U.S. patent application number 15/197113 was filed with the patent office on 2016-10-27 for methods of material hydrophilization by glycidol-containing siloxanes.
The applicant listed for this patent is SAMSUNG ELECTRONICS CO., LTD.. Invention is credited to Oleg Valerievich BARANOV, Boris Alexandrovich IZMAILOV, Won-Cheol JUNG, Galy Dmitrievna MARKOVA, Elena Nikolaevna RODLOVSKAYA, Valeri Alexandrovich VASNEV.
Application Number | 20160312065 15/197113 |
Document ID | / |
Family ID | 48572244 |
Filed Date | 2016-10-27 |
United States Patent
Application |
20160312065 |
Kind Code |
A1 |
IZMAILOV; Boris Alexandrovich ;
et al. |
October 27, 2016 |
METHODS OF MATERIAL HYDROPHILIZATION BY GLYCIDOL-CONTAINING
SILOXANES
Abstract
A method of imparting hydrophilicity to a surface of a material,
which includes providing a base material having a surface; applying
and chemically fixing a siloxane oligomer represented by Chemical
Formula 1 to the surface of the base material to form a
siloxane-modified surface; and applying a glycidol compound
represented by Chemical Formula 2 to the siloxane-modified surface;
and carrying out a reaction therebetween to form an organosiloxane
coating having a N,N-bis(hydroxyalkyl)aminoalkyl group:
##STR00001## wherein R.sub.1, R.sub.2, and R.sub.3 are the same or
different and are each independently hydrogen or a C1 to C3 alkyl
group, A is a single bond or a C1 to C5 alkylene group, and n
ranges from 2 to 30; ##STR00002## wherein each R is the same or
different, and is as defined herein, and L is a substituted or
unsubstituted C1 to C3 alkylene group.
Inventors: |
IZMAILOV; Boris Alexandrovich;
(Moscow, RU) ; RODLOVSKAYA; Elena Nikolaevna;
(Lyubertsy, RU) ; MARKOVA; Galy Dmitrievna;
(Moscow, RU) ; BARANOV; Oleg Valerievich; (Moscow,
RU) ; VASNEV; Valeri Alexandrovich; (Moscow, RU)
; JUNG; Won-Cheol; (Seoul, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SAMSUNG ELECTRONICS CO., LTD. |
Suwon-si |
|
KR |
|
|
Family ID: |
48572244 |
Appl. No.: |
15/197113 |
Filed: |
June 29, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13708687 |
Dec 7, 2012 |
9403183 |
|
|
15197113 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 77/045 20130101;
C08G 77/26 20130101; C08K 5/1515 20130101; Y10T 428/31663 20150401;
C09D 5/00 20130101; C09D 7/00 20130101; C09D 183/08 20130101; B05D
5/00 20130101; C09D 183/08 20130101; Y10T 428/31612 20150401; B05D
1/36 20130101 |
International
Class: |
C09D 183/08 20060101
C09D183/08; C09D 5/00 20060101 C09D005/00; B05D 1/36 20060101
B05D001/36 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 7, 2011 |
RU |
2011149715 |
Nov 7, 2012 |
KR |
1020120125681 |
Claims
1. An article comprising a hydrophilically-modified surface, which
comprises: a base material; and an organosiloxane coating
chemically fixed on a surface of the base material, wherein the
organosiloxane coating comprises a reaction product of a siloxane
oligomer represented by Chemical Formula 1, or a polysiloxane
derived therefrom, with a glycidol compound represented by Chemical
Formula 2 and comprising an N,N-bis(hydroxyalkyl)aminoalkyl group:
##STR00022## wherein in Chemical Formula 1, R.sub.1, R.sub.2, and
R.sub.3 are the same or different and are each independently
hydrogen or a C1 to C3 alkyl group, A is a single bond or a C1 to
C5 alkylene group, and n ranges from 2 to 30; ##STR00023## wherein
in Chemical Formula 2, each R is the same or different, and is
independently hydrogen, a C1 to C3 alkyl group, or a C1 to C3
hydroxyalkyl group, and L is a substituted or unsubstituted C1 to
C3 alkylene group.
2. The article of claim 11, wherein the base material comprises an
organic material, an inorganic material, or an organic-inorganic
hybrid material, and comprises a hydroxyl group, a carboxyl group,
or a combination thereof on the surface.
3. The article of claim 12, wherein the base material comprises a
polymer, wood, leather, glass, a metal, a metal oxide, a metal
nitride, a ceramic material, or a combination thereof.
