초록

The present invention provides for a room temperature cured silicone thermoplastic resin sealant composition with reduced gas permeability useful in the manufacture of glazing such as windows and doors.

대표청구항 ▼

What is claimed is: 1. A curable sealant composition comprising: (a) diorganopolysiloxane exhibiting permeability to gas, wherein the diorganopolysiloxane ranges in amount of from about 50 weight percent to about 99 weight percent of the total composition; (b) at least one polymer having a permeabi

What is claimed is: 1. A curable sealant composition comprising: (a) diorganopolysiloxane exhibiting permeability to gas, wherein the diorganopolysiloxane ranges in amount of from about 50 weight percent to about 99 weight percent of the total composition; (b) at least one polymer having a permeability to gas that is less than the permeability of diorganopolysiloxane polymer (a); (c) cross-linker; and, (d) catalyst for the cross-linker reaction wherein the cross-linkers (c) is an alkylsilicate having the formula: (R14O))(R15O)(R16O)(R17O)Si  where R14, R15, R16 and R17 are chosen independently from monovalent C1 to C60 hydrocarbon radicals, wherein said curable sealant composition, once cured has a permeability to argon of no more than about 800 barrer units at 25 degrees C. and under 100 psi pressure, said composition containing at least one adhesion promoter in an amount of from about 0.5 weight percent to about 20 weight percent of the total composition and further comprising a clay filler, wherein the clay is selected from the group consisting of montmorillonite, sodium montmorilloriite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite, and kaolinite, and mixtures thereof. 2. The sealant composition of claim 1 wherein polymer (b) is selected from the group consisting of low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene (PP), polyisobutylene (PIB), polyvinyl acetate(PVAc), polyvinyl alcohol (PvoH), polystyrene, polycarbonate, polyester, such as, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene napthalate (PEN), glycol-modified polyethylene terephthalate (PETG); polyvinylchloride (PVC), polyvinylidene chloride, polyvinylidene fluoride, thermoplastic polyurethane (TPU), acrylonitrile butadiene styrene (ABS), polymethylmethacrylate (PMMA), polyvinyl fluoride (PVF), Polyamides (nylons), polymethylpentene, polyimide (PI), polyetherimide (PEI), polether ether ketone (PEEK), polysulfone, polyether sulfone, ethylene chlorotrifluoroethylene, polytetrafluoroethylene (PTFE), cellulose acetate, cellulose acetate butyrate, plasticized polyvinyl chloride, ionomers (Surtyn), polyphenylene sulfide (PPS), styrene-maleic anhydride, modified polyphenylene oxide (PPO), ethylene-propylene rubber (EPDM), polybutadiene, polychloroprene, polyisoprene, polyurethane (TPU), styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEEBS), polymethyiphenyl siloxane (PMPS), and mixture thereof. 3. The sealant composition of claim 2 wherein polymer (b) is selected from the group consisting of low density polyethylene (LDPE), very low density polyethylene (VLDPE), liner low density polyethylene (LLDPE), high density polyethylene (HDPE), and mixtures thereof. 4. The sealant composition of claim 1 containing a non-ionic surfactant. 5. The sealant composition of claim 1 wherein the catalyst is a tin catalyst. 6. The sealant composition of claim 5 wherein the tin catalyst is selected from the group consisting of dibutyltindilaurate, dibutyltindiacetate, dibutyltindimethoxide, tinoctoate, isobutyltintriceroate, dibutyltinoxide, solubilized dibutyl tin oxide, dibutyltin bis-diisooctylphthalate, bis-tripropoxysilyl dioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyl tin tris-uberate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin di-neodecanoate, triethyltin tartarate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltintri-2-ethylhexylhexoate, tinbutyrate, diorganotin bis β-diketonates and mixtures thereof. 7. The sealant composition of claim 1 wherein the adhesion promoter is selected from the group consisting of N-2-aminoethyl-3-aminopropyltrimethoxysilane, 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, γ-aminopropyltriethoxysilane, γ-aniinopropyltrimethoxysilane, aminopropyltrimethoxysilane, bis-γ-trimethoxysilypropyl)amine, N-phenyl-γ-aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)propyltrimethoxysilane, β-(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, β-cyanoethyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-ethyl-3-trimethoxysilyl-2-methylpropanamine and mixtures thereof. 