U.S. patent application number 13/609758 was filed with the patent office on 2013-03-07 for protecting agent for concrete, masonry surface, bricks, clay roofing, tiles, marble, granite, concrete slate, stucco, paving stones, unglazed ceramic, sandstone, limestone, wood and other objects against stains, dirt, water and oil penetration.
The applicant listed for this patent is Yassin ELGARHY. Invention is credited to Yassin ELGARHY.
Application Number | 20130059159 13/609758 |
Document ID | / |
Family ID | 44062304 |
Filed Date | 2013-03-07 |
United States Patent
Application |
20130059159 |
Kind Code |
A1 |
ELGARHY; Yassin |
March 7, 2013 |
PROTECTING AGENT FOR CONCRETE, MASONRY SURFACE, BRICKS, CLAY
ROOFING, TILES, MARBLE, GRANITE, CONCRETE SLATE, STUCCO, PAVING
STONES, UNGLAZED CERAMIC, SANDSTONE, LIMESTONE, WOOD AND OTHER
OBJECTS AGAINST STAINS, DIRT, WATER AND OIL PENETRATION
Abstract
An aqueous composition of a non-siliceous fluorocarbon polymer
forms a dry deposit derived from the non-siliceous fluorocarbon
polymer on the surface of construction material; the non-siliceous
fluorocarbon polymer being characterized by the presence of
fluorocarbon units of up to 6 carbon atoms; this non-siliceous
fluorocarbon polymer is a protecting agent imparting an excellent
water and oil repellency and also protection against stains and
dirt, to bricks, clay roofing, different kinds of tiles, marble,
granite, slate, stucco, paving stones, unglazed ceramic,
sandstones, limestone, wood and other objects; it is durable and
can be processed at low temperature; the composition may also
include silicone based agents and acrylics and can provide a
natural, satin or wet look to the construction material
surface.
Inventors: |
ELGARHY; Yassin; (Chomedey,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ELGARHY; Yassin |
Chomedey |
|
CA |
|
|
Family ID: |
44062304 |
Appl. No.: |
13/609758 |
Filed: |
September 11, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12591627 |
Nov 25, 2009 |
8298674 |
|
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13609758 |
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Current U.S.
Class: |
428/421 ;
427/385.5; 524/269; 524/442; 524/544 |
Current CPC
Class: |
C04B 2111/27 20130101;
Y10T 428/4935 20150401; C09D 127/12 20130101; Y10T 428/31663
20150401; C04B 2111/203 20130101; Y10T 428/3154 20150401; C04B
41/4842 20130101 |
Class at
Publication: |
428/421 ;
524/544; 524/269; 524/442; 427/385.5 |
International
Class: |
C09D 133/16 20060101
C09D133/16; B32B 18/00 20060101 B32B018/00; B05D 7/00 20060101
B05D007/00; B32B 13/12 20060101 B32B013/12; C08K 5/5419 20060101
C08K005/5419; C08K 3/34 20060101 C08K003/34 |
Claims
1. A method of imparting water and oil repellency and resistance to
staining to a surface of a construction material, which comprises
applying to the surface an aqueous composition of a non-siliceous
fluorocarbon polymer to form a dry deposit derived from the
non-siliceous fluorocarbon polymer on the surface; the
non-siliceous fluorocarbon polymer being characterized by the
presence of fluorocarbon units of up to 6 carbon atoms.
2. The method of claim 1, wherein said non-siliceous fluorocarbon
polymer is a fluoroalkyl acrylate copolymer derived from a first
monomer having a polyfluoroalkyl group, wherein the melting point
of fine crystals derived from the polyfluoroalkyl groups in a
homopolymer of the monomer, does not exist or is at most 50.degree.
C.; and a second monomer having an organic group other than a
polyfluoroalkyl group and wherein the melting point of fine crystal
derived from the organic groups in a homopolymer of the second
monomer, is at least 30.degree. C.
3. The method of claim 2, wherein polyfluoroalkyl group has up to 6
carbon atoms.
4. The method of claim 3, wherein the construction material is
selected from concrete, masonry surfaces, bricks, clay roofing,
tiles, marble, granite, concrete slate, stucco, paving stones,
unglazed ceramic, sandstone, limestone or wood.
5. The method of claim 1, wherein said aqueous composition further
comprises one or more of: micro silicone emulsion, macro silicone
emulsion, silane, siloxane, siliconates, and acrylic polymer.
6. The method of claim 1, wherein said aqueous composition is an
aqueous solution having a pH less than 10.
7. The method of claim 1, wherein said non-siliceous fluorocarbon
polymer is present in said aqueous composition in an amount of 0.1%
to 10%, by weight, based on the weight of the aqueous
composition.
8. The method of claim 1, wherein said aqueous composition is
applied to said surface by a method selected from wiping, brushing,
immersing, rolling or spraying.
9. The method of claim 1, wherein said aqueous composition is
applied to said surface at room temperature and is fixed and cured
at the same temperature without additional heat.
10. The method of claim 9, wherein said non-siliceous fluorocarbon
polymer is present in said aqueous composition in an amount of 2 to
5%, by weight, based on the weight of the aqueous composition.
11. The method of claim 1, wherein said non-siliceous fluorocarbon
polymer is anionic-cationic or non-ionic and cures, dries or fixes
on said surface at ambient temperature, without need for addition
of heat.
