JP2000336248A - Epoxy resin composition and electrical laminate sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which is excellent in flame retardancy and gives a cured material improved in water resistance by using as the constituents an epoxy resin containing a condensed polycyclic skeleton, a compound having a phenol skeleton and a triazine skeleton, and a phosphorus compound. SOLUTION: The composition contains (A) an epoxy resin containing a condensed polycyclic skeleton and having an epoxy equivalent of 120-500 g/e,q, (B) a compound having a phenol skeleton and a triazine skeleton in an amount sufficient to provide 0.2 to 2.0 phenolic hydroxy groups of component B for one epoxy group of component A, (C) a phosphorus compound such as a condensed phosphoric ester, in an amount of 5-40 wt.% and if necessary, a cure accelerator, an organic solvent and the like. The component A used comprises, e.g. a reaction product of dihydroxynaphthalene with an epihalohydrin, or a reaction product of a monohydroxynaphthalene/aldehyde condensate with an epihalohydrin, The component B used comprises, e.g. a condensation reaction product of a phenol with an aminated triazine compound, such as melannine, and an aldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-halogenated prescription (halogen-free), excellent flame retardancy, excellent heat resistance and moisture resistance, laminated material, semiconductor encapsulating material, electric insulation Epoxy resin composition useful for materials, fiber-reinforced composite materials, coating materials, molding materials, adhesive materials, etc., and particularly useful for electrical laminates (printed wiring boards) for electrical applications, and the varnish as a varnish. The present invention relates to an electric laminate manufactured using the same.

[0002]

2. Description of the Related Art Conventionally, an epoxy resin composition used in combination with an epoxy resin and a curing agent has been used in electric and electronic material parts such as an electric laminate such as a printed wiring board because of its excellent electrical properties and cured product strength. Widely used. These electric and electronic material parts usually have high flame retardancy (UL-9).
4 V-0), a halogenated epoxy resin is usually used. For example, in a glass epoxy laminate, as a FR-4 grade, a brominated bisphenol A type epoxy resin is generally used as a main raw material component, and a phenol novolak type epoxy resin or a cresol novolak type epoxy resin is used to impart heat resistance thereto. Is used, and a composition in which an epoxy resin combined with dicyandiamide as a latent curing agent is used.

However, in recent years, it has been pointed out that incineration of waste containing a halogen-based flame retardant may generate harmful substances such as dioxins which affect the environment during combustion. Therefore, there is a strong demand for a flame retardant formulation that reduces halogen or does not use halogen.

As an alternative to such a flame retardant prescription using halogen, for example, JP-A-10-193516 discloses a composition using a novolak type epoxy resin, a nitrogen compound, a phosphorus compound and an inorganic flame retardant in combination. It has been disclosed.

[0005]

However, Japanese Patent Application Laid-Open No.
In the composition described in JP-A-193516, it is necessary to use a large amount of an inorganic flame retardant such as a metal hydrate in order to develop practical flame retardancy. It was inferior. Especially for electric laminates, in addition to this low water resistance, the use of a large amount of inorganic flame retardants reduces the impregnation of the varnish into the glass cloth. The properties were significantly reduced.

[0006] The problem to be solved by the present invention is to develop excellent flame retardancy as a non-halogen flame retardant formulation, improve the water resistance of the cured product, and particularly to achieve excellent flame retardancy in laminates. And an epoxy resin composition exhibiting moisture resistance and solder resistance, and an electric laminate having excellent flame retardancy and moisture resistance.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an epoxy resin (A) containing a condensed polycyclic skeleton and a compound (B) having a phenol skeleton and a triazine skeleton. ) And a thermosetting composition containing the phosphorus compound (C) as an essential component, it is possible to exhibit excellent flame retardant effects without using a large amount of an inorganic flame retardant and to cure the composition. They have found that the water resistance of the product can be dramatically improved, and have completed the present invention.

That is, the present invention is characterized in that an epoxy resin (A) having a condensed polycyclic skeleton, a compound (B) having a phenol skeleton and a triazine skeleton, and a phosphorus compound (C) are essential components. The present invention relates to an epoxy resin composition to be formed, and an electric laminate, which is obtained by impregnating a fibrous base material with the epoxy resin composition, laminating the fibrous base material, and forming the laminate by heating and pressing.

