U.S. patent application number 17/677964 was filed with the patent office on 2022-06-09 for binder for electricity storage devices.
This patent application is currently assigned to FUJIFILM Corporation. The applicant listed for this patent is FUJIFILM Corporation, FUJIFILM Wako Pure Chemical Corporation. Invention is credited to Kei KAWANO, Kaho MORI, Kazuki TAKIMOTO.
Application Number | 20220181633 17/677964 |
Document ID | / |
Family ID | |
Filed Date | 2022-06-09 |
United States Patent
Application |
20220181633 |
Kind Code |
A1 |
KAWANO; Kei ; et
al. |
June 9, 2022 |
BINDER FOR ELECTRICITY STORAGE DEVICES
Abstract
The present invention relates to a binder for electricity
storage devices containing a salt of a polymer containing
structural units derived from (i) an ethylenically unsaturated
carboxylic acid monomer and (ii) an ethylenically unsaturated
monomer having at least one group selected from a hydroxy group, a
dialkylamino group, an acetyl group, a sulfo group, a phosphate
group, or a cyano group and neutralized with a monoamine, a
polyvalent amine having an amine value of less than 21, and/or an
onium hydroxide; a slurry composition and an electrode, each of
which uses this binder; an electricity storage device which is
provided with this electrode; and the like.
Inventors: |
KAWANO; Kei; (Saitama,
JP) ; TAKIMOTO; Kazuki; (Saitama, JP) ; MORI;
Kaho; (Saitama, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation
FUJIFILM Wako Pure Chemical Corporation |
Tokyo
Osaka |
|
JP
JP |
|
|
Assignee: |
FUJIFILM Corporation
Tokyo
JP
FUJIFILM Wako Pure Chemical Corporation
Osaka
JP
|
Appl. No.: |
17/677964 |
Filed: |
February 22, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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PCT/JP2020/032586 |
Aug 28, 2020 |
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17677964 |
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International
Class: |
H01M 4/62 20060101
H01M004/62; H01M 4/134 20060101 H01M004/134; H01M 4/133 20060101
H01M004/133; C08L 33/10 20060101 C08L033/10; C08L 33/08 20060101
C08L033/08 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 29, 2019 |
JP |
2019-156698 |
Mar 27, 2020 |
JP |
2020-057233 |
Jul 22, 2020 |
JP |
2020-125295 |
Claims
1. A binder for electricity storage devices, comprising: a salt of
a polymer containing structural units derived from (i) an
ethylenically unsaturated carboxylic acid monomer and (ii) an
ethylenically unsaturated monomer having at least one group
selected from a hydroxy group, a dialkylamino group, an acetyl
group, a sulfo group, a phosphate group, or a cyano group, wherein
the salt of the polymer is neutralized with a monoamine, a
polyvalent amine having an amine value of less than 21, and/or an
onium hydroxide.
2. The binder according to claim 1, wherein the polyvalent amine
has a molecular weight of 600 or less.
3. The binder according to claim 1, wherein the monomer of (ii) has
a solubility in water at 20.degree. C. of 1 g/L or more.
4. The binder according to claim 1, wherein the monomer of (ii) has
an SP value of 11.5 (cal/cm.sup.3).sup.1/2 or more.
5. The binder according to claim 1, wherein the monomer of (ii) is
a monomer represented by the following general formula [1]:
##STR00041## in the general formula [1], R.sub.1 represents a
hydrogen atom or a methyl group, Y.sub.1 represents --O-- or
--NR.sub.2--, R.sub.2 represents a hydrogen atom or a methyl group,
and A.sub.1 represents a monovalent group having at least one group
selected from a hydroxy group, a dialkylamino group, an acetyl
group, a sulfo group, a phosphate group, or a cyano group.
6. The binder according to claim 1, wherein the monomer of (ii) is
a monomer represented by the following general formula [2]:
##STR00042## in the general formula [2], R.sub.1 represents a
hydrogen atom or a methyl group, Y.sub.1 represents --O-- or
--NR.sub.2--, R.sub.2 represents a hydrogen atom or a methyl group,
and A.sub.2 represents an alkyl group having 1 to 10 carbon atoms
and having 1 to 3 of any one of a group selected from a hydroxy
group, a dialkylamino group, an acetyl group, a sulfo group, a
phosphate group, or a cyano group; or a linear alkyl group having 3
to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester
bonds in a chain thereof.
7. The binder according to claim 1, wherein the salt of the polymer
further contains a structural unit derived from (iii) a monomer
having two or more polymerizable unsaturated groups.
8. The binder according to claim 1, wherein, in a case where the
polymer contains a structural unit(s) derived from a monomer(s)
other than the monomers (i) and (ii), a total content of the
structural unit(s) derived from the monomer(s) other than the
monomers (i) and (ii) in the polymer is 10 mol % or less with
respect to a total content of the structural units derived from the
monomers (i) and (ii) in the polymer.
9. A slurry composition for electricity storage devices, comprising
the binder according to claim 1.
10. An electrode for electricity storage devices, comprising the
slurry composition according to claim 9.
11. An electricity storage device comprising the electrode
according to claim 10.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of PCT International
Application No. PCT/JP2020/032586, filed on Aug. 28, 2020, which
claims priority under 35 U.S.C. .sctn. 119(a) to Japanese Patent
Application No. 2019-156698, filed on Aug. 29, 2019, Japanese
Patent Application No. 2020-057233, filed on Mar. 27, 2020, and
Japanese Patent Application No. 2020-125295, filed on Jul. 22,
2020. Each of the above application(s) is hereby expressly
incorporated by reference, in its entirety, into the present
application.
TECHNICAL FIELD
[0002] The present invention relates to a binder used in an
electricity storage device, a slurry composition and an electrode,
and an electricity storage device including the electrode.
BACKGROUND ART
[0003] In recent years, a battery (electricity storage device) used
in a mobile terminal such as a notebook computer or a mobile phone,
a hybrid car, an electric vehicle, an electrically power assisted
bicycle, or the like is rapidly becoming widespread, and is
required to be further reduced in size and weight. A lithium ion
secondary battery having an advantage of high energy density and
light weight is attracting attention as an electricity storage
device used in these products.
[0004] Usually, an electrode used for a lithium ion secondary
battery or the like contains a collector and an electrode mixture
layer formed on the collector. A negative electrode mixture layer,
which is an electrode mixture layer in a negative electrode, is
generally formed in such a manner that a negative electrode active
material typified by graphite or silicon, a conductive assistant
typified by acetylene black or carbon black, a binder, and the like
are dispersed or dissolved in a dispersion medium to obtain a
slurry for a negative electrode mixture layer (slurry for an
electrode mixture layer), the obtained slurry is coated on a
collector, followed by drying, and the negative electrode active
material, the conductive assistant, and the like are bound with a
binder.
[0005] The characteristics required for this slurry for an
electrode mixture layer include the uniformity in a case where an
active material or a conductive assistant is dispersed or dissolved
in a dispersion medium. This is because the dispersed state of the
active material and the conductive assistant in the slurry for an
electrode mixture layer is related to the distributed state of the
active material and the conductive assistant in the electrode
mixture layer, which affects the physical properties of the
electrode and the battery performance. In particular, among the
conductive assistants, a carbon material having excellent
conductivity has a small particle size and a large specific surface
area, thus exhibiting a strong cohesive force, which makes it
difficult for the carbon material to be uniformly mixed and
dispersed in the slurry for an electrode mixture layer. In a case
where the dispersibility and particle size of the carbon material
are not sufficiently controlled, the internal resistance of the
electrode cannot be reduced because a uniform conductive network is
not formed, and as a result, there arises a problem that the
performance of the electrode material cannot be sufficiently
brought out. For that reason, improving the dispersibility of the
conductive assistant is an important issue.
[0006] Therefore, various methods for dispersing the conductive
assistant in the slurry for an electrode mixture layer have been
studied. For example, Patent Literature 1 and Patent Literature 2
describe an example in which a surfactant is used as a dispersant
in a case where carbon black is dispersed in a solvent. In
addition, Patent Literature 3 and Patent Literature 4 describe an
example in which various additives are added in a case where a
conductive assistant is dispersed.
[0007] In addition, various studies have been conducted on an
electrode coated with a slurry to improve flexibility of the
electrode in order to prevent cracks due to winding and trimming at
the time of producing a battery, and expansion and contraction of
an active material during repeated charge and discharge of the
battery. For example, Patent Literature 5 and Patent Literature 6
describe an example in which a polymer containing a specific
monomer component in a predetermined ratio is used. In addition,
Patent Literature 7 describes an example in which flexibility of
the electrode is improved by adding a composite body of carbon
nanotubes.
CITATION LIST
Patent Literature
[0008] Patent Literature 1: JP1988-236258A (JP-S63-236258A) [0009]
Patent Literature 2: JP1996-190912A (JP-H08-190912A) [0010] Patent
Literature 3: JP2013-206759A [0011] Patent Literature 4:
JP2012-195243A [0012] Patent Literature 5: JP2016-155927A [0013]
Patent Literature 6: WO2018/003636A [0014] Patent Literature 7:
JP2016-054113A
SUMMARY OF INVENTION
Technical Problem
[0015] However, since the surfactant described in Patent Literature
1 and Patent Literature 2 has a weak adsorption force on the
surface of the carbon material, the amount of the surfactant added
should be increased in order to obtain good dispersion stability.
As a result, there is a problem that the amount of the active
material that can be contained in the electrode mixture layer is
reduced and therefore the battery capacity is lowered. In addition,
in a case where the adsorption of the surfactant to the carbon
material is insufficient, there is a problem that the aggregation
of the carbon material cannot be suppressed and therefore the
dispersibility remains insufficient.
[0016] In addition, the dispersant described in Patent Literature 3
and Patent Literature 4 is a low-molecular-weight substance and
therefore may be eluted from an electrode mixture layer into an
electrolytic solution, which may adversely affect the battery
performance. In addition, in a case where the dispersant to be
added has poor compatibility with a binder polymer or a solvent,
there is a problem that the battery performance is
deteriorated.
[0017] On the other hand, in terms of electrode flexibility, the
polymer to which the monomer described in Patent Literature 5 and
Patent Literature 6 is added exhibits a main skeleton of the
polymer becoming flexible and therefore has a problem that a
conductive path between the active materials is lost, resulting
from the expansion and contraction of the active materials due to
charge and discharge of the battery, and the battery capacity is
lowered. In addition, since a water-dispersible polymer has a low
viscosity, there is a problem that the polymer needs to be used in
combination with a thickener such as carboxymethyl cellulose.
[0018] In addition, since the composite body of carbon nanotubes
described in Patent Literature 7 does not contain a binder polymer,
the composite body may peel off from a current collecting foil of
an electrode in a case where charge and discharge of the battery
are repeated, and the battery may not withstand long-term use. In
addition, it is necessary to increase the formulation amount of
carbon nanotubes in order to increase the strength of the composite
body sheet, and as a result, there is a problem that the proportion
of the active material in the electrode is reduced and the energy
density of the battery is lowered.
[0019] The present invention has been made in view of such
circumstances, and the present invention provides a binder having
excellent dispersibility that solves the problems described above,
or a binder capable of imparting excellent flexibility to an
electrode, a slurry composition and an electrode using the same,
and an electricity storage device provided with the electrode.
Solution to Problem
[0020] As a result of extensive studies, the present inventors have
found that an electricity storage device having excellent
dispersibility of a conductive assistant and capable of maintaining
a high capacity for a long period of time can be obtained by using
a binder in which a loss tangent tan .delta. in a linear region of
an aqueous dispersion liquid containing specific amounts of a
conductive assistant and a binder satisfies tan .delta.>1 in the
strain dispersion measurement in the electricity storage device. A
first invention has been completed based on this finding.
[0021] In addition, as a result of extensive studies, the present
inventors have found that the flexibility of an electrode is
improved, which makes it possible to produce an electrode having
excellent winding properties and an electricity storage device
provided with the electrode, by using a binder containing a salt of
a polymer neutralized by a specific neutralizing agent. A second
invention has been completed based on this finding.
[0022] That is, the first invention encompasses the following
inventions [i] to [xi].
[0023] [i] A binder for an electricity storage device, in which a
loss tangent tan .delta. in a linear region of an aqueous
dispersion liquid of 0.5% by mass of the binder and 4.6% by mass of
a conductive assistant satisfies tan .delta.>1 in a strain
dispersion measurement under measurement conditions of a
measurement temperature of 25.degree. C. and a frequency of 1 Hz,
and here, the conductive assistant is an acetylene black having an
average particle diameter of 30 nm or more and 40 nm or less and a
specific surface area of 65 m.sup.2/g or more and 70 m.sup.2/g or
less (hereinafter, sometimes referred to simply as the binder of
the first invention).
[0024] [ii] The binder according to the invention [i], in which the
binder contains a polymer or a salt thereof containing structural
units derived from (i) an ethylenically unsaturated carboxylic acid
monomer and (ii) an ethylenically unsaturated monomer having at
least one group selected from a hydroxy group, a dialkylamino
group, an acetyl group, a sulfo group, a phosphate group, or a
cyano group.
[0025] [iii] The binder according to the invention [ii], in which
the monomer of (ii) has a solubility in water at 20.degree. C. of 1
g/L or more.
[0026] [iv] The binder according to the invention [ii] or [iii], in
which the monomer of (ii) has an SP value of 11.5
(cal/cm.sup.3).sup.1/2 or more.
[0027] [v] The binder according to any one of the inventions [ii]
to [iv], in which the monomer of (ii) is a monomer represented by
the following general formula [1].
##STR00001##
[0028] (In the general formula [1], R.sub.1 represents a hydrogen
atom or a methyl group, Y.sub.1 represents --O-- or --NR.sub.2--,
R.sub.2 represents a hydrogen atom or a methyl group, and A.sub.1
represents a monovalent group having at least one group selected
from a hydroxy group, a dialkylamino group, an acetyl group, a
sulfo group, a phosphate group, or a cyano group.)
[0029] [vi] The binder according to any one of the inventions [ii]
to [v], in which the monomer of (ii) is a monomer represented by
the following general formula [2].
##STR00002##
[0030] (In the general formula [2], R.sub.1 represents a hydrogen
atom or a methyl group, Y.sub.1 represents --O-- or --NR.sub.2--,
R.sub.2 represents a hydrogen atom or a methyl group, and A.sub.2
represents an alkyl group having 1 to 10 carbon atoms and having 1
to 3 of any one of a group selected from a hydroxy group, a
dialkylamino group, an acetyl group, a sulfo group, a phosphate
group, or a cyano group; or a linear alkyl group having 3 to 36
carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a
chain thereof.)
[0031] [vii] The binder according to any one of the inventions [ii]
to [vi], in which the polymer or the salt thereof further contains
a structural unit derived from (iii) a monomer having two or more
polymerizable unsaturated groups.
[0032] [viii] The binder according to any one of the inventions
[ii] to [vii], in which the polymer or the salt thereof is
neutralized with a hydroxide of an alkali metal and/or a polyvalent
amine having an amine value of 21 or more.
[0033] [ix] A slurry composition for an electricity storage device
containing the binder according to any one of the inventions [i] to
[viii] (hereinafter, sometimes referred to simply as the slurry
composition of the first invention).
[0034] [x] An electrode for an electricity storage device
consisting of the slurry composition according to the invention
[ix] (hereinafter, sometimes referred to simply as the electrode of
the first invention).
[0035] [xi] An electricity storage device including the electrode
according to the invention [x] (hereinafter, sometimes referred to
simply as the electricity storage device of the first
invention).
[0036] In addition, the second invention encompasses the following
inventions [xii] to [xxi].
[0037] [xii] A binder for an electricity storage device
(hereinafter, sometimes referred to simply as the binder of the
second invention), in which the binder contains a salt of a polymer
containing structural units derived from (i) an ethylenically
unsaturated carboxylic acid monomer and (ii) an ethylenically
unsaturated monomer having at least one group selected from a
hydroxy group, a dialkylamino group, an acetyl group, a sulfo
group, a phosphate group, or a cyano group and neutralized with a
monoamine, a polyvalent amine having an amine value of less than
21, and/or an onium hydroxide.
[0038] [xiii] The binder according to the invention [xii], in which
the polyvalent amine has a molecular weight of 600 or less.
[0039] [xiv] The binder according to the invention [xii] or [xiii],
in which the monomer of (ii) has a solubility in water at
20.degree. C. of 1 g/L or more.
[0040] [xv] The binder according to any one of the inventions [xii]
to [xiv], in which the monomer of (ii) has an SP value of 11.5
(cal/cm.sup.3).sup.1/2 or more.
[0041] [xvi] The binder according to any one of the inventions
[xii] to [xv], in which the monomer of (ii) is a monomer
represented by the following general formula [1].
##STR00003##
[0042] (In the general formula [1], R.sub.1 represents a hydrogen
atom or a methyl group, Y.sub.1 represents --O-- or --NR.sub.2--,
R.sub.2 represents a hydrogen atom or a methyl group, and A.sub.1
represents a monovalent group having at least one group selected
from a hydroxy group, a dialkylamino group, an acetyl group, a
sulfo group, a phosphate group, or a cyano group.)
[0043] [xvii] The binder according to any one of the inventions
[xii] to [xvi], in which the monomer of (ii) is a monomer
represented by the following general formula [2].