12. An aqueous composition for imparting water and oil repellency
and resistance to staining to a surface of a construction material,
which comprises a non-siliceous fluorocarbon polymer characterized
by the presence of fluorocarbon units of up to 6 carbon atoms; in
an aqueous vehicle.
13. The aqueous composition of claim 12, wherein said non-siliceous
fluorocarbon polymer is a fluoroalkyl acrylate copolymer derived
from a first monomer having a polyfluoroalkyl group, wherein the
melting point of fine crystals derived from the polyfluoroalkyl
groups in a homopolymer of the monomer, does not exist or is at
most 50.degree. C.; and a second monomer having an organic group
other than a polyfluoroalkyl group and wherein the melting point of
fine crystal derived from the organic groups in a homopolymer of
the second monomer, is at least 30.degree. C.
14. The aqueous composition of claim 13, wherein said
polyfluoroalkyl group has up to 6 carbon atoms.
15. The aqueous composition of claim 12, further comprising one or
more of: micro silicone emulsion, macro silicone emulsion, silane,
siloxane, siliconates, acrylic polymer and urea.
16. The aqueous composition of claim 12, wherein said non-siliceous
fluorocarbon polymer is present in said aqueous composition in an
amount of at least 0.01%, by weight based on the weight of the
aqueous composition.
17. A protected construction material having a surface which is
water and oil repellent and resistant to staining, said surface
having a dry deposit derived from a non-siliceous fluorocarbon
polymer characterized by the presence of fluorocarbon units of up
to 6 carbon atoms, wherein said construction material is selected
from concrete, masonry surfaces, bricks, clay roofing, tiles,
marble, granite, concrete slate, stucco, paving stones, unglazed
ceramic, sandstone, limestone or wood.
18. The protected construction material of claim 17, wherein said
non-siliceous fluorocarbon polymer is a fluoroalkyl acrylate
copolymer derived from a first monomer having a polyfluoroalkyl
group which has up to 6 carbon atoms, wherein the melting point of
fine crystals derived from the polyfluoroalkyl groups in a
homopolymer of the monomer, does not exist or is at most 50.degree.
C.; and a second monomer having an organic group other than a
polyfluoroalkyl group and wherein the melting point of fine crystal
derived from the organic groups in a homopolymer of the second
monomer, is at least 30.degree. C.
19. (canceled)
20. The protected construction material of claim 17, wherein said
dry deposit further comprises one or more of: silicone from a micro
silicone emulsion, silicone from a macro silicone emulsion, silane,
siloxane, siliconates, acrylic polymer and urea.
21. The protected construction material of claim 20, wherein said
acrylic polymer comprises at least one or more of the following
monomers, ethyl acrylate, methyl methacrylate, ethyl hexylacrylate,
ethyl hexyl methacrylate, butyl acrylate, methacrylic acid, and
ethyl methacrylate.
22. The method of claim 1, wherein said non-siliceous fluorocarbon
polymer is a fluorine-containing polymer having an aliphatic
monocyclic structure in the polymer trunk chain, which has a number
average molecular weight of from 500 to 1,000,000 and is
represented by the formula: (Ma): -(M1)-(M2a)-(N)-- (Ma) in which
the structural unit M1 is a structural unit derived from an
ethylenic monomer having 2 or 3 carbon atoms and at least one
fluorine atom, the structural unit M2a is at least one structural
unit which introduces an aliphatic monocyclic structure in the
polymer trunk chain and is represented by the formula: ##STR00002##
wherein R.sup.1 is at least one hydrocarbon group selected from the
group consisting of a divalent hydrocarbon group which has 1 to 8
carbon atoms and constitutes a ring (which may be further
substituted with a hydrocarbon group or a fluorine-containing alkyl
group) and a divalent hydrocarbon group having ether bond which has
the sum of carbon atoms and oxygen atoms of 2 to 8 and constitutes
a ring (which may be further substituted with a hydrocarbon group
or a fluorine-containing alkyl group); R.sup.2 is an alkylene group
which has 1 to 3 carbon atoms and constitutes a ring; R.sup.3 and
R.sup.4 are the same or different and each is a divalent alkylene
group having 1 or 2 carbon atoms; n1, n2 and n3 are the same or
different and each is 0 or 1, the structural unit N is a structural
unit derived from a monomer copolymerizable with the monomers to
introduce the structural units M1 and M2a; (Z)n4 is H or each Z is
the same or different and each is: --(R.sup.5).sub.n5Z.sup.1
wherein Z.sup.1 is at least one functional group selected from the
group consisting of OH group, COOH group, a derivative of
carboxylic acid group and a functional group protected by a
protective group which can convert the functional group to OH group
by reaction with an acid; R.sup.5 is a divalent organic group; n5
is 0 or 1; n4 is an integer of from 1 to 3, and wherein the
structural units M1, M2a and N are contained in amounts of from 1
to 99% by mole, from 1 to 99% by mole and from 0 to 98% by mole,
respectively.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a Continuation of Ser. No. 12/591,627
filed Nov. 25, 2009.
FIELD OF THE INVENTION
[0002] This invention relates to a method of protecting
construction materials against stains and dirt, while also
providing water and oil repellency, and to compositions for use in
such a method, as well as protected construction materials; the
protection provided is based on a fluorine-containing polymer.
