Composition comprising silicone epoxy resin, hydroxyl compound, anhydride and curing catalyst

• US 6,632,892 B2
• Filed: 08/21/2001
• Issued: 10/14/2003
• Est. Priority Date: 08/21/2001
• Status: Expired due to Fees

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Rubinsztajn, Slawomir, Rubinsztajn, Malgorzata Iwona
• Primary Examiner(s): SELLERS, ROBERT E
• Application Number:
  US09/934,235
• Publication Number:
  US 20030071366A1
• Time in Patent Office: 784 Days
• Field of Search: 525/474, 525/533, 525/476, 523/451, 523/456
• US Class Current: 525/476
• CPC Class Codes: C08G 59/24 carbocyclic
• CPC Class Codes: C08G 59/306 containing silicon
• CPC Class Codes: C08G 59/3254 containing atoms other than carbon, hydrogen, oxygen or nitrogen
• CPC Class Codes: C08G 59/4215 cycloaliphatic
• CPC Class Codes: C08G 59/4284 together with other curing agents
• CPC Class Codes: C08G 59/62 Alcohols or phenols
• CPC Class Codes: C08K 5/05 Alcohols; Metal alcoholates
• CPC Class Codes: C08K 5/09 Carboxylic acids; Metal salts thereof; Anhydrides thereof
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/06 containing silicon bound to oxygen-containing groups C08L83/12 takes precedence
• CPC Class Codes: H01L 2224/48091 Arched
• CPC Class Codes: H01L 2224/48247 connecting the wire to a bond pad of the item
• 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 33/56 Materials, e.g. epoxy or silicone resin
• CPC Class Codes: Y10S 362/80 Light emitting diode

Abstract

Epoxy resin compositions are disclosed which comprise (A) at least one silicone epoxy resin, (B) at least one hydroxyl-containing compound, (C) at least one anhydride curing agent, (D) at least one ancillary curing catalyst, and optionally at least one of thermal stabilizers, UV stabilizers, cure modifiers, coupling agents, or refractive index modifiers. Also disclosed are packaged solid state devices comprising a package, a chip (4), and an encapsulant (11) comprising an epoxy resin composition of the invention. A method of encapsulating a solid state device is also provided.

Claims

1. A curable epoxy resin composition for encapsulation of a solid state device, which comprises (A) at least one silicone epoxy resin, (B) at least one hydroxyl-containing compound. (C) at least one anhydride curing agent, and (D) at least one ancillary curing catalyst, wherein component (A) is present at a level of greater than about 40% by weight;

component (B) is present at a level in a range of between about 1% by weight and about 20% by weight;

component (C) is present at a level of less than about 25% by weight; and

component (D) is present at a level in a range between about 0.008% by weight and about 10% by weight based on the combined weight of silicone epoxy resin (A), hydroxyl-containing compound (B), curing agent (C), and ancillary curing catalyst (D).

2. The composition of claim 1, wherein the silicone epoxy resin (A) comprises at least one silicon moiety selected from the group consisting of R₃SiO_0.5, R₂SiO, RSiO_1.5, and SiO₂, in combination with at least one epoxy-containing silicone moiety selected from the group consisting of EpR₂SiO_0.5, EpRSiO, and EpSiO_1.5, wherein Ep is an epoxy moiety selected from the group consisting of a glycidoxy propyl moiety as in formula (I), a 3,4-epoxycyclohexane ethyl moiety as in formula (II), and a 1,2-epoxy hexyl moiety as in formula (III):

wherein R is monovalent alkyl, halogenated alkyl, or aryl, and R¹ is hydrogen or alkyl.

3. The composition of claim 2, wherein the silicone epoxy resin (A) comprises at least one compound selected from the group consisting of those depicted in formulas (IV), (V), (VI), (VII), (VIII), (IX), and (X):

wherein the abbreviation “

Ep”

designates any of the epoxy structures depicted in formulas (I), (II), or (III);

R and R² are each independently monovalent alkyl, halogenated alkyl, or aryl;

R³ is divalent alkyl, halogenated alkyl, or aryl;

x is an integer between 1 and 4 inclusive;

y is an integer between 1 and 3 inclusive;

z is an integer between 3 and 12 inclusive;

p is an integer having a value of 1 to about 80;

m is an integer between about 20 and about 100; and

n is an integer between about 1 and about 20.