##STR00004##
[0044] (In the general formula [2], R.sub.1 represents a hydrogen
atom or a methyl group, Y.sub.1 represents --O-- or --NR.sub.2--,
R.sub.2 represents a hydrogen atom or a methyl group, and A.sub.2
represents an alkyl group having 1 to 10 carbon atoms and having 1
to 3 of any one of a group selected from a hydroxy group, a
dialkylamino group, an acetyl group, a sulfo group, a phosphate
group, or a cyano group; or a linear alkyl group having 3 to 36
carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a
chain thereof.)
[0045] [xviii] A slurry composition for an electricity storage
device containing the binder according to any one of the inventions
[xii] to [xvii] (hereinafter, sometimes referred to simply as the
slurry composition of the second invention).
[0046] [xix] An electrode for an electricity storage device
consisting of the slurry composition according to the invention
[xviii] (hereinafter, sometimes referred to simply as the electrode
of the second invention).
[0047] [xx] An electricity storage device including the electrode
according to the invention [xix] (hereinafter, sometimes referred
to simply as the electricity storage device of the second
invention).
Advantageous Effects of Invention
[0048] Using the binder of the first invention leads to excellent
dispersibility of a conductive assistant, which makes it possible
to provide an electricity storage device capable of maintaining a
high capacity for a long period of time.
[0049] In addition, using the binder of the second invention for
the production of an electrode leads to improved flexibility of the
electrode, which makes it possible to provide an electrode having
excellent winding properties, and an electricity storage device
provided with the electrode.
DESCRIPTION OF EMBODIMENTS
[0050] Binder of First Invention
[0051] The binder of the first invention is a binder in which a
loss tangent tan .delta. in a linear region of an aqueous
dispersion liquid of 0.5% by mass of a binder and 4.6% by mass of a
conductive assistant in the strain dispersion measurement under the
measurement conditions of a measurement temperature of 25.degree.
C. and a frequency of 1 Hz satisfies tan .delta.>1. The upper
limit value of tan .delta. is not particularly limited and is, for
example, 1<tan .delta..ltoreq.100, preferably 1<tan
.delta..ltoreq.50, and more preferably 1<tan
.delta..ltoreq.10.
[0052] The "linear region" indicates a region from the time in a
case where a measurement is started in the strain dispersion
measurement to the time in a case where the structural disorder of
a measurement sample is started, and refers to a region in which
the elastic modulus obtained in the strain dispersion measurement
shows a constant value regardless of the increase in the amount of
strain. It should be noted that the region after the start of
structural disorder (the range in which the elastic modulus
decreases depending on the increase in the amount of strain) is
referred to as a non-linear region.
[0053] The "loss tangent tan .delta." indicates a ratio of a
storage elastic modulus G' and a loss elastic modulus G'' (loss
elastic modulus G''/storage elastic modulus G'), where the storage
elastic modulus G' is an indicator of elastic properties and the
loss elastic modulus G'' is an indicator of viscous properties.
Both the storage elastic modulus G' and the loss elastic modulus
G'' can be obtained by carrying out the strain dispersion
measurement.
[0054] Specifically, the "loss tangent tan .delta." may be
calculated in such a manner that the storage elastic modulus G' and
the loss elastic modulus G'' in a case where the amount of strain
is increased from 10.sup.-2% to 10.sup.3% are measured under the
measurement conditions of a measurement temperature of 25.degree.
C. and a frequency of 1 Hz using a rheometer MCR 102 (dynamic
viscoelasticity measuring device, manufactured by Anton Paar GmbH),
and the loss elastic modulus G''/storage elastic modulus G' is
calculated based on the obtained values.
[0055] Acetylene black having an average particle diameter of 30 nm
or more and 40 nm or less and a specific surface area of 65
m.sup.2/g or more and 70 m.sup.2/g or less shall be used as the
"conductive assistant". Specific examples of the acetylene black
satisfying the average particle diameter conditions and the
specific surface area conditions include DENKA BLACK (registered
trademark) powder (manufactured by Denka Company Limited, average
particle diameter: 35 nm, specific surface area: 68 m.sup.2/g,
representative values posted on the home page of Denka Company
Limited).
[0056] Ion exchange water may be used as the "water" that is a
dispersion medium in the "aqueous dispersion liquid".
[0057] Specific configurations of the binder of the first invention
include a configuration that contains a polymer or a salt thereof
containing structural units derived from (i) an ethylenically
unsaturated carboxylic acid monomer and (ii) an ethylenically
unsaturated monomer having at least one group selected from a
hydroxy group, a dialkylamino group, an acetyl group, a sulfo
group, a phosphate group, or a cyano group (hereinafter, sometimes
referred to simply as the polymer according to the first
invention).
[0058] (i) The ethylenically unsaturated carboxylic acid monomer
(hereinafter, sometimes referred to simply as the monomer of (i))
is a monomer having both an ethylenically unsaturated group and a
carboxy group in one molecule. However, the monomer of (i) has one
ethylenically unsaturated group, unlike the monomer of (iii) which
will be described later. In addition, the monomer of (i) may be an
acid anhydride.
[0059] Specific examples of the monomer of (i) include
ethylenically unsaturated monocarboxylic acid monomers such as
acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid,
mono(2-acryloyloxyethyl)succinate,
mono(2-acryloyloxyethyl)phthalate, and
mono(2-acryloyloxyethyl)hexahydrophthalate; and ethylenically
unsaturated dicarboxylic acid monomers such as maleic acid, fumaric
acid, itaconic acid, maleic acid anhydride, and itaconic anhydride.
Among these specific examples, an ethylenically unsaturated
monocarboxylic acid monomer is preferable; acrylic acid or
methacrylic acid is more preferable; and acrylic acid is
particularly preferable. It should be noted that the monomer of (i)
may be used alone or in combination of two or more thereof, and
only one type thereof is preferably used.
[0060] (ii) The ethylenically unsaturated monomer having at least
one group selected from a hydroxy group, a dialkylamino group, an
acetyl group, a sulfo group, a phosphate group, or a cyano group
(hereinafter, sometimes referred to simply as the monomer of (ii))
is a monomer having both a "group selected from a hydroxy group, a
dialkylamino group, an acetyl group, a sulfo group, a phosphate
group, or a cyano group" and an ethylenically unsaturated group in
one molecule, and is not particularly limited as long as it is
commonly used in the art. However, the monomer of (i) and the
monomer of (ii) have different structures, and the hydroxy group in
the monomer of (ii) does not contain a carboxy group, a sulfo
group, and a phosphate group (the OH present in the carboxy group,
sulfo group, and phosphate group does not correspond to the hydroxy
group in the monomer of (ii)). In addition, the monomer of (ii) has
one ethylenically unsaturated group, unlike the monomer of (iii)
which will be described later.
[0061] Examples of the dialkylamino group in the monomer of (ii)
include a dialkylamino group having 2 to 12 carbon atoms, among
which a dialkylamino group having 2 to 8 carbon atoms is
preferable. In addition, each of the two alkyl groups in the
dialkylamino group may be linear, branched, or cyclic and is
preferably linear or branched. Further, the two alkyl groups in the
dialkylamino group may be the same or different from each other,
and the two alkyl groups may be bonded to each other to form a
heterocyclic structure. Specific examples of the dialkylamino group
include a dimethylamino group, a diethylamino group, a
di(n-propyl)amino group, a diisopropylamino group, a
di(n-butyl)amino group, a diisobutylamino group, a morpholino
group, and a piperidino group.
[0062] Examples of the monomer of (ii) include a monomer having a
high solubility in water. Specifically, the monomer of (ii) is
preferably a monomer having a solubility in water at 20.degree. C.
of 1 g/L or more; more preferably a monomer having a solubility in
water at 20.degree. C. of 100 g/L or more; and particularly
preferably a monomer which dissolves in water at an arbitrary
ratio.
[0063] In addition, the monomer of (ii) preferably has an SP value
of 11.5 (cal/cm.sup.3).sup.1/2 or more. The upper limit value of
the SP value of the monomer of (ii) is not particularly limited and
is preferably 25 (cal/cm.sup.3).sup.1/2 or less. It should be noted
that the SP value (Solubility Parameter) in the present invention
(first invention and second invention) is calculated according to
the Fedors method, and can be specifically obtained from the
following calculation formula.
Calculation formula:
.delta.=(.DELTA.E.sub.coh/.DELTA.V).sup.1/2
[0064] (In the calculation formula, .delta. represents an SP value
(cal/cm.sup.3).sup.1/2, .DELTA.E.sub.coh represents a molar
cohesive energy (cal/mol), and .DELTA.V represents a molar
molecular volume (cm.sup.3/mol).)
[0065] Examples of the ethylenically unsaturated group in the
monomer of (ii) include an allyl group, a vinylaryl group, a
vinyloxy group, an acryloyl group, and a methacryloyl group, among
which the acryloyl group and the methacryloyl group are preferable,
and the acryloyl group is more preferable.
[0066] The monomer of (ii) may be, for example, a monomer having at
least one group selected from a hydroxy group, a dialkylamino
group, an acetyl group, a sulfo group, a phosphate group, or a
cyano group, and having an acryloyl group or a methacryloyl group.
More specifically, the monomer of (ii) may be, for example, a
monomer represented by the following general formula [1].
##STR00005##
[0067] (In the general formula [1], R.sub.1 represents a hydrogen
atom or a methyl group, Y.sub.1 represents --O-- or --NR.sub.2--,
R.sub.2 represents a hydrogen atom or a methyl group, and A.sub.1
represents a monovalent group having at least one group selected
from a hydroxy group, a dialkylamino group, an acetyl group, a
sulfo group, a phosphate group, or a cyano group.)
[0068] R.sub.1 of the general formula [1] is preferably a hydrogen
atom.
[0069] In Y.sub.1 of the general formula [1], R.sub.2 in
--NR.sub.2-- is preferably a hydrogen atom.
[0070] Y.sub.1 of the general formula Ell is preferably --O-- or
--NH-- and more preferably --O--.
[0071] Examples of the dialkylamino group in A.sub.1 of the general
formula [1] include the same dialkylamino groups in the monomer of
(ii).
[0072] The "group selected from a hydroxy group, a dialkylamino
group, an acetyl group, a sulfo group, a phosphate group, or a
cyano group" contained in A.sub.1 of the general formula [1] may be
only one type or two or more types; and is preferably any one of a
group selected from a hydroxy group, a dialkylamino group, an
acetyl group, a sulfo group, a phosphate group, or a cyano group;
more preferably any one of a group selected from a hydroxy group, a
sulfo group, a phosphate group, or a cyano group; still more
preferably any one of a group selected from a hydroxy group, a
sulfo group, or a phosphate group; and particularly preferably a
hydroxy group. In addition, A.sub.1 of the general formula [1] may
have at least one "group selected from a hydroxy group, a
dialkylamino group, an acetyl group, a sulfo group, a phosphate
group, or a cyano group". Above all, A.sub.1 of the general formula
[1] preferably has 1 to 3 groups, more preferably 1 or 2 groups,
and particularly preferably 1 group among those groups.
[0073] The "monovalent group" in A.sub.1 of the general formula [1]
may be, for example, an alkyl group which may have an ester bond in
a chain thereof.
[0074] Examples of the alkyl group in a case where the "alkyl group
which may have an ester bond in a chain thereof" does not have an
ester bond include an alkyl group having 1 to 30 carbon atoms,
among which an alkyl group having 1 to 10 carbon atoms is
preferable, an alkyl group having 1 to 6 carbon atoms is more
preferable, and an alkyl group having 1 to 4 carbon atoms is still
more preferable. In addition, the alkyl group may be linear,
branched, or cyclic, and is preferably linear or branched and more
preferably linear.
[0075] Examples of the alkyl group in a case where the "alkyl group
which may have an ester bond in a chain thereof" has an ester bond
include an alkyl group having 3 to 66 carbon atoms, among which an
alkyl group having 3 to 36 carbon atoms is preferable, an alkyl
group having 5 to 24 carbon atoms is more preferable, and an alkyl
group having 7 to 18 carbon atoms is still more preferable. It
should be noted that the number of carbon atoms in the alkyl group
also contains the number of carbon atoms in the ester bond. In
addition, the alkyl group is preferably linear. Further, the number
of ester bonds contained in the alkyl group may be, for example, 1
to 10 and is preferably 1 to 5, more preferably 1 to 3, and still
more preferably 1 to 2.
[0076] A.sub.1 of the general formula [1] may be, for example, an
alkyl group which has at least one group selected from a hydroxy
group, a dialkylamino group, an acetyl group, a sulfo group, a
phosphate group, or a cyano group, and may have an ester bond in a
chain thereof. Above all, an alkyl group having 1 to 30 carbon
atoms and having 1 to 3 groups selected from a hydroxy group, a
dialkylamino group, an acetyl group, a sulfo group, a phosphate
group, and a cyano group, and an alkyl group having 3 to 66 carbon
atoms and having 1 hydroxy group and 1 to 10 ester bonds in a chain
thereof are preferable; an alkyl group having 1 to 10 carbon atoms
and having 1 to 3 of any one of a group selected from a hydroxy
group, a dialkylamino group, an acetyl group, a sulfo group, a
phosphate group, or a cyano group, and a linear alkyl group having
3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester
bonds in a chain thereof are more preferable; and an alkyl group
having 1 to 10 carbon atoms and having 1 to 2 hydroxy groups, an
alkyl group having 1 to 10 carbon atoms and having one of any one
of a group selected a dialkylamino group, an acetyl group, a sulfo
group, a phosphate group, or a cyano group, and a linear alkyl
group having 5 to 24 carbon atoms and having one hydroxy group and
1 to 3 ester bonds in a chain thereof are still more
preferable.
[0077] Specific examples of A.sub.1 of the general formula [1]
include groups represented by the following general formulae [1-1]
to [1-4], among which a group represented by the general formula
[1-1] is preferable.
##STR00006##
[0078] (In the general formulae [1-1] to [1-4], A.sub.1-1 and
A.sub.1-2 each independently represent an alkylene group having 1
to 10 carbon atoms, R.sub.3 represents a dialkylamino group, an
acetyl group, a sulfo group, a phosphate group, or a cyano group, a
represents an integer of 0 to 4, b represents an integer of 1 to 5,
c represents an integer of 1 to 6, d represents an integer of 3 to
5, and e represents an integer of 1 to 3.)
[0079] The alkylene group having 1 to 10 carbon atoms in A.sub.1-1
of the general formula [1-1] is preferably an alkylene group having
1 to 6 carbon atoms and more preferably an alkylene group having 1
to 4 carbon atoms. In addition, the alkylene group may be linear,
branched, or cyclic, and is preferably linear or branched and more
preferably linear. Specific examples of the alkylene group include
a methylene group, an ethylene group, a methylmethylene group, a
trimethylene group, a propylene group, an ethylmethylene group, a
dimethylmethylene group, a tetramethylene group, a
1-methyltrimethylene group, a 2-methyltrimethylene group, a
1,1-dimethylethylene group, a 1,2-dimethylethylene group, an
ethylethylene group, a propylmethylene group, an
ethylmethylmethylene group, a pentamethylene group, a
1-methyltetramethylene group, a 1-ethyltrimethylene group, an
n-propylethylene group, an n-butylmethylene group, a hexamethylene
group, a 1-methylpentamethylene group, a 1-ethyltetramethylene
group, a 1-n-propyltrimethylene group, an n-butylethylene group, an
n-pentylmethylene group, a heptamethylene group, an octamethylene
group, a nonamethylene group, a decamethylene group, a
--C.sub.6H.sub.10-- group, a --CH.sub.2--C.sub.6H.sub.10-- group, a
--C.sub.2H.sub.4--C.sub.6H.sub.10-- group, a
--C.sub.3H.sub.6--C.sub.6H.sub.10-- group, a
--C.sub.4H.sub.8--C.sub.6H.sub.10-- group, a
--C.sub.6H.sub.10--CH.sub.2-- group, a
--C.sub.6H.sub.10--C.sub.2H.sub.4-- group, a
--C.sub.6H.sub.10--C.sub.3H.sub.6-- group, a
--C.sub.6H.sub.10--C.sub.4H.sub.8-- group, a
--CH.sub.2--C.sub.6H.sub.10--CH.sub.2-- group, and a
--C.sub.2H.sub.4--C.sub.6H.sub.10--C.sub.2H.sub.4-- group. Among
these specific examples, a linear or branched alkylene group having
1 to 6 carbon atoms and a cyclic alkylene group having 6 to 8
carbon atoms are preferable; a linear or branched alkylene group
having 1 to 4 carbon atoms is more preferable; and a linear or
branched alkylene group having 2 to 4 carbon atoms is still more
preferable.
[0080] Examples of the dialkylamino group in R.sub.3 of the general
formula [1-2] include the same dialkylamino groups in the monomer
of (ii).
