JP2003012765A - Flame-retardant epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant epoxy resin composition capable of exhibiting excellent flame-retardant effects even by a halogen-free flame- retardant recipe instead of a flame retardant recipe using a halogen, capable of providing a molded product having excellent properties of heat resistance and moisture resistance, and further having excellent adhesion. SOLUTION: This flame-retardant epoxy resin composition consists essentially of (I) an epoxy resin having an oxazolidone ring, (II) a phosphorus-modified epoxy resin obtained by reacting (A1 ) an epoxy resin with (B) a phosphine compound having an aromatic group on the phosphorus atom, and (III) a curing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant epoxy resin composition which is useful even in a halogen-free flame-retardant composition, and specifically, in a halogen-free flame-retardant epoxy resin composition. Therefore, it is useful as a paint, a composition for encapsulating a semiconductor, or a varnish for a laminated board, and particularly, as a varnish for a laminated board (printed wiring board), it has not only a flame-retardant effect but also excellent adhesion, heat resistance and moisture resistance. The present invention relates to a flame-retardant epoxy resin composition that can provide a laminate.

[0002]

2. Description of the Related Art Epoxy resins are widely used mainly in electric and electronic material parts because of their excellent adhesion and electric characteristics (insulating properties).

These electric and electronic material parts are highly flame-retardant (U) as represented by glass epoxy laminates and IC encapsulants.
L: 94V-0) is required, and thus a halogenated epoxy resin is usually used. For example, in a glass epoxy laminate, as a flame-retardant FR-4 grade, an epoxy resin generally substituted with bromine is used as a main raw material component, an epoxy resin in which various epoxy resins are mixed, and a curing agent for the epoxy resin are used. It is used in combination with agents.

However, the use of such a halogenated epoxy resin is one of the causes of environmental problems represented by dioxins in recent years, and the long-term electrical reliability due to halogen dissociation in a high temperature environment. From adverse effects on
There is a strong demand for flame retardants or other flame retardant formulations that reduce the amount of halogen used or use other compounds that can substitute for halogen.

[0005] Therefore, conventionally, various techniques using, for example, a phosphoric acid ester compound as an additive flame retardant have been studied as a technique to replace the halogen-based flame retardant formulation. In addition, the heat resistance and moisture resistance of the molded product are deteriorated, and moreover, the adhesiveness is deteriorated especially in the use of electric laminates. Therefore, for example, as disclosed in JP-A-2000-80, a molded article having improved heat resistance, moisture resistance and the like while using a reactive phosphorus compound is used.
Japanese Patent No. 251 discloses a technique in which a bisphenol A type epoxy resin is modified with a specific phosphine compound to improve heat resistance, flame retardancy and the like of a molded product.

However, in the invention described in JP-A-2000-80251, a bisphenol A type epoxy resin is reacted with a phosphine compound, and since it is a bifunctional modified epoxy resin, the heat resistance is poor, and particularly, the heat and humidity resistance is high. It was inferior in sex. Further, when a polyfunctional epoxy resin is further added to the modified epoxy resin as a heat resistance-imparting component, the heat resistance is improved, but the phosphorus atom content of the modified epoxy resin is reduced, and thus the flame retardancy is poor. As a result, the balance between heat resistance and flame retardancy was poor.

[0007]

The problem to be solved by the present invention is to produce an excellent flame-retardant effect even in a halogen-free flame-retardant prescription, which is an alternative to the halogen-based flame-retardant prescription. Another object of the present invention is to provide a flame-retardant epoxy resin composition having excellent heat resistance and moisture resistance and excellent adhesion.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that an epoxy resin (I) having an oxazolidone ring, an epoxy resin (A ₁ ) and an aromatic group on a phosphorus atom. A flame-retardant epoxy resin composition containing a phosphorus-modified epoxy resin (II) obtained by reacting a phosphine compound (B) and a curing agent (III) as essential components improves adhesion, heat resistance, and moisture resistance. Along with
The inventors have found that it is possible to achieve flame retardancy by eliminating halogen, and have completed the present invention.

