JP2002226816A - Flame-retardant adhesive composition, flame-retardant adhesive film using the same, metal foil with flame- retardant adhesive and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant adhesive composition having excellent electrical insulating properties and flame retardance, using a nonhalogen-based flame retardant and a flame-retardant adhesive film, a metal foil with a flame- retardant adhesive and a printed wiring board using the flame-retardant adhesive composition. SOLUTION: This flame-retardant adhesive composition is characterized by comprising an epoxy resin and one or more kinds of phosphonates selected from a nitrilotris(methylene)phosphonate metal salt, a nitrilotris(methylene) phosphonate melamine salt, 1-hydroxyethylidene-1,1-diphosphonate metal salt and 1-hydroxyethylidene-1,1-diphosphonate melamine salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition containing a halogen-free flame retardant and having excellent insulation and flame retardancy, a flame-retardant adhesive film using the same, and a flame-retardant adhesive. The present invention relates to an attached metal foil and a printed wiring board.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for smaller, lighter, and faster electronic devices. A flexible printed circuit board (FPC board) is light in weight and can be mounted three-dimensionally, which is very advantageous for a demand for light weight and high density. In the field of printed wiring boards, in recent years, multilayer printed wiring boards using a build-up method have received particular attention. In the build-up method, usually, a circuit is processed on a copper-clad laminate to form a first circuit layer, and a second circuit layer is formed thereon via an insulating layer. Is regarded as one circuit layer, and an insulating layer and a second
Are sequentially formed to form a multilayer. As a method of forming the second circuit layer, an insulating adhesive sheet with a copper foil in which an insulating adhesive sheet on the first circuit layer is formed on one side of a copper foil is laminated, or via an insulating adhesive sheet. Layer copper foil,
A method is used in which a copper foil is laminated by heating and pressing, and the copper foil is etched to form a second circuit layer.

[0003] This multilayer printed wiring board is also required to have excellent flame retardancy from the viewpoint of safety. For this reason, a method has been proposed in which a flame retardant is blended into the insulating adhesive sheet. The use of halogen-based flame retardants, which have been used so far, has been pointed out as the possibility that dioxins, which are toxic to the human body in a small amount during combustion, may be generated.

[0004] Using such non-halogen flame retardants,
As a method for making a printed wiring board flame-retardant, for example, a method using an insulating adhesive sheet in which an insulating adhesive containing a phosphoric acid ester is formed in a sheet shape (JP-A-2000-27)
No. 3411), a sulfur-containing thermoplastic resin, a non-halogenated polyfunctional epoxy resin having an epoxy equivalent of 500 or less, a phosphorus compound having at least one PH bond in a molecule and a compound having at least two epoxy groups (JP-A-2000-239525), a polyfunctional epoxy resin, a roughening component soluble or decomposable in an aqueous solution of an oxidizing agent, basic nitrogen Method using an epoxy resin composition containing a compound, a salt of polyphosphoric acid, and a curing agent (JP-A-200
0-198907) and the like.

[0005]

However, since the above-mentioned phosphorus-based flame retardant has a PO bond, there is a problem in hydrolysis resistance, and an organic phosphorus-based flame retardant having this PO bond is required. The printed wiring board containing the adhesive layer as a flame retardant, phosphoric acid is eluted by the decomposition of the organic phosphorus compound,
There is a problem that electrical characteristics are deteriorated. Accordingly, an object of the present invention is to provide a flame-retardant adhesive composition using a halogen-free flame retardant having excellent electrical insulation and flame retardancy, and a flame-retardant adhesive film and a flame-retardant adhesive using the same. An object of the present invention is to provide an attached metal foil and a printed wiring board.

[0006]

SUMMARY OF THE INVENTION In this situation, the present invention provides an epoxy resin containing nitrilotris (methylene).
Metal phosphonate, melamine nitrilotris (methylene) phosphonate, 1-hydroxyethylidene-1,1-
Diphosphonic acid metal salt and 1-hydroxyethylidene-
Flame retardant having excellent flame retardancy and electrical insulation when using an adhesive composition containing one or more phosphonates obtained from a melamine salt of 1,1-diphosphonic acid The present inventors have found that a printed wiring board having excellent flame retardancy and electrical insulation can be obtained by using this flame-retardant adhesive film, and have completed the present invention.

That is, the first invention of the present invention relates to an epoxy resin, a metal salt of nitrilotris (methylene) phosphonic acid,
Nitrilotris (methylene) phosphonic acid melamine salt, 1
-Hydroxyethylidene-1,1-diphosphonic acid metal salt and 1-hydroxyethylidene-1,1-diphosphonic acid melamine, containing one or more phosphonates The present invention provides a flame-retardant adhesive composition. The phosphonate has an average particle diameter of 20 μm or less and a residual chloride ion concentration of 500 μm.
It is preferably at most ppm.

A second invention of the present invention is characterized in that the above-mentioned flame-retardant adhesive composition is formed into a film or a sheet on a supporting substrate. Is provided.

A third invention of the present invention is directed to a metal having a flame-retardant adhesive, wherein said flame-retardant adhesive composition is formed on a metal foil in a film or sheet form. Provide foil.

According to a fourth aspect of the present invention, there is provided a printed wiring board characterized in that the printed wiring board is bonded using the flame-retardant adhesive film or the metal foil with the flame-retardant adhesive. Is what you do.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Although there is no particular limitation on the epoxy resin used in the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin Resin, cycloaliphatic epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin,
It is preferable to use epoxidized polybutadiene, dicyclopentadiene type epoxy resin, triglycidyl isocyanurate and the like, and these epoxy resins may be brominated or those containing sulfur or other modified products. One or more of these epoxy resins may be used, and an epoxy resin such as a phenoxy resin, a urethane-modified epoxy resin, or a rubber-modified epoxy resin may be used in combination from the viewpoint of imparting flexibility.

The phosphonate used in the present invention includes metal nitrilotris (methylene) phosphonate, melamine nitrilotris (methylene) phosphonate, metal 1-hydroxyethylidene-1,1-diphosphonate and 1-hydroxyethylidene-1,1-diphosphonate.
Hydroxyethylidene-1,1-diphosphonic acid melamine salts, which are hardly water-soluble, are divalent metal salts and melamine salts.

As the metal nitrilotris (methylene) phosphonate, the following general formula (1)

[0014]

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(Wherein M ¹ and M ^{2 each} represent a hydrogen atom or an alkali metal), and a phosphonic acid obtained by reacting nitrilotris (methylene) phosphonic acid or a salt thereof with a divalent metal compound. Salt.

In the formulas of nitrilotris (methylene) phosphonic acid and salts thereof represented by the above general formula (1), M ¹ and M ² are a hydrogen atom or an alkali metal such as K, Na, Li, etc. As the metal, Li, Na, and K are preferable.