The epoxy resin (A) having a condensed polycyclic skeleton used in the present invention is a resin having at least one epoxy group in one molecule having a condensed polycyclic skeleton. In order to make the effect remarkable, a non-halogen epoxy resin is preferable.

Here, the fused polycyclic skeleton refers to π on the aromatic nucleus.
Refers to a structure in which a plurality of rings sharing an electron cloud are connected, specifically, for example, a fused bicyclic skeleton such as an indene skeleton, a naphthalene skeleton, a pentalene skeleton, an azulene skeleton, and a heptalene skeleton, a fluorene skeleton, an anthracene skeleton, and a phenanthrene Condensed tricyclic skeleton such as skeleton, biphenylene skeleton, s-indecene skeleton, condensed tetracyclic skeleton such as naphthacene skeleton and chrysene skeleton, pentacyclic skeleton such as pentacene skeleton and pentaphene skeleton, condensed polycyclic skeleton such as coronene skeleton and pyranthrene skeleton And the like. Further, each of these skeletons may further have a substituent. Of these, a naphthalene skeleton is preferable because of its excellent flame retardant effect and excellent heat resistance.

Specific examples of the epoxy resin (A) having such a condensed polycyclic skeleton include those having a naphthalene skeleton as a condensed polycyclic skeleton, such as a reaction product of dihydroxynaphthalene and epihalohydrin, Reaction product of a condensate of naphthalene and aldehyde and epihalohydrin, reaction product of a mixture of monohydroxynaphthalene and dihydroxynaphthalene and epihalohydrin, reaction product of a mixture of monohydroxynaphthalene and xylylene glycols and epihalohydrin, mono Reaction product of an adduct of hydroxynaphthalene and a diene compound with epihalohydrin, reaction product of dihydroxynaphthalene with epihalohydrin, reaction product of condensate of dihydroxynaphthalene with aldehydes and epihalohydrin, dihydroxynaphthalate Reaction product of a condensate of ethylene and xylylene glycols with epihalohydrin, a reaction product of an adduct of dihydroxynaphthalene with a diene compound and epihalohydrin, a reaction product of a coupling product of monohydroxynaphthalene with epihalohydrin, and the like. .

Among them, in particular, from the viewpoint of excellent performance such as water resistance and heat resistance in laminated board applications, (a1) a reaction product of dihydroxynaphthalene and epihalohydrin (a2) a condensate of monohydroxynaphthalene and aldehyde Reaction product with epihalohydrin (a3) Reaction product of epihalohydrin with condensate of dihydroxynaphthalene and aldehyde (a4) Reaction product of epihalohydrin with mixture of monohydroxynaphthalene and dihydroxynaphthalene, (a5) Cup of monohydroxynaphthalene A reaction product of a ring compound and epihalohydrin is preferred.

Here, (a1), (a3) and (a4)
As the dihydroxynaphthalene used in the above, 1,2-,
1,3-, 1,4-, 1,5-, 1,6-, 2,3-,
Any of those having 2,6- and 2,7-substitution positions can be used.

The reaction product of (a2) a condensate of monohydroxynaphthalene and an aldehyde with an epihalohydrin may be a reaction product of a mixture of 1-naphthol or 2-naphthol with an aldehyde.

The aldehydes in (a2) and (a3) are not particularly limited, and include formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, etc. Among them, the heat resistance of the present invention and the use for glass cloth in laminated board applications. Formaldehyde is preferred from the viewpoint of good impregnation.

The method for producing the epoxy resin (A) represented by the above (a1) to (a5) is not particularly limited, but a raw material phenol having a condensed polycyclic skeleton is converted to sodium hydroxide. Reaction with epihalohydrin such as epichlorohydrin in the presence of an alkali metal hydroxide such as potassium hydroxide.

Further, the raw material phenols are as described in the above (a).
2) and (a3) in the case of a condensate of a raw material phenol monohydroxynaphthalene and an aldehyde or a condensate of dihydroxynaphthalene and an aldehyde,
By adding an aldehyde such as formaldehyde to hydroxynaphthalene or dihydroxynaphthalene and reacting in the presence of an acid catalyst or a basic catalyst, an intermediate is first obtained, and then the intermediate is reacted with an epihalohydrin such as epichlorohydrin. The desired epoxy resin can be manufactured.

