# US 9,439,284 B1 · Ultra low loss dielectric thermosetting resin compositions and high performance laminates manufactured therefrom

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,439,284 B1
- Document ID: US9439284B1
- Status: Granted
- Kind: B1
- Application number: 15/144,503
- Filed: 2016-05-02
- Published: 2016-08-25
- Granted: 2016-09-06
- Earliest claimed: 2013-11-04
- Assignees: Novoset, LLC
- Applicants: Novoset, LLC
- Inventors: Sajal Das; Patrick Shipman
- Web page: https://patentgrep.com/patent/US9439284B1

## CPC

- H05K 1/0326: {containing O}
- B32B 15/06: of {natural rubber or synthetic} rubber
- B32B 15/20: comprising aluminium or copper {(B32B15/016 and B32B15/017 take precedence)}
- B32B 25/02: with fibres or particles {being present as additives in the layer}
- C08F 279/02: on to polymers of conjugated dienes
- C08F 283/12: on to polysiloxanes
- C08J 5/249: {characterised by the additives used in the prepolymer mixture}
- H05K 1/0346: {containing N}
- H05K 1/0366: {reinforced, e.g. by fibres, fabrics (H05K1/036 takes precedence)}
- B32B 2307/204: Di-electric
- B32B 2457/08: PCBs, i.e. printed circuit boards
- C08J 2351/00: Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J 2351/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- H05K 2201/015: Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
- H05K 2201/0158: Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
- H05K 2201/0162: Silicon containing polymer, e.g. silicone
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

A ultra low loss dielectric thermosetting resin composition has at least one cyanate ester component (A) and at least one reactive intermediate component (B) that is capable of copolymerization with said component (A). The invention is a cyanate ester resin of the form: Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2, wherein T is a 1,3,5-substituted-triazine moiety (C3N3); W is a linking atom between triazine and either component A or component B; Z is component (A); H is component (B); OCN is a cyanate ester end group; R is a reactive end group of component B; n is an integer greater than or equal to 1; and f is a weight or mole fraction of component A. The composition exhibits excellent dielectric properties and yields a high performance laminate for use in high layer count, multilayer printed circuit board (PCB), prepregs, resin coated copper (RCC), film adhesives, high frequency radomes, radio frequency (RF) laminates and various composites.

## Claims

### Claim 1

A method of making a thermosetting resin composition, comprising the steps of:
a. selecting at least one cyanate ester component (A)
b. heating said component (A) to a given temperature for a time period;
c. selecting at least one reactive intermediate component (B), said component B being capable of copolymerization with said component (A), said component (B) being a thermoplastic selected from the group consisting of (i) hydroxylated polybutadiene (HPBD) with molecular weights between 100 and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii) reactive polydimethylsiloxane (PDMS) with molecular weights between and including 100-20 000 g/mol and at least 2 functional groups per molecule of either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxane containing between 3-9% OH functional groups;
d. heating component (B);
e. adding component (B) to component (A) to form a reaction mixture;
f. heating said reaction mixture and stirring said reaction mixture to react components together to form a resin;
g. monitoring progress of said reaction by monitoring viscosity and refractive index of said resin at a reaction temperature, said reaction being complete when said viscosity of said resin at said reaction temperature is between 100 cP and 200,000 cP, wherein said resin is cooled to stop said reaction to yield a homogeneous resin of the form:
Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2
wherein T is a 1,3,5-substituted-triazine moiety (C3N3); W is a linking atom between triazine and either component A or component B; Z is component (A); H is component (B); OCN is cyanate ester end group; R is a reactive end group of component B; n is an integer greater than or equal to 1; and f is a weight or mole fraction of component A;
said thermosetting resin composition does not undergo phase separation, but instead forms a neat, homogenous resin consisting of a triazine co-polymer that consists of component (A) and component (B) joined through a triazine moiety.

### Claim 2 (depends on 1)

A method of making a thermosetting resin composition as recited by claim 1, wherein said component (A) is heated to temperatures between 135° C. and 200° C. for between 1 and 5 hours.

