U.S. patent application number 10/559810 was filed with the patent office on 2007-03-22 for masonry-treating agent.
Invention is credited to Teruyuki Fukuda, Masahiko Maeda, Tetsuya Masutani, Akihiko Ueda.
Application Number | 20070066780 10/559810 |
Document ID | / |
Family ID | 33508754 |
Filed Date | 2007-03-22 |
United States Patent
Application |
20070066780 |
Kind Code |
A1 |
Ueda; Akihiko ; et
al. |
March 22, 2007 |
Masonry-treating agent
Abstract
A fluoropolymer for masonry treatment produced from (A) a
fluoromonomer which has been substituted in the .alpha.-position by
a X group and is represented by the formula (I): ##STR1## and (B) a
monomer having a functional group reactive with active hydrogen. It
imparts excellent water- and oil-repellency and unsusceptibility to
fouling to masonries.
Inventors: |
Ueda; Akihiko; (Settsu-shi,
JP) ; Maeda; Masahiko; (Settsu-shi, JP) ;
Fukuda; Teruyuki; (Settsu-shi, JP) ; Masutani;
Tetsuya; (Settsu-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
SUITE 800
WASHINGTON
DC
20037
US
|
Family ID: |
33508754 |
Appl. No.: |
10/559810 |
Filed: |
June 7, 2004 |
PCT Filed: |
June 7, 2004 |
PCT NO: |
PCT/JP04/08243 |
371 Date: |
May 12, 2006 |
Current U.S.
Class: |
526/247 ;
526/286; 526/310; 526/319 |
Current CPC
Class: |
C08F 220/24 20130101;
C04B 41/4842 20130101 |
Class at
Publication: |
526/247 ;
526/286; 526/310; 526/319 |
International
Class: |
C08F 16/24 20060101
C08F016/24 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 9, 2003 |
JP |
2003-163462 |
Claims
1. A fluorine-containing polymer for masonry treatment, comprising:
(A) repeating units derived from a fluorine-containing monomer of
the formula: ##STR6## wherein X is a fluorine atom, a chlorine
atom, a bromine atom, an iodine atom, a CFX.sup.1X.sup.2 group (in
which X.sup.1 and X.sup.2 are each a hydrogen atom, a fluorine
atom, a chlorine atom, a bromine atom or an iodine atom), a cyano
group, a linear or branched fluoroalkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted benzyl group, or a
substituted or unsubstituted phenyl group; Y is an aliphatic group
having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group
having 6 to 10 carbon atoms, a
--CH.sub.2CH.sub.2N(R.sup.1)SO.sub.2-- group (in which R.sup.1 is
an alkyl group having 1 to 4 carbon atoms) or a
--CH.sub.2CH(OY.sup.1)CH.sub.2-- group (in which Y.sup.1 is a
hydrogen atom or an acetyl group); and Rf is a linear or branched
fluoroalkyl or fluroalkenyl group having 1 to 21 carbon atoms, or a
fluoroether group having totally 1 to 200 repeating units selected
from the group consisting of the repeating units:
--C.sub.3F.sub.6O--, --C.sub.2F.sub.4O-- and --CF.sub.2O--, and (B)
repeating units derived from a monomer having a functional group
reactive with active hydrogen.
2. The fluorine-containing polymer according to claim 1, wherein,
in the monomer having a functional group reactive with active
hydrogen (B), the functional group is at least one selected from
the group consisting of a silane group, a phosphate group, a
carboxylate group, sulfate group and a glycidyl group.
3. The fluorine-containing polymer according to claim 1, wherein
the monomer having a functional group reactive with active hydrogen
(B) is a silane compound having a carbon-carbon double bond.
4. The fluorine-containing polymer according to claim 1, wherein
the Rf group in the fluorine-containing monomer (A) is a
fluoroalkyl or fluoroalkenyl group having 1 to 6 carbon atoms.
5. The fluorine-containing polymer according to claim 1, which
comprises the fluorine-containing monomer (A), the monomer having a
finctional group reactive with active hydrogen (B), and (C) a
fluorine-free alkyl group-containing monomer.