[0081] Specific examples of the group represented by the general
formula [1-1] include a hydroxymethyl group, a 2-hydroxyethyl
group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a
2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a
1-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a
4-hydroxybutyl group, a 3-hydroxybutyl group, a
3-hydroxy-2-methylpropyl group, a 3-hydroxy-1-methylpropyl group, a
2-hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a
2-hydroxy-1-methylpropyl group, a 2-hydroxy-1,1-dimethylethyl
group, a 1-hydroxybutyl group, a 1-hydroxy-1-methylpropyl group, a
5-hydroxypentyl group, a 4-hydroxypentyl group, a 2-hydroxypentyl
group, a 1-hydroxypentyl group, a 6-hydroxyhexyl group, a
5-hydroxyhexyl group, a 2-hydroxyhexyl group, a 1-hydroxyhexyl
group, a 7-hydroxyheptyl group, a 6-hydroxyheptyl group, a
2-hydroxyheptyl group, a 1-hydroxyheptyl group, a 8-hydroxyoctyl
group, a 7-hydroxyoctyl group, a 2-hydroxyoctyl group, a
1-hydroxyoctyl group, a 9-hydroxynonyl group, a 8-hydroxynonyl
group, a 2-hydroxynonyl group, a 1-hydroxynonyl group, a
10-hydroxydecyl group, a 9-hydroxydecyl group, a 2-hydroxydecyl
group, a 1-hydroxydecyl group, a --C.sub.6H.sub.10--OH group, a
--CH.sub.2--C.sub.6H.sub.10--CH.sub.2--OH group, and a
--C.sub.2H.sub.4--C.sub.6H.sub.10--C.sub.2H.sub.4--OH group.
[0082] Among these specific examples, a linear or branched
hydroxyalkyl group having 1 to 6 carbon atoms and a cyclic
hydroxyalkyl group having 6 to 8 carbon atoms are preferable; a
linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is
more preferable; and a linear or branched hydroxyalkyl group having
2 to 4 carbon atoms is still more preferable. More specifically, a
hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl
group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a
2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a
4-hydroxybutyl group, a 3-hydroxybutyl group, a 2-hydroxybutyl
group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl
group, a 1-hydroxybutyl group, a 5-hydroxypentyl group, a
2-hydroxypentyl group, a 1-hydroxypentyl group, a 6-hydroxyhexyl
group, a 5-hydroxyhexyl group, a 2-hydroxyhexyl group, a
1-hydroxyhexyl group, a --C.sub.6H.sub.10--OH group, and a
--CH.sub.2--C.sub.6H.sub.10--CH.sub.2--OH group are preferable; the
hydroxymethyl group, the 2-hydroxyethyl group, the 1-hydroxyethyl
group, the 3-hydroxypropyl group, the 2-hydroxypropyl group, the
2-hydroxy-1-methylethyl group, the 1-hydroxypropyl group, the
4-hydroxybutyl group, the 3-hydroxybutyl group, the 2-hydroxybutyl
group, the 2-hydroxy-2-methylpropyl group, the
2-hydroxy-1-methylpropyl group, the 1-hydroxybutyl group, the
5-hydroxypentyl group, the 6-hydroxyhexyl group, and the
--CH.sub.2--C.sub.6H.sub.10--CH.sub.2--OH group are more
preferable; the hydroxymethyl group, the 2-hydroxyethyl group, the
3-hydroxypropyl group, the 2-hydroxypropyl group, the
2-hydroxy-1-methylethyl group, the 4-hydroxybutyl group, and the
2-hydroxybutyl group are still more preferable; and the
2-hydroxyethyl group, the 2-hydroxypropyl group, the
2-hydroxy-1-methylethyl group, and the 4-hydroxybutyl groups are
particularly preferable.
[0083] The alkylene group having 1 to 10 carbon atoms in A.sub.1-2
of the general formula [1-2] is the same as the specific examples
of the alkylene group having 1 to 10 carbon atoms in A.sub.1_i of
the general formula [1-1], among which a linear or branched
alkylene group having 1 to 6 carbon atoms is preferable, and a
linear or branched alkylene group having 1 to 4 carbon atoms is
more preferable.
[0084] R.sub.3 of the general formula [1-2] is preferably a sulfo
group, a phosphate group, or a cyano group and more preferably a
sulfo group or a phosphate group.
[0085] Specific examples of the group represented by the general
formula [1-2] include dialkylaminoalkyl groups having 3 to 12
carbon atoms such as a dimethylaminomethyl group, a
2-(dimethylamino)ethyl group, a 3-(dimethylamino)propyl group, a
4-(dimethylamino)butyl group, a diethylaminomethyl group, a
2-(diethylamino)ethyl group, a 3-(diethylamino)propyl group, a
4-(diethylamino)butyl group, a di(n-propyl)aminomethyl group, a
2-[di(n-propyl)amino] ethyl group, a 3-[di(n-propyl) amino]propyl
group, a 4-[di(n-propyl)amino]butyl group, a diisopropylaminomethyl
group, a 2-(diisopropylamino)ethyl group, a
3-(diisopropylamino)propyl group, a 4-(diisopropylamino)butyl
group, a di(n-butyl)aminomethyl group, a 2-[di(n-butyl)amino] ethyl
group, a 3-[di(n-butyl)amino]propyl group, a
4-[di(n-butyl)amino]butyl group, a diisobutylaminomethyl group, a
2-(diisobutylamino)ethyl group, a 3-(diisobutylamino)propyl group,
a 4-(diisobutylamino)butyl group, a morpholinomethyl group, a
2-morpholinoethyl group, a 3-morpholinopropyl group, a
4-morpholinobutyl group, a piperidinomethyl group, a
2-piperidinoethyl group, a 3-piperidinopropyl group, and a
4-piperidinobutyl group; acetoalkyl groups having 3 to 6 carbon
atoms such as an acetomethyl group, a 2-acetoethyl group, a
3-acetopropyl group, a 4-acetobutyl group, and a
1,1-dimethyl-2-acetoethyl group; sulfoalkyl groups having 1 to 6
carbon atoms such as a sulfomethyl group, a 2-sulfoethyl group, a
1-sulfoethyl group, a 3-sulfopropyl group, a 2-sulfopropyl group, a
1-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, a
2-sulfobutyl group, a 1,1-dimethyl-2-sulfoethylene group, a
1-sulfobutyl group, a 5-sulfopentyl group, and a 6-sulfohexyl
group; phosphonooxyalkyl groups having 1 to 6 carbon atoms (alkyl
phosphate groups) such as a phosphonooxymethyl group, a
2-phosphonooxyethyl group, a 1-phosphonooxyethyl group, a
3-phosphonooxypropyl group, a 2-phosphonooxypropyl group, a
1-phosphonooxypropyl group, a 4-phosphonooxybutyl group, a
3-phosphonooxybutyl group, a 2-phosphonooxybutyl group, a
1-phosphonooxybutyl group, a 5-phosphonooxypentyl group, and a
6-phosphonooxyhexyl group; and cyanoalkyl groups having 2 to 7
carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a
1-cyanoethyl group, a 3-cyanopropyl group, a 2-cyanopropyl group, a
1-cyanopropyl group, a 4-cyanobutyl group, a 3-cyanobutyl group, a
2-cyanobutyl group, a 1-cyanobutyl group, a 5-cyanopentyl group,
and a 6-cyanohexyl group.
[0086] Among these specific examples, a linear or branched
sulfoalkyl group having 1 to 4 carbon atoms, a linear
phosphonooxyalkyl group having 1 to 4 carbon atoms, and a linear
cyanoalkyl group having 2 to 5 carbon atoms more preferable; and
the linear or branched sulfoalkyl group having 1 to 4 carbon atoms
and the linear phosphonooxyalkyl group having 1 to 4 carbon atoms
are more preferable. More specifically, a 2-(dimethylamino)ethyl
group, a 2-(diethylamino)ethyl group, a 2-[di(n-propyeamino]ethyl
group, a 2-(diisopropylamino)ethyl group, a
2-[di(n-butyl)amino]ethyl group, a 2-(diisobutylamino)ethyl group,
a 2-morpholinoethyl group, a 2-piperidinoethyl group, an
acetomethyl group, a 2-acetoethyl group, a
1,1-dimethyl-2-acetoethyl group, a sulfomethyl group, a
2-sulfoethyl group, a 3-sulfopropyl group, a 2-sulfopropyl group, a
1-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, a
2-sulfobutyl group, a 1,1-dimethyl-2-sulfoethylene group, a
phosphonooxymethyl group, a 2-phosphonooxyethyl group, a
1-phosphonooxyethyl group, a 3-phosphonooxypropyl group, a
2-phosphonooxypropyl group, a 4-phosphonooxybutyl group, a
cyanomethyl group, a 2-cyanoethyl group, a 1-cyanoethyl group, a
3-cyanopropyl group, a 1-cyanopropyl group, a 4-cyanobutyl group,
and a 1-cyanobutyl group are preferable; the sulfomethyl group, the
2-sulfoethyl group, the 3-sulfopropyl group, the 4-sulfobutyl
group, the 1,1-dimethyl-2-sulfoethylene group, the
phosphonooxymethyl group, the 2-phosphonooxyethyl group, the
3-phosphonooxypropyl group, the 4-phosphonooxybutyl group, the
cyanomethyl group, the 2-cyanoethyl group, the 3-cyanopropyl group,
and the 4-cyanobutyl group are more preferable; and the
2-sulfoethyl group, the 3-sulfopropyl group, and the
2-phosphonooxyethyl group are still more preferable.
[0087] a and b of the general formula [1-3] are each preferably an
integer of 1 to 4 and is preferably 1 or 2 and more preferably
1.
[0088] Specific examples of the group represented by the general
formula [1-3] include a 1,2-dihydroxypropyl group, a
1,3-dihydroxypropyl group, a 2,3-dihydroxypropyl group, a
1,2-dihydroxybutyl group, a 1,3-dihydroxybutyl group, a
1,4-dihydroxybutyl group, a 2,3-dihydroxybutyl group, a
2,4-dihydroxybutyl group, a 3,4-dihydroxybutyl group, a
1,2-dihydroxypentyl group, a 1,3-dihydroxypentyl group, a
1,4-dihydroxypentyl group, a 1,5-hydroxypentyl group, a
2,3-dihydroxypentyl group, a 2,4-dihydroxypentyl group, a
2,5-hydroxypentyl group, a 3,4-dihydroxypentyl group, a
3,5-dihydroxypentyl group, a 4,5-hydroxypentyl group, a
1,2-dihydroxyhexyl group, a 1,3-dihydroxyhexyl group, a
1,4-dihydroxyhexyl group, a 1,5-hydroxyhexyl group, a
1,6-hydroxyhexyl group, a 2,3-dihydroxyhexyl group, a
2,4-dihydroxyhexyl group, a 2,5-hydroxyhexyl group, a
2,6-hydroxyhexyl group, a 3,4-dihydroxyhexyl group, a
3,5-dihydroxyhexyl group, a 3,6-dihydroxyhexyl group, a
4,5-hydroxyhexyl group, a 4,6-hydroxyhexyl group, and a
5,6-hydroxyhexyl group, among which the 2,3-dihydroxypropyl group,
the 2,4-dihydroxybutyl group, the 3,4-dihydroxybutyl group, the
2,5-hydroxypentyl group, the 4,5-hydroxypentyl group, the
2,6-hydroxyhexyl group, and the 5,6-hydroxyhexyl group are
preferable; the 2,3-dihydroxypropyl group, the 2,4-dihydroxybutyl
group, and the 3,4-dihydroxybutyl group are more preferable; and
the 2,3-dihydroxypropyl group is still more preferable.
[0089] c of the general formula [1-4] is preferably 2 or 4 and more
preferably 2.
[0090] d of the general formula [1-4] is preferably 3 or 5 and more
preferably 5.
[0091] e of the general formula [1-4] is preferably 1 or 2.
[0092] Specific examples of the group represented by the general
formula [1-4] include the groups shown below.
##STR00007##
[0093] Among these specific examples, the groups shown below are
preferable.
##STR00008##
[0094] Among these specific examples, the groups shown below are
more preferable.
##STR00009##
[0095] Preferred specific examples of A.sub.1 of the general
formula [1] include the same specific examples of the groups
represented by the general formulae [1-1] to [1-4], among which a
hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl
group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a
2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a
4-hydroxybutyl group, a 3-hydroxybutyl group, a 2-hydroxybutyl
group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl
group, a 1-hydroxybutyl group, a 5-hydroxypentyl group, a
6-hydroxyhexyl group, a --CH.sub.2--C.sub.6H.sub.10--CH.sub.2--OH
group, a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl
group, a 4-sulfobutyl group, a 1,1-dimethyl-2-sulfoethylene group,
a phosphonooxymethyl group, a 2-phosphonooxyethyl group, a
3-phosphonooxypropyl group, a 4-phosphonooxybutyl group, a
cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a
4-cyanobutyl group, a 2,3-dihydroxypropyl group, a
2,4-dihydroxybutyl group, a 3,4-dihydroxybutyl group, and the
groups shown below are more preferable.
##STR00010##
[0096] Among these preferred specific examples, a hydroxymethyl
group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a
2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a
4-hydroxybutyl group, a 2-hydroxybutyl group, a 2-sulfoethyl group,
a 3-sulfopropyl group, a 2-phosphonooxyethyl group, and a
2,3-dihydroxypropyl group are more preferable; and the
2-hydroxyethyl group, the 2-hydroxypropyl group, the
2-hydroxy-1-methylethyl group, and the 4-hydroxybutyl group are
particularly preferable.
[0097] Examples of the combination of A.sub.1, R.sub.1, and Y.sub.1
in the general formula [1] include combinations 1 to 12 described
in the following table. Among these combinations, combinations 1 to
10 are preferable, combinations 1, 2, 9, and 10 are more
preferable, combinations 1, 2, and 9 are still more preferable, and
combination 1 is particularly preferable.
TABLE-US-00001 Combination A.sub.1 R.sub.1 Y.sub.1 1 Group
represented by general formula Hydrogen --O-- [1-1] atom 2 Group
represented by general formula Methyl --O-- [1-1] group 3 Group
represented by general formula Hydrogen --O-- [1-2] atom 4 Group
represented by general formula Methyl --O-- [1-2] group 5 Group
represented by general formula Hydrogen --O-- [1-3] atom 6 Group
represented by general formula Methyl --O-- [1-3] group 7 Group
represented by general formula Hydrogen --O-- [1-4] atom 8 Group
represented by general formula Methyl --O-- [1-4] group 9 Group
represented by general formula Hydrogen --NH-- [1-1] atom 10 Group
represented by general formula Methyl --NH-- [1-1] group 11 Group
represented by general formula Hydrogen --NH-- [1-2] atom 12 Group
represented by general formula Methyl --NH-- [1-2] group
[0098] Preferred specific examples of the monomer represented by
the general formula [1] include a monomer represented by the
following general formula [2].
##STR00011##
[0099] (In the general formula [2], A.sub.2 represents an alkyl
group having 1 to 10 carbon atoms and having 1 to 3 of any one of a
group selected from a hydroxy group, a dialkylamino group, an
acetyl group, a sulfo group, a phosphate group, or a cyano group;
or a linear alkyl group having 3 to 36 carbon atoms and having 1
hydroxy group and 1 to 5 ester bonds in a chain thereof, and
R.sub.1 and Y.sub.1 are as defined hereinbefore.)
[0100] Specific examples of the "alkyl group having 1 to 10 carbon
atoms and having 1 to 3 of any one of a group selected from a
hydroxy group, a dialkylamino group, an acetyl group, a sulfo
group, a phosphate group, or a cyano group" and the "linear alkyl
group having 3 to 36 carbon atoms and having 1 hydroxy group and 1
to 5 ester bonds in a chain thereof" of A.sub.2 of the general
formula [2] include the same specific examples of the groups
represented by the general formulae [1-1] to [1-4], and preferred
examples thereof are also the same.
[0101] A.sub.2 of the general formula [2] is preferably an alkyl
group having 1 to 10 carbon atoms and having 1 to 2 hydroxy groups;
an alkyl group having 1 to 10 carbon atoms and having one of any
one of a group selected from a dialkylamino group, an acetyl group,
a sulfo group, a phosphate group, or a cyano group; or a linear
alkyl group having 5 to 24 carbon atoms and having 1 hydroxy group
and 1 to 3 ester bonds in a chain thereof, more preferably a group
represented by the general formulae [1-1] to [1-4], and still more
preferably a group represented by the general formula [1-1]. More
specific examples of A.sub.2 of the general formula [2] include the
same preferred specific examples of A.sub.1 of the general formula
[1], and preferred examples thereof are also the same.
[0102] Examples of the combination of A.sub.2, R.sub.1, and Y.sub.1
in the general formula [2] include the same combinations of
A.sub.1, R.sub.1, and Y.sub.1 in the general formula [1], and
preferred examples thereof are also the same.
[0103] Specific examples of the monomer represented by the general
formula [2] include the following monomers.
##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016##
##STR00017##
[0104] Among these specific examples, hydroxymethyl acrylate,
2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl
acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl
acrylate, 2-hydroxybutyl acrylate, 2-(acryloyloxy)ethanesulfonic
acid, 3-(acryloyloxy)ethanesulfonic acid, 2-(acryloyloxy)ethyl acid
phosphate, 2,3-dihydroxypropyl acrylate, hydroxymethyl
methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl
methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl
methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl
methacrylate, 2-(methacryloyloxy)ethanesulfonic acid,
3-(methacryloyloxy)ethanesulfonic acid, 2-(methacryloyloxy)ethyl
acid phosphate, and 2,3-dihydroxypropyl methacrylate are
preferable.
[0105] More preferred specific examples of the monomer represented
by the general formula [1] include a monomer represented by the
following general formula [3].
##STR00018##
[0106] (In the general formula [3], A.sub.3 represents a linear or
branched alkylene group having 1 to 4 carbon atoms, and R.sub.1 is
as defined hereinbefore.)
