 JB01 JB13C JB16C JD04 JG04B JG05 JJ03 JL01 4JAD04AE CD08W AD03 GH08AD08AD0605 AD04 GH08AD04 GH04AD0605 AD06Q06WAD06GHAD0606 AF36 AJ08 AJ18 AJ20 CB11 CB21 CC02 DC13 DC32 DD07 JA08 JA11 5E346 AA12 CC04 CC09 CC32 DD02 DD12 GG22 HH06 5G305 AA06 AB08 AB24 AB25 AB26 AB35 BA18 CA15 CB15 CB23 CD13

Claims (17)

[Claims] 1. A flame-retardant thermosetting resin composition comprising a divalent cyanate ester compound (A), a phosphorus compound (B) and an epoxy resin (C). 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 from each other and represent a hydrogen atom or a methyl group), are cyanate ester compounds represented by the formula (I) and the flame-retardant thermosetting resin composition according to claim 1. . 3. The flame-retardant thermosetting resin composition according to claim 1, which comprises (B) a phosphorus compound having a phenolic hydroxyl group as the phosphorus compound. 4. A phosphorus compound having a phenolic hydroxyl group is represented by the formula [2] or the formula [3]: [Chemical 4] The flame-retardant thermosetting resin composition according to claim 3, which is a phosphorus compound represented by the formula (R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group). 5. The flame-retardant thermosetting resin composition according to claim 2, which contains a phosphorus-containing epoxy resin as the phosphorus compound (B). 6. The flame-retardant 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 flame-retardant thermosetting resin composition according to claim 6, which is a phosphorus compound represented by the formula (R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group). 8. The flame-retardant 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 flame-retardant thermosetting resin composition according to claim 1, wherein the epoxy resin (C) is an epoxy resin having a biphenyl skeleton. 10. The flame-retardant thermosetting resin composition further comprises a thermoplastic resin selected from the group consisting of fluororesin, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyetherimide, polyetheretherketone, and polyarylate. The flame-retardant thermosetting resin composition according to any one of claims 1 to 9, which is a flame-retardant thermosetting resin composition. 11. The flame-retardant thermosetting resin composition according to claim 10, wherein the thermoplastic resin is polyphenylene ether. 12. A prepreg obtained by impregnating or coating a substrate with the flame-retardant thermosetting resin composition according to any one of claims 1 to 11. 13. A laminated plate formed by laminating using the prepreg according to claim 12. 14. An insulating film obtained by applying the flame-retardant thermosetting resin composition according to claim 1 to a support film. 15. A resin-coated metal foil obtained by coating the flame-retardant thermosetting resin composition according to claim 1 on a metal foil. 16. A multilayer wiring board comprising: an insulating resin layer according to claim 14 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. 17. A multi-layer comprising: laminating and integrating the resin-coated metal foil according to claim 15 on a circuit surface of an inner layer circuit board, and subjecting the metal layer derived from the resin-coated metal foil to circuit processing. Wiring board manufacturing method.