The method of reacting the nitrilotris (methylene) phosphonic acid represented by the general formula (1) and a salt thereof with a divalent metal compound to obtain a nitrilotris (methylene) phosphonate metal salt is not particularly limited. For example, a nitrile tris (methylene) phosphonic acid represented by the general formula (1) and a salt thereof and a divalent metal compound can be prepared by using water, a mixed solvent of water-acetone, water-alcohol, or the like. In a water-based solvent.

Examples of the divalent metal compound include oxyacid salts, hydroxides, oxides, and halides of the divalent metal.
Examples of the oxyacid salt of a valent metal include a sulfate, a carbonate, a phosphate, a nitrate, and a nitrite. Examples of the divalent metal include Mg, Ca, Ba, Sr, and Zn.

In the reaction for obtaining the target nitrilotris (methylene) phosphonic acid metal salt of the above-mentioned reaction, the starting material nitrilotris (methylene) phosphonic acid represented by the general formula (1) and a salt thereof and a divalent metal compound Is usually 2 mol per mol of the phosphonic acid of the general formula (1) and a salt thereof.
The amount of the divalent metal compound is in the range of 1 to 3 mol, and the amount of the divalent metal compound to be used is appropriately adjusted depending on the amount of the divalent metal introduced into the object within the range, for example, the amount of 1 to 3 divalent metals. do it.

Specific examples thereof include nitrilotris (methylene) phosphonic acid / magnesium salt, nitrilotris (methylene) phosphonic acid / 2 magnesium salt, nitrilotris (methylene) phosphonic acid / 3 magnesium salt, nitrilotris (methylene) Phosphonic acid / calcium salt,
Nitrilotris (methylene) phosphonic acid / 2 calcium salt, nitrilotris (methylene) phosphonic acid / 3 calcium salt, nitrilotris (methylene) phosphonic acid / barium salt, nitrilotris (methylene) phosphonic acid / 2 barium salt, nitrilotris ( Methylene) phosphonic acid ・ 3
Barium salt, nitrilotris (methylene) phosphonic acid
Strontium salt, nitrilotris (methylene) phosphonic acid / 2 strontium salt, nitrilotris (methylene) phosphonic acid / 3 strontium salt, nitrilotris (methylene) phosphonic acid / zinc salt, nitrilotris (methylene) phosphonic acid / 2 zinc salt, And nitrilotris (methylene) phosphonic acid / 3 zinc salt.

The melamine salt of nitrilotris (methylene) phosphonic acid is represented by the following general formula (2)

[0022]

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(Wherein, M represents melamine, and n represents 1 to 6)
Indicates an integer. ).

The method for producing the melamine nitrilotris (methylene) phosphonate is not particularly limited.
Known methods can be used, for example, the following general formula (5)

[0025]

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Nitrile tris (methylene) phosphonic acid and melamine represented by
The reaction may be performed in an aqueous solvent such as water-alcohol.

In the above reaction for obtaining the target melamine salt of nitrilotris (methylene) phosphonic acid in the above reaction, the mixing ratio of the nitrile tris (methylene) phosphonic acid represented by the general formula (5) and the melamine is usually The amount of melamine is 1 to 6 mol per mol of the phosphonic acid of the general formula (5), and the amount of melamine to be introduced into the target substance within the range is, for example, 1 to 6 melamines. What is necessary is just to adjust the usage-amount suitably.

Specific examples of the compound include nitrilotris (methylene) phosphonic acid / 6 melamine salt, nitrilotris (methylene) phosphonic acid / 5 melamine salt, nitrilotris (methylene) phosphonic acid / 4 melamine salt, nitrilotris ( Methylene) phosphonic acid / 3 melamine salts, nitrilotris (methylene) phosphonic acid / 2 melamine salts, nitrilotris (methylene) phosphonic acid / melamine salts, and the like.

1-hydroxyethylidene-1,1-
As the divalent metal salt of diphosphonate, the following general formula (3)

[0030]

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(Wherein M ¹ and M ^{2 each} represent a hydrogen atom or an alkali metal) by reacting 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof with a divalent metal compound. It is obtained.

In the formulas of 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof represented by the general formula (3), M ¹ and M ² are hydrogen atoms or alkali metals such as K, Na and Li. And alkali metals such as Li and N
a and K are preferred.

The 1-hydroxyethylidene-1,1-diphosphonic acid and its salt represented by the general formula (3) are reacted with a divalent metal compound to give 1-hydroxyethylidene-
The method for obtaining the 1,1-diphosphonic acid metal salt is not particularly limited, and a known method can be used. For example, 1-hydroxyethylidene-1, 1 represented by the general formula (3) can be used.
1-diphosphonic acid and a salt thereof and a divalent metal compound,
The reaction is carried out by a reaction in an aqueous solvent such as water, a mixed solvent of water-acetone, or water-alcohol.

Examples of the divalent metal compound include oxyacid salts, hydroxides, oxides, and halides of the divalent metal.
Examples of the oxyacid salt of a valent metal include a sulfate, a carbonate, a phosphate, a nitrate, and a nitrite. Examples of the divalent metal include Mg, Ca, Ba, Sr, and Zn.

In the above-mentioned reaction to obtain the metal salt of 1-hydroxyethylidene-1,1-diphosphonic acid, which is the target of the reaction, the starting materials 1-hydroxyethylidene-1,1-diphosphonic acid represented by the general formula (3) and The ratio of the salt to the divalent metal compound is usually in the range of 1 to 2 mol of the divalent metal compound per 1 mol of the phosphonic acid of the general formula (3) and the salt thereof, and within this range, the compound is introduced into the target compound. The amount of the divalent metal compound may be appropriately adjusted depending on the amount of the divalent metal to be used, for example, the amount of one or two divalent metals.

Specific examples thereof include 1-hydroxyethylidene-1,1-diphosphonic acid / magnesium salt,
Hydroxyethylidene-1,1-diphosphonic acid / 2 magnesium salt, 1-hydroxyethylidene-1,1-diphosphonic acid / calcium salt, 1-hydroxyethylidene-
1,1-diphosphonic acid / dicalcium salt, 1-hydroxyethylidene-1,1-diphosphonic acid / barium salt, 1
-Hydroxyethylidene-1,1-diphosphonic acid / 2 barium salt, 1-hydroxyethylidene-1,1-diphosphonic acid / strontium salt, 1-hydroxyethylidene-1,1-diphosphonic acid / 2 strontium salt, 1-hydroxyethylidene -1,1-diphosphonic acid / zinc salt,
1-hydroxyethylidene-1,1-diphosphonic acid.2
Zinc salts and the like.