That is, according to the present invention, a phosphorus-modified epoxy resin (I) having an oxazolidone ring, an epoxy resin (A ₁ ) and a phosphine compound (B) having an aromatic group on the phosphorus atom are reacted ( II) and curing agent (I
A flame-retardant epoxy resin composition containing II) as an essential component is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin (I) having an oxazolidone ring used in the present invention is not particularly limited as long as it is an epoxy resin having an oxazolidone ring. For example, the epoxy resin (A ₂ ) and the isocyanate compound ( Examples thereof include isocyanate-modified epoxy resin (I ₁ ) obtained by reacting with C) or cyanate-modified resin obtained by reacting epoxy resin (A ₂ ) with a cyanate compound.

The above-mentioned isocyanate-modified epoxy resin (I ₁ ) can be produced, for example, by charging the epoxy resin (A ₂ ) into a reactor having a stirrer, a reflux condenser, a thermometer and a raw material charging port, and then at 100 to 170 ° C. , Preferably 1
A method of maintaining the temperature at 40 to 160 ° C. and adding the isocyanate compound (C) over several hours to react the epoxy group of the epoxy resin (A ₂ ) with the isocyanate group of the isocyanate compound (C) can be mentioned. This reaction may be carried out using a reaction catalyst. The reaction catalyst is not particularly limited, but for example, tertiary amines such as triethylamine and benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, imidazole compounds, triphenylphosphine and the like can be used. .
The end point of this reaction can be confirmed, for example, by a method such as confirming that the absorption of the isocyanate group is lost with a Fourier transform infrared spectrophotometer (FT-IR).

The above reaction can be carried out in the presence of an organic solvent, if necessary, and as the usable organic solvent, for example, diglyme, cellosolve acetate, xylene, toluene and the like are preferable.

The above-mentioned epoxy resin (A ₂ ) is not particularly limited, but an epoxy resin having at least two epoxy groups in the molecule is preferable from the viewpoint that the heat resistance of the epoxy resin (I) is improved, Of these, bisphenol type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin are preferable.

For example, as the above-mentioned epoxy resin (A ₂ ), an epoxy resin having a cyclohexene oxide group, an epoxy resin having a tricyclodecene oxide group, an epoxy resin having a cyclopentene oxide group, an epoxy of a dicyclopentadiene type phenol resin Compounds such as cycloaliphatic epoxy resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-p-aminophenol, tetra Glycidyl amine type epoxy resins such as glycidyl metaxylylenediamine and tetraglycidyl bisaminomethylcyclohexane; diglycidyl hydantoin, glycidyl glycidoxy Hydantoin-type epoxy resins such as ruquil hydantoin; heterocyclic epoxy resins such as triallyl isocyanurate and triglycidyl isocyanurate; phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, Glycerin triglycidyl ether, 2- [4- (2,3
-Epoxypropoxy) phenyl] -2- [4- [1,
1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1,3-bis [4-
[1- [4- (2,3-Epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] 2-functional epoxy resins such as -2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, tetrafunctional epoxy resins such as tetraglycidoxy biphenyl. These epoxy resins (A ₂ )
Is not limited to one type in use, and two or more types can be used in combination.

As the epoxy resin (A ₂ ), the following compounds may be used together with the above various epoxy resins, for example,
Monofunctional epoxies such as n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-Sec-butyl phenyl glycidyl ether, glycidyl methacrylate, vinyl cyclohexene monoepoxide, etc. Compounds may also be used.

The epoxy resin (A ₂ ) preferably has an epoxy equivalent of 100 to 500 g / equivalent (hereinafter referred to as g / eq) from the viewpoint of improving the flame retardancy of the flame-retardant epoxy resin composition. .

The above-mentioned epoxy resin (A ₂ ) is preferably a halogen atom-free epoxy resin. Here, the halogen atom-free epoxy resin means that when the epoxy resin is produced, it is treated with epichlorohydrin. The raw material phenol resin to be reacted does not contain halogen atoms or is not substantially modified with halogen atoms. That is, the chlorine content mixed in by the usual use of epichlorohydrin may be contained, and specifically, the halogen atom content is preferably 5000 ppm or less. However, when it is not necessary that the halogen atom is not contained, a halogen atom-containing epoxy resin may be used. Examples of these halogen atom-containing epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins and other bisphenol type epoxy resins; phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, bisphenols. Examples of the bromide include novolak type epoxy resins such as A novolac type epoxy resin and bisphenol AD novolac resin.

