KR940002283B1 - Curable dielectric polyphenylene ether polyepoxide compositions - Google Patents

Abstract

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Description

Curable Insulating Polyphenylene Ether-Polyepoxide Compositions Useful for Manufacturing Printed Circuit Boards

The present invention relates to resin compositions useful as insulators, and more particularly to polyphenylene ether-polyepoxysheet compositions suitable for the production of printed circuit boards.

Many polyphenylene ether-polyepoxide compositions having desirable insulating properties and also useful for the production of circuit boards are known. However, most of these have one or more defects in terms of properties, and thus are not widely commercially available. Therefore, although polyphenylene ether has excellent properties as an insulator and also has a favorable compounding property with polyepoxide, they are not only flammable and solderable, but also have poor resistance to solvents used for cleaning and cleaning of circuit boards. Defects have also been found in areas such as resistance and high temperature resistance. Moreover, most of the time required to cure such a composition, a large volume circuit board had the disadvantage that the efficient manufacturing.

In addition to good insulating properties, the resin composition used for the manufacture of printed circuit boards should be flame retardant. The acceptable level of flame retardancy, as measured according to the UL-94 test method of Underwriters Laboratories, requires a V-1 grade in addition to the V-0 grade, but generally V Requires level -0. For class V-0, the burn out time (FOT) for the sample in any test shall be 10 seconds or less, and the FOT cumulative value for 5 samples should be less than 50 seconds. In fact, buyers often require products with a maximum FOT of 35 seconds or less.

The substrate produced should not be substantially reduced in weight, and the surface of the substrate should not be damaged by contact with methylene chloride, a solvent normally used for cleaning. Since the connection between the conductor and the printed circuit is mainly made of solder, a solder-resistant substrate having a minimum thickness increase rate (Z-axis elongation rate) when the substrate is exposed to the liquid solder at 288 占 폚 should be used. In addition to the overall properties of the cured material, it is highly desirable that the curing time be relatively short.

Japanese Patent Laid-Open No. 58/69052 discloses a composition in which polyphenylene ether is blended with various types of polyepoxides. Examples of the latter polyepoxides include epoxy novolac resins and polyglycides which are compounds such as bisphenol A and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (tetrabromo bisphenol A). Dill ethers. Curing treatment of these compositions is carried out by contacting with various known curing agents including amines. However, the cured compositions have been found to contain serious defects in solvent resistance and in some cases solderability.

The co-pending U.S. Patent Application No. 219,106, filed on July 14, 1988, of the Applicant, discloses a halogen-free bisphenol polyglycidyl ether, a halogen-free epoxidized novolak, and an aryl substituent. Curable polyphenylene ethers, which contain partially cured (“upstaged”) products made from bromine-containing bisphenols, and wherein the cured material made from this composition is utilized in the manufacture of laminates and circuit boards. Polyepoxide compositions are disclosed. While these compositions generally have certain properties described above, there is room for improvement in terms of flow rate and fiber saturation, and also variations in soldering levels are occasionally found. The cause of the fluctuation of the soldering degree is caused by the inevitable inclusion of antimony pentoxide (in the form in combination with the dispersing agent described below) in the composition as a flame retardant enhancer.

In addition, a curable composition suitable for producing a bonding sheet is required. Bonding sheets are used when a multi-layer structure is required, such as laminating and etching a plurality of printed circuits into a single unit. For this purpose, a fiber-reinforced resin bonding sheet is used to separate copper circuit elements etched on two successive circuit boards to obtain a predetermined connection made through the bonding sheet.

In general, when the bonding sheet composition is melted under low pressure, it should have a significantly faster fluid flow than the composition used to manufacture the circuit board. In addition, the load of the resin should be relatively high because the voids generated during the etching of the circuit in the printed circuit board must be completely filled with the resin. In addition, a delay in curing occurrence time is required to obtain a predetermined flow before curing occurs. The composition must be compatible with the substrate in the circuit board. Finally, unlike laminates for circuit boards that require rigidity, the bonding sheet is preferably flexible.