6. A composition for treating a masonry, which comprises the
fluorine-containing polymer according to claim 1, and an organic
solvent.
7. A method of producing a treated masonry, which comprises
applying the composition according to claim 6 to a surface of a
masonry, and then eliminating the organic solvent.
8. A masonry produced by the method according to claim 7.
Description
TECHNICAL FIELD
[0001] The present invention relates to a fluorine-containing
polymer for treating a masonry and a composition for treating a
masonry.
BACKGROUND ARTS
[0002] It is studied that water and oil repellency and soil
resistance are imparted by treating a surface of a masonry such as
stone with a compound having a fluoroalkyl group (Rf group).
[0003] For example, JP-A-57-23662 describes that an acrylate having
a Rf group is coated on a concrete and a stone to form a protective
film. JP-A-07-109317 discloses a treatment agent comprising a
fluorine-containing copolymer comprising a monomer having a Rf
group, and a silicone-based vinyl monomer. JP-A-11-507687 discloses
a masonry-treatment agent comprising a water-soluble polymer having
a Rf group, a carboxyl group, an oxyalkylene group and a silyl
group. EP1225187 discloses the treatment of ceramics with a polymer
having a silyl group which comprises a Rf group-containing monomer,
a fluorine-free monomer and a silyl group-containing monomer.
Further, JP-A- 11-077677 proposes that a stone is treated with a
phosphate ester having a Rf group.
[0004] These treatments or these treatment agents, however, do not
have both of sufficient water repellency and sufficient oil
repellency, and cannot impart sufficient soil resistance for a
masonry-treatment agent.
[0005] On the other hand, a water- and oil-repellent agent and a
soil resist agent, comprising a polymer containing a
fluorine-containing acrylate substituted at its .alpha.-position by
a fluorine atom, chlorine atom or the like are disclosed in, for
example, JP-A-63-90588, JP-A-63-99285 and JP-A-1-315471. However,
these have not been practically used as a masonry-treatment
agent.
[0006] Described below are the environmental problems raised by
perfluorooctanoic acid (PFOA). The results of the latest researches
[a report of the Environmental Protection Agency (EPA),
"PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY
ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS"
(http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] have taught that
PFOA (perfluorooctanoic acid), one of long chain fluoroalkyl
compounds, is proved to have a danger to burden the environment.
Under such a situation, EPA announced on Apr. 14, 2003 that the
scientific investigation on PFOA should be more intensively
executed.
[0007] On the other hand, the Federal Register (FR Vol. 68, No.
73/Apr. 16, 2003 [FRL-7303-8],
http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), EPA Environmental
News FOR RELEASE: MONDAY APR. 14, 2003 EPA INTENSIFIES SCIENTIFIC
INVESTIGATION OF A CHEMICAL PROCESSING AID
(http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT
SHEET Apr. 14, 2003
(http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) have published
that telomers have a possibility to produce PFOA when decomposed or
metabolized (herein, the telomer means a long chain fuluoroalkyl
group), and also that telomers have been widely used in foam fire
extinguishers, care products, washing materials, carpets, textiles,
paper, leather, etc., in order to impart water and oil repellency
and soil resistance to them.
DISCLOSURE OF INVENTION
[0008] One of objects of the present invention is to provide a
treatment agent which imparts both of excellent water- and
oil-repellency and excellent soil resistance to a masonry.