4. The article of claim 11, wherein the siloxane oligomer
represented by Chemical Formula 1 is
oligo(aminopropyl)ethoxysilane, oligo(aminopropyl)methosilane,
oligo(aminoethyl)methoxysilane, oligo(aminoethyl)ethoxysilane,
oligo(aminobutyl)ethoxysilane, oligo(aminobutyl)methosilane,
oligo(aminopentyl)ethoxysilane, oligo(aminopentyl)methoxysilane, or
a combination thereof.
5. The article of claim 11, wherein the glycidol compound
represented by Chemical Formula 2 is oxiranylmethanol,
(3-propyl-2-oxiranyl)methanol, oxiranylethanol,
2-(2-methyl-2-oxiranyl)ethanol, oxiranylpropanol, or a combination
thereof.
6. The article of claim 1, wherein the coating displays bands for a
C--OH bond, a C--N bond, a Si--O--Si bond, a Si--O--C bond, and a
Si--C bond in its infrared spectroscopy spectrum.
7. The article of claim 1, wherein the surface of the article has a
water contact angle of about 20.degree. or less.
8. The article of claim 1, wherein the article is an interior or
exterior part of a home appliance, an anti-fogging glass, or a
glass use in a vehicle.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of U.S. Ser. No.
13/708,687, filed Dec. 12, 2012, which claims priority to and the
benefit of Russian Patent Application No. 2011149715, filed on Dec.
7, 2011 and Korean Patent Application No. 10-2012-0125681, filed on
Nov. 7, 2012, and all the benefits accruing therefrom under 35
U.S.C. .sctn.119, the contents of all of which in their entirety
are incorporated herein by reference.
BACKGROUND
[0002] 1. Field
[0003] A method of manufacturing modified materials is disclosed.
The method may be used for imparting hydrophilic surface properties
to various materials.
[0004] 2. Description of the Related Art
[0005] One method of hydrophilic processing of a textile material
with a composition containing a mixture of polyorganosiloxane and
polydiorganosiloxane is described in U.S. Pat. No. 3,932,276 of the
Federal Republic of Germany (Composition for Treatment of Textiles
and Method of Processing). The polyorganosiloxane prepared
according to that method possesses hydrophilic properties, but
insoluble in water. To increase its emulsifying ability in the
processing of fibrous materials another polyorganosiloxane is
added, which functions as a surfactant. The disadvantage of this
method is the instability of the emulsion, and its tendency to
coagulate, caused by the properties of the applied
polyorganosiloxanes.
[0006] Another method of providing a textile material made of
various fibers with hydrophilic properties is disclosed in Russian
Patent No. 2370583 entitled "Method of Providing Fibrous Materials
with Hydrophilic Properties by Means of Oxyalkylenorganosiloxane
Block Copolymers." However, this method uses
oxyalkylenorganosiloxane in an amount of 1-5% based on a total
weight of fibrous material. Thus, there remains a need for a
material with enhanced hydrophilic properties.
[0007] The above information disclosed in this Background section
is only for enhancement of understanding of the background of the
invention and therefore it may contain information that does not
form the prior art that is already known in this country to a
person of ordinary skill in the art.
SUMMARY
[0008] An embodiment provides a method of imparting hydrophilic
properties to a surface of various base materials.
[0009] Another embodiment provides an article including a
hydrophilic surface modified by the aforementioned method.
[0010] According to an embodiment, the method of imparting
hydrophilicity to a surface of a material includes
[0011] providing a base material having a surface; and
[0012] applying and chemically fixing a siloxane oligomer
represented by Chemical Formula 1 to the surface of the base
material to form a siloxane-modified surface; and
[0013] applying a glycidol compound represented by Chemical Formula
2 to the siloxane-modified surface and carrying out a reaction
therebetween to form an organosiloxane coating having an N,
N-bis(hydroxyalkyl)aminoalkyl group:
##STR00003##
[0014] wherein in Chemical Formula 1,
[0015] R.sub.1, R.sub.2, and R.sub.3 are the same or different, and
are each independently hydrogen or a C1 to C3 alkyl group,
[0016] A is a single bond or a C1 to C5 alkylene group, and
[0017] n ranges from 2 to 30;
##STR00004##
[0018] wherein in Chemical Formula 2,
[0019] each R is the same or different, and is independently
hydrogen, a C1 to C3 alkyl group, or a C1 to C3 hydroxyalkyl group,
and
[0020] L is a substituted or unsubstituted C1 to C3 alkylene group.
