Polmerizable fluxing agents and fluxing adhesive compositions therefrom

• US 6,132,646 A
• Filed: 08/11/1999
• Issued: 10/17/2000
• Est. Priority Date: 07/21/1997
• Status: Expired due to Term

• Current Assignee: Creative Electron, Inc.
• Original Assignee: Miguel Albert Capote
• Inventors: Zhou, Zhiming, Capote, Miguel A.
• Primary Examiner(s): Gupta, Yogendra
• Assistant Examiner(s): HAMLIN, DERRICK G
• Application Number:
  US09/372,709
• Time in Patent Office: 433 Days
• Field of Search: 252/512, 252/513, 252/514, 252/519.32-519.33, 252/500, 520/25, 520/1, 148/24
• US Class Current: 252/512
• CPC Class Codes: B23K 35/025 Pastes, creams, slurries
• CPC Class Codes: B23K 35/3613 Polymers, e.g. resins
• CPC Class Codes: B23K 35/3618 Carboxylic acids or salts
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C08F 222/103 of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• CPC Class Codes: C09J 4/00 Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• CPC Class Codes: H01L 2224/0401 Bonding areas specifically adapted for bump connectors, e.g. under bump metallisation [UBM]
• CPC Class Codes: H01L 2224/131 with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
• CPC Class Codes: H01L 2224/16225 the item being non-metallic, e.g. insulating substrate with or without metallisation
• CPC Class Codes: H01L 2224/29111 Tin [Sn] as principal constituent
• CPC Class Codes: H01L 2224/2919 with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
• CPC Class Codes: H01L 2224/32225 the item being non-metallic, e.g. insulating substrate with or without metallisation
• CPC Class Codes: H01L 2224/73104 the bump connector being embedded into the layer connector
• CPC Class Codes: H01L 2224/73204 the bump connector being embedded into the layer connector
• CPC Class Codes: H01L 2224/81191 wherein the bump connectors are disposed only on the semiconductor or solid-state body
• CPC Class Codes: H01L 2224/83191 wherein the layer connectors are disposed only on the semiconductor or solid-state body
• CPC Class Codes: H01L 2224/83192 wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
• CPC Class Codes: H01L 2224/838 Bonding techniques
• CPC Class Codes: H01L 23/49883 the conductive materials containing organic materials or pastes, e.g. for thick films for printed circuits H05K1/092
• CPC Class Codes: H01L 24/29 of an individual layer connector
• CPC Class Codes: H01L 24/32 : of an individual layer connector
• CPC Class Codes: H01L 24/83 : using a layer connector
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/00012 : Relevant to the scope of the group, the symbol of which is combined with the symbol of this group
• CPC Class Codes: H01L 2924/00014 : the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
• CPC Class Codes: H01L 2924/01004 : Beryllium [Be]
• CPC Class Codes: H01L 2924/01005 : Boron [B]
• CPC Class Codes: H01L 2924/01006 : Carbon [C]
• CPC Class Codes: H01L 2924/01009 : Fluorine [F]
• CPC Class Codes: H01L 2924/01015 : Phosphorus [P]
• CPC Class Codes: H01L 2924/01018 : Argon [Ar]
• CPC Class Codes: H01L 2924/01019 : Potassium [K]
• CPC Class Codes: H01L 2924/0102 : Calcium [Ca]
• CPC Class Codes: H01L 2924/01025 : Manganese [Mn]
• CPC Class Codes: H01L 2924/01027 : Cobalt [Co]
• CPC Class Codes: H01L 2924/01029 : Copper [Cu]
• CPC Class Codes: H01L 2924/0103 : Zinc [Zn]
• CPC Class Codes: H01L 2924/01033 : Arsenic [As]
• CPC Class Codes: H01L 2924/01039 : Yttrium [Y]
• CPC Class Codes: H01L 2924/01042 : Molybdenum [Mo]
• CPC Class Codes: H01L 2924/01045 : Rhodium [Rh]
• CPC Class Codes: H01L 2924/01046 : Palladium [Pd]
• CPC Class Codes: H01L 2924/01047 : Silver [Ag]
• CPC Class Codes: H01L 2924/0105 : Tin [Sn]
• CPC Class Codes: H01L 2924/01051 : Antimony [Sb]
• CPC Class Codes: H01L 2924/01078 : Platinum [Pt]
• CPC Class Codes: H01L 2924/01079 : Gold [Au]
• CPC Class Codes: H01L 2924/01082 : Lead [Pb]
• CPC Class Codes: H01L 2924/0132 : Binary Alloys
• CPC Class Codes: H01L 2924/0133 : Ternary Alloys
• CPC Class Codes: H01L 2924/014 : Solder alloys
• CPC Class Codes: H01L 2924/0665 : Epoxy resin
• CPC Class Codes: H01L 2924/0781 : being an ohmic electrical conductor
• CPC Class Codes: H01L 2924/10253 : Silicon [Si]
• CPC Class Codes: H01L 2924/14 : Integrated circuits
• CPC Class Codes: H01L 2924/1579 : with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
• CPC Class Codes: H01L 2924/351 : Thermal stress
• CPC Class Codes: H05K 1/095 : for polymer thick films, i.e. having a permanent organic polymeric binder
• CPC Class Codes: H05K 3/321 : by conductive adhesives