[0107] A.sub.3 of the general formula [3] is preferably a linear or
branched alkylene group having 2 to 4 carbon atoms. Specific
examples thereof include a methylene group, an ethylene group, a
trimethylene group, a propylene group, a tetramethylene group, and
an ethylethylene group, among which the ethylene group, the
propylene group, and the tetramethylene group are preferable; and
the ethylene group and the tetramethylene group are more
preferable.
[0108] Specific examples of the monomer represented by the general
formula [3] include hydroxymethyl acrylate, 2-hydroxyethyl
acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate,
2-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl
methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl
methacrylate, 2-hydroxy-1-methylethyl methacrylate, 4-hydroxybutyl
methacrylate, and 2-hydroxybutyl methacrylate, among which
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
2-hydroxy-1-methylethyl methacrylate, and 4-hydroxybutyl
methacrylate are preferable; 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, and
4-hydroxybutyl acrylate are more preferable; and 2-hydroxyethyl
acrylate and 4-hydroxybutyl acrylate are particularly
preferable.
[0109] It should be noted that the monomer of (ii) may be used
alone or in combination of two or more thereof, and it is
preferable to use only one thereof alone or two thereof in
combination.
[0110] The content ratio (molar ratio) of the structural unit
derived from the monomer of (i) to the structural unit derived from
the monomer of (ii) in the polymer according to the first invention
is usually the monomer of (i):the monomer of (ii)=5:95 to 95:5,
preferably 10:90 to 90:10, and more preferably 15:85 to 85:15. It
should be noted that, in a case where two or more types of the
monomer of (i) and/or the monomer of (ii) are used in combination,
a ratio of the total number of moles of the structural unit derived
from the monomer of (i) to the total number of moles of the
structural unit derived from the monomer of (ii) may be the
above-mentioned content ratio.
[0111] The polymer according to the first invention may further
contain a structural unit derived from (iii) a monomer having two
or more polymerizable unsaturated groups, in addition to the
monomer of (i) and the monomer of (ii).
[0112] The (iii) monomer having two or more polymerizable
unsaturated groups (hereinafter, sometimes referred to simply as
the monomer of (iii)) has a structure different from that of the
monomer of (i) and the monomer of (ii).
[0113] Specific examples of the polymerizable unsaturated group in
the monomer of (iii) include an ethylenically unsaturated group
such as a vinyloxy group, an allyl group, a vinylaryl group, an
acryloyl group, or a methacryloyl group; an isocyanate group; and a
carbodiimide group, among which the ethylenically unsaturated group
is preferable; the allyl group, the acryloyl group, and the
methacryloyl group are more preferable; and the acryloyl group is
particularly preferable.
[0114] Examples of the monomer of (iii) include a monomer
represented by the following general formula [11] or [12], among
which a monomer represented by the general formula [11] is
preferable.
##STR00019##
{In the general formula [11], R.sub.11 represents a hydrogen atom
or a methyl group, Y.sub.11 represents --O-- or --NR.sub.12--,
R.sub.12 represents a hydrogen atom or a methyl group, A.sub.11
represents a group represented by the following general formulae
[11-1] to [11-3], and two R.sub.11's and two Y.sub.11's are each
the same:
##STR00020##
[0115] (In the general formulae [11-1] to [11-3], R.sub.13 and
R.sub.14 each independently represent a hydrogen atom or a methyl
group, Y.sub.12 represents --O-- or --NR.sub.15--, R.sub.15
represents a hydrogen atom or a methyl group, A.sub.12 to A.sub.15
each independently represent an alkylene group having 1 to 6 carbon
atoms, A.sub.16 and A.sub.17 each independently represent an
alkylene group having 1 to 6 carbon atoms which may have an ether
bond in a chain thereof, g represents an integer of 0 to 30, h
represents an integer of 1 to 3, i represents an integer of 0 to 6,
j represents an integer of 1 to 3, and two A.sub.16's, two
R.sub.14's, and two Y.sub.12's are each the same.).}
##STR00021##
[0116] (In the general formula [12], R.sub.16 to R.sub.22 each
independently represent an alkylene group having 1 to 3 carbon
atoms.)
[0117] R.sub.11 of the general formula [11] is preferably a
hydrogen atom.
[0118] In Y.sub.11 of the general formula [11], R.sub.12 in
--NR.sub.12-- is preferably a hydrogen atom.
[0119] Y.sub.11 of the general formula [11] is preferably --O-- or
--NH-- and more preferably --NH--.
[0120] The alkylene group having 1 to 6 carbon atoms in A.sub.12
and A.sub.13 of the general formula [11-1] is preferably an
alkylene group having 1 to 4 carbon atoms and more preferably an
alkylene group having 2 to 3 carbon atoms. In addition, the
alkylene group may be linear, branched, or cyclic, and is
preferably linear or branched and more preferably linear. Specific
examples of the alkylene group include a methylene group, an
ethylene group, a methylmethylene group, a trimethylene group, a
propylene group, an ethylmethylene group, a dimethylmethylene
group, a tetramethylene group, a 1-methyltrimethylene group, a
2-methyltrimethylene group, a 1,1-dimethylethylene group, a
1,2-dimethylethylene group, an ethylethylene group, a
propylmethylene group, an ethylmethylmethylene group, a
pentamethylene group, a 1-methyltetramethylene group, a
1-ethyltrimethylene group, an n-propylethylene group, an
n-butylmethylene group, a hexamethylene group, a
1-methylpentamethylene group, a 1-ethyltetramethylene group, a
1-n-propyltrimethylene group, an n-butylethylene group, an
n-pentylmethylene group, and a --C.sub.6H.sub.10-- group, among
which a linear or branched alkylene group having 1 to 4 carbon
atoms is preferable; and a methylene group, an ethylene group, a
trimethylene group, a propylene group, and a tetramethylene group
are more preferable.
[0121] In g pieces of repeating units in the general formula
[11-1], the repeating units may be the same or different. It is
preferable that all the repeating units are the same. In addition,
g pieces of A.sub.13's in the general formula [11-1] may be the
same or different. In a case where g in the general formula [11-1]
is an integer of 1 or more, it is preferable that A.sub.12 and
A.sub.13 in the g-th repeating unit are the same; and it is more
preferable that A.sub.12 and A.sub.13 in the g-th repeating unit
are the same, and A.sub.13's in the first to g-1-th repeating units
are all the same. It should be noted that the repeating unit in the
general formula [11-1] is counted as the first repeating unit, the
second repeating unit, . . . from the side adjacent to Au, and the
g-th repeating unit is a repeating unit located at the farthest
point from A.sub.12 (a repeating unit adjacent to one of Y.sub.11's
in the general formula [11]).
[0122] g of the general formula [11-1] is preferably an integer of
0 to 15, more preferably an integer of 0 to 10, and still more
preferably an integer of 0 to 3.
[0123] Examples of the combination of A.sub.12, A.sub.13, and gin
the general formula [11-1] include combinations 1 to 29 described
in the following table. Among these combinations, combinations 1,
2, 7 to 13, 15, 17 to 19, 24, and 25 are preferable, and
combinations 1, 7 to 10, 12, 15, 17, 18, and 24 are more
preferable.
TABLE-US-00002 Combination A.sub.12 A.sub.13 g 1 Methylene group
(None) 0 2 Methylene group Methylene group 1 3 Methylene group
Methylene groups in all of two repeating units 2 4 Methylene group
Ethylene group in first repeating unit and methylene 2 group in
second repeating unit 5 Methylene group Methylene groups in all of
three repeating units 3 6 Methylene group Ethylene groups in first
and second repeating units 3 and methylene group in third repeating
unit 7 Ethylene group (None) 0 8 Ethylene group Ethylene group 1 9
Ethylene group Ethylene groups in all of two repeating units 2 10
Ethylene group Ethylene groups in all of three repeating units 3 11
Ethylene group Ethylene groups in all of d pieces of repeating
units 4~30 12 Trimethylene group (None) 0 13 Trimethylene group
Trimethylene group 1 14 Trimethylene group Trimethylene groups in
all of two repeating units 2 15 Trimethylene group Ethylene group
in first repeating unit and 2 trimethylene group in second
repeating unit 16 Trimethylene group Trimethylene groups in all of
three repeating units 3 17 Trimethylene group Ethylene groups in
first and second repeating units 3 and trimethylene group in third
repeating unit 18 Propylene group (None) 0 19 Propylene group
Propylene group 1 20 Propylene group Propylene groups in all of two
repeating units 2 21 Propylene group Ethylene group in first
repeating unit and propylene 2 group in second repeating unit 22
Propylene group Propylene groups in all of three repeating units 3
23 Propylene group Ethylene groups in first and second repeating
units 3 and propylene group in third repeating unit 24
Tetramethylene (None) 0 group 25 Tetramethylene Tetramethylene
group 1 group 26 Tetramethylene Tetramethylene groups in all of two
repeating units 2 group 27 Tetramethylene Ethylene group in first
repeating unit and 2 group tetramethylene group in second repeating
unit 28 Tetramethylene Tetramethylene groups in all of three
repeating units 3 group 29 Tetramethylene Ethylene groups in first
and second repeating units 3 group and tetramethylene group in
third repeating unit
[0124] In h pieces of repeating units in the general formula
[11-2], the repeating units may be the same or different. It is
preferable that all the repeating units are the same. In addition,
h pieces of R.sub.13's in the general formula [11-2] may be the
same or different. It is preferable that all R.sub.13's are the
same, and it is more preferable that all R.sub.13's are the same as
R.sub.11's of the general formula [11].
[0125] Examples of the alkylene group having 1 to 6 carbon atoms in
A.sub.14 and A.sub.15 of the general formula [11-2] include the
same alkylene groups having 1 to 6 carbon atoms in A.sub.12 and
A.sub.13 of the general formula [11-1], among which a linear
alkylene group having 1 to 4 carbon atoms is preferable and an
ethylene group is more preferable.
[0126] h pieces of A.sub.15's in the general formula [11-2] may be
the same or different. It is preferable that all A.sub.15's are the
same. In addition, it is preferable that A.sub.14 of the general
formula [11-2] and A.sub.15 in the h-th repeating unit are the
same, and it is more preferable that A.sub.14 and A.sub.15 in all
repeating units are the same. It should be noted that the repeating
unit in the general formula [11-2] is counted as the first
repeating unit, the second repeating unit, . . . from the side
adjacent to A.sub.14, and the h-th repeating unit is a repeating
unit located at the farthest point from A.sub.14 (a repeating unit
adjacent to one of Y.sub.11's in the general formula [11]).
[0127] e of the general formula [11-2] is preferably 1 or 2.
[0128] Examples of the combination of A.sub.14, A.sub.15, R.sub.13,
and h in the general formula [11-2] include combinations 1 to 12
described in the following table. Among these combinations,
combinations 4 to 6 are preferable and combinations 4 and 5 are
more preferable.
TABLE-US-00003 Combination A.sub.14 A.sub.15 R.sub.13 h 1 Methylene
group Methylene groups in Hydrogen atoms 1 2 Methylene group all of
e pieces of in all of e pieces 2 3 Methylene group repeating units
of repeating 3 4 Ethylene group Ethylene groups in all units or
Methyl 1 5 Ethylene group of e pieces of groups in all of 2 6
Ethylene group repeating units e pieces of 3 7 Trimethylene group
Trimethylene groups repeating units 1 8 Trimethylene group in all
of e pieces of 2 9 Trimethylene group repeating units 3 10
Tetramethylene group Tetramethylene groups 1 11 Tetramethylene
group in all of e pieces of 2 12 Tetramethylene group repeating
units 3
[0129] In j pieces of repeating units in the general formula
[11-3], the repeating units may be the same or different. It is
preferable that all the repeating units are the same. In addition,
2j pieces of R.sub.14's in the general formula [11-3] may be the
same or different. It is preferable that all R.sub.14's are the
same, and it is more preferable that all R.sub.14's are the same as
R.sub.11's of the general formula [11]. In this regard, two
R.sub.14's existing in the same repeating unit are always the
same.
[0130] In Y.sub.12 of the general formula [11-3], R.sub.15 in
--NR.sub.15-- is preferably a hydrogen atom.
[0131] 2j pieces of Y.sub.11's in the general formula [11-3] may be
the same or different. It is preferable that all Y.sub.11's are the
same, and it is more preferable that all Y.sub.11's are the same as
Y.sub.11's of the general formula [11]. In this regard, two
Y.sub.12's existing in the same repeating unit are always the
same.
[0132] Specific examples of the case where the "alkylene group
having 1 to 6 carbon atoms which may have an ether bond in a chain
thereof" in A.sub.16 and A.sub.17 of the general formula [11-3]
does not have an ether bond include the same alkylene groups having
1 to 6 carbon atoms in A.sub.12 and A.sub.13 of the general formula
[11-1], among which a linear alkylene group having 1 to 4 carbon
atoms is preferable and a methylene group is more preferable.
[0133] Specific examples of the case where the "alkylene group
having 1 to 6 carbon atoms which may have an ether bond in a chain
thereof" in A.sub.16 and A.sub.17 of the general formula [11-3] has
an ether bond include --CH.sub.2--O--CH.sub.2--,
--CH.sub.2--O--(CH.sub.2).sub.2--,
--CH.sub.2--O--(CH.sub.2).sub.3--,
--CH.sub.2--O--(CH.sub.2).sub.4--,
--CH.sub.2--O--(CH.sub.2).sub.5--,
--(CH.sub.2).sub.2--O--CH.sub.2--,
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.2--,
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.3--,
--(CH.sub.2).sub.2--O--(CH.sub.2).sub.4--,
--(CH.sub.2).sub.3--O--CH.sub.2--,
--(CH.sub.2).sub.3--O--(CH.sub.2).sub.2--,
--(CH.sub.2).sub.3--O--(CH.sub.2).sub.3--,
--(CH.sub.2).sub.4--O--CH.sub.2--,
--(CH.sub.2).sub.4--O--(CH.sub.2).sub.2--, and
--(CH.sub.2).sub.5--O--CH.sub.2--, among which a linear alkylene
group having 2 to 4 carbon atoms and having an ether bond in a
chain thereof is preferable, and --CH.sub.2--O--CH.sub.2-- or
--CH.sub.2--O--(CH.sub.2).sub.3-- is more preferable.
[0134] 2j pieces of A.sub.16's and j pieces of A.sub.17's in the
general formula [11-3] may be respectively the same or different.
In this regard, two A.sub.16's existing in the same repeating unit
are always the same. In addition, it is preferable that all
A.sub.16's of the general formula [11-3] and A.sub.17 in the j-th
repeating unit are the same. It should be noted that the repeating
unit in the general formula [11-3] is counted as the first
repeating unit, the second repeating unit, . . . from the side
adjacent to --(CH.sub.2).sub.i--, and the j-th repeating unit is a
repeating unit located at the farthest point from
--(CH.sub.2).sub.i-- (a repeating unit adjacent to one of
Y.sub.11's in the general formula [11]).
[0135] i of the general formula [11-3] is preferably an integer of
0 to 4, more preferably 0 or 1, and still more preferably 0.
[0136] j of the general formula [11-3] is preferably 1 or 2 and
more preferably 1.
[0137] Examples of the combination of two A.sub.16's, A.sub.17, two
Y.sub.12's, two R.sub.14's, i, and j in the general formula [11-3]
include combinations 1 to 20 described in the following table.
Among these combinations, combinations 1 to 6 and 11 to 16 are
preferable, combinations 1, 2, 11, 12, 13, and 14 are more
preferable, and combinations 1, 11, and 13 are particularly
preferable. It should be noted that
"--CH.sub.2--O--(CH.sub.2).sub.3--" in the two A.sub.16's is such
that a left end thereof is bonded to a main chain and a right end
thereof is bonded to Y.sub.12.
TABLE-US-00004 Combination Two A16's A.sub.17 Two Y12's Two R14's i
j 1 Methylene group Methylene group --O-- Hydrogen 1 1 2 Ethylene
group Ethylene group --O-- atoms in all 2 1 3 Trimethylene group
Trimethylene group --O-- of g pieces 3 1 4 Tetramethylene group
Tetramethylene group --O-- of repeating 4 1 5
--CH.sub.2--O--(CH.sub.2).sub.3-- --CH.sub.2--O--(CH.sub.2).sub.3--
--O-- units or 0 1 6 --CH.sub.2--O--(CH.sub.2).sub.3--
--CH.sub.2--O--(CH.sub.2).sub.3-- --O-- methyl 1 1 7 Methylene
group Methylene group --NH-- groups in all 1 1 8 Ethylene group
Ethylene group --NH-- of g pieces 2 1 9 Trimethylene group
Trimethylene group --NH-- of repeating 3 1 10 Tetramethylene group
Tetramethylene group --NH-- units 4 1 11
--CH.sub.2--O--(CH.sub.2).sub.3-- --CH.sub.2--O--(CH.sub.2).sub.3--
--NH-- 0 1 12 --CH.sub.2--O--(CH.sub.2).sub.3--
--CH.sub.2--O--(CH.sub.2).sub.3-- --NH-- 1 1 13 Methylene group
--CH2--O--CH2-- in first repeating unit and --O-- in all of 1 2
methylene group in second repeating unit two repeating units 14
Ethylene group --CH2--O--CH2-- in first repeating unit and 2 2
ethylene group in second repeating unit 15 Trimethylene group
--CH2--O--CH2-- in first repeating unit and 3 2 trimethylene group
in second repeating unit 16 Tetramethylene group --CH2--O--CH2-- in
first repeating unit and 4 2 tetramethylene group in second
repeating unit 17 Methylene group --CH2--O--CH2-- in first
repeating unit and --NH-- in all of 1 2 methylene group in second
repeating unit two repeating units 18 Ethylene group
--CH2--O--CH2-- in first repeating unit and 2 2 ethylene group in
second repeating unit 19 Trimethylene group --CH2--O--CH2-- in
first repeating unit and 3 2 trimethylene group in second repeating
unit 20 Tetramethylene group --CH2--O--CH2-- in first repeating
unit and 4 2 tetramethylene group in second repeating unit
[0138] Examples of the combination of A.sub.11, two Y.sub.11's, and
two R.sub.11's in the general formula [11] include combinations 1
to 14 described in the following table.