DESCRIPTION OF PRIOR ART
[0003] Existing techniques of protecting materials such as textiles
and paper, for example to render them water repellent involve
coating the material with hydrophobic solid materials having small
surface tension to modify the surface of the material and render it
water repellent, the coating materials usually are based on
hydrophobic wax, acrylic polymers, vinyl type high molecular weight
polymers, or silicones, these polymer coatings are water repellent
but not oil repellent.
[0004] It has also been proposed to impart water and oil repellency
at the same time, to material, by coating with an organic solvent
solution or an aqueous dispersion of a polymer containing
polyfluoro alkyl groups which contain 8 or more carbon atoms.
[0005] U.S. Pat. No. 6,716,944 describes a composition which
provide water and oil repellency to paper and textile substrates,
which composition is based on a copolymers of two classes in which
one of the comonomers has a fluorine containing organic group of 1
to 20 carbon atoms; one of the two classes employs a comonomer
which has not more than 6 carbon atoms; the other of the two
classes employs a comonomer which is a fluoro ether of 1 to 20
carbon atoms but which bears a fluoro alkyl group of not more than
6 carbon atoms.
[0006] U.S. Pat. No. 7,511,179 describes fluorine-containing
polymers for use in photoresist compositions providing improved dry
etching resistance, wherein the fluorine-containing polymers
include a structural unit derived from an ethylenic monomer of 2 or
3 carbon atoms and having at least one fluorine substituent.
SUMMARY OF THE INVENTION
[0007] It is an object of this invention to provide water and oil
repellency to construction substrate materials including concrete,
masonry surface, bricks, clay roofing, tiles, marble, granite,
slate, stucco, paving stones, unglazed ceramic, sandstone,
limestone, wood and the like.
[0008] It is a further object of this invention to provide method
of rendering such construction materials durable and resistant to
vapour and water.
[0009] It is a still a further object of this invention to provide
an aqueous formulation for providing water, oil repellency and
resistance to staining and dirt for construction materials.
[0010] It is yet another object of this invention to provide a
protected construction material.
[0011] In one aspect of the invention, there is provided a method
of imparting water and oil repellency and resistance to staining to
a surface of a construction material, which comprises applying to
the surface an aqueous composition of a non-siliceous fluorocarbon
polymer to form a dry deposit derived from the non-siliceous
fluorocarbon polymer on the surface; the non-siliceous fluorocarbon
polymer being characterized by the presence of fluorocarbon units
of up to 6 carbon atoms.
[0012] In another aspect of the invention, there is provided an
aqueous composition for imparting water and oil repellency and
resistance to staining to a surface of a construction material,
which comprises a non-siliceous fluorocarbon polymer characterized
by the presence of fluorocarbon units of up to 6 carbon atoms; in
an aqueous vehicle.
[0013] In still another aspect of the invention, there is provided
a protected construction material having a surface which is water
and oil repellent and resistant to staining, said surface having a
dry deposit derived from a non-siliceous fluorocarbon polymer
characterized by the presence of fluorocarbon units of up to 6
carbon atoms.
[0014] The non-siliceous fluorocarbon polymer may be employed alone
or in combination with silicone based products including siloxane,
silane, or combination of these products and also other organic
salts, and/or acrylic polymers. In such case the additional
components such as silicones may be present in the aqueous
composition with the non-siliceous fluorocarbon polymer.
[0015] Suitable silicone based products include siloxane silane,
siliconate, and macro or micro silicone emulsions.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The invention employs polymers which have structural
fluorocarbon units based on Carbon 6 or less ie. up to 6 carbon
atoms, and which impart excellent water, oil and stain repellency
to construction materials at low temperature.
[0017] In particular the fluorine-containing polymers described in
U.S. Pat. No. 6,716,944 and in U.S. Pat. No. 7,511,179 are
surprisingly found to be highly suitable for treating construction
materials, to produce construction materials which are water, oil
and stain repellent, with the treated surfaces being highly durable
to the external environment to which they are exposed, such as the
extremes of weather encountered in North America and exposure as
pedestrian areas. The teachings of U.S. Pat. No. 6,716,944 and U.S.
Pat. No. 7,511,179 are incorporated herein by reference, in so far
as they relate to such fluorine-containing polymers and their
manufacture.
[0018] The fluorine-containing polymers in this invention can be
applied alone or with silicone based products, organic chemicals
compounds, for example urea, and/or acrylic polymers, to provide
improved or other advantageous characteristics to the construction
material substrates. The fluorine-containing polymers are in
particular employed as aqueous dispersions or emulsions.
(I) Fluorine-Containing Polymers
[0019] Non-siliceous fluorocarbon polymer herein refers to
fluorine-containing polymers or copolymers that do not contain
silicon.
[0020] (i) One class of fluorine-containing polymer for use in the
invention comprises a fluorine-containing polymer for use in the
invention comprises a copolymer consisting essentially of
polymerized units of a monomer (a) being an Rf monomer wherein the
melting point of fine crystals derived from the Rf groups in a
homopolymer of the monomer, does not exist or is at most 50.degree.
C.; and polymerized units of a monomer (b) being a monomer having
no Rf group, wherein the melting point of fine crystals derived
from a homopolymer of the monomer is at least 30.degree. C.;
wherein Rf is a poly fluoroaliphatic group.
