WO2021237696A1

WO2021237696A1 - Halogen free very low loss resin composition

Info

Publication number: WO2021237696A1
Application number: PCT/CN2020/093361
Authority: WO
Inventors: Simon YE; Ethan Wang; Emerson Bao
Original assignee: Blue Cube IP LLC
Current assignee: Blue Cube IP LLC
Priority date: 2020-05-29
Filing date: 2020-05-29
Publication date: 2021-12-02
Anticipated expiration: 2022-11-29
Also published as: CN115698178A; TW202206537A; TW202534123A; TWI887423B

Abstract

Provided herein are halogen-free, flame retardant curable resin compositions that provide both good electrical characteristics and good heat resistance characteristics sufficient to allow for their use in high-performance PCB systems. In particular, provided herein are new organophosphorus olefins that are useful as reactive-time flame retardants. Surprisingly, it has been discovered that these reactive-type compounds provide good dielectric performance and heat resistance when incorporated into PCB compositions. The presence of C=C double bonds in these organophosphorus olefins allows them to react with unsaturated resins (for example, C=C double capped polyphenyl ether, bismaleic imide, etc. ) to form a crosslinked network.

Description

HALOGEN FREE VERY LOW LOSS RESIN COMPOSITION

BACKGROUND

Continuing advances in computer engineering have created an increasing demand for high speed, low loss printed circuit board ( “PCB” ) materials. As compared to previous generations of PCB materials, high speed, low loss PCB materials exhibit less change in the dielectric constant (Dk) as the transmission frequency increases, and exhibit a relatively low dielectric loss.

Recently, it has become particularly important to develop high speed, low loss PCB materials that are halogen-free and exhibit a superior low dissipation factor (Df) . Formulations known in the art are typically based on radically cured resin systems, for example, systems comprising hydrocarbon resins containing abundant C=C double bonds, acrylate capped polyphenyl ether (PPE) , and/or crosslinking agents with abundant C=C double bonds.

Unfortunately, there is an absence of phosphorus-based flame retardants having a sufficiently low Df to be useful in these high-performance PCB systems. Currently known reactive-type flame retardants do not provide the required electrical performance characteristics. While certain additive-type flame retardants, such as resorcinol bis [di (2, 6-dimethylphenyl) phosphate] , will provide the required electrical performance characteristics, these additive-type flame retardants will significantly decrease the heat resistance of the composition, including the glass transition temperature (Tg) and decomposition temperature (Td) .

Accordingly, it is desirable to develop halogen-free, flame retardant PCB materials that provide both good electrical characteristics and good heat resistance characteristics sufficient to allow for their use in high-performance PCB systems.

SUMMARY

For example, provided herein is a resin composition comprising: an organophosphorus olefin, in an amount of from about 10%by weight to about 65%by weight of the composition; an unsaturated resin, in an amount of from 0%by weight to about 50%by weight of the composition; silica, in an amount of from about 20%by weight to about 80%by weight of the composition; and a free radical initiator, in an amount of from about 0.5%by weight to about 7.5%by weight of the composition.

In some embodiments, the resin composition provided herein comprises an organophosphorus olefin of Formula A,

wherein each Ar ¹ is independently a moiety of structure (1) ;

R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

R ⁴ and R ⁵ are each independently a moiety comprising at least one C=C double bond;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-; R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl; and n is an integer greater than or equal to 1. For example, the organophosphorus olefin may comprise a compound of Formula I, Formula Ia, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula IId, Formula IIe, Formula IIf, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, or Formula IIIf.

Also provided herein is a printed circuit board comprising a cured resin composition, wherein the resin composition is as provided herein.

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

DETAILED DESCRIPTION

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

In particular, provided herein are new organophosphorus olefins that are useful as reactive-type flame retardants. Surprisingly, it has been discovered that these reactive-type compounds provide good dielectric performance and heat resistance when incorporated into PCB compositions. The presence of C=C double bonds in these organophosphorus olefins allows them to react with unsaturated resins (for example, C=C double capped polyphenyl ether, bismaleic imide, etc. ) to form a crosslinked network.

For example, provided herein is a resin composition comprising an organophosphorus olefin, an unsaturated resin, silica, and a free radical initiator. Each of these components is discussed in further detail below.

Organophosphorus Olefin

The resin composition may comprise one or more organophosphorous olefins as provided herein. As discussed above, it has been discovered that the organophosphorous olefins provided herein are useful as reactive-type flame retardants, and provide surprisingly good dielectric performance and heat resistance when incorporated into PCB compositions.