The present invention provides a series of resin compositions consisting of polyepoxides, polyphenylene ethers and other components together with various catalysts, flame retardants. When used with the present compositions impregnated with a suitable fibrous reinforcing material, such as glass fiber fabrics, they provide a moldable prepreg ("prepreg" herein refers to an uncured or partially cured resin material). Means a curable article consisting of an impregnated substrate. The main substance is readily available in an organic solvent, whereby the impregnation treatment is convenient. The cured material thus produced has not only good solder resistance, solvent resistance and flame resistance, but also excellent insulation properties and dimensional stability at high temperatures. Thus, when the cured material is used as a laminate and bonding sheet for a printed circuit board, an excellent product can be made.

In one aspect, the present invention contains about 5% by weight or more of chemically bonded bromine to the total weight of the following components (I) and (II),

(I) about 40-65 weight percent of one or more polyphenylene ethers,

(II) 30-55% by weight of a polyepoxide composition consisting of at least one bisphenol polyglycidyl ether having an average of up to one aliphatic hydroxy group per molecule, containing about 10-30% bromine as an aryl molar

(III) at least one of the imidazoles and the arylene polyamines is an effective amount of a catalyst, and

(IV) zinc or aluminum in the form of a soluble or stably dispersible salt in the purifying composition comprises an effective amount of a cocatalyst, and includes a curable composition that is dissolved in an effective amount of an inert organic solvent. Polyphenylene ethers useful as component (I) in the compositions of the present invention consist of a plurality of structural units having the general formula:

In the above formula, the units are each independently, and Q ¹ is each independently a halogen atom, a primary or secondary lower alkyl group (ie, an alkali having up to 7 carbon atoms), a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or Halohydrocarbonoxy group, of which at least two carbon atoms separate into halogen atoms and oxygen atoms,

Q ² is independently a hydrogen atom, a halogen atom, a primary or secondary lower alkyl group, a phenyl group, a haloalkylli, a hydrocarbonoxy group, or a halohydrocarbonoxy group as defined for Q ¹ .

Examples of the primary lower alkyl group are methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-amyl group, isoamyl group, 2-methylbutyl group, n-hexyl group, 2,3-dimethylbutyl The group, 2-, 3-, or 4-methylpentyl group, and a corresponding heptyl group are mentioned, As an example of a secondary lower alkyl group, an isopropyl group, a sec-butyl group, and a 3-pentyl group are mentioned. Preferably, the alkyl group tannery is straight rather than branched. In general, each Q ¹ is an alkyl group or a phenyl group, in particular a C _1-4 alkyl group, and each Q ² is a hydrogen atom.

Both homopolymer and copolymer polyphenylene ethers can be used. Suitable homopolymer polyphenylene ethers contain, for example, 2,6-dimeltyl-1,4-phenylene ether units. Suitable copolymers include random copolymers in which the above units are combined with (eg) 2,3,6-trimethyl-1,4-phenylene ether units. Suitable examples of random copolymers in addition to homopolymers are described in the patent. Much has been reported in the literature.

In addition, the polyphenylene ether in the curable composition of the present invention contains components that improve properties such as molecular weight, melt viscosity and / or impact strength. Such polymers are reported in the patent literature, and non-hydroxy group-containing vinyl monomers such as acrylonitrile and vinylaromatic compounds (e.g. styrene), or non-hydroxy group-containing polymers such as polystyrene and elastomers on polyphenylene ethers. It can be manufactured by grafting by a well-known method. Most of these products contain both grafted and ungrafted components. Other polymers include coupled polyphenylene ethers in which the coupling agent reacts in a conventional manner with the hydroxy groups in the two poly phenylene ether chains to produce a high molecular weight polymer containing the hydroxy group and the reaction product of the coupling agent. Is suitable. Examples of coupling agents are low molecular weight polycarbonates, quinones, heterocycles, and formals.

For the purposes of the present invention, the polyphenylene ether has a number average molecular weight of about 3,000-40,000, preferably about 12,000 or more, most preferably about 15,000 or more, as measured by gel and chromatographic methods. It is preferred that the average molecular weight is in the range of about 20,000-80,000. It is preferable that the intrinsic viscosity is highest in the range of about 0.35-0.60 Pa./g. When measured in 25 degreeC chloroform. Typically, polyphenylene ethers are prepared by oxidatively coupling one or more corresponding monohydroxyaromatic compounds in a conventional manner. Particularly useful and readily available among the monohydroxyaromatic compounds are 2,6-xyleneol which can be specified as poly (2,6-dimethyl-1,4-phenylene ether) by an oxidative coupling reaction. In the general formula (I), each Q ¹ and one Q ² is a methyl group, the remaining Q ² is a hydrogen atom, and 2,3,6-trimethylphenol (which is represented by the general formula (I)). Each Q ¹ and one Q ² is a methyl group, and the remaining Q ² is a hydrogen atom.