[0021] The presence or absence of fine crystals derived from Rf
groups can be confirmed by observing a peak attributable to their
self packing by means of a wide angle or small angle X-ray
scattering. If the fine crystals are present in the polymer,
usually the spacing of their characteristic packing planes is
observed to be about 5 .ANG..
[0022] The Rf monomer means a monomer having an R group and a
polymerizable unsaturated group. The Rf monomer is preferably a
compound represented by the formula (Z--Y).sub.n X wherein an Rf
group Z and a polymerizable unsaturated group X are bonded to each
other via a specific bivalent organic group Y. Here, Z is an Rf
group having a number of carbon atoms of at most 6, or a group
represented by the formula
C.sub.mF.sub.2m+1O(CF.sub.2CF(CF.sub.3)O).sub.dCF(CF.sub.3)-- in
which m is an integer of from 1 to 6, and d is an integer of from 1
to 4, n is 1 or 2, and when n is 2, two (Z--Y) may be the same or
different from each other. X may be:
--CR.dbd.CH.sub.2 --COOCR.dbd.CH.sub.2, --OCOCR.dbd.CH.sub.2,
--OCH.sub.2-Ph-CR.dbd.CH.sub.2 or --OCH.dbd.CH.sub.2 when n is 1,
and may be: .dbd.CH(CH.sub.2).sub.qCR.dbd.CH.sub.2,
.dbd.CH(CH.sub.2).sub.qCOOCR.dbd.CH.sub.2
.dbd.CH(CH.sub.2).sub.qOCOCR.dbd.CH.sub.2 or
--OCH.sub.2OCH.dbd.CHCOO-- when n is 2; in which R is a hydrogen
atom, a methyl group or a halogen atom, Ph is a phenylene group,
and q is an integer from 0 to 4. Further, Y is a bivalent organic
group or a single bond. The Rf group is a group having a part or
all of hydrogen atoms of an alkyl group substituted by fluorine
atoms, and its carbon number is preferably from 1 to 20. The Rf
group is preferably a group having at least from 20 to 80% in
number of hydrogen atoms of an alkyl group substituted by fluorine
atoms. Further, a part or all of the remaining hydrogen atoms may
be substituted by chlorine atoms. The Rf group may be of linear
type or branched type. In the case of branched type, one having a
short branch at the end far from the connecting bond or in the
vicinity of the end, is preferred.
[0023] Among the above-mentioned preferred Rf groups, a linear Rf
group represented by the formula F(CF.sub.2).sub.k--in which k is
an integer of from 1 to 20, or a group represented by the formula
C.sub.j F.sub.2j+1(CM.sup.1 M.sup.2 CM.sup.3 M.sup.4).sub.i-, in
which M.sup.1, M.sup.2, M.sup.3 and M.sup.4 are each independently
a hydrogen atom, a fluorine atom or a chlorine atom, and one of
them is a fluorine atom, and j and i are each an integer of at
least 1 and satisfy 20.gtoreq.(j+2.times.i).gtoreq.6, is preferred.
Particularly, an Rf group having a carbon number of at most 6, or a
group represented by the formula C.sub.mF.sub.2m+1
O(CF.sub.2CF(CF.sub.3)O).sub.dCF(CF.sub.3)-- in which m is an
integer of from 1 to 6, and d is an integer of from 1 to 4, is
preferred.
[0024] The carbon number of the Rf group is preferably from 1 to
20, particularly preferably from 1 to 12. One having a small carbon
number is preferred since fine crystals derived from the Rf groups
are not likely to be formed when the homopolymer is formed, and the
copolymer can form a film. The Rf group may be a linear
polyfluorohydrocarbon group having at least one unsaturated group
such as a carbon-carbon unsaturated double bond.
[0025] The Rf group may be a polyfluorooxaalkyl group having a part
of its carbon atoms substituted by etheric oxygen atoms.
Particularly, a polyfluorooxaalkyl group, more particularly, a
perfluorooxaalkyl group, having at least one perfluorooxypropylene
group, is preferred. The carbon number in this case is preferably
from 6 to 18 including carbon atoms before substitution by oxygen
atoms.
[0026] A specific Rf group may be one of the following Rf groups,
but is not limited thereto:
F(CF.sub.2).sub.4--, F(CF.sub.2).sub.5--, F(CF.sub.2).sub.6--,
(CF.sub.3).sub.2CF(CF.sub.2).sub.2--, H(CF.sub.2).sub.6--,
HCF.sub.2CF.sub.2--, Cl(CF.sub.2).sub.4--,
F(CF.sub.2).sub.4(CH.sub.2CF.sub.2).sub.3--,
F(CF.sub.2).sub.6(CH.sub.2CF.sub.2).sub.3--,
F(CF.sub.2).sub.4(CFClCF.sub.2).sub.2--,
CF.sub.3CF.sub.2C(CF.sub.3)--CH(CF.sub..sub.3)(CF.sub.2CF.sub.3),
CF.sub.2e+1O[CF(CF.sub.3)CF.sub.2O].sub.h--CF(CF.sub.3)--,
C.sub.3F.sub.7O[CF(CF.sub.3)CF.sub.2O].sub.h(CF.sub.2).sub.v--
or
CF.sub.3CF.dbd.CFCF.sub.2CF.dbd.CF--
[0027] in which e is an integer of from 3 to 6, h is an integer of
from 0 to 3, and v is an integer of from 2 to 6.
