HK1094509A - Curable flame retardant epoxy resin compositions - Google Patents

Description

Curable flame retardant epoxy resin compositions

Technical Field

The present invention relates to a curable flame retardant epoxy resin composition which has tough and chip-resistant properties and which is particularly useful for the preparation of electronic laminates (electrical laminates).

Background

Thermosetting resins such as epoxy resins are often used in the microelectronics and aerospace industries. The microelectronics and aerospace industries are both regulated to use flame retardant epoxy resins. Typical flame retardant epoxy resins include bromine-containing epoxy resins. Although brominated epoxy resins can increase fire resistance, they can decrease their fracture resistance, and it can be difficult to process these materials into finished products.

For example, a significant problem in the electronics industry is the drillability of brominated epoxy compositions for use in printed circuit board manufacture, since brominated epoxy compositions are very brittle. Therefore, when brominated epoxy compositions must be used to improve the fire resistance properties of epoxides, particularly when such epoxides are used in the microelectronics industry, the brominated epoxy materials are susceptible to cracking during the drilling process, thus limiting their applicability.

Other known flame retardant epoxy resins for use in electronic laminates are non-brominated epoxy resins, such as phosphorous-containing epoxy resins, as disclosed, for example, in U.S. Pat. No. 6,403,220, U.S. patent publication No. 2002/0119317A 1, and PCT publication No. WO 99/00451. These bromine-free epoxy resins have the disadvantage of being easily chipped and therefore difficult to apply in printed circuit board manufacturing processes.

Generally known epoxides are difficult to toughen and some epoxides are too brittle to toughen. Furthermore, increasing the toughness of brittle epoxies tends to compromise the modulus and service temperature, making the applicability of these resins unacceptably limited.

Some recent techniques use the self-assembling property of block copolymers to make epoxies tough with minimal impact on glass transition temperature and modulus, and have the advantages of simple processing and low cost. For example, in Dean, j.m.; lipic, p.m.; grubbs, r.b.; cook, r.f.; bates, f.s.j., "mesoporous Structure and Mechanical properties of Block Copolymer-Modified epoxides," j.polymer.sci.part B Polymer Physics, 2001, 39, 2996-3010, disclose that Block copolymers self-assemble into bubble and sphere shaped micelles, which increase the resistance to cracking of bisphenol a (bisphenol a) epoxides, which are cured by a tetrafunctional aromatic amine curing agent. The mechanism of stiffening is generally seen from the relationship between the ratio of separation between the particles and the particle diameter. These forms share the same basic spherical shape, but a larger size bubble would increase the burst resistance by a factor of three.

It is therefore preferable to find other ways to further increase the crack resistance and fire resistance properties of the epoxy resin without sacrificing other properties of the epoxy resin, such as the use temperature and modulus (modulius).

It would also be desirable to provide a composition that improves fracture resistance to overcome the disadvantages of known materials, and in particular to overcome the drilling problems of existing materials.

Disclosure of Invention

The object of the present invention is to propose a curable epoxy resin composition comprising (a) at least one flame retardant epoxy resin; (b) at least one amphiphilic (amphpilic) block copolymer; and (c) a curing agent.

Another object of the present invention is to propose a process for the preparation of a curable epoxy resin composition comprising mixing:

(a) at least one flame retardant epoxy resin;

(b) at least one amphiphilic (amphpilic) block copolymer; and

(c) and (3) a curing agent.

It is another object of the present invention to provide a cured resin product, such as a printed circuit board, made from the above curable resin composition.

The invention further proposes a new form of modifier comprising a self-assembled nanoparticle structure, which is for example an insect-like or spherical micelle. In a particular embodiment, the appropriate amounts and ratios of the components of the present invention are based on the morphology of the cured, block copolymer self-assembled into worm-like micelles, which results in improved fracture resistance of the cured product.

Drawings

FIG. 1A is a Transmission Electron Microscope (TEM) picture of worm-like colloidal particles of an epoxy cured with a phenol formaldehyde resin. FIG. 1A is an example of a modified flame retardant epoxy block copolymer of the present invention and clearly shows the difference in size and shape between the cylindrical geometry of the present invention and the geometry of the prior art.

FIG. 1B shows a representation of the worm-like geometry and configuration of FIG. 1A.

Fig. 2A is a TEM image of spherical colloidal particles of an epoxy cured with a phenol formaldehyde resin.

Figure 2B is a spherical micelle geometry of the structure of figure 2A.

Fig. 3A is a TEM image of bubbles of an epoxy cured with a phenol formaldehyde resin.

Fig. 3B is a bubble geometry of the structure of fig. 3A.

FIG. 4 shows the efficacy of the epoxy resin components in the epoxy composition as wormhole-like micelles, spherical micelles and modified epoxy vesicles as well as the strain energy release rate of the resin in a uniform manner. FIG. 4 shows that the worm-like colloidal particles can be increased by about 1000J/m²Even machine samples (50 weight percent epoxy) that are too brittle to be used for mechanical testing are well-balanced epoxy fracture resistant.

Detailed Description

The curable composition of the present invention comprises (a) an epoxy resin or a mixture of a plurality of different epoxy resins, wherein at least one of the epoxy resins is a flame retardant epoxy resin; (b) at least one amphiphilic (amphpilic) block copolymer comprising one epoxy miscible block and one epoxy immiscible block; and (c) a curing agent or mixture of curing agents. The block copolymer is used as a modifier to improve the mechanical properties of the mixture.

The compositions of the present invention have excellent high fracture resistance properties. The present invention allows for the use of a block copolymer additive that allows the block copolymer to be incorporated into a thermoset resin at low concentrations (e.g., less than 5 weight percent) and at low cost; but with minimal variation in the processing equipment.

The present invention provides a morphology that is created in the uncured state due to thermodynamics and non-extreme sensitivity to the curing process. In addition, the present invention allows thermosetting resins, such as epoxies, to be used in more applications where fracture resistance is a concern.

The present invention provides a process for preparing a thermosetting epoxy resin that greatly improves the crack resistance of flame retardant epoxies with minimal acceptable loss of modulus (between 5 and 20 percent) without affecting the glass transition temperature.

The present invention demonstrates that the toughness of thermosetting resins, such as epoxy resins, such as bisphenol a epoxies cured with phenol formaldehyde resins, can be significantly improved, even though the epoxies contain brominated epoxies to improve fire resistance. An important object of the present invention is to provide thermosetting resins, such as epoxy resins, which are highly tough and flame retardant, for applications such as microelectronics and advanced aircraft construction. In particular, it provides excellent service temperature, fire resistance and toughness for printed circuit boards and other applications during manufacturing.

The compositions provided by the present invention have a novel morphology which is self-assembling worm-like or spherical by the addition of block copolymers having the correct composition and architecture. The colloidal particle structure of the present invention contributes to the toughness of the epoxy resin material, for example, due to the worm-like or spherical shape, which is a bubble shape relative to other geometric shapes.

The worm-like micelles will self-assemble, which again improves their fracture resistance, for example by a factor of 190, for example from two different types of block copolymers. The cross section of the worm-like colloidal particles is round or oval. Generally the length of the worm-like colloidal particles is relatively long compared to their width, and the average aspect ratio is about 3: 1 or higher, more preferably 5: 1 or higher, and even more preferably 10: 1 or higher.

Flame-retardant epoxy resin

An example of a flame retardant epoxy resin used in the present invention is a brominated epoxy resin. The brominated epoxy resin component used in the curable epoxy resin composition of the present invention may be any of the well-known brominated epoxy resins. Examples of bromine-containing epoxy resins of the present invention include tetrabromobisphenol A, propylene oxide ethers of tetrabromobisphenol A, and other brominated epoxides, such as the commercially available epoxides, such as the trademarks D.E.R.560, D.E.R.542, D.E.R 592, D.E.R 593, D.E.R 530, and D.E.R 53, produced by the Dow Chemical Company, and mixtures thereof. The epoxy resin containing bromine used in the present invention is preferably a propylene dioxide ether including tetrabromobisphenol a, which is, for example, d.e.r.560.

