U.S. patent application number 15/766330 was filed with the patent office on 2019-04-25 for reactive surfactant composition for emulsion polymerization.
This patent application is currently assigned to KAO CORPORATION. The applicant listed for this patent is KAO CORPORATION. Invention is credited to Takayuki IKENAGA, Shogo KAMENOUE, Atsuhito MORI.
Application Number | 20190119410 15/766330 |
Document ID | / |
Family ID | 58487586 |
Filed Date | 2019-04-25 |
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United States Patent
Application |
20190119410 |
Kind Code |
A1 |
KAMENOUE; Shogo ; et
al. |
April 25, 2019 |
REACTIVE SURFACTANT COMPOSITION FOR EMULSION POLYMERIZATION
Abstract
The present invention is concerned with a reactive surfactant
composition for emulsion polymerization, which is able to micronize
the particle diameter of a polymer emulsion and to reduce the
addition amount of the reactive surfactant composition to be used.
The reactive surfactant composition for emulsion polymerization of
the present invention contains a reactive anionic surfactant
(component A) represented by the following formula (I), the
component A being satisfied with the following requirement R:
##STR00001## wherein AO represents an alkyleneoxy group having a
carbon number of 3 or more and 18 or less; EO represents an
ethyleneoxy group; p represents an integer of 1 or more and 15 or
less; m' represents an integer of 0 or more; n' represents an
integer of 0 or more; W represents a hydrogen ion or a cation; and
plural kinds of AOs may coexist. Requirement R: An average addition
molar number m of AO is a number of 1 or more and 50 or less; an
average addition molar number n of EO is a number of 0 or more and
200 or less; and when in the component A, a component having an
addition molar number of AO of (m-3) or less is defined as
(component A-1), and a component having an addition molar number of
AO of (m+2) or more is defined as (component A-2), X in the
following formula (I) is less than 30, provided that when m is less
than 3, (m'=0) is defined as (component A-1): X={(molar number of
component A-1)+(molar number of component A-2)}/(molar number of
component A).times.100 (I).
Inventors: |
KAMENOUE; Shogo;
(Wakayama-shi, Wakayama, JP) ; IKENAGA; Takayuki;
(Wakayama-shi, Wakayama, JP) ; MORI; Atsuhito;
(Wakayama-shi, Wakayama, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
KAO CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
KAO CORPORATION
Tokyo
JP
|
Family ID: |
58487586 |
Appl. No.: |
15/766330 |
Filed: |
October 3, 2016 |
PCT Filed: |
October 3, 2016 |
PCT NO: |
PCT/JP2016/079204 |
371 Date: |
April 5, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 116/12 20130101;
C09D 5/02 20130101; C09D 5/022 20130101; C08F 2800/20 20130101;
C08F 128/02 20130101; C08F 290/06 20130101; C09D 157/04 20130101;
C08F 2/26 20130101; C08F 220/16 20130101; C08F 2/24 20130101; C08F
2500/02 20130101 |
International
Class: |
C08F 2/26 20060101
C08F002/26; C08F 290/06 20060101 C08F290/06; C08F 116/12 20060101
C08F116/12; C08F 128/02 20060101 C08F128/02; C09D 157/04 20060101
C09D157/04; C09D 5/02 20060101 C09D005/02 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 9, 2015 |
JP |
2015-201128 |
Claims
1.-7. (canceled)
8. A method of emulsion polymerization using a reactive surfactant
composition, wherein the reactive surfactant composition comprises
a reactive anionic surfactant (component A) represented by the
following formula (1), and the component A is satisfied with the
following requirement R: ##STR00014## wherein AO represents an
alkyleneoxy group having a carbon number of 3 or more and 18 or
less; EO represents an ethyleneoxy group; p represents an integer
of 1 or more and 15 or less; m' represents an integer of 0 or more;
n' represents an integer of 0 or more; M.sup.+ represents a
hydrogen ion or a cation; and plural kinds of AOs may coexist, and
Requirement R: an average addition molar number m of AO is a number
of 1 or more and 50 or less; an average addition molar number n of
EU is a number of 0 or more and 200 or less; and when in the
component A, a component having an addition molar number of AO of
(m-3) or less is defined as (component A-1), and a component having
an addition molar number of AO of (m+2) or more is defined as
(component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1): X={(molar number of component A-1)+(molar number
of component A-2)}/(molar number of component A).times.100 (I).
9. A method of producing a polymer emulsion, comprising subjecting
a radical polymerizable monomer to emulsion polymerization in the
presence of a reactive surfactant composition wherein the reactive
surfactant composition comprises a reactive anionic surfactant
(component A) represented by the following formula (1), and the
component A is satisfied with the following requirement R:
##STR00015## wherein AO represents an alkyleneoxy group having a
carbon number of 3 or more and 18 or less; EO represents an
ethyleneoxy group; p represents an integer of 1 or more and 15 or
less; m' represents an integer of 0 or more; n' represents an
integer of 0 or more; M.sup.+ represents a hydrogen ion or a
cation; and plural kinds of AOs may coexist, and Requirement R: an
average addition molar number m of AO is a number of 1 or more and
50 or less; an average addition molar number n of EO is a number of
0 or more and 200 or less; and when in the component A, a component
having an addition molar number of AO of (m-3) or less is defined
as (component A-1), and a component having an addition molar number
of AO of (m+2) or more is defined as (component A-2), X in the
following formula (I) is less than 30, provided that when m is less
than 3, (m'=0) is defined as (component A-1): X={(molar number of
component A-1)+(molar number of component A-2)}/(molar number of
component A).times.100 (I).
10. A coating material composition comprising the polymer emulsion
obtained by the production method according to claim 9.
11. A method of producing a polymer coating film foimed of the
coating material composition according to claim 10.
12. A method of producing a reactive anionic surfactant, comprising
the following steps (i) to (iii), the reactive anionic surfactant
being represented by the following formula (1) and being satisfied
with the following requirement R (provided that in the requirement
R, when n is 0, then the step (ii) is not performed): Step (i): a
step of adding an alkylene oxide having a carbon number of 3 or
more and 18 or less to a compound represented by the following
formula (2) in the presence of an aluminum-magnesium complex oxide
catalyst to thereby obtain a compound represented by the following
formula (3); Step (ii): a step of adding ethylene oxide to the
compound represented by the following formula (3) in the presence
of an alkali catalyst to thereby obtain a compound represented by
the following formula (4); and Step (iii): a step of sulfating the
compound represented by the following formula (4) with a sulfating
agent and neutralizing with a basic substance: ##STR00016## wherein
AO represents an alkyleneoxy group having a carbon number of 3 or
more and 18 or less; EO represents an ethyleneoxy group; p
represents an integer of 1 or more and 15 or less; m' represents an
integer of 0 or more; n' represents an integer of 0 or more;
M.sup.+ represents a hydrogen ion or a cation; and plural kinds of
AOs may coexist: and Requirement R: an average addition molar
number m of AO is a number of 1 or more and 50 or less; an average
addition molar number n of EO is a number of 0 or more and 200 or
less; and when in the compound represented by the formula (1)
(component A), a component having an addition molar number of AO of
(m-3) or less is defined as (component A-1), and a component having
an addition molar number of AO of (m+2) or more is defined as
(component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1): X={(molar number of component A-1)+(molar number
of component A-2)}/(molar number of component A).times.100 (I).
13. The method of emulsion polymerization according to claim 8,
wherein in the formula (1), m' is an integer of 1 or more and an
integer of 100 or less.
14. The method of emulsion polymerization according to claim 8,
wherein in the formula (1), m' is an integer of 2 or more and an
integer of 50 or less.
15. The method of emulsion polymerization according to claim 8,
wherein in the formula (1), n' is an integer of 1 or more and an
integer of 400 or less.
16. The method of emulsion polymerization according to claim 8,
wherein in the formula (1), n' is an integer of 2 or more and an
integer of 200 or less.
17. The method of emulsion polymerization according to claim 8,
wherein in the formula (1), the carbon number of the alkyleneoxy
group represented by AO is 8 or less.
18. The method of emulsion polymerization according to claim 8,
wherein in the requirement R, m is 2 or more and 20 or less.
19. The method of emulsion polymerization according to claim 8,
wherein in the requirement R, m is 3 or more and 10 or less.
20. The method of emulsion polymerization according to claim 8,
wherein in the requirement R, n is 1 or more and 150 or less.
21. The method of emulsion polymerization according to claim 8,
wherein in the requirement R, (m+n) is
{3.ltoreq.(m+n).ltoreq.100}.
22. The method of emulsion polymerization according to claim 8,
wherein in the formula (I), X is 10 or more and 29 or less.
23. The method of producing a polymer emulsion according to claim
9, wherein the use amount of the reactive surfactant composition
for emulsion polymerization is 0.1% by mass or more and 10% by mass
or less relative to the total amount of the radical polymerizable
monomer.
24. A polymer emulsion obtained by the production method according
to claim 9, wherein an average particle diameter of the polymer
emulsion is 30 nm or more and 500 nm or less.
