JP2002003702A - Epoxy resin composition, insulation film, metal foil with resin, and multilayer printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition having flame retardancy, hardly generating a toxic substance at the time of combustion, capable of being suitably used for production of a multilayer printed circuit board, hardly causing the cracking or pealing of an insulation layer, and capable of providing the multilayer printed circuit board excellent in electrical reliability and heat resistance. SOLUTION: This epoxy resin composition contains a phosphorus-containing compound (B) obtained by reacting 1.01-2 mol organophosphorus compounds (b) having one active hydrogen bonded to a phosphorus atom with 1 mol quinone compounds, an epoxy resin component (A) comprising epoxy resins (C) represented by general formula (1) (wherein, R1 and R2 are each a hydrogen atom or a phenyl group; m is a positive integer including 0) or the like, and 3-15 wt.% cross-linked elastomer (D) having <=1 μm particle diameter based on the whole amount of the epoxy resin component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, a metal foil with resin, an insulating film used for manufacturing a multilayer printed wiring board, and a multilayer printed wiring board manufactured from these epoxy resin compositions.

[0002]

2. Description of the Related Art Heretofore, flame-retardant epoxy resins have self-extinguishing properties and good mechanical and electrical properties, and have been used in various electrical insulating materials.

For example, when manufacturing a multilayer printed wiring board, an epoxy resin composition composed of a flame-retardant epoxy resin is applied to a conductive metal foil or a carrier film and semi-cured to form a resin-coated metal foil or an insulating resin. 2. Description of the Related Art There is known a method of manufacturing a multilayer printed wiring board by forming films and laminating them on an inner layer substrate on which a circuit pattern is formed.

[0004]

These conventional flame-retardant epoxy resins contain a halogen-based compound mainly containing bromine for imparting flame-retardancy to the resin. Resin moldings have self-extinguishing properties, but when these moldings burn in a fire, etc., depending on the combustion conditions, substances that have a bad effect on the human body, such as polybrominated dibenzodioxin and furan, are generated. There is a problem.

When a bromine-containing compound is added, bromine is easily decomposed when the molded product is heated,
It has been difficult to maintain heat resistance for a long period of time.

[0006] Therefore, there has been a demand for an epoxy resin composition that can achieve the required flame retardancy without adding a halogen compound mainly containing bromine.

On the other hand, when a metal foil or an insulating film with a resin is used as described above to manufacture a multilayer printed wiring board, the resin layer made of a semi-cured epoxy resin composition is generally brittle, and the resin layer is difficult to handle during handling. When a large force is applied to the layer, the resin layer is cracked, and the cracked powder of the resin layer may peel off from the metal foil or the carrier film.

[0008] When a printed wiring board is manufactured using a resin-coated metal foil or an insulating film in which the resin layer is cracked or peeled, a cavity is formed in the cracked or peeled portion of the insulating layer, and the inner layer circuit and the inner layer circuit are separated. In some cases, the electrical insulation between the outer layer circuit and the outer circuit was reduced.

When a resin-coated metal foil from which the resin layer has been peeled off is used, the resin powder released from the resin layer floats during lamination and adheres to the surface of the metal foil on which the resin layer is not formed, In some cases, a fine resin cured product was formed on the conductive metal foil of the obtained laminate. Then, in order to manufacture a multilayer printed wiring board, when the conductive metal foil is subjected to an etching process to form a conductive circuit, a portion where the cured resin is formed remains without being etched, and the conductive circuit is formed between the conductive circuits. In some cases, a short-circuit defect occurred, and the yield of the multilayer printed wiring board was poor.

In order to suppress the occurrence of cracking and peeling of the resin layer, a suitable amount of a phenoxy resin or a non-crosslinkable elastomer is added to the resin composition as a flexibility-imparting component, and the resin composition is softened. Although it has been studied to adopt a structure, in the case of a resin-coated metal foil or an insulating film in which such a flexibility-imparting component is blended with an epoxy resin composition, the glass transition temperature of a cured molded product of the resin is low. There is a problem that the heat resistance of a multilayer printed wiring board obtained by laminating such a resin-attached metal foil or insulating film becomes low.

[0011] Further, as a component for imparting flexibility other than the above,
Crosslinkable elastomers, butyral resins, and the like are included, but in any case, if the addition amount is small, the insulating resin layer may be cracked or peeled off, and if the addition amount is large, as a multilayer printed wiring board The electrical reliability (particularly, interlayer insulation reliability) during moisture absorption is reduced, and the heat resistance required for the multilayer printed wiring board is also reduced.

Therefore, there has been a demand for a resin-attached metal foil and an insulating film which are less likely to cause cracking or peeling of the insulating resin layer and which can produce a multilayer printed wiring board having excellent electrical reliability.

The present invention has been made in view of the above points, and is a flame-retardant epoxy resin composition which does not generate harmful substances when burned. When a multilayer printed wiring board is produced using this resin-coated metal foil or insulating film, cracking or peeling of the insulating resin layer hardly occurs, and electrical reliability and heat resistance are improved. An object of the present invention is to obtain an epoxy resin composition capable of obtaining an excellent multilayer printed wiring board, and a resin-attached metal foil, an insulating film and a multilayer printed wiring board manufactured using the epoxy resin composition. .

[0014]

The epoxy resin composition according to claim 1 of the present invention comprises an organic phosphorus compound (b) having one active hydrogen bonded to a phosphorus atom per mole of a quinone compound. And a phosphorus-containing organic compound (B) obtained by reacting at least one of epoxy resins (C) selected from the following general formulas (1) to (3). An epoxy resin component (A) containing
A crosslinked elastomer (D) having a particle diameter of 1 μm or less is blended, and the blending amount of the crosslinked elastomer (D) having a particle diameter of 1 μm or less is 3 to 15 with respect to the total amount of the epoxy resin component (A).
% By mass.

[0015]

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[0016]

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[0017]

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[0018]

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Further, the invention of claim 2 is characterized in that in claim 1, the polyvinyl acetal resin (E) is contained in an amount of 3 to 15% by mass based on the total amount of the epoxy resin component (A).

The invention of claim 3 is characterized in that, in claim 1 or 2, the phosphorus content is 0.8 to 5.0% by mass of the total amount of the epoxy resin component (A). .

According to a fourth aspect of the present invention, there is provided a metal foil with a resin, wherein a resin layer molded from the epoxy resin composition according to any one of the first to third aspects is provided on the surface of the metal foil. It is characterized by the following.