The compositions of the present invention may comprise at least one or more brominated epoxy resins. Two or more different brominated epoxy resins may be mixed together to make up the flame retardant epoxy component of the present invention. The bromine content of the epoxy resin composition may be from about 5 weight percent to about 50 weight percent, more preferably from about 10 weight percent to about 25 weight percent, and more preferably from about 18 weight percent to about 21 weight percent.

Other examples of flame retardant epoxy resins useful in the present invention are "bromine-free" epoxy resins, such as phosphorous-containing epoxy resins, which are disclosed in U.S. patent publication No. 2002/0119317A 1 entitled "flame retardant phosphorous element-containing epoxy resin composition", which is disclosed on 8/29 of 2002. Examples of the phosphorous flame retardant epoxy resins disclosed in the above-mentioned U.S. patent publication include epoxy resins containing non-halogenated phosphorus elements, which have been described in U.S. Pat. No. 5,376,453, including, for example, methyl propenyl diphosphate, ethyl propenyl diphosphate, propyl propenyl diphosphate, butyl propenyl diphosphate, vinyl propenyl diphosphate, phenyl propenyl diphosphate, and diphenyl propenyl diphosphate; methyl propylene dioxide phosphate, ethyl propylene dioxide phosphate, n-propyl propylene dioxide phosphate, n-butyl propylene dioxide phosphate, isobutyl propylene dioxide phosphate, allyl propylene dioxide phosphate, phenyl propylene dioxide phosphate, p-methoxyphenyl propylene dioxide phosphate, p-ethoxyphenyl propylene dioxide phosphate, p-propoxyphenyl propylene dioxide phosphate, p-isopropoxyphenyl propylene dioxide phosphate, thiophenyl propylene dioxide phosphate, propenyl trioxide phosphate, tetrakis (oxypropylethyl) phosphate, p-oxypropylphenylethynyl oxypropylene oxide phosphate, phenyl propylenedioxypropenyl thiophosphate, and combinations thereof.

Other examples of non-halogenated phosphorus element-containing epoxy resins useful in the present invention are obtained by phosphorus element-containing epoxy compounds including epoxide products of phosphorus element-containing compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, such as "Sanko-HCA", available from Sanko corporation of Japan, or "Struktol polydis PD 3710", available from Schill-Seilacher of Germany; 10- (2 ', 5' -dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (for example "SankoHCA-HQ"); bis (4-hydroxyphenyl) phosphine oxide; tetrakis (2-hydroxyphenyl) phosphine oxide; dimethyl-1-bis (4-hydroxyphenyl) -1-phenylmethyl ester; tetrakis (2-hydroxy-4/5-methylphenyl) phosphine oxide; tetrakis (4-hydroxyphenyl) phosphine oxide, bis (2-hydroxyphenyl) phenylphosphine oxide, bis (2-hydroxyphenyl) phenylphosphate, tetrakis (2-hydroxy-5-methylphenyl) phosphine oxide; or a mixture thereof. The person skilled in the art will generally work with an epoxidised compound containing the phosphorus element together with an epihalohydrin, such as epichlorohydrin.

Phosphorous flame retardant epoxy resins include, for example, XZ92530, which is a phosphorous epoxy resin and is commercially available from the Dow Chemical Company.

Other phosphorous containing epoxy resins useful in the present invention are disclosed in, for example, U.S. Pat. No. 6,403,220 and PCT publication No. WO 99/00451.

The composition of the present invention may comprise at least one or more phosphorous containing epoxy resins. And two or more different phosphorous-containing epoxy resins can be mixed together to make up the flame retardant epoxy component of the present invention. The phosphorous content of the epoxy resin composition may be from about 0.05 weight percent to about 20 weight percent, more preferably from about 1 weight percent to about 10 weight percent, and more preferably from about 0.2 weight percent to about 5 weight percent.

The brominated epoxy resin and the phosphorous-containing epoxy resin may be used alone or in a mixture. The epoxy resin may also be used in combination with other flame retardant epoxy resins.

In other embodiments of the invention, the components of the flame retardant epoxy resin may be intermixed or mixed with other non-flame resistant epoxy resins. The non-fire resistant epoxy resin may be a halogenated epoxy resin, in addition to a brominated epoxy resin. The non-brominated halogenated epoxy resin may be, for example, a chlorine-containing epoxy resin. The non-flameproof epoxy resin may also be a non-halogenated epoxy resin, which is, for example, the propylene dioxide ether of bisphenol A.

If other epoxy resins than the flame retardant epoxy resin are to be used, it is known that some epoxy resins may be selected to be mixed with the brominated epoxy resin. These additional epoxy resin compounds used in the present invention are, for example, known polyepoxides. The polyepoxide compounds used in the present invention are suitably compounds or mixtures of compounds having more than one 1, 2-epoxy group. In general, polyepoxide compounds having more than one 1, 2-epoxy group are saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compounds. The polyepoxide compound may be substituted with one or more substituents, such as lower alkyl and halogen. Such polyepoxide compounds are known. Polyepoxide compounds useful in the present invention are described in Handbook of EpoxyResins by H.E.Lee and K.Neville, published in 1967 by McGraw-Hill, New York, and U.S. patent No.4,066,628.

The polyepoxide compound used in the present invention has the following formula:

wherein R is a substituted or unsubstituted aromatic, aliphatic, cycloaliphatic or heterocyclic polyvalent radical and n has an average value of from about 1 to about 8.

Polyepoxides useful in the present invention include, for example, partially modified epoxy resins formed by the reaction of a polyepoxide with a chain extender to produce a product having an average of more than one unreacted epoxide unit per molecule.

Examples of known epoxy resins which can be used in the present invention include, for example, aliphatic polyepoxides, which are prepared, for example, from the reaction of a halogen epoxide, propane, and polyethylene glycol. Specific examples of other aliphatic epoxides include trimethylpropane epoxide and propylene oxide-1, 2-cyclohexane-dicarboxylate. Polyepoxides useful in the present invention may also include epoxy resins such as the oxypropylene ethers of polyhydric phenols, which are compounds having an average of more than one aromatic hydroxyl group per molecule, for example, dihydric phenols, diphenols, bisphenols, halogenated diphenols, halogenated bisphenols, alkylated diphenols, alkylated bisphenols, trisphenols, phenol-aldehyde-formaldehyde resins, substituted phenol-aldehyde-formaldehyde resins, phenol hydrocarbon resins, substituted phenol hydrocarbon resins, and combinations thereof.

More preferably, the polyepoxide (polyoxypropylene ether of a polyhydroxyhydrocarbon) is prepared by reacting an epihalohydrin with a polyhydroxyhydrocarbon or a halogenated polyhydroxyhydrocarbon. It is known to prepare such polyepoxide compounds (see Kirk-Othmer encyclopedia of Chemical Technology, 3rd Ed., Vol.9, pp.267-289).

The chemical formula of the epihalohydrin is as follows:

wherein Y is halogen, more preferably chlorine or bromine, most preferably chlorine; r is hydrogen or has C_1-4The alkyl group of (1) is preferably a methyl group.