TABLE-US-00005 Two Combination A11 Y11's Two R11's 1 Combinations 1
to 29 of groups --O-- Hydrogen atom 2 represented by general
formula --O-- Methyl group 3 [11-1] --NH-- Hydrogen atom 4 --NH--
Methyl group 5 Combinations 1 to 12 of groups --NH-- Hydrogen atom
6 represented by general formula --NH-- Methyl group [11-2] 7
Combinations 1 to 6 of groups --O-- Hydrogenatom 8 represented by
general formula --O-- Methyl group [11-3] 9 Combinations 7 to 12 of
groups --NH-- Hydrogen atom 10 represented by general formula
--NH-- Methyl group [11-3] 11 Combinations 13 to 16 of --O--
Hydrogen atom 12 groups represented by general --O-- Methyl group
formula [11-3] 13 Combinations 17 to 20 of --NH-- Hydrogen atom 14
groups represented by general --NH-- Methyl group formula
[11-3]
[0139] The alkylene group having 1 to 3 carbon atoms in R.sub.16 to
R.sub.22 of the general formula [12] may be linear or branched and
is preferably linear. Specific examples thereof include a methylene
group, an ethylene group, a methylmethylene group, a trimethylene
group, a propylene group, an ethylmethylene group, and a
dimethylmethylene group, among which the methylene group, the
ethylene group, or the trimethylene group is preferable; the
methylene group or the trimethylene group is more preferable; and
the methylene group is particularly preferable.
[0140] R.sub.16 to R.sub.22 of the general formula [12] may be the
same or different. It is preferable that R.sub.17 to R.sub.19 and
R.sub.20 to R.sub.22 are respectively the same, and it is more
preferable that all of R.sub.16 to R.sub.22 are the same.
[0141] Examples of the combination of R.sub.16 to R.sub.22 in the
general formula [12] include combinations 1 to 27 described in the
following table. Among these combinations, combinations 1 to 3 are
preferable, combinations 1 and 3 are more preferable, and
combination 1 is particularly preferable.
TABLE-US-00006 Combination R.sub.16 R.sub.17 to R.sub.19 R.sub.29
to R.sub.22 1 Methylene group Methylene group for all Methylene
group for all 2 Methylene group Methylene group for all Ethylene
group for all 3 Methylene group Methylene group for all
Trimethylene group for all 4 Methylene group Ethylene group for all
Methylene group for all 5 Methylene group Ethylene group for all
Ethylene group for all 6 Methylene group Ethylene group for all
Trimethylene group for all 7 Methylene group Trimethylene group for
all Methylene group for all 8 Methylene group Trimethylene group
for all Ethylene group for all 9 Methylene group Trimethylene group
for all Trimethylene group for all 10 Ethylene group Methylene
group for all Methylene group for all 11 Ethylene group Methylene
group for all Ethylene group for all 12 Ethylene group Methylene
group for all Trimethylene group for all 13 Ethylene group Ethylene
group for all Methylene group for all 14 Ethylene group Ethylene
group for all Ethylene group for all 15 Ethylene group Ethylene
group for all Trimethylene group for all 16 Ethylene group
Trimethylene group for all Methylene group for all 17 Ethylene
group Trimethylene group for all Ethylene group for all 18 Ethylene
group Trimethylene group for all Trimethylene group for all 19
Trimethylene group Methylene group for all Methylene group for all
20 Trimethylene group Methylene group for all Ethylene group for
all 21 Trimethylene group Methylene group for all Trimethylene
group for all 22 Trimethylene group Ethylene group for all
Methylene group for all 23 Trimethylene group Ethylene group for
all Ethylene group for all 24 Trimethylene group Ethylene group for
all Trimethylene group for all 25 Trimethylene group Trimethylene
group for all Methylene group for all 26 Trimethylene group
Trimethylene group for all Ethylene group for all 27 Trimethylene
group Trimethylene group for all Trimethylene group for all
[0142] Specific examples of the monomers represented by the general
formulae [11] and [12] include the following monomers.
##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032## ##STR00033##
[0143] Among the above specific examples, the following monomers
are preferable.
##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038##
##STR00039## ##STR00040##
[0144] Among the above preferred specific examples, methylene
diacrylate, ethylene glycol diacrylate, diethylene glycol
diacrylate, triethylene glycol diacrylate, tetraethylene glycol
diacrylate, trimethylene diacrylate, propylene diacrylate,
tetramethylene diacrylate, N,N'-methylene bisacrylamide,
N,N'-ethylene bisacrylamide,
N,N'-(4,7,10-trioxytridecamethylene)bisacrylamide,
N,N',N''-triacryloyldiethylenetriamine,
N,N',N'',N'''-tetraacryloyltriethylenetetramine,
N-[tris(3-acrylamidepropoxymethyl)methyl]acrylamide, methylene
dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol
dimethacrylate, triethylene glycol dimethacrylate, tetraethylene
glycol dimethacrylate, trimethylene dimethacrylate, propylene
dimethacrylate, tetramethylene dimethacrylate,
N,N'-methylenebismethacrylamide, N,N'-ethylenebismethacrylamide,
N,N'-(4,7,10-trioxytridecamethylene)bismethacrylamide,
N,N',N''-trimethacryloyldiethylenetriamine,
N,N',N'',N'''-tetramethacryloyltriethylenetetramine,
N-[tris(3-methacrylamidepropoxymethyl)methyl]methacrylamide, and
pentaerythritol triallyl ether are more preferable. It should be
noted that these more preferred specific examples will be referred
to as "a more preferred specific example group of the monomer of
(iii)".
[0145] As the monomer of (iii), monomers generally used as a
"crosslinking agent" in the art can be appropriately used in
addition to the specific examples. For example, the crosslinking
agents described in WO2014/065407A, WO2015/163302A, WO2018/143382A,
WO2018/143383A, and the like can be used.
[0146] In a case where the polymer according to the first invention
contains a structural unit derived from the monomer of (iii), the
content thereof is usually 0.01 mol % or more and 5 mol % or less,
preferably 0.05 mol % or more and 2 mol % or less, and more
preferably 0.1 mol % or more and 1 mol % or less with respect to
the total content of the structural units derived from the monomer
of (i) and the monomer of (ii).
[0147] The monomer of (i), the monomer of (ii), and the monomer of
(iii) may all be commercially available or appropriately
synthesized by a method known per se.
[0148] The polymer according to the first invention may
appropriately contain a structural unit derived from a monomer
commonly used in the art (hereinafter, sometimes referred to simply
as another monomer), in addition to the monomer of (i), the monomer
of (ii), and the monomer of (iii). In a case where the polymer
according to the first invention contains a structural unit derived
from the another monomer, the content thereof is usually 0.01 mol %
or more and 5 mol % or less, preferably 0.05 mol % or more and 2
mol % or less, and more preferably 0.1 mol % or more and 1 mol % or
less with respect to the total content of the structural units
derived from the monomer of (i) and the monomer of (ii).
[0149] In addition, the polymer according to the first invention
may contain two or more structural units derived from the monomer
of (i), the monomer of (ii), and the monomer of (iii),
respectively.
[0150] The polymer according to the first invention is preferably a
polymer consisting of structural units derived from one monomer of
(i) and one or two monomers of (ii), or a polymer consisting of
structural units derived from one monomer of (i), one or two
monomers of (ii), and one monomer of (iii); and more preferably a
polymer consisting of structural units derived from one monomer of
(i), and one or two monomers of (ii) having a solubility in water
at 20.degree. C. of 1 g/L or more, a polymer consisting of
structural units derived from one monomer of (i), and one or two
monomers of (ii) having an SP value of 11.5 (cal/cm.sup.3).sup.1/2
or more, a polymer consisting of structural units derived from one
monomer of (i), one or two monomers of (ii) having a solubility in
water at 20.degree. C. of 1 g/L or more, and one monomer of (iii),
or a polymer consisting of structural units derived from one
monomer of (i), one or two monomers of (ii) having an SP value of
11.5 (cal/cm.sup.3).sup.1/2 or more, and one monomer of (iii).
[0151] More specifically, the polymer according to the first
invention is preferably a polymer consisting of structural units
derived from one ethylenically unsaturated monocarboxylic acid
monomer and one or two monomers represented by the general formula
[1], or a polymer consisting of structural units derived from one
ethylenically unsaturated monocarboxylic acid monomer, one or two
monomers represented by the general formula [1], and one monomer
represented by the general formula [11]; more preferably a polymer
consisting of structural units derived from one ethylenically
unsaturated monocarboxylic acid monomer and one or two monomers
represented by the general formula [2], or a polymer consisting of
structural units derived from one ethylenically unsaturated
monocarboxylic acid monomer, one or two monomers represented by the
general formula [2], and one monomer represented by the general
formula [11]; and still more preferably a polymer consisting of
structural units derived from one acrylic acid or methacrylic acid
and one or two monomers represented by the general formula [3], or
a polymer consisting of structural units derived from one acrylic
acid or methacrylic acid, one or two monomers represented by the
general formula [3], and one monomer represented by the general
formula [11].
[0152] Still more specifically, the polymer according to the first
invention is preferably a polymer consisting of structural units
derived from one acrylic acid or methacrylic acid, and one or two
selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxy-1-methylethyl acrylate, or 4-hydroxybutyl acrylate, or a
polymer consisting of structural units derived from one acrylic
acid or methacrylic acid, one or two selected from 2-hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl
acrylate, or 4-hydroxybutyl acrylate, and one selected from the
more preferred specific example group of the monomer of (iii); and
more preferably a polymer consisting of structural units derived
from one acrylic acid and 2-hydroxyethyl acrylate and/or
4-hydroxybutyl acrylate, or a polymer consisting of structural
units derived from one acrylic acid, 2-hydroxyethyl acrylate and/or
4-hydroxybutyl acrylate, and one selected from the more preferred
specific example group of the monomer of (iii).
[0153] In a case where the polymer according to the first invention
is neutralized (in a case where the polymer forms a salt), it is
preferable that a part or all of the carboxy group in the
structural unit derived from the monomer of (i) and/or the sulfo
group or the phosphate group in the structural unit derived from
the monomer of (ii) is neutralized. In addition, examples of the
neutralizing agent used in a case of neutralizing the polymer
according to the first invention include an inorganic base such as
a hydroxide, a carbonate, or a hydrogen carbonate of an alkali
metal or an alkaline earth metal; and an organic base such as a
polyvalent amine having an amine value of 21 or more, an ammonium
salt, an aliphatic phosphine, an aromatic phosphine, a phosphonium
salt, an aliphatic thiol, an aromatic thiol, a thiol derivative, or
a sulfonium salt. Specific examples of the neutralizing agent
include a hydroxide of an alkali metal such as sodium hydroxide,
lithium hydroxide, or potassium hydroxide; a carbonate of an alkali
metal such as sodium carbonate, lithium carbonate, or potassium
carbonate; a hydrogen carbonate of an alkali metal such as lithium
hydrogen carbonate, sodium hydrogen carbonate, or potassium
hydrogen carbonate; a hydroxide of an alkaline earth metal such as
magnesium hydroxide or calcium hydroxide; a carbonate of an
alkaline earth metal such as magnesium carbonate or calcium
carbonate; a polyvalent amine having an amine value of 21 or more
such as ethylenediamine, 1,2-propanediamine,
N-methyl-1,3-propanediamine, bis(2-aminoethyl)amine,
tris(2-aminoethyl)amine, or polyethyleneimine; an ammonium salt
such as tetrabutylammonium tetrafluoroborate or
hexadecyltrimethylammonium hexafluorophosphate; an aliphatic
phosphine such as trimethylphosphine; an aromatic phosphine such as
triphenylphosphine; a phosphonium salt such as
tetraethylphosphonium hexafluorophosphate, or
1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium
hexafluorophosphate; an aliphatic thiol such as 1-butanethiol; an
aromatic thiol such as phenylmethanethiol or thiophene; a thiol
derivative such as 2-hydroxyethyl mercaptan; and a sulfonium salt
such as 1,3-benzodithiolylium tetrafluoroborate or
dimethylphenacylsulfonium tetrafluoroborate. Among these specific
examples, a hydroxide of an alkali metal and a polyvalent amine
having an amine value of 21 or more are preferable; sodium
hydroxide, lithium hydroxide, potassium hydroxide, ethylenediamine,
1,2-propanediamine, and N-methyl-1,3-propanediamine,
tris(2-aminoethyl)amine, and polyethyleneimine are more preferable;
and sodium hydroxide and polyethyleneimine are particularly
preferable. The neutralizing agents may be used alone or in
combination of two or more thereof. It is preferable to use only
one neutralizing agent alone or two neutralizing agents in
combination. In particular, it is preferable that only one
hydroxide of an alkali metal is used alone; or one hydroxide of an
alkali metal and one polyvalent amine having an amine value of 21
or more are used in combination.
[0154] It should be noted that the "polyvalent amine having an
amine value of 21 or more" refers to a polyvalent amine which has
two or more basic functional groups such as an amino group and has
an amine value of 21 or more, indicating an amount of the basic
functional groups in a structure thereof. The amine value in the
present invention (first invention and second invention) can be
specifically obtained from the calculation formula shown below. It
should be noted that the basic functional group in the present
invention (first invention and second invention) represents a
functional group showing basicity, such as an amino group, an
amidino group (amidine structure), a guanidino group (guanidine
structure), a pyridino group (pyridine structure), or a phosphazeno
group (phosphazene structure).
Calculation formula: amine value (meq./g)=number of basic
functional groups/molecular weight
[0155] (provided that, in a case of a high molecular weight
substance, the calculation shall be carried out with the molecular
weight as the molecular weight per monomer unit and the number of
basic functional groups as the number of basic functional groups
per monomer unit.)
[0156] In a case where the polymer according to the first invention
is neutralized, a degree of neutralization is usually 50% or more
and 200% or less, preferably 60% or more and 150% or less, and more
preferably 70% or more and 100% or less. It should be noted that
the degree of neutralization referred to here represents a ratio of
the total number of moles of the neutralizing agent to the total
number of moles of the carboxy group, the sulfo group, and the
phosphate group contained in the polymer according to the first
invention. In a case where the binder of the first invention
contains a salt of the polymer according to the first invention,
the dispersibility of the conductive assistant is further improved,
and the conductive assistant can be more uniformly distributed on
the collector, which makes it possible to further improve the
electrical characteristics of the electrode.
[0157] The polymer according to the first invention may be produced
by carrying out a polymerization reaction according to a method
known per se. Specifically, the polymer according to the first
invention can be produced, for example, by subjecting the monomer
of (i) and the monomer of (ii), and if necessary, the monomer of
(iii) and/or the another monomer, according to a desired polymer,
to a polymerization reaction in the presence of a polymerization
initiator.
[0158] The amounts of the monomer of (i) and the monomer of (ii)
used in the polymerization reaction may be appropriately set
according to a content ratio (molar ratio) of the structural unit
derived from the monomer of (i) to the structural unit derived from
the monomer of (ii) in the polymer according to the first
invention. In addition, the amount of the monomer of (iii) and/or
the another monomer used in the polymerization reaction may be
appropriately set according to the content in a case where the
polymer according to the first invention contains a structural unit
derived from the monomer of (iii) and/or the another monomer.
[0159] The polymerization reaction may be carried out according to
a method known per se. Specifically, the reaction may be carried
out in a suitable solvent, usually at 30.degree. C. or higher and
200.degree. C. or lower, preferably 60.degree. C. or higher and
150.degree. C. or lower, more preferably 70.degree. C. or higher
and 100.degree. C. or lower for usually 0.1 hours or longer and 24
hours or shorter, preferably 1 hour or longer and 10 hours or
shorter.
[0160] The polymerization initiator is not particularly limited as
long as it is commonly used in the art, and specific examples
thereof include 2,2'-azobis(isobutyronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(2-methylpropionate),
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(2-methylpropionamidine) dihydrochloride,
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]
tetrahydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane],
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], ammonium
persulfate (ammonium peroxodisulfate), potassium persulfate
(potassium peroxodisulfate), benzoyl peroxide, and lauroyl
peroxide. These polymerization initiator compounds may be used
alone or in combination of two or more thereof. The amount of the
polymerization initiator used is usually 0.001 mol % or more and 30
mol % or less with respect to the total mass of reactants.
[0161] The solvent is not particularly limited as long as it is
commonly used in the art, and specific examples thereof include
water, methanol, N-methyl-2-pyrrolidone (NMP), toluene,
1,4-dioxane, tetrahydrofuran, isopropanol, methyl ethyl ketone, and
propylene glycol monomethyl ether acetate, among which water is
preferable. These solvent compounds may be used alone or in
combination of two or more thereof. The amount of the solvent used
is 1 time (equal amount) or more and 20 times or less with respect
to the total mass of reactants.