8. The sealant composition of claim 1, wherein the a diorganopolysiloxane polymer, component (a), ranges from in amount from about 60 weight percent to about 95 weight percent of the total composition. 9. The sealant composition of claim 1, wherein the polymer, component (b), ranges from in amount from about 1 weight percent to about 50 weight percent of the total composition. 10. The sealant composition of claim 1, wherein the polymer, component (b), ranges from in amount from about 5 weight percent to about 40 weight percent of the total composition. 11. The sealant composition of claim 1 further comprising at least one additional filler is selected from the group consisting of ground calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, calcium carbonate treated with compounds stearate or stearic acid; fitmed silica, precipitated silica, silica gels, hydrophobized silicas, hydrophilic silica gels, crushed quartz, ground quartz, alumina, aluminum hydroxide, titanium hydroxide, clay, kaolin, bentonite montmorillonite, diatomaceous earth, iron oxide, carbon black and graphite, talc, mica, and mixtures thereof. 12. The sealant composition of claim 4 wherein the non-ionic surfactant is selected from the group consisting of polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkyiphenol ethoxylates, copolymers of ethylene oxide and propylene oxide and copolymers of silicones and polyethers, copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof in an amount ranging from about 0.1 weight percent to about 10 weight percent. 13. The sealant composition of claim 12 wherein the non-ionic surfactant selected from the group consisting of copolymers of ethylene oxide and propylene oxide, copolymers of silicones and polyethers, copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof. 14. The sealant composition of claim 1 wherein the amount of the cross-linker, component (c), ranges in amount from about 0.1 weight percent to about 10 weight percent of the total composition. 15. The sealant composition of claim 1 wherein the amount of catalyst, component (d), ranges in amount from about 0.005 weight percent to about 1 weight percent of the total composition. 16. The sealant composition of claim 1 wherein the amount of clay, ranges in amount from 0 to about 80 weight percent of the total composition. 17. The sealant composition of claim 1 wherein the clay is modified with an amine compound or the corresponding aninionium ion having the structure R3R4R5N, wherein R3, R4, and R5 are C1 to C30 ailcyls or alkenes, and mixtures thereof. 18. The sealant composition of claim 17 wherein R3, R4, and R5 are C1 to C20 alkyls or alkenes, and mixtures thereof. 19. The sealant composition of claim 18 wherein clay is modified with a tertiary amine wherein R3 a C14 to C20 alkyl or alkene, and mixtures thereof. 20. The sealant composition of claim 19 wherein R4 and or R5 is a C14 to C20 alkyl or alkene, and mixtures thereof. 21. The sealant composition of claim 1 wherein the clay is modified with an amine or the corresponding ammonium ion having the structure R6R7R8N, wherein at least one R6, R7, and R8 is C1 to C30 alkoxy silanes and the remaining are C1 to C30 alkyls or alkenes. 22. The sealant composition of claim 21 wherein at least one of R6, R7 and R8 is a C1 to C20 alkoxy silanes and the remaining are C1 to C20 alkyls or alkenes. 23. The sealant composition of claim 1 wherein the clay is modified with ammoniuni chloride, or the corresponding primary alkylammonium, secondary alkylammonium, tertiary alkylammonium, or quaternary alkylanmionium cationic surfactants, phosphonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides, and mixtures thereof. 24. The sealant composition of claim 1 wherein the clay is present in an amount from about 0.1 to about 50 weight percent of said composition. 25. The curable sealant composition of claim 1 having a permeability to argon of no more than about 400 barrer units at 25 degrees C. and under 100 psi pressure. 