A polyhydroxyhydrocarbon is a compound having a hydrocarbon backbone and on average more than one primary or secondary hydroxyl moiety, more preferably two or more. A halogenated polyhydroxyhydrocarbon is a compound having a hydrocarbon backbone, preferably two or more, substituted with one or more halogens, and a major or minor hydroxyl moiety. The hydroxyl moiety can be aromatic, aliphatic, or cycloaliphatic. Multifunctional based dihydroxy hydrocarbons or halogenated dihydroxy hydrocarbons are well known in the art (see Lee and Neville, supra; and Bertram, U.S. patent No.4,594,291, col.8, lines 24-36).

Among the polyhydroxyhydrocarbons and halogenated polyhydroxyhydrocarbons, preferred are dihydric phenols; diphenols; a bisphenol; a halogenated bisphenol; an alkylated bisphenol; a trisphenol; hydrogenated bisphenols; formaldehyde-based resins, which are phenol reaction products including halogenated and alkylated phenols, and simple acetaldehydes, preferably formaldehyde and hydroxybenzaldehydes; and a polytetalene glycol.

More preferably, the polyhydroxylated hydrocarbon is a dihydric phenol which includes a substituent which is unreactive with the phenol-formaldehyde. Such phenols are, for example, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane; 2, 2-bis (4-hydroxyphenyl) propane; 2, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane; bis (4-hydroxyphenyl) methane; 1, 1-bis (4-hydroxyphenyl) -1-phenylethane; 1, 1' -bis (2, 6-dibromo-3, 5-dimethyl-4-hydroxyphenyl) propane; bis (4-hydroxyphenyl); bis (4-hydroxyphenyl) sulfide; resorcinol and hydroquinone.

More preferred dihydric phenol compounds are 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A), trimethylolpropane, 1, 3, 5-tetrakis (2-hydroxyethyl) -1, 3, 5-triazacyclo-2, 4, 6-1H, 3H, 5H) -trione and 2, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol AP (1, 1-bis (4-hydroxyphenyl) -1-phenylethane), bisphenol F, bisphenol K, tetrabromobisphenol A, phenol-formaldehyde resins, alkyl-substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene phenol resins, dicyclopentadiene-substituted phenol resins, Propylene dioxide ethers of tetramethyl diphenol, tetramethyl tetrabromobisphenol, tetramethyl tribromodiphenol, tetrachlorobisphenol a, and combinations thereof.

Examples of diepoxides useful in the present invention include the propylene oxide ether of 2, 2-bis (4-hydroxyphenyl) propane (generally referred to as bisphenol a) and the propylene oxide ether of 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane (generally referred to as tetrabromobisphenol a). Any mixture of two or more polyepoxides can be used in the present invention.

Other cycloaliphatic epoxides may be used in the present invention. Cycloaliphatic epoxides include a saturated carbocyclic ring having an epoxide oxygen bonded to two adjacent atoms in the carbocyclic ring and have the formula:

wherein R is as defined above and n is as defined above.

The cycloaliphatic epoxide may be a monoepoxide, a diepoxide, a polyepoxide, or a mixture thereof. Examples of such cycloaliphatic epoxides are described in U.S. Pat. No. 3,686,359. Cycloaliphatic epoxides that may be used in the present invention herein include, for example, (3, 4-epoxycyclohexyl-methyl) -3, 4-epoxy-cyclohexane carboxylate, bis (3, 4-epoxycyclohexyl) adipic acid, vinylcyclohexane mono-oxide, and mixtures thereof.

The flame retardant epoxy resin component used in the present invention may be present in an amount greater than 10phr in a typical coating composition. The flame retardant epoxy resin is suitably present in an amount of from about 30phr to about 90phr, more preferably from about 40phr to about 70phr, and even more preferably from about 55phr to about 65phr, based on the total weight of the coating composition (resin + curing agent + catalyst + solvent, as defined herein). If the content of the epoxy resin is less than 10phr, the finally obtained epoxy resin becomes extremely brittle and very difficult to handle. If the content of the epoxy resin ingredient exceeds 90phr, the epoxy resin finally obtained will not achieve sufficient flame resistance and the rigidity or modulus of the epoxy resin may be lowered.

As noted above, epoxy resin compositions that may be used in the present invention include, for example, halogenated and non-halogenated epoxy resins. For example, brominated and non-brominated bisphenol a type epoxides, which can be cured by phenol formaldehyde type resins.

In one embodiment of the present invention, the epoxy resin composition of the present invention may be formed by mixing a dimeric (bisphenol-A-co-chloroepoxypropane) epoxide and an epoxy resin having brominated aromatic rings, such as D.E.R.560 (available from Dow Chemical Company), M._wIs 900g/mole and EEW is 450; and unbrominated epoxy resins such as D.E.R.383 (available from Dow Chemical Company), M of which_wIs 360g/mole and EEW is 178. Both epoxides can be cured by a stoichiometric amount of a hardener, such as a phenol formaldehyde resin hardener, such as a phenolic hardener, M_wIs 472.5g/mole and the OH number averages 104. Phenolic hardeners are commercially available from the Dow Chemical Company.

Block copolymer

The amphiphilic block copolymers used in the present invention comprise an epoxy miscible block and an epoxy immiscible block.

Examples of epoxy-immiscible fractions of block copolymers include polyethylene propylene (PEP), polybutadiene, polyisoprene, polydimethylsiloxane, polybutylene oxide, polyhexene oxide, polyalkyl carbinol methacrylic acid such as polyethylhexyl methacrylic acid and mixtures thereof. Examples of epoxy miscible parts of block copolymers include polyethylene oxide, polymethacrylate, and mixtures thereof.

The composition of the invention may comprise at least one or more amphiphilic (amphpilicic) block copolymers. Two or more different amphiphilic (amphpilic) block copolymers may be mixed together to make up the block copolymer component of the present invention. In general, one of the blocks is miscible and the other block is immiscible. More than one block copolymer may be combined to enable additional control over the nanostructure, including shape and size.

Small amounts of homopolymer from each block may be present in the final amphiphilic (amphpilicic) block copolymer formed in the present invention.

The amphiphilic block copolymer used in the present invention preferably has increased fracture resistance, which is a block copolymer with low loading in the brominated epoxy resin composition. The increase in the crack resistance of the epoxy resin may be more than 5 times, more preferably more than 10 times, and still more preferably about 50 times. The block copolymer may be loaded in the epoxy resin composition from about 0.1 weight percent to about 30 weight percent, more preferably from about 0.5 weight percent to about 20 weight percent, and still more preferably from about 1 weight percent to about 10 weight percent. And most preferably from about 2 weight percent to about 50 weight percent. Generally, the loading used is about 5 weight percent or less.

It is believed that the fracture resistance properties are increased when the block copolymer self-assembles into a nano-sized morphology, such as a worm-like or spherical micelle morphology. While it is not clear how worm-like or globular micelle morphology occurs, it is believed that factors that contribute to self-assembling morphology may include, for example, (i) the choice of monomers in the block copolymer, (ii) the degree of asymmetry in the block copolymer, (iii) the molecular weight of the block copolymer, (iv) the composition of the epoxy resin, and (v) the choice of curing agent for the epoxy. Apparently, the nano-sized morphology plays an important role in creating toughness in the epoxy resin product.

Examples of suitable block copolymers for use in the present invention include amphiphilic block copolymers such as poly (ethylene oxide) -b-poly (ethylene-alt-propylene) (PEO-PEP); poly (methyl methacrylate-co-oxypropylene methacrylate) -b-poly (octylmethyl methacrylate); and poly (methyl methacrylate-ran-propylene oxide methacrylate) -poly (2-ethylhexyl methacrylate) (P (MMA-ran-GMA) -pehma table 1 lists the physical properties of various block copolymers, including the weight percentage of epoxy miscible blocks in the block copolymer, the molecular weight and the polydispersity of the block copolymer.