25. A polymer emulsion obtained by the production method according
to claim 9, wherein a viscosity of the polymer emulsion is 10 mPas
or more and 50,000 mPas or less.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a reactive surfactant
composition for emulsion polymerization, a production method of a
polymer emulsion using the same, a polymer emulsion produced by
this production method, a coating material composition containing
this polymer emulsion, a polymer coating film formed using this
coating material composition, a production method of a reactive
anionic surfactant, and use of the reactive surfactant composition
for emulsion polymerization.
BACKGROUND OF THE INVENTION
[0002] An emulsifier in emulsion polymerization not only influences
initiation reaction of polymerization and growth reaction but also
influences stability of a polymer emulsion during the
polymerization as well as mechanical stability, chemical stability,
freeze stability, and storage stability of the formed polymer
emulsion. In addition, the emulsifier has much influence on
emulsion physical properties, such as particle diameter, viscosity,
foamability, etc., of the polymer emulsion, and when forming into a
film, on film physical properties, such as water resistance,
humidity resistance, heat resistance, adhesiveness, pressure
sensitive adhesion, etc.
[0003] In applications of a coating material, an adhesive, and so
on, a polymer coating film is formed through drying of a polymer
emulsion; however, it is known that the emulsifier remaining in the
polymer coating film causes lowering in water resistance,
adhesiveness, weather resistance, heat resistance, and so on. For
example, for an aqueous coating material, a polymer emulsion
resulting from emulsion polymerization of a (meth)acrylic acid
ester is frequently used. However, in the case where the water
resistance of this polymer coating material is poor, such a polymer
emulsion cannot be used for an application in which the water
resistance is required, such as a building outer wall, a bathroom
wall, etc. In addition, in production of a synthetic rubber or the
like, on taking out the polymer from the polymer emulsion by means
of salting-out or the like, there is involved such a problem that
the emulsifier is contained in drainage, whereby a burden of the
waste water treatment becomes large.
[0004] In order to solve such defects, there is proposed a method
of using a so-called reactive surfactant having an ethylenically
unsaturated bond as a polymerizable group in the molecule.
[0005] For example, JP 2002-80506 A (PTL 1) and JP 2002-88104 A
(PTL 2) describe a reactive surfactant composition containing an
unsaturated compound and a production method of a polymer emulsion
in which emulsion polymerization is performed using this reactive
surfactant composition; and JP 2003-261605 A (PTL 3) describes a
reactive surfactant, a production method of a polymer emulsion in
which emulsion polymerization is performed using this, a polymer
emulsion with good water resistance as produced, and a polymer
coating film prepared using this.
SUMMARY OF THE INVENTION
[0006] The present invention is concerned with the following [1] to
[7].
[0007] [1] A reactive surfactant composition for emulsion
polymerization containing a reactive anionic surfactant (component
A) represented by the following formula (1), the component A being
satisfied with the following requirement R:
##STR00002##
[0008] wherein AO represents an alkyleneoxy group having a carbon
number of 3 or more and 18 or less; EO represents an ethyleneoxy
group; p represents an integer of 1 or more and 15 or less; m'
represents an integer of 0 or more; n' represents an integer of 0
or more; M.sup.+ represents a hydrogen ion or a cation; and plural
kinds of AOs may coexist.
[0009] Requirement R: An average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the component A, a component having an addition molar number of
AO of (m-3) or less is defined as (component A-1), and a component
having an addition molar number of AO of (m+2) or more is defined
as (component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
[0010] [2] A method of producing a polymer emulsion, including
subjecting a radical polymerizable monomer to emulsion
polymerization in the presence of the reactive surfactant
composition for emulsion polymerization as set forth in the above
[1].
[0011] [3] A polymer emulsion obtained by the production method as
set forth in the above [2].
[0012] [4] A coating material composition containing the polymer
emulsion as set forth in the above [3].
[0013] [5] A polymer coating film formed of the coating material
composition as set forth in the above [4].
[0014] [6] A method of producing a reactive anionic surfactant,
including the following steps (i) to the reactive anionic
surfactant being represented by the following formula (1) and being
satisfied with the following requirement R (provided that in the
requirement R, when n is 0, then the step (ii) is not
performed):
[0015] Step (i): a step of adding an alkylene oxide having a carbon
number of 3 or more and 18 or less to a compound represented by the
following formula (2) in the presence of an aluminum-magnesium
complex oxide catalyst to thereby obtain a compound represented by
the following formula (3);
[0016] Step (ii): a step of adding ethylene oxide to the compound
represented by the following formula (3) in the presence of an
alkali catalyst to thereby obtain a compound represented by the
following formula (4); and
[0017] Step (iii): a step of sulfating the compound represented by
the following formula (4) with a sulfating agent and neutralizing
with a basic substance,
##STR00003##
[0018] wherein AO represents an alkyleneoxy group having a carbon
number of 3 or more and 18 or less; EO represents an ethyleneoxy
group; p represents an integer of 1 or more and 15 or less; m'
represents an integer of 0 or more; n' represents an integer of 0
or more; M.sup.+ represents a hydrogen ion or a cation; and plural
kinds of AOs may coexist.
[0019] Requirement R: an average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the compound represented by the formula (1) (component A), a
component having an addition molar number of AO of (m-3) or less is
defined as (component A-1), and a component having an addition
molar number of AO of (m+2) or more is defined as (component A-2),
X in the following formula (I) is less than 30, provided that when
m is less than 3, (m'=0) is defined as (component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
[0020] [7] Use of a reactive surfactant composition containing a
reactive anionic surfactant (component A) represented by the
following formula (1), the component A being satisfied with the
following requirement R, for emulsion polymerization:
##STR00004##
[0021] wherein AO represents an alkyleneoxy group having a carbon
number of 3 or more and 18 or less; EO represents an ethyleneoxy
group; p represents an integer of 1 or more and 15 or less; m'
represents an integer of 0 or more; n' represents an integer of 0
or more; M.sup.+ represents a hydrogen ion or a cation; and plural
kinds of AOs may coexist.
[0022] Requirement R: an average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the component A, a component having an addition molar number of
AO of (m-3) or less is defined as (component A-1), and a component
having an addition molar number of AO of (m+2) or more is defined
as (component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1);
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
BRIEF DESCRIPTION OF THE DRAWING
[0023] FIG. 1 is a chromatogram chart of a compound represented by
the formula (3) as produced in Production Example 1 of the
Examples.
DETAILED DESCRIPTION OF THE INVENTION
[0024] In the reactive surfactants described in PTLs 1 to 3, the
distribution of the alkylene oxide addition molar number in the
polyalkylene oxide unit is broad, and therefore, one with
excessively high hydrophobicity and one with excessively high
hydrophilicity are coexistent. Accordingly, on performing the
emulsion polymerization, a surfactant with an insufficient surface
active performance is existent, and therefore, there is involved
such a problem that the particle diameter of the obtained polymer
emulsion is large, and on forming a polymer coating film, the water
resistance is worsened. In addition, for the purpose of micronizing
the particle diameter of the polymer emulsion to obtain the water
resistance on forming a polymer coating film, in the emulsion
polymerization, it is necessary to make the reactive surfactant
thoroughly function, and in the case where one with excessively
high hydrophobicity and one with excessively high hydrophilicity
are coexistent, it was necessary to use the reactive surfactant in
a high concentration.
[0025] The present invention is concerned with a reactive
surfactant composition for emulsion polymerization, which is able
to micronize the particle diameter of a polymer emulsion and to
reduce the addition amount of the reactive surfactant composition
to be used; a production method of a polymer emulsion using this
reactive surfactant composition for emulsion polymerization; a
polymer emulsion produced by this production method; a coating
material composition containing this polymer emulsion; a polymer
coating film with excellent water resistance, which is formed of
this coating material composition; a production method of a
reactive anionic surfactant; and use of a reactive surfactant
composition for emulsion polymerization.
[0026] The present inventors have found that the aforementioned
problem can be solved by using a specified reactive surfactant
composition for emulsion polymerization.
[0027] In accordance with the present invention, it is possible to
provide a reactive surfactant composition for emulsion
polymerization, which is able to micronize the particle diameter of
a polymer emulsion and to reduce the addition amount of the
reactive surfactant composition to be used; a production method of
a polymer emulsion using this reactive surfactant composition for
emulsion polymerization; a polymer emulsion produced by this
production method; a coating material composition containing this
polymer emulsion; a polymer coating film with excellent water
resistance, which is formed of this coating material composition; a
production method of a reactive anionic surfactant; and use of a
reactive surfactant composition for emulsion polymerization.
[Reactive Surfactant Composition for Emulsion Polymerization, and
Use of Reactive Surfactant for Emulsion Polymerization]
[0028] The reactive surfactant composition for emulsion
polymerization of the present invention (hereinafter also referred
to simply as "reactive surfactant composition") contains a reactive
anionic surfactant (component A) represented by the following
formula (1) and is satisfied with the following requirement R. The
component A is an agglomeration of plural compounds having a
distribution in the number of m' and/or n', each being different in
the number of m' and/or n'. Then, in the present invention, though
the term "composition" is used, it may also be a composition
substantially composed of only the component A.
[0029] It is suitable that the reactive surfactant composition of
the present invention is used for emulsion polymerization.
