Compositions – Leather or fur treating
Reexamination Certificate
2000-11-15
2002-12-10
Green, Anthony J. (Department: 1755)
Compositions
Leather or fur treating
C008S094140, C106S002000, C106S018320, C106S287110, C106S287130, C106S287150, C528S029000, C528S031000, C528S034000, C528S038000
Reexamination Certificate
active
06491838
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to triamino- and fluoroalkyl-functional organosiloxanes. More particularly, the present invention relates to a composition which comprises at least one aminoalkyl- and fluoroalkyl-functional organosiloxane containing hydroxyl groups and/or alkoxy groups, water, and optionally an alcohol and/or an acid. The present organosiloxanes contain hydroxyl groups and/or alkoxy groups and are formulated in aqueous compositions. The present organosiloxanes are completely or partially hydrolyzed, which is to say that they contain hydroxyl and/or alkoxy groups in the context of the equilibrium being established. The present invention furthermore relates to the preparation of the triamino- and fluoroalkyl-functional organosiloxanes and their use.
2. Description of the Background
Fluoroalkylalkoxysilanes and their corresponding polycondensates are well known, as well as their use as hydrophobicizing and olephobicizing agents, as described in, for example DE 834 002, U.S. Pat. No. 3,012,066, British Patent 935 380, DE 31 00 555, EP 0 382 557, EP 0 493 747, EP 0 587 667 and DE 195 44 763.
Fluoroalkylalkoxysilanes are usually not used in concentrated form, since they are extremely expensive products. Furthermore, fluoroalkylalkoxysilanes are not soluble in water.
In order to prepare sufficiently stable solutions or formulations of fluoroalkyl functional silanes and corresponding cocondensates, organic solvents or emulsifiers have been employed as described in, for example DE 34 47 636, DE 36 13 384, WO 95/23830, WO 95/23804, WO 96/06895, WO 97/23432 and EP 0 846 716.
A disadvantage of solvent- and emulsifier-containing formulations and of organosiloxanes with a high content of alkoxy groups is the fact that such systems are undesirable on ecological and work safety grounds. Efforts have, therefore, increasingly been made to provide water-based systems with the lowest possible content of volatile organic compounds (abbreviation: “VOC”).
Nitrogen-containing and aminoalkyl- and fluoroalkyl-functional organosiloxanes which are substantially free of alkoxy groups are known as water-soluble constituents in otherwise emulsifier- and surfactant-free compositions for rendering surfaces water-, oil- and dirt-repellent as described in DE 15 18 551, EP 0 738 771 and EP 0 846 717).
A relatively high content of aminoalkyl groups must always be used in the water-based systems mentioned in order to ensure a good solubility in water. On the other hand, a high content of aminoalkyl groups is counterproductive, since these groups have hydrophilic properties and, therefore, counteract the efforts to provide a system which, as far as possible, exhibits hydrophobic properties. A need continues to exist for water-soluble aminoalkyl- and fluoroalkyl-functional organosiloxanes, but which retain hydrophobic properties.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide a water-soluble aminoalkyl- and fluoroalkyl-functional organosiloxane which has acceptable hydrophobic properties.
Another object of the present invention is to provide organosiloxanes which have the highest possible number of fluoroalkyl groups in relation to the number of aminoalkyl groups.