TABLE 1

Molecular characterization of Block copolymer modifiers

Diblock with one blockab

Of epoxy-miscible blocks

Mn(all)

Mw/Mn

	Weight percent of	(g/mole)
				PEO-PEP-15PEO-PEP-9	3248	8,00016,800	1.041.10

^aThe first block represents a miscible epoxy block

^bPEO: polyethylene oxide; PEP: poly (ethylene-alt-propylene)

Description and preparation of block copolymers useful in the present invention are disclosed, for example, in a) methacrylic block copolymers "Macromolecules, 34, 8593(2001) of r.b. grubbs, j.m. dean, f.s. bates" to modify thermoset epoxies by metal mediated radical polymerization; b) r.b. grubbs, j.m. dean, m.e. broz, f.s. bates "modifies a reactive block copolymer of thermosetting epoxy" Macromolecules, 33, 9522 (2000); and c) M.A. Hillmyer, F.S. Bates, "Synthesis and characterization of Polyalkane-Poly (ethylene oxide) Block copolymers" Macromolecules, 29, 6994 (1996).

The molecular weight of the PEO-PEP block copolymer is generally from about 2000g/mole to about 300,000g/mole, more preferably from about 5,000g/mole to about 30,000g/mole, and more preferably from about 6,000g/mole to about 15,000 g/mole. PEO weight proportion (W) of general PEO-PEP block copolymer_PEO) From about 0.1 to about 0.8; more preferably from about 0.2 to about 0.6; and more preferably from about 0.25 to about 0.5. The polydispersity (PDT or Mw/Mn) ratio of typical PEO-PEP block copolymers is from about 1.001 to about 2.5; more preferably from about 1.01 to about 1.5; more preferably from about 1.01 to about 1.2.

Curing agent

The curing agent component (also referred to as a hardener or a crosslinking agent) used in the present invention may be any compound having a reactive group which is easily reactive with an epoxy group of an epoxy resin. The chemistry of such curing agents has been described in the prior references to epoxy resins. The curing agent used in the present invention includes nitrogen-containing compounds such as amines and derivatives thereof; oxygen-containing compounds which are, for example, hydroxy acids and whose terminals are polyesters, anhydrides, phenol-formaldehyde resins, amino-formaldehyde resins, phenols, bisphenol A and cresol-formaldehyde resins, epoxy resins whose terminals are phenolics; sulfur-containing compounds such as polysulfide compounds, polythiols; and catalytic curing agents such as quaternary amines, lewis acids, lewis bases, and combinations thereof.

In practice, it is possible to use, in the examples of the invention, for example, polyamines, dicyanodiamines, diamine diphenyl and isomers thereof, aminobenzoates, various acid anhydrides, phenol-formaldehyde resins and cresol-formaldehyde resins. However, the present invention is not limited to the use of these compounds.

Other examples of cross-linking agents useful in the present invention are described in U.S. patent application No. 09/008983 entitled "latent catalyst for epoxy curing System" filed by Gan et al at 20/1 of 1998. The crosslinking agent is, for example, phenylethyleneCopolymers of olefins and maleic anhydride, their molecular weight (M)_w) Is between 1500 and 50,000 and has a content of anhydride of more than 15 percent. Commercially available examples of these materials include SMA 1000, SMA 2000, and SMA 3000 with styrene-maleic anhydride ratios of 1: 1, 2: 1, and 3: 1, respectively, and molecular weights between 6,000 and 15,000, available from Elf Atochem S.A.

Other optional ingredients

In addition to the polyepoxide, block copolymer, and curing agent, the curable epoxy resin composition of the present invention may also include a catalyst, which is an optional ingredient. The catalyst may be a single component or a combination of two or more different components. Catalysts that may be used in the present invention are catalysts that catalyze the reaction of polyepoxides with curing agents (i.e., curing agents that are hardeners or crosslinkers). The preferred catalyst is one that retains its latent ability in the presence of an inhibitor and under low temperature conditions (non-curing temperature). More preferably, the catalyst is capable of incubation at a temperature of 140 degrees celsius or less, and even more preferably at a temperature of 150 degrees celsius or less. Latency is known by performing a cure test in a range of about 150 degrees celsius to about 170 degrees celsius to measure an increase in gel of at least about 10 percent. Examples of catalysts are preferably compounds containing an amine, phosphine, heterocyclic nitrogen, amino salt, phosphonium, arsonium (arsonium) or sulfonium moiety. Examples of more preferred catalysts are heterocyclic nitrogen-containing and amine-containing compounds, and more preferred compounds are heterocyclic nitrogen-containing compounds.

Known catalysts that can be used in the present invention are described in U.S. Pat. No.4,925,901. Examples of known catalysts that can be used in the present invention include, for example, suitable onium (onium) or amine compounds such as ethyl triphenyl phosphonium acetate, ethyl triphenyl phosphonium acetate acetic acid complex, triethylammonia, methyldiethanolamine, benzyldimethylamine; and imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and benzimidazole.

If a catalyst is present, the catalyst must be used in an amount that, together with the crosslinking agent, completely cures the epoxy resin. For example, the catalyst is used in an amount of about 0.01 to 5 parts per 100 parts of the resin, preferably about 0.01 to 1.0 part per 100 parts of the resin, and more preferably about 0.02 to 0.5 part per 100 parts of the resin.

The concentrations of ingredients used in the present invention are expressed in parts by weight per 100 parts by weight of resin (phr), unless otherwise indicated. "resin" as defined by "phr" includes polyepoxide, block copolymer, and curing agent in the composition.

Other optional ingredients for use in the present invention also include reaction inhibitors for the epoxy resin composition. Reaction inhibitors include boric acid, boron-containing Lewis acids such as alkylborates, alkylboranes, trimethoxyboroxines, acids having a weak nucleophilic anion such as perchloric acid, tetrafluoroboric acid, and organic acids having a pKa of from 1 to 3 such as salicylic acid, oxalic acid, and maleic acid. Boric acid, as used herein, refers to boric acid or derivatives thereof, including phosphorus (metaboric) and boron-containing anhydrides; and combinations of Lewis acids with boron salts such as alkyl borates or trimethoxyboroxine. When an inhibitor is used in the present invention, boric acid is preferably used. The inhibitor and the catalyst may be added separately and in any order to the curable epoxy resin composition of the present invention, or may be added as a composite.

In the epoxy resin composition of the present invention, the amount of the inhibitor used relative to the catalyst can be adjusted to adjust the gel time of the epoxy resin composition. In the case of fixed catalyst amounts, an increase in the amount of inhibitor results in an increase in the gel time. Under the conditions of ideal catalyst usage, it is preferable to reduce the amount of inhibitor to reduce the gel time. The amount of inhibitor can be increased without changing the catalyst in order to increase the gel time.

The molar ratio of inhibitor (or mixture of different inhibitors) to catalyst must be sufficient to inhibit the reaction of the polyepoxide, which exhibits a significant increase in gel time compared to the composition without inhibitor. Simple experimentation may determine the specific degree of inhibitor or mixture that still increases gel time at elevated temperatures and also enables complete curing. Preferably, the molar ratio of inhibitor to catalyst, 5.0phr boric acid, is from about 0.1: 1.0 to about 10.0: 1.0, and preferably ranges from about 0.4: 1.0 to about 7.0: 1.0.

Other ingredients that may be added to the curable epoxy resin composition of the present invention include solvents or solvent mixtures. The solvent used in the epoxy resin composition is preferably miscible with the components of the other resin composition. In addition, the curable epoxy resin composition of the present invention may be a clear solution or a stable dispersion depending on the solvent used in the composition. The optional solvent is typically used in the manufacture of electronic laminates. Examples of solvents useful in the present invention include, for example, ketones, ethers, acetates, aromatic hydrocarbons, cycloethanones, dimethylformamide, glycol ethers, and combinations thereof.