Particularly useful polyphenylene ethers for the purposes of the present invention are those consisting of molecules having aminoalkyl substituted end groups, as reported in many patents and patent publications. Often, a significant amount of polyphenylene ether, mainly up to about 90% by weight, consists of these molecules. Polymers of this type can be obtained by incorporating only suitable primary or secondary monoa in the oxidative coupling reaction mixture as a member of its constituents.

Those skilled in the art can clearly see from the foregoing that the polyphenylene ethers contemplated for use of the present invention include all of which are presently known, regardless of structural units or incidental chemical changes. will be.

Component (II) is a polyepoxide composition composed of one or more bisphenol polyglycidyl ethers. In general, component (II) consists of a mixture of these ethers, some of which contain no halogen and the other containing bromine as aryl substituents. The total amount of bromine in component (II) is about 10-30% by weight.

Compounds of this type are prepared by reacting bisphenols with epechlorohydrin in a conventional manner (wherein "bisphenol" means a compound containing two hydroxyphenyl groups bonded to an aliphatic or cycloaliphatic moiety, or And aliphatic substituents). The said compound can be represented by the following general formula (II).

Wherein m is 0-4, n is a number having an average value of at most 1, A ¹ and A ² are each monocyclic divalent aromatic groups, and Y is one or two valences A ¹ and A ² Bridging group that separates each other. The bond of OA ¹ and A ² -O in formula (II) is generally made in the meta or para position of A ¹ and A ² with respect to Y.

In the general formula (II), A ¹ and A ² may be an unsubstituted phenylene group or a derivative thereof substituted with one or more substituents such as an alkyl group, a nitro group, an alkoxy group and the like. Among these, an unsubstituted waste arylene group is preferable. A ¹ and A ² may each be, for example, an o- or m-phenylene group and the remaining-may be a p-phenylene group, but preferably all are p-phenylene groups.

A bridging group, ie, Y, is a bridging group that separates one or two valences (preferably one valence) A ¹ and A ² from each other. In general, the bridging group is a hydrocarbon group, specifically methylene, cyclohexylmethylene, ethylene, isopropylidene, neopentylidene, cyclohexylidene or cyclopentadedecylidene, in particular gem-alkylene (alkylidene) It is a saturated free group like a group, and isopropylidene group is the most preferable among these. However, bridging groups also include radicals containing atoms other than carbon and hydrogen, such as those containing carbonyl, oxy, thio, sulfoxy and sulfone groups.

In most cases, component (II) consists of at least two or more bisphenol glycidyl ethers, one of which is brominated (m is 1-4, preferably 2) and the other does not contain bromine (M is 0). The predetermined bromine content ratio is about 10-30% with respect to component (II). Preferred materials are those products marketed as reaction products of epichlorohydrin with 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), for example EPON 825 sold by Shell Chemical Co. (n = 0) and EPON 828 (n = about 0.14); similar products may be prepared from epichlorohydrin and terrabromobisphenol A. The main purpose of using brominated compounds is to provide flame retardancy.

Component (III) is at least one compound selected from the group consisting of imidazoles and arylene polyamines. Any of these imidazoles and polyamides can be used as long as they are known to be useful as curing agents for epoxy resins. Among the imidazoles, imidazole, 1,2-dimethylimidazole, 2-methylimidazole, 2-heptadecylimidazole and 1- (2-cyanoethyl) -2-phenylimidazole are particularly useful. Commercially available imidazole-arylene polyamide mixtures are also often preferred, especially those containing arylene polyamides having a high degree of alkyl substitution on the aliphatic ring, typically having at least three alkyl substituents. Dimethylmethyl substituted m- and p-phenylenediamines are generally the most preferred polyamides.