1-hydroxyethylidene-1,1-
The melamine salt of diphosphonic acid is represented by the following general formula (4)

[0038]

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(Wherein, M represents melamine, and n is 1 to
4. ). In the general formula (4), M is melamine, and n represents an integer of 1 to 4.

Specifically, 1-hydroxyethylidene-1,1-diphosphonic acid / melamine 1-hydroxyethylidene-1,1-diphosphonic acid / 2
Melamine 1-hydroxyethylidene-1,1-diphosphonic acid-3
Melamine 1-hydroxyethylidene-1,1-diphosphonic acid ・ 4
Melamine, and these compounds are used alone or in combination of two or more.

The method for producing 1-hydroxyethylidene-1,1-diphosphonate represented by the general formula (4) according to the present invention is not particularly limited, and a known method can be used. The following general formula (6)

[0042]

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1-hydroxyethylidene represented by
1,1-Diphosphonic acid and melamine may be reacted in an aqueous solvent such as water, a mixed solvent of water-acetone, or water-alcohol.

In the above-mentioned reaction for obtaining a melamine salt of 1-hydroxyethylidene-1,1-diphosphonic acid as a target product, 1-hydroxyethylidene-1,1-diphosphonic acid represented by the general formula (6) as a raw material is used. The mixing ratio with melamine is usually in the range of 1 to 4 mol of melamine per 1 mol of the phosphonic acid of the general formula (6), and within that range, the amount of melamine introduced into the target substance, for example, 1 to 4 The amount of melamine used may be appropriately adjusted depending on the amount of melamine.

The above-mentioned phosphonates are used alone or in combination of two or more, and these compounds may be hydrated or anhydrous. In the present invention, the above-mentioned phosphonate has an average particle size of 1 to 3 determined by a laser method.
20 μm, preferably 1 to 15 μm, particularly preferably 2 to
The thickness of 10 μm is preferable for imparting excellent flame retardancy and adhesiveness to the epoxy resin.

In the present invention, in the reaction of phosphonic acid or a salt thereof with melamine or a divalent metal compound, chloride ions derived from the raw material phosphonic acid or a salt thereof are added during the reaction. The phosphonate obtained by filtering, washing with water, and / or repulp treatment after reacting with melamine or a divalent metal compound as a raw material and partially forming chloride in the target phosphonate. It is particularly preferable to use an acid salt having a residual chlorine ion concentration of 500 ppm or less, preferably 450 ppm or less from the viewpoint of imparting electrical insulation.

Next, the product is dried and pulverized to obtain a product.

The amount of the phosphonate is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, as P, based on 100 parts by weight of the epoxy resin.
The reason is that if the blending amount of the phosphonate is less than 1 part by weight as P, sufficient flame retardancy cannot be imparted to the substrate,
Further, when P is more than 20 parts by weight, various physical properties of the base material tend to decrease, which is not preferable.

The flame-retardant adhesive composition of the present invention can be used in combination with a flame-retardant auxiliary. Examples of the flame retardant auxiliary include inorganic flame retardants, melamine derivatives, and phosphorus flame retardants.

[0050] As the inorganic flame retardant is preferably hydrated metal compound, the hydrated metal compound, a burn suppressing action by endothermic reaction _{M m O n · XH 2 O} (M is a metal, m, n
Represents an integer of 1 or more determined by the valence of the metal, and X represents contained crystal water. Or a double salt containing the compound, specifically, calcium hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, barium hydroxide, zirconium hydroxide, dawsonite, zinc stannate , Zinc borate, aluminum borate, antimony pentoxide, basic zinc carbonate, cobalt oxide, zirconium oxide, tin oxide, aluminum oxide,
Titanium oxide, magnesium oxide, calcium silicate, borax, zinc molybdate, zinc phosphate, magnesium phosphate, hydrotalcite, hydrocalumite, kaolin, talc, sericite, pyrophyllite, bentonite, kaolinite, calcium sulfate , 1 such as zinc sulfate
Species or two or more species. These hydrated metal compounds may be surface-treated, and those hydrated metal compounds having an average particle diameter determined by a laser method are usually 20 μm or less, preferably 1 to 10 μm. It is preferable from the viewpoint of dispersibility with respect to.

Examples of the melamine derivative include melamine, melamine cyanurate, methylolated melamine,
(Iso) cyanuric acid, melam, melem, melon, succinogamine, melamine sulfate, acetoguanamine sulfate,
Melam sulfate, guanyl melamine sulfate, melamine resin, B
Examples include T resin, cyanuric acid, isocyanuric acid, isocyanuric acid derivatives, melamine derivatives such as melamine isocyanurate, benzoguanamine, and acetoguanamine, and guanidine compounds.

Examples of phosphorus-based flame retardants include triethyl phosphate, tricresyl phosphate, triphenyl phosphate,
Cresyl phenyl phosphate, octyl diphenyl phosphate,
Ethyl diethylene phosphate, butyl dihydroxypropylene phosphate, disodium ethylene phosphate, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid,
Propylphosphonic acid, butylphosphonic acid, 2-methyl-
Propylphosphonic acid, t-butylphosphonic acid, 2,3-
Dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphine Acid, bis (4-methoxyphenyl) phosphinic acid, red phosphorus, ammonium phosphate, ammonium polyphosphate, melamine phosphate, guanylurea phosphate, melamine polyphosphate, guanidine phosphate, ethylenediamine phosphate, phosphazene, melamine methylphosphonate And the like.

Red phosphorus whose surface is modified by an organic or / and inorganic substance is preferable. Examples thereof include a phenol resin, an epoxy resin, an ethylene-vinyl acetate copolymer, a melamine-formaldehyde polycondensate, Mg, Ca, and Ti. , A
Examples thereof include, but are not limited to, hydroxides of l, Co, and Zr and those surface-treated with one or more selected from these oxides.

The above-mentioned flame-retardant auxiliaries are used alone or in combination of two or more. Among them, hydrated metal compounds are particularly preferred.
The mixing ratio of these flame retardant auxiliaries is 100% for epoxy resin.
It is usually 0.1 to 200 parts by weight, preferably 30 to 150 parts by weight, based on parts by weight.

Also, the flame-retardant adhesive composition of the present invention includes:
As long as the effects of the present invention are not impaired, it can be used in combination with a curing agent, a curing accelerator, a rubber component, a coupling agent, an inorganic filler, an ion scavenger, another resin, and the like.