According to a fifth aspect of the present invention, an insulating film is formed by molding the epoxy resin composition according to any one of the first to third aspects into a sheet.

According to a sixth aspect of the present invention, there is provided a multilayer printed wiring board, wherein the inner layer substrate on which the circuit pattern is formed has the resin-coated metal foil according to the fourth aspect and the insulating film according to the fifth aspect. Characterized in that at least one of them is formed by lamination.

[0024]

Embodiments of the present invention will be described below. In this specification, the epoxy resin is heated and dried to be semi-cured to obtain a B-stage resin.
The product obtained by further curing by heating is referred to as a cured product.

As the epoxy resin component (A), those containing at least one of the epoxy resins (C) represented by the general formulas (1) to (3) are used. Here, the upper limit of the value of m in the general formula (1), the value of n in the general formula (2), and the value of 1 in the general formula (3) are not particularly limited. It becomes 10.

A specific example of the epoxy resin (C) represented by the above general formula (1) in the present invention is Epototh ZX-1.
027 (hydroquinone type epoxy resin manufactured by Toto Kasei Co., Ltd.), but is not limited thereto. Epoxy resins (C) represented by the general formula (2)
Specific examples include, but are not limited to, Epototh ZX-1355 (1,4-dihydroxynaphthalene type epoxy resin manufactured by Toto Kasei Co., Ltd.).
Specific examples of the epoxy resins (C) represented by the general formula (3) are Epotote YDF-170 and YDF-8170.
(Bisphenol F-type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ZX-1251 (biphenyl epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ZX-1
201 (bisphenol fluorene type epoxy resin manufactured by Toto Kasei Co., Ltd.), ESLV-80DE (diphenyl ether type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), E
SLV-50TE (diphenyl sulfide type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) is exemplified, but not limited thereto. Further, the epoxy resins (C) represented by the general formulas (1) to (3) may be used alone or in combination of two or more.

As the epoxy resin component (A), epoxy resins other than the epoxy resins (C) of the general formulas (1) to (3) can be used in combination. Specifically, general formula (3)
Other than bisphenol type epoxy resin, resorcin type epoxy resin, polyglycol type epoxy resin, trifunctional type epoxy resin, tetrafunctional type epoxy resin, novolak type epoxy resin, etc., which have two or more epoxy groups in one molecule Examples include, but are not limited to:

Here, when an epoxy resin having an average of two epoxy groups in the molecule is used, the plasticity of the B-stage resin and the cured product can be effectively improved.

When a bisphenol A type epoxy resin is used as the epoxy resin having two epoxy groups on average in the molecule, a cured product having good adhesive strength and the like can be obtained. In addition, when a bisphenol F type epoxy resin is used, the epoxy resin composition and the cured product thereof can easily have flame retardancy. When a biphenyl type epoxy resin is used, a cured product having a low water absorption and a high glass transition temperature can be obtained. When a naphthalene type epoxy resin is used, a cured product having a high glass transition temperature can be obtained.

When an epoxy resin having an average of three epoxy groups in a molecule is used as the epoxy resin, a cured product having a higher glass transition temperature can be obtained.

When a trifunctional epoxy resin is used as the epoxy resin having an average of three epoxy groups in the molecule, a cured product having low water absorption and high glass transition temperature can be obtained. When a phenol novolak type epoxy resin is used, a cured product having a high glass transition temperature and excellent flame retardancy can be obtained.

As a curing agent for these epoxy resins,
Various commonly used curing agents for epoxy resins such as phenolic resins, acid anhydrides, amines, hydrazides, acidic polyesters, etc. can be used. More than one kind may be used.
In particular, when dicyandiamide is used, a cured product having a good balance of performance such as adhesiveness, heat resistance, electric insulation, and high glass transition temperature can be obtained. The compounding amount of the curing agent is preferably in the range of 0.3 to 0.7 in equivalent ratio to the epoxy resin.

Further, as the phosphorus-containing organic compound (B),
The organic phosphorus compound (b) having one active hydrogen bonded to a phosphorus atom per mole of the quinone compound is 1.01.
Those obtained by reacting in the range of ~ 2 mol are blended.

Specific examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone. These quinones may be used alone or in combination of two or more, and are not limited thereto.

Specific examples of the organic phosphorus compounds (b) having one active hydrogen bonded to a phosphorus atom in the present invention include 3,4,5,6-dibenzo-1,2-oxaphosphane-2. -Oxide (abbreviation: HCA, manufactured by Sanko Chemical Co., Ltd.), diphenylphosphine oxide and the like. These organic phosphorus compounds (b) may be used alone or in combination of two or more, and are not limited thereto.

The reaction of a quinone compound with an organic phosphorus compound (b) having one active hydrogen bonded to a phosphorus atom is described, for example, in JP-A-5-214068, Russian General Chemical Magazine (Zh. Obshch.Khi
m. ), 42 (11), pp. 2415-2418 (19
72), JP-A-60-126293 and JP-A-61-61293.
The reaction is carried out according to the methods described in JP-A-236787 and JP-A-5-331179. However, in the present invention, the organic phosphorus compound (b) having one active hydrogen bonded to a phosphorus atom per mole of the quinone compound is 1.01.
The reaction is carried out in a range of from 1 to 2 mol, more preferably from 1.01 to less than 1.5 mol, still more preferably from 1.01 to less than 1.4 mol. The reaction between the group and the organic phosphorus compound (b) having one active hydrogen bonded to the phosphorus atom as a raw material occurs, and many components having no epoxy group which is a cross-linking point with the curing agent are generated, This leads to a decrease in heat resistance and a decrease in adhesive strength. When less than 1.01 mol of the organic phosphorus compound (b) having one active hydrogen bonded to a phosphorus atom is reacted with respect to 1 mol of the quinone compound,
These two reactions do not proceed as intended, and the organophosphorus compounds (b) or quinone compounds remain. In particular, when a quinone compound having sublimability remains, it has no reactive group that reacts with the epoxy resin, and thus adversely affects physical properties such as heat resistance.

