TW202204373A - A curable thermoset for high speed low loss electrical laminates - Google Patents

Abstract

Provided herein are curable resin compositions comprising (a) an epoxy resin component; (b) a phosphorated anhydride component; and (c) an active ester component. For example, the curable resin composition may comprise a phosphorated anhydride of Formula III or Formula IV: wherein each R4 and R5 is independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl; l is 0, 1, 2, or 3; m is 0, 1, 2, 3 or 4; and n is 0, 1, 2, 3 or 4.

Description

Curable Thermoset Materials for High Speed Low Dissipation Electrical Laminates

The present invention provides halogen-free, flame retardant curable resin compositions, particularly a printed circuit board comprising such cured compositions.

Epoxies are used in both industrial and consumer electronics due to their chemical resistance, mechanical strength, and electrical properties, among others. For example, epoxy resins can be used in electronic products as laminates, adhesive materials, and/or insulating materials, such as interlayer insulating films. To be useful for these applications, epoxy resins need to provide certain necessary physical, thermal, electrical insulating and moisture resistance properties. For example, it is advantageous for epoxy resins used in electrical applications to have a high glass transition temperature (Tg).

However, epoxy resins can be flammable. As such, various approaches have been undertaken to impart flame retardancy to epoxy resins. Two main approaches have been taken to provide flame retardancy. The first method uses halogen compounds. Halogen-containing compounds have been commonly used in the electronics industry to impart flame retardancy to electrical and electronic components. For example, tetrabromobisphenol-A (TBBA) is a typical halogen-containing compound that has been widely used as a flame retardant for epoxy resins. Although halogen-containing compounds may be effective for this purpose, they are highly undesirable from an environmental point of view. Therefore, there is a need to develop halogen-free compounds that can be used as effective flame retardants in epoxy resin compositions.

Recent advances in the art have shown that phosphoric anhydride-containing compounds are particularly useful as flame retardants in epoxy resin compositions. For example, WO 2019/090563 discloses a class of phosphoric anhydride-containing compounds that are effective as epoxy hardeners and provide flame retardant properties. However, there is still a need to develop improved halogen-free flame retardants that provide better electrical properties than currently available products, especially for use in high-speed, low-dissipation electrical laminates for printed circuit boards (PCBs). laminate) production. In particular, there is a need to develop improved flame retardants that provide lower dielectric dissipation than existing solutions without compromising other performance aspects of the laminate.

For example, provided herein is a curable resin composition comprising (a) an epoxy resin component; (b) a phosphoric anhydride-containing component and (c) an active ester component.

式III                      、                       式VI， 其中每個R₄ 和R₅ 獨立地選自烷基、烷氧基、烷氧基、芳基、芳氧基、芳基烷基、烯基和炔基；l為0、1、2或3；m為0、1、2、3或4和n為0、1、2、3或4。In one aspect, the curable resin composition can include a phosphoric acid-containing anhydride of Formula III or Formula IV:

Formula III, Formula VI, wherein each R ₄ and R ₅ are independently selected from alkyl, alkoxy, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl; l is 0 , 1, 2, or 3; m is 0, 1, 2, 3, or 4 and n is 0, 1, 2, 3, or 4.

Also provided are cured compositions prepared by curing the resin compositions described herein. Also provided herein are printed circuit boards comprising such cured compositions.

Other objects and features will be in part apparent and in part pointed out hereinafter.

Provided herein are halogen-free, flame retardant curable resin compositions that provide both good electrical properties and good thermal properties sufficient to allow their use in high performance PCB systems.

In particular, provided herein are curable resin compositions comprising (a) an epoxy resin component; (b) a phosphoric anhydride-containing component and (c) an active ester component. Each of these components is discussed in further detail below.

(a) epoxy resin

The curable resin composition may include an epoxy resin component, wherein the epoxy resin component includes at least one epoxy resin.

Various epoxy resins can be used to make the curable and cured compositions disclosed herein. Types of epoxy resins that can be used include aromatic epoxy resins, cycloaliphatic epoxy resins, aliphatic epoxy resins, and combinations thereof.

The curable resin composition may comprise a compound selected from the group consisting of divinylarene dioxide, diglycidyl ether of bisphenol A, diglycidyl ether of bromobisphenol A, oligomeric or polydiglycidyl ether of bisphenol A , oligomeric or polydiglycidyl ethers of tetrabromobisphenol A, diglycidyl ethers of bisphenol F or derivatives thereof, epoxy novolac resins, epoxy cresol novolac resins or mixtures thereof One or more epoxy resins from the group. In one embodiment, the divinylarene dioxide is selected from the group consisting of substituted divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenyl ether dioxide group of substances and their mixtures.

The curable resin composition may include one or more epoxy resins selected from the group consisting of glycidyl ether compounds of polyphenols selected from hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, phenol novolac, cresol novolac, trisphenol (tris-(4-hydroxyphenyl)methane), 1,1,2, 2-tetrakis(4-hydroxyphenyl)ethane, tetrabromobisphenol A, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 1, The group consisting of 6-dihydroxynaphthalene and combinations thereof. Non-limiting examples of epoxy resins include dicyclopentadiene phenol novolac epoxy resins and biphenylphenol novolac epoxy resins.

Examples of alicyclic epoxy resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring or cyclohexene oxide including cyclohexene oxide obtained by epoxidizing a compound including a cyclohexene ring or a cyclopentene ring with an oxidizing agent. Compounds that oxidize cyclopentene. Specific examples include, but are not limited to, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-1- Methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4- Epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy -5-Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, methylene Alkyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene-bis(3,4 - epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, and combinations thereof.

Examples of aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or oxyalkylene adducts thereof, polyglycidyl esters of aliphatic long-chain polyacids, glycidyl acrylate or glycidyl methacrylate by vinyl-polymerization Homopolymers synthesized from glycerides and copolymers synthesized by vinyl-polymerization of glycidyl acrylate or methacrylate with other vinyl monomers. Some specific examples include, but are not limited to, glycidyl ethers of polyols, such as 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; triglycidyl ether of glycerol; trimethylol Triglycidyl ether of propane; tetraglycidyl ether of sorbitol; hexaglycidyl ether of dipentaerythritol; diglycidyl ether of polyethylene glycol; diglycidyl ether of polypropylene glycol; polyglycidyl ether of polyether polyol Glyceryl ethers obtained by adding one type or two or more types of alkylene oxides to aliphatic polyols such as propylene glycol, trimethylolpropane and glycerol; diglycidyl esters of aliphatic long-chain dibasic acids and its combinations.

