# US 7,745,516 B2 · Composition of polyimide and sterically-hindered hydrophobic epoxy

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- Number: US 7,745,516 B2
- Document ID: US7745516B2
- Status: Granted
- Kind: B2
- Application number: 11/248,803
- Filed: 2005-10-12
- Published: 2007-04-12
- Granted: 2010-06-29
- Earliest claimed: 2005-10-12
- Assignees: E. I. Du Pont de Nemours and Company
- Inventors: Thomas Eugene Dueber; John D. Summers; Brian C. Auman; Munirpallam Appadorai Subramanian; Nyrissa S. Rogado
- Web page: https://patentgrep.com/patent/US7745516B2

## CPC

- H10P 14/683: {carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC}
- C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L 79/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- G03F 7/023: Macromolecular quinonediazides; Macromolecular additives, e.g. binders {(G03F7/0226 takes precedence)}
- G03F 7/0387: {Polyamides or polyimides}
- H05K 1/095: {for polymer thick films, i.e. having a permanent organic polymeric binder}
- H10P 14/6342: {Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating}
- C08L 2205/02: containing two or more polymers of the same C08L -group
- H05K 2201/0154: Polyimide
- Y10T 428/31522: Next to metal
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Water absorption resistant polyimide/epoxy-based compositions, like pastes (or solutions), are particularly useful to make electronic screen-printable materials and electronic components. A group of hydrophobic epoxies (and soluble polyimides) was discovered to be particularly resistant to moisture absorption. The polyimide/epoxy pastes made with these epoxies (and these polyimides) may optionally contain thermal crosslinking agents, adhesion promoting agents, blocked isocyanates, and other inorganic fillers. The polyimide/epoxy pastes of the present invention can have a glass transition temperature greater than 250° C., a water absorption factor of less than 2%, and a positive solubility measurement.

## Claims

### Claim 1

A screen-printable composition comprising a polyimide component, a sterically hindered hydrophobic epoxy and an organic solvent;
wherein the polyimide component is represented by a polyimide having a repeat unit represented the formula;
wherein X can be equal to SO2 or C(CF3)2, C(CF3)phenyl, C(CF3)CF2CF3, or C(CF2CF3)phenyl, and combinations thereof, and
wherein Y is derived from a diamine component comprising from between and including any two of the following numbers, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50 mole percent of a diamine selected from the group consisting of, 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6F-AP), 2,4-diaminophenol, 2,3-diaminophenol, 3,3′-diamino-4,4′-dihydroxy-biphenyl and 2,2′-bis(3-amino-3-hydroxyphenyl)hexafluoropropane;
wherein the sterically hindered epoxy is represented by the following formula,
wherein Y is either a covalent bond, oxygen, sulfur, methylene, fluorenylidene, ethylidene, sulfonyl, cyclohexylidene, 1-phenylethylidene, or C(CH3)2, C(CF3)2;
wherein Z is an alkyl, alkoxy, phenyl, phenoxy, halogen, or combinations thereof; and
wherein m is an integer between and including any two of the following numbers, 0, 1, 2, 3, 4 and 5; and
wherein the organic solvent is selected from the group consisting of dibasic acid esters, propyleneglycol diacetate (PGDA), propylene glycol phenyl ether and mixtures of these.

### Claim 2 (depends on 1)

A composition in accordance with claim 1 further comprising an electrically conductive material.

### Claim 3 (depends on 1)

A composition in accordance with claim 1 wherein the sterically hindered epoxy is selected from the group comprising tetramethyl biphenol epoxy (TMBP), tetramethylbisphenol A epoxy (TMBPA), and tetrabromobisphenol-A epoxy.

### Claim 4 (depends on 1)

A composition in accordance with claim 1 wherein the diamine component further comprises from 50 to 98 mole percent of a diamine selected from the group consisting of 3,4′-diaminodiphenyl ether (3,4′-ODA), 4,4′-diamino-2,2′-bis(trifluoromethyl)biphenyl (TFMB), 3,3′,5,5′-tetramethylbenzidine, 2,3,5,6-tetramethyl -1,4-phenylenediamine, 3,3′-diaminodiphenyl sulfone, 3,3′dimethylbenzidine, 3,3′-bis(trifluoromethyl)benzidine, 2,2′-bis-(p-aminophenyl)hexafluoropropane, bis(trifluoromethoxy)benzidine (TFMOB), 2,2′-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2′-trifluoromethyl -4,4′-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2′-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminobenzotrifluoride (3,5-DABTF), 3,5-diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2′-dimethylbenzidine (DMBZ), 2,2′,6,6′-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)xanthene (6FCDAM), 3,6-diamino-9-trifluoromethyl -9-phenylxanthene (3FCDAM), 3,6-diamino-9,9-diphenyl xanthene and combinations thereof.