[0162] If necessary, the product obtained after the polymerization
reaction may be subjected to general post-treatment operations and
purification operations commonly carried out in the art.
Specifically, for example, filtration, washing, extraction,
concentration under reduced pressure, recrystallization,
distillation, and column chromatography may be carried out.
[0163] In a case where the polymer according to the first invention
is neutralized, the polymer according to the first invention
obtained by the polymerization reaction may be neutralized
according to a method known per se. Specifically, the polymer
according to the first invention may be neutralized, for example,
by adding the neutralizing agent in an amount such that the polymer
according to the first invention has a desired degree of
neutralization. Examples of the solvent used for neutralization
include the same solvents as those used in the polymerization
reaction.
[0164] Specifically, the polymer or salt thereof according to the
first invention is produced as follows.
[0165] That is, the monomer of (i) and the monomer of (ii) in a
molar ratio of 5:95 to 95:5, and if necessary, the monomer of (iii)
and/or the another monomer of 0.01 mol % or more and 5 mol % or
less with respect to the content of the structural units derived
from the monomer of (i) and the monomer of (ii) are dissolved or
dispersed in a solvent such as water in an amount equal to or more
and 20 times or less the total mass of reactants, in the presence
of a polymerization initiator such as 2,2'-azobis(isobutyronitrile)
of 0.001 mol % or more and 30 mol % or less with respect to the
total mass of the reactants. Then, a polymerization reaction is
carried out at 30.degree. C. or higher and 200.degree. C. or lower
for 0.1 hours or longer and 24 hours or shorter to produce the
polymer according to the first invention. In addition, if
necessary, the neutralizing agent may be added in an amount such
that the obtained polymer according to the first invention has a
desired degree of neutralization to obtain a salt of the polymer
according to the first invention.
[0166] Binder Solution
[0167] The binder of the first invention may be contained in a
slurry composition of the first invention or an electrode of the
first invention which will be described later, in a form dissolved
in a solvent. In the first invention, a solution in which the
binder is dissolved in a solvent is referred to as a "binder
solution", and in particular, a solution in which the binder of the
first invention is dissolved in a solvent is referred to as a
"binder solution according to the first invention".
[0168] The solvent in the binder solution according to the first
invention is not particularly limited as long as it is commonly
used in the art, and specific examples thereof include water,
N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide,
methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran,
.gamma.-butyrolactone, toluene, methyl ethyl ketone, ethyl acetate,
and dioxane, among which water is preferable. These solvent
compounds may be used alone or in combination of two or more
thereof. It is preferable to use only one solvent compound alone.
It should be noted that, in a case where the solvent is water, the
binder solution may be referred to as "the binder aqueous solution
according to the first invention".
[0169] The content (mass of solid content) of the binder of the
first invention in the binder solution according to the first
invention may be appropriately set according to a desired
concentration of the binder solution according to the first
invention, and is usually 1% by mass or more and 70% by mass or
less, preferably 5% by mass or more and 50% by mass or less.
[0170] The binder solution according to the first invention may
contain various additives commonly used in the art, in addition to
the binder of the first invention and a solvent. Examples of
various additives include a dispersant, a thickener, a metal binder
(for example, aminotriazole), a reducing agent (for example,
ascorbic acid), a preservative (for example, cetylpyridinium
chloride), a rust inhibitor, a fungicide, an antibacterial agent, a
deodorant, a leveling agent, a defoamer, a blister inhibitor, an
anti-yellowing agent, an antistatic agent, a charge regulator, an
electrolyte decomposition inhibitor, an antioxidant, an anti-aging
agent, a light stabilizer, an ultraviolet absorber, a thixotropic
agent, a freeze stabilizer, a pH adjuster, a lubricant, a rheology
control agent, and a film forming aid. These additives may be used
alone or in combination of two or more thereof, depending on the
purpose. The content of various additives in the binder solution
according to the first invention is usually 10% by mass or less,
preferably 5% by mass or less, and more preferably 1% by mass or
less with respect to the content of the binder of the first
invention.
[0171] Slurry Composition of First Invention
[0172] The slurry composition of the first invention is a
composition for preparing an electrode for an electricity storage
device, which contains the binder of the first invention. More
specifically, the slurry composition of the first invention is a
composition containing an active material and a solvent, and if
necessary, a conductive assistant, in addition to the binder of the
first invention (or the binder solution according to the first
invention). The slurry composition of the first invention may be
used for preparing a positive electrode or a negative electrode,
and is preferably used for preparing a negative electrode.
[0173] The content of the binder of the first invention in the
slurry composition of the first invention is usually 0.1% by mass
or more and 30% by mass or less, preferably 0.5% by mass or more
and 20% by mass or less, and more preferably 1% by mass or more and
10% by mass or less with respect to the total mass of the slurry
composition of the first invention containing no solvent.
[0174] The active material in the slurry composition of the first
invention is not particularly limited as long as it is commonly
used in the art, and specific examples thereof include carbon,
silicon, germanium, tin, lead, zinc, aluminum, indium, antimony,
bismuth, sodium, magnesium, titanium, and compounds containing
these as elements (such as oxides), among which carbon, silicon, or
a compound containing silicon as an element is preferable. These
active materials may be used alone or in combination of two or more
thereof.
[0175] Examples of the carbon include a graphite-based carbon
material (graphite) such as natural graphite, artificial graphite,
or expanded graphite, carbon black, activated carbon, carbon fiber,
coke, soft carbon, and hard carbon. Among these specific examples,
graphite such as natural graphite, artificial graphite, or expanded
graphite is preferable. Examples of the natural graphite include
flake graphite and vein graphite. Examples of the artificial
graphite include vein graphite, vapor-grown graphite, flake
graphite, and fibrous graphite.
[0176] Examples of the silicon or compound containing silicon as an
element include silicon as well as a silicon oxide such as SiO or
SiO.sub.2, and silicon bonded to a metal, SiM (M represents a metal
such as magnesium, iron, calcium, cobalt, nickel, boron, copper,
manganese, silver, vanadium, cerium, or zinc), among which the
silicon or the silicon oxide is preferable, and the silicon is more
preferable. In addition, the surface of silicon may be partially or
completely coated with carbon, and examples of the surface-coated
silicon include carbon-coated silicon, a silicon oxide, and silicon
bonded to a metal, among which the carbon-coated silicon or the
silicon oxide is preferable and the carbon-coated silicon oxide is
more preferable.
[0177] The active material in the slurry composition of the first
invention preferably contains one or more carbons and/or one or
more silicons or compounds containing silicon as an element, and
more preferably contains one or more carbons and one or more
silicons or compounds containing silicon as an element. More
specific examples of the active material include an active material
containing a mixture of at least one selected from natural
graphite, artificial graphite, or expanded graphite and at least
one selected from silicon, a silicon oxide, carbon-coated silicon,
or a carbon-coated silicon oxide, among which an active material
containing natural graphite and a carbon-coated silicon oxide is
preferable.
[0178] The average particle diameter of the active material in the
slurry composition of the first invention varies depending on the
type of active material used, and is usually 0.001 .mu.m or more
and 100 .mu.m or less, preferably 0.01 .mu.m or more and 50 .mu.m
or less, and more preferably 0.1 .mu.m or more and 30 .mu.m or
less.
[0179] The content of the active material in the slurry composition
of the first invention is usually 30% by mass or more and 99.9% by
mass or less, preferably 40% by mass or more and 99% by mass or
less, and more preferably 50% by mass or more and 98% by mass or
less with respect to the total mass of the slurry composition of
the first invention containing no solvent.
[0180] The conductive assistant in the slurry composition of the
first invention is not particularly limited as long as it is
commonly used in the art, and specific examples thereof include
carbon blacks such as acetylene black, Ketjen black, furnace black,
and thermal black; and nanocarbons such as carbon nanotubes and
carbon nanohorns, among which the acetylene black and the Ketjen
black are preferable and the acetylene black is more preferable.
These conductive assistants may be used alone or in combination of
two or more thereof.
[0181] The average particle diameter of the conductive assistant in
the slurry composition of the first invention varies depending on
the type of the conductive assistant used, and is usually 0.001
.mu.m or more and 50 .mu.m or less, preferably 0.01 .mu.m or more
and 10 .mu.m or less, and more preferably 0.02 .mu.m or more and 1
.mu.m or less.
[0182] The content of the conductive assistant in the slurry
composition of the first invention is usually 0.1% by mass or more
and 40% by mass or less, preferably 0.5% by mass or more and 30% by
mass or less, and more preferably 1% by mass or more and 20% by
mass or less with respect to the total mass of the slurry
composition of the first invention containing no solvent.
[0183] The solvent in the slurry composition of the first invention
is not particularly limited as long as it is commonly used in the
art, and specific examples thereof include water,
N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide,
methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran,
.gamma.-butyrolactone, toluene, methyl ethyl ketone, ethyl acetate,
and dioxane, among which water is preferable. These solvent
compounds may be used alone or in combination of two or more
thereof. It is preferable to use only one solvent compound alone.
In addition, in a case where the binder of the first invention is
contained in the slurry composition of the first invention in the
form of a binder solution, the solvent in the slurry composition of
the first invention is preferably the same as the solvent in the
binder solution according to the first invention.
[0184] The slurry composition of the first invention may contain a
supporting salt, an additive, and the like commonly used in the
art, in addition to the binder of the first invention, an active
material, a conductive assistant, and a solvent.
[0185] Examples of the supporting salt include
Li(C.sub.2F.sub.5SO.sub.2).sub.2N(LiBETI), LiPF.sub.6, LiBF.sub.4,
LiClO.sub.4, LiAsF.sub.6, and LiCF.sub.3SO.sub.3. Examples of the
additive include a dispersant, a thickener, a metal binder, a
reducing agent, a preservative, a rust inhibitor, a fungicide, an
antibacterial agent, a deodorant, a leveling agent, a defoamer, a
blister inhibitor, an anti-yellowing agent, an antistatic agent, a
charge regulator, an electrolyte decomposition inhibitor, an
antioxidant, an anti-aging agent, a light stabilizer, an
ultraviolet absorber, a thixotropic agent, a freeze stabilizer, a
pH adjuster, a lubricant, a rheology control agent, and a film
forming aid. These additives may be used alone or in combination of
two or more thereof, depending on the purpose. The contents of the
supporting salt and the additive may be appropriately set according
to the amounts commonly used in the art.
[0186] The slurry composition of the first invention may be
prepared according to a method known per se. Specifically, the
slurry composition of the first invention can be prepared, for
example, by appropriately mixing the binder of the first invention,
an active material, and if necessary, a conductive assistant, a
supporting salt and/or an additive in a solvent so as to have the
above-mentioned contents, according to a desired slurry
composition.
[0187] Electrode of First Invention
[0188] The electrode of the first invention is an electrode for an
electricity storage device consisting of the slurry composition of
the first invention. More specifically, the electrode of the first
invention is an electrode having an electrode mixture layer derived
from the slurry composition of the first invention, which contains
the binder of the first invention (or the binder solution according
to the first invention), an active material, a solvent, and if
necessary, a conductive assistant, a supporting salt and/or an
additive, and a collector. The electrode of the first invention can
be used as both a negative electrode and a positive electrode, and
is preferably used as a positive electrode.
[0189] The collector in the electrode of the first invention is not
particularly limited as long as it is commonly used in the art, and
specific examples thereof include a collector made of a conductive
material such as platinum, copper, stainless steel (SUS),
Hastelloy, aluminum, iron, chromium, nickel, titanium, Inconel,
molybdenum, graphite, or carbon, and having a shape such as a
plate, a foil (sheet or paper), a mesh, an expanded grid (expanded
metal), or a punched metal. The mesh opening, wire diameter, number
of meshes, and the like of the collector are not particularly
limited, and conventionally known ones can be used. The thickness
of the collector is usually 1 .mu.m or more and 300 .mu.m or less,
and preferably 5 .mu.m or more and 30 .mu.m or less. The size of
the collector is determined according to the intended use of the
battery. In a case where a large electrode used for a large battery
is to be prepared, a collector having a large area is used, and in
a case where a small electrode is to be prepared, a collector
having a small area is used.
[0190] The electrode of the first invention may be produced
according to a method known per se. Specifically, the electrode of
the first invention can be prepared, for example, by coating or
crimping the slurry composition of the first invention on a
collector and drying the slurry composition to form an electrode
mixture layer on the collector. The thickness of the electrode
mixture layer is usually 1 .mu.m or more and 1000 .mu.m or less,
preferably 1 .mu.m or more and 500 .mu.m or less, and more
preferably 1 .mu.m or more and 300 .mu.m or less.
[0191] In the production of the electrode of the first invention,
the amount of the slurry composition of the first invention used
may be appropriately set such that the thickness of the electrode
mixture layer falls within the above-mentioned range after
drying.
[0192] In the production of the electrode of the first invention,
the slurry composition of the first invention may be coated or
crimped on the collector according to a method known per se. As a
specific coating/crimping method, for example, a self-propelled
coater, an ink jet method, a doctor blade method, a spray method, a
die coating method, or a combination thereof can be used. Among
these specific examples, the doctor blade method, the ink jet
method, and the die coating method capable of forming a thin layer
are preferable, and the doctor blade method and the die coating
method are more preferable.
[0193] In the production of the electrode of the first invention,
the slurry composition of the first invention may be dried
according to a method known per se, and is usually dried by a heat
treatment. The drying conditions during heating (necessity of
vacuum, drying time, and drying temperature) may be appropriately
set according to the coating amount of the slurry composition of
the first invention and the volatilization rate of the solvent in
the slurry composition of the first invention. As a specific drying
method, the slurry composition may be dried, for example, in air or
vacuum, usually at 50.degree. C. or higher and 400.degree. C. or
lower, preferably 70.degree. C. or higher and 200.degree. C. or
lower, usually for 1 hour or longer and 20 hours or shorter,
preferably 3 hours or longer and 15 hours or shorter. In addition,
the heat treatment may be carried out twice or more by changing the
drying conditions.
[0194] In the production of the electrode of the first invention,
if necessary, a press treatment may be carried out before and after
the drying. The press treatment may be carried out according to a
method known per se, and specific press treatment methods include,
for example, a calender roll method and a flat plate press, among
which the calender roll method is preferable.
[0195] Electricity Storage Device of First Invention
[0196] The electricity storage device of the first invention refers
to a device, an element, or the like having the electrode of the
first invention and capable of chemically, physically, or
physicochemically storing electricity. Specific examples thereof
include devices that can be charged and discharged, such as
secondary batteries (storage batteries), for example, a secondary
battery with multivalent ions such as magnesium ions, a lithium ion
secondary battery, a sodium ion secondary battery, a potassium ion
secondary battery, a nickel hydrogen storage battery, a nickel
cadmium storage battery, and a lead storage battery; and electric
double layer capacitors (electric double layer condensers), for
example, a lithium ion capacitor. Among these specific examples, an
electricity storage device using lithium ions such as a lithium ion
capacitor or a lithium ion secondary battery is preferable, and the
lithium ion secondary battery is more preferable.
[0197] The configuration of the electricity storage device of the
first invention may be the same as that of a general electricity
storage device commonly used in the art. Specifically, for example,
the electricity storage device is configured such that a positive
electrode and a negative electrode are placed facing each other
through a separator, and if necessary, impregnated with an
electrolytic solution. The electricity storage device of the first
invention may be any electricity storage device provided with the
electrode of the first invention as the positive electrode and/or
the negative electrode. As a member constituting the electricity
storage device of the first invention other than the electrode of
the first invention, a member commonly used in the art can be
appropriately adopted.
[0198] The separator in the electricity storage device of the first
invention may be a separator that electrically insulates a positive
electrode and a negative electrode while allowing ions to pass
therethrough, and examples thereof include a glass fiber and a
microporous polymer such as porous polyolefin. Specific examples of
the porous polyolefin include porous polyethylene, porous
polypropylene, and a product in which porous polyethylene and
porous polypropylene are superposed to form a multi-layer.
[0199] The electrolytic solution in the electricity storage device
of the first invention is preferably a non-aqueous electrolytic
solution containing an electrolyte, an organic solvent, and an
additive. The electrolyte varies depending on a desired electricity
storage device. For example, in a case where the desired
electricity storage device is a lithium ion secondary battery,
examples of the electrolyte include lithium salts such as
LiBF.sub.4, LiPF.sub.6, LiAsF.sub.6, LiSbF.sub.6, LiAlCl.sub.4,
LiCl, LiBr, LiClO.sub.4, LiBrO.sub.4, LiIO.sub.4,
LiCH.sub.3SO.sub.3, and LiCF.sub.3SO.sub.3, among which LiPF.sub.6
is preferable. These lithium salts may be used alone or in
combination of two or more thereof. The content of the electrolyte
in the non-aqueous electrolytic solution is usually 0.05 mol/L or
more and 15 mol/L or less and preferably 0.1 mol/L or more and 5
mol/L or less.
[0200] Specific examples of the organic solvent in the non-aqueous
electrolytic solution include ethylene carbonate, dimethyl
carbonate, propylene carbonate, diethyl carbonate, ethyl methyl
carbonate, .gamma.-butyrolactone (lactones), and sulfolane, among
which ethylene carbonate, ethyl methyl carbonate, diethyl
carbonate, and dimethyl carbonate are preferable. These organic
solvents may be used alone or in combination of two or more
thereof.