The isocyanate compound (C) is not particularly limited, but for example, phenylene diisocyanate, tolylene diisocyanate (TDI),
Aromatic isocyanates such as diphenylmethane diisocyanate (MDI), xylylene diisocyanate, and metaxylylene diisocyanate; Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate; Isophorone diisocyanate, hydrogenated trireisocyanate Alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated metaxylylene diisocyanate, norbornene diisocyanate; polymethylene polyphenyl isocyanate, dimethyltriphenylmethane tetraisocyanate, triphenylmethane triisocyanate, or tris (Isocyanate Eniru) - triphosphate and the like. Further, modified products of the above-mentioned various isocyanate compounds can also be used for the purpose of adjusting the number of functional groups, reactivity, or other purposes. Examples of these modified products include urethane prepolymers that are reaction products of isocyanate compounds and alcohols, allophanate-modified isocyanates and biuret-modified isocyanates obtained by addition-reacting isocyanate groups, and uretdione-modified isocyanates, Examples thereof include isocyanate dimers such as isocyanurate-modified isocyanates, trimers, and the like. Further, a carbodiimide modified product, a uretonimine modified product, an acylurea diisocyanate product, and the like, which utilize a condensation reaction of an isocyanate group and the like, can be mentioned.

Of these, methylene diisocyanate and tolylene diisocyanate are preferred.

Regarding the use ratio of the epoxy resin (A ₂ ) and the isocyanate compound (C), the number of functional groups and the reactivity can be adjusted, so that the epoxy resin (A ₂ ) and the isocyanate compound (C) can be adjusted. ) Weight ratio is 70
The range of / 30 to 99/1 is preferable.

Next, the phosphorus-modified epoxy resin (II) obtained by reacting the epoxy resin (A ₁ ) with the phosphine compound (B) having an aromatic group on the phosphorus atom will be described.

The epoxy resin (A ₁ ) is not particularly limited, but an epoxy resin having at least two epoxy groups in the molecule is preferable from the viewpoint of improving the heat resistance of the epoxy resin (II), and among them, Bisphenol type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin are preferable.

For example, as the above-mentioned epoxy resin (A ₁ ), bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin; phenol novolac type epoxy resin, orthocresol novolac Type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol AD novolac resin and other novolak type epoxy resins; cyclohexene oxide group-containing epoxy resin, tricyclodecene oxide group containing epoxy resin, cyclopentene oxide group containing epoxy resin, di Cycloaliphatic epoxy resins such as epoxidized cyclopentadiene type phenol resin; glycidyl such as dimer acid glycidyl ester and triglycidyl ester Ester type epoxy resins; tetraglycidyl diaminodiphenylmethane, triglycidyl -p-
Glycidylamine type epoxy resins such as aminophenol, triglycidyl-p-aminophenol, tetraglycidyl metaxylylenediamine, tetraglycidyl bisaminomethylcyclohexane; hydantoin type epoxy resins such as diglycidyl hydantoin, glycidyl glycidoxyalkyl hydantoin Heterocyclic epoxy resins such as triallyl isocyanurate and triglycidyl isocyanurate; phlorogricinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2-
[4- (2,3-epoxypropoxy) phenyl] -2
-[4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1,
3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-
Epoxypropoxy) phenyl] -1-methylethyl]
Phenyl] ethyl] phenoxy] -2-propanol and other trifunctional epoxy resins; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, tetraglycidoxy biphenyl and other tetrafunctional epoxy resins And so on. These epoxy resins (A ₁ ) are not limited to one type when used, and two or more types can be used in combination.

As the epoxy resin (A ₁ ), the following compounds may be used together with the above various epoxy resins, for example,
Monofunctional epoxies such as n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-Sec-butyl phenyl glycidyl ether, glycidyl methacrylate, vinyl cyclohexene monoepoxide, etc. Compounds may also be used.

The epoxy resin (A ₁ ) preferably has an epoxy equivalent of 100 to 500 g / equivalent (hereinafter referred to as g / eq) from the viewpoint of improving the flame retardancy of the flame-retardant epoxy resin composition. .