[0009] The present invention provides a fluorine-containing polymer
for masonry treatment, comprising: [0010] (A) repeating units
derived from a fluorine-containing monomer of the formula: ##STR2##
[0011] wherein X is a fluorine atom, a chlorine atom, a bromine
atom, an iodine atom, a CFX.sup.1X.sup.2 group (in which X.sup.1
and X.sup.2 are each a hydrogen atom, a fluorine atom, a chlorine
atom, a bromine atom or an iodine atom), a cyano group, a linear or
branched fluoroalkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted benzyl group, or a substituted or
unsubstituted phenyl group; [0012] Y is an aliphatic group having 1
to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to
10 carbon atoms, a --CH.sub.2CH.sub.2N(R.sup.1)SO.sub.2-- group (in
which R.sup.1 is an alkyl group having 1 to 4 carbon atoms) or a
--CH.sub.2CH(OY.sup.1)CH.sub.2-- group (in which Y.sup.1 is a
hydrogen atom or an acetyl group); and [0013] Rf is a linear or
branched fluoroalkyl or fluroalkenyl group having 1 to 21 carbon
atoms, or a fluoroether group having totally 1 to 200 repeating
units selected from the group consisting of the repeating units:
--C.sub.3F.sub.6O--, --C.sub.2F.sub.4O-- and --CF.sub.2O--, and
[0014] (B) repeating units derived from a monomer having a
functional group reactive with active hydrogen.
[0015] That is, the present invention provides a
fluorine-containing polymer for masonry treatment, comprising:
[0016] (A) a fluorine-containing monomer of the formula (I) which
is substituted at the .alpha.-position with a X group, and [0017]
(B) a monomer having a functional group reactive with active
hydrogen.
[0018] The present invention provides also a composition for
treating a masonry, which comprises the fluorine-containing polymer
comprising (A) the fluorine-containing monomer of the formula (I)
and (B) the monomer having a functional group reactive with active
hydrogen, and a solvent.
[0019] The present invention further provides a method of producing
a treated masonry, which comprises applying said composition to a
surface of a masonry, and then eliminating the organic solvent.
[0020] The repeating units (A) are derived from the
fluorine-containing monomer of the formula (I).
[0021] When the Rf group in the formula (I) is a fluoroalkyl group
or a fluoroalkenyl group, the Rf group is preferably a
perfluoroalkyl group or a perfluoroalkenyl group. The fluoroalkyl
group or the fluoroalkenyl group has 1 to 21 carbon atoms,
particularly 1 to 6 carbon atoms, for example, 1 to 4 carbon atoms.
Examples of the fluoroalkyl group include --CF.sub.3,
--CF.sub.2CF.sub.3, --CF.sub.2CF.sub.2CF.sub.3,
--CF(CF.sub.3).sub.2, --CF.sub.2CF.sub.2CF.sub.2CF.sub.3,
--CF.sub.2CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CF.sub.2).sub.4CF.sub.3, --(CF.sub.2).sub.2CF(CF.sub.3).sub.2,
--CF.sub.2C(CF.sub.3).sub.3,
--CF(CF.sub.3)CF.sub.2CF.sub.2CF.sub.3, --(CF.sub.2).sub.5CF.sub.3,
--(CF.sub.2).sub.3CF(CF.sub.3).sub.2,
--(CF.sub.2).sub.4CF(CF.sub.3).sub.2, --(CF.sub.2).sub.7CF.sub.3,
--(CF.sub.2).sub.5CF(CF.sub.3).sub.2,
--(CF.sub.2).sub.6CF(CF.sub.3).sub.2, and
--(CF.sub.2).sub.9CF.sub.3.
[0022] Y is an aliphatic group having 1 to 10 carbon atoms, an
aromatic group or a cycloaliphatic group, each having 6 to 10
carbon atoms, a group --CH.sub.2CH.sub.2N(R.sup.1)SO.sub.2-- group
(in which R.sup.1 is an alkyl group having 1 to 4 carbon atoms) or
a --CH.sub.2CH(OY.sup.1)CH.sub.2-- group (in which Y.sup.1 is a
hydrogen atom or an acetyl group). The aliphatic group is
preferably an alkylene group, particularly having 1 to 4 carbon
atoms, for example, 1 or 2 carbon atoms. The aromatic group and the
cycloaliphatic group may be substituted or unsubstituted.
