Flame-retardant UV and UV/moisture curable silicone compositions

• US 6,323,253 B1
• Filed: 09/09/1999
• Issued: 11/27/2001
• Est. Priority Date: 06/01/1998
• Status: Expired due to Fees

• Current Assignee: Henkel Loctite Corporation (Henkel AG & Co KGaA)
• Original Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Inventors: Bennington, Lester D.
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US09/392,527
• Time in Patent Office: 810 Days
• Field of Search: 522/99, 522/39, 522/42, 522/46, 522/48, 522/64, 522/66, 522/71, 522/77, 522/83, 522/13, 522/16, 522/63, 522/43, 522/40, 522/41, 522/53, 524/437, 528/33
• US Class Current: 522/16
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08F 299/08 from polysiloxanes
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08K 5/0066 Flame-proofing or flame-retarding additives
• CPC Class Codes: C08K 5/5425 containing at least one C=C bond
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 2666/54 Inorganic substances
• 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

Abstract

The present invention is directed to silicone formulations which are capable of being rapidly cured to tough elastomeric materials through exposure to UV radiation, and optionally through exposure to moisture as well. The cured products demonstrate high resistance to flammability and combustibility. The flame-retardant components is a combination of hydrated alumina and an organo ligand complex of a transition metal or an organosiloxane ligand complex of a transition metal or a combination thereof.

Claims

1. A silicone composition curable by UV irradiation and exposure to moisture to an elastomer, which is resistant to flammability, comprising:

(a) a reactive silicone resin component comprising a reactive polyorganosiloxane within the formula;

wherein R¹, R² and R³ may be the same or different and are organo groups selected from the group consisting of alkyl, halo alkyls, substituted or unsubstituted aryl, alkoxy, substituted or unsubstituted aryloxy, vinyl, methacryloxypropyl, mercaptopropyl, hydrogen and benzoin;

R⁴ is H or C_1-5 alkyl;

R⁵ is C_1-8 alkylene; and

n is at least 80

(b) optionally, an inorganic filler component;

(c) a photoinitiator component;

(d) a flame-retardant component in an amount effective to enhance the resistance of said composition to flammability, wherein the flame-retardant component is the combination of hydrated alumina and a member selected from the group consisting of organo ligand complexes of transition metals, organosiloxane ligand complexes of transition metals, and combinations thereof; and

(e) a moisture cure catalyst.

2. The composition according to claim 1, further comprising a triazole component.

3. The composition according to claim 2, wherein the triazole component is a member selected from the group consisting of benzotriazole and derivatives thereof.

4. The composition according to claim 1, further comprising a reactive diluent component.

5. The composition according to claim 4, wherein the reactive diluent is (meth)acrylate-terminated-dimethoxypropyldimethyl siloxane.

6. The composition according to claim 4, wherein the reactive diluent is within the formula, H₂C═

CGCO₂R⁶, wherein G may be hydrogen, halogen or alkyl of 1 to about 4 carbon atoms, and R⁶ may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl or aryl groups of 1 to about 16 carbon atoms, any of which may be optionally substituted or interrupted as the case may be with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, amine, amide, sulfur, sulonate, and sulfone.

7. The composition according to claim 4, wherein the reactive diluent is a (meth)acrylate selected from the group consisting of polyethylene glycol di(meth)acrylates, bisphenol-A di(meth)acrylates, tetrahydrofuran (meth)acrylates and di(meth)acrylates, citronellyl acrylate and citronellyl methacrylate, hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, ethoxylated trimethylol propane triacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, isobornyl acrylate, isobornyl methacrylate, and an acrylate ester corresponding to structure III as shown below:

wherein R⁷ may be selected from hydrogen, alkyl of 1 to about 4 carbon atoms, hydroxyalkyl of 1 to about 4 carbon atoms or

R⁸ may be selected from hydrogen, halogen, and alkyl of 1 to about 4 carbon atoms;

R⁹ may be selected from hydrogen, hydroxy and

m is an integer equal to at least 1, e.g., from 1 to about 8 or higher, for instance, from 1 to about 4;

n is an integer equal to at least 1, e.g., 1 to about 20 or more; and

v is 0 or 1.

8. The composition according to claim 4, wherein the reactive diluent is isobornyl acrylate.

9. The composition according to claim 1, wherein the inorganic filler component is a fumed hydrophobic silica filler.

10. The composition according to claim 9, wherein the fumed silica filler is a member selected from the group consisting of dimethyldichlorosilane-treated silica, hexamethyldisilazane-treated silica, and combinations thereof.

11. The composition according to claim 9, wherein the fumed silica filler is present at a level in range of about 4 to about 10 weight percent.

12. The composition according to claim 1, wherein the transition metals are selected from the group consisting of platinum, ruthenium, rhodium, and palladium.

13. The composition according to claim 1, wherein the photoinitiator component is a member selected from the group consisting of benzoin and substituted benzoins, Michler'"'"'s ketone, benzophenone and substituted benzophenones, acetophenone and substituted acetophenones, xanthone and substituted xanthones, and combinations thereof.

14. The composition according to claim 1, wherein the photoinitiator component is a member selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone, benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, bis(2,6-dimethoxybenzoyl-2,4-,4-trimethyl pentyl) phosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propane, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, visible light [blue] photoinitiators, dl-camphorquinone, bis(η

⁵-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium, and combinations thereof.

15. The composition according to claim 1, wherein the moisture cure catalyst is selected from the group consisting of compounds of titanium, tin, zirconium and combinations thereof.

16. The composition according to claim 1, further comprising an adhesion promotor.

17. The composition according to claim 16, wherein the adhesion promotor is a member selected from the group consisting of (meth)acryloxypropyltrimethoxysilane, trialkyl- or triallyl-isocyanurate, glycidoxypropyl trimethoxysilane, vinyl trimethoxysilane and combinations thereof.

18. Reaction products of the composition according to claim 1.

19. A process for preparing a composition in accordance with claim 1, the steps of which comprise:

providing and mixing together (a) a reactive silicone resin component comprising a reactive polyorganosiloxane having at least one functional carboxylate group selected from the group consisting of (meth)acrylate, maleate, cinnamate and combinations thereof;

(b) an optional, inorganic filler component;

(c) a photoinitiator component;

(d) a flame-retardant component in an amount effective to enhance the resistance of said composition to flammability, wherein the flame-retardant component is the combination of hydrated alumina and a member selected from the group consisting of organo ligand complexes of transition metals, organosiloxane ligand complexes of transition metals, and combinations thereof;

(e) a moisture cure catalyst; and

optionally (f) a triazole component; and

optionally (g) a reactive diluent component, and optionally (h) an adhesion promoter.

20. The composition according to claim 19, further comprising an adhesion promotor.