##STR00005##
[0030] In the formula, AO represents an alkyleneoxy group having a
carbon number of 3 or more and 18 or less; EO represents an
ethyleneoxy group; p represents an integer of 1 or more and 15 or
less; m' represents an integer of 0 or more; n' represents an
integer of 0 or more; M.sup.+ represents a hydrogen ion or a
cation; and plural kinds of AOs may coexist.
[0031] Requirement R: An average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the component A, a component having an addition molar number of
AO of (m-3) or less is defined as (component A-1), and a component
having an addition molar number of AO of (m+2) or more is defined
as (component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
[0032] The reactive anionic surfactant (hereinafter also referred
to as "surfactant of the present invention" or "reactive surfactant
of the present invention") which is represented by the
aforementioned formula (1) and is satisfied with the requirement R
is hereunder described.
[0033] In the aforementioned formula (1), the alkyleneoxy group
represented by AO has a carbon number of 3 or more and 18 or less.
From the viewpoints of micronization of the polymer emulsion
particle diameter and water resistance of the coating film, the
carbon number of the alkyleneoxy group is preferably 12 or less,
more preferably 8 or less, still more preferably 6 or less, and yet
still more preferably 4. The alkylene group in the alkyleneoxy
group may be either branched or linear.
[0034] Specific examples of AO include a propyleneoxy group, a
butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, an
octyleneoxy group, a 2-ethylhexyleneoxy group, a nonyleneoxy group,
a decyleneoxy group, an undecyleneoxy group, a dodecyleneoxy group,
a tetradecyleneoxy group, a hexadecyleneoxy group, an
octadecyleneoxy group, and the like, with a butyleneoxy group being
preferred.
[0035] In the formula (1), AO may be a single kind, or plural kinds
of AOs may coexist.
[0036] A small amount of an ethyleneoxy group may be contained as
AO within a range where the effects of the present invention are
not impaired, and such an embodiment is included in the present
invention, too.
[0037] p represents the methylene group number and is an integer of
1 or more and 15 or less. From the viewpoint of micronizing the
particle diameter at the time of emulsion polymerization, p is
preferably 10 or less, more preferably 5 or less, still more
preferably 3 or less, and yet still more preferably 2.
[0038] m' represents an addition molar number of the alkyleneoxy
group represented by AO and is an integer of 0 or more. From the
viewpoint of micronizing the particle diameter at the time of
emulsion polymerization, m' is preferably an integer of 1 or more,
more preferably an integer of 2 or more, and still more preferably
an integer of 3 or more; and from the same viewpoint, m' is
preferably an integer of 100 or less, more preferably an integer of
50 or less, still more preferably an integer of 30 or less, and yet
still more preferably an integer of 15 or less.
[0039] n' represents an addition molar number of the ethyleneoxy
group represented by EO and is an integer of 0 or more. From the
viewpoint of micronizing the particle diameter at the time of
emulsion polymerization, n' is preferably an integer of 1 or more,
more preferably an integer of 2 or more, and still more preferably
an integer of 5 or more; and from the same viewpoint, n' is
preferably an integer of 400 or less, more preferably an integer of
200 or less, still more preferably an integer of 100 or less, and
yet still more preferably an integer of 50 or less.
[0040] M.sup.+ represents a hydrogen ion (H.sup.+) or a cation.
Examples of the cation include an alkali metal ion, such as a
sodium ion (Na.sup.+), a potassium ion (K.sup.+), etc.; an alkaline
earth metal ion, such as a calcium ion (Ca.sup.2+), a magnesium ion
(Mg.sup.2+), etc.; an ammonium ion (NH.sub.4.sup.+); an ammonium
ion substituted with an alkyl group having a carbon number of 1 to
4; and the like, with an ammonium ion (NH.sub.4.sup.+) being
preferred. In the case where M.sup.+ is a divalent or higher valent
cation, such a cation may exist so as to become a counter ion to
the anion of --SO.sub.3.sup.-, and for example, so far as a
divalent cation is concerned, it may exist in an amount of 1/2 of
the amount of --SO.sub.3.sup.-.
[0041] In the present invention, the component A is satisfied with
the following requirement R.
[0042] Requirement R: An average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the component A, a component having an addition molar number of
AO of (m-3) or less is defined as (component A-1), and a component
having an addition molar number of AO of (m+2) or more is defined
as (component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
[0043] m is an average addition molar number of the alkyleneoxy
group represented by AO and is a number of 1 or more and 50 or
less. From the viewpoint of micronizing the particle diameter at
the time of emulsion polymerization, m is preferably 2 or more,
more preferably 3 or more, and still more preferably 4 or more; and
from the same viewpoint, m is preferably 20 or less, more
preferably 10 or less, and still more preferably 8 or less.
[0044] n is an average addition molar number of the ethyleneoxy
group represented by EO and is a number of 0 or more and 200 or
less. From the viewpoint of micronizing the particle diameter at
the time of emulsion polymerization, n is preferably 1 or more,
more preferably 5 or more, still more preferably 10 or more, and
yet still more preferably 12 or more; and from the same viewpoint,
n is preferably 150 or less, more preferably 50 or less, still more
preferably 25 or less, and yet still more preferably 18 or
less.
[0045] (m+n) is in a range of {1.ltoreq.(m+n).ltoreq.250}. From the
viewpoint of micronizing the particle diameter at the time of
emulsion polymerization, (m+n) is preferably
{3.ltoreq.(m+n).ltoreq.100}, more preferably
{5.ltoreq.(m+n).ltoreq.50}, still more preferably
{10.ltoreq.(m+n).ltoreq.35}, yet still more preferably
{15.ltoreq.(m+n).ltoreq.30}, even yet still more preferably
{16.ltoreq.(m+n).ltoreq.26}, and even still more preferably
{18.ltoreq.(m+n).ltoreq.25}.
[0046] In the reactive surfactant of the present invention, when in
the component A, a component having an AO addition molar number of
(m-3) or less is defined as (component A-1), and a component having
an AO addition molar number of (m+2) or more is defined as
(component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
[0047] In the component A, the component having an AO addition
molar number of (m-3) or less means a component in which an integer
is determined by rounding off the first decimal place of (m-3), and
the AO addition molar number in the component A is the foregoing
integer or less. In consequence, for example, in the case where m
is 4.2, the component having an AO addition molar number of (m-3)
or less means a component having an AO addition molar number of 1
or less. The same is also applicable to the component in which the
AO addition molar number in the component A is (m+2) or more.
[0048] When X is less than 30, the polymer emulsion may be
micronized in the particle diameter.
[0049] X is preferably 29 or less, more preferably 28 or less, and
still more preferably 27 or less. Though a lower limit of X is not
particularly limited, from the viewpoint of synthesis, X is
preferably 10 or more, more preferably 15 or more, and still more
preferably 20 or more.
<Synthesis Method of Reactive Anionic Surfactant of the Present
Invention>
[0050] It is preferred that a compound represented by the following
formula (3) that is an intermediate of the reactive anionic
surfactant represented by the aforementioned formula (1) is
synthesized by a method of adding an alkylene oxide having a carbon
number of 3 or more and 18 or less to a compound represented by the
following formula (2) in the presence of a catalyst composed of a
complex oxide of aluminum and magnesium (hereinafter also referred
to as "aluminum-magnesium complex oxide catalyst").
##STR00006##
[0051] In the formulae, p and m' are the same as in the formula
(1), and preferred ranges thereof are also the same.
[0052] The preferred catalyst which is used for alkyleneoxy group
addition polymerization of the reactive surfactant of the present
invention is an aluminum-magnesium complex oxide catalyst
(hereinafter also referred to as "Al--Mg complex oxide catalyst")
which is activated through calcination of aluminum
hydroxide-magnesium (also expressed as "aluminum
hydroxide-magnesium hydroxide coprecipitate"). The content of
aluminum of the Al--Mg complex oxide catalyst is preferably 4% by
mass or more, and more preferably 10% by mass or more, and
preferably 40% by mass or less, and more preferably 25% by mass or
less. In addition, the content of magnesium is preferably 5% by
mass or more, and more preferably 10% by mass or more, and
preferably 50% by mass or less, and more preferably 40% by mass or
less.
[0053] Examples of a commercially available product of the
aforementioned Al--Mg complex oxide catalyst include "KW-2000"
(aluminum content: 17.5% by mass, magnesium content: 35.4% by mass,
manufactured by Kyowa Chemical Industry Co., Ltd.), "KYOWAAD 300S"
(aluminum content: 14% by mass, magnesium content: 16% by mass,
manufactured by Kyowa Chemical Industry Co., Ltd.), and "KYOWAAD
1000" (aluminum content: 10% by mass, magnesium content: 21% by
mass, manufactured by Kyowa Chemical Industry Co., Ltd.), with
"KW-2000" being preferred.