The epoxy resin (A) having a condensed polycyclic skeleton used in the present invention may be any of the above-mentioned (a1) to (a5)
A high molecular weight epoxy resin having a structure in which phenols are further reacted with each of the above epoxy resins can also be used. As the high molecular weight epoxy resin, specifically, a reaction product (a1) of dihydroxynaphthalene and epihalohydrin
Is preferably an epoxy resin extended with a polyfunctional phenol. Examples of the polyfunctional phenols that can be used here include bisphenols such as bisphenol A, bisphenol F, bisphenol AD, and bisphenol S, phenol novolak resins, cresol novolak resins, and BPA novolak resins. Among them, bisphenols are preferred. It can be preferably used from the viewpoint of excellent adhesiveness between prepregs and adhesiveness with a copper foil in a laminated board application. Therefore, among the high molecular weight epoxy resins, the epoxy resin obtained by elongating the reaction product (a1) of dihydroxynaphthalene and epihalohydrin with a bisphenol is most preferable.

The epoxy resin (A) thus obtained
It is preferable that the epoxy equivalent is in the range of 120 to 500 g / eq because it is excellent in heat resistance and adhesion when a final cured product is obtained. That is, when the epoxy equivalent is 120 g / eq or more, good adhesiveness is obtained, while when the epoxy equivalent is 500 g / eq or less, good heat resistance is obtained. From the viewpoint that these performance balances are good, the range of 120 to 350 g / eq is particularly preferable.

In the composition of the present invention, the epoxy resin (A) is added to the epoxy resin (A) in a range that does not impair the effects of the present invention, specifically, the total epoxy equivalent of the epoxy resin component in the composition is from 120 to 500 g / g. Other epoxy resins may be used in combination within a range of eq and in such a proportion that the proportion of the epoxy resin (A) in the total epoxy resin component in the composition is 25% by weight or more.

The epoxy resin which can be used in combination with the epoxy resin (A) is preferably a non-halogen epoxy resin, for example, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene Oxide, phenyl glycidyl ether, cresyl glycidyl ether,
P. Monofunctional epoxy resins such as Sec-butylphenyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene monoepoxide; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, tetramethyl bisphenol A type epoxy resin, bisphenol S type Bisphenol type epoxy resins such as epoxy resin; other bifunctional epoxy resins such as resorcinol diglycidyl ether and dimethyl bisphenol C diglycidyl ether; phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, Novolak-type epoxy resins such as bisphenol AD novolak resin; epoxy resins having cyclohexene oxide group Cycloaliphatic epoxy resins such as epoxy resins, epoxy resins having a tricyclodecene oxide group, epoxy resins having a cyclopentene oxide group, and epoxidized dicyclopentadiene; diglycidyl phthalate, diglycidyl tetrahydrophthalate, hexa Glycidyl ester type epoxy resins such as diglycidyl hydrophthalate, diglycidyl p-oxybenzoic acid, glycidyl dimer acid, and triglycidyl ester; diglycidyl aniline, tetraglycidylaminodiphenylmethane, triglycidyl p-aminophenol, and tetraglycidyl methaxylyl Glycidylamine type epoxy resins such as diamine, diglycidyltoluidine, tetraglycidylbisaminomethylcyclohexane; Heterocyclic epoxy resins such as hydantoin-type epoxy resins such as glycinyl and glycidylglycidoxyalkylhydantoin; triallyl isocyanurate and triglycidyl isocyanurate; phlorogrisinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether and 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] Trifunctional epoxy resins such as ethyl] phenoxy] -2-propanol; tetrafunctional epoxy resins such as tetrahydroxyphenylethanetetraglycidyl ether, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl. .

The other epoxy resin (A) which can be used in combination is not limited to one kind in use, but two or more kinds in combination or various modified resins can be used.

Next, the compound (B) having a phenol skeleton and a triazine skeleton is not particularly limited, but various compounds obtained by a condensation reaction of a triazine compound, a phenol and an aldehyde can be used. It is preferably used as a mixture of compounds (hereinafter, abbreviated as “mixture (B)”).