The above-mentioned epoxy resin (A ₁ ) is preferably a halogen atom-free epoxy resin. Here, the halogen atom-free epoxy resin reacts with epichlorohydrin during the production of the epoxy resin. The raw material phenol resin is an epoxy resin containing no halogen atom or substantially not modified with a halogen atom. That is, the chlorine content mixed in by the usual use of epichlorohydrin may be contained, and specifically, the halogen atom content is preferably 5000 ppm or less. However, when it is not necessary that the halogen atom is not contained, a halogen atom-containing epoxy resin may be used. Examples of these halogen atom-containing epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins and other bisphenol type epoxy resins; phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, bisphenols. Examples of the bromide include novolak type epoxy resins such as A novolac type epoxy resin and bisphenol AD novolac resin.

Next, the phosphines (B) having an aromatic ring on the phosphorus atom will be described. The (B) is not particularly limited, but for example, the following general formula (1)

[0028]

[Chemical 2] (In the formula, R ₀ is a divalent hydrocarbon group having 1 to 3 carbon atoms, R _{1 to} R ₄ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ₅ is , Ar ₂ or a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, Ar ₁ represents an aromatic group containing two or more phenolic hydroxyl groups, and Ar ₂ has 1 to 1 carbon atoms. 8 hydrocarbon groups,
It represents an aromatic group which may be substituted with an alkyl group having 1 to 18 carbon atoms or an alkyloxyalkyl group. Also,
Ar ₂ may form a ring with the phosphorus atom in the formula, m
And n each independently represent an integer of 0 or 1. )
A structure represented by is preferred.

Ar ₁ in the general formula (1) is not particularly limited as long as it is an aromatic group containing two or more phenolic hydroxyl groups. For example, Ar ₁ having a structure represented by the following chemical structural formula group (2) can be used. There are things.

[0030]

[Chemical 3]

Further, Ar ₂ in the general formula (1) may form a ring together with the phosphorus atom in the formula, a hydrocarbon group having 1 to 8 carbon atoms and a hydrocarbon group having 1 to 18 carbon atoms. A naphthyl group and a phenyl group which may be substituted with an alkyl group or an alkyloxyalkyl group are preferable, and a phenyl group is particularly preferable.

Among these, compounds represented by the following general formula (3) or general formula (4) are preferable.

[0033]

[Chemical 4] (In the formula, R _{1 to} R ₄ and R _{6 to} R ₁₀ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms;
₅ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which is bonded to Ar _2, and Ar ₁ represents an aromatic group containing two or more phenolic hydroxyl groups. )

Among them, particularly those represented by the general formula (3) include 9,10-dihydro-9-oxa-1.
0-phosphaphenanthrene-10-oxide is preferable, and diphenylphosphinyl hydroquinone is preferable as the compound represented by the general formula (4).

Next, a method for producing the phosphorus-modified epoxy resin (II) used in the present invention will be described. The method for producing the phosphorus-modified epoxy resin (II) is not particularly limited. For example, the epoxy resin (A ₁ ) and the phosphine compound (B) having an aromatic group on the phosphorus atom are charged into a reaction vessel, A method of reacting by heating while stirring in an inert gas atmosphere can be mentioned. This reaction may be carried out using a reaction catalyst. The reaction catalyst is not particularly limited as long as it is a compound used as a reaction catalyst of an epoxy group and a phenolic hydroxyl group, or an epoxy group and a carboxyl group, for example, sodium hydroxide, potassium hydroxide and the like. Alkali metal hydroxides, alkali metal salts such as sodium carbonate, amines such as tributylamine, phosphines such as triphenylphosphine, quaternary ammonium compounds such as tetramethylammonium chloride, and quaternary ammonium compounds such as tetrabutylphosphonium chloride. Examples thereof include phosphonium compounds. The reaction temperature for this reaction is
100 ° C or higher is preferable from the viewpoint of shortening the reaction time,
Further, it is preferably 250 ° C. or lower from the viewpoint that side reactions are unlikely to occur and the reaction control is easy.

The above reaction can be carried out in the presence of an organic solvent, if necessary, and examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, xylene and toluene.

The curing agent (III) used in the present invention is not particularly limited, but examples thereof include latent amine type curing agents such as dicyandiamide, imidazole, BF ₃ -amine complex, guanidine derivative; metaphenylenediamine. , Aromatic amines such as diaminodiphenylmethane and diaminodiphenyl sulfone; phosphorus- and nitrogen-containing compounds such as cyclophosphazene oligomers; compounds having phenols and triazine rings; mixtures or condensates of phenols, triazine rings and aldehydes, etc. Nitrogen atom-containing compounds; novolak resins such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin; polyamide resins; maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, etc. Acid anhydride curing agents and the like. These curing agents may be used alone or in combination of two or more.