[0023] The fluoroether group has at least one repeating unit (an
oxyperfluoroalkylene group) selected from the group consisting of
the repeating units: --C.sub.3F.sub.6O--, --C.sub.2F.sub.4O-- and
--CF.sub.2O--. The --C.sub.3F.sub.6O-- group is
--CF.sub.2CF.sub.2CF.sub.2O-- or --CF.sub.2C(CF.sub.3)FO--. The
--C.sub.2F.sub.4O-- group is generally --CF.sub.2CF.sub.2O--. The
total number of the oxyperfluoroalkylene repeating units is 1 to
200, for example, 1 to 100, and particularly 5 to 50. The
fluoroether group has a terminal group which is directly bonded to
the oxyperfluoroalkylene repeating unit. Examples of the terminal
group include a hydrogen atom, a halogen atom (e.g., a fluorine
atom), an alcohol group (e.g., HOCH.sub.2--), an epoxy group (for
example, ##STR3## an amine group (e.g., H.sub.2N--), a carboxylic
acid group (e.g., HOOC--), an acid halide group (e.g.,
F(O.dbd.)C--) and a chloromethyl group (ClH.sub.2C--). The
fluoroether group may have a fluoroalkylene group having 1 to 10
carbon atoms, particularly a perfluoroalkylene group, in addition
to the oxyperfluoroalkylene repeating unit and the terminal group.
Examples of the fluoroalkylene group having 1 to 10 carbon atoms
are --CF.sub.2-- and --CF.sub.2CF.sub.2--.
[0024] Examples of the fluoroether group (particularly, a
perfluoroether group) which is an example of the Rf group include
the followings: [0025]
F--(CF.sub.2CF.sub.2CF.sub.2O).sub.n--CF.sub.2CF.sub.2-- (n is a
number of 1 to 200), [0026]
F--(CF.sub.2C(CF.sub.3)FO).sub.n--CF.sub.2CF.sub.2-- (n is a number
of 1 to 200), [0027]
F--(CF.sub.2C(CF.sub.3)FO).sub.n--(CF.sub.2O).sub.m--CF.sub.2CF.sub.2--
(the total of n and m is 1 to 200), and [0028]
F--(CF.sub.2CF.sub.2O).sub.n--(CF.sub.2O).sub.m--CF.sub.2CF.sub.2--
(the total of n and m is 1 to 200).
[0029] Examples of the fluorine-containing monomer include the
followings: ##STR4## ##STR5## wherein Rf is a linear or branched
fluoroalkyl or fluoroalkenyl group having 1 to 21 carbon atoms, or
a fluoroether group having totally 1 to 200 repeating units
selected from the group consisting of the repeating units:
--C.sub.3F.sub.6O--, --C.sub.2F.sub.4O-- and --CF.sub.2O--.
[0030] In the monomer having a functional group reactive with
hydrogen atom (B), examples of the functional group reactive with
hydrogen atom includes a silane group, a phosphate group (or a
phosphoric acid group), a carboxylate group (a carboxylic acid
group), a sulfonate group (or a sulfonic acid group) and a glycidyl
group.
[0031] The monomer (B) is preferably a compound having a
carbon-carbon double bond and a functional group reactive with
active hydrogen.
[0032] A monomer having the silane group is preferably a compound
having a silane group (particularly a terminal silane group) and a
carbon-carbon double bond. The monomer having the silane group may
be a terminal silane coupling agent.
