Stain resistant compositions

Details Stain resistant compositions Stain resistant compositions

2000-10-13

2001-08-07

Hoke, Veronica P. (Department: 1714)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Processes of preparing a desired or intentional composition...

C252S008610, C252S008620, C427S393600, C428S422000, C524S139000, C524S144000, C524S117000

Reexamination Certificate

active

06271289

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to new aqueous fluorine-containing coatings that provide enhanced stain resistance to stone, masonry, and other surfaces
BACKGROUND OF THE INVENTION
Stone, masonry and various other substrates with surface porosity are used decoratively in the indoor and exterior environment. However, such surfaces are easily stained, for instance by oils, hydraulic fluids, and oily and aqueous foodstuffs, including oils, coffee, ketchup, salad dressings, mustard, red wine, other beverages, and fruit preserves. Many of the prior art treatments, such as clear sealants based on polyurethanes or epoxies, disadvantageously alter the appearance of the substrate. Such sealants can also trap moisture within the treated substrate, promoting spalling.
U.S. Pat. No. 4,957,948, of Terry and McIntosh describes biocidal protective coatings for heat exchangers which consist of an organic water-resistant polymer with an associated mixture of mono-alkyl and bis-alkyl phosphates. The heat exchanger coatings of Terry and McIntosh contain perfluoroalkyl methacrylate copolymers and up to 10% and preferably 1-5% by weight of an alkyl phosphoric acid or its derivative. The coatings are applied to heat exchanger coils, such as coils of aluminum or copper, to provide durable biocidal adherent coatings. In a related patent, U.S. Pat. No. 4,935,232, McIntosh describes microbiocidal phosphate additives which contain at least one free hydroxyl group. McIntosh notes in U.S. Pat. No. 4,935,232 that if all the hydroxyl groups of the microbiocidal phosphate are replaced by alkyl or other organic groups, the phosphate will no longer exhibit microbiocidal activity. There is no teaching of use of their compositions for stain resistance on hard porous surfaces.
It is desirable to improve the degree of stain resistance conferred on such substrates and also not promote spalling. The present invention provides such treatment for surfaces subject to staining.
SUMMARY OF THE INVENTION
This invention comprises a composition comprising a mixture of a fluoroalkyl phosphate and a fluoroacrylate polymer wherein the fluoroalkyl phosphate is of Formula 1A or 1B
wherein:
R
f
is selected from the group consisting of
F(CF
2
CF
2
)
d
(CH
2
)
a
—,
F(CF
2
CF
2
)
d
CH
2
CH
2
(OCH
2
CH
2
)
b
—,
F(CF
2
CF
2
)
d
—,
F(CF
2
CF
2
)
d
CH═CH(CH
2
)
c
—, and
C
8
F
17
SO
2
N(R)CH
2
CH
2
—,
R
f
′ is a fluoroaliphatic group having a linear or branched perfluorocarbon chain having from 2 to 20 carbon atoms,
x is from about 1 to about 2,
j is 1 or 0, or a mixture thereof,
d is 1 to about 8, or a mixture thereof,
X is hydrogen or M,
M is an ammonium ion, an alkali metal ion, or an alkanolammonium ion,
R
3
is an alkylene group having from 1 to about 8 carbon atoms,
Z is —O—, —S—, or —NH—,
a is from about 2 to about 10,
b is from about 3 to about 20,
c is from about 2 to about 20, and
R is H or an aliphatic group containing 1 to about 4 carbon atoms;
and the fluoroacrylate polymer has the five repeating units 1 to 5 as shown in Formula 2, said repeating units occurring in random distribution,
wherein:
each R
2
is independently hydrogen or an aliphatic group having from 1 to about 4 carbon atoms,
each R
3
is independently an alkylene group having from 1 to about 8 carbon atoms,
each R4 is independently an aliphatic group having from 1 to about 20 carbon atoms,
each R
5
is independently a short chain alkylene group having from 1 to bout 4 carbon atoms,
R
f
′ is a fluoroaliphatic group having a linear or branched perfluorocarbon chain having from 2 to 20 carbon atoms,
R
OA
is a group of the formula
—(C
2
H
4
O)
e
(C
3
H
6
O)
g
(C
4
H
8
O)
h
R
1
wherein R
1
is hydrogen or alkyl having 1 to about 4 carbon atoms, e is 0 to about 20, and g and h are each individually zero or a positive integer, provided that the value of (e+g+h) is equal to or greater than 1,