The reaction between the quinone compound and the organic phosphorus compound (b) having one active hydrogen bonded to a phosphorus atom is carried out by dissolving the organic phosphorus compound (b) in an inert solvent in advance and then converting the quinone compound. The reaction is performed by adding and stirring with heating. Examples of the inert solvent include methanol, ethanol, isopropanol, chloroform, N, N-dimethylformamide, dioxane, ethylene glycol, methoxypropanol, ethyl cellosolve, benzene, toluene, xylene and the like, and the organic phosphorus compounds (b ) May be any solvent as long as it is a solvent that can dissolve), but is not limited thereto. However, some quinone compounds contain trace amounts of organic acids as impurities, such as maleic anhydride and phthalic anhydride.Solvents having an alcoholic hydroxyl group may cause these acids to react with the alcoholic hydroxyl group of the solvent. Since a reaction occurs to generate a substance that does not participate in the curing reaction at all, it affects heat resistance and the like. Therefore, more preferably dioxane, benzene, toluene,
Xylene and the like are preferred. In carrying out the reaction, quinone compounds are used in the form of powder or dissolved in a solvent. The reaction between the quinones and the organophosphorus compounds (b) is exothermic,
A quinone compound is added in a predetermined amount in a divided amount or by a dropping method so as not to cause rapid heat generation. 50 ° C to 15 after addition
The reaction is carried out while maintaining at 0 ° C. for 1 to 4 hours.

As the phosphorus-containing organic compound (B) thus synthesized, a phosphorus-containing organic compound (B) represented by the following chemical structural formulas (5) to (7) can be used. The phosphorus-containing organic compound (B) represented by the chemical structural formula (7) is a compound in which two types of structures coexist in an equilibrium state.

[0039]

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Although the optimum amount of the phosphorus-containing organic compound (B) used in the epoxy resin composition varies depending on the epoxy resin used, the content of phosphorus atoms in the phosphorus-containing organic compound (B) (phosphorus content) Is preferably in the range of 0.8 to 5.0% by mass with respect to the total amount of the epoxy resin component (A) of the epoxy resin composition. In this case, stable flame retardancy is imparted. be able to. When the phosphorus content is less than 0.8% of the total amount of the epoxy resin component (A), it is difficult to obtain stable flame retardancy. On the other hand, when the phosphorus content exceeds 5.0%, the properties of the cured product deteriorate. Or the compatibility with butyral resin blended as a flexibilizer or the dispersibility with the crosslinked elastomer (D) may be deteriorated.

In blending the phosphorus-containing organic compound (B) and the epoxy resin component (A) into the epoxy resin composition, the phosphorus-containing organic compound (B) is reacted with the epoxy resin component (A). Before being compounded in the epoxy resin composition, it may be reacted with part or all of the epoxy resin component (A) compounded in the epoxy resin, and the phosphorus obtained by this preliminary reaction may be used. The contained epoxy resin can be blended in the epoxy resin composition. This reaction can be performed by a known method. That is, a part or all of the epoxy resin component (A) is added to the phosphorus-containing organic compound (B), and the reaction temperature is set to 100.
The reaction is carried out under stirring at a temperature of from 200C to 200C, more preferably from 120C to 180C. When the rate of this reaction is low, productivity can be improved by using a catalyst as necessary. Specific catalysts include tertiary amines such as benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride; phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine; Various catalysts such as phosphonium salts such as phenylphosphonium bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used.

The use of such a phosphorus-containing epoxy resin significantly improves the heat resistance and water resistance of the cured product, and further suppresses the increase in viscosity of the B-stage resin during long-term storage, thereby improving storage stability. It is possible to prevent deterioration of moldability and the like even when stored for a long time in a state of a metal foil with resin or an insulating film.

The ratio of the epoxy resin and the phosphorus-containing organic compound (B) to be subjected to the preliminary reaction for producing the phosphorus-containing epoxy resin is not particularly limited, but the epoxy resin of the epoxy resin to be subjected to the reaction is not limited. The total number of moles of the phenolic hydroxyl group and the carboxylic acid of the phosphorus-containing organic compound (B) is preferably in the range of 0.4 to 1.0 with respect to the number of moles of the group of 1.0, and in this case, particularly excellent. A good B-stage resin or cured product having storage stability can be obtained. Here, the content of phosphorus atoms (phosphorus content) in the phosphorus-containing epoxy resin is preferably 1.2 to 4% by mass, more preferably 1.8 to 3.6% by mass, and still more preferably 2 to 4% by mass.
3.1% by mass. Further, the epoxy equivalent of the phosphorus-containing epoxy resin is preferably 200 to 600 g / eq, more preferably 250 to 550 g / eq, and further preferably 3 to 500 g / eq.
It is 00-500 g / eq. Epoxy equivalent is 200g
If it is less than / eq, the adhesiveness is inferior, and if it exceeds 600 g / eq, the heat resistance is adversely affected.
/ Eq is desirably adjusted.

As the epoxy resin to be subjected to this preliminary reaction, a bifunctional or trifunctional epoxy resin is desirable. When an epoxy resin having a small number of these functional groups is subjected to the preliminary reaction, a particularly stable product is obtained. can get. Further, among the epoxy resins subjected to the preliminary reaction, the total amount of the epoxy resins (C) represented by the above general formulas (1) to (3) is based on 100% by mass of the phosphorus-containing epoxy resin after the reaction. It is preferably from 20% to 45% by mass, more preferably from 20% to 43% by mass, still more preferably from 20% to 41% by mass. This compounding ratio is 20% by mass.
When the amount is less than the above, the adhesive strength, particularly the interlayer adhesive strength, becomes low. When the amount is more than 45% by mass, the heat resistance becomes low, which is not preferable.

The epoxy resin composition contains a crosslinked elastomer (D) having a particle diameter of 1.0 μm or less as a rubber component, thereby further improving the flexibility of the B-stage resin and the cured product. It can be improved effectively. Here, the crosslinked elastomer (D) means an elastomer which does not dissolve when dissolved in a solvent and exists as a gel, and at least methyl ethyl ketone (ME
K), which exists as a gel when dispersed in methoxypropanol (MP) or dimethylformamide (DMF). For example, linear elastomers (non-crosslinked elastomers) usually having an NBR (nitrile butadiene rubber) skeleton are MEK, MP, DMF,
It dissolves in solvents such as MIBK (methyl isobutyl ketone) and chloroform.
Crosslinked linear elastomer having a BR skeleton, for example, trade name “XER-91” manufactured by JSR Corporation
Does not dissolve when dispersed in these solvents and exists at a gel content of 90% or more.