The base material may include an organic material, an inorganic
material, or an organic-inorganic hybrid material, and may have a
hydroxyl group, a carboxyl group, or a combination thereof on the
surface thereof.
[0021] The base material may be subjected to a corona treatment, an
ultraviolet ("UV") treatment, a plasma treatment, or a chemical
treatment using hydrogen peroxide, hexafluoride isopropanol, or an
acid to have a hydroxyl group, a carboxyl group, or a combination
thereof on its surface.
[0022] The siloxane oligomer represented by Chemical Formula 1 may
include oligo(aminopropyl)ethoxysilane,
oligo(aminopropyl)methoxysilane, oligo(aminoethyl)methoxysilane,
oligo(aminoethyl)ethoxysilane, oligo(aminobutyl)ethoxysilane,
oligo(aminobutyl)methoxysilane, oligo(aminopentyl)ethoxysilane,
oligo(aminopentyl)methoxysilane, or a combination thereof.
[0023] In Chemical Formula 1 of the siloxane oligomer, "n" may
range from 4 to 16.
[0024] The glycidol compound represented by Chemical Formula 2 may
be oxiranylmethanol, (3-propyl-2-oxiranyl)methanol,
oxiranylethanol, 2-(2-methyl-2-oxiranyl)ethanol, oxiranylpropanol,
or a combination thereof.
[0025] Applying and chemically fixing the siloxane oligomer to the
surface of the base material may include wetting the surface of the
base material with a solution containing the siloxane oligomer, and
drying, heating, or drying and heating the wetted surface.
[0026] The solution containing the siloxane oligomer may be
prepared by dissolving the siloxane oligomer represented by
Chemical Formula 1 in a C1 to C10 alcohol in an amount of about
0.05 to about 10 weight % based on a total weight of the
solution.
[0027] Applying and chemically fixing the glycidol compound to the
siloxane-modified surface may include wetting the siloxane-modified
surface with a solution containing the glycidol compound, and
drying and heating the wetted surface.
[0028] The solution containing the glycidol compound may be
prepared by dissolving the glycidol compound represented by
Chemical Formula 2 in a C1 to C10 alcohol in an amount of about 1
to about 50 weight % based on a total weight of the solution.
[0029] According to another embodiment, an article having a
hydrophilically-modified surface includes a base material and an
organosiloxane coating chemically fixed on a surface of the base
material, wherein the coating comprises a reaction product of a
siloxane oligomer represented by Chemical Formula 1, or a
polysiloxane derived therefrom with a glycidol compound represented
by Chemical Formula 2 and comprising an
N,N-bis(hydroxyalkyl)aminoalkyl group:
##STR00005##
[0030] wherein in Chemical Formula 1,
[0031] R.sub.1, R.sub.2, and R.sub.3 are the same or different and
are each independently hydrogen or a C1 to C3 alkyl group,
[0032] A is a single bond or a C1 to C5 alkylene group, and
[0033] n ranges from 2 to 30.
##STR00006##
[0034] In Chemical Formula 2,
[0035] each R is the same or different, and is independently
hydrogen, a C1 to C3 alkyl group, or a C1 to C3 hydroxyalkyl group,
and
[0036] L is a substituted or unsubstituted C1 to C3 alkylene group.
The base material may include an organic material, an inorganic
material, or an organic-inorganic hybrid material, and may have a
hydroxyl group, a carboxyl group, or a combination thereof on the
surface.
[0037] The base material may include a polymer, wood, leather,
glass, a metal, a metal oxide, a metal nitride, a ceramic material,
or a combination thereof.
[0038] The siloxane oligomer represented by Chemical Formula 1 may
include oligo(aminopropyl)ethoxysilane,
oligo(aminopropyl)methoxysilane, oligo(aminoethyl)methoxysilane,
oligo(aminoethyl)ethoxysilane, oligo(aminobutyl)ethoxysilane,
oligo(aminobutyl)methoxysilane, oligo(aminopentyl)ethoxysilane,
oligo(aminopentyl)methoxysilane, or a combination thereof.
[0039] The glycidol compound represented by Chemical Formula 2 may
be oxiranylmethanol, (3-propyl-2-oxiranyl)methanol,
oxiranylethanol, 2-(2-methyl-2-oxiranyl)ethanol, oxiranylpropanol,
or a combination thereof.
[0040] The coating may display bands for a C--OH bond, a C--N bond,
a Si--O--Si bond, a Si--O--C bond, and a Si--C bond in its infrared
spectroscopy spectrum.
[0041] The surface of the article may have a water contact angle of
about 20.degree. or less.