[0028] The Rf group and the polymerizable unsaturated group may be
bonded by a single bond or via a bivalent organic group. As the
bivalent organic group, a group containing an alkylene group is
preferred. The alkylene group may be linear or one having a branch.
Further, in the bivalent organic group, e.g. --O--, --NH--, --CO--,
--SO.sub.2-- or --CD.sup.1.dbd.CD.sup.2-- in which D.sup.1 and
D.sup.2 each independently represents a hydrogen atom or a methyl
group may. As the bivalent organic group, an alkylene group is
preferred.
[0029] As Y, a bivalent organic group represented by the formula
--R.sup.M--Q--R.sup.N-- in which R.sup.M and R.sup.N each
independently represents a single bond or a saturated or
unsaturated hydrocarbon group having a carbon number of from 1 to
22 which may contain at least one oxygen atom, and Q represents a
single bond, --OCONH--, --CONH--, --SO.sub.2NH-- or --NHCONH-- is
preferred.
[0030] As Y, --CH.sub.2--, --CH.sub.2CH.sub.2--,
--(CH.sub.2).sub.11--, --CH.sub.2CH.sub.2CH(CH.sub.3)--,
--(CH.sub.2CHR.sup.2O).sub.w CH.sub.2CH.sub.2-- in which w is an
integer of from 1 to 10, and R.sup.2 represents a hydrogen atom or
a methyl group, --C.sub.2H.sub.4OCONHC.sub.2H.sub.4--,
--C.sub.2H.sub.4OCOOC.sub.2H.sub.4--, --COOC.sub.2H.sub.4-- or
--CH.dbd.CHCH.sub.2-- may be preferably mentioned.
[0031] As X, an ethylenic polymerizable unsaturated group, namely,
e.g. a residue of an olefin, a residue of a vinyl ether, a residue
of a vinyl ester, a residue of a (meth)acrylate, a residue of a
maleic acid ester or a residue of a fumaric acid ester, is
preferred. Here, the residue of an olefin means a group represented
by:
--CR.dbd.CH.sub.2,
[0032] the residue of a vinyl ester means a group represented
by:
--COOCR.dbd.CH.sub.2,
[0033] the residue of a vinyl ether means a group represented
by:
--OCR.dbd.CH.sub.2,
[0034] the residue of a (meth)acrylate means a group represented
by: --OCOCR.dbd.CH.sub.2, and the residue of a maleic acid or
fumaric acid ester means a group represented by:
--OCOCH.dbd.CHCOO--.
[0035] In addition to these, may be mentioned:
--OCH.sub.2-Ph-CR.dbd.CH.sub.2 and --CH.sub.2 .dbd.OCH.sub.2,
[0036] in which Ph represents a phenylene group. In the above R is
preferably a hydrogen atom, a halogen atom (a fluorine atom, a
chlorine atom, etc.) or a short-chain alkyl group having a carbon
number of from 1 to 3, particularly a methyl group, in order not to
hinder polymerization. In consideration of the polymerizability to
form a copolymer, X is preferably a residue of a (meth)acrylate, or
a residue of maleic acid or fumaric acid ester, and from the
viewpoint of e.g. the solubility or easiness of emulsion
polymerization, the residue of a (meth)acrylate is particularly
preferred.
[0037] As the Rf monomer, particularly a (meth)acrylate having an
Rf group is preferred. As such an Rf monomer, various monomers such
as the following monomer (a) may be used. As such monomers, known
monomers may be used. As the monomer (a) employed in the present
invention, a (meth)acrylate is particularly preferred as mentioned
above from the viewpoint of e.g. the polymerizability with other
monomers, flexibility of the film to be formed, adhesion to the
substrate, solubility and easiness of emulsion polymerization.
[0038] The Rf group preferably has a carbon number of at most 6.
And, it is most preferably a linear Rf group having a carbon number
of from 4 to 6.
[0039] When Y is --CH.sub.2CH..sub.2CH(CH.sub.3)-- or
--CH.dbd.CHCH.sub.2-- and X is a (meth)acrylate, the carbon number
of the Rf group is preferably from 1 to 10, particularly preferably
from 4 to 8. When the Rf group is a polyfluoropolyether group
containing an oxygen, and X is a (meth)acrylate, the carbon number
of the Rf group is preferably from 4 to 18.
[0040] As the monomer (b) of the present invention, a
(meth)acrylate, a vinyl ether or a vinyl ester may preferably be
mentioned. The monomer (b) may contain a small number of isolated
fluorine atoms which are usually not regarded as Rf groups.
Further, as an organic group contained in the monomer (b), a
long-chain hydrocarbon group wherein the melting point of fine
crystals is at least 30.degree. C., is preferred.
[0041] As the monomer (b) having a long-chain hydrocarbon group, a
monomer having a linear hydrocarbon group having a carbon number of
at least 14, particularly a monomer having a linear saturated alkyl
group having a carbon number of from 16 to 24, is preferred. As the
monomer (b), a (meth)acrylate containing a saturated hydrocarbon
group having a carbon number of at least 15, is particularly
preferred. Further, a vinyl ester containing a saturated
hydrocarbon group having a carbon number of at least 15, is also
preferred.