Abstract

A thermally curable adhesive composition that includes a fluxing agent that also acts as an adhesive is provided. The composition includes: (a) a fluxing agent represented by the formula RCOOH, wherein R comprises a moiety having two or more carbon--carbon double bonds; (b) optionally, an effective amount of a crosslinkable diluent; (c) optionally, an effective amount of a source of free radical initiators; and (d) optionally, an effective amount of a resin to react with remnant carboxylic acid moieties. The composition can be applied directly onto the surface(s) of devices that are to be joined electrically and mechanically. These devices include, printed circuit substrates, connectors, components, cables, and other electrical devices having metallization patterns to be soldered together by means of a solder-bumped pattern on one or both surfaces. Alternatively, a solder paste, comprising solder powder mixed with the fluxing agent of the present invention can be used. During the reflow step, the fluxing agent promotes wetting of the solder to the metallization patterns and, simultaneously, the fluxing agent itself crosslinks to mechanically bond and encapsulate the surfaces and their metallizations. The compositions can also be used to formulate sinterable conductive inks.

Claims

1. An electrically conductive ink composition formed by curing an adhesive composition comprising:

a) 1 to 65% (wt) of a high melting point metal that is selected from the group consisting of Cu, Ag, Au, Pt, Pd Be, Rh, Ni, Co, Fe, Mo, and alloys thereof;

b) 6 to 65% (wt) of a solder that is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Hg, Sb, and alloy thereof; and

c) 5% to 50% (wt) of the thermally curable adhesive flux composition that comprises;

(i) a fluxing agent represented by the formula RCOOH, wherein R comprises a moiety having two or more carbon--carbon double bonds;

(ii) an effective amount of a double bond containing diluent that is capable of crosslinking with the fluxing agent;

(iii) optionally, an effective amount of a source of free radical initiators; and

(iv) optionally, an effective amount of a resin.

2. The composition of claim 1 wherein the fluxing agent is selected from the group consisting carboxylic acids selected from the group consisting of compounds represented by Formulae I, II, III, and IV and mixtures thereof,

3. The composition of claim 1 wherein the diluent is selected from the group consisting of pentaerythritol tetraacrylate, triallyl-1,3,5-triazine-2,4 ,6 (1H,3H ,5H)-trione, tris isocyanurate, and mixtures thereof.

4. The composition of claim 1 wherein the source of free radical initiators is selected from the group consisting of benzoyl peroxide, butyl hydroperoxide, 1,2'"'"'-azobisisobutyronitrile, and mixtures thereof.

5. The composition of claim 1 wherein the resin is selected from the group consisting of 1,4-cyclohexanedimethanol diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, N,N-diglycidyl-4-glycidyl-oxyanilline, bisphenol A based epoxy resins, and mixtures thereof.