[0054] From the viewpoint of obtaining a high catalytic ability, a
calcination temperature of the aluminum hydroxide-magnesium is
preferably 200.degree. C. or higher, and more preferably
300.degree. C. or higher, and preferably 1,000.degree. C. or lower,
and more preferably 800.degree. C. or lower. In order to prevent
adsorption of water or carbon dioxide from occurring, though it is
preferred that the catalyst after the calcination is cooled in an
inert gas or in vacuo, and after cooling, the resulting catalyst is
dipped in an active hydrogen-containing organic compound to be used
for the reaction or stored in a vacuum desiccator, the catalyst
resulting from coming into contact with air to adsorb water or
carbon dioxide thereon may also be used for the reaction.
[0055] As a reaction operation, there is exemplified a method in
which starting raw materials, such as the compound represented by
the formula (2), etc., and the Al--Mg complex oxide catalyst are
charged in a reaction vessel, and the alkylene oxide is introduced
at a predetermined temperature in a nitrogen atmosphere while being
dropped under reflux, to achieve the reaction. From the viewpoint
of reaction rate, a reaction temperature is preferably 70.degree.
C. or higher, more preferably 80.degree. C. or higher, and still
more preferably 90.degree. C. or higher; and from the same
viewpoint, the reaction temperature is preferably 200.degree. C. or
lower, more preferably 150.degree. C. or lower, and still more
preferably 130.degree. C. or lower.
[0056] Though the use amount of the catalyst varies with a molar
ratio between the alkylene oxide and the staring raw materials,
such as the compound represented by the formula (2), etc., both of
which are provided for the reaction, from the viewpoints of
reaction rate and easiness in catalyst removal, the use amount of
the catalyst is preferably 0.05% by mass or more, more preferably
0.1% by mass or more, still more preferably 0.5% by mass or more,
and yet still more preferably 1% by mass or more relative to the
compound represented by the formula (2). From the same viewpoints,
the use amount of the catalyst is preferably 20% by mass or less,
and more preferably 10% by mass or less.
[0057] It is also possible to perform the reaction operation in an
autoclave. The reaction may also be performed in such a manner that
the starting raw materials, such as the compound represented by the
formula (2), etc., and the Al--Mg complex oxide catalyst are
charged, and after purging with nitrogen, the alkylene oxide is
introduced under predetermined temperature-pressure conditions.
[0058] Though a method of catalyst separation is not particularly
limited, there may be considered a method in which after the
reaction, the reaction product is cooled, and for example, water or
a filter aid (e.g., diatomaceous earth, a cellulose-based aid,
activated clay, etc.) for the purpose of reducing the viscosity is
added, followed by filtration of the catalyst.
[0059] In order to obtain the component A in which X of the formula
(I) is less than 30, as mentioned above, in the AO addition
reaction, it is preferred to use the Al--Mg complex oxide catalyst,
but such is not limited to the foregoing method. As another method,
there is exemplified a method in which the compound represented by
the formula (3) having a broad distribution of the added
polyalkyleneoxy group number is subjected to distillation or
preparative chromatography to remove one having a small alkyleneoxy
group (AO) addition molar number and one having a large AO addition
molar number, thereby obtaining the compound represented by the
formula (3) having a narrow distribution of the AO addition molar
number.
[0060] In order to regulate the average addition molar number m of
AO to a number of 1 or more and 50 or less, the reaction amounts of
the compound represented by the formula (2) and the alkylene oxide
may be properly regulated.
[0061] The compound represented by the formula (4) that is an
intermediate of the reactive surfactant of the present invention
may be synthesized by a known method. For example, the compound
represented by the formula (4) may be synthesized by a method in
which ethylene oxide is added to the compound represented by the
aforementioned formula (3) in the presence of an alkali catalyst,
such as sodium hydroxide, potassium hydroxide, etc., at atmospheric
pressure or under an elevated pressure at a temperature of room
temperature or higher and 200.degree. C. or lower.
[0062] From the viewpoint of reactivity, the pressure is preferably
0.1 MPa or more, and more preferably 0.15 MPa or more; and from the
same viewpoint, the pressure is preferably 3 MPa or less, and more
preferably 1 MPa or less. In addition, from the viewpoint of
reactivity, the reaction temperature is preferably room temperature
or higher, more preferably 60.degree. C. or higher, and still more
preferably 100.degree. C. or higher; and from the same viewpoint,
the reaction temperature is preferably 200.degree. C. or lower,
more preferably 170.degree. C. or lower, and still more preferably
150.degree. C. or lower.
[0063] The addition of ethylene oxide is arbitrary, and in the case
where n is 0 in the formula (1), the subject step may not be
performed.
[0064] In order to regulate the average addition molar number n of
EO to a number of 1 or more and 50 or less, the reaction amounts of
the compound represented by the formula (3) and ethylene oxide may
be properly regulated.
##STR00007##
[0065] In the formula, p, m', and n' are the same as in the formula
(1), and preferred ranges thereof are also the same.
[0066] The reactive anionic surfactant represented by the
aforementioned formula (1) is obtained by sulfating the compound
represented by the formula (4) with a sulfating agent and
neutralizing with a basic substance. Examples of the sulfating
agent include chlorosulfonic acid, sulfuric anhydride, and
amidosulfuric acid. From the viewpoint of minimizing a side
reaction, such as an addition reaction of a sulfate group to the
double bond group, isomerization of the double bond group, etc.,
use of amidosulfuric acid is preferred.
[0067] On obtaining the compound represented by the aforementioned
formula (1) through sulfation, by allowing amidosulfuric acid to
react in the presence of an amide compound (exclusive of a sulfonic
acid amide compound) or an amine compound at a temperature of
preferably 60.degree. C. or higher, more preferably 75.degree. C.
or higher, and still more preferably 90.degree. C. or higher, and
preferably 140.degree. C. or lower, more preferably 135.degree. C.
or lower, and still more preferably 130.degree. C. or lower, the
double bond group is thoroughly protected, whereby a side reaction,
such as isomerization of a terminal double bond group to an
internal double bond group, sulfate group addition to the double
bond group, etc., may be substantially completely prevented from
occurring. According to this, a sulfuric acid ester salt of the
terminal unsaturated compound with a high purity represented by the
formula (1) may be produced.
[0068] Though the reaction time with amidosulfuric acid is not
particularly limited, from the viewpoint of thoroughly advancing
the sulfation, it is preferably 0.1 hours or more, more preferably
0.5 hours or more, and still more preferably 1 hour or more. In
addition, from the viewpoint of suppressing the side reaction, the
reaction time with amidosulfuric acid is preferably 50 hours or
less, more preferably 20 hours or less, and still more preferably
10 hours or less.
[0069] Examples of the amide compound which is preferably used for
the production method of the reactive anionic surfactant of the
present invention may include urea; a urea derivative, such as
methylurea, 1,1-dimethylurea, ethylurea, butylurea, acetylurea,
etc.; and an acid amide compound, such as acetamide, formamide,
propionamide, butylamide, diacetamide, succinic acid amide,
etc.
[0070] In the present invention, examples of the amine compound
which is preferably used for the production method of the reactive
anionic surfactant represented by the formula (1) include
morpholine, triethylamine, tributylamine, isopropylamine,
diisopropylamine, and the like.
[0071] Among those, urea is preferred as the amide compound or
amine compound which is used for the production method of the
reactive anionic surfactant of the present invention.
[0072] As for the amide compound and the amine compound, each of
which is preferably used for the production method of the reactive
anionic surfactant of the present invention, in the case where the
molecular weight is small, the effect is brought through use of a
small amount, and the molecular weight is preferably 150 or less,
and more preferably 100 or less.
[0073] From the viewpoint of suppressing the formation of a
by-product, the use amount of the aforementioned amide compound or
the aforementioned amine compound is preferably 0.5 mol % or more,
more preferably 1 mol % or more, and still more preferably 3 mol %
or more; and from the same viewpoint, 50 mol % or less, more
preferably 30 mol % or less, and still more preferably 10 mol % or
less, relative to the amidosulfuric acid.
[0074] Though a charge ratio (molar ratio) of amidosulfuric acid to
the compound represented by the formula (4) is not particularly
limited, from the viewpoint of increasing a degree of sulfation, it
is preferably 1 time or more and 1.3 times or less, and more
preferably 1 time or more and 1.1 times or less relative to the
compound represented by the formula (4).
[0075] In sulfation with amidosulfuric acid, when moisture is
incorporated into the raw materials, there is a concern that the
moisture decomposes the amidosulfuric acid, thereby bringing a
lowering of the degree of sulfation and an increase of the side
reaction. Therefore, it is desired that the moisture contained in
the compound represented by the formula (4) is removed as far as
possible by a method, such as reduced pressure dehydration, etc.,
prior to the reaction.
[0076] From the viewpoints of antioxidation and color protection,
it is preferred to perform the sulfation reaction with
amidosulfuric acid in an atmosphere of an inert gas, such as a
nitrogen gas, etc. The reaction temperature in the presence of the
amide compound or amine compound is preferably 60.degree. C. or
higher, and more preferably 90.degree. C. or higher, and preferably
140.degree. C. or lower, and more preferably 130.degree. C. or
lower. After completion of the reaction, substances not dissolved
in the reaction system, such as excessive amidosulfuric acid or
amide compound, etc., may be removed through filtration.