### Claim 3 (depends on 1)

A method of making a thermosetting resin composition as recited by claim 1, wherein said component (B) is heated to about 130° C. and added into component (A).

### Claim 4 (depends on 1)

A method of making a thermosetting resin composition as recited by claim 1, wherein said reaction mixture is heated to between 100° C. and 195° C.

### Claim 5 (depends on 1)

A method of making a thermosetting resin composition as recited by claim 1, wherein said resin is completed when said viscosity of the resin at 95° C. is between 100 cP and 200,000 cP.

### Claim 6 (depends on 1)

A method of making a thermosetting resin composition as recited by claim 1, wherein at room temperature said viscosity of said resin ranges between 50-1000 cP.

### Claim 7

A thermosetting resin composition for use in multilayer printed circuit boards for high performance applications defined by the formula:
Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2
wherein “T” is a 1,3,5-substituted-triazine moiety (C3N3); “W” is a linking atom between triazine and either component A or component B; “Z” is component (A); “H” is component (B); “OCN” is cyanate ester end group; “R” is a reactive end group of component B; “n” is an integer greater than or equal to 1; and “f” is a weight or mole fraction of component A;
wherein said thermosetting resin composition is formed by chemical reaction between:
a. at one cyanate ester component (A); and
b. at least one reactive intermediate component (B), said component B being capable of copolymerization with said component (A), said component (B) is a thermoplastic selected from the group consisting of (i) hydroxylated polybutadiene (HPBD) with molecular weights between 100 and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii) reactive polydimethylsiloxane (PDMS) with molecular weights between and including 100-20 000 g/mol and at least 2 functional groups per molecule of either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxane containing between 3-9% OH functional groups;
whereby said the setting resin composition does not undergo phase separation, but instead forms a neat, homogenous resin consisting of a triazine co-polymer that consists of component (A) and component (B) joined through a triazine moiety.

### Claim 8 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein said component (A) is a member selected from the group consisting of 2,2-bis(4-Cyanatophenyl) isopropylidene, Bisphenol F Cyanate ester, Bisphenol E Cyanate ester, Bisphenol M Cyanate ester, dicyanate of Oxydiphenol, resorcinol Cyanate ester, Cyanated novolac, Cyanated phenol-dicyclopentadiene, diphenyl cyanate ester, naphthol aralkyl Cyanate ester and mixtures thereof.

### Claim 9 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein said component (A) is defined by the formula
wherein X1 and X2 individually represent R, and R is a member selected from the group consisting of —CH(CH3)—, —CH2—, —C(CH3)2—, dicyclopentadiene (DCP), and functionalized DCP; n is an integer greater than 1; and Y represents at least one functional group.

### Claim 10 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein said component (A) is defined by the formula:
wherein X1 and X2 individually represent at least alkyl groups, aromatic groups, SO2, O, or S; n is an integer greater than 1; and Y represents at least one functional group.

### Claim 11 (depends on 10)

A thermosetting resin composition as recited by claim 10, wherein R is a member selected from the group consisting of —CH(CH3)—, —CH2—, —C(CH3)2—, dicyclopentadiene (DCP), and functionalized DCP.

### Claim 12 (depends on 10)

A thermosetting resin composition as recited by claim 10, wherein Ar is a member selected from the group consisting of a functionalized or non-functionalized benzene, biphenyl, naphthalene, phenol novolac, bisphenol A, bisphenol A novolac, bisphenol F, and bisphenol F novolac.

### Claim 13 (depends on 10)

A thermosetting resin composition as recited by claim 10, wherein Y is a member selected from the group consisting of hydrogen, aliphatic groups, aromatic groups, and halogens.

### Claim 14 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein said component (A) is defined by the formula
wherein X1 and X2 are alkyl groups, aromatic groups, SO2, O, or S; n is an integer greater than 1; and Y represents at least one functional group.