Amount of epoxy resin

The curable resin composition can include, for example, from about 10% by weight to about 80% by weight, from about 20% by weight to about 70% by weight, from about 30% by weight to about 30% by weight of the composition. The epoxy resin component in an amount of about 60% by weight or about 40% by weight to about 60% by weight.

For example, the curable resin composition can include epoxy in an amount of at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, or at least about 45% by weight of the composition resin component.

(b) containing phosphoric anhydride

The curable resin composition may further include a phosphoric anhydride-containing component, wherein the phosphoric anhydride-containing component includes at least one phosphoric anhydride-containing component.

The phosphoric anhydride-containing compounds provided herein are useful as reactive flame retardants and provide surprisingly good dielectric properties and thermal resistance when incorporated into PCB compositions. The phosphoric anhydride-containing anhydrides provided herein also impart the advantage of being halogen-free, while serving as flame retardants for cured resins (eg, cured epoxy resins) formed in part with phosphoric anhydride-containing anhydrides. Such cured resins formed with phosphoric anhydrides may also have suitable thermal and electrical properties useful for electronic applications including electrical laminates, interconnect substrates, build-up films, solder masks, castings and adhesives performance.

In particular, the phosphoric acid anhydride-containing anhydrides provided herein can impart improvements in thermomechanical properties, such as increasing the glass transition temperature of cured epoxy resins. Such improvements can include, for example, increasing the glass transition temperature (T _g ) of the cured epoxy resin formed with the phosphoric anhydride-containing epoxy resin so that the cured epoxy resin composition can be used to experience temperatures of at least about 150°C, such as A mid-to-high range of temperatures of at least about 170°C applies. In addition, the curable compositions formed with the phosphoric anhydride-containing phosphoric acid anhydrides provided herein can also provide other desirable physical properties in addition to flame retardancy, such as heat resistance. One method for measuring thermal resistance is to measure the thermal decomposition temperature (T _d ) by determining the temperature at which 5 weight percent (wt %) of the cured epoxy resin degrades when the sample is heated at a fixed rate. For example, the phosphoric acid anhydride-containing anhydrides of the present disclosure can be used to provide cured epoxy resin compositions having a _Td of at least about 350°C.

式I， 其中 R₁ 和R₂ 每個獨立地選自由烷基、烷氧基、環烷基、-O-烷基-環烷基、-O-環烷基、芳基和芳氧基組成的組或R₁ 和R₂ 一起形成多環部分，其中每個芳基或多環部分任選地被獨立地選自由烷基、烷氧基、芳基、芳氧基、芳基烷基、烯基和炔基組成的組的一個或多個基團獨立地取代； R₃ 獨立地選自由烷基、環烷基和芳基組成的組，其中每個芳基任選地被獨立地選自由烷基、烷氧基、芳基、芳氧基、烯基和炔基組成的組中的一個或多個基團獨立地取代；以及 l為0、1、2、3、4、5或6。For example, the curable resin composition can include a phosphoric acid anhydride of formula I:

Formula I, wherein R ₁ and R ₂ are each independently selected from the group consisting of alkyl, alkoxy, cycloalkyl, -O-alkyl-cycloalkyl, -O-cycloalkyl, aryl, and aryloxy _The group or R and R together form _a polycyclic moiety, wherein each aryl or polycyclic moiety is optionally independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, One or more groups of the group consisting of alkenyl and alkynyl are independently substituted; _R is independently selected from the group consisting of alkyl, cycloalkyl, and aryl, wherein each aryl is optionally independently selected independently substituted with one or more groups from the group consisting of alkyl, alkoxy, aryl, aryloxy, alkenyl, and alkynyl; and 1 is 0, 1, 2, 3, 4, 5, or 6.

式II， 其中 R₁ 和R₂ 每個獨立地選自由烷基、烷氧基、環烷基、-O-烷基-環烷基、-O-環烷基、芳基和芳氧基組成的組或R₁ 和R₂ 一起形成多環部分，其中每個芳基或多環部分任選地被獨立地選自由烷基、烷氧基、芳基、芳氧基、芳基烷基、烯基和炔基組成的組的一個或多個基團獨立地取代； R₃ 獨立地選自由烷基、環烷基和芳基組成的組，其中每個芳基任選地被獨立地選自由烷基、烷氧基、芳基、芳氧基、烯基和炔基組成的組中的一個或多個基團獨立地取代；以及 l為0、1、2、3、4、5或6。The curable resin composition may include a phosphoric acid anhydride of formula II:

Formula _II , wherein R1 and R2 are each independently selected from the group consisting _of alkyl, alkoxy, cycloalkyl, -O-alkyl-cycloalkyl, -O-cycloalkyl, aryl, and aryloxy _The group or R and R together form _a polycyclic moiety, wherein each aryl or polycyclic moiety is optionally independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, One or more groups of the group consisting of alkenyl and alkynyl are independently substituted; _R is independently selected from the group consisting of alkyl, cycloalkyl, and aryl, wherein each aryl is optionally independently selected independently substituted with one or more groups from the group consisting of alkyl, alkoxy, aryl, aryloxy, alkenyl, and alkynyl; and 1 is 0, 1, 2, 3, 4, 5, or 6.

In one embodiment, each R ₃ is independently C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, or phenyl; wherein each phenyl is optionally independently selected from C ₁ -C Substituted with one or more groups of ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, phenoxy, C ₂ -C ₄ alkenyl and C ₂ -C ₄ alkynyl. In another embodiment, each _R3 is independently _{C1 - C4} alkyl, C3 _{- C6} cycloalkyl, or phenyl; wherein each phenyl is optionally independently selected from C1- One or more groups of _{C4 -} alkyl, C1 _{- C4alkoxy} , phenyl, phenoxy, C2 _{- C4alkenyl} and C2 _- C4alkynyl are substituted. In yet another embodiment, each _R3 is independently methyl, ethyl, cyclopentyl, cyclohexyl, or phenyl. In yet another embodiment, each R ₃ is independently C ₁ -C ₄ alkyl. In further embodiments, each _R3 is independently methyl or ethyl. In still further embodiments, _R3 is methyl.