The crosslinked elastomer (D) is not particularly limited, but may be, for example, styrene-butadiene rubber (SBR), butadiene rubber (BR), butyl rubber, or the like, or have the structure of these rubbers in the structural formula. Copolymers and the like can be used. Especially butadiene-
When acrylonitrile copolymer rubber is used, appropriate plasticity can be obtained in a B-stage resin or a cured product, and a decrease in the glass transition temperature (Tg) after molding of the B-stage resin or the cured product can be suppressed. Further, the epoxy resin composition of the crosslinked elastomer (D) and its B-stage resin and the cured product have good dispersibility in the cured product.

When the particle size of the crosslinked elastomer (D) exceeds 1.0 μm, the dispersibility of the crosslinked elastomer (D) in the epoxy resin composition, its B-stage resin, and the cured product decreases, It is difficult to obtain uniform plasticity. Therefore, it is desirable that the particle size of the crosslinked elastomer (D) is smaller, more preferably 0.5 μm or less. However, in order to effectively impart plasticity, the particle size of the crosslinked elastomer (D) is 0.0
Preferably it is 2 μm or more.

When the amount of the crosslinked elastomer (D) having a particle diameter of 1.0 μm or less in the epoxy resin composition is 3% by mass or more based on the total amount of the epoxy resin component (A), it is sufficient. Preferably, the effect of imparting flexibility can be obtained. If the amount is less than 3% by mass, the effect of imparting plasticity is reduced. When this addition amount is 15% by mass or less based on the total amount of the epoxy resin component (A), appropriate plasticity can be obtained, and a decrease in the glass transition temperature (Tg) after molding can be further suppressed. , Addition amount is 1
If it exceeds 5% by mass, the strength of the cured product may be reduced.

On the other hand, when a non-crosslinked elastomer is used as the rubber component, the glass transition temperature (Tg) after molding may decrease, or the strength may decrease during heating.

The epoxy resin composition preferably contains a polyvinyl acetal resin (E), whereby the flexibility of the B-stage resin and the cured product can be more effectively improved. The polyvinyl acetal resin (E) is not particularly limited, but has a degree of polymerization of 30.
What is 0 to 2500 is used. The degree of polymerization is 3
If it is less than 00, the flexibility of the B-stage resin or the cured product cannot be improved, and when the resin layer or the insulating film of the metal foil with the resin is formed with the B-stage resin, the resin layer is cracked, It is easy to peel off. Conversely, this degree of polymerization is 2
When it exceeds 500, when the resin layer of the metal foil with resin or the insulating film is formed with the epoxy resin composition, the resin layer is difficult to be cracked or peeled, but the phosphorus-containing organic compound (B) or the like is obtained. Compatibility with phosphorus-containing compounds such as phosphorus-containing epoxy resin decreases, and electrical reliability (interlayer insulation reliability) when an insulating layer of a multilayer printed wiring board is formed with a resin layer of a metal foil with resin or an insulating film. ) Is significantly reduced.

The amount of the polyvinyl acetal resin (E) added is 3 to 15% by mass based on the total amount of the epoxy resin component (A). When the amount added is 3
If the amount is less than 10% by mass, the flexibility of the B-stage resin or the cured product cannot be improved. , And easily come off. Conversely, if the addition amount exceeds 15% by mass, when a resin layer or an insulating film of a metal foil with a resin is formed with the epoxy resin composition, a resin layer that is difficult to crack or peel is obtained, The moisture absorption property of the resin layer is reduced, and the compatibility with the phosphorus-containing compound such as the phosphorus-containing organic compound (B) and the phosphorus-containing epoxy resin is also reduced. The electrical reliability (interlayer insulation reliability) when the insulating layer is formed decreases.

Other additives other than those described above include 2-
A curing accelerator such as ethyl-4-methylimidazole and other property imparting agents may be added as necessary. In particular, when butyral resin is blended as a flexible agent, the flexibility of the B-stage resin and the cured product can be more effectively improved.

When a filler is blended in the epoxy resin composition, an inorganic filler such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, silica balloon and the like is used. However, a pigment or the like may be blended. When the inorganic filler is blended in this way, impact resistance can be improved. In addition, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it acts as a flame-retardant aid and can ensure flame retardancy even if the phosphorus content is small. When the filler is blended, the blending amount is 10 to 15 with respect to the total amount of the epoxy resin component (A).
When the amount is less than 10% by mass, the effect of impact resistance is reduced, and the amount is less than 1% by mass.
If the content exceeds 50% by mass, the adhesiveness, which is an item necessary for a laminated board, is reduced. Also, glass fiber, pulp fiber,
The resin composition may contain a fibrous filler such as a synthetic fiber or a ceramic fiber, or an organic filler such as a fine particle rubber or a thermoplastic elastomer.

An epoxy resin composition can be prepared by sufficiently mixing the above components. Here, when a phosphorus-containing epoxy resin is used, the phosphorus-containing epoxy resin is generated in advance by a preliminary reaction as described above, and then other components are added and mixed sufficiently. At this time, if necessary, N, N
Amides such as dimethylformamide (DMF), ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone (MEK);
Methanol, ethanol, methoxypropanol (M
Organic solvents such as alcohols such as P) and aromatic hydrocarbons such as benzene and toluene may be blended, and a mixture of one or more of these organic solvents can be used.

As an example of the method for preparing the epoxy resin composition, when the phosphorus-containing epoxy resin is not used, the phosphorus-containing organic compound (B), the epoxy resin component (A) containing the epoxy resins (C), the polyvinyl acetal resin (E),
In addition, a particulate crosslinked elastomer (D) previously dispersed uniformly in a methyl ethyl ketone solvent or the like is charged into the solvent and sufficiently stirred and mixed, and then a curing accelerator is further blended and further stirred and mixed. Thus, an epoxy resin composition having a viscosity at 25 ° C. of 500 to 1000 P (poise) is obtained.

When a phosphorus-containing epoxy resin is used, a phosphorus-containing epoxy resin, a polyvinyl acetal resin (E), a particulate crosslinked elastomer (D) uniformly dispersed in a methyl ethyl ketone solvent or the like in advance, and if necessary, an epoxy An epoxy resin such as resins (C) is charged into a solvent and sufficiently stirred and mixed, and then a curing accelerator is blended and further stirred and mixed.
An epoxy resin composition having a viscosity at 500C of 500 to 1000 P (poise) is obtained.