Preferred solvents for the catalyst and inhibitor are polar solvents. Lower alcohols having 1 to 20 carbon atoms, such as methanol, provide good solubility and volatility to remove from the resin when the prepreg is formed.

The polar solvent is particularly capable of dissolving boric acid or a Lewis acid inhibitor, which is derived from boron. If the polar solvent contains a hydroxyl group, there will be potential competition for the formation of a hydroxy anhydride between the hydroxyl moiety of the solvent and the secondary hydroxyl group forming the opening in the oxirane ring. Polar solvents which do not contain a hydroxyl moiety such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide and tetrahydrofuran. Dihydroxy and trihydroxy hydrocarbons, which optionally contain ether moieties or glycol ethers having two or three hydroxyl groups, are also useful. Particularly useful is C_2-4Two-or threeHydroxyl compounds, which are, for example, 1, 2-propane diol, 1, 2-ethylene diol and glycerol. The polyhydroxy group of the solvent may facilitate the solvent to act as a chain extender, or as a co-crosslinker, as described for prior co-crosslinkers.

The total amount of solvent used in the curable epoxy resin composition is generally between about 20 to about 60 weight percent, more preferably between about 30 to about 50 weight percent, and most preferably between about 35 to about 45 weight percent.

The curable epoxy resin composition of the present invention may further comprise other additives such as fillers, dyes, pigments, denaturants, surfactants, fluid control agents, stabilizers, diluents, adhesion promoters, softeners, tougheners and flame retardants.

Preparation of the mixture

In the preparation of the mixtures or compositions of the present invention, these ingredients are passed through known mixing equipment and conditions to form a curable composition, preferably in liquid form. The curable epoxy resin composition of the present invention is prepared by mixing all the ingredients together in any order to make. In addition, the curable epoxy resin composition of the present invention can be prepared by first preparing a first composition comprising a brominated epoxy resin component and a block copolymer; and a second composition comprising a curative component. Other ingredients useful in the epoxy resin composition may also be present in the same composition, or some may be present in the first composition and some in the second composition. The first composition and the second composition are then mixed to form a curable epoxy resin composition. The curable epoxy resin composition mixture is then cured to form an epoxy resin thermoset. Preferably, the curable epoxy resin composition is in the form of a solution, wherein the components of the composition are dissolved in a solvent. Such solutions or paints may be used to produce coatings.

As noted above, neutral solvents may also be used in the mixture to facilitate homogeneous mixing of the block copolymer, brominated epoxy, and curing agent. More preferably, the solvent used in the present invention comprises, for example, acetone MEK. In addition, other solvents may be optionally used as long as it can dissolve all the components.

The time and temperature of preparation is not critical, but in general, the ingredients may be mixed at a temperature of 10 ℃ to 60 ℃, more preferably from about 20 ℃ to about 60 ℃, and even more preferably from about 25 ℃ to about 40 ℃, for a sufficient period of time until homogenization is achieved.

Curing process

The mixture of epoxy resin, curing agent, block copolymer, solvent, catalyst, and other modifiers in the composition can be cured according to typical industrial processes. These processes include the use of heat, radiation, or a combination of various energy sources to increase the ambient temperature to increase the temperature of the cure. Typically in the electronics industry, curing of curable compositions may be accomplished in one or more steps, such as A, B two-stage curing. Alternatively, the curable composition may be cured by a different temperature or energy source after the initial cure cycle. A typical curing process for electronic laminates includes an A-to-B stage cure, for example, at about 90 ℃ to about 210 ℃ for about 1 minute to about 15 minutes, followed by a B-to-C stage cure under conditions such as at about 100 ℃ to about 230 ℃ for about 1 minute to about 200 minutes, and at from about 50N/cm²Down to about 500N/cm²Under pressure of (3).

The curable epoxy resin composition of the present invention can be used to coat any article. The method of applying the composition of the present invention to an article may employ any known method including, for example, powder coating, spin coating, and contacting an object with a liquid containing the composition of the present invention. In this manner, the article can be coated with the epoxy resin composition, and the coating can be partially cured or fully cured. In one embodiment, the coating is partially cured, so that the article can be further processed so that the partially cured resin can be finally re-cured. The article to be coated may be any substrate, such as metal, cement or a reinforcing material. In one embodiment, the article is a fiber reinforced material, as a composite, prepreg or laminate.

The curable epoxy resin composition of the present invention can be used for materials for use in the electronic, architectural, aerospace and automotive industries. The curable epoxy resin composition of the present invention can be manufactured into a synthetic material by techniques known in the industry, for example, by dip-dyeing the reinforcing material with a dissolved or melted resin, or by resin transfer molding, filament winding, reinforced glass plastic (pultrusion) or RIM (reaction injection molding) and other molding, sealing or coating techniques. Of course, the curable epoxy resin composition of the present invention may be used in conventional epoxy resin applications such as cements, coatings, molding resins, embedding resins, condensation resins, slab casting compounds or large block molding compounds.

The epoxy resin compositions of the present invention are particularly useful in the manufacture of B-staged prepregs and laminates, such as printed circuit boards, which are known in the industry. More preferably, the epoxy resin composition of the present invention can be used for laminates in the electronics industry. Since the resin composition of the present invention can provide excellent properties for use in the electronics industry even when the resin composition is a simple bifunctional epoxy compound.

Generally, thin layers used in the electronics industry, particularly in printed circuit boards, are prepared by impregnating a support or reinforcing material with the epoxy resin composition of the present invention, followed by partial or complete curing of the resin. Reinforcing materials impregnated with partially cured resins are commonly referred to as "prepregs". To produce printed circuit boards from prepregs, one or more layers of the prepreg are laminated with one or more layers of a metallic material, such as copper.

Reinforcing materials that can be impregnated with the epoxy resin composition of the present invention include any material known to be useful in forming composite materials, prepregs and laminates. Examples of reinforcing materials include woven fabrics, cloths, screens, nets or fibres or laminates of parallel filaments in the form of cross-linked layers and without orientation. In general, such reinforcing materials can be made of various materials, such as glass fibers, paper, plastics, such as aramids, graphite, glass, quartz, carbon, boron fibers, and organic fibers, such as aramids, polytetrafluorethylene, syndiotactic polystyrene, in particular as thin layers of printed circuit boards. In a more preferred embodiment, the reinforcing material comprises glass or glass fibers, which are in the form of a cloth or mesh. The epoxy resin composition of the present invention is very suitable for exhaust dyeing such as woven glass fiber.

Cured product

The process for obtaining the cured resin product may be by heating the curable epoxy resin composition at a temperature of from about 100 c to about 230 c, more preferably from about 165 c to about 190 c, for a time of from about 1 minute to about 200 minutes, more preferably from 45 minutes to about 90 minutes. Alternatively, the cured product may be shaped by curing at a temperature of about 120 ℃ to about 250 ℃ for a time of about 30 minutes to about 12 hours in a vacuum. This way a homogeneous, void-free and well-cured epoxy resin product can be formed.

The fully cured compositions made from the curable compositions of the invention, which comprise a worm-like micelle morphology, have at least three non-trivial features, as compared to other compositions comprising block copolymers and self-aggregating into other forms, such as bubbles. The first feature is a glass transition temperature of up to 50 ℃ which is measured on the mixture by dynamic mechanical spectroscopy, but the glass transition of the block copolymer itself is not described. The second feature is that the modulus of these materials does not decrease. The third characteristic is the key stress intensity factorSeed K_IcThe increase in pressure is measured by a compression and extension instrument. Calculation of Strain energy Release Rate G Using a Linear elastic fragmentation mechanism_cThus combining the reduction in modulus with K_IcCan improve G_c。

The advantage of the present invention is that epoxy compositions containing brominated epoxides, which are known to be very brittle and have problems with drillability, can be used in the electronics industry, but because of the addition of the block copolymer and the correct composition of the present invention, and the structural self-assembly of worm-like morphology, the problem of drillability in these fracture-resistant materials is avoided.