[0033] Specific examples of the silane group-containing monomer are
as follows: [0034]
CH.sub.2.dbd.CHCO.sub.2(CH.sub.2).sub.3Si(OCH.sub.3).sub.3, [0035]
CH.sub.2.dbd.CHCO.sub.2(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3,
[0036]
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2(CH.sub.2).sub.3Si(OCH.sub.3).sub.3
(.gamma.-methacryloxypropyltrimethoxysilane), [0037]
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3-
, [0038]
CH.sub.2.dbd.CHCO.sub.2(CH.sub.2).sub.3SiCH.sub.3(OC.sub.2H.sub-
.5).sub.2, [0039]
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2(CH.sub.2).sub.3SiC.sub.2H.sub.5(OCH.sub.-
3).sub.2, [0040]
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2(CH.sub.2).sub.3Si(CH.sub.3).sub.2(OC.sub-
.2H.sub.5), [0041]
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH,
[0042]
CH.sub.2.dbd.CHCO.sub.2(CH.sub.2).sub.3SiCH.sub.3[ON(CH.sub.3)C.s-
ub.2H.sub.5].sub.2, [0043]
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2(CH.sub.2).sub.3SiC.sub.6H.sub.5[ON(CH.su-
b.3)C.sub.2H.sub.5].sub.2, [0044]
CH.sub.2.dbd.CHSi(OCH.sub.3).sub.3, [0045]
CH.sub.2.dbd.CHSi(OC.sub.2H.sub.5).sub.3, [0046]
CH.sub.2.dbd.CHSiCH.sub.3(OCH.sub.3).sub.2, [0047]
CH.sub.2.dbd.CHSi(CH.sub.3).sub.2(OC.sub.2H.sub.5), [0048]
CH.sub.2.dbd.CHSi(CH.sub.3).sub.2SiCH.sub.3(OCH.sub.3).sub.2,
[0049] CH.sub.2.dbd.CHSiCH.sub.3[ON(CH.sub.3)C.sub.2H.sub.5].sub.2
vinyltrichlorosilane, and [0050] vinyl
tris(2-methoxyethoxy)silane.
[0051] Specific examples of a monomer having the phosphate group
include 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl
acid phosphate, acid phosphoxypropyl methacrylate, 3-chloro-2-acid
phosphoxypropyl methacrylate, and 2-methacryloyloxyethyl acid
phosphate monoethanolamine half salt.
[0052] Specific examples of a monomer having the carboxylate group
include methacrylic acid, acrylic acid, 2-methacryloyloxyethyl
succinic acid, 2-acryloyloxyethyl succinic acid,
2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate,
2-methacryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl
hexahydrophthalate, 2-acryloyloxypropyl phthalate,
2-acryloyloxypropyl hexahydrophthalate, 2-acryloyloxypropyl
tetrahydrophthalate, maleic anhydride and citraconic anhydride.
[0053] Specific examples of a monomer having the sulfonate group
include acrylamide-tert-butyl sulfonic acid, and
2-acrylamide-2-methylpropane sulfonic acid.
[0054] Specific examples of a monomer having the glycidyl group
include glycidyl methacrylate and glycidyl acrylate.
[0055] The amount of the monomer having a functional group reactive
with hydrogen atom (B) may be from 0.01 parts to 50 parts by
weight, from 0.1 parts to 20 parts by weight, based on 100 parts by
weight of the fluorine-containing polymer.
[0056] The fluorine-containing polymer may contain (C) an other
monomer, in addition to the fluorine-containing monomer (A) and the
monomer having a functional group (B). The other monomer (C) may be
a fluorine-free monomer. The fluorine-free monomer may be an alkyl
group-containing monomer.
[0057] The fluorine-free monomer may be a fluorine-free alkyl
(meth)acrylate.
[0058] The fluorine-free alkyl (meth)acrylate is generally a
monomer of the formula: X.sup.1--CX.sup.2.dbd.CH.sub.2 (i) wherein
X.sup.1 is an alkyl carboxylate group (the number of carbon atoms
in the alkyl group: 1 to 18), and X.sup.2 is a hydrogen atom or a
methyl group. The fluorine-containing polymer may not contain the
fluorine-free alkyl (meth)acrylate.
[0059] The fluorine-containing polymer may contain the other
monomer other than the fluorine-free alkyl (meth)acrylate. Examples
of the other monomer are Rf group-free monomers such as ethylene,
vinyl halide (for example, vinyl chloride), vinylidene halide (for
example, vinylidene chloride), styrene, vinyl alkyl ketone,
isoprene, chloroprene, butadiene, benzyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
glycerol mono(meth)acrylate, methoxypolyethyleneglycol
(meth)acrylate, polypropyleneglycol (meth)acrylate,
tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate,
trimethyl-(2-hydroxy-3-methacryloyloxypropyl) ammonium chloride and
3-chloro-2-hydroxypropyl methacrylate.
[0060] The amount of the other monomer may be from 0 to 100 parts
by weight, for example, from 0 to 90 parts by weight; particularly
from 1 to 70 parts by weight, based on 100 parts by weight of the
fluorine-containing monomer (A).