Here, the phenol skeleton represents a phenol structural site derived from phenols, and the triazine skeleton represents a triazine structural site derived from a triazine compound.

The phenols used here include:
There is no particular limitation, for example, phenol, o
Polyhydric compounds such as alkyl phenols such as cresol, m-cresol, p-cresol, xylenol, ethylphenol, butylphenol, nonylphenol, and octylphenol, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, tetramethylbisphenol A, resorcinol, and catechol; Examples include phenols, naphthols such as monohydroxynaphthalene and dihydroxynaphthalene, and other phenylphenols and aminophenols. These phenols can be used alone or in combination of two or more. However, phenol is preferable because the final cured product is excellent in flame retardancy and excellent in reactivity with an amino group-containing triazine compound.

Next, the compound containing a triazine ring is not particularly limited, but is preferably the following general formula 1 or isocyanuric acid.

[0027]

Embedded image (In the general formula 1, R ₁ , R ₂ , and R ₃ represent any one of an amino group, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group, an ether group, an ester group, an acid group, an unsaturated group, and a cyano group. Represents.)

Among the compounds represented by the above-mentioned general formula 1, melamine, acetamate, and the like, in which two or three of R ₁ , R ₂ and R ₃ are amino groups, because of their excellent reactivity. Amino group-containing triazine compounds represented by guanamine derivatives such as guanamine and benzoguanamine are preferred.

These compounds are not limited to one kind in use, and two or more kinds can be used in combination.

The aldehyde is not particularly limited, but formaldehyde is preferred from the viewpoint of easy handling. Formaldehyde includes, but is not limited to, formalin, paraformaldehyde, and the like as typical sources.

Among the mixture (B) obtained by subjecting these triazine compounds, phenols and aldehydes to a condensation reaction, the triazine compounds are represented by the above-mentioned guanamine derivatives such as melamine, acetoguanamine and benzoguanamine. A mixture obtained using an amino group-containing triazine compound (hereinafter, abbreviated as “mixture (B ′)”) is preferable because the effect of improving flame retardancy is remarkable.

Examples of the mixture (B ′) include: B1: a condensation reaction product of an amino group-containing triazine compound, a phenol and an aldehyde, and B2: a condensation reaction product of an amino group-containing triazine compound and an aldehyde. , B3: the condensation reaction of phenols and aldehydes, B4: phenols, B5: a mixture of an amino group-containing triazine compound, and, -NH- -X-NH-CH ₂ in the mixture (b1 _{) -X-NH-CH 2 -Y-} (b2) ( wherein, X is a triazine skeleton, Y is showing a phenol skeleton.) comprising a structural moiety and (b2) / (b1) = 1.5~20 Those contained in proportions are preferred because the effect of improving the flame retardant effect is dramatically improved and the compatibility with the epoxy resin (A) is excellent.

In the mixture (B '), phenols (B4), which are unreacted components, and an amino group-containing triazine compound (B
5) may slightly remain, but is preferably in a range of 3% by weight or less.

In the present invention, the mixture obtained by subjecting a triazine compound, a phenol and an aldehyde to a condensation reaction, or a mixture (B ′) using an amino group-containing triazine compound as the triazine compound is a mixture (B ′). The nitrogen atom content in B) or the mixture (B ′) is preferably 5% by weight or more, especially 8% by weight or more, and the softening point measured in glycerin by a ball and ring method is 50 ° C. or more, preferably 80 ° C. or higher is preferred. In addition, 150 ° C measured with a cone plate type viscometer
The melt viscosity at 0.1 Pas or more, preferably 0.3 Pas
The above is preferred.

Next, the phosphorus compound (C) used in the present invention
As the compound, any compound containing no halogen atom and containing a phosphorus atom can be used. For example, phosphates, phosphonates, phosphinates, phosphine oxides, condensed phosphate esters, 9,10-hydro -9-oxa-10-phosphaphenanthrene-1
Pentavalent phosphorus compounds such as 0-oxide, phosphites,
Phosphonites, phosphinites, trivalent phosphorus compounds such as phosphines, red phosphorus, phosphoric acid, acidic phosphate esters, phosphazene ring-containing compounds and the like,
9,10-
Hydro-9-oxa-10-phosphaphenanthrene-
Preferred are 10-oxide and condensed phosphoric esters represented by the following general formula 2.