Among these, a curing agent containing a nitrogen atom represented by dicyandiamide, or a mixture or condensate of a phenol, a triazine ring and an aldehyde, among others, in view of synergistically improving the adhesion and the difficult effect. An aminotriazine-modified novolak resin consisting of is preferred.

The above-mentioned aminotriazine-modified novolak resin means an aminotriazine-modified novolak resin in which an aminotriazine ring structure and a phenol structure are randomly bonded via a methylene group. For example, in the presence of aminotriazine compounds such as melamine, benzoguanamine, acetoguanamine and phenols, bisphenol A, cresol, butylphenol, phenylphenol and formaldehyde in the presence or absence of a weak alkaline catalyst such as alkylamines. A molecule of an aminotriazine structure and a phenol structure and a methylene group connecting them obtained by a cocondensation reaction in the vicinity of the property or by reacting an alkyl ether compound of an aminotriazine compound such as methyl etherified melamine with a phenol Examples thereof include novolac resins having therein and having substantially no methylol group. Molecules in which only the aminotriazine structure is methylene-bonded, molecules in which only the phenol structure is methylene-bonded, and a small amount of unreacted monomer may be unintentionally contained. The phenol structure in the aminotriazine-modified novolac resin is a structure selected from the group consisting of a phenol residue, a cresol residue, a bisphenol A residue, a butylphenol residue, a phenylphenol residue, a naphthol residue and a resorcin residue. Is preferred. Here, the above-mentioned residue means one having a structure in which at least one hydrogen atom bonded to carbon of the aromatic ring is eliminated. For example,
In the case of phenol, it means a hydroxyphenyl group. The triazine skeleton in the above aminotriazine-modified novolak resin is not particularly limited, but preferably has a structure of aminotriazine compounds such as melamine, benzoguanamine, acetoguanamine and the like.

In the flame-retardant epoxy resin composition of the present invention, the amount of the curing agent (III) blended is such that the active hydrogen of the curing agent is 0.
It is preferable to adjust and mix it in the range of 2 to 1.2 equivalents.

It is preferable to adjust the content of phosphorus atoms in the flame-retardant epoxy resin composition of the present invention to be in the range of 2 to 8% by weight based on the total epoxy resin components, which lowers the mechanical properties of the cured product. However, it is preferable from the viewpoint that flame retardancy, moisture resistance, and adhesion are improved, and it is preferable to adjust the reaction ratio of the phosphorus atom-containing compound and the epoxy resin so as to match the above range of the content ratio. Here, in the present invention, the phosphorus atom content is a value measured by an absorptiometry.

The ratio [N] / [P] (molar ratio) between the phosphorus atom content and the isocyanate-derived nitrogen content in the flame-retardant epoxy resin composition of the present invention improves heat resistance and adhesion. In view of the above, [N] / [P] (molar ratio) is preferably 0.3 or more, and from the viewpoint that mechanical properties are good, [N] / [P] (molar ratio) is 4. It is preferably 0 or less.

The total epoxy resin in the flame-retardant epoxy resin composition of the present invention has an epoxy equivalent of 100 to 100.
The range of 2500 g / eq is preferable, but above all,
From the viewpoint of improving the mechanical performance and heat resistance of the cured product,
1500 g / eq is more preferable.

The flame-retardant epoxy resin composition according to the present invention comprises the above-mentioned oxazolidone ring-containing epoxy resin (I), phosphorus-modified epoxy resin (II), and curing agent (II).
Although I) is an essential component, other epoxy resins, curing accelerators, organic solvents (E), additives, flame retardants, fillers and the like can be added.