The resin composition may comprise an organophosphorus olefin, for example, in an amount of from about 10%by weight to about 65%by weight, from about 15%by weight to about 50%by weight, from about 20%by weight to about 40%by weight, from about 20%by weight to about 35%by weight, or from about 25%by weight to about 35%by weight of the composition.

In preferred embodiments, the resin composition comprises a compound of Formula A,

wherein each Ar ¹ is independently a moiety of structure (1) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

and n is an integer greater than or equal to 1.

In preferred embodiments, R ⁴ and R ⁵ are each independently selected from the group consisting of structure (1) , structure (2) , and structure (3) ;

As used herein, the term “alkyl” refers to a straight or branched chain moiety comprising up to 10 carbon atoms. Non-limiting examples of suitable alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. The alkyl group may be a straight-chain alkyl group or a branched alkyl group (e.g., isopropyl) . In some embodiments, the alkyl group is optionally independently substituted with one or more substituents selected from the group consisting of methoxyl, carboxyl, .

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

As used herein, the term “alkoxyl” refers to a group of the form -OR′, wherein R′ is alkyl as defined herein. For example, the group -OCH ₃ may be referred to herein as “methoxyl. ” The group -OCH ₂CH ₃ may be referred to herein as “ethoxyl. ”

As used herein, the term “aryloxyl” refers to a group of the form -OR′, wherein R′ is aryl as defined herein. For example, the group -O (C ₆H ₆) may be referred to herein as “phenoxyl. ”

As used herein, the term “hydrogen” includes both stable isotopes of hydrogen, namely ¹H (also known as protium) and ²H (also known as deuterium) .

As used herein, the term “carboxyl” refers to a group of the form -C (O) OH.

In preferred embodiments, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In some embodiments, each Ar ² is the same. For example, each Ar ² may be a moiety of structure (4) wherein each X is the same. In other embodiments, each Ar ² is a moiety of structure (5) .

In preferred embodiments, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments, n is an integer of from 1 to 10. For example, n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one exemplary embodiment, n is 1.

For example, the resin composition may comprise a compound of Formula I,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, ;

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, Ar ², X, and n may be selected as described above with respect to Formula A.

In preferred embodiments of the compound of Formula I, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula I, Ar ² is selected from the group consisting of structure (4) and structure (5) , and each Ar ² is the same.

In exemplary embodiments of the compound of Formula I, Ar ² is a moiety of structure (4) , and X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula I, n is 1.

For example, when Ar ² is a moiety of structure (4) , the compound is of Formula Ia,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, X, and n may be selected as described above with respect to Formula A and/or Formula I.

In preferred embodiments of the compound of Formula Ia, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula Ia, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula Ia, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula Ia-i.

The resin composition may comprise a compound of Formula II,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula II, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula II, Ar ² is selected from the group consisting of structure (4) and structure (5) , and each Ar ² is the same.

In exemplary embodiments of the compound of Formula II, Ar ² is a moiety of structure (4) , and X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula II, n is 1.

For example, when Ar ² is a moiety of structure (4) , the compound is of Formula IIa,

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, X, and n may be selected as described above with respect to Formula A and/or Formula II.

In preferred embodiments of the compound of Formula IIa, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIa, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIa, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIa-i.

The resin composition may comprise a compound of Formula IIb,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, and n may be selected as described above with respect to Formula A and/or Formula II.

In preferred embodiments of the compound of Formula IIb, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIb, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIb-i.

The resin composition may comprise a compound of Formula IIc,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIc, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIc, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIc-i.

The resin composition may comprise a compound of Formula IId,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IId, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IId, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IId-i.

The resin composition may comprise a compound of Formula IIe,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIe, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIe, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIe-i.

The resin composition may comprise a compound of Formula IIf,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, R ⁶, R ⁷, X, and n may be selected as described above with respect to Formula A and/or Formula II.

In preferred embodiments of the compound of Formula IIf, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIf, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIf, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³, R ⁶, and R ⁷ are each hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIf-i.

Further provided herein is a compound of Formula III,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula III, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula III, Ar ² is selected from the group consisting of structure (4) and structure (5) , and each Ar ² is the same.

In exemplary embodiments of the compound of Formula III, Ar ² is a moiety of structure (4) , and X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula III, n is 1.