[0042] The molar ratio of polymerized units of monomer
(a)/polymerized units of monomer (b) in the copolymer is preferably
from 0.1/1 to 9/1, more preferably from 0.2/1 to 5/1, particularly
preferably from 0.2/1 to 1.5/1. The composition in this range is
excellent in the water and oil repellency and in the flexibility of
the film, such being preferred. Further, the copolymer may contain
a monomer (also referred to as another monomer) other than the
monomer (a) and the monomer (b), for the purpose of improving
physical properties other than the water and oil repellency, such
as the adhesion to a substrate, the bonding property, and the
durability against abrasion. Another monomer may, for example, be
ethylene, vinylidene chloride, vinyl chloride, vinylidene fluoride,
vinyl acetate, styrene, .alpha.-methylstyrene, p-methylstyrene,
glycidyl(meth)acrylate, (meth)acrylamide,
N,N-dimethy(meth)acrylamide, diacetone(meth)acrylamide,
methyloldiacetone(meth)acrylamide, N-methylol(meth)acrylamide,
vinyl alkyl ether, an alkyl vinyl ether halide, a vinyl alkyl
ketone, butadiene, isopropylene, chloroprene, aziridinylethyl
(meth)acrylate, benzyl (meth)acrylate, aziridinyl(meth)acrylate, a
polyoxyalkylene(meth)acrylate, a
methylpolyoxyalkylene(meth)acrylate, a
2-ethylhexylplyoxyalkylene(meth)acrylate, a polyoxyalkylene
di(meth)acrylate, a (meth)acrylate having polysiloxane, triallyl
cyanurate, allylglycidyl ether, allyl acetate, N-vinylcarbazole,
maleimide, N-methylmaleimide, (2-dimethylamino)ethyl
(meth)acrylate, a (meth)acrylate having an alkyl group having a
carbon number of from 8 to 20, a cycloalkyl(meth)acrylate,
hydroxyethyl (meth)acrylate, glycerol(meth)acrylate, a
(meth)acrylate having a silicone in its side chain, a
(meth)acrylate having an urethane bond, an alkylenedi(meth)acrylate
or polyoxyalkylene di(meth)acrylate.
[0043] Particularly, vinyl chloride, a hydroxyethyl (meth)acrylate
having a reactive group such as a hydroxyl group in its molecule, a
polyoxyalkylene(meth)acrylate, a
methylpolyoxyalkylene(meth)acrylate, a glycidyl(meth)acrylate, a
bifunctional polyoxyethylene di(meth)acrylate,
ethyleneglycoldi(meth)acrylate or a blocked isocyanate ethyl
(meth)acrylate, is preferred with a view to improving the adhesion
to the construction material surface of the composition of the
invention.
[0044] In the composition of the present invention, the method of
preparing the copolymer to be the active component, is not
particularly limited. For example, a common polymerization method
such as a solution polymerization method using an organic solvent,
a dispersion polymerization method using water as a dispersion
medium and containing a non-ionic surfactant and/or a cationic
surfactant, or an emulsion polymerization method, may be employed.
The obtained solution, dispersion or emulsion of the copolymer may
be used as it is, or may be used as diluted. Otherwise, the
copolymer may be isolated, and then, dissolved, dispersed or
emulsified in a solvent, dispersion medium or emulsion medium.
[0045] (ii) A second class of fluorine--containing polymer for use
in the invention is a fluorine-containing polymer having an
aliphatic monocyclic structure in the polymer trunk chain, which
has a number average molecular weight of from 500 to 1,000,000 and
is represented by the formula:
(Ma): -(M1)-(M2a)-(N)-- (Ma)
in which the structural unit M1 is a structural unit derived from
an ethylenic monomer having 2 or 3 carbon atoms and at least one
fluorine atom, the structural unit M2a is at least one structural
unit which introduces an aliphatic monocyclic structure in the
polymer trunk chain and is represented by the formula:
##STR00001##
wherein R.sup.1 is at least one hydrocarbon group selected from the
group consisting of a divalent hydrocarbon group which has 1 to 8
carbon atoms and constitutes a ring (which may be further
substituted with a hydrocarbon group or a fluorine-containing alkyl
group) and a divalent hydrocarbon group having ether bond which has
the sum of carbon atoms and oxygen atoms of 2 to 8 and constitutes
a ring (which may be further substituted with a hydrocarbon group
or a fluorine-containing alkyl group); R.sup.2 is an alkylene group
which has 1 to 3 carbon atoms and constitutes a ring; R.sup.3 and
R.sup.4 are the same or different and each is a divalent alkylene
group having 1 or 2 carbon atoms; n1, n2 and n3 are the same or
different and each is 0 or 1, the structural unit N is a structural
unit derived from a monomer copolymerizable with the monomers to
introduce the structural units M1 and M2a; (Z).sub.n4 is H or each
Z is the same or different and each is:
--(R.sup.5).sub.n5Z.sup.1
wherein Z.sup.1 is at least one functional group selected from the
group consisting of OH group, COOH group, a derivative of
carboxylic acid group and a functional group protected by a
protective group which can convert the functional group to OH group
by reaction with an acid; R.sup.5 is a divalent organic group; n5
is 0 or 1; n4 is an integer of from 1 to 3, and wherein the
structural units M1, M2a and N are contained in amounts of from 1
to 99% by mole, from 1 to 99% by mole and from 0 to 98% by mole,
respectively. An especially preferred fluorine-containing polymer
of the invention is a fluoroalkyl acrylate copolymer derived from a
first monomer having a polyfluoroalkyl group, wherein the melting
point of fine crystals derived from the polyfluoroalkyl groups in a
homopolymer of the monomer, does not exist or is at most 50.degree.