The curing agent is a component for curing the epoxy resin, and the type of the curing agent is not particularly limited, and a known curing agent can be used. As the curing agent, for example,
C ₂ -C such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.
₂₀ 0 of linear aliphatic diamines, meta-phenylenediamine,
Paraphenylenediamine, paraxylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone,
4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyano Amines such as diamide, phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, novolak type phenol resin such as nonylphenol novolak resin, resol type phenol resin, polyoxystyrene such as polyparaoxystyrene, phenol aralkyl resin, naphthol type Obtained by co-condensation of a phenol compound in which a hydrogen atom bonded to a benzene ring, naphthalene ring, or other aromatic ring of an aralkyl resin is substituted with a hydroxyl group, and a carbonyl compound Phenolic resin, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, trimetic anhydride, Examples thereof include acid anhydrides such as pyromellitic anhydride and benzophenonetetracarboxylic anhydride, and amine complexes such as boron trifluoride. These may be used alone or in combination of two or more. A curing accelerator may be added as necessary, but there is no particular limitation on the curing accelerator. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine Tertiary amine compounds such as 2-methylimidazole, 2
Imidazole compounds such as -ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole, organic phosphine compounds such as triphenylphosphine and tributylphosphine, phosphonium salts, and ammonium salts. One or two or more can be used. In the present invention, the curing agent and the curing accelerator may be epoxy adducts or microencapsulations thereof.

The rubber component is a component that improves the flexibility required for an adhesive film and further improves the heat resistance of the insulating layer. The type of the rubber component is not particularly limited, and a known rubber component is used. Can be used. For example, acrylic rubber such as acrylonitrile butadiene rubber, carboxy group-containing acrylonitrile butadiene rubber,
Modified products, polybutadiene and the like are mentioned.
Seeds or two or more can be used. When the rubber component is blended, a commonly known vulcanizing agent such as an alkylphenol resin is blended if necessary.

The coupling agent is a component for improving the adhesion between the insulating layer, the circuit layer and the copper foil. The type of the coupling agent is not particularly limited, and a known coupling agent can be used. As the coupling agent, for example,
Examples thereof include silane coupling agents such as epoxy silane, amino silane, and urea silane, and titanate coupling agents. These may be used alone or in combination of two or more.

The inorganic filler is a component for improving the mechanical strength and adjusting the viscosity when the adhesive is used as a varnish. The type of inorganic filler is not particularly limited, and known inorganic fillers can be used.Examples of the inorganic filler include alumina, crystalline silica, fused silica, aluminum hydroxide, zirconium silicate, talc,
Clay, white carbon, calcium carbonate, magnesium carbonate, mica, E glass fine powder, calcium silicate,
Examples thereof include aluminum nitride, boron nitride, calcium oxide, aluminum borate whiskers, and barium sulfate. These may be used alone or in combination of two or more. The amount of these inorganic fillers is preferably not more than 50% by weight based on the epoxy resin.

The ion scavenger is a component that adsorbs ionic impurities and improves insulation reliability during moisture absorption. For example, vinyl triazine, triazine thiol,
Oxins, thiazoles, bisphenol-based reducing agents,
A zirconium-based compound, an antimony-bismuth-based compound, a magnesium-aluminum-based compound, and the like may be mentioned, and one or more of these may be used. The compounding amount of these ion scavengers is desirably 0.1 to 10 parts by weight based on 100 parts by weight of the resin solids.

The other resin component is a component for improving mechanical strength and flexibility when used as an adhesive film. Other resin components that can be used include, for example, phenolic resins, acrylic resins, butyral resins, polyester resins, amino resins, polyimide resins, and the like.These other resins are hydroxyl groups, carboxyl groups, amino groups,
Alternatively, it may be a modified product containing a sulfur atom. The amount of these other resin components is not particularly limited, but may be 0.1
It is preferable to set it to 50% by weight.

Further, the flame-retardant adhesive composition of the present invention includes:
Commonly known additives such as an organic solvent, an antioxidant, a colorant (pigment, dye), a crosslinking agent, a crosslinking aid, an antistatic agent, an antifoaming agent, and a leveling agent can be blended.

The flame-retardant adhesive composition of the present invention is produced by uniformly mixing the epoxy resin, the phosphonate, the flame-retardant auxiliary added as required, and other additives. can do. The flame-retardant adhesive composition of the present invention can be used in the form of a solution, a paste, a pellet, or the like, and is usually dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, Dissolve or disperse the components in any organic solvent such as sulfolane, cyclohexanone, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, 1-acetoxy-2-ethoxyethane, ethylene glycol monomethyl ether, methanol, ethanol, etc. The liquid adhesive is preferably used. When this liquid adhesive is used, the solid content concentration is not particularly limited, but is preferably 5 to 80% by weight.

The flame-retardant adhesive composition of the present invention can be used as an adhesive composition for electric parts requiring good electrical insulation and adhesion, for example, for flat cables, flexible printed wiring boards, and multilayer prints. Printed wiring boards for wiring boards,
It can be used not only for flexible printed wiring coverlays but also for bonding copper-clad laminates to copper foils / substrates and for bonding other electrical components.

The flame-retardant adhesive film according to the present invention comprises
The above-mentioned dissolved or dispersed liquid adhesive can be applied to a glass plate or a carrier sheet and dried to produce the adhesive.

The carrier sheet that can be used is not particularly limited, and copper foil, aluminum foil, metal foil such as brass, polyester sheet, polyimide sheet, polyethylene terephthalate sheet, polybutylene terephthalate sheet, polyamide imide sheet, and poly (imide) sheet. Ether imide sheet, polyether sulfone sheet, polytetrafluoroethylene sheet, polycarbonate sheet, copolymer of ethylene and tetrafluoroethylene (ETFE),
Examples include polymer material sheets such as a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP) and a copolymer of perfluoroalkoxyethylene and tetrafluoroethylene (PFA). Except when used as a metal foil adhesive film, since the carrier sheet is peeled off, it is preferable to use a carrier sheet whose surface has been treated with a release agent.

The thickness of the adhesive film is appropriately selected depending on the thickness of the insulating layer to be formed, with the upper limit being the thickness capable of maintaining a flexible range, and is not particularly limited. When using a metal foil with an adhesive, the thickness of the adhesive layer is 15 to 150 μm.
m is preferable.

In order to obtain a printed wiring board using the flame-retardant adhesive film or the flame-retardant adhesive-attached metal foil-attached film according to the present invention, a conventionally known insulating adhesive film or a metal foil-attached insulating adhesive film is used. It can be performed by a process of manufacturing a printed wiring board using the same. For example, a multilayer printed wiring board is to laminate a metal foil with a flame retardant adhesive of the present invention on an inner layer circuit board by an ordinary vacuum press or a laminator and harden to easily form a multilayer printed wiring board having an outer layer circuit. Can be.