26. A curable sealant composition comprising: (a) diorganopolysiloxane exhibiting permeability to gas, wherein the diorganopolysiloxane ranges in amount of from about 50 weight percent to about 99 weight percent of the total composition; (b) at least one polymer having a permeability to gas that is less than the permeability of diorganopolysiloxane polymer (a); (c) cross-linker; and (d) catalyst for the cross-linker reaction wherein the cross-linkers (c) is an alkylsilicate having the formula: (R14O)(R15O)(R16O))(R17O)Si  where R14, R15, R16 and R17 are chosen independently from monovalent C1 to C60 hydrocarbon radicals wherein polymer (b) is selected from the group consisting of low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and mixture thereof. 27. The sealant composition of claim 26 wherein polymer (b) is linear low density polyethylene (LLDPE). 28. A curable sealant composition comprising: (a) dioreanopolysiloxane exhibiting permeability to gas, wherein the diorganopolysiloxane polymer, component (a), is a silanol terminated diorganopolysiloxane; (b) at least one polymer having a permeability to gas that is less than the permeability of diorganoyolvsiloxane polymer (a); (c) cross-linker; and, (d) catalyst for the cross-linker reaction wherein the cross-linkers (c) is an alkylsilicate having the formula: (R14O)(R15O)(R16O)(R17O)Si  where R14, R15, R16 and R17 are chosen independently from monovalent C1 to C60 hydrocarbon radicals, wherein said curable sealant composition, once cured has a permeability to argon of no more than about 800 barrer units at 25 degrees C. and under 100 psi pressure, wherein polymer (b) is selected from the group consisting of low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and mixture thereof. 29. The sealant composition of claim 28 wherein polymer (b) is linear low density polyethylene (LLDPE). 30. The sealant composition of claim 28 containing at least one adhesion promoter in an amount of from about 0.5 weight percent to about 20 weight percent of the total composition and an optional component selected from the group consisting of filler and non-ionic surfactant. 31. The sealant composition of claim 28 wherein the catalyst is a tin catalyst. 32. The sealant composition of claim 31 wherein the tin catalyst is selected from the group consisting of dibutyltindilaurate, dibutyltindiacetate, dibutyltindimethoxide, tinoctoate, isobutyltintriceroate, dibutyltinoxide, solubilized dibutyl tin oxide, dibutyltin bis-diisooctylphthalate, bis-tripropoxysilyl dioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyl tin tris-uberate, isobutyltin riceroate, dimethyltin dibutyrate, dimethyltin di-neodecanoate, triethyltin tartarate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltintri-2-ethylhexylhexoate, tinbutyrate, diorganotin bis β-diketonates and mixtures thereof. 33. The sealant composition of claim 30 wherein the adhesion promoter is selected from the group consisting of N-2-aminoethyl-3-aminopropyltrimethoxysilane, 1,3,5-tris(triniethoxysilylpropyl)isocyanurate, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, bis-γ-trimethoxysilypropyl)amine, N-phenyl-γ-aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, γ-aminopropylniethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, methaciyloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)propyltrimethoxysilane, β-(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, β-cyanoethyihimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-ethyl-3-trimethoxysilyl-2-methylpropanamine and mixtures thereof. 34. The sealant composition of claim 28 wherein the a diorganopolysiloxane polymer, component (a), ranges in amount from about 50 weight percent to about 99 weight percent of the total composition. 35. The sealant composition of claim 28, wherein the a diorganopolysiloxane polymer, component (a), ranges in amount from about 60 weight percent to about 95 weight percent of the total composition. 36. The sealant composition of claim 28, wherein the polymer, component (b), ranges in amount from about 1 weight percent to about 50 weight percent of the total composition. 37. The sealant composition of claim 28, wherein the polymer, component (b), ranges in amount from about 5 weight percent to about 40 weight percent of the total composition. 