The amount of component (III) is, after removal of the solvent, preferably an effective amount of catalyst for quickly achieving curing. In general, it is present in an amount of at least 4.5 milligrams equivalent of basic nitrogen, preferably at least 10 milligrams equivalent, including any basic nitrogen present in the polyphenylene ether per 100 parts of the total curable composition (mainly as an aminoalkyl substituted end group). do. Therefore, when using polyphenylene ether which is essentially free of basic nitrogen, the proportion of component (III) must be increased (for the purpose of the present invention, the equivalent of imidazole is equal to its molecular weight and the equivalent of diamine is Half the molecular weight).

Component (IV) is chemically bonded to zinc or aluminum, preferably zinc, in the form of a soluble or stably dispersible salt in the curable composition. Examples of suitable forms of zinc or aluminum for this purpose include salts of diketones (particularly acetylacetonates) and salts of fatty acids (particularly stearates) in which one carbon atom separates carbonyl groups from one another. In general, fatty acid salts are preferred when component (III) contains an alkylene polyamide, and diketone salts are preferred when component (III) is all imidazole.

Under certain conditions, acetylacetonates, such as zinc acetylacetonate, can form hydrates, which easily lose acetylacetone and become insoluble in the organic system used for the manufacture of the laminate. Therefore, measures are needed to maintain zinc or aluminum in stable dispersions.

Continued stirring of the composition is one means to solve the problem, but is generally not practical. A better method is to form an alcoholate of acetylacetonate by reacting with methanol. This alcoholate easily loses alcohol rather than acetylacetone under similar conditions, resulting in a solution or homogeneous suspension.

Another way to improve homogeneity is to use fatty acid salts. As another method, as described below, there is also a method of using a titanium compound as a compatibilizer.

Component (IV) is used in an effective amount of cocatalyst and also generally improves solvent resistance and flame retardancy. Zinc or aluminum is usually present in an amount of about 0.1-1.0% relative to the total curable composition.

In addition, although various other materials can be used for the curable composition of the present invention, it is usually preferable to use a specific material. As one of these, (V) is at least one novolac epoxidized with little halogen. It is usually used in an amount of about 5-10 parts by weight per 100 parts by weight of the total amount of components (I) and (II).

Suitable novolacs for use as precursors for component (V) are known in the art and typically formaldehyde with hydroxyaromatic compounds (preferably phenol) such as phenol, cresol or t-butylphenol. It is made by making it react. The novolac is then reacted with an epoxy reagent such as epichlorohydrin to produce a resin useful as component (V).

Various products are commercially available as epoxidized novolacs, and any of these may be used in accordance with the present invention. In general, it is highly desirable that epoxidized novolacs contain virtually no phenolic hydrogen atoms.

In addition, as a preferable material (VI), 1 or more types of novolak in which virtually all oxygen is in the form of phenolic hydroxyl group is mentioned. In addition, it generally contains "halogen." Component (VI) acts as a curing agent and in particular promotes curing of the composition used for the circuit board rather than the bonding sheet. Its molecular structure is similar to the molecular structure of the epoxidized novolacs described above, but not epoxidized. Often, t-butylphenol formaldehyde novolac is preferred. The amount of the novolac is generally about 10-15 parts by weight per 100 parts by weight of the total amount of components (I) and (II).

The curable composition of the present invention is dissolved in an effective amount of an inert organic solvent, with the dual solute content typically being about 30-60 weight 9%. The homogeneity of the solvent is not critical, but can be removed by any suitable means such as evaporation. As such a solvent, aromatic hydrocarbons, in particular, toluene are preferable. The order of mixing and dissolving is also not important, but in order to prevent premature curing, the catalyst and curing agent should not preferentially contact polyphenylene ether and polyepoxide at temperatures generally above about 60 ° C. The ratio of the components of the composition and bromine is the ratio excluding the solvent.

Regarding the total weight of the curable composition including a solvent, the usual proportions and preferred ratios of bromine and various components in the curable composition of the present invention containing components (V) and (VI) are as follows.

Other materials that can be used include inerts such as talc, clay, mica, silica, alumina and particulate fillers such as calcium carbonate. In addition, the bromine content in the curable composition can be partially replaced by materials such as alkyl tetrabromophthalate and / or epichlorohydrin reaction products of bisphenol A with a mixture of tetrabromobisphenol A, double alkyl tetrabro Morphthalates also act as plasticizers and flow improvers. Under certain conditions, ie, fabric wettability enhancers, which are mainly polar liquids such as n-butyl alcohol, methyl ethyl ketone and tetrahydrofuran, may be advantageously used. In addition, materials such as antioxidants, heat and ultraviolet stabilizers, lubricants, antistatic agents, dyes and pigments may also be used.