[0077] While the sulfated product owing to amidosulfuric acid
becomes an ammonium salt, it is also possible to replace the
ammonium salt to other salt by a method, such as addition of a
sodium hydroxide aqueous solution, etc., as the need arises.
[Production Method of Polymer Emulsion and Polymer Emulsion]
[0078] The production method of a polymer emulsion of the present
invention is a method of subjecting a radical polymerizable monomer
(hereinafter also referred to as "vinyl-based monomer") to emulsion
polymerization with, as an emulsifier, the reactive surfactant
composition of the present invention. In the production method of a
polymer emulsion of the present invention, another anionic
surfactant or a nonionic surfactant may also be used in combination
as the emulsifier. It is preferred that such another anionic
surfactant or nonionic surfactant is a reactive surfactant.
[0079] A proportion of the reactive surfactant of the present
invention is preferably 50% by mass or more, more preferably 60% by
mass or more, still more preferably 70% by mass or more, yet still
more preferably 80% by mass or more, and most preferably 100% by
mass relative to the total amount of the reactive surfactant
composition.
[0080] In the emulsion polymerization according to the production
method of a polymer emulsion of the present invention, from the
viewpoints of dispersion stability and reactivity, the use amount
of the reactive surfactant composition of the present invention is
preferably 0.1% by mass or more, more preferably 0.5% by mass or
more, and still more preferably 0.8% by mass or more relative to
the total amount of the vinyl-based monomer. From the same
viewpoint, the use amount of the reactive surfactant composition of
the present invention is preferably 10% by mass or less, more
preferably 8% by mass or less, and still more preferably 5% by mass
or less relative to the total amount of the vinyl-based
monomer.
[0081] Examples of the vinyl-based monomer which is used in the
present invention include an aromatic vinyl monomer, a
(meth)acrylic acid ester, (meth)acrylic acid, a vinyl halide and a
vinylidene halide, a vinyl ester, a nitrile, and a conjugated
diene. Specifically, examples of the aromatic vinyl monomer include
styrene, .alpha.-methylstyrene, chlorostyrene, and the like;
examples of the (meth)acrylic acid ester include methyl
(meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
and the like; examples of the vinyl halide and the vinylidene
halide include vinyl chloride, vinyl bromide, vinylidene chloride,
and the like; examples of the vinyl ester include vinyl acetate,
vinyl propionate, and the like; examples of the nitrile include
(meth)acrylonitrile and the like; and examples of the conjugated
diene include butadiene, isoprene, and the like. These monomers may
be polymerized singly, or two or more thereof may be
copolymerized.
[0082] The (meth)acrylic acid ester means a single kind or two
kinds selected from a methacrylic acid ester and an acrylic acid
ester. The (meth)acrylic acid means one or two selected from
methacrylic acid and acrylic acid. Others expressed with the term
"(meth)" are used in the same meanings.
[0083] The use amount of the vinyl monomer is preferably 30% by
mass or more, and more preferably 40% by mass or more, and
preferably 70% by mass or less, and more preferably 60% by mass or
less, relative to the entire system of emulsion polymerization (all
components inclusive of water).
[0084] Examples of a polymerization initiator which is used for the
emulsion polymerization in the present invention include an
inorganic peroxide, an organic peroxide, and an azo-based compound.
Specifically, examples of the inorganic peroxide include potassium
persulfate, ammonium persulfate, hydrogen peroxide, and the like;
examples of the organic peroxide include t-butyl peroxide, cumene
hydroperoxide, p-menthane hydroperoxide, and the like; and examples
of the azo-based compound include azobisdiisobutyronitrile,
2,2'-azobis(2-amidinopropane) dihydrochloride, and the like. Among
those, a water-soluble polymerization initiator is preferred, and a
persulfate, such as potassium persulfate, ammonium persulfate,
etc., is preferred.
[0085] Sodium hydrogen sulfite, ammonium ferrous sulfate, and so on
may also be used as a polymerization promoter.
[0086] As an addition method of monomers, though a monomer dropping
method, a monomer batch charging method, a pre-emulsion method, or
the like may be adopted, from the viewpoint of micronizing the
particle diameter at the time of emulsion polymerization, a
pre-emulsion method is preferred.
[0087] A dropping time is preferably 1 hour or more, and more
preferably 1.5 hours or more, and preferably 8 hours or less, and
more preferably 5 hours or less.
[0088] A aging time is preferably 0.3 hours or more, and more
preferably 0.5 hours or more, and preferably 5 hours or less, and
more preferably 3 hours or less.
[0089] While a polymerization temperature is regulated owing to the
decomposition temperature of the polymerization initiator, in the
case of a persulfate, it is preferably 60.degree. C. or higher, and
more preferably 70.degree. C. or higher, and preferably 90.degree.
C. or lower, and more preferably 80.degree. C. or lower.
[0090] Though an average particle diameter of the polymer emulsion
of the present invention which is obtained by the aforementioned
method varies with an application, it is preferably 30 nm or more,
and more preferably 80 nm or more, and preferably 500 nm or less,
and more preferably 300 nm or less.
[0091] In the case of using the polymer emulsion as a coating
material, from viewpoint of coating properties, a viscosity of the
polymer emulsion of the present invention is preferably 10 mPas or
more, and more preferably 50 mPas or more, and preferably 50,000
mPas or less, and more preferably 10,000 mPas or less.
[0092] Here, the average particle diameter and viscosity of the
polymer emulsion are each a value measured by the method shown in
the Examples as described later.
[Coating Material Composition and Polymer Coating Film]
[0093] A polymer coating film prepared from the polymer emulsion of
the present invention is excellent in the water resistance and may
be preferably used in the field of a coating material, particularly
an aqueous coating material as well as in the field of a pressure
sensitive adhesive product.
[0094] The preparation method of a polymer coating film of the
present invention varies with an application. For example, in a
pressure sensitive adhesive application, the polymer emulsion of
the present invention having a low glass transition temperature
(Tg) of a polymer of 2-ethylhexyl acrylate, n-butyl acrylate, etc.
is produced through emulsion polymerization using the reactive
surfactant composition of the present invention. When a material
obtained by optionally blending a thickener, a tackifier, or the
like in this polymer emulsion of the present invention is applied
onto a base material, such as a paper, a film, etc., followed by
hot-air drying to form a polymer coating film having a thickness of
about 20 .mu.m, a pressure sensitive adhesive product with
excellent water resistance and pressure sensitive adhesive
performance may be obtained.
[0095] In a coating material application, the polymer emulsion of
the present invention, such as a n-butyl acrylate/methyl
methacrylate copolymer, etc., is produced through emulsion
polymerization using the reactive surfactant composition of the
present invention. A coating material composition obtained by
optionally blending a film-forming aid, a pigment, or the like in
this polymer emulsion of the present invention is prepared. Though
the polymer coating film of the present invention is not
particularly limited so long as it is a polymer coating film formed
of the aforementioned coating material composition, a coating film
with excellent water resistance and weather resistance may be
obtained by applying the coating material composition onto a
building wall material or the like such that a dry film thickness
is about 100 .mu.m, followed by drying (e.g., natural drying,
hot-air drying, etc.).
[0096] With respect to the aforementioned embodiments, the present
invention further discloses the following reactive surfactant
compositions for emulsion polymerization, production methods of a
polymer emulsion, polymer emulsions, coating material compositions,
polymer coating films, production methods of a reactive anionic
surfactant, and uses of a reactive surfactant composition for
emulsion polymerization.
<1> A reactive surfactant composition for emulsion
polymerization containing a reactive anionic surfactant (component
A) represented by the following formula (1), the component A being
satisfied with the following requirement R.
##STR00008##
[0097] In the formula, AO represents an alkyleneoxy group having a
carbon number of 3 or more and 18 or less; EO represents an
ethyleneoxy group; p represents an integer of 1 or more and 15 or
less; m' represents an integer of 0 or more; n' represents an
integer of 0 or more; M.sup.+ represents a hydrogen ion or a
cation; and plural kinds of AOs may coexist.
[0098] Requirement R: An average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the component A, a component having an addition molar number of
AO of (m-3) or less is defined as (component A-1), and a component
having an addition molar number of AO of (m+2) or more is defined
as (component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
<2> The reactive surfactant composition for emulsion
polymerization as set forth in the above <1>, wherein in the
formula (1), m' is an integer of 1 or more, preferably an integer
of 2 or more, and more preferably an integer of 3 or more, and is
an integer of 100 or less, preferably an integer of 50 or less,
more preferably an integer of 30 or less, and still more preferably
an integer of 15 or less. <3> The reactive surfactant
composition for emulsion polymerization as set forth in the above
<1> or <2>, wherein in the formula (1), n' is an
integer of 1 or more, preferably an integer of 2 or more, and more
preferably an integer of 5 or more, and is an integer of 400 or
less, preferably an integer of 200 or less, more preferably an
integer of 100 or less, and still more preferably an integer of 50
or less. <4> The reactive surfactant composition for emulsion
polymerization as set forth in any of the above <1> to
<3>, wherein in the formula (1), the carbon number of the
alkyleneoxy group represented by AO is 12 or less, preferably 8 or
less, more preferably 6 or less, and still more preferably 4.