4. The composition of claim 3, wherein the silicone epoxy resin (A) comprises 1,1,3,3-tetramethyl-1,3-bis[2(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]disiloxane.

5. The composition of claim 1, wherein the hydroxyl-containing compound (B) comprises at least one compound selected from the group consisting of a primary alcohol, a secondary alcohol, a tertiary alcohol, a polyfunctional alcohol, a diol, a triol, a bisphenol, a trisphenol, benzyl alcohol, cyclohexanemethanol, an alkyl diol, cyclohexanedimethanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, polyethylene glycol, glycerol, a polyether polyol, at least one compound with the formula (i):

$\begin{array}{cc}{R}_a^4<br><br>S<br><br>\text{\hspace{1em}<br><br>}<br><br>i<br><br>\text{\hspace{1em}<br><br>}<br><br>{O_{\left(\frac{4-a-b}{2}\right)}<br><br>\left(O<br><br>\text{\hspace{1em}<br><br>}<br><br>H\right)}_b& \left(i\right)\end{array}$

wherein R⁴ is a monovalent hydrocarbon radical or a halogenated monovalent hydrocarbon radical; and

mixtures thereof.

6. The composition of claim 5, wherein the value for the parameter b is such that at least about 0.2 wt. % OH groups are present in hydroxyl-containing compound (B).

7. The composition of claim 5, wherein the hydroxyl-containing compound (B) comprises at least one silicone T resin.

8. The composition of claim 5, wherein the hydroxyl-containing compound (B) comprises at least one silicone T/D copolymer.

9. The composition of claim 8, wherein R⁴ comprises a mixture of methyl and phenyl groups.

10. The composition of claim 9, wherein hydroxyl-containing compound (B) comprises the hydrolysis product of a mixture of phenyltrichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane.

11. The composition of claim 1, wherein the anhydride curing agent (C) comprises at least one member selected from the group consisting of bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, phthalic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, dodecenylsuccinic anhydride, dichloromaleic anhydride, chlorendic anhydride, and tetrachlorophthalic anhydride.

12. The composition of claim 11, wherein the anhydride curing agent (C) comprises hexahydro-4-methylphthalic anhydride.

13. The composition of claim 1, wherein the ancillary curing catalyst (D) comprises at least one member selected from the group consisting of an organometallic salt, a sulfonium salt and an iodonium salt.

14. The composition of claim 13, wherein the ancillary curing catalyst (D) comprises at least one member selected from the group consisting of a metal carboxylate, a metal acetylacetonate, zinc octoate, stannous octoate, triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, diaryliodonium hexafluoroantimonate, and diaryliodonium tetrakis(pentafluorophenyl)borate.

15. The composition of claim 1, further comprising at least one of thermal stabilizers, UV stabilizers, cure modifiers, coupling agents, or refractive index modifiers.

16. The composition of claim 15, comprising at least one of a thermal stabilizer or a UV stabilizer.

17. The composition of claim 16, comprising at least one of a hindered phenol stabilizer or a phosphite stabilizer.

18. The partially cured composition of claim 1.

19. The cured composition of claim 1.

20. A curable epoxy resin composition for encapsulation of a solid state device, which comprises (A) a silicone epoxy resin comprising 1,1,3,3-tetramethyl-1,3-bis[2(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]disiloxane, (B) a hydroxyl-containing silicone resin comprising the hydrolysis product of a mixture of phenyltrichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane, (C) a curing catalyst comprising hexahydro-4-methylphthalic anhydride, and (D) zinc octoate, wherein component (A) is present at a level of greater than about 40% by weight;

component (B) is present at a level in a range of between about 1% by weight and about 20% by weight;

component (C) is present at a level of less than about 25% by weight; and

component (D) is present at a level in a range between about 0.008% by weight and about 10% by weight based on the combined weight of silicone epoxy resin (A), hydroxyl-containing compound (B), curing agent (C), and ancillary curing catalyst (D).

21. The composition of claim 20, further comprising at least one of a thermal stabilizer or a UV stabilizer.

22. The partially cured composition of claim 20.

23. The cured composition of claim 20.