An important feature of the present invention is that flame retardant enhancers such as antimony pentoxide are generally unnecessary. However, these can be contained as needed.

When antimony pentoxide is used, its dispersion must be kept stable. This problem can be solved by agitation and / or blending with a suitable dispersant in many of the methods known in the art. The content of antimony pentoxide is usually used in an amount of up to about 4 parts per 100 parts of components (I)-(VI).

Preferred dispersants are compatible with the resin component in the present curable compositions, but typically polymers that are substantially non-reactive under the conditions in which the polyester is used. If component (IV) is a fatty acid salt, more powerful dispersants such as amines may be needed because these salts may form insoluble complexes with antimony pentoxide in different ways.

At least one aliphatic tris (dialkylphosphate) titanate is mentioned as a material which exists in a small amount and can improve the solvent resistance and compatibility of a curable composition, Therefore, its presence is preferable in this composition. . Suitable phosphate titanates are known in the art and are also commercially available. This is represented by the following general formula (i).

Wherein R ¹ is a primary or secondary C _2-6 alkyl or alkenyl group, preferably an alkenyl group, R ² is a C _1-3 alkylene group, preferably methylene group, and R ³ is primary or Is a secondary C _1-5 alkyl group, x is from 0 to about 3, preferably 0 or 1. Most preferably, R ¹ is an alkyl group, R ³ is an ethyl group, R ⁴ is an octyl group, and x is 0. The phospho titotate is generally present in an amount of about 0.1-1.0 parts per 100 parts of the resin composition.

The present invention includes all compositions composed of the components described above, including compositions containing other unspecified components. However, it is often desirable for the composition to consist primarily of components (I)-(VI), since only these components physically affect the basic and novel properties of the composition.

Another aspect of the invention consists of a fibrous substrate (fabric or nonwoven) such as glass, quartz, polyester, polyamide, polypropylene, cellulose, nylon or acrylic fibers and preferably glass, and impregnated with the curable composition And prepregs obtained upon removal of the solvent by evaporation or the like. Such prepregs can be cured by applying heat and pressure. The resulting article is another aspect of the present invention.

Typically, two or twenty ply laminates are compression molded under a temperature range of about 200-250 ° C. and a pressure of about 20-60 kg / cm 2. In this way, a laminate coated with a conductive metal such as copper and useful for a printed circuit board can be produced and cured by an art-recognized method. As mentioned above, the chained circuit board blank composed of the laminate exhibits excellent insulation, solderability, flame retardancy, high temperature resistance and solvent resistance.

Subsequently, a metal coating process can be performed by a conventional method.

The following examples illustrate the curable compositions, cured compositions, and methods of making laminates of the present invention. All parts and percentages are by weight unless otherwise indicated.

In the examples below, the following materials were used.

Component (I) -poly (2,6-dimethyl-1,4-phenylene ether) having an average molecular weight of about 20,000, an intrinsic viscosity of 25 ° C., 0.40 dl / g in chloroform, and a nitrogen content of about 960 ppm.

A mixture of component (II) -bisphenol A diglycidyl ether with diglycidyl ether of tetra bromobisphenol A.

A mixture of 1,2-dimetalthymidazole and diethylmethylphenylenediamine isomer having component (III) -average equivalent weight.

Component (IV) -zinc acetylacetonate or zinc stearate.

Epoxy novolak resin sold as "EPN 1138" by component (V) -Ciba-Geigy.

Component (VI) -commercially available t-butylphenol novolac in the range of about 700-900.

Phosphate titanate- (Formula) wherein R ¹ is an allyl group, R ² is a methylene group, R ³ is an -ethyl group, R ⁴ is an octyl group, and x is 0 Commercially available compounds.

A commercial colloidal dispersant comprising about 75% of antimony pentoxide coated with ADP-480-amine powder and dispersed in toluene.

Example 1

Curable compositions are prepared by dissolving the following components in the indicated amounts in toluene with a total concentration of solids of 30%.

