Aqueous emulsions of functional alkoxysilanes and condensed oligomers thereof, their preparation and use for surface treatment

1. An aqueous oil-in-water emulsion, comprising:

from 1 to 70% by weight, based on the total weight of the emulsion, of a condensed oligomer of a functional alkoxysilane; an organoalkoxysiloxane; a combination thereof; or a mixture of a functional alkoxysilane and at least one of a condensed oligomer thereof and an organoalkoxysiloxane;

an emulsifier; and

water,

wherein

the emulsion has a pH of from 5 to 9;

the emulsion has a disperse phase having a mean droplet size of from 0.1 to 0.3 μm;

the width of the droplet size distribution, expressed as

D

⁢

⁢

90

-

D

⁢

⁢

10

D

⁢

⁢

50

,

is from 0.6 to 1.2;

said D50 has a value of from 0.1 to 0.3 um, wherein the D50 represents the diameter of that droplet is larger than 50% by weight of all droplets and smaller than 50% by weight of all droplets;

said emulsifier comprises a silicon-functional surfactant represented by

where

each R 1 and R 2 is identical or different and is a straight-chain or branched C 1 -C 20 -alkyl group or a phenyl group,

R 3 is an C 1 -C 10 -alkyl group,

p is an integer of from 0 to 3, and

Ts is a surfactant radical represented by

where

n is an integer of from 3 to 15,

m is an integer of from 3 to 50,

l is an integer of from 3 to 25,

R 4 is H, a C 1 -C 20 -alky group, a C 2 -C 36 -alkenyl group, a C 5 -C 8 -cycloalkyl group, or a C 7 -C 36 -aralkyl group;

said emulsifier optionally further comprises is at least one member selected from the group consisting of

an alkylsulfate having a C 8 -C 18 -alkyl radical,

an alkyl ether sulfate having a C 8 -C 18 -alkyl radical as hydrophobic radical and from 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units,

an alkaryl ether sulfate having a C 8 -C 18 -alkyl radical as hydrophobic radical and from 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units,

an alkylsulfonate having a C 8 -C 18 -alkyl radical,

an alkarylsulfonate having a C 8 -C 18 -alkyl radical,

a monoester of sulfosuccinic acid with a monohydric alcohol having from 5 to 15 carbon atoms,

a monoester of sulfosuccinic acid with an alkylphenol having from 5 to 15 carbon atoms,

an alkali metal salt of a carboxylic acid having from 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical,

an ammonium salt of a carboxylic acid having from 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical,

an alkylphosphate having from 8 to 20 carbon atoms in the organic radical,

an alkarylphosphate having from 8 to 20 carbon atoms in the organic radical,

an alkyl ether phosphate having from 8 to 20 carbon atoms in the alkyl radical and from 1 to 40 EO units,

an alkaryl ether phosphate having from 8 to 20 carbon atoms in the alkaryl radical and from 1 to 40 EO units,

an addition product of an alkylamine having C 8 -C 22 -alkyl radicals with ethylene oxide or propylene oxide, and

an alkyl polyglycoside having a linear or branched, saturated or unsaturated C 8 -C 24 -alkyl radical and an oligoglycoside radical having from 1 to 10 hexose or pentose units; and

said condensed oligomer of the functional alkoxysilane is at least one compound represented by

where

each R 1 group is, independently, a C 3 -C 18 -alkyl group, a halogen- or amino-substituted C 3 -C 18 -alkyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane,

each R 2 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms, and

n represents the degree of oligomerization and is an integer of from 2 to 20, or

is at least one compound represented by

where

m and n are identical or different and are each from 0 to 20, with the proviso that (n+m)≧2,

each R and R 2 group is, independently, hydrogen, a C 1 -C 18 -alkyl group, a halogen- or amino-substituted C 1 -C 18 -alkyl group, a phenyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane, and

each R 1 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms.

2. The aqueous oil-in-water emulsion according to claim 1 , wherein said at least one emulsifier is present in said emulsion in an amount of from 0.02 to 2% by weight, relative to the total weight of the emulsion.

3. The aqueous oil-in-water emulsion according to claim 1 , wherein said at least one emulsifier is present in said emulsion in an amount of from 1.6 to 2% by weight, relative to the total weight of the emulsion.

4. The emulsion as claimed in claim 1 , wherein the emulsion has a disperse phase having a mean droplet size of from 0.1 to 0.27 μm.

5. The emulsion as claimed in claim 1 , wherein the emulsion has a disperse phase having a mean droplet size of from 0.1 to 0.25 μm.

6. The emulsion as claimed in claim 1 , wherein said condensed oligomer of a functional alkoxysilane is present in an amount of from 1 to 100% by weight, based on the total weight of the oil phase.

7. The emulsion as claimed in claim 1 , wherein said functional alkoxysilane is at least one alkylalkoxysilane represented by

R 1 —Si(OR 2 ) 3 or

(R 1 ) 2 —Si(OR 2 ) 2 ,

where each R 1 radical is, independently, a C 3 -C 18 -alkyl group, a halogen- or amino-substituted C 3 -C 18 -alkyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane, and

each R 2 radical is an alkyl radical having from 1 to 6 carbon atoms.

8. The emulsion as claimed in claim 7 , wherein R 2 is an alkyl radical having 1 or 2 carbon atoms.

9. The emulsion as claimed in claim 1 , wherein said condensed oligomer of a functional alkoxysilane is at least one compound represented by

where

each R 1 group is, independently, a C 3 -C 18 -alkyl group, a halogen- or amino-substituted C 3 -C 18 -alkyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane,

each R 2 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms, and

n represents the degree of oligomerization and is an integer of from 2 to 20.

10. The emulsion as claimed in claim 9 , wherein the groups R 2 are identical or different and are each a hydrogen atom or an alkyl radical having 1 or 2 carbon atoms.