At the limit of dilution, the block copolymer will self-assemble into chaotic worm-like micelles or spherical micelles. Each of these morphologies may be produced in cured brominated and non-brominated epoxy resins, representative of which are shown in FIGS. 1-2. Spherical micelles are shown in fig. 2A and 2B and comprise a hydrocarbon core surrounded by an epoxy crown. In contrast, cylindrical ("worm-like") micelles are shown in FIGS. 1A and 1B as long tubes, and the crown formed by the epoxy miscible block shields the interior of the epoxy immiscible cylinder. The two morphologies are formed by PEO-PEP and P (MMA-ran-GMA) -PEHMA diblock copolymers, respectively, and the equilibrium phase is determined by the asymmetry of the block copolymer, which is the relative length of the epoxy miscible blocks. This morphology is established in the initially unreacted block copolymer-resin mixture, which becomes permanently fixed during the stage of curing. The epoxy resin used in FIGS. 1-3 is a 3: 1 mixture of D.E.R.383/D.E.R.560 epoxide.

Modifying the epoxy resin with the block copolymer can reduce the modulus, although very significantly. However, the strain energy release rate G shown in FIG. 4_cThis is significantly increased by the use of worm-like modified epoxides (e.g., d.e.r.560), even with up to 50 weight percent of brominated epoxide. FIG. 4 shows the crack resistance properties of a homogeneous epoxy resin, which is, for exampleD.e.r.560. The resins include the amines of cured bisphenol A epoxide (BPA348, M)_w348g/mole, cured with 4, 4' -Methylenedianiline (MDA). The insect-like colloidal particles provide optimal G_cAs shown in fig. 4.

The present invention proposes a method to increase both the fracture resistance and the fire resistance of epoxy resins. The current findings are of great interest for the application of flame retardant epoxy resins in the microelectronics and aircraft industries. In general, increasing the fire resistance of an epoxy resin reduces its fracture resistance, making it difficult to process these materials to form the final product. For example, one significant problem in the microelectronics industry is the drillability of brominated epoxy compositions when applied to the manufacture of printed circuit boards. Such a problem is clearly influential for machine test samples, e.g., the 1: 1DER 383/DER560 compositions, which are all known. The materials of the invention can be handled easily, since the phenomenon of self-assembly occurs spontaneously upon mixing and the final viscosity is only slightly affected in the case of low block copolymer loading.

Generally, the increase in burst resistance sacrifices the service temperature and modulus. However, in the present invention, both the fracture resistance and the fire resistance can be achieved without decreasing the modulus, and the use temperature can be increased. Therefore, the method can avoid the situation that the strong toughness and other properties in the common epoxy bad object are mutually restricted. For example, the modulus of the partially toughest resins of the invention may be reduced, for example, from 5 to 10 percent, however, for example, up to 16 percent, T_gIt will increase.

The patterns of the material of the present invention are not described in the prior art epoxy toughened documents, some of which are too brittle to be effectively toughened.

The thermosetting epoxy composition of the present invention has good utility and provides a cured resin product having high toughness, high elongation, high modulus, low internal stress. Even with other high stability including high heat resistance and low water absorptionAnd (4) characteristic of sex. In the present invention, the cured resin product is, for example, a strain energy release rate (GIC) of at least about 100J/m²And a glass transition temperature (Tg) of at least about 100 ℃.

Some preferred embodiments of the invention will be described below. However, the present invention is not limited to the following examples.

Preparation of resin mixtures and samples as a general method of testing

In a neutral solvent, acetone to promote uniform mixing of the block copolymer, brominated epoxide, and a curing agent at room temperature (about 25 ℃), 23mL of acetone was added to a 40 gram batch of resin containing 1 to 2 grams of block copolymer. Once completely homogeneous (which takes several minutes to several days), the solvent is removed under vacuum and at 50 ℃ for one hour, after which the homogeneous resin mixture is dried, first at 75 ℃ for one hour and then at 100 ℃ for 30 minutes. This process can concentrate the epoxy sludge and alcohol groups prior to casting.

By heating the dried resin mixture to 150 ℃ and rapidly pouring the liquid into a preheated mold, a uniform and foam-free mass is obtained. After curing overnight (in air) at 150 ℃, the above casting was slowly cooled to room temperature, demolded, and post-cured for one hour at 220 ℃ and under vacuum. The above procedure produced uniform, non-voided and fully cured epoxy blocks having dimensions of about 10cm x 8cm x 4 mm. The extrusion, tensile and three point bending properties were then tested using a machine.

In the above process, 17.62 grams of d.e.r.383 was added to a 200mL round bottom flask. 5.8735 g of D.E.R.560 and 1.85g of MMG (0.4)_5.5EH_20.0The block copolymer was added to the flask. Then 21mL of acetone was added to the mixture and the mixture was shaken until d.e.r.383 started to melt. The mixture was then agitated on a stir plate. After stirring (about 1 day, 11.80g of SD-1731 phenol formaldehyde resin was added toIn the mixture. The ratio of the above-described epoxy composition D.E.R.383 to D.E.R.560 was 3: 1 (by weight), which was cured with a considerable amount of SD-1731 phenol formaldehyde resin, which was cured to the epoxy and epoxy groups in the block copolymer. The mixture was stirred for an additional 2 days until all ingredients were completely dissolved. Thereafter, the bottom flask was connected to a vacuum system using an 24/40 connector to remove the acetone solvent in vacuo.

The acetone is removed in a series of stages to minimize the exposure of the mixture to temperature and foaming. First at room temperature for one hour to slowly remove the acetone. An oil bath was then used, which was temperature controlled and maintained at 50 ℃, for one hour to heat the mixture to 50 ℃. Thereafter, the temperature was increased to 75 ℃ for one hour. The mixture was then heated to 100 ℃ for 30 minutes. The oil bath was then set to 150 ℃ and while the oil bath was heating, the sample was removed from the 140 ℃ vacuum system (after 15 minutes) and quickly poured into a pre-heated (150 ℃) mold.

The mold was placed in an oven at 150 ℃ and cured in air overnight. The sample was allowed to slowly cool back to room temperature and removed from the mold. After which a post-curing step was carried out under vacuum and at 220 ℃ for 1 hour. After sufficient curing, the solvent in the imperforate cast sample will be completely removable and its dimensions are 10cm x 8cm x 0.4 cm.

The samples were moved to a mechanical factory to make extruded, stretched and dynamic mechanical spectroscopic samples of the product.

General test procedure

(1) Dynamic Mechanical Spectroscopy (DMS) samples were machined into sample bars 28 mm long by 6 mm wide by 2 mm thick. The modified and unmodified samples were subjected to a three-point bending test using a Rheometrics Scientific Mark IV Dynamic Mechanical Testing Apparatus (DMTA) device. At least two, but typically five DMS samples of each material are tested. A steel bar is typically first used for testing to determine if the current meter needs calibration.

The DMS samples were first sinusoidally deformed to measure their dynamic elasticity (E ') and loss (E') flexural modulus at a fixed frequency of 10rad/s and 0.01 percent strain, and the temperature was raised from 25 ℃ to 185 ℃ at a 2 ℃/minute ramp rate. T is_gIs defined as the temperature at which the modulus of elasticity drops significantly, which corresponds to the peak of the tan delta curve where delta ═ E "/E'. Room temperature flexural modulus, E' and glass transition temperature T of the respective samples_gWill be recorded. The modulus is reduced to 50 percent (about 1.5GPa) because of the use of block copolymers. T is_gThe increase in (c) ranges from 30 c to 50 c depending on the block copolymer.