In an alternative embodiment, when l is 1, R ₃ is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, allyl or C ₂ -C ₄ alkynyl. In another embodiment, _R3 is methyl or allyl. In yet another alternative embodiment, _R3 is methyl.

In another embodiment, R ₁ and R ₂ are independently C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, -O -C ₁ -C ₆ alkane yl-cycloalkyl, -O _- cycloalkyl, aryl, aryloxy, or R and R together form _a polycyclic moiety, wherein each aryl or polycyclic moiety is optionally independently selected from alkyl , alkoxy, aryl, aryloxy, arylalkyl, alkenyl and alkynyl groups are substituted with one or more groups. In a further embodiment, one of R ₁ and R ₂ is methyl, methoxy, cyclopentyl, cyclohexyl, -O-C ₁ -C alkoxy _- cycloalkyl, -O-cyclopentyl , -O _- cyclohexyl, phenyl, phenoxy, or R and R together form _a polycyclic moiety, wherein the phenyl, phenoxy or polycyclic moiety is optionally independently selected from alkyl, alkoxy , aryl, aryloxy, arylalkyl, alkenyl, and alkynyl groups are substituted with one or more groups. In further embodiments, R ₁ and R ₂ are optionally independently selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, naphthyl, phenoxy, benzyl, benzene One or more groups of ethyl, C2 _{- C6alkenyl} and C2 _{- C6alkynyl} are substituted. In still further embodiments, R ₁ and R ₂ are the same. In an alternative embodiment, R ₁ and R ₂ are different.

_In various embodiments, R1 and R2 form _an optionally substituted polycyclic moiety, wherein the polycyclic moiety is optionally independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkane One or more groups of alkenyl, alkenyl and alkynyl are substituted. In one embodiment, the polycyclic moiety consists of two optionally substituted fused rings. In alternative embodiments, the polycyclic moiety consists of at least three optionally substituted fused rings. The polycyclic moiety may include one or more heteroatoms selected from the group consisting of P, N, O, and S. For clarity, P, N, O and/or S replace one or more carbons in the polycyclic moiety. In preferred embodiments, the polycyclic moiety includes at least one of P, N, O, and S. Preferably, the polycyclic moiety includes P. Still more preferably, at least one ring heteroatom within the polycyclic moiety is bonded directly to P. In further embodiments, the heteroatom is O or S. In a preferred embodiment, the heteroatom is O.

式I-i 式II-i的化合物，

式II-i 式I-ii的化合物，

式I-ii 式II-ii的化合物，

式II-ii 和具有以下結構的兩種化合物

、

。Non-limiting examples of phosphoric anhydride-containing compounds that may be present in the curable resin composition include compounds of formula li,

a compound of formula II-i,

compound of formula II-i formula I-ii,

a compound of formula I-ii, a compound of formula II-ii,

Formula II-ii and two compounds having the following structures

,

.

Preferred phosphoric anhydride-containing

In a preferred embodiment, the curable resin composition includes a phosphoric acid-containing anhydride of Formula III or Formula IV as provided herein.

式III， 其中 每個R₄ 和R₅ 獨立地選自烷基、烷氧基、芳基、芳氧基、芳基烷基、烯基和炔基； l為0、1、2或3； m為0、1、2、3或4； 以及n為0、1、2、3或4。For example, the curable resin composition may include a compound of formula III:

Formula III, wherein each R and R is independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl; l is ₀ , ₁ , 2, or 3; m is 0, 1, 2, 3, or 4; and n is 0, 1, 2, 3, or 4.

式IV， 其中 每個R₄ 和R₅ 獨立地選自烷基、烷氧基、芳基、芳氧基、芳基烷基、烯基和炔基； l為0、1、2或3； m為0、1、2、3或4； 以及n為0、1、2、3或4。The curable resin composition may include a compound of formula IV:

Formula _IV , wherein each R and R is independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl; l is 0, ₁ , 2, or 3; m is 0, 1, 2, 3, or 4; and n is 0, 1, 2, 3, or 4.

In some embodiments, at least one of m and n is not zero. Optionally, when at least one of m and n is not ₀ , each _R4 and R5 is independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl, and alkynyl formed group.

In one embodiment, each R ₄ and R ₅ is independently selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, naphthyl, phenoxy, benzyl, phenethyl , C ₂ -C ₆ alkenyl and C ₂ -C ₆ alkynyl group. R ₄ and R ₅ may be the same. Alternatively, they may be different.

In one embodiment, m and n are zero. In further embodiments, 1 is also zero.

In one embodiment, l is zero. In another embodiment, l is one. In yet another embodiment, 1 is 2. In yet another embodiment, 1 is 3. In yet another embodiment, 1 is 1 or 2. In each of these embodiments (except when l is 0), each _R3 is independently _C1 - _C6 alkyl, C3 _{- C6} cycloalkyl, or phenyl; wherein each phenyl is either optionally independently selected from the group consisting of C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, phenoxy, C ₂ -C ₄ alkenyl, and C ₂ -C ₄ alkynyl One or more groups are substituted. In another embodiment, each R ₃ is independently C ₁ -C ₄ alkyl. In further embodiments, each _R3 is independently methyl or ethyl. In still further embodiments, _R3 is methyl.

In an alternative embodiment, m and n are independently 0, 1 or 2, wherein at least one of m and n is 1 or 2. In this case, then each R ₄ and R ₅ is then independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy, benzyl, phenethyl, C The group consisting of ₂ - _C6alkenyl and C2 _{- C6alkynyl} . _In still further embodiments, each R4 and _R5 is independently methyl, ethyl, phenyl, benzyl, phenethyl, methoxy, ethoxy, vinyl, ethynyl. _In an optional further embodiment, each R4 and _R5 is independently phenyl, phenoxy, benzyl or phenethyl. _In one embodiment, R4 and _R5 are the same. Alternatively, they may be different.