[0061] The fluorine-containing polymer can be prepared by any of
conventional polymerization methods. The conditions of
polymerization reaction can be arbitrarily selected. The
polymerization procedure includes a bulk polymerization, a solution
polymerization and an emulsion polymerization. The solution
polymerization is generally preferable.
[0062] The molecular weight of the fluorine-containing polymer may
be generally from 5,000 to 1,000,000 (for example, measured in GPC
and in terms of polystyrene).
[0063] The treatment agent is in the form of a solution wherein the
fluorine-containing polymer is dissolved in an organic solvent. The
organic solvent may be an alcohol, an ester, a ketone, a
halogenated hydrocarbon, or a petroleum organic solvent.
[0064] In the treatment agent comprising the fluorine-containing
polymer and the organic solvent, the concentration of the
fluorine-containing polymer may be, for example, from 0.1 to 50% by
weight.
[0065] The treatment agent may contain an antifreezing agent, a
viscosity-adjusting agent, an ultraviolet absorbing agent, an
antioxidant, a pH adjuster, a defoaming agent, an antiseptic agent,
a flame retardant, etc. according to necessity.
[0066] In the present invention, the treatment agent is applied to
a substrate (masonry) to impart the water- and oil-repellency and
the soil resistance to the substrate.
[0067] The substrate is masonry such as stone. Examples of the
masonry include stone, brick, concrete and tile. Examples of stone
include natural stone (for example, marble and granite), and
artificial stone.
[0068] A method of treating the substrate is as follows. The
treatment agent is applied to the substrate. The application can be
can be performed by coating, dipping, brushing, etc. Then, the
organic solvent is removed. The removal of the organic solvent can
be performed by, for example, the drying. The drying can be
performed at a temperature of, for example, 0.degree. C. to
200.degree. C.
[0069] The application amount of the fluorine-containing polymer
may be 0.05 to 50 g, for example, 0.1 to 20 g, especially 1 to 10
g, per 1 m.sup.2 of the surface area of the masonry.
[0070] The treatment agent can give the water-repellent
oil-repellent performance to the masonry surface, since the
treatment agent contains the fluorine-containing polymer. The
adhesion of a soil to masonry can be prevented, even if the soil is
an aqueous soil or is an oily soil.
PREFERABLE EMBODIMENTS OF THE INVENTION
[0071] Although Examples of this invention are described below,
these are only examples of this invention and this invention is not
limited thereto. Hereinafter % is % by weight, unless
specified.
[0072] In the following Examples and Comparative Examples, a soil
resistance test was conducted as follows:
[0073] A soil was put on a treated substrate, and droplets were
left for 24 hours and wiped off with a paper towel. The evaluation
was conducted according to the following criteria. [0074] 1: Deep
stain, and broad oil droplet spread [0075] 2: Deep stain, and
slight or no oil droplet spread [0076] 3: Medium stain, and no
spread [0077] 4: Slight stain [0078] 5: No stain.
EXAMPLE 1
[0079] Into a 200 cc four-necked flask equipped with a stirrer, an
inert gas inlet, a condenser and a thermometer, 13.0 g of
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCCl.dbd.CH.sub.2,
6.5 g of stearyl acrylate, 0.5 g of
.gamma.-methacryloxypropyltrimethoxysilane (SZ6030 manufactured by
Dow Corning Toray Co., Ltd.) and 113.3 g of
tetrachlorohexafluorobutane (S-316 manufactured by Daikin
Industries, Ltd.) were charged and heated to 60.degree. C. A
solution of t-butyl peroxypivalate (1.5 g) (PERBUTYL PV
manufactured by NOF Corp.) in trichloroethane (7.3 g) was added and
the polymerization reaction was conducted with stirring at
60.degree. C. for at least 12 hours. A gas chromatography revealed
that a polymerization reaction conversion was at least 97%. The
resultant polymer solution was diluted with butyl acetate to give a
treatment liquid having a solid content of 3%.