[0042] The article may be an interior or exterior part of a home
appliance, an anti-fogging glass, or a glass for use in a
vehicle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] These and/or other aspects of the present disclosure will
become apparent and more readily appreciated from the following
description of the embodiments, taken in conjunction with the
accompanying drawings in which:
[0044] FIG. 1 schematically shows a chemical structure of the
coatings formed on a material surface in accordance with an
embodiment.
DETAILED DESCRIPTION
[0045] This disclosure will be described more fully hereinafter
with reference to the accompanying drawings, in which embodiments
are shown. This disclosure may, however, be embodied in many
different forms and is not to be construed as limited to the
exemplary embodiments set forth herein.
[0046] In the drawings, the thickness of layers, films, panels,
regions, etc., are exaggerated for clarity. Like reference numerals
designate like elements throughout the specification. It will be
understood that when an element such as a layer, film, region, or
substrate is referred to as being "on" another element, it can be
directly on the other element or intervening elements may also be
present. In contrast, when an element is referred to as being
"directly on" another element, there are no intervening elements
present.
[0047] The terminology used herein is for the purpose of describing
particular embodiments only and is not intended to be limiting. As
used herein, the singular forms "a," "an" and "the" are intended to
include the plural forms as well, unless the context clearly
indicates otherwise. The term "or" means "and/or." It will be
further understood that the terms "comprises" and/or "comprising,"
or "includes" and/or "including" when used in this specification,
specify the presence of stated features, regions, integers, steps,
operations, elements, and/or components, but do not preclude the
presence or addition of one or more other features, regions,
integers, steps, operations, elements, components, and/or groups
thereof. The term "combination thereof" means that a combination
comprising at least one of the listed elements is present,
optionally together with a like element not listed.
[0048] Unless otherwise defined, all terms (including technical and
scientific terms) used herein have the same meaning as commonly
understood by one of ordinary skill in the art to which this
general inventive concept belongs. It will be further understood
that terms, such as those defined in commonly used dictionaries,
should be interpreted as having a meaning that is consistent with
their meaning in the context of the relevant art and the present
disclosure, and will not be interpreted in an idealized or overly
formal sense unless expressly so defined herein.
[0049] Exemplary embodiments are described herein with reference to
cross section illustrations that are schematic illustrations of
idealized embodiments. As such, variations from the shapes of the
illustrations as a result, for example, of manufacturing techniques
and/or tolerances, are to be expected. Thus, embodiments described
herein should not be construed as limited to the particular shapes
of regions as illustrated herein but are to include deviations in
shapes that result, for example, from manufacturing. For example, a
region illustrated or described as flat may, typically, have rough
and/or nonlinear features. Moreover, sharp angles that are
illustrated may be rounded. Thus, the regions illustrated in the
figures are schematic in nature and their shapes are not intended
to illustrate the precise shape of a region and are not intended to
limit the scope of the present claims.
[0050] "Alkyl" as used herein means a monovalent group derived from
a straight or branched chain saturated aliphatic hydrocarbon having
the specified number of carbon atoms.
[0051] "Alkylene" as used herein means a divalent group derived
from a straight or branched chain saturated aliphatic hydrocarbon
having the specified number of carbon atoms.
[0052] "Hydroxyalkyl" as used herein means an alkyl group wherein
at least one hydrogen is replaced with a hydroxyl group.
[0053] "Substituted" as used herein refers to replacing at least
one hydrogen with a C1 to C3 alkyl group, a hydroxyl group, a cyano
group, a nitro group, a sulfhydryl group, a halogen (e.g., Cl, Br,
I, or F), or a combination thereof, provided that the valence of
the atom is not exceeded. In an embodiment, the substituent is a C1
to C3 alkyl group, a hydroxyl group, or a combination thereof.
[0054] In an embodiment, the method of imparting hydrophilicity to
a surface of a material may include the steps of: providing a base
material having a surface; applying and chemically fixing a
siloxane oligomer represented by Chemical Formula 1 to the surface
of the base material to form a siloxane-modified surface; and
applying a glycidol compound represented by Chemical Formula 2 to
the siloxane-modified surface and carrying out a reaction
therebetween to form an organosiloxane coating having a
N,N-bis(hydroxyalkyl)aminoalkyl group on the surface:
##STR00007##
[0055] wherein in Chemical Formula 1,
[0056] R.sub.1, R.sub.2, and R.sub.3 are the same or different, and
are each independently hydrogen or a C1 to C3 alkyl group,
[0057] A is a single bond or a C1 to C5 alkylene group, and
[0058] n ranges from 2 to 30;
##STR00008##
[0059] In Chemical Formula 2,
[0060] each R is the same or different, and is independently
hydrogen, a C1 to C3 alkyl group, or a C1 to C3 hydroxyalkyl group,
and
[0061] L is a substituted or unsubstituted C1 to C3 alkylene
group.