### Claim 5 (depends on 1)

A composition in accordance with claim 1 wherein the polyimide component is derived from a dianhydride component and a diamine component, the diamine comprising from 2 to 50 mole percent of a phenolic containing diamine and the dianhydride component being a dianhydride selected from the group consisting of 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA), 2,2-bis(3,4-dicarboxyphenyl)1,1,1,3,3,3-hexafluoropropane dianhydride (6-FDA), 1-phenyl -1,1-bis(3,4-dicarboxyphenyl)-2,2,2-trifluoroethane dianhydride, 1,1,1,3,3,4,4,4-octylfluoro-2,2-bis(3,4-dicarboxyphenyl)butane dianhydride, 1-phenyl -2,2,3,3,3-pentafluoro-1,1-bis(3,4-dicarboxylphenyl)propane dianhydride, 4,4′-oxydiphthalic anhydride (ODPA), 2,2′-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2′-bis(3,4-dicarboxyphenyl)-2-phenylethane dianhydride, 2,3,6,7-tetracarboxy-9-trifluoromethyl -9-phenylxanthene dianhydride (3FCDA), 2,3,6,7-tetracarboxy-9,9-bis(trifluoromethyl)xanthene dianhydride (6FCDA), 2,3,6,7-tetracarboxy-9-methyl-9-trifluoromethylxanthene dianhydride (MTXDA), 2,3,6,7-tetracarboxy-9-phenyl-9-methylxanthene dianhydride (MPXDA), 2,3,6,7-tetracarboxy-9,9-dimethylxanthene dianhydride (NMXDA) and combinations thereof.

### Claim 6 (depends on 2)

A composition in accordance with claim 2 wherein the electrically conductive material is a metal oxide.

### Claim 7 (depends on 2)

A composition in accordance with claim 2 wherein the electrically conductive material is an oxide of a metal selected from the group consisting of Ru, Pt, Ir, Sr, La, Nd, Ca, Cu, Bi, Gd, Mo, Nb, Cr and Ti.

### Claim 8 (depends on 2)

A composition in accordance with claim 2 wherein the electrically conductive material is a material selected from the group consisting of metal carbides, metal nitrides and metal borides.

### Claim 9 (depends on 2)

A composition in accordance with claim 2 wherein the electrically conductive material is a material selected from the group consisting of, titanium nitride and carbide, zirconium boride and carbide, and tungsten boride.

### Claim 10 (depends on 2)

A composition in accordance with claim 2 wherein the electrically conductive material is a material selected from the group consisting of barium titanate, barium strontium titanate, lead magnesium niobate, barium nitride, aluminum nitride, boron nitride, beryllium oxide, silver, copper, and diamond.

### Claim 11 (depends on 2)

A composition in accordance with claim 2 further comprising a non-electrically conductive filler, the filler being selected from the group consisting of talc, fumed silica, silica, fumed aluminum oxide, aluminum oxide, bentonite, calcium carbonate, iron oxide, titanium dioxide, mica and glass.

### Claim 12 (depends on 2)

A composition in accordance with claim 2 wherein the electrically conductive material is a material selected from the group consisting of carbon, graphite, carbon nanotubes, multi-wall carbon nanotubes, carbon fiber and carbon nanofibers.

### Claim 13 (depends on 2)

A composition in accordance with claim 2 wherein the electrically conductive material is present in an amount ranging from 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 and 80 weight percent of the total weight of the composition.

### Claim 14 (depends on 1)

A composition in accordance with claim 1, wherein the organic solvent is a liquid capable of suspending or dissolving the polyimide component, wherein the organic solvent has a Hanson polar solubility parameter between and including any two of the following numbers 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 and 3.0, and wherein the organic solvent has a normal boiling point between and including any two of the following numbers 210, 220, 230, 240, 250 and 260° C.

### Claim 15 (depends on 1)

A composition in accordance with claim 1 wherein the organic solvent is a dibasic acid ester selected from the group consisting of dimethyl succinate, dimethyl glutarate, dimethyl adipate and mixtures of these.

### Claim 16 (depends on 2)

A composition according to claim 2 wherein the polyimide component and the sterically hindered epoxy component are present at a weight ratio of A:B, wherein A is the polyimide component and B is the epoxy component, and wherein A is between and including any two of the following numbers 1, 2, 3, 4, 5, 10, 12 and 15, and wherein B is 1.0.

### Claim 17 (depends on 2)

A composition in accordance with claim 2, having the organic solvent removed, the composition being useful as a component in an electronic circuit package, wherein polyimide component portion and the sterically hindered epoxy component both have a glass transition temperature greater than 250° C. and wherein both have a water absorption factor of 2% or less.

### Claim 18 (depends on 17)

A composition in accordance with claim 17, wherein both the polyimide component and the sterically hindered epoxy component both have a glass transition temperature greater than 280° C. and wherein both have a water absorption factor of 1% or less.