In a further embodiment, n is 1 and m is 1. In a further embodiment, R ₄ and R ₅ are independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy, benzyl, phenethyl, C ₂ -C The group consisting of ₆ alkenyl and C ₂ -C ₆ alkynyl. In still further aspects, l is 0 or 1. _In still further embodiments, R4 and _R5 are independently methyl, ethyl, phenyl, benzyl, phenethyl, methoxy, ethoxy, vinyl, ethynyl. _In an optional further embodiment, R4 and _R5 are independently phenyl, phenoxy, benzyl or phenethyl. _In one embodiment, R4 and _R5 are the same. Optionally, they are different.

In another embodiment, n is 1 and m is 0. In a further embodiment, R ₄ is selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy, benzyl, phenethyl, C ₂ -C ₆ alkenyl and C ₂ -C ₆ alkynyl. In still further aspects, l is 0 or 1. _In still further embodiments, R4 is methyl, ethyl, phenyl, benzyl, phenethyl, methoxy, ethoxy, vinyl, ethynyl. _In the alternative, R4 is independently phenyl, phenoxy, benzyl or phenethyl. _In yet another embodiment, R4 is benzyl.

In another embodiment, m is 1 and n is 0. In a further embodiment, R ₅ is selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy, benzyl, phenethyl, C ₂ -C ₆ alkenyl and C ₂ - the group consisting of C ₆ alkynyl groups. In still further embodiments, 1 is 0 or 1. In still further embodiments, R ₅ is methyl, ethyl, phenyl, benzyl, phenethyl, methoxy, ethoxy, vinyl, ethynyl. _In the alternative, R5 is independently phenyl, phenoxy, benzyl or phenethyl. _In yet another embodiment, R5 is benzyl.

Amount of phosphoric anhydride

The curable resin composition may comprise, for example, from about 10% by weight to about 70% by weight, from about 20% by weight to about 60% by weight, from about 30% by weight to about 30% by weight of the composition. about 60% by weight, about 30% by weight to about 55% by weight, about 30% by weight to about 50% by weight, about 35% by weight to about 60% by weight, The phosphoric acid anhydride-containing component in an amount of from about 35% by weight to about 55% by weight, from about 35% by weight to about 50% by weight, or from about 35% by weight to about 45% by weight.

For example, the curable resin composition can include at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, or at least about 35% by weight of the composition. Phosphoric anhydride-containing components in an amount of about 40%.

Active ester

The curable resin composition may further comprise at least one active ester. It has been found that the presence of the active ester component improves the dielectric properties of electrical laminates prepared from the cured resin compositions, including but not limited to the dielectric constant ( _Dk ) or dissipation factor ( _Df ) of the laminate ). Without being bound by a particular theory, it is believed that the water absorption of electrical laminates can be improved by the presence of active esters.

As used herein, the term "active ester" refers to a compound that includes an ester functional group that is highly susceptible to nucleophilic attack.

Non-limiting examples of active esters include diamides, thioesters (eg, acetyl CoA), esters of phosphoric acid and sulfuric acid (eg, dimethyl sulfate), ester derivatives of nitrophenols (eg, bis(4 carbonate) -nitrophenyl) ester), ester derivatives of pentafluorophenol (eg, bis(pentafluorophenyl) carbonate), ester derivatives of acrylic acid (eg, N-hydroxysuccinimidyl acrylate), N -Ester derivatives of hydroxysuccinimide (eg, N,N'-disuccinimidyl carbonate) and ester derivatives of hydroxybenzotriazole (eg, 1-hydroxybenzotriazole hydrate) and ester derivatives of phenol novolac resins.

Non-limiting examples of commercially available active esters include EPICLON HPC-8000-65T and EXB-8150-65T, which are dicyclopentadiene phenol novolac-based active esters obtained from DIC.

In an exemplary embodiment, the active ester component includes one or more ester derivatives of phenol novolac resins. For example, the active ester component may include a dicyclopentadiene phenol novolak or a naphthalene phenol novolak based active ester.

， 其中每個X獨立地選自由氫、C₁ –C₆ 烷基和C₁ -C₆ 烷氧基組成的組；每個Y獨立地選自由C₁ –C₆ 亞烴基(alkylene)組成的組並且每個Z獨立地選自由羥基、C₁ –C₆ 烷基和C₁ –C₆ 烷氧基組成的組。As a further example, the active ester component can include a compound having the structure,

, wherein each X is independently selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy; each Y is independently selected from the group consisting of C ₁ -C ₆ alkylene group and each Z is independently selected from the group consisting of hydroxy, _C1 - _C6 alkyl, and _C1 - _C6 alkoxy.

As a non-limiting example, each X can be independently selected from the group consisting of hydrogen and methyl.

As a non-limiting example, each Y can be independently selected from the group consisting of -CH ₂ - and -C(CH ₃ ) ₂ -. For example, each Y can be -C(CH ₃ ) ₂ -.

As a non-limiting example, each Z can be independently selected from the group consisting of hydroxy and methoxy. For example, each Z can be a hydroxyl group.

Amount of active ester

The curable resin composition may include, for example, from about 1% by weight to about 30% by weight, from about 2% by weight to about 25% by weight, from about 4% by weight to about 4% by weight of the composition. The active ester component in an amount of about 20% by weight or about 8% by weight to about 20% by weight.

For example, the curable resin composition can include at least about 1% by weight, at least about 2% by weight, at least about 4% by weight, at least about 8% by weight, or at least about 8% by weight of the composition. Active ester component in an amount of about 10%.

optional ingredients

Known additives useful for the preparation, storage, and curing of resin compositions can be used as optional additional components in the curable resin compositions provided herein.

The curable resin composition may optionally contain one or more other additives useful for its intended use. Non-limiting examples of optional additives that may be useful in curable resin compositions include: stabilizers; surfactants such as silicones; flow modifiers; dyes; matting agents; , inorganic flame retardants, halogenated flame retardants and non-halogenated flame retardants such as phosphorus-containing materials); toughening agents such as elastomers and liquid block copolymers; curing inhibitors; wetting agents; colorants; thermoplastics; processing Adjuvants; fluorescent compounds; inert fillers such as clay, talc, silica and calcium carbonate; fiber reinforcements; fibers such as glass fibers and carbon fibers; antioxidants; impact modifiers, including thermoplastic particles; solvents such as ethers and alcohols ; and mixtures thereof. The above list is intended to be illustrative and not restrictive. Preferred additives for formulation can be optimized by the skilled artisan.