[0036]

Embedded image (Wherein, R1, R2, and R3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Y represents a methylene group, a propylidene group, —SO ₂ —, —CO—, —S—, or —O— And k represents an integer of 0 or 1, and m represents an integer of 1 to 4.)

The mixing ratio of each of the components (A) to (C) is not particularly limited, but first, the mixing ratio of the epoxy resin (A) and the compound (B) is set to the epoxy resin (A). ), The ratio of the phenolic hydroxyl group of the compound (B) to 0.2 to 2.0 per epoxy group can reduce unreacted components in the cured product, and can improve the moisture resistance and mechanical properties of the cured product. It is preferable in that the target strength is improved. Especially, it is particularly preferable to be in the range of 0.5 to 1.5.
The amount of compound (C) to be used is not particularly limited, but is preferably in the range of 5 to 40% by weight in the composition. That is, when the composition is used in an amount of 5% by weight or more in the composition, the flame retardant effect becomes remarkable, and when it is 40% by weight or less, the heat resistance and the moisture resistance can be improved.

The composition of the present invention may further contain a curing accelerator (D) in addition to the above components (A) to (C). Examples of the curing accelerator (D) include tertiary amines such as benzyldimethylamine, various imidazoles, tertiary phosphines, and various metal compounds.

In the epoxy resin composition of the present invention, an organic solvent (E) can be used, if necessary, in addition to the above components. In particular, when preparing a varnish for a printed wiring laminate, the components (A), (B), (C) and (E) are essential components. In addition, in other uses such as paint use, of course, (A), (B), (C),
You may use together each component of (D) and (E).

The organic solvent (E) is not particularly restricted but includes, for example, acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether,
N, N-dimethylformamide, methanol, ethanol, isopropyl alcohol, n-butanol, methoxypropanol, ethyl carbitol, toluene, cyclohexanone and the like. These solvents can be used as a mixture of two or more solvents as appropriate.

The amount of the organic solvent (E) to be used is not particularly limited. However, the solid content concentration is 30% by weight, since the base material has good impregnating properties and resin adhesion when preparing a prepreg. %, Especially 40 to 70% by weight.

Various curing agents, additives, flame retardants, fillers, and the like can be appropriately added to the epoxy resin composition of the present invention, if necessary, but the effect of the present invention is remarkable. In order to do so, it is desirable to avoid the use of inorganic flame retardants and other inorganic fillers as much as possible. Even when they are used, it is preferable that the content be within 5% by weight of the composition.

As described above, the epoxy resin composition of the present invention, which has been described in detail above, is extremely useful for electric laminates. The method for producing an electric laminate from the epoxy resin composition of the present invention is not particularly limited, and among the above components, a solid composition composed of each component except for the organic solvent (E) is heated and melted. To impregnate the cloth-like base material at a ratio of the resin amount of 30 to 70% by weight, or (A) to
A varnish is prepared by blending the components of (E), and the varnish is impregnated into a cloth-like substrate at a ratio of 30 to 70% by weight of a resin to form a prepreg, and then a plurality of prepregs, preferably 1 to There is a method in which ten sheets are hot-pressed together with a copper foil.

Here, the cloth substrate is not particularly limited, and examples thereof include glass cloth and aramid cloth.

The conditions for the heat and pressure molding are not particularly limited.
The range of -220 ° C and the range of 2-10 MPa as a pressure condition can be preferably applied.

[0046]

The present invention will be described in more detail with reference to the following examples.

Synthesis Example 1 160 g (1 mol) of 1,6-dihydroxynaphthalene was dissolved in 740 g (8 mol) of epichlorohydrin, and 440 g of a 20% aqueous NaOH solution was stirred at 80 ° C.
(2.2 mol) was added dropwise over 5 hours, and the reaction was further performed for 1 hour. Then, the aqueous layer was discarded, and excess epichlorohydrin was recovered by distillation, and toluene 4 was added to the reaction product.
08 g was added and dissolved uniformly, 130 g of water was added and washed with water, oil-water separation was performed, water was removed from the oil layer by azeotropic distillation, filtration was performed, and toluene was further distilled off to obtain an epoxy equivalent of 150 g / eq. An epoxy resin was obtained. Hereinafter, this is abbreviated as resin (A-1).