For example, when Ar ² is a moiety of structure (4) , the compound is of Formula IIIa,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, X, and n may be selected as described above with respect to Formula A and/or Formula III.

In preferred embodiments of the compound of Formula IIIa, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIa, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIIa, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIIa-i.

The resin composition may comprise a compound of Formula IIIb,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, and n may be selected as described above with respect to Formula A and/or Formula III.

In preferred embodiments of the compound of Formula IIIb, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIb, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIIb-i.

The resin composition may comprise a compound of Formula IIIc,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIIc, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIc, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIIc-i.

The resin composition may comprise a compound of Formula IIId,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula Id, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIId, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIId-i.

The resin composition may comprise a compound of Formula IIIe,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIIe, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIe, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIIe-i.

The resin composition may comprise a compound of Formula IIIf,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, R ⁶, R ⁷, X, and n may be selected as described above with respect to Formula A and/or Formula III.

In preferred embodiments of the compound of Formula IIIf, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIf, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIIf, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³, R ⁶, and R ⁷ are each hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIIf-i.

Unsaturated Resin

The resin composition may further comprise one or more unsaturated resins. As discussed above, it has been discovered the presence of C=C double bonds in the organophosphorus olefins allows them to react with unsaturated resins to form a crosslinked network.

As used herein, the term “unsaturated resin” refers to a resin comprising at least one C=C double bond.

The resin composition may comprise the one or more unsaturated resins, for example, in an amount of from about 0%by weight to about 50%by weight, from about 10%to about 40%by weight, from about 10%to about 30%by weight, from about 15%to about 30%by weight, or from about 15%to about 25%by weight of the composition.

Non-limiting examples of unsaturated resins include acrylate capped polyphenyl ether; bismaleimide; and mixtures thereof.

Acrylate Capped Polyphenyl Ethers

The resin composition may comprise an acrylate capped polyphenyl ether of Formula B

wherein Y is an aliphatic backbone comprising 1 or more carbon atoms, and m and n are each independently greater than or equal to 1.

In some embodiments, Y is an aliphatic backbone comprising between 1 and 20 carbon atoms, for example, between 1 and 10 carbon atoms, between 1 and 8 carbon atoms, or between 1 and 6 carbon atoms.

When the resin composition comprises an acrylate capped polyphenyl ether, the concentration of the acrylate capped polyphenyl ether is preferably from about 20%by weight to about 80%by weight, for example, from about 40%by weight to about 70%by weight, from about 45%by weight to about 65%by weight, or from about 50%by weight to about 60%by weight of the composition.

Bismaleimides

The resin composition may comprise a bismaleimide of Formula C

wherein R ¹ is selected from the group consisting of: an aliphatic backbone comprising 1 or more carbon atoms, and a cycloaliphatic backbone comprising a ring with 3 or more members;

and R ², R ³, R ⁴, and R ⁵ are each independently selected from the group consisting of hydrogen and C ₁–C ₃ alkyl.

In some embodiments, R ¹ is an aliphatic backbone comprising between 1 and 20 carbon atoms, for example, between 1 and 10 carbon atoms, between 1 and 8 carbon atoms, or between 1 and 6 carbon atoms.

When the resin composition comprises a bismaleimide, the concentration of the bismaleimide is preferably from about 1%by weight to about 50%by weight, for example, from about 10%by weight to about 40%by weight, from about 15%by weight to about 35%by weight, or from about 20%by weight to about 30%by weight of the composition.

Combinations of Unsaturated resins

In some embodiments, the resin composition comprises a combination of two or more unsaturated resins. For example, the resin composition may comprise a combination of (1) an acrylate capped polyphenyl ether (including but not limited to a compound of Formula B) , and (2) a bismaleimide (including but not limited to a compound of Formula C) .

As a non-limiting example, when the composition comprises both an acrylate capped polyphenyl ether and a bismaleimide, the concentration of the acrylate capped polyphenyl ether may range from 1%by weight to about 30%by weight, from about 2%by weight to about 25%by weight, from about 5%by weight to about 20%by weight, or from about 5%by weight to about 15%by weight of the composition. Likewise, the concentration of the bismaleimide may range, for example, from 1%by weight to about 30%by weight, from about 2%by weight to about 25%by weight, from about 5%by weight to about 20%by weight, or from about 5%by weight to about 15%by weight of the composition.

Filler Component

The resin composition may further comprise a filler component. Without being bound to a particular theory, the presence of a filler component can improve the dimensional stability, mechanical strength, and/or thermal conductivity of the composition.