Next, an insulating film obtained from the above epoxy resin composition will be described. The method for producing the insulating film is not particularly limited. For example, the epoxy resin composition as described above is preferably added to a carrier film that does not dissolve in an epoxy resin composition such as a polyester film or a polyimide film.
After coating to a thickness of 100 μm, it is dried by heating at 100 to 200 ° C. for 1 to 40 minutes to form a sheet. The insulating film is formed by a method generally called a casting method. At this time, if the sheet on which the epoxy resin composition is applied is previously subjected to a surface treatment with a release agent, the formed insulating film can be easily peeled off. Here, it is preferable that the thickness of the insulating film is 5 to 80 μm.

Next, the resin-attached metal foil obtained from the above epoxy resin composition will be described. For metal foil, copper, aluminum, brass, nickel, etc.
Alloys and composite metal foils can be used. Metal foil is
The thickness is preferably 3 μm to 80 μm, more preferably 9 μm.
７０70 μm is used. The method for producing the resin-attached metal foil is not particularly limited.For example, the epoxy resin composition is applied to one surface of the metal foil using a roll coater, a comma coater, a transfer coater, a curtain coater, a die coater, or the like. And then heat-dry continuously or discontinuously to semi-harden the resin component (B-stage)
To form a resin layer.
When semi-curing the resin component, for example, 100 to 2
It can be dried by heating at 00 ° C. for 1 to 40 minutes. Here, the thickness of the resin portion of the metal foil with resin is 20 to 200 μm.
m.

Next, a method of manufacturing a laminate using the above-mentioned insulating film or resin-coated metal foil will be described.

As the base material for the inner layer, an appropriate single-layer or multilayer printed wiring board can be used. For example, a printed wiring board formed from a prepreg made of the epoxy resin composition according to the present invention and a metal foil can be used. Can be used.

Here, a prepreg obtained by using the above epoxy resin composition will be described. As the sheet-like substrate, a woven or non-woven fabric of inorganic fibers such as glass or organic fibers such as polyester, polyamine, polyacryl, polyimide, Kevlar or the like can be used, but is not limited thereto. The method for producing the prepreg from the flame-retardant resin composition and the base material comprising the epoxy resin is not particularly limited, for example, after the base material is immersed in the epoxy resin composition and impregnated, Heat drying to semi-harden the resin component (B stage)
For example, at 100 to 200 ° C. for 1 hour.
It can be dried by heating for up to 40 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80% by mass.

A specific example of a method for producing the inner layer base material is as follows. First, one or a plurality of prepregs are laminated, a metal foil is arranged on one or both sides to form a laminate, and the laminate is heated.・ Lamination is integrated by pressing. Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, or the like can be used. The conditions for heating and pressing the laminate may be adjusted appropriately under the conditions for curing the epoxy resin composition, and heating and pressing may be performed. However, if the pressing pressure is too low, bubbles remain inside the obtained laminate. However, since the electrical characteristics may decrease, it is preferable to apply pressure under conditions that satisfy the moldability. For example, if the temperature is 1
60-220 ° C, pressure 49.0-490.3N / cm
² (5-50 kgf / cm ² ), heating and pressing time is 40-2
Each can be set for 40 minutes. Then, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution to perform a blackening treatment to obtain an inner layer base material.

On one or both sides of the circuit forming surface of such an inner layer base material, an insulating layer is formed with an insulating film or a metal foil with a resin, and a conductor layer is formed on the surface of the insulating layer. A plate is formed.

When the insulating layer is formed of an insulating film, the insulating film is arranged on the circuit forming surface of a plurality of substrates for the inner layer to form a laminate. Alternatively, an insulating film is disposed between the circuit forming surface of the inner layer base material and the metal foil to form a laminate. Then, the laminate is heated and pressed to be integrally formed, whereby a cured product of the insulating film is formed as an insulating layer and the base material for the inner layer is multi-layered. Alternatively, a metal foil is used as a conductor layer, an insulating film is formed as an insulating layer, and the base material for the inner layer is multi-layered. Here, the same metal foil as that used for the laminate used as the base material for the inner layer may be used.
Heat-press molding can be performed under the same conditions as in the formation of the inner layer base material.

A multilayer printed wiring board can be formed by further forming via holes and circuits on the surface of the multilayer laminate thus formed by an additive method or a subtractive method.

When the insulating layer is formed of a resin-coated metal foil, the resin-coated metal foil is coated on the circuit-forming surface of the inner-layer substrate, and the circuit-formed surface of the inner-layer substrate is formed of the resin-coated metal foil. To form a laminate.
Then, the laminate is heated and pressed to be integrally formed, whereby a cured product of the resin layer of the metal foil with resin is formed as an insulating layer, and the outer metal foil is formed as a conductor layer. Here, the heat and pressure molding can be performed under the same conditions as the formation of the inner layer base material.

A multilayer printed wiring board can be formed by further forming via holes or circuits on the surface of the multilayer laminate thus formed by an additive method or a subtractive method.

By using the printed wiring board obtained as described above as a base material for an inner layer and repeating the above-mentioned method using an insulating film or a metal foil with resin, a multilayer printed wiring board is formed. Can be done.

When the insulating layer of the inner layer base material is formed or when the insulating layer is further formed on the multilayer printed wiring board, a resin may be applied to form the insulating layer. In this case, the epoxy resin composition is preferably applied to a thickness of 5 to 100 μm on the circuit forming surface of the outermost layer of the laminated board or the multilayer printed wiring board, and then applied at 100 to 200 ° C.
To form a sheet by heating and drying for 1 to 90 minutes. It is formed by a method generally called a casting method. The thickness after drying is desirably 5 to 80 μm.

[0070]

The present invention will be described below in detail with reference to examples.