Synthesis Example 2 2 L equipped with thermometer, cooling tube, dropping funnel and stirrer
160 g of 2,7-dihydroxynaphthalene in a flask
(1 mol) was dispersed in 1600 g of water, and 49%
4.1 g (0.05 mol) of NaOH was added. Then 8
While heating to 0 ° C., 41% aqueous formalin solution.
2 g (containing 0.55 mol of formaldehyde) were continuously added from the dropping funnel in 0.5 hours. 80 ° C after dropping
, And neutralized by adding 5.1 g of 36% hydrochloric acid. Thereafter, the reaction product is filtered off, washed with warm water, dried, and

[0049]

Embedded image 160 g of a dimer represented by the following formula: was obtained. This dimer 83
g (0.25 mol) of epichlorohydrin 463 g (5
Mol) and 20% NaO at 80 ° C. with stirring.
An H aqueous solution (220 g) was added dropwise over 5 hours, and the mixture was further kept at the same temperature for 1 hour. Thereafter, after the water tank was discarded, 210 g of methyl isobutyl ketone was added to the reaction product obtained by distilling and recovering the excess epichlorohydrin to dissolve it uniformly, and then 70 g of water was added thereto, followed by washing with water and oil-water separation. The water was removed from the oil layer by azeotropic distillation, filtered, and methyl isobutyl ketone was distilled off.

[0050]

Embedded image A solid epoxy resin at room temperature containing the compound represented by the following formula as a main component was obtained. The softening point of this resin is 96 ° C, 150 ° C
Had a melt viscosity of 3 ps. The epoxy equivalent is 1
It was 59 g / eq. Hereinafter, this is abbreviated as resin (A-2).

Synthesis Example 3 1000 g of resin A-1 and 319 g of cyclohexanone were charged into a flask equipped with a thermometer, a stirrer and a condenser, and the temperature was raised to 80 ° C. while stirring. Bisphenol A there
275 g and 0.13 g of 5% NaOH are added,
The reaction was carried out at a temperature of 5 ° C. for 5 hours to obtain an epoxy resin having an epoxy equivalent of 300 g / eq. Hereinafter, this is abbreviated as resin (A-3).

Synthesis Example 4 41.5 was added to 94 parts of phenol and 12 parts of benzoguanamine.
% Formalin and 0.4 parts of triethylamine were added to adjust the pH of the system to 8.2, and the temperature was gradually raised to 100 ° C. while paying attention to heat generation. After reacting at 100 ° C. for 5 hours, the temperature was raised to 120 ° C. over 2 hours while removing water under normal pressure. Next, after reacting for 3 hours under reflux, the temperature was raised to 160 ° C. over 2 hours while removing water under normal pressure. After further reacting for 3 hours under reflux,
The temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under reduced pressure to obtain a mixture having a softening point of 111 ° C. and a hydroxyl equivalent of 120 g / eq.

Hereinafter, this mixture is abbreviated as "B-1".
The resulting weight ratio of the phenols and triazines in the composition, unreacted formaldehyde amount, presence or absence of methylol groups, the structural units _{b1 (-X-NH-CH 2} -NH
-), the structural unit _{b2 (-X-NH-CH 2} -Y-) molar ratio of unreacted phenol monomer amount, and triazines reaction rate was determined as follows.

<Weight ratio of phenol to triazine (benzoguanamine)> The phenol content in the effluent removed from the reaction system at 180 ° C. under reduced pressure was calculated by gas chromatography, subtracted from the number of phenol parts charged, and calculated in the mixture. Of phenol. Benzoguanamine was included in the composition as it was charged. The ratio between the two was defined as the abundance ratio. [Column: 30% Celite 545 carnauba wax 2m
× 3mmΦ Column temperature: 170 ° C Injection port temperature: 230 ° C
Detector: FID Carrier gas: N2 gas 1.0 kg / c
m2 measurement method: internal standard method]

<Molar Ratio of Structural Unit b1 (—X—NH—CH ₂ —NH—) Structural Unit b2 (—X—NH—CH ₂ —Y —)> Measured using a 13C-NMR chart under the following conditions. . [Apparatus: GSX270 Proton: 2 manufactured by JEOL Ltd.]
70 MHZ measurement solvent: DMSO or heavy acetone Reference substance: Tetramethylsilane Measurement condition Pulse condition: 45 ° × 10000 times Pulse interval: 2 seconds] The integrated value of the peak appearing at 42.5 to 45 ppm in the chart is Bp, 47 to 48.5 ppm. Was defined as Ap, and the molar ratio was determined by the following equation. Structural unit b1 / structural unit b2 = Bp / Ap

<Amount of unreacted phenol monomer> The phenol monomer content in the effluent was measured under the same measurement conditions as in the gas chromatography described above.