<5> The reactive surfactant composition for emulsion
polymerization as set forth in any of the above <1> to
<4>, wherein in the formula (1), p is 10 or less, preferably
5 or less, more preferably 3 or less, and still more preferably 2.
<6> The reactive surfactant composition for emulsion
polymerization as set forth in any of the above <1> to
<5>, wherein in the requirement R, m is 2 or more, preferably
3 or more, and more preferably 4 or more, and is 20 or less,
preferably 10 or less, and more preferably 8 or less. <7> The
reactive surfactant composition for emulsion polymerization as set
forth in any of the above <1> to <6>, wherein in the
requirement R, n is 1 or more, preferably 5 or more, more
preferably 10 or more, and still more preferably 12 or more, and is
150 or less, preferably 50 or less, more preferably 25 or less, and
still more preferably 18 or less. <8> The reactive surfactant
composition for emulsion polymerization as set forth in any of the
above <1> to <7>, wherein in the requirement R, (m+n)
is {3.ltoreq.(m+n).ltoreq.100}, preferably
{5.ltoreq.(m+n).ltoreq.50}, more preferably
{10.ltoreq.(m+n).ltoreq.35}, still more preferably
{15.ltoreq.(m+n).ltoreq.30}, yet still more preferably
{16.ltoreq.(m+n).ltoreq.26}, and even yet still more preferably
{18.ltoreq.(m+n).ltoreq.25}. <9> The reactive surfactant
composition for emulsion polymerization as set forth in any of the
above <1> to <8>, wherein in the formula (1), M.sup.+
is at least one selected from the group consisting of a hydrogen
ion, an alkali metal ion (for example, a sodium ion (Nat) or a
potassium ion (K.sup.+)), an alkaline earth metal ion (for example,
a calcium ion (Ca.sup.2+) or a magnesium ion (Mg.sup.2+)), an
ammonium ion (NH.sub.4.sup.+), and an ammonium ion substituted with
an alkyl group having a carbon number of 1 to 4, and preferably an
ammonium ion. <10> The reactive surfactant composition for
emulsion polymerization as set forth in any one of the above
<1> to <9>, wherein in the formula (I), X is 29 or
less, preferably 28 or less, and more preferably 27 or less, and is
10 or more, preferably 15 or more, and more preferably 20 or more.
<11> A method of producing a polymer emulsion including
subjecting a radical polymerizable monomer to emulsion
polymerization in the presence of the reactive surfactant
composition for emulsion polymerization as set forth in any one of
the above <1> to <10>. <12> The method of
producing a polymer emulsion as set forth in the above <11>,
wherein the use amount of the reactive surfactant composition for
emulsion polymerization is 0.1% by mass or more, preferably 0.5% by
mass or more, and more preferably 0.8% by mass or more, and is 10%
by mass or less, preferably 8% by mass or less, and more preferably
5% by mass or less, relative to the total amount of the radical
polymerizable monomer. <13> A polymer emulsion obtained by
the production method as set forth in the above <11> or
<12>. <14> The polymer emulsion as set forth in the
above <13>, wherein an average particle diameter of the
polymer emulsion is 30 nm or more, and preferably 80 nm or more,
and is 500 nm or less, and preferably 300 nm or less. <15>
The polymer emulsion as set forth in the above <13> or
<14>, wherein a viscosity of the polymer emulsion is 10 mPas
or more, and preferably 50 mPas or more, and is 50,000 mPas or
less, and preferably 10,000 mPas or less. <16> A coating
material composition containing the polymer emulsion as set forth
in any one of the above <13> to <15>. <17> A
polymer coating film formed of the coating material composition as
set forth in the above <16>. <18> A method of producing
a reactive anionic surfactant, including the following steps (i) to
the reactive anionic surfactant being represented by the following
formula (1) and being satisfied with the following requirement R
(provided that in the requirement R, when n is 0, then the step
(ii) is not performed):
[0099] Step (i): a step of adding an alkylene oxide having a carbon
number of 3 or more and 18 or less to a compound represented by the
following formula (2) in the presence of an aluminum-magnesium
complex oxide catalyst to thereby obtain a compound represented by
the following formula (3);
[0100] Step (ii): a step of adding ethylene oxide to the compound
represented by the following formula (3) in the presence of an
alkali catalyst to thereby obtain a compound represented by the
following formula (4); and
[0101] Step (iii): a step of sulfating the compound represented by
the following formula (4) with a sulfating agent and neutralizing
with a basic substance.
##STR00009##
[0102] In the formulae (1) to (4), AO represents an alkyleneoxy
group having a carbon number of 3 or more and 18 or less; EO
represents an ethyleneoxy group; p represents an integer of 1 or
more and 15 or less; m' represents an integer of 0 or more; n'
represents an integer of 0 or more; M.sup.+ represents a hydrogen
ion or a cation; and plural kinds of AOs may coexist.
[0103] Requirement R: an average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the compound represented by the formula (1) (component A), a
component having an addition molar number of AO of (m-3) or less is
defined as (component A-1), and a component having an addition
molar number of AO of (m+2) or more is defined as (component A-2),
X in the following formula (I) is less than 30, provided that when
m is less than 3, (m'=0) is defined as (component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
<19> The method of producing a reactive anionic surfactant as
set forth in the above <18>, wherein the content of aluminum
of the aluminum-magnesium complex oxide catalyst is 4% by mass or
more, and preferably 10% by mass or more, and is 40% by mass or
less, and preferably 25% by mass or less. <20> The method of
producing a reactive anionic surfactant as set forth in the above
<18> or <19>, wherein the content of magnesium of the
aluminum-magnesium complex oxide catalyst is 5% by mass or more,
and preferably 10% by mass or more, and is 50% by mass or less, and
preferably 40% by mass or less. <21> The method of producing
a reactive anionic surfactant as set forth in any of the above
<18> to <20>, wherein a reaction temperature in the
step (i) is 70.degree. C. or higher, preferably 80.degree. C. or
higher, and more preferably 90.degree. C. or higher, and is
200.degree. C. or lower, preferably 150.degree. C. or lower, and
more preferably 130.degree. C. or lower. <22> The method of
producing a reactive anionic surfactant as set forth in any of the
above <18> to <21>, wherein in the step (1), the use
amount of the aluminum-magnesium complex oxide catalyst is 0.05% by
mass or more, preferably 0.1% by mass or more, more preferably 0.5%
by mass or more, and still more preferably 1% by mass or more, and
is 20% by mass or less, and preferably 10% by mass or less,
relative to the compound represented by the formula (2). <23>
The method of producing a reactive anionic surfactant as set forth
in any of the above <18> to <22>, wherein a pressure in
the step (ii) is 0.1 MPa or more, and preferably 0.15 MPa or more,
and is 3 MPa or less, and preferably 1 MPa or less. <24> The
method of producing a reactive anionic surfactant as set forth in
any of the above <18> to <23>, wherein a reaction
temperature in the step (ii) is room temperature or higher,
preferably 60.degree. C. or higher, and more preferably 100.degree.
C. or higher, and is 200.degree. C. or lower, preferably
170.degree. C. or lower, and more preferably 150.degree. C. or
lower. <25> The method of producing a reactive anionic
surfactant as set forth in any of the above <18> to
<24>, wherein the sulfating agent is at least one selected
from the group consisting of chlorosulfonic acid, sulfuric
anhydride, and amidosulfuric acid, and is preferably amidosulfuric
acid. <26> The method of producing a reactive anionic
surfactant as set forth in any of the above <18> to
<25>, wherein the step (iii) is a step of sulfation with
amidosulfuric acid in the presence of an amide compound (exclusive
of a sulfonic acid amide compound) or an amine compound and
neutralization with a basic substance; a reaction temperature of
the sulfation is 60.degree. C. or higher, preferably 75.degree. C.
or higher, and more preferably 90.degree. C. or higher, and is
140.degree. C. or lower, preferably 135.degree. C. or lower, and
more preferably 130.degree. C. or lower; and a reaction time is 0.1
hours or more, preferably 0.5 hours or more, and more preferably 1
hour or more, and is 50 hours or less, preferably 20 hours or less,
and more preferably 10 hours or less. <27> Use of a reactive
surfactant composition containing a reactive anionic surfactant
(component A) represented by the following formula (1), the
component A being satisfied with the following requirement R, for
emulsion polymerization.
##STR00010##
[0104] In the formula, AO represents an alkyleneoxy group having a
carbon number of 3 or more and 18 or less; EO represents an
ethyleneoxy group; p represents an integer of 1 or more and 15 or
less; m' represents an integer of 0 or more; n' represents an
integer of 0 or more; M.sup.+ represents a hydrogen ion or a
cation; and plural kinds of AOs may coexist.
[0105] Requirement R: An average addition molar number m of AO is a
number of 1 or more and 50 or less; an average addition molar
number n of EO is a number of 0 or more and 200 or less; and when
in the component A, a component having an addition molar number of
AO of (m-3) or less is defined as (component A-1), and a component
having an addition molar number of AO of (m+2) or more is defined
as (component A-2), X in the following formula (I) is less than 30,
provided that when m is less than 3, (m'=0) is defined as
(component A-1).