Non-limiting examples of stabilizers useful in the compositions provided herein include 2,6-di-tert-butyl-4-methylphenol (BHT), styrene phenol, 2,2'-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4- Ethylphenol, 2,6-dicyclopentylphenol, 2,6-dicyclooctyl-4-methylphenol, 2-tert-butyl-4-methyl-6-cyclohexylphenol, 2,6- Dibenzyl-4-n-butylphenol, 2,6-bis(1-naphthyl)phenol and mixtures thereof.

Non-limiting examples of surfactants that may optionally be used in the curable resin composition include polysiloxane-type surfactants, fluorinated surfactants, acrylic copolymers, and mixtures thereof. Non-limiting examples of preferred toughening agents useful in the compositions provided herein include carboxyl terminated liquid nitrile rubber (CTBN), liquid block copolymers, liquid polyols, core-shell rubber particles, and mixtures thereof.

Non-limiting examples of fillers that may optionally be used in the curable resin composition include _SiO2 and Al(OH) ₃ .

The concentration of the additional additive is generally from about 0% by weight to about 20% by weight, preferably from about 0.01% by weight to about 15% by weight, more preferably from about 0.1% by weight to about 15% by weight of the composition Between about 10% by weight and most preferably between about 0.1% by weight and about 5% by weight.

Laminate for electrical use

Electrical laminates can be prepared from the curable compositions disclosed herein. And printed circuit boards can be prepared from the curable compositions and electrical laminates disclosed herein. If desired, electrical laminates include alternating layers of prepreg and conductive material.

The curable compositions disclosed herein may further include at least one curing agent (also referred to as a "hardener") and/or a curing accelerator. Examples of curing agents include acid anhydrides, carboxylic acids, amine compounds, phenolic compounds, polyols, and mixtures thereof. In one embodiment, the composition includes from about 0.01 weight percent to about 90 weight percent curing agent. Examples of curing agents include, but are not limited to, dicyandiamide; diaminodiphenylmethane and diaminodiphenylene; polyamides; polyamides; polyphenols; polymeric mercaptans; polycarboxylic acids; Formic anhydride, tetrahydrophthalic anhydride (THPA), methyltetrahydrophthalic anhydride (MTHPA), hexahydrophthalic anhydride (HHPA), methylhexahydrophthalic anhydride (MHHPA) , nadic methyl anhydride (NMA), polyazapoly anhydride, succinic anhydride and maleic anhydride styrene-maleic anhydride copolymer. Phenolic curing agents such as phenol novolacs, cresol novolacs, and bisphenol A novolacs can also be used. The curing agent is preferably used in an amount ranging from 2 wt % to 80 wt % based on the total weight of the curable composition.

Curing accelerators (or catalysts) include substituted or epoxy-modified imidazoles such as 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole. It is also possible to use, for example, 1,8-diazabicyclo[5.4.0]undec-7-ene (also known as DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene ( Other heterocyclic amines also known as DBN). Tertiary amines and phosphines including, but not limited to, triethylamine, tripropylamine, tributylamine, and triphenylphosphine can also be used. In addition, phosphonium salts such as ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium acetate, and ammonium salts such as benzyltrimethylammonium acetate and benzyltrimethylamine hydroxide can also be used as curing accelerators. Halogen salts (iodides, bromides, chlorides, and fluorides) can also be used, but are generally less desirable in halogen-free applications. The catalyst is preferably used in an amount ranging from about 0.01 wt % to about 2.00 wt % based on the total weight of the curable composition.

The optimum ratio of curing agent to phosphorus-containing epoxy resin is usually expressed in terms of equivalence ratio. The equivalent ratio of epoxy resin to reactive hydrogen (-SH, -OH, -NH or -COOH) or acid anhydride in the curing agent may be 1.00:1.00. The curable compositions of the present disclosure are preferably prepared with an equivalence ratio in the range of 1.20:1.00 to 1.00:1.20, more preferably 1.10:1.00 to 1.00:1.10, and most preferably 1.10:1.00 to 1.00:1.05.

method of preparation

In another aspect, disclosed herein is a method for preparing a curable epoxy resin composition comprising admixing the curable composition disclosed herein with at least one curing agent. Also disclosed are cured thermoset products prepared by curing the curable epoxy resin compositions disclosed herein.

Generally, in accordance with the present disclosure, curing of curable compositions formed using phosphorus-containing epoxy resins of Formulas I, II, III, and/or IV can be accomplished by first melting the phosphorus-containing epoxy resin in the curable composition to This is done by obtaining a homogeneous melt or dissolving it in a suitable solvent. Examples of suitable solvents include, but are not limited to, ketones, esters and/or aromatic hydrocarbons such as acetone and/or methyl ethyl ketone. For embodiments, the solvent may be used in an amount up to about 50 wt % based on the total weight of the curable composition. During or at the end of the curing process, the solvent can be removed by distillation or simple evaporation.

The phosphorus-containing epoxy resins of the present disclosure can be mixed with thermoplastic resins to form hybrid crosslinked networks. Preparation of the curable compositions of the present disclosure can be accomplished by suitable mixing methods known in the art, including dry blending of the individual components and sequential melt mixing, directly in the extruder used to make the finished product or Premixed in a separate extruder.

When softened or melted by the application of heat, the curable compositions formed with the phosphorus-containing epoxy resins and thermoplastic resins of the present disclosure can be used alone or in combination such as compression molding, injection molding, gas-assisted injection molding, calendering, vacuum Formed or formed by conventional techniques of molding, thermoforming, extrusion and/or blow molding. Curable compositions formed with the phosphorous-containing epoxy resins and thermoplastic resins of the present disclosure may also be formed, spun or drawn into films, fibers, multilayer laminates, or extruded sheets, or may be used with one or more organic or inorganic material compounding.