A more specific method for manufacturing a multilayer printed wiring board will be described below. First, a printed circuit board having a first circuit layer formed by etching using a single-sided or double-sided copper-clad laminate as a starting material is manufactured. Next, if necessary, the surface of the first circuit layer is subjected to an oxidation treatment, or a reduction treatment is further performed after the oxidation treatment. By this step, the surface of the first circuit layer is roughened, and the adhesiveness with the insulating layer is improved. Next, a copper foil is laminated on the surface of the first circuit layer via the flame-retardant adhesive film according to the present invention, or a copper foil with a flame-retardant adhesive,
The copper foils are stacked so that the copper foils are on the outside, and the copper foils are laminated via an adhesive layer (insulating layer) by heating and pressing. Next, via holes for connecting the first circuit layer and the first circuit layer are formed in the first circuit layer and the adhesive layer (insulating layer). The via hole can be formed by a known method such as a method using a laser or a method using a drill, and is not particularly limited. When a via hole is formed by a laser, it is necessary to remove the copper foil at a portion to be the via hole by etching and irradiate the portion with a laser. Next, after a desmear treatment for removing the resin residue in the formed via hole is performed as necessary, an electroless copper plating is performed, and an electroplating is performed by using a ditch.
Further, the copper foil is etched to form a second circuit layer. Through a series of these steps, for example, when a single-sided copper-clad laminate is used as a starting material, a two-layer printed wiring board is manufactured. Then, the circuit layer in the two-layer printed wiring board is regarded as the first circuit layer, the surface of the circuit layer is roughened if necessary, and the steps following the lamination of the copper foil are repeated to produce a three-layer printed wiring board. I do. Hereinafter, a higher multilayer printed wiring board can be manufactured in the same manner.

[0070]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Examples 1-2 and Comparative Examples 1-4 <Nitrilotris (methylene) phosphonic acid · 3Ca · 4
Water salt> 11 L of water and 1373.0 g (13.64 mol) of calcium carbonate were added to a stainless steel container and stirred (slurry state). After raising the temperature to 80 ° C., nitrilotris (methylene) phosphonic acid (hereinafter abbreviated as “NTP”).
2720.9 g (4.55 mol) of (50% aqueous solution) was added dropwise. After completion of the dropwise addition, the pH of the reaction solution is maintained at a constant value (approximately 2.2).
Stirring was continued at ° C. Thereafter, centrifugal filtration was performed to obtain 2578 g of the separated wet white crystals. The crystals were divided into two, and one was washed with 6 L of water and centrifuged. Next, the obtained crystals were dried at 110 ° C. for 24 hours and further at 250 ° C. for 24 hours, pulverized with a mixer, and sieved to obtain phosphonate samples having various average particle sizes. Dissolve the obtained white crystals in hydrochloric acid,
As a result of measuring the concentrations of P and Ca by ICP, P: 19.76
%, Ca; 26.93%. The residual chloride ion concentration was measured by an ion chromatogram method, and the average particle diameter was measured by a laser scattering particle size measurement method (Microtrack). In the following examples of the present invention, the residual chloride ion concentration and the average particle diameter were measured by the same method.

[0071]

[Table 1]

<Preparation of polyimide film with adhesive layer>
An adhesive component having the composition shown in Table 2 and toluene were mixed and stirred to prepare a solution-type flame-retardant adhesive composition having a nonvolatile content of 65%. Further, the flame-retardant adhesive composition in a solution
Is applied to a polyimide film having a thickness of 70 μm with a bar coater so that the film thickness after drying is 70 μm.
After drying for a time, a polyimide film with an adhesive layer was prepared. Next, the adhesiveness, flame retardancy, solder heat resistance, and electrolytic corrosion resistance were evaluated using the obtained polyimide film with an adhesive layer, and the results are shown in Table 3. In addition, each evaluation method is as follows, and P content in a table | surface shows P content with respect to an epoxy resin component. <Adhesiveness> A polyimide film with an adhesive layer was roll-laminated on a rolled copper foil (glossy surface) or a polyimide film while heating at 120 ° C., and was heated and cured at 170 ° C. for 2 hours to obtain a test sample. The 90 ° peel strength and 180 ° peel strength of this sample were measured at 23 ° C. <Flame retardancy> For the adhesive test sample obtained above, UL-
The evaluation was made according to the flame retardancy test method of the 94 standard. <Solder heat resistance> Solder heat resistance was measured in accordance with JIS C 6481, and after performing moisture absorption treatment for 2 hours by boiling, 26
After floating in a solder bath at 0 ° C. for 180 seconds, the appearance was examined for abnormalities. ○: No abnormality, ×: Swelling occurred <Electrostatic corrosion test> The adhesive composition was cured on a copper substrate to a film thickness of 80.
It was applied so as to form a comb having a line and space of 120 μm, and was cured by heating at 140 ° C. for 5 minutes and further at 170 ° C. for 2 hours to obtain a test sample. 85 of this sample
The interlayer insulation resistance between the adhesive layer and the copper substrate was measured when left at 1000C in an atmosphere of 85% humidity for 1000 hours.

[0073]

[Table 2]

Note) Cresol novolak type epoxy resin; epoxy equivalent: 198 g / eq, manufactured by Sumitomo Chemical Co., Ltd., E
SCN-195 Bisphenol A type epoxy resin; epoxy equivalent 18
9g / eq, Yuka Shell Epoxy Co., Ltd., EP-828 ・ Resole resin Hitachi Chemical Co., Ltd., HP-180R

[0075]

[Table 3]

From the results in Table 3, the residual chlorine ion concentration and
Those using phosphonates with controlled average particle size,
Those having high residual chlorine ion concentration (Comparative Example 2, Comparative Example 3, and Comparative Example 4) have poor electric properties and average particle diameter, while having good flame retardancy, corrosion resistance and adhesion. It can be seen that those using phosphonates (Comparative Example 1 and Comparative Example 4) having a particle size larger than 20 μm cannot obtain good flame retardancy and adhesiveness.