(2) Fracture testing of Compact Tensile (CT) of non-voided specimens was performed with epoxy panels. The compact tensile test was performed on samples under a 4mm thick plane strain test. Critical plane strain fracture toughness K of block copolymers of modified epoxy materials_IcWas tested using the compact tensile geometry method ASTM D5045. The indented end was first tapped with a new blade to pre-fracture the sample. The sample was then initialized by tapping the pre-fractured sample and the liquid nitrogen chill blade in the machine indentation. Typically, these samples are difficult to pre-fracture due to their high fracture toughness. Tests were performed on a MTS test frame and in a tensile mode at a cross speed of 10 mm/minute. The samples were split at a rate of 10mm/minute and their peak loads were recorded. Six to ten samples were tested for each material. The strain energy release rate can be calculated from the peak load, the sample size and the key stress intensity factor, and then the linear elastic fracture mechanism is used for calculating the strain energy release rate.

The fracture toughness of each sample is calculated by the following mathematical formula:

P_maxis the maximum load at failure, B is the thickness of the sample, W is the overall length, a is the crack length, and f (a/W) is the geometry of the sample as defined by ASTM D5045 method.

Strain energy release rate G_cIs from K_IcAnd is calculated using the following mathematical formula:

(Flat drawing)

Where v is the Poisson's ratio, which is 0.34, and E is the Young's modulus. Young's modulus was measured by performing a compact tensile test on the same MTS frame at the same crossover speed.

The typical strain energy release rate is 50J/m²Increased to 450J/m²To 1650J/m²。

(3) The morphology of the block copolymer of the modified epoxy composition is known from Transmission Electron Microscopy (TEM). The TEM described above is a representative piece of material that is cured to determine its morphology. Representative fragments of the epoxide plates were sectioned at room temperature using a Reicherultra-micro S-ordered device equipped with a diamond knife. TEM samples were prepared by cutting the samples to a thickness of about 70 nm using a Reichert Ultra-micro S equivalent apparatus with a diamond knife at a speed of 1.0 mm/S. The thin (70 nm) fraction was floated on water and recovered at copper grids at 0.5 weight percent steam and RuO₄Dyeing in an aqueous solution of (1). The sample was then placed on a 400 mesh copper grid at 0.5 weight percent steam and RuO₄For 20 minutes.

RuO for PEP-PEO mixtures₄The staining will be in the following order: PEO > epoxide > PEP. RuO for methacrylic acid-based block copolymers₄The staining will be in the following order: MMG (x) > epoxide > EH. While PMMA will not absorb RuO₄The dye therefore penetrates significantly through the epoxy in the vicinity of the PMMA, which is more visible than the dyeing of the monolithic epoxy. In addition, the unreacted oxypropylene group in the epoxy miscible block will react with RuO₄Reacted and combined to mmg (x), which was dyed black. Various types of block copolymers and RuO₄The staining time of (2) was 20 minutes.

The stained sample was photographed with a JEOL 1210 TEM electron microscope at a voltage of 120 kV. These samples had a worm-like colloidal particle morphology with a diameter of 10 nanometers and an aspect ratio of approximately 20: 1.

Example 1

2g of PEO-PEP block copolymer (f)_PEO＝0.25，M_n＝8,000g/mole，M_w/M_n1.04) was added to a round bottom flask and 24.00 grams of d.e.r.383 was already in the flask. Thereafter, 23mL of acetone was added to the flask and stirred until the block copolymer was completely melted (approximately two weeks). Then, 14.00g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until the phenol formaldehyde resin was melted. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. Then theThe mixture of epoxide and block copolymer was poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.62±0.07MPa m^{0 5}，E＝2.4±0.1GPa，T_g＝154℃，

G_c＝967±23J/m²。

Example 2

2g of PEO-PEP block copolymer (f)_PEO＝0.25，M_n＝8,000g/mole，M_w/M_n1.04) was added to a round bottom flask and 23mL of acetone was in the flask. Thereafter, 24.00 grams of d.e.r.383 was added to the flask and stirred until the contents of the flask were completely melted (approximately 1 or 2 days). Then 14.00g of phenol formaldehyde resin was added to the flask and stirred until dissolved. The flask was then connected to a vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath is arranged inThe flask was surrounded and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.64±0.06MPa m^{0 5}，E＝2.96±0.35Gpa，T_g＝152℃，G_c＝803±47J/m²。

Example 3

2g of PEO-PEP block copolymer (f)_PEO＝0.25，M_n＝8,000g/mole，M_w/M_n1.04) was added to a round bottom flask and 19.05g of d.e.r.383 and 6.35g of d.e.r.560 were in the flask. Thereafter, 23mL of acetone was added to the flask and stirred until the block copolymer was completely melted (approximately two weeks). Then the12.6g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until dissolved. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.72±0.15MPa m^{0 5}，E＝2.37±0.16Gpa，T_g＝155℃，G_c＝1101±47J/m²。

Example 4

2g of PEO-PEP block copolymer (f)_PEO＝0.25，M_n＝8,000g/mole，M_w/M_n1.04) was added to a round bottom flask and 23mL of acetone was in the flask. Then 19.05g of d.e.r.383 and 6.35g of d.e.r.560 were added to the flask and stirred until the block copolymer was completely melted (about one to two days). Then, 12.6g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until dissolved. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.75±0.05MPa m^{0 5}，E＝2.84±0.2Gpa，T_g＝153℃，G_c＝955±31J/m²。

Example 5

2g of PEO-PEP block copolymer (f)_PEO＝0.25，M_n＝8,000g/mole，M_w/M_n1.04) was added to a round bottom flask and 13.5g of d.e.r.383 and 13.5g of d.e.r.560 were in the flask. Thereafter, 23mL of acetone was added to the flask and stirred until the block copolymer was completely melted (approximately two weeks). Then, 11.0g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until dissolved. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and with a strain sum of 0.01 percent for a sample 28 mm long, 6 mm wide and 2 mm thickThe test was performed in 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.74±0.07MPa m^{0 5}，E＝2.85±0.13GPa，T_g＝156℃，G_c＝943±27J/m²。

Example 6

2g of PEO-PEP block copolymer (f)_PEO＝0.25，M_n＝8,000g/mole，M_w/M_n1.04) was added to a round bottom flask and 23mL of acetone was in the flask. 13.5g of D.E.R.383 and 13.5g of D.E.R.560 were then added to the flask and stirred until the block copolymer was completely melted (approximately one to two days). Then, 11.0g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until dissolved. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. StretchingThe test of (2) was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.67±0.02MPa m^{0 5}，E＝2.85±0.11Gpa，T_g＝155℃，G_c＝870±15J/m²。

Example 7

1.85g of poly (methacrylic acid-co-oxypropylene methacrylate) -poly (2-ethylhexyl methacrylate) block copolymer (MMG (0.4)_{5 5}EH_{20 0}: the MMG block weight fraction is 0.22, the oxypropylene methacrylate fraction in the MMG block is 0.4, M_n＝25,500g/mole，M_w/M_n1.21) was added to a round bottom flask and 17.62g of d.e.r.383 and 5.87g of d.e.r.560 were in the flask. Thereafter, 21mL of acetone was added to the flask and stirred until the block copolymer was completely melted (one day). Then, 11.80g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until dissolved. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting samples were takenAnd cooling to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.16±0.12MPa m^{0 5}，E＝2.75±0.05Gpa，T_g＝127℃，G_c＝431±30J/m²。