<Reaction rate of triazines> This was calculated using a 13 C-NMR chart measured under the same conditions as those for measuring the b1 / b2 ratio. 167.2 to 167 of the chart.
The integrated value of a sharp peak appearing at 4 ppm is defined as Tm, 1
The peak integration value of the broad peak appearing at 63 to 167.2 ppm was defined as Tr, and the reaction rate was determined by the following equation.

Reaction rate (%) = (Tr / (Tr + Tm)) × 100 The results of the amounts of the respective components thus obtained are summarized in Table 1.

Synthesis Example 5 To 94 parts of phenol and 18 parts of melamine, 45 parts of 41.5% formalin and 0.4 part of triethylamine were added.
The pH of the system was adjusted to 8.2, and the temperature was gradually raised to 100 ° C. while paying attention to heat generation. After reacting at 100 ° C. for 5 hours, the temperature was raised to 120 ° C. over 2 hours while removing water under normal pressure. Next, after reacting for 3 hours under reflux, the temperature was raised to 140 ° C. over 2 hours while removing water under normal pressure. After reacting for 3 hours under reflux, the temperature was raised to 160 ° C. over 2 hours while removing water under normal pressure. After further reacting under reflux for 3 hours, the temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under reduced pressure to obtain a mixture having a softening point of 128 ° C. and a hydroxyl equivalent of 120 g / eq. Hereinafter, this mixture is abbreviated as “B-2”. The weight ratio of phenol to melamine, the molar ratio of structural unit b1, the structural unit b2, the amount of unreacted phenol monomer, and the conversion of triazines were determined in the same manner as in Example 1. The results are shown in Table 1.

[0060]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 and 2 Next, varnishes were prepared according to the formulations shown in Table 2 or Table 3.
The varnish was prepared by mixing an epoxy resin and a curing agent and a phosphorus compound previously dissolved in a mixed solution of methyl cellosolve and N, N-dimethylformamide, and then adding a curing agent 2-ethyl-4-methylimidazole to the final mixture. It was prepared by adjusting with methyl ethyl ketone such that the nonvolatile content (NV) of the compounded epoxy resin composition was 56% by weight.

At this time, the amount of the curing agent was compounded in such a ratio as to be 1.0 equivalent to the epoxy equivalent in the base epoxy resin. The curing accelerator is used in an amount of 0.1 part per 100 parts of the resin (total of epoxy resin, curing agent and phosphorus compound).
The ratio was 1 part. Thereafter, each mixed solution was cured under the following conditions to produce a double-sided copper-clad laminate. The evaluation results are shown in Tables 2 and 3.

"1051-75M" is bisphenol A
Type epoxy resin (trade name: EPICLON 1051N-75M, epoxy equivalent: 474 g / eq, manufactured by Dainippon Ink and Chemicals, Inc.), and "N-690-75M" is a cresol novolac type epoxy resin (Dainippon Ink and Chemicals, Inc.) (Trade name: N-690-75M, epoxy equivalent: 220 g / eq).

"PX-200" is a condensed phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: PX-200, phosphorus content 9.0%), and "PX-202" is a condensed phosphate ( Product name: PX-, manufactured by Daihachi Chemical Industry Co., Ltd.
202, phosphorus content 8.0%), "HCA" is 9.1
0-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: H, manufactured by Sanko Co., Ltd.)
CA), 2E4MZ indicates 2-ethyl-4-methyl-imidazole.