Examples 3-6 and Comparative Examples 5-6 <Sample D: Nitrilotris (methylene) phosphonic acid · 3
11 L of water and 1304.6 g (13.50 mol) of magnesium carbonate were added to a stainless steel container of Mg · monohydrate> 15 L and stirred (slurry state). After heating this to 80 ° C, NTP
2720.9 g (4.55 mol) of (50% aqueous solution) was added dropwise. After completion of the dropwise addition, stirring was continued at 80 ° C. until the pH of the reaction solution reached 6. Thereafter, centrifugal filtration was performed to obtain white crystals.
Next, the entire amount of the obtained crystals was charged into 12 L of water.
Washed with stirring for 0 minutes. Next, centrifugal filtration was performed, and the separated white crystals were separated at 110 ° C. for 24 hours and further at 250 ° C.
For 24 hours, and pulverized by a mixer to have an average particle diameter of 4.2 μm and a residual chlorine ion concentration of 8 ppm.
1598.4 g of the desired product were obtained. Yield 92.3% (V.
S. NTP). The obtained white crystals are dissolved in hydrochloric acid, and IC
As a result of measuring the concentrations of P and Mg by P, P: 23.62%, M
g: 19.24%. <Sample E: Nitrilotris (methylene) phosphonic acid · 3
Zn · octahydrate> 15 L Into a stainless steel container, 5 L of water and 826.85 g (12.60 mol) of potassium hydroxide are added and stirred. NTP (50% aqueous solution) 1256.19 g (2.10 mol) is added dropwise to obtain an NTP-K salt aqueous solution. Also, separately
7 L of water and zinc sulfate heptahydrate were added to an 18 L stainless steel container and stirred. Here, the above aqueous solution of NTP-K salt was added dropwise. After completion of the dropwise addition, stirring was continued at room temperature until the pH of the reaction solution became constant (about 6.2). Thereafter, centrifugal filtration was performed to obtain white crystals. Next, the entire amount of the obtained crystals was charged into 12 L of water and washed with stirring for 30 minutes. Then
After centrifugal filtration, the separated white crystals are dried at 110 ° C. for 24 hours, further at 250 ° C. for 24 hours, and pulverized by a mixer to obtain a target product having an average particle diameter of 4.2 μm and a residual chlorine ion concentration of 10 ppm. 1153.8 g were obtained.
Yield 86.7% (VS NTP). The obtained white crystals were dissolved in hydrochloric acid, and the concentrations of P and Zn were measured by ICP.
P: 15.18%, Zn: 27.65%.

An adhesive component having the composition shown in Table 4 was mixed well with toluene to prepare a flame-retardant adhesive composition in the form of a solution having a nonvolatile content of 65%. Further, this solution-type flame-retardant adhesive composition was applied to a polyimide film having a thickness of 25 μm by a bar coater so that the thickness after drying became 70 μm, and dried at 140 ° C. for 5 hours to form an adhesive layer. A polyimide film was made. Next, using the obtained polyimide film with an adhesive layer, the adhesiveness, flame retardancy, solder heat resistance and electric corrosion resistance were evaluated in the same manner as in Examples 1 and 2, and the results are shown in Table 5. The P content in the table indicates the content relative to the epoxy resin, and commercially available ammonium polyphosphate and triallyl phosphate were used.

[0079]

[Table 4]

Note) Cresol novolak type epoxy resin; epoxy equivalent 220 g / eq, KR, manufactured by Asahi Denka Co., Ltd.
M-2650 ・ Acrylic rubber fine particle dispersed epoxy resin; epoxy equivalent 189 g / eq, manufactured by Toto Kasei Co., Ltd., YR-528 ・ Resole resin: manufactured by Hitachi Chemical Co., Ltd., HP-180R

[0081]

[Table 5]

Examples 5 to 6 <Sample F; 1-hydroxyethylidene-1,1′-diphosphonic acid · 2Ca> Tap water 1 was placed in a 15 L stainless steel container.
5 L and 1000.9 g (10.00 mol) of calcium carbonate were added and stirred (slurry state). After raising the temperature to 80 ° C., 1
-Hydroxyethylidene-1,1'-diphosphonic acid (hereinafter abbreviated as HEDP) (60% aqueous solution) 1716.8 g (5.0
0 mol) was added dropwise. After completion of the dropwise addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 3.4), and then centrifugal filtration was performed to obtain white crystals. Then, 12L of water
, All of the obtained crystals were charged and washed with stirring for 30 minutes. Next, centrifugal filtration was performed, and the separated white crystals were separated into 1
Dried at 10 ° C. for 24 hours and further at 250 ° C. for 24 hours,
By crushing with a mixer, the average particle size is 4.2μ.
m, 1442.0 g of the target product having a residual chlorine ion concentration of 15 ppm was obtained. Yield 95.4% (vs HEDP). The obtained white crystals were dissolved in hydrochloric acid, and the concentrations of P and Ca were measured by ICP. As a result, P was 20.8% and Ca was 25.8%. <Sample G; 1-hydroxyethylidene-1,1′-diphosphonic acid · 2Mg> Tap water 1 in a 15 L stainless steel container
5 L and 966.4 g (10.00 mol) of magnesium carbonate were added and stirred (slurry state). After the temperature was raised to 80 ° C., 1716.8 g (5.00 mol) of HEDP (60% aqueous solution) was added dropwise. After completion of the dropwise addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 3.4), and then centrifugal filtration was performed to obtain white crystals. . Next, the entire amount of the obtained crystals was charged into 12 L of water and washed with stirring for 30 minutes. Next, centrifugal filtration was performed, and the separated white crystals were collected at 110 ° C. for 2 hours.
After drying for 4 hours and further at 250 ° C. for 24 hours and pulverizing with a mixer, 1200 g of the target product having an average particle size of 4.2 μm and a residual chlorine ion concentration of 12 ppm was obtained. Yield 96.0% (vs HEDP). The obtained white crystals were dissolved in hydrochloric acid, and the concentrations of P and Mg were measured by ICP.
23.6%, Mg; 17.3%.

An adhesive component having the composition shown in Table 6 was mixed well with methyl ethyl ketone to prepare a solution-type flame-retardant adhesive having a nonvolatile content of 65%. Further, a solution-like flame-retardant adhesive was applied to a polyimide film having a thickness of 25 μm with a bar coater so that the film thickness after drying became 70 μm.
After drying at 0 ° C. for 5 hours, a polyimide film with an adhesive layer was prepared. Next, using the obtained polyimide film with an adhesive layer, the adhesiveness, flame retardancy, solder heat resistance, and electrolytic corrosion resistance were evaluated in the same manner as in Examples 1 and 2, and the results were shown in Table 7.
It was shown to. Incidentally, the P content in the table is the P content relative to the epoxy resin.
Shows the content.