The above-mentioned other epoxy resin is not particularly limited, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Bisphenol type epoxy resins such as bisphenol AD type epoxy resin; novolac type epoxy resins such as phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol AD novolac resin; cyclohexene oxide group Epoxy resins, epoxy resins having tricyclodecene oxide groups, epoxy resins having cyclopentene oxide groups, cycloaliphatic epoxy resins such as epoxidized dicyclopentadiene type phenolic resins; dimer acid glycidyl ester, triglycidyl ester, etc. Glycidyl ester type epoxy resins; tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-p Glycidyl amine type epoxy resins such as aminophenol, tetraglycidyl metaxylylenediamine, tetraglycidyl bisaminomethylcyclohexane; hydantoin type epoxy trees such as diglycidyl hydantoin, glycidyl glycidoxyalkyl hydantoin; triallyl isocyanurate, triglycidyl Heterocyclic epoxy resins such as isocyanurate; phloroglysinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-
Epoxypropoxy) phenyl] -2- [4- [1,1
-Bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1,3-bis [4-
[1- [4- (2,3-Epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] 2-functional epoxy resins such as -2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, tetrafunctional epoxy resins such as tetraglycidoxy biphenyl. These epoxy resins are not limited to only one type when used.
Combinations of more than one type are also possible.

In addition to each of the above epoxy resins, the following compounds such as n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-Sec-butyl. 1 such as phenyl glycidyl ether, glycidyl methacrylate, vinyl cyclohexene monoepoxide
The functional epoxy compound may be used as the other epoxy resin.

Epoxy resin (A ₁ ), epoxy resin (A
_In addition to ₂ ), even when other epoxy resin is used in combination, the content of atoms with respect to all epoxy resin components in the flame-retardant epoxy resin composition is in the range of 2 to 8% by weight. It is preferable because the physical properties are not deteriorated, and the flame retardancy, moisture resistance, and adhesion are improved.

Various curing accelerators can be used in combination with the flame-retardant epoxy resin composition of the present invention. Examples thereof include tertiary amines such as benzyldimethylamine, imidazole, organic acid metal salts, Lewis acids, amine complex salts and the like, and these may be used alone or in combination of two or more kinds. The curing accelerator is preferably used in the range of 0.01 to 5 parts by weight with respect to the total amount of the resin in the flame-retardant epoxy resin composition of the present invention.

An organic solvent (D) can be added to the flame-retardant epoxy resin composition of the present invention. In particular, when the flame-retardant epoxy resin composition of the present invention is used as the composition for electric laminates, it is preferable to use the organic solvent (D) together. The organic solvent (D) is not particularly limited, but for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, n-butanol, methoxypropanol, methyl cellosolve, ethyl carbitol, ethyl acetate, Xylene, toluene, cyclohexanol, N,
Examples thereof include N-dimethylformamide, and these solvents can be used not only alone but also as a mixed solvent of two or more kinds.

The amount of the organic solvent (D) used is not particularly limited, but especially for electric laminates, from the viewpoint of impregnation into glass cloth, the total amount of the composition for electric laminates is 1
It is preferable that the amount of the organic solvent (D) is 20 to 80 parts by weight with respect to 00 parts by weight.

The flame-retardant epoxy resin composition of the present invention is extremely useful especially for electric laminates, but when used in combination with a curing agent, it is used in various applications such as adhesives, castings and paints. it can. That is, since the flame-retardant epoxy resin composition of the present invention can obtain a halogen-free flame-retardant cured product without lowering heat resistance, sealing,
Applications such as laminates and paints, especially glass epoxy laminates and ICs
It is possible to provide a flame-retardant epoxy resin composition for coating, which is suitable for use as a sealing material and has excellent metal adhesion, and is therefore suitable for use in resists and paints. Further, it is particularly useful as a flame-retardant epoxy resin composition for so-called build-up laminated plates such as a resin-coated copper foil because it has excellent adhesion to copper foil for electric laminated plates.

The method for producing a laminated board from the above-mentioned flame-retardant epoxy resin composition of the present invention is not particularly limited and may be produced by various methods. For example, it can be produced on a substrate such as glass cloth. Examples include a method in which the epoxy resin composition of the invention is impregnated at a ratio of 30 to 70% by weight to form a prepreg, and 1 to 10 sheets of this prepreg are then heat pressed.

[0053]

EXAMPLES The present invention will now be specifically described with reference to synthesis examples, examples and comparative examples. In the examples, "parts" and "%" are based on weight unless otherwise specified.