Lewis acids can also be used in compositions including epoxy resins. Lewis acids may include, for example, one or a mixture of two or more of halides, oxides, hydroxides, and alkoxides of zinc, tin, titanium, cobalt, manganese, iron, silicon, aluminum, and boron. Examples of such Lewis acids and Lewis acid anhydrides include boric acid, metaboric acid, optionally substituted boroxanes such as trimethoxyboroxane, trimethylboroxane, or triethylboroxane alkanes), oxides of optionally substituted boron, alkyl borates, boron halides, zinc halides (eg, zinc chloride), and other Lewis acids that tend to have relatively weaker conjugated phosphoniums.

Phosphorus-containing epoxy resins and/or curable compositions formed with phosphorus-containing epoxy resins can be used in the preparation of various articles. Accordingly, the disclosure also includes prepregs as well as shaped articles, reinforcing compositions, laminates, electrical laminates, coatings, molded articles, adhesives, cured or partially derived from the above compositions A cured phosphorous-containing epoxy resin or composite product described below of a composition comprising a phosphorous-containing epoxy resin of the present disclosure. Furthermore, the compositions of the present disclosure can be used for various purposes in the form of dry powders, pellets, homogenates, impregnated products, and/or compounds.

Various additional additives can be added to the curable compositions of the present disclosure. Examples of these additional additives include reinforcing materials, fillers, pigments, dyes, thickeners, wetting agents, lubricants, flame retardants, and the like. Suitable reinforcing materials include silica, alumina trihydrate, alumina, aluminum hydroxide oxide, metal oxides, nanotubes, glass fibers, quartz fibers, carbon fibers, boron fibers, Kevlar fibers, and Teflon Dragon (Teflon) fiber and so on. The fibrous and/or particulate reinforcement may range in size from 0.5 nanometers (nm) to 100 micrometers (μm). For various embodiments, the fiber reinforcement may be in the form of mats, cloths, or continuous fibers.

Embodiments of the curable composition may also include at least one synergist to illustrate improved flame-out properties of the cured composition. Examples of such synergists include, but are not limited to, aluminum hydroxide, magnesium hydroxide, zinc borate, metal phosphites such as Exolit® OP-930 (available from Clariant), and combinations thereof. Additionally, embodiments of the curable composition may also include adhesion promoters such as modified organosilanes (epoxidized, methacrylic, amino), acetylacetonates, sulfur-containing molecules, and combinations thereof. Other additives may include but are not limited to wetting and dispersing aids such as modified organosilanes, Byk® 900 series and W 9010 (Byk-Chemie GmbH), modified fluorocarbons and combinations thereof; air release additives such as Byk® A530, Byk® A525, Byk® A555 and Byk® A 560 (Byk-Chemie GmbH); surface modifiers such as slip and gloss additives; mold release agents such as waxes; and other functionalities to improve polymer properties Additives or pre-reaction products such as isocyanates, isocyanurates, cyanates, allyl-containing molecules or other ethylenically unsaturated compounds, acrylates, and combinations thereof.

For various embodiments, the resin sheet may be formed from the phosphorus-containing epoxy resins and/or curable compositions of the present disclosure. In one embodiment, a plurality of sheets may be bonded together to form a laminate, wherein the sheets include at least one resin sheet. Phosphorus-containing epoxy resins and/or curable compositions formed with phosphorus-containing epoxy resins can also be used to form resin clad metal foils. For example, metal foils such as copper foils may be coated with the phosphorous-containing epoxy resins of the present disclosure and/or curable compositions formed with phosphorous-containing epoxy resins.

For various embodiments, the phosphorus-containing epoxy resins and/or curable compositions of the present disclosure may be applied to substrates as coatings or adhesive layers. Alternatively, the phosphorus-containing epoxy resins and/or compositions of the present disclosure may be formed or laminated in the form of powders, pellets, or impregnated in, for example, fiber-reinforced substrates. The phosphorus-containing epoxy resin and/or curable composition of the present disclosure can then be cured by applying heat.

The amount of heat required to provide suitable curing conditions may depend on the proportions of the composition components that make up the curable composition and the nature of the composition components employed. Generally, the curable compositions of this disclosure can be cured by heating them at a temperature in the range of about 25°C to about 250°C, preferably 100°C to 220°C, although depending on the presence of a curing agent and its amount or type of composition components in the curable composition. The time required for heating can range from 60 seconds to 24 hours, where the precise time will depend on whether the curable composition is used as a thin coating, as a relatively thick molded article, as a laminate, or as a Matrix resins acting on fiber-reinforced composites, especially for electrical and electronic applications, for example, differ when applied to non-conductive materials and subsequently cured of curable compositions.

Other objects and features will be in part apparent and in part pointed out hereinafter.

definition

As used herein, the term "alkyl" refers to straight or branched chain moieties including up to 10 carbon atoms. Non-limiting examples of suitable alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. The alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group (eg, isopropyl). In some embodiments, alkyl groups are optionally substituted independently with one or more substituents. For example, an alkyl group can optionally be independently substituted with one or more alkoxy groups (eg, methoxy) or carboxyl groups. In other embodiments, the alkyl group is unsubstituted.

As used herein, the term "aryl" refers to an aromatic moiety comprising 6 to 14 carbon atoms. In some embodiments, aryl groups are optionally substituted independently with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, and carboxy. Non-limiting examples of suitable aryl groups include phenyl, naphthyl, benzyl, tolyl, and tolyl.

As used herein, the term "alkoxy" refers to groups of the form -ORʹ, where Rʹ is an alkyl group as defined herein. For example, the group _-OCH3 may be referred to herein as "methoxy." _The group _-OCH2CH3 may be referred to herein as "ethoxy".

As used herein, the term "carboxy" refers to a group of the form -C(O)OH.

Example

The following non-limiting examples are provided to further illustrate the present disclosure.

Material

The materials described below were used in each of the following examples unless otherwise stated.

EPICLON HP-7200H is a DCPD phenol novolac epoxy resin available from DIC Corporation.

NC3000H is a biphenylphenol novolac epoxy resin obtained from Nippon Kayaku.

HPC8000 is a dicyclopentadiene phenol novolak-based active ester available from DIC Corporation.

EXB8150 is a naphthalene phenol novolac based active ester available from DIC Corporation.