[0062] In an embodiment, L is unsubstituted or substituted with a
C1 to C3 alkyl group, a hydroxyl group, or a combination
thereof.
[0063] The base material may include a hydroxyl group, a carboxyl
group, or a combination thereof on its surface. The base material
may include an organic material, an inorganic material, or an
organic-inorganic hybrid material. Specifically, the base material
may include various polymers such as polyester, polyethylene,
polypropylene, polycarbonate, or polyvinylchloride, or natural
materials such as wood or leather, a glass, a metal, a metal oxide
or nitride such as SiO.sub.2, TiO.sub.2, SnO.sub.2, ZnO.sub.2,
Fe.sub.2O.sub.3, Al.sub.2O.sub.3, AAO (anodic aluminum oxide), and
SiN.sub.4, a ceramic material, or a combination thereof, but is not
limited thereto. The base material may have any shape such as a
fiber, a film, a plate, a sphere, a cube, a cuboid, and a
polyhedron, or an irregular shape, but is not limited thereto. The
base material may be subjected to a surface treatment so that the
surface of the base material has a hydroxyl group, a carboxyl
group, or a combination thereof on the surface. Non-limiting
examples of the surface treatment may include a corona treatment,
an ultraviolet ("UV") treatment, a plasma treatment, or a chemical
treatment using hydrogen peroxide, hexafluoride isopropanol, or an
acid such as concentrated or dilute sulfuric acid.
[0064] In an embodiment, the method may impart hydrophilicity to
various materials by forming an organosiloxane coating having an
N,N-bis(hydroxyalkyl)aminoalkyl group via molecular assembly on a
surface of the material. The method may first include applying and
chemically fixing the siloxane oligomer represented by Chemical
Formula 1 on the surface of the base material to provide a
siloxane-modified surface. In the second step of, the method may
further include applying and chemically fixing the glycidol
compound represented by Chemical Formula 2 to the siloxane-modified
surface to form an organosiloxane coating having an
N,N-bis(hydroxyalkyl)aminoalkyl group.
[0065] Specific examples of the siloxane oligomer represented by
Chemical Formula 1 include oligo(aminopropyl)ethoxysilane,
oligo(aminopropyl)methoxysilane, oligo(aminoethyl)methoxysilane,
oligo(aminoethyl)ethoxysilane, oligo(aminobutyl)ethoxysilane,
oligo(aminobutyl)methoxysilane, oligo(aminopentyl)ethoxysilane, and
oligo(aminopentyl)methoxysilane, but are not limited thereto. A
combination comprising at least one of the foregoing siloxane
oligomers may be used. The siloxane oligomer may be
oligo(aminopropyl)ethoxysilane represented by Chemical Formula
3.
##STR00009##
[0066] Specific examples of the glycidol compound represented by
Chemical Formula 2 include oxiranylmethanol,
(3-propyl-2-oxiranyl)methanol, oxiranylethanol,
2-(2-methyl-2-oxiranyl)ethanol, and oxiranylpropanol, but are not
limited thereto. A combination comprising at least one of the
foregoing glycidol compounds may be used.
[0067] For example, the glycidol compound may be oxiranylmethanol
represented by Chemical Formula 4.
##STR00010##
[0068] Initially, the siloxane-modified surface is prepared by
applying the siloxane oligomer represented by Chemical Formula 1,
such as oligo(aminopropyl)ethoxysilane, to the material surface and
chemically fixing, i.e., reacting the same with a reactive group on
the surface, e.g., a hydroxyl group (see, for example, Reaction
Scheme 1).
##STR00011##
[0069] The chemical fixing of the siloxane oligomer may involve
dissolving the siloxane oligomer in an appropriate solvent, e.g., a
C1 to C10 alcohol to prepare a siloxane oligomer solution, and
wetting (e.g., soaking) the surface of the base material with the
siloxane oligomer solution, followed by drying and/or heating the
wetted surface in the air, or in an oven. The siloxane oligomer
represented by Chemical Formula 1 may have an appropriate
solubility in order to uniformly modify (e.g., coat) the surface of
the base material with siloxane moieties. Drying and/or heating may
enable the siloxane oligomer represented by Chemical Formula 1 to
be chemically fixed (reacted) on the surface of the base
material.