X={(molar number of component A-1)+(molar number of component
A-2)}/(molar number of component A).times.100 (I)
<28> The use of a reactive surfactant composition as set
forth in the above <27>, wherein in the formula (1), m' is an
integer of 1 or more, preferably an integer of 2 or more, and more
preferably an integer of 3 or more, and is an integer of 100 or
less, preferably an integer of 50 or less, more preferably an
integer of 30 or less, and still more preferably an integer of 15
or less. <29> The use of a reactive surfactant composition as
set forth in the above <27> or <28>, wherein in the
formula (1), n' is an integer of 1 or more, preferably an integer
of 2 or more, and more preferably an integer of 5 or more, and is
an integer of 400 or less, preferably an integer of 200 or less,
more preferably an integer of 100 or less, and still more
preferably an integer of 50 or less. <30> The use of a
reactive surfactant composition as set forth in any of the above
<27> to <29>, wherein in the formula (1), the carbon
number of the alkyleneoxy group represented by AO is 12 or less,
preferably 8 or less, more preferably 6 or less, and still more
preferably 4. <31> The use of a reactive surfactant
composition as set forth in any of the above <27> to
<30>, wherein in the formula (1), p is 10 or less, preferably
5 or less, more preferably 3 or less, and still more preferably 2.
<32> The use of a reactive surfactant composition as set
forth in any of the above <27> to <31>, wherein in the
requirement R, m is 2 or more, preferably 3 or more, and more
preferably 4 or more, and is 20 or less, preferably 10 or less, and
more preferably 8 or less. <33> The use of a reactive
surfactant composition as set forth in any of the above <27>
to <32>, wherein in the requirement R, n is 1 or more,
preferably 5 or more, more preferably 10 or more, and still more
preferably 12 or more, and is 150 or less, preferably 50 or less,
more preferably 25 or less, and still more preferably 18 or less.
<34> The use of a reactive surfactant composition as set
forth in any of the above <27> to <33>, wherein in the
requirement R, (m+n) is {3.ltoreq.(m+n).ltoreq.100}, preferably
{5.ltoreq.(m+n).ltoreq.50}, more preferably
{10.ltoreq.(m+n).ltoreq.35}, still more preferably
{15.ltoreq.(m+n).ltoreq.30}, yet still more preferably
{16.ltoreq.(m+n).ltoreq.26}, and even yet still more preferably
{18.ltoreq.(m+n).ltoreq.25}. <35> The use of a reactive
surfactant composition as set forth in any of the above <27>
to <34>, wherein in the formula (1), M.sup.+ is at least one
selected from the group consisting of a hydrogen ion, an alkali
metal ion (for example, a sodium ion (Na.sup.+) or a potassium ion
(K.sup.+)), an alkaline earth metal ion (for example, a calcium ion
(Ca.sup.2+) or a magnesium ion (Mg.sup.2+)), an ammonium ion
(NH.sub.4.sup.+), and an ammonium ion substituted with an alkyl
group having a carbon number of 1 to 4, and preferably an ammonium
ion. <36> The use of a reactive surfactant composition as set
forth in any of the above <27> to <35>, wherein in the
formula (I), X is 29 or less, preferably 28 or less, and more
preferably 27 or less, and is 10 or more, preferably 15 or more,
and more preferably 20 or more.
EXAMPLES
[0106] In the following Production Examples, Examples, and
Comparative Examples, the terms "parts" and "%" are "parts by mass"
and "% by mass", respectively unless specifically indicated.
[Measurement of Aluminum and Magnesium Contents in Al--Mg Complex
Oxide Catalyst]
[0107] The contents of aluminum and magnesium in the Al--Mg complex
oxide catalyst were measured in the following manner. First of all,
0.1 g of an Al--Mg complex oxide catalyst was precisely weighed in
a quartz crucible and dissolved in 4 mL of 6N hydrochloric acid,
followed by diluting with pure water in measuring flask to 50 mL.
This was diluted 25 times with pure water, thereby preparing a
measurement sample. A concentration of each of aluminum and
magnesium ions in the measurement sample was measured with an
atomic absorption photometer (Varian SpectrAA 220, manufactured by
Agilent Technologies, Inc.). The concentration (% by mass) of an
aluminum ion and the concentration (% by mass) of a magnesium ion
were calculated, respectively and defined as the respective
contents.
Production Example 1
[0108] In a 10-liter four-necked flask equipped with an agitator, a
thermometer, a dropping funnel, and a reflux pipe, 860 g (10 mol)
of 3-methyl-3-buten-1-ol and 34.4 g of an Al--Mg complex oxide
catalyst ("KW-2000", aluminum content: 17.5% by mass, magnesium
content: 35.4% by mass, manufactured by Kyowa Chemical Industry
Co., Ltd.) were charged, and 4,320 g (60 mol) of butylene oxide
(1,2-epoxybutane) was dropped in a nitrogen atmosphere at
110.degree. C. over 13 hours, followed by aging at this temperature
for 2 hours. To the resulting reaction product, a filter aid
"Radiolite #900" (manufactured by Showa Chemical Industry Co.,
Ltd.) was added, and the catalyst was then removed by means of
filtration, thereby obtaining a polybutyleneoxy alkenyl ether
(compound represented by the formula (3)).
[0109] 518 g (1 mol) of this polybutyleneoxy alkenyl ether and 15.5
g of potassium hydroxide were charged in a 2-liter autoclave, and
660 g (15 mol) of ethylene oxide was added under the conditions at
125.degree. C. and 0.3 MPa. This reaction system was neutralized
with acetic acid. Subsequently, 1,178 g (1 mol) of the resulting
compound (polybutyleneoxy-polyethyleneoxy alkenyl ether which is a
compound represented by the formula (4)), 97 g (1 mol) of
amidosulfuric acid, and 3 g of urea were charged in a 2-liter
four-necked flask equipped with an agitator and a thermometer and
allowed to react with each other for sulfation in a nitrogen
atmosphere at 125.degree. C. for 4 hours. Thereafter, the unreacted
amidosulfuric acid was removed by means of filtration under
pressure, and the residue was neutralized with ammonia, thereby
obtaining a reactive surfactant composition for emulsion
polymerization [A-1] represented by the following formula. In the
formula, m and n each represent an average addition molar
number.
##STR00011##
[0110] In the formula, BO represents a butyleneoxy group.
Production Examples 2 and 3
[0111] Reactive surfactant compositions for emulsion polymerization
[A-2] and [A-3] were obtained in the same production method as in
Production Example 1, except that the addition amount of the
butylene oxide was changed to 3,600 g (50 mol) and 5,040 g (70
mol), respectively. In the formulae, m and n each represent an
average addition molar number.
##STR00012##
[0112] In the formulae, BO represents a butyleneoxy group.
Comparative Production Example 4
[0113] In a 1-liter four-necked flask equipped with an agitator, a
thermometer, and a dropping funnel, 120.0 g (1.39 mol) of
3-methyl-3-buten-1-ol was charged and cooled to 10.degree. C. in a
nitrogen atmosphere; 3.96 g (0.028 mol) of a boron trifluoride
diethyl ether complex (manufactured by Wako Chemical Industries,
Ltd.) was added; 602 g (8.36 mol) of butylene oxide was dropped at
7 to 10.degree. C.; and after dropping, the contents were aged at
10.degree. C. for 1 hour. For the purpose of removing the boron
trifluoride diethyl ether complex, 12.4 g of an adsorbing agent
"KYOWAAD 500SH" (manufactured by Kyowa Chemical Industry Co., Ltd.)
was added, and the contents were agitated at room temperature for 1
hour, followed by filtration under reduced pressure, thereby
obtaining a polyoxybutylene alkenyl ether.
[0114] 518 g (1 mol) of this polyoxybutylene alkenyl ether and 15.5
g of potassium hydroxide were charged in a 2-liter autoclave, and
660 g (15 mol) of ethylene oxide was added under the conditions at
125.degree. C. and 0.3 MPa. This reaction system was neutralized
with acetic acid. Subsequently, 1,178 g (1 mol) of the resulting
compound (polyoxybutylene-polyoxyethylene alkenyl ether), 97 g (1
mol) of amidosulfuric acid, and 3 g of urea were charged in a
2-liter four-necked flask equipped with an agitator and a
thermometer and allowed to react with each other for sulfation in a
nitrogen atmosphere at 125.degree. C. for 4 hours. Thereafter, the
unreacted amidosulfuric acid was removed by means of filtration
under pressure, and the residue was neutralized with ammonia,
thereby obtaining a reactive surfactant composition for emulsion
polymerization [B-1] represented by the following formula. In the
formula, m and n each represent an average addition molar
number.
##STR00013##
[0115] In the formula, BO represents a butyleneoxy group.