[Laminate Plate Manufacturing Conditions] Base material: 180 μm; glass cloth “WEA 7628 30 H258 N” manufactured by Nitto Boseki Co., Ltd. Number of plies: 8 Pre-preg conditions: 160 ° C./3 minutes Copper foil: 35 μm; Curing conditions: 170 ° C., 40 kg / cm 2 for 1 hour Sheet thickness after molding: 1.6 mm Resin content: 40%

[Physical property test conditions] Combustion test: Based on UL-94 vertical test. Glass transition temperature: Measured by the DMA method after etching treatment to remove copper foil. Heating speed 3 ° C / min Water absorption: Weight change before and after a PCT (pressure cooker) test of a test piece (25 mm x 50 mm) was measured. Test conditions: temperature; 121 ° C., humidity; 100%, time; 2 hours. Moisture resistance and solder resistance: The sample whose water absorption was measured was immersed in a solder bath at 260 ° C. for 30 seconds, and the state change before and after that was observed. (Judgment criteria) ○: No change in appearance △: 5 or less blisters with a diameter of 5 mm or less. ×: swelling larger than 5 mm in diameter or 6 or more swelling less than 5 mm in diameter

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

According to the present invention, it is possible to provide an epoxy resin composition exhibiting practical non-halogen flame retardancy and having excellent water resistance of a cured product. Accordingly, the epoxy resin composition of the present invention can be used for laminated component materials, semiconductor sealing materials, electrical insulating materials, fiber reinforced composite materials, coating materials, molding materials, adhesive materials, etc. In (printed wiring board) applications, particularly excellent flame retardancy and moisture resistance and solder resistance can be exhibited.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 59/06 C08G 59/06 59/20 59/20 59/50 59/50 59/62 59 / 62F Term (reference) 4F100 AB01B AB17B AB33B AG00A AH02A AH03A AK53A BA02 CA02A CA08A DG11A DH01A GB43 JB06 JD04 JJ03 JJ07 4J002 CD031 DA057 EE016 EJ016 EN058 EU118 EU186 EW007 EW007CA08 DC08 DCA4 JA11

Claims (9)

[Claims] 1. An epoxy resin composition comprising an epoxy resin (A) having a condensed polycyclic skeleton, a compound (B) having a phenol skeleton and a triazine skeleton, and a phosphorus compound (C). 2. The epoxy resin composition according to claim 1, wherein in the epoxy resin (A) having a condensed polycyclic skeleton, the condensed polycyclic skeleton is a naphthalene skeleton. 3. An epoxy resin (A) containing a condensed polycyclic skeleton is a reaction product (a1) of dihydroxynaphthalene and epihalohydrin or a reaction product (a2) of a condensate of monohydroxynaphthalene and aldehydes with epihalohydrin The composition according to claim 1 or 2, wherein 4. The epoxy resin (A) having a condensed polycyclic skeleton is an epoxy resin having a structure obtained by further extending a polycondensate (a1) of dihydroxynaphthalene and epihalohydrin with a polyfunctional phenol. 4. The composition according to 1, 2, or 3. 5. The composition according to claim 1, wherein the epoxy equivalent of the epoxy resin (A) having a condensed polycyclic skeleton is in the range of 100 to 500 g / eq. 6. A compound (B) comprising: a triazine compound;
The composition according to any one of claims 1 to 5, having a structure in which a phenol and an aldehyde are subjected to a condensation reaction. 7. A compound (B) comprising: B1: a condensation reaction product of an amino group-containing triazine compound with a phenol and an aldehyde; B2: a condensation reaction product of an amino group-containing triazine compound with an aldehyde; B3: a phenol compound condensation reaction product of the aldehyde compound, B4: phenols, B5: a mixture of an amino group-containing triazine compound, and, -NH- -X-NH-CH ₂ in the mixture (b1) -X-NH —CH ₂ —Y— (b2) (wherein, X represents a triazine skeleton and Y represents a phenol skeleton). A mixture containing a structural site of (b2) / (b1) = 1.5 to 20 The composition according to claim 6, which is used as: 8. In addition to an epoxy resin (A) having a condensed polycyclic skeleton, a compound (B) having a phenol skeleton and a triazine skeleton, and a phosphorus-containing compound (C), a curing accelerator (D) and an organic solvent ( The composition according to any one of claims 1 to 7, which contains E). 9. An electric laminate comprising a cloth-like substrate impregnated with the epoxy resin composition according to any one of claims 1 to 8, laminated, and heated and pressed. .