C.; and a second monomer having an organic group other than a
polyfluoroalkyl group and wherein the melting point of fine crystal
derived from the organic groups in a homopolymer of the second
monomer, is at least 30.degree. C.
[0046] Examples of specific fluorine-containing polymers which can
be used to achieve the purpose of this invention include, but not
limited to TG8731 and TG 8111 from Daikin Industries; and AGE-060
from Asahi Glass.
[0047] The aqueous composition of the fluorine-containing polymer
is suitably at a pH below 10, preferably below 7. The composition
will suitably contain the fluorine-containing polymer in an amount
of at least 0.1%, by weight, more especially 0.1 to 10%, typically
2 to 5%, based on the weight of the aqueous composition.
[0048] The fluorine-containing polymers once they are applied on a
construction material substrate surface, cross link and bond or
adhere to the substrate surface and have good durability at low
temperature without any need for heating.
[0049] The fluorine-containing polymers can be applied outdoors or
indoors without any problem, and can be applied at ambient
temperatures and dry at ambient ambient temperatures.
[0050] In particular the aqueous composition of the invention can
be applied by wiping- brushing- rolling- immersing or spraying
method, and cured at room temperature.
[0051] This aqueous composition provides a protecting agent which
is durable, and the composition can be processed at low
temperature, and has the advantage of being a water based product,
not containing organic solvents and it is not considered a
hazardous or dangerous product to use.
[0052] As the aqueous composition dries the fluorine-containing
polymer adheres to the construction material surface as a deposit
of very fine particles, typically crystals. This deposit is not a
sealer and will not yellow nor leave a surface film, moreover it is
UV stable and vapour permeable thus increasing life of the
construction material, and reduces spalling, cracking and
freeze/thaw damage.
(b) Silicones
[0053] When a silicone based product is employed in the aqueous
composition of the invention in combination with the
fluorine-containing polymer; the composition may be formulated to
produce a wet look or a satin look or a natural look, on the
treated construction material surface.
[0054] A wet look is achieved by an aqueous composition of the
invention in which the silicone is present as a micro silicone
emulsion. A satin look is achieved when the silicone is present as
a macro silicone emulsion. Also a combination of micro and macro
emulsions can be used to obtain a desired look.
[0055] A micro emulsion herein is one in which the silicone is
present as droplets having an average particle size of up to 1
micron; whereas a macro emulsion herein is one in which the
silicone is present as droplets having an average particle size of
more than 1 micron, more especially 1 to 10,000 microns, typically
50 to 120 microns, preferably about 100 microns.
[0056] The silicone materials penetrate the construction material
surface to enhance water repellency.
[0057] The products based on silicone which can be applied with the
fluorine-containing polymers include but are not limited to
silanes, siloxane, and silicone emulsions which emulsions may be
microemulsions or macroemulsions, siliconates and combination
therefore.
[0058] Examples of commercially available silicone products that
can be used in this invention are but not limited to:
TABLE-US-00001 1) Silane Dow Corning IE 6694 Dow Corning Z-9034 2)
Siloxane Dow Corning Z-6184 Dow Corning Z-60 3) Silane/Siloxane Dow
Corning 520 Dow Corning 6694 Dow Corning IE-6683 Dow Corning Z-9034
4) Siliconate Dow Corning 772 Dow Corning 777
[0059] Examples of other commercially available silicones which can
be used in this invention are:
TABLE-US-00002 K C89 from Shin ETSU K P 359 from Shin ETSU KP 390
from Shin ETSU Polon MF 40 from Shin ETSU Polon A from Shin ETSU K
F413 from Shin ETSU
5) Silicone macro or micro emulsions which are used in this
invention may be based on modified silicone fluids which are
reacted with themselves, or with other silicone polymers or
coupling agents, then emulsified to produce micro or macro
emulsions.
c) Acrylics
[0060] Acrylics may also be employed in combination with the
fluorine-containing polymer and may be employed in the aqueous
composition with the fluorine-containing polymer to enhance the
properties of the composition. In particular the presence of an
acrylic increases the resistance to absorption of water.
[0061] The acrylics form a film or coating on the construction
material surface and in this respect function as sealants on the
surface.
[0062] Examples of acrylic polymers that can be used in this
invention are acrylic copolymers based on two or more of the
following monomers: ethyl acrylate, methyl methacrylate,
methacrylic acid, acrylic acid, butyl acrylate, ethyl hexyl
acrylate-ethyl hexy/methacrylate, with TG from 0 to 60.degree. C.
(32 to 140.degree. F.) preferably from 20 to 40.degree. C. (68 to
104.degree. F.).
c) Construction Materials
[0063] Construction materials as contemplated by this invention
comprise materials employed in construction of structures such as
buildings and bridges and paved surfaces and which have surfaces
which are exposed to water, oil and stains and dirt in the
environment and as a result of human and animal passage. Typical
construction materials include concrete, masonry surface, bricks,
clay roofing, tiles, marble, granite, concrete slate, stucco,
paving stones, unglazed ceramic, sandstone, limestone and wood.