11. The emulsion as claimed in claim 1 , wherein the condensed oligomer is at least one compound represented by

where

m and n are identical or different and are each from 0 to 20, with the proviso that (n+m)≧2,

each R and R 2 group is, independently, hydrogen, a C 1 -C 18 -alkyl group, a halogen- or amino-substituted C 1 -C 18 -alkyl group, a phenyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane, and

each R 1 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms.

12. The emulsion as claimed in claim 11 , wherein at least one emulsifier is present in an amount of from 0.02 to 2% by weight, based on the total weight of the emulsion.

13. The emulsion as claimed in claim 11 , wherein the groups R 1 are identical or different and are each a hydrogen atom or an alkyl radical having 1 or 2 carbon atoms.

14. The emulsion as claimed in claim 1 , which further comprises an auxiliary selected from the group consisting of an inorganic acid, an organic acid, a buffer, a fungicide, a bactericide, an algaecide, a microbicide, a fragrance, a corrosion inhibitor, a preservative, a water repellant, a viscosity modifier, and a catalyst.

15. An aqueous oil-in-water emulsion, comprising:

from 1 to 70% by weight, based on the total weight of the emulsion, of a condensed oligomer of a functional alkoxysilane; an organoalkoxysiloxane; a combination thereof; or a mixture of a functional alkoxysilane and at least one of a condensed oligomer thereof and an organoalkoxysiloxane;

an emulsifier; and

water,

wherein

the emulsion has a pH of from 5 to 9;

the emulsion has a disperse phase having a mean droplet size of from 0.1 to 0.3 μm;

the width of the droplet size distribution, expressed as

D

⁢

⁢

90

-

D

⁢

⁢

10

D

⁢

⁢

50

,

is from 0.6 to 1.2;

said D50 has a value of from 0.1 to 0.3 um, wherein the D50 represents the diameter of that droplet is larger than 50% by weight of all droplets and smaller than 50% by weight of all droplets;

said emulsifier comprises an alkylsulfate having a C 8 -C 18 -alkyl radical and a silicon-functional surfactant represented by

where each R represents a methyl group and Ts represents

where n is an integer of 1 to 30 and R 5 is an isononyl group;

said emulsifier optionally further comprises at least one member selected from the group consisting of

an alkylsulfate having a C 8 -C 18 -alkyl radical,

an alkyl ether sulfate having a C 8 -C 18 -alkyl radical as hydrophobic radical and from 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units,

an alkaryl ether sulfate having a C 8 -C 18 -alkyl radical as hydrophobic radical and from 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units,

an alkylsulfonate having a C 8 -C 18 -alkyl radical,

an alkarylsulfonate having a C 8 -C 18 -alkyl radical,

a monoester of sulfosuccinic acid with a monohydric alcohol having from 5 to 15 carbon atoms,

a monoester of sulfosuccinic acid with an alkylphenol having from 5 to 15 carbon atoms,

an alkali metal salt of a carboxylic acid having from 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical,

an ammonium salt of a carboxylic acid having from 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical,

an alkylphosphate having from 8 to 20 carbon atoms in the organic radical,

an alkarylphosphate having from 8 to 20 carbon atoms in the organic radical,

an alkyl ether phosphate having from 8 to 20 carbon atoms in the alkyl radical and from 1 to 40 EO units,

an alkaryl ether phosphate having from 8 to 20 carbon atoms in the alkaryl radical and from 1 to 40 EO units,

an addition product of an alkylamine having C 8 -C 22 -alkyl radicals with ethylene oxide or propylene oxide, and

an alkyl polyglycoside having a linear or branched, saturated or unsaturated C 8 -C 24 -alkyl radical and an oligoglycoside radical having from 1 to 10 hexose or pentose units; and

said condensed oligomer of the functional alkoxysilane is at least one compound represented by

where

each R 1 group is, independently, a C 3 -C 18 -alkyl group, a halogen- or amino-substituted C 3 -C 18 -alkyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane,

each R 2 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms, and

n represents the degree of oligomerization and is an integer of from 2 to 20, or

is at least one compound represented by

where

m and n are identical or different and are each from 0 to 20, with the proviso that (n+m)≧2,

each R and R 2 group is, independently, hydrogen, a C 1 -C 18 -alkyl group, a halogen- or amino-substituted C 1 -C 18 -alkyl group, a phenyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane, and

each R 1 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms.

16. The emulsion as claimed in claim 15 , wherein said condensed oligomer of a functional alkoxysilane is at least one compound represented by

where

each R 1 group is, independently, a C 3 -C 18 -alkyl group, a halogen- or amino-substituted C 3 -C 18 -alkyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane,

each R 2 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms, and

n represents the degree of oligomerization and is an integer of from 2 to 20.

17. The emulsion as claimed in claim 15 , wherein the condensed oligomer is at least one compound represented by

where

m and n are identical or different and are each from 0 to 20, with the proviso that (n+m)≧2,

each R and R 2 group is, independently, hydrogen, a C 1 -C 18 -alkyl group, a halogen- or amino-substituted C 1 -C 18 -alkyl group, a phenyl group, a vinyl group, a mercaptoalkyl group, a methacryloxyalkyl group, an acryloxyalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a diethyleneaminoalkyl group, a triethyleneaminoalkyl group, a glycidyloxyalkyl group, a bisalkoxysilylalkyl group, a monosulfane or a polysulfane, and

each R 1 group is, independently, a hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms.

18. The emulsion as claimed in claim 15 , wherein the emulsion has a disperse phase having a mean droplet size of from 0.1 to 0.27 μm.

19. The emulsion as claimed in claim 15 , wherein the emulsion has a disperse phase having a mean droplet size of from 0.1 to 0.25 μm.