Non-limiting examples of suitable filler components include spherical silica, fused silica, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, boron nitride, mica, talc, and mixtures thereof. In preferred embodiments, the filler component comprises an inorganic filler. For example, the filler component may comprise silica.

The resin composition may comprise the filler component, for example, in an amount of from about 20%by weight to about 80%by weight, from about 30%to about 70%by weight, or from about 40%by weight to about 60%by weight of the composition.

Free Radical Initiator

The resin composition may comprise one or more free radical initiators. Without being bound to a particular theory, the free radical initiator may act to release free radicals at elevated temperature, and thereby trigger the cross linking of all the components in the composition.

Non-limiting examples of free radical initiators include dicumyl peroxide, di-tert-butyl peroxide, and benzoyl peroxide. For example, the free radical initiator may comprise a peroxide compound.

The resin composition may comprise the one or more free radical initiators, for example, in an amount of from about 0.5%by weight to about 7.5%by weight, from about 0.5%by weight to about 5%by weight, from about 0.5%by weight to about 2.5%by weight, from about 1%by weight to about 2.5%by weight, or from about 1.5%by weight to about 2.5%by weight of the composition.

Printed Circuit Boards

Also provided is a printed circuit board comprising a resin composition as provided herein.

EXAMPLES

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

Experimental Materials

The compositions provided herein can be formulated using typical techniques that are known to those skilled in the art.

Unless otherwise indicated, the materials described below were used in each of the following examples.

SA9000 is acrylate terminated polyphenyl ether available from SABIC.

TAIC is triallyl isocyanurate available from Tokyo Chemical Industry Co.

PX200 is resorcinol bis [di (2, 6-dimethylphenyl) phosphate] available from Daihachi Chemical Industry Co.

BMI 5100 is 3, 3'-dimethyl-5, 5'-diethyl-4, 4'-diphenylmethane bismaleimide available from Daiwakasei Industry Co.

SC2300-SVJ is spherical silica available from Admatechs Co., Ltd.

DCP is dicumyl peroxide available from Sinopharm Chemical Reagent Co.

SPB100 is hexaphenoxycyclotriphosphazene available from Otsuka Chemical Co.

As used herein, the abbreviation (tBuO) ₂ refers to di-tert-butyl peroxide, available from Sinopharm Chemical Reagent Co.

Preparation of Test Compositions

Inventive Examples 1–6 and Comparative Examples 1–2 were prepared as described in Table 1 below.

Table 1

Laminate Application

The Comparative and Inventive Examples prepared as described in Table 1 were tested for use in a laminate application.

A varnish was prepared by combining the Example formulations with methyl ethyl ketone solvent (50%of the varnish composition by weight) . Into a tray was poured about 200 grams of varnish. One piece of 2116 glass cloth (about 30 cm × 30 cm) was dipped into the varnish and then hand pulled through a gapped pair of rollers to control the thickness. One edge of the prepared glass cloth was fixed by clamps and then hung in a fume hood to allow the varnish to evenly spread and promote solvent evaporation. The glass cloth was then baked in a mini-treater (with good ventilation capability) at elevated temperature for a period of time sufficient to remove the solvent and generate a reasonable prepreg gel time, so the temperature and the time could be adjusted according to specific cases. Following the baking, the desired prepregs were obtained.

Six pieces of the resulting prepreg were stacked together, and half of the top and bottom surface was covered with a sheet of 35 μm standard copper foil. The stack was then laminated in a press at 200℃ for 1.0 hours. The resulting laminate composition was then tested for the properties shown in Table 2 below.

Table 2 demonstrates that the Inventive Examples comprising an Organophosphorus Olefin provide an ideal balance between Tg, Td, and Df when used in a laminate application.

Table 2

In Comparative Examples 1 and 2, additive type flame retardants SPB-100 and PX-200 were formulated with SA9000 and TAIC, respectively. The laminate Tg was far below 170℃, and could not be regarded as high Tg. Both examples showed low loss performance. PX-200 could further lower the laminate Df to 0.0020 at 1 GHz, better than SPB-100.

In Inventive Examples 1 and 2, the Organophosphorous Olefin of Formula Ia and IIb were formulated with SA9000 and TAIC, respectively. Both laminates had significant improvement on Tg as the Organophosphorous Olefin could react with other components to increase the crosslinking density. Both laminates also achieved promising low loss performance, with 0.0030 Df at 1 GHz, and 0.0028 Df at 1 GHz, respectively. The flame retardancy rankings were V-1 level.