Examples
Test Methods:
[0064] Water repellency drop test:
TABLE-US-00003 Rating Composition 1 98 water 2 Isopropy alcohol
(IPA) 2 95 water 5 IPA 3 90 water 10 IPA 4 80 water 20 IPA 5 70
water 30 IPA 6 60 water 40 IPA
[0065] In the evaluation 6 is best 1 is mediocre.
[0066] In this test the drop should stay on surface for 10 second
before rating is taken.
[0067] Oil Repellency test is evaluated as follows:
TABLE-US-00004 Rating Composition 1 Kaydol (trademark for Mineral
Oil ) 2 65/35 Kaydol/N-Hexadecane 3 N-hexadecane 4 Tetradecane 5
Dodecane 6 Decane
[0068] In the evaluation 6 is best 1 is mediocre.
[0069] In this test the drop should stay on surface for 30 seconds
before rating is taken.
Absorbancy Test:
[0070] ASTM Designation C-272-01
[0071] In this test a small piece of the core material is
conditioned under various moisture conditions and the amount of
moisture absorbed is measured by the weight increase in the
specimen.
[0072] Five (5) specimens are tested for each example.
[0073] Examples of products used to evaluate the performance:
TABLE-US-00005 Example #1 80 parts water 20 parts Carbon 6
Fluorochemical 20% solid content Example #2 16 parts Carbon 6
Fluorochemical (20% solid) 4 parts Silane/Siloxane (40% solid) 80
parts Water Example #3 80 parts water 16 parts Carbon 6
Fluorochemical (20% solid) 4 parts Silane (60% solid ) Example #4
80 parts water 16 parts Carbon 6 Fluorocarbon (20% solid) 4 parts
Siloxane Example #5 Water 16 parts Carbon 6 Fluorochemical (20%
solid) 10 parts Macro emulsion (40% solid) Example #6 64 parts
water 16 parts Carbon 6 Fluorochemical (20% solid) 20 parts Micro
emulsion (20% solid) Example #7 74 parts water 16 parts Carbon 6
Fluorochemical (20% solid) 10 parts Acrylic copolymer (50% solid)
Example #8 60 parts water 16 parts Carbon 6 Fluorochemical (20%
solid) 4 parts Macro emulsion (40% solid) 20 parts Acrylic
copolymer Example #9 68 parts water 20 parts Carbon 6
Fluorochemical (20% solid) 12 parts Urea Example #10 70 parts water
20 parts Acrylic polymer (50% solid) 10 parts Silane/Slioxane (40%
solid)
[0074] In the above Carbon 6 Fluorochemical refers to a preferred
fluorine-containing copolymer of the invention, namely the
fluoroalkyl acrylate copolymer described hereinbefore.
Test Procedure:
[0075] In this evaluation surface dirt on the substrate should be
remove using standard maintenance procedures. The substrate should
be allowed to dry completely before application. The formulations
of the above Examples were applied evenly over a substrate by a
rolling method, and allowed to dry for at least 12 hours, the
formulations were applied at a temperature above 0.degree. C.
(32.degree. F.).
Test Results:
TABLE-US-00006 [0076] Example Water Repellency Oil Repellency 1 6 6
2 6 4 3 6 4 4 6 4 5 6 3 6 6 3 7 6 6 8 6 5 9 6 6 10 6 0
Absorbency Test:
[0077] In this test 5 samples were selected for testing, they are
samples of example #1, #3, #6, and #8.
[0078] In these tests, 5 specimens are tested for each example.
Each sample was weighed then immersed in water for 7 days, then
removed from the water and the excess of water was removed, then
the moisture absorbed was measured by the weight increase in each
specimen, then the average of the weight increase of the 5 samples
was taken.
[0079] In the evaluation, the reference is an untreated specimen
immersed in water in the same way as the treated samples, and the
weight was taken before and after immersing this sample in
water.
Test Results:
TABLE-US-00007 [0080] Example Example Example Example Reference #1
#3 #6 #8 Initial mass 196.15 209.62 212.1 213.43 217.73 Final mass
218.85 231.24 233.78 236.34 237.55 Absorbed 22.68 22.91 19.82 mass
22.7 21.62 Absorbed % 11.57 10.31 10.22 10.73 9.10
Absorbency test results of example #9:
[0081] In this test 3 specimens were tested for 7 days.
TABLE-US-00008 Example #9 Example #9 Example #9 Reference Sample #1
Sample #2 Sample #3 Initial mass 228.56 232.83 227.87 223.93 Final
Mass 253.52 256.07 250.40 246.23 Absorbed mass 24.96 23.24 22.53
22.23 Absorbed % 10.92 9.98 9.89 9.95
Conclusions:
[0082] From the test results of the previous Examples it can be
seen that the best way to obtain water repellency stain repellency
and oil repellency is by using formulations of this invention. When
these products are applied they provide natural look to the
substrate and they have no adverse effect and they are not
considered as sealers.
[0083] Also if satin look or wet look is needed then a micro and/or
macro silicone emulsion can be added to the formulation.
[0084] If the minimum absorbency is needed then an acrylic polymer
may be added; when this combination is applied, it is considered a
sealer.
* * * * *