DMAP is 4-dimethylaminopyridine, obtained from Sinopharm Chemical.

2E4MI is 2-ethyl-4-methylimidazole, available from Sinopharm Chemical.

Preparation of laminates

Dip the varnish on 2116 glass cloth. The glass cloth with resin is baked in a processor to become a partially cured prepreg. Stack six pieces of prepreg together and cover the surface with a piece of 35 μm standard copper foil. The stacks were then laminated in a hot press at 200 ^° C for 90 minutes.

glass transition temperature (T _g )

_Tg was measured by Differential Scanning Calorimetry (DSC) on a DSC2500 (from TA Instruments) according to IPC-TM650-2.4.25. Typically, a thermal scan range of 40 ^° C to 210°C and a heating rate of 20°C/min are used. Two heating loops were performed, the curve of the second loop being used to determine _Tg by the "half height" method.

Thermal decomposition temperature (T _d )

_Td is defined as the temperature at which 5% of the weight is lost in nitrogen. It was measured on a TA Q50 (from TA Instruments) according to IPC-TM650-2.4.24.6. The heating rate was 10 °C/min.

exist 288°C delamination time (T288)

T288 was measured on a TA Q400 (from TA Instruments) according to IPC-TM-2.4.24.1. The delamination time was determined as the elapsed time from when the temperature reached 288 °C to when a sudden significant dimensional change occurred.

Dielectric constant (D _k )/ Dissipation factor (D _f )

Dielectric constant and dissipation factor of laminate specimens by Keysight E4991B Impedance Analyzer at 1 GHz at 25 °C per IPC-TM-2.5.5.9 and Rohde & Schwarz at 10 GHz at 25 °C per IPC-TM-2.5.5.13 ZVL network analyzer measurement.

Copper peel strength (CPS)

Copper peel strength was measured using an IMASS SP-2000 slip/peel tester equipped with a variable angle peel jig capable of maintaining the desired peel angle of 90° throughout the test. For copper etching, cut out a 2" x 4" copper clad laminate. Two 0.25 inch graphite ribbons were placed longitudinally of the sample on both sides of the laminate with at least 0.5 inch spacing between them. The laminate pieces were then placed in a KeyPro benchtop etcher. Once the samples were removed from the etcher and properly dried, the graphite ribbons were removed to expose the copper strips. Pull up each copper bar with a razor blade. The laminates were then loaded onto the IMASS tester. The copper tape was clamped and a copper peel test was performed at a 90° angle at a pull rate of 2.8 inches/minute.

Pressure Cooking Test (PCT)

Cut the copper uncovered laminate into 4 pieces each measuring 2 inches by 3 inches. Samples were accurately weighed and placed into an autoclave (Thermo Electron Corp. 8000-DSE). The samples were treated under 121 ^o C water vapor for 1 hour. Surface water was wiped and the sample was accurately weighed again to calculate the average water absorption.

UL94 Flame Retardant Test

Each of the five specimens (13 cm x 12 mm) was ignited twice for 10 seconds in a standard UL94 test chamber (Atlas UL94 Chamber VW-1). The time from leaving the ignition source to self-extinguishing was recorded as burn time. UL94 V-0 rating requires a burn time of less than 10 seconds per ignition and a total burn time of less than 50 seconds for 10 ignitions.

The following examples are given to illustrate, but not to limit, the scope of the present disclosure.

Preparation of test compositions

Inventive Examples 1-2 and Comparative Example 1 were prepared as described in Table 1 below. Table 1 component Invention Example 1 Invention Example 2 Comparative Example 1 EPICLON HP-7200H 48.0 \ 45.0 Biphenyl Epoxy Resin (NC3000H) \ 48.0 \ Phosphoric anhydride-containing formula IV 40.0 40.0 55.0 Active ester (HPC8000) 12.0 \ \ Active ester (EXB8150) \ 12.0 \ DMAP 0.070 0.070 \ 2E4MI \ \ 0.10

Laminate Applications

Table 2 below describes the results obtained when Inventive Examples 1-2 and Comparative Example 1 were cured and used in electrical laminate applications. Table 2 Laminate Properties Invention Example 1 Invention Example 2 Comparative Example 1 Tg ( ^oC ) 187 179 202 Td ( ^oC ) 375 400 350 T288 (coverage, min) > 60 > 60 > 60 Copper peel strength (N/mm, 1 Oz copper) 1.59 1.54 1.42 Water absorption % (PCT 1 h) 0.42% 0.38% 0.70% UL94 rating V-0 V-0 V-0 _Dk (1 GHz) 3.65 3.75 3.67 D _f (1 GHz) 0.0064 0.0045 0.0071 _Dk (10 GHz) 4.10 4.20 3.88 D _f (10 GHz) 0.0090 0.0076 0.0101

Both Inventive Examples 1 and 2 achieved a V-0 UL94 rating, which indicates that phosphoric anhydride-containing compounds can act as effective flame retardants.

Compared with Comparative Example 1, the active ester (HPC8000) was introduced into Inventive Example 1, and the thermal characteristics were at the same level as Comparative Example 1. The _Df of Inventive Example 1 _is 0.001 lower than that of Comparative Example 1 at 10 GHz.

In Inventive Example 2, rigid biphenyl epoxy resin (NC3000H) and active ester (EXB8150) were used. The laminates showed higher _Td , up to 400 °C, and reduced water absorption, as low as 0.38%, indicating further improved thermal performance. D _f is as low as 0.0045 at 1 GHz and as low as 0.0076 at 10 GHz, which is Megtron 4 level (D _f <= 0.008 at 10 GHz). This indicates that excellent laminate properties can be achieved with a curable thermoset containing phosphoric anhydride as a hardener and flame retardant.

When introducing elements of the present disclosure or the preferred embodiments thereof, the articles "a" ("a"), "an" ("an"), "the" and "said" are intended to mean There are one or more elements. The terms "comprising", "including", and "having" are intended to be inclusive and mean in addition to the listed elements There may be other elements.

In view of the foregoing, it will be seen that several objectives and other advantageous results of the present disclosure are achieved.