### Claim 15 (depends on 14)

A thermosetting resin composition as recited by claim 14, wherein R is a member selected from the group consisting of —CH(CH3)—, —CH2—, —C(CH3)2—, dicyclopentadiene (DCP), and functionalized DCP.

### Claim 16 (depends on 14)

A thermosetting resin composition as recited by claim 14, wherein Ar is a member selected from the group consisting of a functionalized or non-functionalized benzene, biphenyl, naphthalene, phenol novolac, bisphenol A, bisphenol A novolac, bisphenol F, and bisphenol F novolac.

### Claim 17 (depends on 14)

A thermosetting resin composition as recited by claim 14, wherein Y is a member selected from the group consisting of hydrogen, aliphatic groups, aromatic groups, and halogens.

### Claim 18 (depends on 14)

A thermosetting resin composition as recited by claim 14, wherein said wherein X2 is R, Ar, SO2, O, or S.

### Claim 19 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein Z has a wt % of at least 50% in reaction with component B.

### Claim 20 (depends on 7)

A thermosetting resin composition as recited by claim 7 comprising secondary reactive groups selected from the group consisting of allyls, vinyls, acrylates, halogens, ethoxys, and methoxys.

### Claim 21 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein R is a member selected from the group consisting of OH, SH, NH2, Allyl, Vinyl, Phenol, Anhydrides, Carboxylic acids and Acetylenes.

### Claim 22 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein component B ranges from about 5%-50% by wt.

### Claim 23 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein component B ranges from about 20%-35% by wt.

### Claim 24 (depends on 7)

A thermosetting resin composition as recited by claim 7, wherein content of each component in said resin comprises 50-95 wt % component A, 5-50 wt % component B, and up to 30 wt % flame-retardant.

### Claim 25

A thermosetting resin composition for use in prepregs/pre-impregnated composite fibers applications defined by the formula:
Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2
wherein “T” is a 1,3,5-substituted-triazine moiety (C3N3); “W” is a linking atom between triazine and either component A or component B; “Z” is component (A); “H” is component (B); “OCN” is cyanate ester end group; “R” is a reactive end group of component B; “n” is an integer greater than or equal to 1; and “f” is a weight or mole fraction of component A;
wherein said thermosetting resin composition is formed by chemical reaction between:
a. at least one cyanate ester component (A); and
b. at least one reactive intermediate component (B), said component B being capable of copolymerization with said component (A), said component (B) is a thermoplastic selected from the group consisting of (i) hydroxylated polybutadiene (HPBD) with molecular weights between 100 and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii) reactive polydimethylsiloxane (PDMS) with molecular weights between and including 100-20 000 g/mol and at least 2 functional groups per molecule of either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxane containing between 3-9% OH functional groups;
whereby said thermosetting resin composition does not undergo phase separation, but instead forms a neat, homogenous resin consisting of a triazine co-polymer that consists of component (A) and component (B) joined through a triazine moiety.

### Claim 26

A thermosetting resin composition for use in resin coated copper (RCC) applications defined by the formula:
Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2
wherein “T” is a 1,3,5-substituted-triazine moiety (C3N3); “W” is a linking atom between triazine and either component A or component B; “Z” is component (A); “H” is component (B); “OCN” is cyanate ester end group; “R” is a reactive end group of component B; “n” is an integer greater than or equal to 1; and “f” is a weight or mole fraction of component A;
wherein said thermosetting resin composition is formed by chemical reaction between:
a. at least one cyanate ester component (A); and
b. at least one reactive intermediate component (B), said component B being capable of copolymerization with said component (A), said component (B) is a thermoplastic selected from the group consisting of (i) hydroxylated polybutadiene (HPBD) with molecular weights between 100 and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii) reactive polydimethylsiloxane (PDMS) with molecular weights between and including 100-20 000 g/mol and at least 2 functional groups per molecule of either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxane containing between 3-9% OH functional groups;
whereby said thermosetting resin composition does not undergo phase separation, but instead forms a neat, homogenous resin consisting of a triazine co-polymer that consists of component (A) and component (B) joined through a triazine moiety.