[0070] The siloxane oligomer having a desired value of "n" may be
prepared by reacting a proper amount of trialkoxysilane compound
having an aminoalkyl group in the presence of an appropriate amount
of water.
[0071] The concentration of the siloxane oligomer solution is not
particularly limited and may range from about 0.05 to about 10
percent by weight ("weight % or "wt %"), specifically from about
0.1 to about 1 wt %, based on a total weight of the solution. The
temperature of drying and/or heating in the air is not particularly
limited and may be room temperature (about 20.degree. C.) or
higher, specifically a temperature of about 30.degree. C. to
150.degree. C. In addition, the time for drying and/or heating is
not particularly limited, and may be selected from about 5 minutes
to about 24 hours.
[0072] Due to a condensation reaction of an alkoxy group of the
oligomer with a reactive functional group (e.g., a hydroxyl group)
on the surface of material, the siloxane oligomer of Chemical
Formula 1 is covalently fixed on the surface of a material, thus
forming micro- or nano-coating containing the siloxane oligomer of
Chemical Formula 1 or a polysiloxane derived therefrom (see,
Reaction Scheme 1).
[0073] The weight of the organosiloxane coating formed on the
surface of the material after wetting, drying and/or heat treatment
may be estimated by an increase in the weight of the material, and
may be expressed as a percentage of the initial weight of the
material. If after single soaking, drying and heat treatment the
material gain does not reach desired values, then soaking, drying
and heat treatment of the material may be repeated until the weight
gain does not reach the desired values. The coatings thus formed
may have a micrometer (e.g., 1 to 100 micrometer) or nanometer
(e.g., 1 to 999 nanometer) thickness as desired for the particular
application.
[0074] Next, the glycidol compound represented by Chemical Formula
2 may be used in the molecular assembly. Specifically, the surface
of the siloxane-modified surface may be treated with the glycidol
compound either neat or as a solution containing the glycidol
compound. Subsequent drying, heating, or drying and heating in the
air or in an oven may trigger a condensation reaction of grafted
aminopropyl containing organosiloxane coating with a glycidol
compound (e.g., oxiranyl methanol). As a result, the glycidol
compound may react with the amino groups of the organosiloxane
coating fixed on the surface of the base material to form the
hydrophilic N,N-bis(1,2-dihydroxypropyl)aminopropyl groups thereon
(see, for example, Reaction Scheme 2).
##STR00012##
[0075] The concentration of the glycidol solution is not
particularly limited and may be selected as desired. For example,
the concentration of the glycidol solution may range from about 1
to about 50 wt %, based on a total weight of the solution but is
not limited thereto. The temperature of drying or heating in the
air is also not particularly limited and it may be room temperature
(or about 20.degree. C.) or higher, specifically a temperature of
about 30.degree. C. to about 150.degree. C. In addition, the time
for drying and/or heating may not be particularly limited, and for
example, may be selected from about 5 minutes to about 24
hours.
[0076] By the aforementioned method of molecular assembly, the
surface may be modified by a coating layer of "brush geometry" as
illustrated in FIG. 1.
[0077] The presence in the coatings of hydrophilic (water-soluble)
N,N-bis(hydroxyalkyl)aminoalkyl groups may add hydrophilicity to
the material surface.
[0078] While not wanting to be bound by a theory, it is understood
that the mechanism of the formation of hydrophilic organosiloxane
coatings on the surface of silicate glass is based on the
interaction of reactive hydrophilic alkoxysilyl groups of the
siloxane oligomer (e.g., oligo(aminopropyl)ethoxysiloxane (I-III))
with silanolic groups present on the surface of silicate glass
(see, Reaction Scheme 3).
##STR00013##
[0079] In Reaction Scheme 3, ethanol may be separated and removed
during the drying and/or the heat treatment of the material,
specifically heat treatment.
[0080] While not wanting to be bound by a theory, it is also
understood that, the mechanism of the formation of hydrophilic
organosiloxane coatings is based on the interaction of grafted
aminopropyl containing coatings with the glycidol compound (see,
for example, Reaction Scheme 2), leading to formation of the
hydrophilic N,N-bis(hydroxyalkyl)aminoalkyl groups on the
siloxane-modified surface (i.e., the surface of the organosiloxane
coatings).
[0081] While not wanting to be bound by a theory, it is understood
that the mechanism of the formation of hydrophilic organosiloxane
coatings on the surface of a polyester film is based on the
interaction of reactive hydrophilic alkoxy (e.g., ethoxy) groups of
the siloxane oligomer of Chemical Formula 1 (e.g.,
oligo(aminopropyl)ethoxysiloxane (I-III)) with the terminal
carboxyl (--COOH) and hydroxyl (--OH) groups, located on the
surface of a polyester film (see, for example, Reaction Scheme
4).