[0084]

[Table 6]

Note) Cresol novolak type epoxy resin; epoxy equivalent: 198 g / eq, manufactured by Sumitomo Chemical Co., Ltd., E
SCN-195 Bisphenol A type epoxy resin; epoxy equivalent 18
9g / eq, manufactured by Yuka Shell Epoxy Co., Ltd., EP-828 ・ Resole resin manufactured by Hitachi Chemical Co., Ltd., HP-180R ・ Crosslinked acrylonitrile butadiene rubber; JSR Corporation
Manufactured by PNR-1H ・ Alkylphenol resin Hitachi Chemical Co., Ltd., H-2400 ・ Aluminum hydroxide; Sumitomo Chemical Co., Ltd., CL-310 ・ Magnesium hydroxide; Kyowa Chemical Industry Co., Ltd., Kisuma 54
A

[0086]

[Table 7]

Examples 9 to 14 <Sample H: Nitrilotris (methylene) phosphonic acid · 6
Melamine> 18 L In a stainless steel container, 13 L of tap water and 807.43 g (1.35 mol) of nitrilotris (methylene) phosphonic acid (hereinafter abbreviated as NTP) (50% aqueous solution) were added and stirred. After raising the temperature to 80 ° C., melamine 969.48
g (7.68 mol) was gradually added and stirred. After completion of the melamine addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 4.5). Thereafter, centrifugal filtration was performed to obtain white crystals. Then, the whole amount of the obtained crystals was charged into 12 L of water, and washed with stirring for 30 minutes. Next, centrifugal filtration was performed, and the separated white crystals were dried at 100 ° C. for 24 hours.
By crushing with a mixer, the average particle size is 4.2μ.
m, 1144.53 g of the target substance with a residual chlorine ion concentration of 401 ppm
I got 84.3% yield (vs NTP). Next, as a result of measuring C, H, and N by elemental analysis, C: 23.41%, H;
4.53%, N; 46.63%. <Sample I: Nitrilotris (methylene) phosphonic acid · 2
Melamine> 10L tap water in an 18L stainless steel container, NTP
(50% aqueous solution) 1802.0 g (3.00 mol) was added and stirred.
After the temperature was raised to 80 ° C, 762.0 g of melamine (6.00mo
l) was added slowly and stirred. After completion of the melamine addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 1.5). Thereafter, centrifugal filtration was performed to obtain white crystals. Next, the whole amount of the obtained crystals was charged into 12 L of water, and washed with stirring for 30 minutes. Next, centrifugal filtration was performed, and the separated white crystals were dried at 100 ° C. for 24 hours and pulverized with a mixer to obtain 1494.5 g of the target product having an average particle diameter of 4.2 μm and a residual chlorine ion concentration of 402 ppm. Yield 93.9% (VS NTP). Next, as a result of measuring C, H, and N by elemental analysis, C: 19.79%, H;
4.38%, N: 32.02%. <Sample J: Nitrilotris (methylene) phosphonic acid · 3
Melamine> 18L stainless steel container with 15L of tap water, NTP
1802.0 g (3.01 mol) of (50% aqueous solution) was added and stirred.
After raising the temperature to 80 ° C., 1140.0 g of melamine (9.03mo
l) was added slowly and stirred. After completion of the melamine addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 1.5). Thereafter, centrifugal filtration was performed to obtain white crystals. The crystals are dried at 100 ° C. for 24 hours, and then
, All of the obtained crystals were charged and washed with stirring for 30 minutes. Next, centrifugal filtration was performed, and the separated white crystals were separated into 1
After drying at 00 ° C. for 24 hours and pulverizing with a mixer, the average particle diameter is 4.2 μm and the residual chlorine ion concentration is 41%.
There were obtained 1909.66 g of the target product at 5 ppm. Yield 93.
9% (VS NTP). Then, by elemental analysis, C,
As a result of measuring H and N, C: 20.84%, H: 4.41
%, N; 38.49%. <Sample K: Nitrilotris (methylene) phosphonic acid · 4
Melamine> 18L stainless steel container with 15L of tap water, NTP
(50% aqueous solution) 897.0 g (1.49 mol) was added and stirred.
After heating this to 80 ° C, melamine 751.6g (5.96mo
l) was added slowly and stirred. After completion of the melamine addition, stirring was continued at 80 ° C. until the pH of the reaction solution became constant (about 4.2). Thereafter, centrifugal filtration was performed to obtain white crystals. Next, the entire amount of the obtained crystals was charged into 12 L of water and washed with stirring for 30 minutes. Next, centrifugal filtration was performed, and the separated white crystals were dried at 100 ° C. for 24 hours and pulverized with a mixer to obtain 1144.06 g of a target product having an average particle size of 4.2 μm and a residual chloride ion concentration of 425 ppm. Yield 95.2% (VS NTP). Next, as a result of measuring C, H, and N by elemental analysis, C: 21.52%,
H: 4.41%, N: 41.82%. <Sample L; 1-hydroxyethylidene-1,1′-diphosphonic acid · 2 melamine> 15 L of tap water and 1030.0 g (2.99 mol) of HEDP (60% aqueous solution) were added to an 18 L stainless steel container and stirred. After heating this to 80 ° C, melamine
756.0 g (5.99 mol) was gradually added and stirred. After completion of the melamine addition, 80 until the pH of the reaction solution becomes constant (about 1.3).
Continue stirring at ° C. Thereafter, centrifugal filtration was performed to obtain white crystals. Next, the entire amount of the obtained crystals was charged into 12 L of water and washed with stirring for 30 minutes. Next, centrifugal filtration is performed, and the separated white crystals are dried at 100 ° C. for 24 hours and pulverized by a mixer to have an average particle diameter of 4.
Target product 145 having 2 μm and residual chlorine ion concentration of 421 ppm
6.3 g were obtained. Yield 106.2% (vs HEDP). Next, as a result of measuring C, H, and N by elemental analysis, C: 19.9%,
H: 4.2%, N: 34.8%. <Sample M; 1-hydroxyethylidene-1,1'-diphosphonic acid / 4 melamine> 15 L of tap water and 833.3 g (2.42 mol) of HEDP (60% aqueous solution) were added to an 18 L stainless steel container and stirred. After raising the temperature to 80 ° C, melamine 12
23.2 g (9.69 mol) was gradually added and stirred. After addition of melamine, 80 ° C until the pH of the reaction solution becomes constant (about 5.2)
And continued stirring. Thereafter, centrifugal filtration was performed to obtain white crystals. . Next, the entire amount of the obtained crystals was charged into 12 L of water and washed with stirring for 30 minutes. Next, centrifugal filtration is performed, and the separated white crystals are dried at 100 ° C. for 24 hours and pulverized by a mixer to have an average particle diameter of 4.
170 µm of target product with 2 µm and residual chloride ion concentration of 431 ppm
9.7 g were obtained. Yield 99.4% (vs HEDP). Next, as a result of measuring C, H, and N by elemental analysis, C: 22.5%,
H: 4.2%, N: 44.8%.

An adhesive component having the composition shown in Table 8 was mixed well with toluene to prepare a flame-retardant adhesive composition in the form of a solution having a nonvolatile content of 65%. Further, the flame-retardant adhesive composition in the form of a solution was applied to a polyimide film having a thickness of 25 μm by a bar coater so that the film thickness after drying became 70 μm.
It dried at 40 degreeC for 5 hours, and produced the polyimide film with an adhesive layer. Next, using the obtained polyimide film with an adhesive layer, the adhesiveness, flame retardancy, solder heat resistance, and electrolytic corrosion resistance were evaluated in the same manner as in Examples 1 and 2, and the results are shown in Table 9.