### Claim 27

A thermosetting resin composition for use in film adhesives defined by the formula:
Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2
wherein “T” is a 1,3,5-substituted-triazine moiety (C3N3); “W” is a linking atom between triazine and either component A or component B; “Z” is component (A); “H” is component (B); “OCN” is cyanate ester end group; “R” is a reactive end group of component B; “n” is an integer greater than or equal to 1; and “f” is a weight or mole fraction of component A;
wherein said thermosetting resin composition is formed by chemical reaction between:
a. at least one cyanate ester component (A); and
b. at least one reactive intermediate component (B), said component B being capable of copolymerization with said component (A), said component (B) is a thermoplastic selected from the group consisting of (i) hydroxylated polybutadiene (HPBD) with molecular weights between 100 and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii) reactive polydimethylsilaxane (PDMS) with molecular weights between and including 100-20 000 g/mol and at least 2 functional groups per molecule of either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxane containing between 3-9% OH functional groups;
whereby said thermosetting resin composition does not undergo phase separation, but instead forms a neat, homogenous resin consisting of a triazine co-polymer that consists of component (A) and component (B) joined through a triazine moiety.

### Claim 28

A thermosetting resin composition for use in high frequency radomes defined by the formula:
Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2
wherein “T” is a 1,3,5-substituted-triazine moiety (C3N3); “W” is a linking atom between triazine and either component A or component B; “Z” is component (A); “H” is component (B); “OCN” is cyanate ester end group; “R” is a reactive end group of component B; “n” is an integer greater than or equal to 1; and “f” is a weight or mole fraction of component A;
wherein said thermosetting resin composition is formed by chemical reaction between:
a. at least one cyanate ester component (A); and
b. at least one reactive intermediate component (B), said component B being capable of copolymerization with said component (A), said component (B) is a thermoplastic selected from the group consisting of (i) hydroxylated polybutadiene (HPBD) with molecular weights between 100 and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii) reactive polydimethylsiloxane (PDMS) with molecular weights between and including 100-20 000 g/mol and at least 2 functional groups per molecule of either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxane containing between 3-9% OH functional groups;
whereby said thermosetting resin composition does not undergo phase separation, but instead forms a neat, homogenous resin consisting of a triazine co-polymer that consists of component (A) and component (B) joined through a triazine moiety.

### Claim 29

A thermosetting resin composition for use in radio frequency (RF) laminates defined by the formula:
Tn-[W-(Z)f/(H)1−f-W]n−1-[W-(Z)f/(H)1−f-(OCN)f/(R)1−f]n+2
wherein “T” is a 1,3,5-substituted-triazine moiety (C3N3); “W” is a linking atom between triazine and either component A or component B; “Z” is component (A); “H” is component (B); “OCN” is cyanate ester end group; “R” is a reactive end group of component B; “n” is an integer greater than or equal to 1; and “f” is a weight or mole fraction of component A;
wherein said thermosetting resin composition is formed by chemical reaction between:
a. at least one cyanate ester component (A); and
b. at least one reactive intermediate component (B), said component B being capable of copolymerization with said component (A), said component (B) is a thermoplastic selected from the group consisting of (i) hydroxylated polybutadiene (HPBD) with molecular weights between 100 and 10 000 g/mol, (ii) Hydrogenated hydroxylated polybutadiene (HHPBD), (iii) reactive polydimethylsiloxane (PDMS) with molecular weights between and including 100-20 000 g/mol and at least 2 functional groups per molecule of either hydroxyl or epoxy groups, and (iv) polymethylphenylsiloxane containing between 3-9% OH functional groups;
whereby said thermosetting resin composition does not undergo phase separation, but instead forms a neat, homogenous resin consisting of a triazine co-polymer that consists of component (A) and component (B) joined through a triazine moiety.