38. The sealant composition of claim 30 wherein at least one filler is selected from the group consisting of clays, nano-clays, organo-clays, ground calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, calcium carbonate treated with compounds stearate or stearic acid; fumed silica, precipitated silica, silica gels, hydrophobized silicas, hydrophilic silica gels, crushed quartz, ground quartz, alumina, aluminum hydroxide, titanium hydroxide, clay, kaolin, bentonite montmorillonite, diatomaceous earth, iron oxide, carbon black and graphite, talc, mica, and mixtures thereof. 39. The sealant composition of claim 30 wherein the non-ionic surfactant is selected from the group consisting of polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers of ethylene oxide and propylene oxide and copolymers of silicones and polyethers, copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof in an amount ranging from about 0.1 weight percent to about 10 weight percent. 40. The sealant composition of claim 39 wherein the non-ionic surfactant selected from the group consisting of copolymers of ethylene oxide and propylene oxide, copolymers of silicones and polyethers, copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof. 41. The sealant composition of claim 28 wherein the amount of the cross-linker, component (c), ranges in amount from about 0.1 weight percent to about 10 weight percent of the total composition. 42. The sealant composition of claim 28 wherein the amount of catalyst, component (d), ranges in amount from about 0.005 weight percent to about 1 weight percent of the total composition. 43. The sealant composition of claim 30 wherein the amount of filler, ranges in amount from 0 to about 80 weight percent of the total composition. 44. The curable sealant composition of claim 28 having a permeability to argon of no more than about 400 barrer units at 25 degrees C. and under 100 psi pressure. 45. A curable sealant composition comprising: (a) diorganonolysiloxane exhibiting permeability to gas, wherein the diorganopolysiloxane polymer, component (a), is a silanol terminated diorganonolvsiloxane; (b) at least one polymer having a permeability to gas that is less than the permeability of diorganovolysiloxane polymer (a); (c) cross-linker; and, (d) catalyst for the cross-linker reaction wherein the cross-linkers (c) is an alkylsilicate having the formula: (R14O))(R15O)(R16O)(R17O)Si  where R14, R15, R16 and R17 are chosen independently from monovalent C1 to C60 hydrocarbon radicals, wherein said curable sealant composition, once cured has a permeability to argon of no more than about 800 barrer units at 25 degrees C. and under 100 psi pressure, said composition containing at least one adhesion Promoter in an amount of from about 0.5 weight percent to about 20 weight percent of the total composition and further comprising a clay, wherein the clay is selected from the group consisting of montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite, and kaolinite, and mixtures thereof. 46. The sealant composition of claim 45 wherein the clay is modified with an amine compound or the corresponding ammonium ion having the structure R3 R4R5N, wherein R3, R4, and R3 are C1 to C30 alkyls or alkenes, and mixtures thereof. 47. The sealant composition of claim 46 wherein R3, R4, and R5 are C1 to C20 alkyls or alkenes, and mixtures thereof. 48. The sealant composition of claim 47 wherein clay is modified with a tertiary amine wherein R3 is a C14 to C20 alkyl or alkene, and mixtures thereof. 49. The sealant composition of claim 48 wherein R4 and or R5 is a C14 to C20 alkyl or alkene, and mixtures thereof. 50. The sealant composition of claim 45 wherein the clay is modified with an amine or the corresponding animonium ion having the structure R6R7R8N, wherein at least one R6, R7, and R8 is C1 to C30 alkoxy silanes and the remaining are C1 to C30 alkyls or alkenes. 51. The sealant composition of claim 50 wherein at least one of R6, R7 and R8 is a C1 to C20 alkoxy silanes and the remaining are C1 to C20 alkyls or alkenes. 52. The sealant composition of claim 45 wherein the clay is modified with ammonium chloride, or the corresponding primaiy alkylammoniuxn, secondary alkylammonium, tertiary alkylanimonium, or quaternaly alkylammonium cationic surfactants, phosphonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides, and mixtures thereof. 53. The sealant composition of claim 45 wherein the clay is present in an amount from about 0.1 to about 50 weight percent of said composition.