The following epoxy resins were used. Here, among the following epoxy resins, the epoxy resin 10 corresponds to the epoxy resin (C) represented by the general formula (1), and the epoxy resin 4 corresponds to the epoxy resin (C) represented by the general formula (2). The epoxy resins 2, 6, and 8 correspond to the epoxy resins (C) represented by the general formula (3). -Epoxy resin 1: Bisphenol A type bifunctional epoxy resin having an epoxy equivalent of 190 g / eq (manufactured by Yuka Shell Epoxy Co., Ltd .; trade name "Epicoat 828")-Epoxy resin 2: Bisphenol F type bifunctional having an epoxy equivalent of 172 g / eq Epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc .; trade name "EPICLON-830") Epoxy resin 3: biphenyl type bifunctional epoxy resin having an epoxy equivalent of 195 g / eq (trade name: YX4000H; manufactured by Yuka Shell Epoxy Co., Ltd.) Epoxy resin 4: Naphthalene-type bifunctional epoxy resin with an epoxy equivalent of 150 g / eq (manufactured by Dainippon Ink and Chemicals, Inc .; trade name "EPICLON-HP4032") Epoxy resin 5: Trifunctional with an epoxy equivalent of 210 g / eq Epoxy resin (manufactured by Mitsui Chemicals, Inc .; Product name "VG3
101 ") Epoxy resin 6: phenol novolak-type functional epoxy resin having an epoxy equivalent of 190 g / eq (manufactured by Dainippon Ink and Chemicals, Inc .; trade name" EPICLON-N77 ")
0 ") Epoxy resin 7: a tetrafunctional epoxy resin that emits fluorescence with an epoxy equivalent of 220 g / eq (manufactured by Shell Inc .;
・ Epoxy resin 8: A brominated bisphenol A type epoxy resin having an epoxy equivalent of 400 g / eq (manufactured by Toto Kasei Co., Ltd .; trade name “YDB400”; bromination ratio about 48%) ・ Epoxy resin 9: Epoxy Cresol novolak type epoxy resin with an equivalent weight of 220 g / eq (manufactured by Toto Kasei Co., Ltd .; trade name “YDCN704”) Epoxy resin 10: Hydroquinone type epoxy resin with an epoxy equivalent weight of 144 g / eq (manufactured by Toto Kasei Corporation; trade name “ZX- 1027 ") The following curing agents were used. Curing agent 1: dicyandiamide (molecular weight: 84; theoretical active hydrogen equivalent: 21 g / eq) Curing agent 2: phenol novolak resin (manufactured by Gunei Chemical Industry Co., Ltd .; Trade name "PSM6200"; hydroxyl equivalent 1
(05 g / eq; melting point: about 80 ° C.) As the phosphorus-containing organic compound (B), the following compound was used. -Phosphorus-containing organic compound 1: a phosphorus-containing organic compound represented by the chemical structural formula (5) (manufactured by Sanko Co., Ltd .; trade name "HCA")
-HQ "; hydroxyl equivalent: about 162 g / eq; phosphorus content: about 9.6 mass%)-phosphorus-containing organic compound 2: a phosphorus-containing organic compound represented by the above chemical structural formula (6) (manufactured by Sanko Corporation; trade name" HCA
-NQ "; hydroxyl equivalent: about 188 g / eq; phosphorus content: about 8.2% by mass)-phosphorus-containing organic compound 3: phosphorus-containing organic compound represented by the above chemical structural formula (7) (carboxyl equivalent: about 173 g /
eq; phosphorus content about 9.0% by mass) As the polyvinyl acetal resin (D), the following was used. -Polyvinyl acetal resin 1: manufactured by Sekisui Chemical Co., Ltd .; trade name "KS1"; degree of polymerization 500-Polyvinyl acetal resin 2: manufactured by Sekisui Chemical Co., Ltd .; trade name "KS3"; degree of polymerization 2000 As a crosslinked elastomer (E) Are crosslinked elastomer particles of a butadiene-acrylonitrile copolymer having a particle size of 0.5 μm or less (manufactured by JSR Corporation; trade name “X
ER-91 ") was used.

The following solvents were used as the solvent. Solvent 1: methyl ethyl ketone (MEK) Solvent 2: methoxypropanol (MP) Solvent 3: dimethylformamide (DMF) (Preparation of phosphorus-containing epoxy resin 1) Epoxy resin 1 (7
0 parts by mass) and the phosphorus-containing organic compound 1 (30 parts by mass) are heated and stirred in a flask at 130 ° C. without a solvent.
Triphenylphosphine (0.2 parts by mass) as an accelerator
Was added and heating and stirring were continued for 3 hours. As a result, the epoxy equivalent was about 570 g / eq, the melt viscosity at 150 ° C. was about 40 P (poise), and the phosphorus content was about 2.7 mass%.
Thus, a phosphorus-containing epoxy resin 1 was obtained.

(Preparation of phosphorus-containing epoxy resin 2) Epoxy resin 2 (70 parts by mass) and phosphorus-containing organic compound 1 (3
(0 parts by mass) was heated and stirred in a flask at 130 ° C. without solvent, and then triphenylphosphine (0.2 parts by mass) was added as a promoter, and the heating and stirring were continued for 4 hours. As a result, an epoxy equivalent of about 530 g / eq, 150
A phosphorus-containing epoxy resin 2 having a melt viscosity at about 100 P (poise) and a phosphorus content of about 2.9% by mass was obtained.

(Examples 1 to 21, Comparative Examples 1 to 6) For each of Examples and Comparative Examples, an epoxy resin composition was prepared by the following Method A or Method B using each component shown in Tables 1 to 3. .

<Method A> Of the phosphorus-containing organic compound, epoxy resin, polyvinyl acetal resin, and crosslinked elastomer particles uniformly dispersed in a methyl ethyl ketone solvent at a content of about 20% in advance, the components shown in the table were dissolved in the solvent. Put it in, and use “Homomixer” manufactured by Tokushu Kika Kogyo Co., Ltd.
The mixing was performed at a rotation speed of 1000 rpm for 90 minutes. Thereafter, 2-ethyl-4-methylimidazole was blended as a curing accelerator, and the mixture was further stirred for 15 minutes.
Viscosity at 5 ° C is 500-1000P (poise)
Was obtained.

<Method B> Phosphorus-containing epoxy resin, polyvinyl acetal resin, crosslinked elastomer particles uniformly dispersed in a methyl ethyl ketone solvent at a content of about 20% in advance, and if necessary, other epoxy resin and phosphorus-containing organic compound Among them, the components shown in the table were put into a solvent, and the mixture was added to a “Homomixer” manufactured by Tokushu Kika Kogyo Co., Ltd.
The mixing was performed at a rotation speed of 00 rpm for 90 minutes. Thereafter, 2-ethyl-4-methylimidazole was blended as a curing accelerator, and the mixture was further stirred for 15 minutes and then degassed to obtain an epoxy resin composition having a viscosity at 25 ° C of 500 to 1000 P (poise). .

Using the epoxy resin composition thus obtained, a metal foil with resin or an insulating film was prepared by any of the following methods.

<Preparation of Metal Foil with Resin> Thickness 0.018
mm on a roughened surface of a copper foil (manufactured by Furukawa Circuit Foil Co., Ltd .; trade name "GT") with a comma coater at room temperature, and then at 160 ° C. by a non-contact type heating unit. By heating, the solvent in the composition was dried and B-staged, and a resin-coated metal foil having a resin layer thickness of 75 μm was obtained.