[0201] Specific examples of the additive in the non-aqueous
electrolytic solution include vinylene carbonate, fluorovinylene
carbonate, methylvinylene carbonate, fluoromethylvinylene
carbonate, ethylvinylene carbonate, propylvinylene carbonate,
butylvinylene carbonate, dipropylvinylene carbonate,
4,5-dimethylvinylene carbonate, 4,5-diethylvinylene carbonate,
vinylethylene carbonate, divinylethylene carbonate, phenylethylene
carbonate, diallyl carbonate, fluoroethylene carbonate, catechol
carbonate, 1,3-propane sultone, and butane sultone, among which
vinylene carbonate and fluoroethylene carbonate are preferable.
These additives may be used alone or in combination of two or more
thereof. The content of the additive in the non-aqueous
electrolytic solution is usually 0.05% by mass or more and 15% by
mass or less and preferably 0.1% by mass or more and 5% by mass or
less.
[0202] The non-aqueous electrolytic solution in the electricity
storage device of the first invention may contain additives such as
a film forming agent, an overcharge inhibitor, an oxygen scavenger,
a dehydrating agent, and a flame retardant, and a coordinating
additive such as crown ether, which are commonly used in the art,
in addition to an electrolyte and an organic solvent.
[0203] The shape of the electricity storage device of the first
invention is not particularly limited. A shape commonly used in the
art, such as a wound type or a laminated type as an internal shape,
and a coin type, a laminated type (pouch type), a square type, or a
cylindrical type as an external shape, can be appropriately
adopted.
[0204] Binder of Second Invention
[0205] The binder according to the second invention contains a salt
of a polymer which contains structural units derived from (i) an
ethylenically unsaturated carboxylic acid monomer and (ii) an
ethylenically unsaturated monomer having at least one group
selected from a hydroxy group, a dialkylamino group, an acetyl
group, a sulfo group, a phosphate group, or a cyano group and is
neutralized with a monoamine, a polyvalent amine having an amine
value of less than 21, and/or an onium hydroxide (hereinafter,
sometimes referred to simply as the polymer according to the second
invention).
[0206] Specific examples of each of the monomer of (i) and the
monomer of (ii) in the polymer according to the second invention
include the same specific examples of each of the monomer of (i)
and the monomer of (ii) in the polymer according to the first
invention, and preferred specific examples thereof are also the
same. In addition, the content ratio (molar ratio) of the
structural unit derived from the monomer of (i) to the structural
unit derived from the monomer of (ii) in the polymer according to
the second invention is the same as the content ratio in the
polymer according to the first invention.
[0207] The polymer according to the second invention may further
contain a structural unit derived from (iii) a monomer having two
or more polymerizable unsaturated groups, in addition to the
monomer of (i) and the monomer of (ii). Specific examples of the
monomer of (iii) in the polymer according to the second invention
include the same specific examples of the monomer of (iii) in the
polymer according to the first invention, and preferred specific
examples thereof are also the same. In addition, in a case where
the polymer according to the second invention contains a structural
unit derived from the monomer of (iii), the content thereof is the
same as the content of the monomer of (iii) in a case where the
polymer according to the first invention contains a structural unit
derived from the monomer of (iii).
[0208] The polymer according to the second invention may
appropriately contain a structural unit derived from a monomer
commonly used in the art, in addition to the monomer of (i), the
monomer of (ii), and the monomer of (iii). The monomer is the same
as the another monomer in the polymer according to the first
invention, and the content thereof is also the same as the content
of the another monomer in a case where the polymer according to the
first invention contains a structural unit derived from the another
monomer.
[0209] In addition, the polymer according to the second invention
may contain two or more structural units derived from the monomer
of (i), the monomer of (ii), and the monomer of (iii),
respectively.
[0210] Specific examples of the polymer according to the second
invention include the same specific examples of the polymer
according to the first invention, and preferred specific examples
thereof are also the same.
[0211] The polymer according to the second invention is a salt of a
polymer neutralized with a monoamine, a polyvalent amine having an
amine value of less than 21, and/or an onium hydroxide
(hereinafter, sometimes referred to simply as a neutralizing agent
according to the second invention). The polymer according to the
second invention is preferably a polymer in which a part or all of
carboxy groups in the structural unit derived from the monomer of
(i) and/or sulfo groups or phosphate groups in the structural unit
derived from the monomer of (ii) are neutralized by the
neutralizing agent according to the second invention.
[0212] The monoamine in the neutralizing agent according to the
second invention is a monovalent amine having only one basic
functional group. Specific examples of the monoamine include a
monoamine having one amino group or a derivative thereof, such as
tert-butylamine, amylamine (pentylamine), octylamine,
diisopropylethylamine, dibutylamine, triethylamine, benzylamine,
aniline, monoethanolamine, N,N-diethylethanolamine,
bis(2-cyanoethyl)amine, tris(2-cyanoethyl)amine,
3-aminopropionitrile, 3-methoxypropylamine, 3-aminotriazole, or
3-aminopropyltrimethoxysilane; a monoamine having one amidino group
(amidine structure) or a derivative thereof, such as
diazabicyclononene; a monoamine having one guanidino group
(guanidine structure) or a derivative thereof, such as
tetramethylguanidine or diazabicycloundecene; a monoamine having
one pyridino group (pyridine structure) or a derivative thereof,
such as pyridine; and a monoamine having one phosphazeno group
(phosphazene structure) or a derivative thereof, such as
hexafluorocyclotriphosphazene or hexachlorocyclotriphosphazene.
Among these specific examples, monoethanolamine,
N,N-diethylethanolamine, 3-methoxypropylamine, and 3-aminotriazole
are preferable, and 3-methoxypropylamine and 3-aminotriazole are
particularly preferable.
[0213] The polyvalent amine having an amine value of less than 21
in the neutralizing agent according to the second invention refers
to a polyvalent amine which has two or more basic functional groups
and has an amine value of less than 21, indicating an amount of the
basic functional groups in a structure thereof. A polyvalent amine
having a low molecular weight is preferable among the polyvalent
amines. Specifically, the polyvalent amine having a molecular
weight of 600 or less is preferable. Specific examples thereof
include 3,5-diaminotriazole, 4-dimethylaminopyridine,
poly(propylene glycol) bis(2-aminopropyl ether) (JEFFAMINE
(registered trademark) D-400), and
O,O'-bis(2-aminopropyl)polypropylene glyco-block-polyethylene
glycol-block-polypropylene glycol (JEFFAMINE (registered trademark)
ED-600). Among these specific examples, 3,5-diaminotriazole,
poly(propylene glycol) bis(2-aminopropyl ether), and
O,O'-bis(2-aminopropyl)polypropylene glyco-block-polyethylene
glycol-block-polypropylene glycol are preferable, and
3,5-diaminotriazole and O,O'-bis(2-aminopropyl)polypropylene
glyco-block-polyethylene glycol-block-polypropylene glycol are
particularly preferable.
[0214] Examples of the onium hydroxide in the neutralizing agent
according to the second invention include ammonium hydroxide,
phosphonium hydroxide, and sulfonium hydroxide, which may have a
substituent. Specific examples thereof include an ammonium
hydroxide such as benzyltrimethylammonium hydroxide or
tetrabutylammonium hydroxide; a phosphonium hydroxide such as
tetrabutylphosphonium hydroxide; and a sulfonium hydroxide such as
trimethylsulfonium hydroxide. Among these specific examples,
ammonium hydroxide is preferable, and benzyltrimethylammonium
hydroxide or tetrabutylammonium hydroxide is particularly
preferable.
[0215] Among the specific examples of the neutralizing agent
according to the second invention, 3-methoxypropylamine,
3-aminotriazole, 3,5-diaminotriazole, poly(propylene glycol)
bis(2-aminopropyl ether) (JEFFAMINE (registered trademark) D-400),
O,O'-bis(2-aminopropyl)polypropylene glyco-block-polyethylene
glycol-block-polypropylene glycol (JEFFAMINE (registered trademark)
ED-600), or tetrabutylammonium hydroxide is preferable;
3-methoxypropylamine, 3-aminotriazole, 3,5-diaminotriazole,
poly(propylene glycol) bis(2-aminopropyl ether) (JEFFAMINE
(registered trademark) D-400), or
O,O'-bis(2-aminopropyl)polypropylene glyco-block-polyethylene
glycol-block-polypropylene glycol (JEFFAMINE (registered trademark)
ED-600) is more preferable; and 3,5-diaminotriazole or
O,O'-bis(2-aminopropyl)polypropylene glyco-block-polyethylene
glycol-block-polypropylene glycol (JEFFAMINE (registered trademark)
ED-600) is particularly preferable. The neutralizing agent
according to the second invention may be used alone or in
combination of two or more thereof. It is preferable to use only
one neutralizing agent alone.
[0216] In addition, a conventionally known neutralizing agent may
be used in combination, in addition to the neutralizing agent
according to the second invention. Examples of the neutralizing
agent used in combination include inorganic bases such as
hydroxides, carbonates, and hydrogen carbonates of alkali metals or
alkaline earth metals. Specific examples thereof include a
hydroxide of an alkali metal such as sodium hydroxide, lithium
hydroxide, or potassium hydroxide; a carbonate of an alkali metal
such as sodium carbonate, lithium carbonate, or potassium
carbonate; a hydrogen carbonate of an alkali metal such as lithium
hydrogen carbonate, sodium hydrogen carbonate, or potassium
hydrogen carbonate; a hydroxide of an alkaline earth metal such as
magnesium hydroxide or calcium hydroxide; and a carbonate of an
alkaline earth metal such as magnesium carbonate or calcium
carbonate. Among these specific examples, a hydroxide of an alkali
metal is preferable, and sodium hydroxide is particularly
preferable. With regard to the neutralizing agent to be used in
combination, only one type thereof may be used in combination with
the neutralizing agent according to the second invention, or two or
more types thereof may be used in combination with the neutralizing
agent according to the second invention. It is preferable to use
only one type thereof in combination with the neutralizing agent
according to the second invention. In particular, it is preferable
to use only one hydroxide of an alkali metal in combination with
the neutralizing agent according to the second invention.
[0217] The degree of neutralization of the polymer according to the
second invention is usually 50% or more and 300% or less,
preferably 60% or more and 200% or less, and more preferably 70% or
more and 150% or less. It should be noted that the degree of
neutralization referred to here represents a ratio of the total
number of moles of the neutralizing agent according to the second
invention to the total number of moles of the carboxy group, the
sulfo group, and the phosphate group contained in the polymer
according to the second invention. Incorporation of the polymer
according to the second invention in the binder of the second
invention leads to improved flexibility of an electrode to be
produced, which makes it possible to produce an electrode having
excellent winding properties.
[0218] The polymer according to the second invention may be
produced by carrying out a polymerization reaction and
neutralization according to a method known per se. Specifically,
for example, the polymer according to the second invention may be
produced in such a manner that the same polymerization reaction as
that of the polymer according to the first invention is carried
out, and the polymer obtained by the polymerization reaction is
neutralized by adding an amount of the neutralizing agent according
to the second invention to obtain a desired degree of
neutralization. Examples of the solvent used for neutralization
include the same solvents as those used in the polymerization
reaction of the polymer according to the first invention.
[0219] Binder Solution
[0220] The binder of the second invention may be contained in a
slurry composition of the second invention or an electrode of the
second invention which will be described later, in a form dissolved
in a solvent. In the second invention, a solution in which the
binder is dissolved in a solvent is referred to as a "binder
solution", and in particular, a solution in which the binder of the
second invention is dissolved in a solvent is referred to as a
"binder solution according to the second invention".
[0221] Examples of the solvent in the binder solution according to
the second invention include the same solvents as those in the
binder solution according to the first invention, and preferred
examples thereof are also the same. It should be noted that, in a
case where the solvent is water, the binder solution may be
referred to as "the binder aqueous solution according to the second
invention".
[0222] The content (mass of solid content) of the binder of the
second invention in the binder solution according to the second
invention may be appropriately set according to a desired
concentration of the binder solution according to the second
invention, and is usually 1% by mass or more and 70% by mass or
less, preferably 5% by mass or more and 50% by mass or less.
[0223] The binder solution according to the second invention may
contain various additives commonly used in the art, in addition to
the binder of the second invention and a solvent. Examples of the
additive include the same various additives in the binder solution
according to the first invention, and the content thereof is also
the same as the content of the additive in a case where the binder
solution according to the first invention contains various
additives.
[0224] Slurry Composition of Second Invention
[0225] The slurry composition of the second invention is a
composition for preparing an electrode for an electricity storage
device, which contains the binder of the second invention. More
specifically, the slurry composition of the second invention is a
composition containing an active material and a solvent, and if
necessary, a conductive assistant, in addition to the binder of the
second invention (or the binder solution according to the second
invention). The slurry composition of the second invention may be
used for preparing a positive electrode or a negative electrode,
and is preferably used for preparing a negative electrode.
[0226] The content of the binder of the second invention in the
slurry composition of the second invention is usually 0.1% by mass
or more and 30% by mass or less, preferably 0.5% by mass or more
and 20% by mass or less, and more preferably 1% by mass or more and
10% by mass or less with respect to the total mass of the slurry
composition of the second invention containing no solvent.
[0227] Examples of the active material, conductive assistant, and
solvent in the slurry composition of the second invention include
the same active material, conductive assistant, and solvent in the
slurry composition of the first invention, and preferred examples
thereof are also the same. In addition, the content of the active
material, the conductive assistant, and the solvent in the slurry
composition of the second invention is the same as the content of
the active material, the conductive assistant, and the solvent in
the slurry composition of the first invention.
[0228] The slurry composition of the second invention may contain a
supporting salt, an additive, and the like commonly used in the
art, in addition to the binder of the second invention, an active
material, a conductive assistant, and a solvent. Examples of the
supporting salt and additive include the same supporting salt and
additive in the slurry composition of the first invention, and the
content thereof may be appropriately set according to the amount
commonly used in the art.
[0229] The slurry composition of the second invention may be
prepared according to a method known per se. Specifically, the
slurry composition of the second invention can be prepared, for
example, by appropriately mixing the binder of the second
invention, an active material, and if necessary, a conductive
assistant, a supporting salt and/or an additive in a solvent so as
to have the above-mentioned contents, according to a desired slurry
composition.
[0230] Electrode of Second Invention
[0231] The electrode of the second invention is an electrode for an
electricity storage device consisting of the slurry composition of
the second invention. More specifically, the electrode of the
second invention is an electrode having an electrode mixture layer
derived from the slurry composition of the second invention, which
contains the binder of the second invention (or the binder solution
according to the second invention), an active material, a solvent,
and if necessary, a conductive assistant, a supporting salt and/or
an additive, and a collector. The electrode of the second invention
can be used as both a negative electrode and a positive electrode,
and is preferably used as a positive electrode.
[0232] Examples of the collector in the electrode of the second
invention include the same collector as in the electrode of the
first invention, and preferred examples thereof are also the
same.
[0233] The electrode of the second invention may be produced by the
same production method as the electrode of the first invention.
[0234] In the production of the electrode of the second invention,
the amount of the slurry composition of the second invention used
may be appropriately set such that the thickness of the electrode
mixture layer becomes a desired thickness after drying.
[0235] In the production of the electrode of the second invention,
the coating or crimping of the slurry composition of the second
invention on the collector may be carried out in the same manner as
in the coating or crimping of the slurry composition of the first
invention on the collector.
[0236] In the production of the electrode of the second invention,
the drying of the slurry composition of the second invention may be
carried out in the same manner as in the drying of the slurry
composition of the first invention.
[0237] In the production of the electrode of the second invention,
if necessary, a press treatment may be carried out before and after
the drying. The press treatment may be carried out in the same
manner as in the press treatment in the production of the electrode
of the first invention.
[0238] Electricity Storage Device of Second Invention
[0239] The electricity storage device of the second invention
refers to a device, an element, or the like having the electrode of
the second invention and capable of chemically, physically, or
physicochemically storing electricity. Specifically, for example,
the electricity storage device of the second invention may be the
same as the electricity storage device of the first invention, and
the preferred one thereof is also the same.
[0240] The configuration of the electricity storage device of the
second invention may be the same as that of the electricity storage
device of the first invention. In addition, examples of the members
constituting the electricity storage device of the second invention
other than the electrode of the second invention include the same
members as those constituting the electricity storage device of the
first invention other than the electrode of the first invention,
and preferred examples thereof are also the same.
[0241] The shape of the electricity storage device of the second
invention is not particularly limited. A shape commonly used in the
art, such as a wound type or a laminated type as an internal shape,
and a coin type, a laminated type (pouch type), a square type, or a
cylindrical type as an external shape, can be appropriately
adopted.
[0242] Hereinafter, the present invention (first invention and
second invention) will be described in more detail with reference
to Examples and Comparative Examples, but the present invention is
not limited to these examples.
EXAMPLES
Example 1
[0243] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 435 parts by mass of ion exchange water, 22 parts by mass
(0.31 mol) of acrylic acid (manufactured by Toagosei Co., Ltd.), 22
parts by mass (0.19 mol) of 2-hydroxyethyl acrylate (manufactured
by Osaka Organic Chemical Industry Ltd.), and 0.21 parts by mass
(0.0014 mol) of N,N-methylenebisacrylamide (manufactured by
FUJIFILM Wako Pure Chemical Corporation), followed by heating under
a nitrogen stream until the internal temperature reached 77.degree.