##STR00014##
[0082] In Reaction Scheme 4, ethanol may be separated and removed
by the drying and/or the heat treatment of the material,
specifically heat treatment.
[0083] While not wanting to be bound by a theory, it is also
understood that the mechanism of the formation of hydrophilic
organosiloxane coatings is based on the interaction of grafted
aminopropyl containing coatings with the glycidol compound (see,
Scheme 2), leading to formation of the hydrophilic
N,N-bis(1,2-dihydroxypropyl)aminoalkyl groups on the organosiloxane
coating surface.
[0084] In another embodiment, an article having a
hydrophilically-modified surface may include a base material and an
organosiloxane coating chemically fixed, for example formed, on a
surface of the base material, wherein the organosiloxane coating is
formed by a reaction of a siloxane oligomer represented by Chemical
Formula 1, or a polysiloxane derived therefrom with a glycidol
compound represented by Chemical Formula 2 and having an
N,N-bis(hydroxyalkyl)aminoalkyl group, and the siloxane oligomer or
the polysiloxane derived therefrom is chemically fixed on the
surface of the base material.
##STR00015##
[0085] In Chemical Formula 1,
[0086] R.sub.1, R.sub.2, and R.sub.3 are the same or different, and
are each independently hydrogen or a C1 to C3 alkyl group,
[0087] A is a single bond or a C1 to C5 alkylene group, and
[0088] n ranges from 2 to 30;
##STR00016##
[0089] wherein in Chemical Formula 2,
[0090] each R is the same or different, and is independently
hydrogen, a C1 to C3 alkyl group, or a C1 to C3 hydroxyalkyl group,
and
[0091] L is a substituted or unsubstituted C1 to C3 alkylene
group.
[0092] In this embodiment, the base material, the siloxane oligomer
represented by Chemical Formula 1, the glycidol compound
represented by Chemical Formula 2, and the formation of
N,N-bis(hydroxyalkyl)aminoalkyl by the reaction therebetween are
the same as set forth above.
[0093] As used herein, the term "chemically fixing" means a linking
through a bond (e.g., a covalent bond) formed by interaction
between the compounds.
[0094] The infrared spectroscopy spectrum of the coating may
display vibrational bands for a C--OH bond, a C--N bond, a
Si--O--Si bond, a Si--O--C bond, and a Si--C bond. The
organosiloxane coating may further include a vibrational band for a
C(.dbd.O)O bond. The IR-spectra of the modified samples of
materials contain bands of valent vibrations of the C--OH bonds in
the 3635-3625 cm.sup.-1 range, for C(.dbd.O)OR bonds--in the
1750-1730 cm.sup.-1 range, for C--N bonds--in the 1,230-1030
cm.sup.-1 range, for Si--O--Si bonds--in the 1080-1020 cm.sup.-1
range, for Si--O--C bonds--in the 880-810 cm.sup.-1 range, and
deformation vibrations of Si--C bonds in the 1260-800 cm.sup.-1
range, which is consistent with the formation of the aforementioned
organosiloxane coating.
[0095] The article includes a coating formed on the base material
and thereby has a hydrophilically modified surface, and the surface
of the coating has a water contact angle of about 20.degree. or
less. Such a low level of water contact angle has an effect of
preventing dew condensation phenomenon at the surface of the
article. Therefore, such an article may find utility in various
applications requiring the prevention of the dew condensation. For
example, the article may be an interior or exterior part material
for various appliances such as a refrigerator, an air conditioner,
and a humidifier, or an anti-fogging glass or a glass use in
vehicles.
[0096] Hereinafter, embodiments are illustrated in more detail with
reference to examples. It should be understood, however, that the
following are exemplary embodiments and therefore are not
limiting.
EXAMPLES
Example 1
[0097] The surface of a silicate glass is wetted with an ethanolic
or aqueous solution of a siloxane oligomer represented by the
following chemical formula (I) in a concentration of 0.1% and 1%,
respectively, dried in the air and heat-treated at a temperature of
140.degree. C. to fix the siloxane oligomer on the surface of the
glass.
##STR00017##
[0098] The silicate glass having the siloxane-modified surface is
wetted with a 10% ethanolic solution of oxiranylmethanol, dried in
the air, and heat-treated at a temperature of 140.degree. C. The
water contact angle is determined by tensiometer "Tracker IT
Concept" (France) two minutes (in static conditions) after the
water drop had been placed on the surface of the base material.