Example 8

2g of PEO-PEP block copolymer (f)_PEO＝0.39，M_n＝16,800g/mole，M_w/M_n1.10) was added to a round bottom flask and 23mL of acetone was in the flask. Thereafter, 24.00g of D.E.R.383 was added to the flask and stirred until the block copolymer was completely melted (one to two days). Then, 14.0g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until dissolved. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. Then mixing the mixture of epoxide and block copolymer and pouring into oneA 4mm thick rectangular mold (heated to 150 c in advance) which was p.t.f.e. mold release spray coated with Sprayon drying chips. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.03±0.17MPa m^{0 5}，E＝2.56±0.09Gpa，T_g＝103℃，G_c＝411±43J/m²。

Example 9

2g of PEO-PEP block copolymer (f)_PEO＝0.39，M_n＝16,800g/mole，M_w/M_n1.10) was added to a round bottom flask and 23mL of acetone was in the flask. Then 19.05g of d.e.r.383 and 6.35g of d.e.r.560 were added to the flask and stirred until the block copolymer was completely melted (one to two days). Then, 12.6g of a phenol formaldehyde resin was added to the flask, and the contents of the flask were stirred until dissolved. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. Removing the solvent at 50 deg.C for 1 hrAnd the temperature was raised to 75 deg.c (1 hour) and then further raised to 100 deg.c (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured. The test results for this sample were: k_Ic＝1.17±0.20MPa m^{0 5}，E＝2.37±0.16Gpa，T_g＝111℃，G_c＝582±56J/m²。

Example 10Block copolymers using phosphorous-containing epoxy resins

2g of PEO-PEP block copolymer (f)_PEO＝0.25，M_n＝8,000g/mole，M_w/M_n1.04) was added to a round bottom flask and 24.00 grams of phosphorous containing epoxy resin, such as XZ92530 resin, was present in the flask. Thereafter, 23mL of acetone was added to the flask and stirred until the block copolymer was completely melted (approximately two weeks). Then 14.00g of phenol formaldehyde was addedThe phenol formaldehyde resin was added to the flask and the contents of the flask were stirred until the phenol formaldehyde resin melted. The flask was connected to the vacuum system using an 24/40 connector. The acetone solvent will slowly be removed at room temperature until the final foam subsides (30 minutes). An oil bath was placed around the flask and the temperature was set at 50 ℃. The solvent was removed at 50 ℃ for 1 hour and the temperature was raised to 75 ℃ (1 hour) and then to 100 ℃ (30 minutes). Thereafter, the oil bath temperature was set at 150 ℃, and after waiting for 10 minutes, the flask was separated from the vacuum system. The mixture of epoxide and block copolymer was then poured into a 4mm thick rectangular mold (preheated to 150 ℃ C.) which had been coated with a Sprayon dryer sheet P.T.F.E. mold release spray. The mold was then allowed to cure overnight in air at 150 ℃. After the oven was turned off, the resulting sample was cooled to room temperature. The sample was then removed from the mold and the mixture was post-cured under vacuum at 220 ℃ for one hour. After the oven was turned off, the cured sample was slowly cooled to room temperature. The cured samples obtained were finally prepared as extrusion, tensile and three-point bending test samples.

The compression test was performed using a test speed of 10mm/minute and pre-fragmenting a 4mm thick sample with a knife (new) frozen in liquid nitrogen. The tensile test was performed using a test speed of 10 mm/minute. The three-point bend test was performed on a Rheometrics scientific Mark IV Dynamic Mechanical Testing Apparatus and tested on a 28 mm long, 6 mm wide and 2 mm thick sample at 0.01 percent strain and 10rad/s conditions. The temperature was increased from room temperature to 185 ℃ at a ramp rate of 2 ℃/minute, and the elastic flexibility and loss modulus were measured.

Claims (26)

1. A curable flame retardant epoxy resin composition characterized by increased toughness comprising:

(a) at least one flame retardant epoxy resin;

(b) an amphiphilic block copolymer; and

(c) and (3) a curing agent.

2. The curable flame retardant epoxy resin composition according to claim 1, wherein the flame retardant epoxy resin is a brominated epoxy resin.

3. The curable flame retardant epoxy resin composition according to claim 1, wherein the flame retardant epoxy resin is a phosphorous epoxy resin.

4. The curable flame retardant epoxy resin composition according to claim 1 wherein the amount of the block copolymer is based on the mixture in the uncured state, which is sufficient to allow the block copolymer to self-assemble into a worm-like micell morphology; this pattern is retained by curing of the composition; and the fracture resistance of the cured product obtained as a result is improved.

5. The curable flame retardant epoxy resin composition according to claim 1, wherein the amount of the block copolymer is based on the mixture in an uncured state, which is sufficient to allow the block copolymer to self-assemble into a spherical micelle form; the form is retained by curing of the composition; and the fracture resistance of the cured product obtained as a result is improved.

6. The curable flame retardant epoxy resin composition according to claim 1, wherein the block copolymer is a diblock copolymer.

7. The curable flame retardant epoxy resin composition according to claim 1, wherein the block copolymer is poly (ethylene oxide) -poly (ethylene-alt-propenyl) (PEO-PEP).

8. The curable flame retardant epoxy resin composition according to claim 1 wherein the block copolymer is poly (ran-methacrylate propylene oxide) -poly (2-ethylhexyl methacrylate) (P (MMA-ran-GMA) -PEHMA).

9. The curable flame retardant epoxy resin composition according to claim 1, wherein the block copolymer is contained in an amount of 0.1 to 30% by weight.

10. The curable flame retardant epoxy resin composition according to claim 1 wherein said epoxy resin is a propylene oxide ether of bisphenol A.

11. The curable flame retardant epoxy resin composition according to claim 1, wherein the curing agent is a phenol formaldehyde resin, dicyanodiamine or anhydride.

12. The curable flame retardant epoxy resin composition according to claim 1, further comprising a solvent.

13. The curable flame retardant epoxy resin composition according to claim 1 further comprising a catalyst in an amount to accelerate the reaction of the epoxy resin with the curing agent.

14. The curable flame retardant epoxy resin composition according to claim 13, wherein the catalyst is imidazole.

15. The curable flame retardant epoxy resin composition according to claim 2 wherein said brominated epoxy resin is tetrabromobisphenol A propylene oxide ether.

16. A cured resin product comprising a fire resistant epoxy resin, the fire resistant epoxy resin comprising a block copolymer and which self-assembles into a worm-like micell configuration.

17. A reinforced fiber composite comprising the curable flame retardant epoxy resin composition of claim 1.

18. The reinforced fiber composite of claim 17, wherein the reinforced fiber composite is a laminate or a prepreg of an electronic circuit.

19. An electronic circuit member comprising an insulating coating of the epoxy resin composition according to claim 1.

20. A prepreg characterized by comprising:

(a) weaving fibers; and

(b) the curable flame retardant epoxy resin composition of claim 1.

21. A laminate, comprising:

(a) a substrate comprising the curable flame retardant epoxy resin composition of claim 1; and

(b) the metal layer is arranged on at least one surface of the substrate.

22. The laminate of claim 21, wherein the substrate includes reinforced woven glass fibers and the epoxy resin composition is impregnated on the woven glass fibers.

23. A printed wiring board made of the thin layer according to claim 22.

24. A process for preparing a curable resin composition, characterized by comprising mixing:

(a) at least one flame retardant epoxy resin;

(b) an amphiphilic block copolymer; and

(c) and (3) a curing agent.

25. A process for preparing a curable resin composition, characterized in that it comprises heating a mixture of:

(a) at least one flame retardant epoxy resin;

(b) an amphiphilic block copolymer; and

(c) and (3) a curing agent.

26. A process for producing a coated article comprising applying the curable epoxy resin of claim 1 to an article and heating the coated article to cure the epoxy resin.