In Inventive Example 3, the Organophosphorous Olefin of Formula II was formulated with SA9000. The flame retardancy ranking further improved to V-0 level, although the Df was increased a little, to 0.0040 at 1 GHz.

In Inventive Example 4, the Organophosphorous Olefin of Formula IIa was formulated with SA9000. The laminate could achieve 182℃ Tg and promising low loss, 0.0028 Df at 1 GHz, while the flame retardancy was compromised to V-1 level.

In Inventive Example 5, to further increase the thermal resistance, BMI resin and spherical silica were included into the formulation. The laminate Tg increased to 205℃ with a good low loss, 0.0025 Df at 1 GHz.

In Inventive Example 6, SA9000 was excluded. The Organophosphorous Olefin of Formula IIa was formulated with a BMI resin. The laminate showed 152℃ Tg, indicating a good crosslinking was still formed without SA9000 in the formulation. Df was not compromised, and stayed below 0.003 at 1 GHz.

When introducing elements of the present disclosure or the preferred embodiment (s) thereof, the articles “a” , “an” , “the” , and “said” are intended to mean that there are one or more of the elements. The terms “comprising” , “including” , and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.

In view of the above, it will be seen that the several objects of the disclosure are achieved and other advantageous results attained.

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

Claims

A resin composition comprising:

an organophosphorus olefin; and

an unsaturated resin;

wherein the organophosphorus olefin comprises a compound of Formula A,

wherein each Ar ¹ is independently a moiety of structure (1) ;

R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

R ⁴ and R ⁵ are each independently a moiety comprising at least one C=C double bond;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 1 wherein R ⁴ and R ⁵ are each independently selected from the group consisting of:

structure (1) , structure (2) , and structure (3) .
The resin composition of claim 1 or 2 comprising:

an organophosphorus olefin, in an amount of from about 10%by weight to about 65%by weight of the composition;

an unsaturated resin, in an amount of from 0%by weight to about 50%by weight of the composition;

a filler component, in an amount of from about 20%by weight to about 80%by weight of the composition; and

a free radical initiator, in an amount of from about 0.5%by weight to about 7.5%by weight of the composition.
The composition of any one of claims 1 to 3 comprising the unsaturated resin in an amount of from about 10%to about 40%by weight, from about 10%to about 30%by weight, from about 15%to about 30%by weight, or from about 15%to about 25%by weight of the composition.
The composition of any one of claims 1 to 4 comprising an unsaturated resin selected from the group consisting of acrylate capped polyphenyl ether; bismaleimide; and mixtures thereof.
The composition of any one of claims 1 to 5 wherein the unsaturated resin comprises an acrylate capped polyphenyl ether of Formula B

wherein Y is an aliphatic backbone comprising 1 or more carbon atoms, and m and n are each independently greater than or equal to 1.
The composition of claim 6 wherein Y is an aliphatic backbone comprising between 1 and 20 carbon atoms, between 1 and 10 carbon atoms, between 1 and 8 carbon atoms, or between 1 and 6 carbon atoms.
The composition of claim 6 or 7 wherein the concentration of the acrylate capped polyphenyl ether is from about 20%by weight to about 80%by weight, from about 40%by weight to about 70%by weight, from about 45%by weight to about 65%by weight, or from about 50%by weight to about 60%by weight of the composition.
The composition of any one of claims 1 to 8 wherein the unsaturated resin comprises a bismaleimide of Formula C

wherein R ¹ is selected from the group consisting of: an aliphatic backbone comprising 1 or more carbon atoms, and a cycloaliphatic backbone comprising a ring with 3 or more members;

and R ², R ³, R ⁴, and R ⁵ are each independently selected from the group consisting of hydrogen and C ₁–C ₃ alkyl.
The composition of claim 8 wherein R ¹ is an aliphatic backbone comprising between 1 and 20 carbon atoms, between 1 and 10 carbon atoms, between 1 and 8 carbon atoms, or between 1 and 6 carbon atoms.
The composition of claim 9 or 10 wherein the concentration of the bismaleimide is from about 1%by weight to about 50%by weight, for example, from about 10%by weight to about 40%by weight, from about 15%by weight to about 35%by weight, or from about 20%by weight to about 30%by weight of the composition.
The composition of any one of claims 1 to 11 wherein the unsaturated resin comprises a mixture of:

(1) an acrylate capped polyphenyl ether; and

(2) a bismaleimide.
The composition of claim 12 wherein:

the concentration of the acrylate capped polyphenyl ether is from about from about 1%by weight to about 30%by weight, from about 2%by weight to about 25%by weight, from about 5%by weight to about 20%by weight, or from about 5%by weight to about 15%by weight of the composition; and

the concentration of the bismaleimide is from 1%by weight to about 30%by weight, from about 2%by weight to about 25%by weight, from about 5%by weight to about 20%by weight, or from about 5%by weight to about 15%by weight of the composition.
The composition of any one of claims 1 to 12 comprising a filler component in an amount of from about 20%by weight to about 80%by weight, from about 30%to about 70%by weight, or from about 40%by weight to about 60%by weight of the composition.
The composition of claim 14 wherein the filler component comprises silica.
The composition of any one of clams 1 to 15 comprising a free radical initiator selected from the group consisting of dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, and mixtures thereof.
The composition of any one of clams 1 to 16 comprising a free radical initiator in an amount of from about 0.5%by weight to about 7.5%by weight, from about 0.5%by weight to about 5%by weight, from about 0.5%by weight to about 2.5%by weight, from about 1%by weight to about 2.5%by weight, or from about 1.5%by weight to about 2.5%by weight of the composition.
The composition of any one of claims 1 to 17 wherein the organophosphorous olefin comprises a compound of Formula I,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 18 wherein the organophosphorous olefin comprises a compound of Formula Ia,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.
The composition of claim 19 wherein X is selected from the group consisting of -CH ₂- and -C (CH ₃) ₂-.
The composition of any one of claims 1 to 20 wherein the organophosphorous olefin comprises a compound of Formula II,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 21 wherein the organophosphorous olefin comprises a compound of Formula IIa,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.
The composition of claim 22 wherein X is selected from the group consisting of -CH ₂- and -C (CH ₃) ₂-.
The composition of claim 21 wherein the organophosphorous olefin comprises a compound of Formula IIb,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 21 wherein the organophosphorous olefin comprises a compound of Formula IIc,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 21 wherein the organophosphorous olefin comprises a compound of Formula IId,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 21 wherein the organophosphorous olefin comprises a compound of Formula IIe,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 21 wherein the organophosphorous olefin comprises a compound of Formula IIf,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 28 wherein X is selected from the group consisting of -CH ₂- and -C (CH ₃) ₂-.
The composition of any one of claims 1 to 29 wherein the organophosphorous olefin comprises a compound of Formula III,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 30 wherein the organophosphorous olefin comprises a compound of Formula IIIa,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.
The composition of claim 31 wherein X is selected from the group consisting of -CH ₂- and -C (CH ₃) ₂-.
The composition of claim 30 wherein the organophosphorous olefin comprises a compound of Formula IIIb,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 30 wherein the organophosphorous olefin comprises a compound of Formula IIIc,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 30 wherein the organophosphorous olefin comprises a compound of Formula IIId,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 30 wherein the organophosphorous olefin comprises a compound of Formula IIIe,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 30 wherein the organophosphorous olefin comprises a compound of Formula IIIf,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The composition of claim 37 wherein X is selected from the group consisting of -CH ₂- and -C (CH ₃) ₂-.
The composition of any one of claims 1 to 38 wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl.
The composition any one of claims 1 to 38 wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and methyl.
The composition of any one of claims 1 to 40 wherein R ³ is hydrogen.
The composition of any one of claims 1 to 41 wherein n is an integer of from 1 to 10.
The composition of any one of claims 1 to 42 wherein n is 1.
The composition of any one of clams 1 to 43 wherein the organophosphorous olefin comprises a compound of Formula Ia-i,

Formula IIa-i,

Formula IIb-i,

Formula IIc-i,

Formula IId-i,

Formula IIe-i,

Formula IIf-i,

Formula IIIa-i,

Formula IIIb-i,

Formula IIIc-i,

Formula IIId-i,

Formula IIIe-I,

and Formula IIIf-I
The composition of any one of claims 1 to 44 comprising the organophosphorus olefin in an amount of from about 10%by weight to about 65%by weight, from about 15%by weight to about 50%by weight, from about 20%by weight to about 40%by weight, from about 20%by weight to about 35%by weight, or from about 25%by weight to about 35%by weight of the composition.
A printed circuit board comprising a composition of any one of claims 1 to 45.