Example 2
[0099] The silicate glass is treated in the same manner as set
forth in Example 1, except that 0.1% and 1% solutions of the
siloxane oligomer represented by the following chemical formula
(II) are used.
##STR00018##
[0100] The water contact angle listed in Table 1 confirms an
increase in hydrophilicity of the silicate glass.
Example 3
[0101] The silicate glass is treated in the same manner as set
forth in Example 1, except that 0.1% and 1% solutions of the
siloxane oligomer represented by the following chemical formula
(III) are used.
##STR00019##
[0102] The water contact angle listed in Table 1 confirms an
increase in hydrophilicity of the silicate glass.
Example 4
[0103] A base material is treated in the same manner as set forth
in Example 1, except that a polyester film is used as the base
material. The water contact angle listed in Table 1 confirms an
increase in hydrophilicity of the polyester film.
Example 5
[0104] A base material is treated in the same manner as set forth
in Example 1, except that a polyester film is used as the base
material and 0.1% and 1% solutions of the siloxane oligomer
represented by the following chemical formula (II) are used.
##STR00020##
[0105] The water contact angle listed in Table 1 confirms an
increase in hydrophilicity of the polyester film.
Example 6
[0106] A base material is treated in the same manner as set forth
in Example 1, except that a polyester film is used as the base
material and 0.1% and 1% solutions of the siloxane oligomer
represented by the following chemical formula (III) are used.
##STR00021##
[0107] The water contact angle listed in Table 1 confirms an
increase in hydrophilicity of the polyester film.
TABLE-US-00001 TABLE 1 Contact angel of wetting the surface of
materials, modified by organosiloxane coatings, containing the
hydrophilic glycidol groups Area of the Concentration modified
Weight of organosiloxane coating on Contact of oligomer surface, S,
the material surface Weight of glycidol angel, Material Oligomer
solution, % cm.sup.2 g mmole g/cm.sup.2 mmole/cm.sup.2 mmole g
mmole/cm.sup.2 g/cm.sup.2 degree Silicate I 0.1 6 0.1 0.9 0.017
0.15 1.8 0.13 0.1 0.007 17 glass 1 1 9.07 0.17 1.51 18.15 1.34
3.025 0.22 16 II 0.1 0.1 0.9 0.017 0.15 1.8 0.13 0.1 0.007 16 1 1
9.07 0.17 1.51 18.15 1.34 3.025 0.22 16 III 0.1 0.1 0.9 0.017 0.15
1.8 0.13 0.1 0.007 16 1 1 9.07 0.17 1.51 18.15 1.34 3.025 0.22 16
Polyester I 0.1 18 0.1 0.9 0.0055 0.15 1.8 0.13 0.1 0.007 18 film 1
1 9.07 0.055 0.50 18.15 1.34 1.008 0.07 17 II 0.1 0.1 0.9 0.0055
0.15 1.8 0.13 0.1 0.007 17 1 1 9.07 0.055 0.50 18.15 1.34 1.008
0.07 17 III 0.1 0.1 0.9 0.0055 0.15 1.8 0.13 0.1 0.007 17 1 1 9.07
0.055 0.50 18.15 1.34 1.008 0.07 17 Silicate Not 46 glass Polyester
Not 43 film
[0108] Analysis of the results of materials surface treatment
described in examples 1-6, showed that the aforementioned method of
imparting hydrophilicity to produces a variety of materials with a
high level of hydrophilicity. Contact angle of the material surface
decreases in 2.5-2.8 times by the use of 0.1 to 1% by weight of
oligo(aminopropyl)ethoxysiloxane (1-111).
[0109] Thus, the aforementioned method of imparting hydrophilic
properties allows an increase the hydrophilicity of the surface of
a material (silicate glass, polyester films) of about 2.5-2.8
times. The hydrophilic ability of such organosiloxane coatings with
hydrophilic N, N-bis(1,2-dihydroxypropyl)aminoalkyl groups
surpasses that of the analogs not having the
N,N-bis(1,2-dihydroxypropyl)aminoalkyl groups, and their production
by the method of molecular assembly requires minimal amounts of
initial material, i.e., siloxane oligomer.
[0110] While this disclosure has been described in connection with
what is presently considered to be practical exemplary embodiments,
it should be understood that the invention is not limited to the
disclosed embodiments, but, on the contrary, is intended to cover
various modifications and equivalent arrangements included within
the spirit and scope of the appended claims.
* * * * *