Component (I) -50.81%

Component (II) -non-brominated-15.25%; Bromination-15.24%

Component (III) -1.42%

Component (IV)-Zinc Acetyl Acetate 2.03%

Component (Ⅴ) -5.08%

Component (VI)-10.16%

0.50 part per 100 parts of phosphate titanate-component (I)-(VI)

The glassy fabric was impregnated in toluene solution, and the resulting prepreg was dried in a forced hot air tower at 165 ° C. The laminate was then prepared by compression molding the eight ply prepregs at 235 ° C. for 10 minutes. Prior to molding, the prepreg dust was removed. The cured product showed essentially no Z-axis elongation and had good solvent resistance.

Example 2-3

Two compositions were prepared in a roluene solution as described in Example 1 using a mixture in which the weight ratio of toluene to tetrahydrofuran was 92: 8. Four layers of glass fiber fabric were stacked and the stack was immersed in solution to form a prepreg, then dried by hot air for 10 minutes in an oven at 173 ° C. and then again turned over and dried for 10 minutes. . The resulting composite laminate was sandwiched between sheets of aluminum foil coated with polytetrafluoroethylene and compressed to 200 ° C. and 1.38 MPa. The flame retardancy of the laminate of Example 3 was evaluated according to the UL-94 test method of Underwriters Laboratories and various test procedures of US Defense Standard MIL-P-13949. The results of Examples 2-3 are shown in Table 1.

TABLE 1

* Based on the total weight of components (I)-(VI).

Example 4

The composition was prepared in toluene solution. The composition of Example 2-3 was similar to that of Example 2-3, except that ADP-480 was used instead of phosphate titanate.

Seven-ply prepreg laminates were prepared from them, which were sufficiently cured using the method described in Example 2-3. The component ratios and test results are shown in Table 2 below.

TABLE 2

* Based on the total weight of components (I)-(VI).

Claims (37)

Regarding the weight of the following components (I) and (II), 5% by weight or more of chemically bonded bromine is contained, and (I) one or more polyphenylene ethers: 40-65% by weight, (II) molecules Polyepoxide composition consisting of 10-30% bromine as an aryl substituent, consisting of at least one bisphenol polyglycidyl ether having an average of up to one aliphatic hydroxy group per sugar: 30-55% by weight, (III) imidazoles And at least one of arylene polyamines: an effective amount of a catalyst and (IV) a zinc or aluminium cocatalyst in the form of a soluble or stably dispersible salt in the curable composition: an effective amount, and in an effective amount of an inert solvent The curable composition dissolved. The composition according to claim 1, wherein component (II) is a compound represented by the following general formula.

Wherein m is 0-4 and n is a number having an average value of at most 1. The composition of claim 2, wherein n is 0 and component (I) is poly (2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight in the range of 12,000-40,000. The composition of claim 3 wherein the solvent is toluene. The composition of claim 3 wherein component (III) is at least one imidazoling composition. 4. The composition of claim 3 wherein component (III) is a mixture of at least one imidazole with at least one arylene polyamine. 4. The composition of claim 3 wherein component (IV) is zinc acetylacetonate or zinc stearate. 4. A composition according to claim 3, wherein component (III) contains at least one aliphatic tris (dialkyl posufaceto) titanate represented by the following general formula in an amount of 0.1-1.0 parts by weight per 100 parts by weight of the resin composition.