<Preparation of Insulating Film> On one side of a carrier film made of polyethylene terephthalate (PET),
After applying the epoxy resin composition with a comma coater,
The solvent in the composition was dried and B-staged by heating at 160 ° C. by a non-contact type heating unit to obtain a 75 μm thick insulating film.

(Evaluation Test) The following evaluation test was performed on the metal foil with resin and the insulating film formed as described above.

Resin crack angle test The resin-coated metal foil and insulating film obtained in each of the examples and comparative examples were cut into a size of 100 × 100 mm to obtain a sample piece 1. This sample piece 1 is placed on a test stand 2 such that the resin layer side or the insulating film side faces the lower side as shown in FIG. 1, and a 10 mm diameter rod-shaped bend is formed on the upper surface of the copper foil. The jig 3 was arranged so that the outer peripheral surface thereof was in contact with the copper foil surface, and the test piece 1 was bent upward along the bending jig 3. At this time, the minimum bending angle θ at which a crack (crack) occurred in the resin layer was measured.

Resin storage stability test The resin-coated metal foil and insulating film obtained in each of the examples and comparative examples were left standing in a dryer at 40 ° C. and heated.
130 ° C of the sample obtained by shaving off only the resin layer
Was measured for melt viscosity. The heating time required for the melt viscosity to increase by 50% with respect to the initial melt viscosity of the sample before heating was measured.

Evaluation of Flame Retardancy A flame retardant 0.2 mm double-sided copper-clad laminate (manufactured by Matsushita Electric Works Co., Ltd .; "CR1766") was obtained by removing the copper foil on both sides of the laminate as a base material for the inner layer. On both sides of this inner layer substrate,
The resin-attached metal foil or insulating film obtained in each of the examples and comparative examples is stacked one by one so that the resin layer faces the inner layer base material side, and heated at 170 ° C. and 2.94 MPa for 90 minutes. It was molded under pressure. When using a metal foil with resin, after removing the copper foil on the surface of this molded plate, 125
mm × 13mm, underwrite
“Test for” by rs Laboratories
Flammability of Plastic M
A test of the combustion behavior was carried out in accordance with the materials-UL94 ".
The average time required for extinction was derived.

Heat resistance test A copper foil on the surface of a double-sided copper-clad laminate (manufactured by Matsushita Electric Works, Ltd .; “CR1766”) having a thickness of 0.2 mm and a copper foil thickness of 35 μm was subjected to a blackening treatment and used as an inner layer base. Material. On both surfaces of this inner layer base material, the resin-attached metal foil or insulating film obtained in each of the Examples and Comparative Examples, one by one each so that the resin layer faces the inner layer base material side, 170 ℃, 2.
It was heated and pressed under the conditions of 94 MPa for 90 minutes to obtain a multilayer board. This multilayer board was cut to obtain four samples having dimensions of 50 mm × 50 mm. After heating this sample in an oven for 60 minutes, the surface of the sample was observed, and the maximum temperature at which no appearance abnormality such as blisters occurred in all four samples was measured.

Evaluation of water absorption The two metal foils with resin or the insulating films obtained in each of the examples and comparative examples were stacked with the resin layers facing each other.
After heat and pressure molding at 0 ° C. and 2.94 MPa for 90 minutes, when a metal foil with resin was used, the copper foil on both sides was removed to obtain a cured product having a resin thickness of about 160 μm. The cured product was cut into a size of 500 mm × 400 mm, boiled in water at 100 ° C. for 2 hours, and the water absorption after boiling was measured. Here, the water absorption was derived by the following formula. Water absorption = {(weight after water absorption-weight before water absorption) / weight before water absorption} x 100 (%)-Glass transition temperature measurement A cured product similar to the sample subjected to water absorption evaluation was measured for 30 m.
cut into dimensions of mx 5 mm, dynamic viscoelasticity and loss tangent tan to temperature change with viscoelastic spectrometer
The change in δ was measured, and the glass transition temperature was determined from the peak temperature of tan δ.

Evaluation of Dakone With respect to only the copper foil with resin, by observing the surface of the laminated board similar to that used for the evaluation of flame retardancy by visual inspection, it was possible to obtain a dakone (resin) by the resin peeled from the metal foil with resin at the time of molding. (Cured product) was observed. Then, the number of samples generated with respect to the total number of samples was derived to evaluate the frequency of occurrence of the defective samples.

Interlayer insulation reliability (HAST) test FR-4 type double-sided copper-clad laminate (Matsushita Electric Works; CR176) having a thickness of 0.5 mm and a copper foil thickness of 18 μm
6 ") The copper foil on one side was removed and a circuit was formed on the copper foil on the other side to form an inner layer circuit, thereby forming an inner layer base material. On the inner layer circuit forming surface of the inner layer base material, the resin-attached metal foil or insulating film obtained in each of the examples and comparative examples is stacked so that the resin layer faces the circuit forming surface side, and 170 ° C.
It was heated and pressed under the conditions of 2.94 MPa for 90 minutes to obtain a multilayer board. An outer layer circuit having a grid width of 150 μm and a line interval of 150 μm is formed on the surface of the multilayer board by an etching method when using a metal foil with a resin or by a plating method when using an insulating film. did. Thus, as shown in FIG. 2, the inner insulating layer 4 formed of the insulating layer of the inner layer base material, the outer layer circuit 5, the resin layer of the metal foil with resin or the outer insulating layer 6 formed of the insulating film. And multilayer printed wiring board 9 in which outer layer circuit 7 is laminated and formed in order
Was formed, and a solder resist 8 was further formed on the entire surface on which the outer layer circuit 7 was formed.

A voltage of 20 V DC is applied between the outer layer circuit 7 and the inner layer circuit 5 in the multilayer printed wiring board 9 in an atmosphere of a temperature of 121 ° C. and a humidity of 85%, and the outer layer circuit 7 and the inner layer circuit 5 at that time are applied. Was measured every 50 hours of continuous voltage application time. This insulation resistance is 10 ⁸
Those having Ω or more were evaluated as acceptable, and those less than Ω were evaluated as unacceptable. If the test was successful even if the continuous voltage application time exceeded 300 hours, it can be determined that there is no practical problem as a general printed wiring board. Therefore, the test was performed until the continuous voltage application time reached a total of 300 hours. .