6. The composition of claim 2 wherein the fluxing agent has the structure of Formula I.

7. The composition of claim 2 wherein the fluxing agent has the structure of Formula II.

8. The composition of claim 2 wherein the fluxing agent has the structure of Formula II.

9. The composition of claim 8 wherein X¹, X², and X³ are each --CH₂ OC(O)CH═

CHCOOH and X⁴ is H.

10. The composition of claim 2 wherein the fluxing agent has the structure of Formula IV.

11. The composition of claim 10 wherein the fluxing agent is represented by the formula [(CH₂ CH₂ OR¹⁹)(CH₂ CH₂ OR²⁰)(CH₂ CH₂ OR²¹)]N wherein R¹⁹, R²⁰, and R²¹ are each independently selected from the --

12. The composition of claim 1 wherein the fluxing agent comprises about 0.01% to 100% by volume, the diluent comprises up to about 90% by volume, the source of free radical initiators comprises about 0% to 5% by weight, and the resin comprises about 0% to 80% by volume of the composition.

13. The composition of claim 1 wherein the fluxing agent comprises about 10% to 70% by volume and the diluent comprises about 50% to 80% by volume of the composition.

14. The composition of claim 2 wherein the fluxing agent comprises about 0.01% to 100% by volume, the diluent comprises about 0% to 90% by volume, the source of free radical initiators comprises about 0% to 5% by weight, and the resin comprises up to about 80% by volume of the composition.

15. The composition of claim 2 wherein the fluxing agent comprises about 10% to 70% by volume and the resin comprises about 10% to 80% by volume of the composition.

16. An electrically conductive ink composition formed by curing an adhesive composition comprising:

a) 1 to 65% (wt) of a high melting point metal that is selected from the group consisting of Cu, Ag, Au, Pt, Pd Be, Rh, Ni, Co, Fe, Mo, and alloys thereof;

b) 6 to 65% (wt) of a solder that is selected from the group consisting of Sn, Bi, Pb, Cd, Zn, Ga, In, Hg, Sb, and alloy thereof; and

c) 5% to 50% (wt) of the thermally curable adhesive flux composition that comprises;

(i) a fluxing agent represented by the formula RCOOH, wherein R comprises a moiety having two or more carbon--carbon double bonds;

(ii) an effective amount of a resin;

(iii) optionally, an effective amount of a source of free radical initiators; and

(iv) optionally, an effective amount of a double bond containing diluent that is capable of crosslinking with the fluxing agent.

17. The composition of claim 16 wherein the fluxing agent is selected from the group consisting carboxylic acids selected from the group consisting of compounds represented by Formulae I, II, III, and IV and mixtures thereof,

18. The composition of claim 16 wherein the diluent is selected from the group consisting of penta erythritol tetraacrylate, triallyl-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione, tris[2-(acryloxy)ethyl]isocyanurate, and mixtures thereof.

19. The composition of claim 16 wherein the source of free radical initiators is selected from the group consisting of benzoyl peroxide, butyl hydroperoxide, 2,2'"'"'-azobisisobutyronitrile, and mixtures thereof.

20. The composition of claim 16 wherein the resin is selected from the group consisting of 1,4-cyclohexanedimethanol diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, N,N-diglycidyl-4-glycidyl-oxyanilline, bisphenol A based epoxy resins, and mixtures thereof.

21. The composition of claim 17 wherein the fluxing agent has the structure of Formula I.

22. The composition of claim 17 wherein the fluxing agent has the structure of Formula II.

23. The composition of claim 17 wherein the fluxing agent has the structure of Formula III.

24. The composition of claim 23 wherein X¹, X², and X³ are each --CH₂ OC(O)CH═

CHCOOH and X⁴ is H.

25. The composition of claim 17 wherein the fluxing agent has the structure of Formula IV.

26. The composition of claim 25 wherein the fluxing agent is represented by the formula [(CH₂ CH₂ OR¹⁹) (CH₂ CH₂ OR²⁰) (CH₂ CH₂ OR²¹)]N wherein R¹⁹, R²⁰, and R²¹ are each independently selected from the --OCCH═

CHCOOH, and --H.