As various changes could be made in the above products and methods without departing from the scope of the present disclosure, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

without

Claims (31)

A curable resin composition comprising: a) epoxy resin components, including at least one epoxy resin; b) a phosphoric acid anhydride-containing component, including at least one phosphoric acid anhydride-containing component; and c) an active ester component, including at least one active ester. The curable resin composition of claim 1, wherein the epoxy resin component comprises a resin selected from the group consisting of aromatic epoxy resins, cycloaliphatic epoxy resins, aliphatic epoxy resins, and mixtures thereof at least one epoxy resin. The curable resin composition according to claim 1 or 2, wherein the epoxy resin component comprises a divinylarene dioxide selected from the group consisting of divinylarene dioxide, diglycidyl ether of bisphenol A, diglycidyl ether of bromobisphenol A Glycidyl ether, oligo- or poly-diglycidyl ether of bisphenol A, oligo- or poly-diglycidyl ether of tetrabromobisphenol A, diglycidyl ether of bisphenol F or its derivatives, epoxy novolac At least one epoxy resin from the group consisting of varnish resins, epoxy cresol novolac resins, and mixtures thereof. The curable resin composition of any one of claims 1 to 3, comprising from about 10% by weight to about 80% by weight, from about 20% by weight to about 20% by weight of the composition The epoxy resin component is present in an amount of about 70%, about 30% by weight to about 60% by weight, or about 40% by weight to about 60% by weight. The curable resin composition of any one of claims 1 to 4, comprising at least about 30% by weight, at least about 35% by weight, at least about 40% by weight of the composition or the epoxy resin component in an amount of at least about 45% by weight. The curable resin composition according to any one of claims 1 to 5, comprising a phosphoric acid anhydride-containing formula III or formula IV:

Formula III, Formula IV, wherein each R ₄ and R ₅ are independently selected from alkyl, alkoxy, aryl, aryloxy, arylalkyl, alkenyl and alkynyl; l is 0, 1, 2 or 3; m is 0, 1, 2, 3 or 4 and n is 0, 1, 2, 3 or 4. The curable resin composition according to claim 6, wherein m and n are zero. The curable resin composition according to claim 6, wherein at least one of m and n is not zero. The curable resin composition according to claim 8, wherein each R ₄ and R ₅ is independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy, the group consisting of benzyl, C ₂ -C ₆ alkenyl, and C ₂ -C ₆ alkynyl; and 1 is 0 or 1. The curable resin composition according to claim 8 or 9, wherein each R ₄ and R ₅ is independently selected from methyl, ethyl, phenyl, benzyl, phenethyl, methoxy, ethoxy group consisting of vinyl, vinyl, and ethynyl. The curable resin composition of any one of claims 8 to 10, wherein each of R ₄ and R ₅ is independently selected from the group consisting of phenyl, phenoxy, and benzyl. The curable resin composition according to any one of claims 6 to 11, wherein each R ₃ is independently selected from the group consisting of C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl and phenyl group; wherein each phenyl group is optionally independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, phenoxy, C ₂ -C ₄ alkenyl, and C ₂ - Substituted with one or more groups of the group consisting of _C4alkynyl . The curable resin composition of any one of claims 6 to 12, wherein each R ₃ is independently selected from the group consisting of methyl, ethyl, cyclopentyl, cyclohexyl, and phenyl. The curable resin composition of any one of claims 1 to 13, comprising from about 10% by weight to about 70% by weight, from about 20% by weight to about 20% by weight of the composition about 60% by weight, about 30% by weight to about 60% by weight, about 30% by weight to about 55% by weight, about 30% by weight to about 50% by weight, by weight From about 35% to about 60% by weight, from about 35% by weight to about 55% by weight, from about 35% by weight to about 50% by weight, or from about 35% by weight to about 45% of the phosphoric anhydride-containing component. The curable resin composition of any one of claims 1 to 14, comprising at least about 20% by weight, at least about 25% by weight, at least about 30% by weight of the composition , the phosphoric acid anhydride-containing component in an amount of at least about 35% by weight or at least about 40% by weight. The curable resin composition according to any one of claims 1 to 15, wherein the active ester component comprises an ester selected from the group consisting of diamides, thioesters, esters of phosphoric acid and sulfuric acid, ester derivatives of nitrophenols , ester derivatives of pentafluorophenol, ester derivatives of acrylic acid, ester derivatives of N-hydroxysuccinimide, ester derivatives of hydroxybenzotriazole, and ester derivatives of phenol novolac resins. An active ester. The curable resin composition of claim 16, wherein the active ester component comprises one or more ester derivatives of a phenol novolac resin. The curable resin composition of claim 17, wherein the active ester component comprises a dicyclopentadiene phenol novolak or a naphthalene phenol novolak-based active ester. The curable resin composition of any one of claims 1 to 18, comprising from about 1% by weight to about 30% by weight, from about 2% by weight to about 2% by weight of the composition The active ester component is present in an amount of about 25% by weight, about 4% by weight to about 20% by weight, or about 8% by weight to about 20% by weight. The curable resin composition of any one of claims 1 to 19, comprising at least about 1% by weight, at least about 2% by weight, at least about 4% by weight of the composition , the active ester component in an amount of at least about 8% by weight or at least about 10% by weight. A prepreg prepared from the curable resin composition according to any one of claims 1 to 20. The prepreg according to claim 21, further comprising a reinforcing component. The prepreg of claim 22, wherein the reinforcing component comprises fiber, cloth, or a combination thereof. An electrical laminate prepared from the curable composition of any one of claims 1-20. A printed circuit board prepared from the electrical laminate of claim 24. The electrical laminate of claim 24, wherein the electrical laminate comprises alternating layers of prepreg and conductive material. A curable epoxy resin composition comprising the composition according to any one of claims 1 to 20 and at least one curing agent. The curable composition of claim 27, wherein the composition comprises 0.01 to 90 weight percent of the curing agent. The curable composition of any one of claims 27 or 28, wherein the curing agent is selected from the group consisting of acid anhydrides, carboxylic acids, amine compounds, phenolic compounds, polyols, and mixtures thereof. A method for preparing a curable epoxy resin composition comprising mixing (i) the composition of any one of claims 1-20 and (ii) at least one curing agent. A cured thermoset product prepared by curing a curable epoxy resin composition according to any one of claims 1-20 or 27-29.