Wherein R ¹ is a primary or secondary C _2-6 alkyl or alkenyl group, R ² is a C _1-3 alkylene group, R ³ is a primary or secondary C _1-5 alkyl group, and R ⁴ is 1 A secondary or secondary C _5-12 alkyl group, x being from 0 to about 3. The composition of claim 8, wherein R ¹ is an alkyl group, R ² is a methylene group, R ³ is an ethyl group, R ⁴ is an octyl group, and x is 0 or 1. 10. The composition of claim 4 containing stably dispersed antimony pentoxide in an amount of up to about 4 parts per 100 parts of components (I)-(IV). Regarding the total weight of the curable composition excluding the solvent, it contains 5% by weight of chemically bonded bromine, and also (I) at least one polyphenylene ether: 35-55% by weight, (II) on average up to 1 aliphatic per molecule A polyepoxide composition comprising one or more bisphenol polyglycidyl ethers having a hydroxy group and containing l0-30% bromine as an aryl substituent: 20-60 wt%, (III) the total amount of basic nitrogen is added to the curable composition 100 At least one of the imidazoles and the arylene polyamines, in an amount of providing more than 4.5 milligram equivalents per mole, (IV): 0.1-1.0% by weight of zinc or aluminum in soluble or stably dispersible salt form in the curable composition (V) containing 3-10% by weight of one or more epoxidized novolacs containing no halogen and (VI) halogen containing almost all of the oxygen atoms in the form of phenolic hydroxy groups. That one or more kinds of novolak: 4-15, and characterized by made of an% by weight, curability is dissolved in an inert organic solvent, an effective amount of the composition. The composition according to claim 11, wherein component (II) is a compound represented by the following general formula.

Wherein m is 0-4 and n is a number having an average value of 1 at most. 13. The composition of claim 12 wherein n is 0 and component (I) is a poly (2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight in the range of 12,000-40,000. The composition of claim 13 wherein the solvent is toluene. The composition of claim 13 wherein component (V) is prepared from phenol, formaldehyde and epichlorohydrin. The composition of claim 13, wherein component (III) is at least one imidazole. The composition of claim 13 wherein component (II) is a mixture of at least one imidazole with at least one arylene polyamine. The composition of claim 13 wherein component (IV) is acetal acetone zinc or zinc stearate. The composition according to claim 13, wherein the composition contains at least one aliphatic tris (dialkylphosphate) titanate represented by the following general formula in an amount of 0.1 to 1.0 parts by weight per 100 parts by weight of the resin composition.

Wherein R ¹ is a primary or secondary C _2-6 alkyl or alkenyl group, R ² is a C _1-3 alkylene group, R ³ is a primary or secondary C _1-5 alkyl group, and R ⁴ is 1 A secondary or secondary C _5-12 alkyl group, x being from 0 to about 3. 20. The composition of claim 19, wherein R ¹ is an alkyl group, R ² is a methylene group, R ³ is an ethyl group, R ⁴ is an octyl group, and x is 0 or 1. 15. The composition of claim 14 containing stably dispersed antimony pentoxide in an amount of up to 4 parts per 100 parts of components (I)-(VI). Regarding the total weight of the curable composition excluding the solvent, chemically, it contains at least 5% by weight of bound bromine, and furthermore, (I) at least one polyphenylene ether: 35-45% by weight, (II) average maximum per molecule Epoxide composition consisting of one or more bisphenol polyglycidyl ethers having one aliphatic hydroxy group, containing 10-30% bromine as an aryl substituent: 25-45% by weight, the total amount of (III) basic nitrogen is curable At least one of imidazoles and arylene polyamines in an amount that provides at least 15-30 milligram equivalents per 100 parts of the composition, (IV) zinc or aluminum in the form of soluble or stably dispersible salts in the curable composition: 0.1- 0.6% by weight, (V) one or more epoxidized novolacs without halogen: 3-10% by weight and (VI) halogen containing almost all of the oxygen atoms in the form of phenolic hydroxy groups. At least one novolac, which is basically 4-15% by weight, and is curable composition dissolved in an effective amount of inert solvent. A curable article consisting of a fibrous substrate impregnated with the composition of claim 3. Curable water consisting of a fibrous substrate impregnated with the composition of claim 13. A curable article consisting of a fibrous substrate impregnated with the composition of claim 22. The article of claim 23, wherein the substrate is glass fiber. The article of claim 24, wherein the substrate is glass fiber. The article of claim 25, wherein the substrate is glass fiber. A cured article made by applying heat and pressure to the article of claim 26. A cured article made by applying heat and pressure to the article of claim 27. A cured article made by applying heat and pressure to the article of claim 28. A printed circuit board blank comprising the article of claim 29 coated with a conductive metal. A semi-finished printed circuit board comprising the article of claim 30 coated with a conductive metal. A printed circuit board semi-finished product comprising the article of claim 31 coated with a conductive metal. 33. The finished product of claim 32, wherein the metal is copper. 34. The finished product of claim 33 wherein the metal is copper. 35. The printed circuit board finished product of claim 34, wherein the metal is copper.