Synthesis Example 1 To 100 parts of a bisphenol A type epoxy resin (EPICLON 840S: manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 183 g / eq, 0.03 part of 2-methylimidazole as a catalyst was added, and an isocyanate equivalent was 1
11 parts of 25 g / equivalent (hereinafter referred to as g / eq) of methylene diisocyanate (Millionate MT-F: manufactured by Nippon Polyurethane Co., Ltd.) was added portionwise over 1 hour and reacted at 150 ° C. for 5 hours. It was confirmed by FT-IR that the isocyanate group had disappeared, and an objective resin having an epoxy equivalent of 245 g / eq was obtained. Hereinafter, this is abbreviated as resin (I-1).

Synthesis Example 2 Instead of the bisphenol A type epoxy resin (EPICLON 840S: Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 183 g / eq, the epoxy equivalent was 17
0 g / eq of bisphenol F type epoxy resin (EPI
CLON 830: manufactured by Dainippon Ink and Chemicals, Inc.)
A target resin having an epoxy equivalent of 223 g / eq was obtained in the same manner as in Example 1 except that was used. Hereinafter, this is abbreviated as resin (I-2).

Synthesis Example 3 Instead of the bisphenol A type epoxy resin (EPICLON 840S: Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 183 g / eq, the epoxy equivalent was 14
3g / eq naphthalene type epoxy resin (EPICLO
N HP-4032D: manufactured by Dainippon Ink and Chemicals, Inc. was used to obtain an objective resin having an epoxy equivalent of 185 g / eq in the same manner as in Example 1. Hereinafter, this is abbreviated as resin (I-3).

Synthesis Example 4 0.03 parts of triphenylphosphine as a catalyst was added to 100 parts of a bisphenol F type epoxy resin (EPICLON 830S: manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 170 g / eq to obtain 9,10- Dihydro-
72 parts of 9-oxa-10-phosphaphenanthrene-10-oxide was added and reacted at 150 ° C. for 5 hours to give a phosphorus atom content of 4.0% by weight and an epoxy equivalent of 1%.
200 g / eq of the target resin was obtained. Hereinafter, this is abbreviated as resin (II-4).

Synthesis Example 5 Instead of the bisphenol F type epoxy resin (EPICLON 830S: manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 170 g / eq, the epoxy equivalent was 14
3g / eq naphthalene type epoxy resin (EPICLO
N HP-4032D: manufactured by Dainippon Ink and Chemicals, Inc.)) was used in the same manner as in Example 4 to obtain a target resin having a phosphorus atom content of 4.0% and an epoxy equivalent of 680 g / eq. . Hereinafter, this is abbreviated as resin (II-5).

Synthesis Example 6 To 100 parts of a bisphenol A type epoxy resin (EPICLON 840S: manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 183 g / eq, 0.03 part of triphenylphosphine was added as a catalyst and 11 parts of bisphenol A was added. Then, the mixture was reacted at 150 ° C. for 5 hours to obtain a target resin having an epoxy equivalent of 250 g / eq. Hereinafter, this is abbreviated as resin (I ')

Examples 1 to 4 Respective resins (I-1) obtained in Synthesis Examples 1 to 5
(II-5) is separately dissolved with methyl ethyl ketone,
Epoxy resin was mixed in the ratio shown in Table 1, and then a curing agent dicyandiamide and a curing accelerator 2-ethyl-4-methylimidazole, which had been dissolved in methylcellosolve and dimethylformamide in advance, were added, and a nonvolatile content (NV) was added.
A flame-retardant epoxy resin composition having a content of 55% was prepared. At this time, the amount of the curing agent is such that the active hydrogen equivalent is 0.5 equivalent to 1 equivalent of the epoxy group in the epoxy resin, and the amount of the curing accelerator is 120 when the gel time of the prepreg is 170 ° C. It was blended so that it would be seconds.

After that, using each mixed solution,
Glass cloth WEA 7628 H258N which is a base material
[Nitto Boseki] was impregnated and dried at 160 ° C. for 3 minutes to prepare a prepreg having a resin content of 40%. Then, 8 sheets of the obtained prepreg were piled up, and the pressure was 3.9 MN / m.
^{2. The} laminate was prepared by curing under conditions of a heating temperature of 170 ° C. and a heating time of 120 minutes.

Example 5 Resins (I-1) and (II) obtained in Synthesis Examples 1 and 5 above were used.
-5) are separately dissolved in methyl ethyl ketone and mixed at the ratios shown in Table 1, and then aminotriazine novolac resin (Phenolite KA-7054, Dainippon Ink and Chemicals) having a phenol skeleton and a triazine skeleton and having a nitrogen atom content of 13%. Chemical Industry Co., Ltd.) was added in an equivalent amount, and a curing accelerator 2-ethyl-4-methylimidazole was added to prepare an epoxy resin composition having a nonvolatile content (NV) of 55%. Then, a varnish / laminate was prepared in the same manner as in Example 1.