[0089]

[Table 8]

Note) EP-1001: Bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. EP-828: Bisphenol A manufactured by Yuka Shell Epoxy
Type epoxy resin ・ EP-154; manufactured by Yuka Shell Epoxy, bisphenol A
Type epoxy resin ・ N-690; Phenol novolak type epoxy resin manufactured by Dainippon Ink Co., Ltd. ・ YP-50S; Phenoxy resin manufactured by Toto Kasei Co., Ltd. ・ R-45EPT; Idemitsu Petrochemical Co., Ltd. Imidazole-based curing accelerator manufactured by Shikoku Chemicals Co., Ltd. ・ Aluminum hydroxide; CL-310 manufactured by Sumitomo Chemical Co., Ltd. ・ Magnesium hydroxide;
A ・ Zinc borate; Borax, FB500: Fire Break 500

[0091]

[Table 9]

Example 15 The adhesive composition of Example 1 in Table 1 was replaced with 1-acetoxy-2
-A varnish having a nonvolatile content of 65% by weight was prepared by dissolving in ethoxyethane. The prepared varnish was coated with a 18 μm-thick copper foil (GTS-1 manufactured by Furukawa Circuit Foil Co., Ltd.
8 (trade name) is applied to one side so that the thickness after drying is 50 μm, and is applied at 100 ° C. for 1 minute, and further at 140 ° C.
For 1 minute to produce an insulating adhesive sheet with copper foil. 0.4mm thick (18μm thick copper foil)
Glass cloth base epoxy resin single-sided copper-clad laminate (MCL-E-67 (trade name) manufactured by Hitachi Chemical Co., Ltd.)
Was etched to form a printed circuit board on which a first circuit layer was formed. On the first circuit layer of this printed wiring board, the copper-peeled insulating adhesive sheet prepared above was placed so that the copper foil was on the outside, and heated at a temperature of 170 ° C. and a pressure of 2.5 MPa. Pressurized. Next, the copper foil at the portion to be the via hole was removed by etching, and the portion was irradiated with a carbon dioxide gas laser to form a via hole having a diameter of 100 μm. Next, the resin residue in the via hole was removed by immersing in a desmear permanganate solution (potassium permanganate 60 g / liter, sodium hydroxide 38 g / liter) at 70 ° C. for 10 minutes. Next, an electroless plating catalyst solution (Hitachi Chemical Industries, Ltd., H
After immersing in S-202B (trade name) at 20 ° C. for 7 minutes, a cedar treatment of washing with water was performed. Next, an electroless copper plating solution (CUST-201, manufactured by Hitachi Chemical Co., Ltd.)
(Using trade name) at 25 ° C. for 30 minutes to precipitate electroless copper plating. Next, 12 μm thick copper plating was applied on the electroless copper plating by electroplating, and annealing was performed at a temperature of 160 ° C. for 1 hour. Next, a two-layer printed wiring board was prepared by forming a second circuit layer by performing etching by a known method.

[0093]

As described above, by using the flame-retardant adhesive composition of the present invention, an adhesive film or a metal foil with an adhesive excellent in electrical insulation and flame retardancy can be obtained. Use of an adhesive film or a metal foil with an adhesive provides an effect that a printed wiring board having excellent electrical insulation and flame retardancy can be obtained.

 ────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Yoshibo Hara 9-11-1, Kameido, Koto-ku, Tokyo Nippon Kagaku Kogyo Co., Ltd. Research and Development Division F-term (reference) 4H028 AA34 AA38 AA42 BA04 BA06 4J004 AA13 AA17 CA01 CA08 FA05 4J040 EC001 HD23 JA09 KA03 LA08 NA20 5E346 AA12 AA16 AA22 AA32 AA51 CC08 CC32 CC41 EE12 EE13 GG28 HH13

Claims (13)

[Claims] 1. An epoxy resin and a metal salt of nitrilotris (methylene) phosphonic acid, nitrilotris (methylene)
Melamine phosphonate, 1-hydroxyethylidene-
A flame-retardant adhesive containing one or more phosphonates obtained from a metal salt of 1,1-diphosphonic acid and a melamine salt of 1-hydroxyethylidene-1,1-diphosphonic acid. Composition. 2. A metal salt of nitrilotris (methylene) phosphonic acid having the following general formula (1): ## STR1 ## (Wherein, M ¹ and M ² represent a hydrogen atom or an alkali metal). Nitrilotris (methylene) phosphonic acid or a salt thereof represented by the formula: and a phosphonate obtained by reacting with a divalent metal compound. The flame-retardant adhesive composition according to claim 1. 3. A melamine salt of nitrilotris (methylene) phosphonic acid is represented by the following general formula (2): The flame-retardant adhesive composition according to claim 1, which is a phosphonate represented by the formula: wherein M represents melamine and n represents an integer of 1 to 6. 4. The metal salt of 1-hydroxyethylidene-1,1-diphosphonic acid is represented by the following general formula (3). (Wherein M ¹ and M ² represent a hydrogen atom or an alkali metal.) 1-hydroxyethylidene-1,1
The flame-retardant adhesive composition according to claim 1, which is a phosphonate obtained by reacting diphosphonic acid or a salt thereof with a divalent metal compound. 5. A 1-hydroxyethylidene-1,1-diphosphonic acid melamine salt represented by the following general formula (4): (Wherein M represents melamine and n represents an integer of 1 to 4). The flame-retardant adhesive composition according to claim 1, which is a phosphonate. 6. The phosphonate has an average particle diameter of 20.
The flame-retardant adhesive composition according to any one of claims 1 to 5, wherein the thickness is not more than μm. 7. The flame-retardant adhesive composition according to claim 1, wherein the phosphonate has a residual chlorine ion concentration of 500 ppm or less. 8. The flame-retardant adhesive composition according to claim 1, further comprising a flame-retardant auxiliary. 9. The flame-retardant adhesive composition according to claim 8, wherein the flame-retardant auxiliary is a hydrated metal compound. 10. The flame-retardant adhesive composition according to claim 1, wherein the content of the metal phosphonate is in the range of 1 to 20 parts by weight as P based on 100 parts by weight of the epoxy resin. 11. A flame-retardant adhesive obtained by forming the flame-retardant adhesive composition according to claim 1 on a supporting substrate in the form of a film or a sheet. the film. 12. A flame-retardant adhesive comprising the flame-retardant adhesive composition according to any one of claims 1 to 10 formed on a metal foil in a film or sheet form. Metal foil. 13. A printed wiring board which is bonded using the flame-retardant adhesive film or the metal foil with a flame-retardant adhesive according to claim 11.