<Measurement Method of X of the Formula (I)>
[0116] The addition molar number of each alkylene oxide of the
compound represented by the formula (3) was calculated from an area
ratio of peaks of the chromatogram obtained under the following
conditions. A chromatogram chart of the compound (polybutyleneoxy
alkenyl ether) represented by the formula (3) as produced in
Production Example 1 is shown in FIG. 1. In FIG. 1, the peak of
7.732 minutes is a peak of a 3-mol adduct of the butyleneoxy group;
the peak of 11.459 minutes is a peak of a 4-mol adduct; and the
followings are each a peak of the compound in which the addition
number of the butyleneoxy group increases with every 1 mol. The
retention time, the addition molar number of the butyleneoxy group,
and the peak area are shown in Table 1.
[0117] With respect to Production Examples 2 and 3 and Comparative
Production Example 4, the same measurement was also performed to
calculate X of the formula (I). The results are shown in Table
2.
[0118] Measuring instrument: Agilent 6890N (gas chromatograph,
manufactured by Agilent Technologies, Inc.)
[0119] Column: DB-1ht (manufactured by Agilent Technologies, Inc.)
(length: 30 m, inside diameter: 0.25 mm, film thickness: 0.10
.mu.m)
[0120] Carrier gas: He (constant flow mode)
[0121] Split ratio: 50/1
[0122] Detector: FID
[0123] Injection port temperature: 330.degree. C.
[0124] Detector temperature: 330.degree. C.
[0125] Measurement temperature conditions: 100.degree.
C..fwdarw.temperature rise at 10.degree. C./min.fwdarw.holding at
380.degree. C. for 27 minutes
[0126] Detection sensitivity: [0127] Uptake rate: 20 Hz [0128]
Minimum peak width: 0.01 min
[0129] Injection amount: 1 .mu.L (split method)
TABLE-US-00001 TABLE 1 Addition molar number No. Retention time of
butyleneoxy group Area % 1 7.732 3 3.64 2 11.459 4 17.05 3 14.528 5
24.08 4 17.122 6 21.32 5 19.384 7 14.72 6 21.381 8 9.00 7 23.100 9
5.18 8 24.749 10 3.08 9 26.416 11 1.92
TABLE-US-00002 TABLE 2 Mol % of Mol % of component A-1 component
A-2 X of formula (I) [A-1] 3.6 19.2 22.8 [A-2] 0.2 24.0 24.2 [A-3]
7.1 18.6 25.7 [B-1] 6.9 28.6 35.5
<Measurement Method of Average Addition Molar Number>
[0130] The average addition molar numbers m and n of the
alkyleneoxy group and the ethyleneoxy group of the reactive anionic
surfactant were calculated according to the following hydroxyl
value.
Measurement of Hydroxyl Value
[0131] The hydroxyl value was measured according to the method
described in "JIS K0070-1992 7.1: Neutralization titration method".
An acid value to be used for calculation of the hydroxyl value was
measured according to the method described in "JIS K0070-1992 3.1:
Neutralization titration method". Here, in order to perform the
analysis with a higher precision, the measurement method using a
synthetic intermediate is shown; however, it is also possible to
directly measure the reactive surfactant composition by general
liquid chromatography.
[0132] m and n are determined from the measured hydroxyl value
according to the following formulae.
m=(M.sub.a/OHV.sub.1.times.1,000-M.sub.b)/M.sub.c
n=(M.sub.a/OHV.sub.2-M.sub.a/OHV.sub.1)/M.sub.d.times.1,000
[0133] OHV.sub.1: Hydroxyl value of the compound represented by the
formula (3) (mgKOH/g)
[0134] OHV.sub.2: Hydroxyl value of the compound represented by the
formula (4) (mgKOH/g)
[0135] M.sub.a: Molecular weight of potassium hydroxide
[0136] M.sub.b: Molecular weight of the compound represented by the
formula (2)
[0137] M.sub.c: Molecular weight of the alkyleneoxy group (AO)
[0138] M.sub.d: Molecular weight of the ethyleneoxy group (EO)
Examples 1 to 5 and Comparative Examples 1 to 3
[0139] Using each of the reactive surfactant compositions obtained
in Production Examples 1 to 4 as an emulsifier for emulsion
polymerization, the emulsion polymerization was performed by the
following method, and the performance was evaluated by the
following method. The results are shown in Table 3.
<Emulsion Polymerization Method>
Example 1
[0140] In a 1-liter three-necked flask equipped with an agitator
and a raw material input port, 112.5 g of ion-exchange water, 0.36
g of potassium persulfate as a polymerization initiator, and 1.80 g
of the reactive surfactant composition [A-1] were mixed, to which
was then dropped a monomer mixture of 109.7 g of butyl acrylate,
109.7 g of styrene, and 5.6 g of acrylic acid over about 5 minutes
while agitating at a rate of 500 r/min, and the contents were
agitated for 30 minutes, thereby obtaining an emulsion for
dropping.
[0141] Subsequently, in a 1-liter separable flask equipped with an
agitator, a reflux condenser, and a raw material input port, 162.5
g of ion-exchange water, 0.09 g of potassium persulfate as a
polymerization initiator, 0.45 g of the reactive surfactant
composition [A-1], and 17.1 g (corresponding to 5% by mass) of the
aforementioned emulsion for dropping were charged, the temperature
was raised to 80.degree. C., and first-stage polymerization was
performed for 30 minutes. Thereafter, the remaining emulsion for
dropping was dropped over 3 hours, and after completion of
dropping, the contents were aged at 80.degree. C. for 1 hour. The
resulting polymer emulsion was cooled to 30.degree. C.
Examples 2 to 5 and Comparative Examples 1 to 3
[0142] Examples 2 to 5 and Comparative Examples 1 to 3 were each
performed in the kind and addition amount of the reactive
surfactant composition as shown in Table 3 in accordance with the
aforementioned method.
<Performance Evaluation Method>
(1) Average Particle Diameter
[0143] Using a submicron particle-size distribution measuring
device "Coulter N4 Plus" (manufactured by Beckman Coulter, Inc.),
polymer emulsion particles which had been neutralized with 25%
ammonia water were diluted thirty thousand times and measured for
an average particle diameter. As the measurement analysis method, a
unimodal mode was adopted.
(2) Viscosity
[0144] Using a BII viscometer (manufactured by Toki Sangyo Co.,
Ltd.), a viscosity of the polymer emulsion which had been
neutralized with 25% ammonia water was measured at 25.degree. C.
and a rotation frequency of 12 r/min.
(3) Water Resistance of Polymer Film
[0145] Using a Baker type film applicator No. 510 (0 to 50 mil)
(manufactured by Yasuda Seiki Seisakusho, Ltd.), the polymer
emulsion which had been neutralized with 25% ammonia water was
applied on a transparent acrylic resin plate such that a dry film
thickness was 50 .mu.m, and then dried at 100.degree. C. for 10
minutes by using an air-forced oven SPS-222 (manufactured by ESPEC
Corp.). This acrylic resin plate was dipped in warm water at
60.degree. C. for 16 hours and then dried, and a haze value of the
polymer film was measured using a haze-transmittance meter HM-150
(manufactured by Murakami Color Research Laboratory Co., Ltd.). The
smaller the haze value, the more favorable water resistance, and it
is judged that in the case where the haze value is 15% or less, the
water resistance is especially favorable.
TABLE-US-00003 TABLE 3 Reactive surfactant composition Addition
amount Total Average Water Addition amount (g) at the time of
addition particle resistance of (g) in emulsion start of emulsion
amount diameter Viscosity polymer film Kind p m n X dropping liquid
polymerization (g) (nm) (mPa s) (haze value, %) Example 1 A-1 2 6
15 22.8 1.80 0.45 2.25 155 86 8 2 A-1 2 6 15 22.8 3.60 0.90 4.50
141 121 13 3 A-1 2 6 15 22.8 5.44 1.36 6.80 122 250 22 4 A-2 2 5 15
24.2 5.44 1.36 6.80 141 272 25 5 A-3 2 7 15 25.7 5.44 1.36 6.80 133
1,300 27 Comparative 1 B-1 2 6 15 35.5 1.80 0.45 2.25 185 91 17
Example 2 B-1 2 6 15 35.5 3.60 0.90 4.50 158 180 20 3 B-1 2 6 15
35.5 5.44 1.36 6.80 137 515 29
[0146] It has been noted from Table 3 that by using the reactive
surfactant composition of the present invention, the polymer
emulsion having a small particle diameter is obtained; and that the
amount of the reactive surfactant composition to be used can be
reduced. Furthermore, it has become clear that the polymer film
produced using the obtained polymer emulsion is excellent in the
water resistance.
[0147] On the other hand, in Comparative Examples 1 to 3, in the
case of using the reactive surfactant composition in the same
amount as in the Examples, it has become clear that the particle
diameter of the obtained polymer emulsion is larger; and that the
polymer film produced using the obtained polymer emulsion is
inferior in the water resistance.
INDUSTRIAL APPLICABILITY
[0148] By using the reactive surfactant composition for emulsion
polymerization of the present invention, it is possible to
micronize the particle diameter of the obtained polymer emulsion,
and the addition amount of the reactive surfactant composition to
be used can be reduced. In addition, the polymer coating film
prepared from the polymer emulsion of the present invention is
excellent in the water resistance and can be preferably used in the
field of a coating material, particularly an aqueous coating
material as well as in the field of a pressure sensitive adhesive
product.
* * * * *