[0080] A surface of each of polished natural granite (mined in
China, and purchased from Nittai Kogyo Kabushiki-Kaisha) and
limestone (purchased from Inax Corp.) was coated with the treatment
liquid (1 mL of the treatment liquid was applied to an area of 5
cm.times.10 cm). After left at room temperature for 10 minutes, a
superfluous treatment liquid was wiped off After left at room
temperature for 24 hours, the soil resistance test was conducted.
The results are shown in Table 1 (granite) and Table 2
(limestone).
COMPARATIVE EXAMPLE 1
[0081] The polymerization reaction was conducted to give a polymer
solution in the same procedure as in Example 1 except that
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCCl.dbd.CH.sub.2
was changed to
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCH.dbd.CH.sub.2.
In the same manner as in Example 1, the polymer solution was
diluted with butyl acetate to adjust the solid concentration to 3%,
the treatment was conducted and the soil resistance test was
conducted. The results are shown in Table 1 and Table 2.
COMPARATIVE EXAMPLE 2
[0082] Into a 200 cc four-necked flask equipped with a stirrer, an
inert gas inlet, a condenser and a thermometer, 13.0 g of
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCCl.dbd.CH.sub.2,
7.0 g of stearyl acrylate and 113.3 g of
tetrachlorohexafluorobutane (S-316 manufactured by Daikin
Industries, Ltd.) were charged and heated to 60.degree. C. A
solution of t-butyl peroxypivalate (1.5 g) (PERBLTYL PV
manufactured by NOF Corp.) in trichloroethane (7.3 g) was added and
the polymerization reaction was conducted with stirring at
60.degree. C. for at least 12 hours. A gas chromatography revealed
that a polymerization reaction conversion was at least 97%. In the
same manner as in Example 1, the polymer solution was diluted with
butyl acetate to adjust the solid concentration to 3%, the
treatment was conducted and the soil resistance test was conducted.
The results are shown in Table 1 and Table 2.
EXAMPLE 2
[0083] Into a 200 cc four-necked flask equipped with a stirrer, an
inert gas inlet, a condenser and a thermometer, 16.8 g of
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCCl.dbd.CH.sub.2,
2.7 g of stearyl acrylate, 0.5 g of
.gamma.-methacryloxypropyltrimethoxysilane (SZ6030 manufactured by
Dow Corning Toray Co., Ltd.) and 60 g of butyl acetate were charged
and heated to 70.degree. C. Azobisisobutyronitrile (0.15 g) was
added and the polymerization reaction was conducted with stirring
at 70.degree. C. for at least 12 hours. A gas chromatography
revealed that a polymerization reaction conversion was at least
97%. In the same manner as in Example 1, the polymer solution was
diluted with butyl acetate to adjust the solid concentration to 3%,
the treatment was conducted and the soil resistance test was
conducted. The results are shown in Table 1 and Table 2.
EXAMPLE 3
[0084] The polymerization reaction was conducted to give a polymer
solution in the same procedure as in Example 1 except that
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCCl.dbd.CH.sub.2
was changed to
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OCOCF.dbd.CH.sub.2.
In the same manner as in Example 1, the polymer solution was
diluted with butyl acetate to adjust the solid concentration to 3%,
the treatment was conducted and the soil resistance test was
conducted. The results are shown in Table 1 and Table 2.
TABLE-US-00001 TABLE 1 Soil resistance test (granite) Olive Oil
Waste oil Red wine Coffee Example 1 5 5 4 5 Comparative Example 1 2
2 2 2 Comparative Example 2 3 3 2 3 Untreated 1 1 1 1 Example 2 5 5
5 5 Example 3 5 4 4 5
[0085] TABLE-US-00002 TABLE 2 Soil resistance test (limestone)
Olive Oil Waste oil Red wine Coffee Example 1 5 4 4 5 Comparative
Example 1 2 2 2 2 Comparative Example 2 3 2 2 3 Untreated 1 1 1 1
Example 2 5 5 5 5 Example 3 5 4 4 5
EFFECTS OF THE INVENTION
[0086] According to the present invention, excellent water- and
oil-repellency and stain resistance are imparted to masonries.
* * * * *
References