each Z is independently —O—, —S—, or —NH—,
Y is —N(R)SO
2
— wherein R is H or an aliphatic group containing 1 to about 4 carbon atoms,
M is an ammonium ion, an alkali metal ion or an alkanolammonium ion,
s and t are each independently 0 or 1, and
m, n, p, q, and r are each integers such that m and n are each independently at least 1 and p, q, and r are each independently zero or a positive integer.
This invention further comprises a method of improving stain resistance of substrate surfaces comprising application to the surface of a composition as described above, and a substrate having a surface to which such a composition has been applied.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises new fluorinated aqueous compositions that, when applied to substrate surfaces, provide improved stain resistance, and the process for treating such substrates with the compositions of this invention. The present invention also comprises substrate surfaces treated with the stain resist compositions
The term “substrate surfaces”, as used herein, includes porous mineral surfaces. Specific examples of such substrates include unglazed concrete, brick, tile, stone, grout, mortar, composite materials such as terrazzo, gypsum board, statuary, monuments, wood, and leather. These are used in the construction of buildings, roads, parking ramps, driveways, floorings, fireplaces, fireplace hearths, counter tops, and other decorative uses in interior and exterior applications.
While not wishing to be bound by theory, it is believed that the mechanism for the generation of the advantageous properties of the composition of this invention is the simultaneous provision of a chemically bound surface oil- and water-repellent layer from the fluorophosphate component of the composition, and a deeper or penetrating oil and water repellent layer from the fluoroacrylate polymer component of the composition.
The composition of the present invention comprises a mixture of at least 11% by weight of a fluoroalkyl phosphate and not more than 89% by weight of a fluoroacrylate polymer. The fluorophosphate is a mixture of mono(perfluoroalkyl) phosphate and bis(perfluoroalkyl) phosphate of the structure of Formula 1A or a phosphate of the structure of Formula 1B. Formula 1A typically contains ranges of 20 mole % bis(perfluoroalkyl) phosphate and 80 mole % mono(perfluoroalkyl) phosphate to up to 85 mole % bis(perfluoroalkyl) phosphate and 15 mole % of mono(perfluoroalkyl) phosphate. Alternatively, Formula 1A is a mixture of perfluorinated phosophonic and phosphinic acids or their corresponding salts.
wherein:
R
f
is selected from the group consisting of
F(CF
2
CF
2
)
d
(CH
2
)
a
—,
F(CF
2
CF
2
)
d
CH
2
CH
2
(OCH
2
CH
2
)
b
—,
F(CF
2
CF
2
)
d
—,
F(CF
2
CF
2
)
d
CH═CH(CH
2
)
c
—, and
C
8
F
17
SO
2
N(R)CH
2
CH
2
—,
R
f
′ is a fluoroaliphatic group having a linear or branched perfluorocarbon chain having from 2 to 20 carbon atoms,
x is from about 1 to about 2,
j is 1 or 0 or a mixture thereof,
d is 1 to about 8, or a mixture thereof, and preferably is from about 3 to about 6,
X is hydrogen or M,
M is an ammonium ion, an alkali metal ion, or an alkanolammonium ion, such as ethanolammonium or diethanolammonium, and is preferably ammonium,
R
3
is an alkylene group having from 1 to about 8 carbon atoms, and is preferably ethylene,
Z is —O—, —S—, or —NH—,
a is from about 2 to about 10, and preferably is 2,
b is from about 3 to about 20, and preferably is from about 6 to about 13,
c is from about 2 to about 20, and preferably is 8, and
R is H or an aliphatic group containing 1 to about 4 carbon atoms.
The fluoroalkylphosphates are prepared according to the method described by Brace and Mackenzie, in U.S. Pat. No. 3,083,224. Typically, either phosphorus pentoxide (P
2
O
5
) or phosphorus oxychloride (POCl
3
) are reacted with the fluoroalcohols to give mixtures of the mono- and bis(perfluoroalkyl)phosphoric acids. Neutralization, using common bases such as ammonium or sodium hydroxides provides the corresponding phosphates. Reacting an excess of fluoroalcohol with P
2
O
5
followed by neutralization provides an equimolar mixture of mono(perfluoroalkyl)phosphat

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