Tables 1 to 3 show the above results.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

As is clear from Tables 1 to 3, Comparative Example 1
However, since a brominated epoxy resin is blended without using a phosphorus-containing organic compound, the flame retardancy is excellent, but the halogen content is high, and there is a risk that toxic gas is generated during combustion. In Comparative Examples 2 and 3, the phosphorus-containing organic compound was not used, and the flame retardancy was low. In Comparative Examples 3 and 4, the crosslinked elastomer was not contained, and in Comparative Example 5, the content of the crosslinked elastomer was low. Therefore, the evaluation of the resin crack angle was low, and the flexibility of the resin layer was low. In Comparative Example 6, the amount of the crosslinked elastomer was too large, so that the evaluation of Dakone was low and the evaluation of interlayer insulation reliability was also low.

On the other hand, in Examples 1 to 21, the halogen content was low, and the flexibility of the resin layer made of the epoxy resin composition, the flame retardancy of the insulating layer, and the reliability of interlayer insulation were all excellent. Evaluation results were obtained, and favorable results were obtained for other evaluation items.

Further, in Examples 9, 17, and 18 in which the polyvinyl acetal resin was blended, the flexibility of the resin layer was particularly excellent.

[0096]

As described above, the epoxy resin composition according to claim 1 of the present invention comprises an organophosphorus compound (b) having one active hydrogen bonded to a phosphorus atom per mol of a quinone compound. With the phosphorus-containing organic compound (B) obtained by reacting
An epoxy resin component (A) containing at least one or more epoxy resins (C) selected from (A) to (3), and a crosslinked elastomer (D) having a particle diameter of 1 μm or less are blended. )) To the epoxy resin component (A)
And 20 to 45 with respect to the total amount of the phosphorus-containing organic compound (B).
%, And the blending amount of the crosslinked elastomer (D) having a particle diameter of 1 μm or less with respect to the total amount of the epoxy resin component (A) is 3 to 15% by mass. B-stage resin obtained by semi-curing this epoxy resin composition, and the flexibility of the cured product can be improved, and the insulation reliability of the cured product can be improved. Is what you can do.

The invention of claim 2 is characterized in that, in claim 1, the polyvinyl acetal resin (E) is contained in an amount of 3 to 15% by mass based on the total amount of the epoxy resin component (A).
The flexibility of the B-stage resin obtained by semi-curing the epoxy resin composition and the cured product thereof can be further improved.

[0098] In the invention of claim 3, since the phosphorus content is 0.8 to 5.0 mass% of the total amount of the epoxy resin component (A), the flame retardancy is further improved. Is what you can do.

In the metal foil with resin according to claim 4 of the present invention, a resin layer formed from the epoxy resin composition according to any one of claims 1 to 3 is provided on the surface of the metal foil. The layer has excellent flame retardancy and excellent flexibility despite containing no halogen, and the insulation reliability of the insulating layer when the insulating layer is formed from a cured resin layer Can be improved.

The insulating film according to claim 5 of the present invention is excellent in spite of containing no halogen since the epoxy resin composition according to any one of claims 1 to 3 is formed into a sheet. It has flame retardancy and excellent flexibility, and can improve the insulation reliability of the insulating layer when the insulating layer is formed from a cured product of the insulating film.

According to a sixth aspect of the present invention, there is provided a multilayer printed wiring board comprising: a resin-coated metal foil according to the fourth aspect; Because at least one of them is formed by lamination, the resin layer of the resin-coated metal foil or the insulating layer made of the insulating film has excellent flame retardancy and excellent flexibility despite not containing halogen. And the insulation reliability of the insulating layer can be improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a test method of a resin crack angle test of a metal foil with resin in an example.

FIGS. 2A and 2B are diagrams for explaining a test method of an interlayer insulation reliability test in Examples, where FIG. 2A is a front cross-sectional view and FIG.
FIG. 3A is a plan view showing a state where a solder resist is not provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 63/02 C08L 63/02 5G333 101/12 101/12 H01B 3/40 H01B 3/40 CD 17 / 56 17/56 A 17/62 17/62 H05K 1/03 610 H05K 1/03 610L 3/46 3/46 T // (C08L 63/00 (C08L 63/00 C 29:14) 29:14) ( C08L 63/02 (C08L 63/02 29:14) 29:14) F-term (Reference) 4F071 AA12 AA12X AA22X AA34X AA40 AA42 AA76X AC15 AF14 AF39 AF47 AH13 BA02 BB02 BC01 BC02 4F100 AB01B AB17 AB33B AH01A00A23A BA03 BA07 BA10B BA10C BA13 DE01A EH46 EJ05A GB43 HB08 JG04 JJ03 JJ07 JK06 JK17 JL11 YY00A 4J002 AC032 AC072 AC082 BB182 BC052 BE063 BG102 CD041 CD051 CD111 EW136 FA082 FD136 HQ08H13H11 CC08 05 AA06 AA14 AB17 AB25 AB35 BA12 BA13 BA18 BA25 CA15 CA47 CB23 CD04 CD13 5G333 AA03 AB13 AB21 CB04 CB13 DA04 DB02 FB02 FB14

Claims (6)

[Claims] 1. A phosphorus-containing organic compound obtained by reacting an organic phosphorus compound (b) having one active hydrogen bonded to a phosphorus atom with respect to 1 mol of a quinone compound in a range of 1.01 to 2 mol. Compound (B) and the following general formulas (1) to
An epoxy resin component (A) containing at least one or more epoxy resins (C) selected from (3) and a crosslinked elastomer (D) having a particle size of 1 μm or less are blended. An epoxy resin composition characterized in that the blending amount of the crosslinked elastomer (D) is 3 to 15% by mass based on the total amount of the epoxy resin component (A). Embedded image Embedded image Embedded image Embedded image 2. The epoxy resin composition according to claim 1, comprising 3 to 15% by mass of the polyvinyl acetal resin (E) based on the total amount of the epoxy resin component (A). 3. The epoxy resin composition according to claim 1, wherein the phosphorus content is 0.8 to 5.0% by mass of the total amount of the epoxy resin component (A). 4. A metal foil with resin, comprising a resin layer molded from the epoxy resin composition according to claim 1 on a surface of the metal foil. 5. An insulating film formed by molding the epoxy resin composition according to claim 1 into a sheet. 6. An inner layer base material on which a circuit pattern is formed, wherein at least one of the resin-coated metal foil according to claim 4 and the insulating film according to claim 5 is laminated and formed. Characteristic multilayer printed wiring board.