Briefly, these objects and other objects of the present invention as hereinafter will become more readily apparent can be attained by an organosiloxane which has at least one triamino group of formula I:
[NH
x
(CH
2
)
a
NH
y
(CH
2
)
b
NH
z
]— (I)
wherein the group is bonded to at least one silicon atom via at least one N-bonded alkylene group having 1 to 4 C atoms, a and b are identical or different and are an integer ranging from 1 to 6, x is 0 or 1 or 2, y is 0 or 1, z is 0 or 1 or 2, with the proviso that (x+y+z)≦4, and at least one Si—C-bonded fluoroalkyl group of formula II:
F
3
C(CF
2
)
r
(CH
2
)
s
— (II)
wherein r is 0 or an integer ranging from 1 to 18 and s is 0 or 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
It has now been found, surprisingly, that a low-viscosity, that is to say preferably a viscosity of <100 mPas, composition, which, as a rule it is clear to slightly opalescent and which is also outstandingly stable to storage for several months on dilution with water and comprises at least one water-soluble, triamino- and fluoroalkyl-functional organosiloxane containing hydroxyl groups and/or alkoxy groups or a mixture of corresponding organosiloxanes, water, and optionally a content of alcohol and/or a content of acid, can be prepared by i) mixing at least one aminoalkylalkoxysilane of formula IIIa:
NH
2
(CH
2
)
2
NH(CH
2
)
2
NH(CH
2
)
3
Si(R′)
j
(OR)
(3−j)
(IIIa)
wherein R and R′ are identical or different and are a linear or branched alkyl group having 1 to 4 C atoms and j is 0 or 1, and/or of formula IIIb:
[NH
2
(CH
2
)
2
]
2
N(CH
2
)
3
Si(R′)
k
(OR)
(3k)
(IIIb)
wherein R and R′ are identical or different and are a linear or branched alkyl group having 1 to 4 C atoms and k is 0 or 1, and/or a “bis-product” or a mixture of “bis-products” of formula IIIc:
[NH
x
(CH
2
)
a
NH
y
(CH
2
)
b
NH
z
].[(CH
2
)
c
Si(R′)
d
(OR)
(3−d)
]
e
(IIIc)
wherein R and R′ are identical or different and are a linear or branched alkyl group having 1 to 4 C atoms, a is an integer from 1 to 6, b is 1, 2, 3, 4, 5 or 6, c is 1, 2, 3 or 4, d is 0 or 1 e is 1, 2, 3, 4 or 5, x is 0 or 1 or 2, y is 0 or 1, z is 0 or 1 or 2, and with the proviso that (x+y+z)≦4, where e in the case where (x+y+z)=0 assumes the numerical value 5, for (x+y+z)=1e=4, for (x+y+z)=2e=3, for (x+y+z)=3e=2, and in the case where (x+y+z)=4e=1; and ii) at least one fluoroalkylalkoxysilane of formula IV:
F
3
C(CF
2
)
r
(CH
2
)
s
Si(R″)
t
(OR)
(3−t)
(IV)
wherein r is 0 or an integer of 1 to 18, s is 0 or 2 and t is 0 or 1, and R and R″ are identical or different and are a linear or branched alkyl group having 1 to 4 C atoms. Optionally, an alcohol, water and/or a water/alcohol mixture can be added to this material and also optionally, a catalyst. These materials are allowed to react or they are reacted. That is, these components may be pre-hydrolyzed or they may be hydrolyzed and are then subjected to cocondensation. The alcohol is completely or partly removed, that is to say suitably down to residual amounts of less than 5% by weight, and then optionally, adjusting the resulting product mixture to a pH of <12 by addition of an inorganic or organic acid. The composition suitably has a pH of <11.
The present composition moreover has the effect of further improved liquid-repellent properties of a correspondingly treated mineral surface—using both hydrophilic and hydrophobic standard test liquids (tests according to the “Teflon® specification test kit” from DuPont). Reference is made to the Examples here.
In particular, at a molar ratio of starting substances which are either an N-[N′-(2-aminoethyl)-2-aminoethyl]-3-aminopropyltrialkoxysilane or an aminoalkylalkoxysilane of formula IIb or formula IIIc, to a fluoroalkylalkoxysilane having formula IV of 1:≦3.5 preferably 1:3 to 1:0.5, particularly preferably 1:3 to 1:1, especially preferably 1:3 to 1:2, a particularly high fluoroalkyl group content can be achieved in the water-soluble cocondensates of the present invention.
The composition of the invention can be diluted with water in all proportions if desired. In the case of completely hydrolyzed systems, as a rule no additional alcohol, as a result of hydrolysis, is formed here. In general, compositions of the invention and dilute systems are outstandingly stable upon storage for more than 6 months.
The invention thus relates to a composition which comprises at least one organosiloxane containing hydroxyl groups and/or alkoxy groups and water, wherein the
Horn Michael
Jenkner Peter
Monkiewicz Jaroslaw
Standke Burkhard
Degussa - AG
Green Anthony J.
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