Comparative Example 1 A varnish / laminate was prepared in the same manner as in Example 1 except that the resin (I ′) obtained in Synthesis Example 6 and the resin (II-4) obtained in Synthesis Example 4 were used. It was made.

For each of the laminates obtained as described above, peel strength, delamination strength, flame retardancy, Tg (glass transition temperature), pressure cooker test (PC
T) Each physical property of water absorption and solder resistance was tested. The results obtained are shown in Table 1.

Each test was conducted according to the following method. [Peel strength] Based on JIS-K6481. [Delamination strength between layers] Based on JIS-K6481. [Flame retardancy] Compliant with UL standard. [Tg (Glass Transition Temperature)] Dynamic Mechanical Analysis (DMA)
Measured by the method. Temperature rising speed 3 ° C / min. [PCT water absorption rate] 121 ° C / 100% humidity in PCT
The change in weight (%) before and after the treatment for 1 hour or 2 hours was measured as water absorption. [Solder resistance] Normal and PCT treated laminates 2
It was dipped in a solder bath at 60 ° C. for 30 seconds, and its state change was observed, and evaluated according to the following criteria. Judgment criteria: ◎: No change in appearance, △: Mesling is present,
×: blister occurs

[0066]

[Table 1]

INDUSTRIAL APPLICABILITY According to the present invention, as a halogen-free flame-retardant prescription replacing the flame-retardant prescription by halogen, an excellent flame-retardant effect is exhibited, and a molded product is also excellent in heat resistance and moisture resistance, and is electrically laminated It is possible to provide a flame-retardant epoxy resin composition having excellent adhesion in board applications. Therefore, although the composition of the present invention can be used in various fields such as electric / electronics, adhesives, casting, and coatings, it is particularly useful in electrical lamination applications.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 CC033 CD20W CD20X CL003                       EL136 EN006 ER026 ET006                       EU116 EY016 FD143 FD146                       GQ01                 4J036 AA01 AA05 CB20 CC02 DA01                       DB15 DC02 DC41 JA08 KA01                 4M109 AA01 EA03 EB02 EB07

Claims (8)

[Claims] 1. An epoxy resin (I) having an oxazolidone ring, and a phosphorus-modified epoxy resin (II) obtained by reacting the epoxy resin (A ₁ ) with a phosphine compound (B) having an aromatic group on the phosphorus atom. A flame-retardant epoxy resin composition containing a curing agent (III) as an essential component. 2. The composition according to claim 1, wherein the epoxy resin (I) having an oxazolidone ring is an isocyanate-modified epoxy resin (I ₁ ) obtained by reacting an epoxy resin (A ₂ ) with an isocyanate compound (C). object. 3. The composition according to claim 2, wherein the isocyanate compound (C) has two or more isocyanate groups in the molecule. 4. The weight ratio (A ₂ ) / (C) of the epoxy resin (A ₂ ) and the isocyanate compound (C) is 70/30 to.
The composition according to claim 2 or 3, which is 99/1. 5. A phosphine compound (B) having an aromatic group on a phosphorus atom is represented by the following general formula (1): (In the formula, R ₀ is a divalent hydrocarbon group having 1 to 3 carbon atoms, R _{1 to} R ₄ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ₅ is , Ar ₂ or a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, Ar ₁ is an aromatic group containing two or more phenolic hydroxyl groups, and Ar ₂ is 1 to 8 carbon atoms. Represents a hydrocarbon group, an alkyl group having 1 to 18 carbon atoms or an aromatic group which may be substituted with an alkyloxyalkyl group.
Ar ₂ may form a ring with the phosphorus atom in the formula, and m and n each independently represent 0 or 1. ) Any one of claims 1 to 4
The composition according to the item. 6. The composition according to claim 1, wherein the content of phosphorus atoms in the total epoxy resin component in the composition is 2 to 8% by weight. 7. The epoxy resin composition according to claim 1, wherein the curing agent (III) contains a nitrogen atom. 8. The composition according to claim 1, which further contains an organic solvent (D).