### Claim 19 (depends on 2)

A composition in accordance with claim 2 further comprising a crosslinking agent selected from the group consisting of blocked isocyanates, polyhydroxystyrene, an epoxidized copolymer of phenol and aromatic hydrocarbon, a reaction product of a epichlorohydrin and a bisphenol, phenol formaldehyde, and 1,1,1-tris(p-hydroxyphenyl)ethane triglycidyl ether.

### Claim 20

A screen-printable composition comprising a polyimide component, a sterically hindered hydrophobic epoxy and an organic solvent;
wherein the polyimide component is represented by a polyimide having a repeat unit represented the formula;
wherein X can be equal to SO2 or C(CF3)2, C(CF3)phenyl, C(CF3)CF2CF3, or C(CF2CF3)phenyl, and combinations thereof, and
wherein Y is derived from a diamine component comprising from between and including any two of the following numbers, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50 mole percent of a diamine selected from the group consisting of, 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6F-AP), 2,4-diaminophenol, 2,3-diaminophenol, 3,3′-diamino-4,4′-dihydroxy-biphenyl and 2,2′-bis(3-amino-3-hydroxyphenyl)hexafluoropropane;
wherein the sterically hindered epoxy is represented by the following formula,
wherein Z is an alkyl, alkoxy, phenyl, phenoxy, halogen, or combinations thereof;
wherein Y is either a covalent bond, oxygen, sulfur, methylene, fluorenylidene, ethylidene, sulfonyl, cyclohexylidene, 1-phenylethylidene, or C(CH3)2, C(CF3)2; and
wherein m is an integer between and including any two of the following numbers, 0, 1, 2, 3, 4 and 5; and
wherein the organic solvent is selected from the group consisting of dibasic acid esters, propyleneglycol diacetate (PGDA), propylene glycol phenyl ether and mixtures of these, said composition further comprising a sterically hindered phenol represented by the following formula,
wherein Z is an alkyl, alkoxy, phenyl, phenoxy, halogen or combinations thereof,
wherein Y is a covalent bond, oxygen, sulfur, methylene, fluorenylidene, ethylidene, sulfonyl, cyclohexylidene, 1-phenylethylidene, C(CH3)2, or C(CF3)2, and,
wherein m is an integer between and including any two of the following numbers 0, 1, 2, 3, 4 and 5.

### Claim 21 (depends on 2)

A composition in accordance with claim 2 further comprising a sterically hindered phenol selected from the group consisting of 3,3′,5,5′-tetramethylbiphenol-4,4′-diol, 4,4′-isopropylidenebis(2,6-dimethylphenol), and 4,4′-isopropylidenebis(2,6-dibromophenol).

### Claim 22 (depends on 2)

A composition in accordance with claim 2 further comprising an adhesion promoter selected from the group consisting of polyhydroxyphenylether, polybenzimidazole, polyetherimide, polyamideimide, PKHH-polyhydroxyphenyl ether, 2-amino-5-mercaptothiophene, 5-amino-1,3,4-thiodiazole-2-thiol, benzotriazole, 5-chloro-benzotriazole, 1-chloro-benzotriazole, 1-carboxy- benzotriazole, 1-hydroxy-benzotriazole, 2-mercaptobenzoxazole, 1H-1,2,4-triazole-3-thiol, and mercaptobenzimidazole.

### Claim 23 (depends on 2)

A composition in accordance with claim 2 further comprising a tertiary aromatic amine catalyst or the salt of a tertiary aromatic amine catalyst.

### Claim 24 (depends on 2)

A composition in accordance with claim 2 further comprising a catalyst selected from the group consisting of dimethylbenzylamine and dimethylbenzylammonium acetate.

### Claim 25 (depends on 2)

A composition in accordance with claim 2, having the organic solvent removed, wherein the remaining composition is used in integrated circuitry, chip-scale packaging and wafer-level packaging as semiconductor stress buffers, interconnect dielectrics, protective overcoats, bond pad redistributors, or solder bump under fills.

### Claim 26 (depends on 2)

A composition in accordance with claim 2, having the organic solvent removed wherein the remaining composition is used as a binder in a polymer thick film (PTF) resistor, polymer thick film (PTF) electrical conductor, a discrete capacitor, a planar capacitor, a coating in an electronic device, a film, a substrate in an electronic device, an encapsulant, an adhesive, and as an electrically or thermally conductive material.

### Claim 27 (depends on 2)

A composition in accordance with claim 2, having the organic solvent removed, wherein the remaining composition is used in a printed circuit board (PCB) or embedded into a multi-layer circuit board.

### Claim 28 (depends on 2)

A composition in accordance with claim 2 screen-printed onto non metal-plated copper.