C. Next, 0.34 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
(trade name: VA-057, manufactured by FUJIFILM Wako Pure Chemical
Corporation) were added thereto, and the obtained solution was
reacted at 77.degree. C. for 4 hours. After the reaction was
complete, the reaction solution was cooled to room temperature, and
20 parts by mass of 48% sodium hydroxide aqueous solution
(manufactured by Toagosei Co., Ltd.) were added to obtain a binder
aqueous solution 1 (solid content: 10%).
Example 2
[0244] A binder aqueous solution 2 (solid content: 10%) was
obtained in the same manner as in Example 1, except that ion
exchange water was used in an amount of 461 parts by mass instead
of 435 parts by mass, acrylic acid was used in an amount of 5.0
parts by mass (0.069 mol) instead of 22 parts by mass,
2-hydroxyethyl acrylate was used in an amount of 45 parts by mass
(0.39 mol) instead of 22 parts by mass, N,N-methylenebisacrylamide
was used in an amount of 0.20 parts by mass (0.0013 mol) instead of
0.21 parts by mass,
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
was used in an amount of 0.31 parts by mass instead of 0.34 parts
by mass, and 48% sodium hydroxide aqueous solution was used in an
amount of 4.6 parts by mass instead of 20 parts by mass.
Example 3
[0245] A binder aqueous solution 3 (solid content: 10%) was
obtained in the same manner as in Example 1, except that ion
exchange water was used in an amount of 521 parts by mass instead
of 435 parts by mass, acrylic acid was used in an amount of 11
parts by mass (0.15 mol) instead of 22 parts by mass,
2-hydroxyethyl acrylate was used in an amount of 44 parts by mass
(0.38 mol) instead of 22 parts by mass, N,N-methylenebisacrylamide
was used in an amount of 0.27 parts by mass (0.0018 mol) instead of
0.21 parts by mass,
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
was used in an amount of 0.42 parts by mass instead of 0.34 parts
by mass, and 48% sodium hydroxide aqueous solution was used in an
amount of 4.9 parts by mass instead of 20 parts by mass.
Example 4
[0246] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 460 parts by mass of ion exchange water, 36 parts by mass
(0.50 mol) of acrylic acid, 9 parts by mass (0.11 mol) of
4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical
Industry Ltd.), and 0.20 parts by mass (0.00078 mol) of
pentaerythritol triallyl ether (manufactured by FUJIFILM Wako Pure
Chemical Corporation), followed by heating under a nitrogen stream
until the internal temperature reached 77.degree. C. Next, 0.084
parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
were added thereto, and the obtained solution was reacted at
77.degree. C. for 4 hours. After the reaction was complete, the
reaction solution was cooled to room temperature, and 32 parts by
mass of 50% sodium hydroxide aqueous solution (manufactured by
Toagosei Co., Ltd.) were added to obtain a binder aqueous solution
4 (solid content: 10%).
Example 5
[0247] A binder aqueous solution 5 (solid content: 10%) was
obtained in the same manner as in Example 1, except that ion
exchange water was used in an amount of 400 parts by mass instead
of 435 parts by mass, acrylic acid was used in an amount of 5.0
parts by mass (0.069 mol) instead of 22 parts by mass,
2-hydroxyethyl acrylate was used in an amount of 45 parts by mass
(0.39 mol) instead of 22 parts by mass,
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
was used in an amount of 0.38 parts by mass instead of 0.34 parts
by mass, and 48% sodium hydroxide aqueous solution was used in an
amount of 4.6 parts by mass instead of 20 parts by mass, and
N,N-methylenebisacrylamide was not used.
Example 6
[0248] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 720 parts by mass of ion exchange water, 9.0 parts by mass
(0.12 mol) of acrylic acid, and 81 parts by mass (0.70 mol) of
2-hydroxyethyl acrylate, followed by heating under a nitrogen
stream until the internal temperature reached 77.degree. C. Next,
0.69 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
were added thereto, and the obtained solution was reacted at
77.degree. C. for 4 hours. After the reaction was complete, the
reaction solution was cooled to room temperature, and 7.3 parts by
mass of 48% sodium hydroxide aqueous solution and 0.43 parts by
mass of polyethyleneimine aqueous solution (molecular weight: about
10,000, manufactured by FUJIFILM Wako Pure Chemical Corporation)
were added to obtain a binder aqueous solution 6 (solid content:
11%).
Example 7
[0249] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 350 parts by mass of ion exchange water, 5.0 parts by mass
(0.069 mol) of acrylic acid, 40 parts by mass (0.34 mol) of
2-hydroxyethyl acrylate, and 5.0 parts by mass (0.035 mol) of
4-hydroxybutyl acrylate, followed by heating under a nitrogen
stream until the internal temperature reached 77.degree. C. Next,
0.38 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
were added thereto, and the obtained solution was reacted at
77.degree. C. for 4 hours. After the reaction was complete, the
reaction solution was cooled to room temperature, and 4.5 parts by
mass of 48% sodium hydroxide aqueous solution were added to obtain
a binder aqueous solution 7 (solid content: 11%).
Example 8
[0250] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 320 parts by mass of ion exchange water, 4.0 parts by mass
(0.056 mol) of acrylic acid, 32 parts by mass (0.28 mol) of
2-hydroxyethyl acrylate, and 4.0 parts by mass (0.028 mol) of
4-hydroxybutyl acrylate, followed by heating under a nitrogen
stream until the internal temperature reached 77.degree. C. Next,
0.31 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
were added thereto, and the obtained solution was reacted at
77.degree. C. for 4 hours. After the reaction was complete, the
reaction solution was cooled to room temperature, and 4.5 parts by
mass of 48% sodium hydroxide aqueous solution and 0.19 parts by
mass of polyethyleneimine aqueous solution (molecular weight: about
10,000) were added to obtain a binder aqueous solution 8 (solid
content: 11%).
Comparative Example 1
[0251] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 420 parts by mass of ion exchange water, 40 parts by mass
(0.59 mol) of acrylic acid, and 0.24 parts by mass (0.0016 mol) of
N,N-methylenebisacrylamide, followed by heating under a nitrogen
stream until the internal temperature reached 77.degree. C. Next,
0.30 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
were added thereto, and the obtained solution was reacted at
77.degree. C. for 4 hours. After the reaction was complete, the
reaction solution was cooled to room temperature, and 37 parts by
mass of 48% sodium hydroxide aqueous solution were added to obtain
a binder aqueous solution 101 (solid content: 10%).
Comparative Example 2
[0252] To a 200 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 135 parts by mass of ion exchange water and 15 parts by mass
(0.13 mol) of 2-hydroxyethyl acrylate, followed by heating under a
nitrogen stream until the internal temperature reached 75.degree.
C. Next, 0.054 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
were added thereto, and the obtained solution was reacted at
75.degree. C. for 4 hours. After the reaction was complete, the
reaction solution was cooled to room temperature to obtain a binder
aqueous solution 102 (solid content: 10%).
Comparative Example 3
[0253] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 575 parts by mass of ion exchange water, 45 parts by mass
(0.62 mol) of acrylic acid, 11 parts by mass (0.056 mol) of
2-acryloyloxyethyl acid phosphate (trade name: LIGHT ACRYLATE P-1A
(N), manufactured by Kyoeisha Chemical Co., Ltd.), and 0.18 parts
by mass (0.00097 mol) of diethylene glycol diallyl ether
(manufactured by FUJIFILM Wako Pure Chemical Corporation), followed
by heating under a nitrogen stream until the internal temperature
reached 77.degree. C. Next, 0.10 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
were added thereto, and the obtained solution was reacted at
77.degree. C. for 4 hours. After the reaction was complete, the
reaction solution was cooled to room temperature, and 41 parts by
mass of 48% sodium hydroxide aqueous solution were added to obtain
a binder aqueous solution 103 (solid content: 10%).
[0254] With regard to the binder aqueous solutions 1 to 8 obtained
in Examples 1 to 8 and the binder aqueous solutions 101 to 103
obtained in Comparative Examples 1 to 3, Table 1 shows the "binder
component corresponding to the monomer of (i)", the "binder
component corresponding to the monomer of (ii)", the "content ratio
(molar ratio) of the structural unit derived from the monomer of
(i) to the structural unit derived from the monomer of (ii)", the
"binder component corresponding to the monomer of (iii)", and the
"content (mol %) of structural units derived from the monomer of
(iii) with respect to the total content of the structural units
derived from the monomer of (i) and the monomer of (ii)" for the
binder in each binder aqueous solution. In addition, Table 1 also
shows the "components of a neutralizing agent" and the "degree of
neutralization (%) by the neutralizing agent" for the binder in
each binder aqueous solution.
TABLE-US-00007 TABLE 1 Neutralizing agent Content Degree of Degree
of Monomer ratio Content of neutralization neutralization Monomer
of (ii) (i):(ii) Monomer monomer Neutralizing of neutralizing
Neutralizing of neutralizing of (i) (ii)-1 (ii)-2 (molar ratio) of
(iii) of (iii) agent 1 agent 1 agent 2 agent 2 Binder aqueous AA
2HEA -- 62:38 MBAA 0.28 mol % NaOH 80% -- -- solution 1 (Example 1)
Binder aqueous AA 2HEA -- 15:85 MBAA 0.28 mol % NaOH 80% -- --
solution 2 (Example 2) Binder aqueous AA 2HEA -- 28:72 MBAA 0.34
mol % NaOH 80% -- -- solution 3 (Example 3) Binder aqueous AA 4HBA
-- 82:18 PETE 0.13 mol % NaOH 80% -- -- solution 4 (Example 4)
Binder aqueous AA 2HEA -- 15:85 -- -- NaOH 80% -- -- solution 5
(Example 5) Binder aqueous AA 2HEA -- 15:85 -- -- NaOH 72% PEI 8%
solution 6 (Example 6) Binder aqueous AA 2HEA 4HBA 16:84 -- -- NaOH
80% -- -- solution 7 (Example 7) Binder aqueous AA 2HEA 4HBA 16:84
-- -- NaOH 72% PEI 8% solution 8 (Example 8) Binder aqueous AA --
-- 100:0 MBAA 0.27 mol % NaOH 80% -- -- solution 101 (Comparative
Example 1) Binder aqueous -- 2HEA -- 0:100 -- -- -- -- -- --
solution 102 (Comparative Example 2) Binder aqueous AA 2AOEP --
92:8 DGDA 0.14 mol % NaOH 80% -- -- solution 103 (Comparative
Example 3) AA: acrylic acid, 2HEA: 2-hydroxyethyl acrylate, 4HBA:
4-hydroxybutyl acrylate MBAA: N,N-methylenebisacrylamide, PETE:
pentaerythritol triallyl ether PEI: polyethyleneimine 2AOEP:
2-(acryloyloxy)ethyl acid phosphate, DGDA: diethylene glycol
diallyl ether
Experimental Example 1
[0255] (1) Sample Preparation
[0256] Using a planetary mixer (product name: AWATORI RENTARO,
Model ARE-310, manufactured by Thinky Corporation), 0.92 parts by
mass of acetylene black (trade name: DENKA BLACK (registered
trademark) powder, average particle diameter: 35 nm, specific
surface area: 68 m.sup.2/g, manufactured by Denka Company Limited)
as a conductive assistant, 1.0 parts by mass of the binder aqueous
solution 1 (solid content: 10%) obtained in Example 1, and 18.1
parts by mass of water as a solvent were mixed and stirred. The
obtained aqueous dispersion liquid of the conductive assistant and
the binder is referred to as a slurry for measurement.
[0257] (2) Measuring Method of Loss Tangent Tan .delta.
[0258] The obtained slurry for measurement was set on a sample
table. The slurry for measurement was adjusted to a thickness of 1
mm with a parallel plate (PP50). Then, strain dispersion
measurement was carried out using a rheometer (product name: MCR
102, manufactured by Anton Paar GmbH) at a measurement temperature
of 25.degree. C., a frequency of 1 Hz, and a strain amount in a
range of 10.sup.-2% to 10.sup.3%. The loss tangent tan .delta.
(loss elastic modulus G''/storage elastic modulus G') in the linear
region of the slurry for measurement was calculated from the
obtained values of the storage elastic modulus G' and the loss
elastic modulus G''.
Experimental Examples 2 to 8
[0259] Slurries for measurement were prepared in the same manner as
in Experimental Example 1, except that each of the binder aqueous
solutions 2 to 8 obtained in Examples 2 to 8 was used instead of
the binder aqueous solution 1, and then the loss tangent tan
.delta. was calculated.
Comparative Experimental Examples 1 to 3
[0260] Slurries for measurement were prepared in the same manner as
in Experimental Example 1, except that each of the binder aqueous
solutions 101 to 103 obtained in Comparative Examples 1 to 3 was
used instead of the binder aqueous solution 1, and then the loss
tangent tan .delta. was calculated.
Experimental Example 9
[0261] (1) Preparation of Slurry Composition
[0262] The following components were weighed: 2.1 g of
carbon-coated SiO powder (particle size: 5 .mu.m, manufactured by
Osaka Titanium Technologies Co., Ltd.), 5.0 g of natural graphite
(particle size: 20 .mu.m, manufactured by Hitachi Kasei Kogyo
Kabushiki Kaisha), 0.50 g of acetylene black (trade name: DENKA
BLACK (registered trademark) powder, manufactured by Denka Company
Limited), and 4.0 g of the binder aqueous solution 1 (solid
content: 10%) obtained in Example 1. 8.6 g of water was further
added thereto. These components were mixed and stirred using a
planetary mixer (product name: AWATORI RENTARO, Model ARE-310,
manufactured by Thinky Corporation) at a rotation speed of 2000 rpm
for 30 minutes. The obtained mixture was used as a slurry
composition.
[0263] (2) Production of Electrode for Lithium Secondary
Battery
[0264] The slurry composition obtained in (1) was coated to a
copper collector using a doctor blade so as to have a thickness of
75 .mu.m. Next, it was first dried in air at 80.degree. C., and
then the dried electrode was pressed with a roll press machine such
that a volume density was 1.5 g/cm.sup.3. The pressed electrode was
dried under vacuum at 150.degree. C. for 12 hours.
[0265] (3) Production of Coin Cell Battery
[0266] A coin cell battery was produced in a glove box filled with
argon. Here, a coin cell battery consisting of the electrode
obtained in (2), a lithium foil electrode, a solution of 2% by mass
of vinylene carbonate (VC) added to ethylene carbonate
(EC)/dimethyl carbonate (DMC) (volume ratio=1:1) containing 1 M
LiPF.sub.6, and a separator was assembled.
[0267] (4) Charge/Discharge Test
[0268] A charge/discharge test was carried out under the following
conditions, using the coin cell battery produced in (3). [0269]
Counter electrode: lithium foil [0270] Electrolytic solution: 1M
LiPF.sub.6 EC/DMC mixed solution (volume ratio=1:1)+VC 2% by mass
[0271] Measuring device: ABE1024-5V 0.1A-4 charge/discharge test
device (manufactured by ElectroField Co., Ltd.) [0272]
Charge/discharge conditions
[0273] First Cycle
[0274] Charge constant current constant voltage 0.1 C 0.02 V 15
hours termination
[0275] Discharge constant current 0.1 C 1.5 V termination
[0276] After Second Cycle
[0277] Charge constant current constant voltage 0.5 C 0.02 V 3
hours termination
[0278] Discharge constant current 0.5 C 1.5 V termination
[0279] The capacity retention rate (%) after 20 cycles was
calculated using the following formula, from the values of the
discharge capacity of the negative electrode (the electrode
obtained in (2)) after the first charge/discharge and 20
cycles.
[0280] Capacity retention rate (%)=discharge capacity after 20
cycles/discharge capacity after first
charge/discharge.times.100
Experimental Examples 10 to 16
[0281] Coin cell batteries were produced in the same manner as in
Experimental Example 9, except that each of the binder aqueous
solutions 2 to 8 obtained in Examples 2 to 8 was used instead of
the binder aqueous solution 1, and the capacity retention rate (%)
after 20 cycles was calculated in a charge/discharge test.
[0282] Comparative Experimental Examples 4 to 6
[0283] Coin cell batteries were produced in the same manner as in
Experimental Example 9, except that each of the binder aqueous
solutions 101 to 103 obtained in Comparative Examples 1 to 3 was
used instead of the binder aqueous solution 1, and the capacity
retention rate (%) after 20 cycles was calculated in a
charge/discharge test.
[0284] Table 2 shows the tan .delta. values obtained in
Experimental Examples 1 to 8 and Comparative Experimental Examples
1 to 3, and the capacity retention rates obtained in Experimental
Examples 9 to 16 and Comparative Experimental Examples 4 to 6.
TABLE-US-00008 TABLE 2 Capacity Experimental Example Binder aqueous
solution (Example) tan.delta. retention rate (%) Experimental
Example 1.cndot.9 Binder aqueous solution 1 (Example 1) 1.83 84
Experimental Example 2.cndot.10 Binder aqueous solution 2 (Example
2) 1.20 84 Experimental Example 3.cndot.11 Binder aqueous solution
3 (Example 3) 1.05 83 Experimental Example 4.cndot.12 Binder
aqueous solution 4 (Example 4) 1.40 84 Experimental Example
5.cndot.13 Binder aqueous solution 5 (Example 5) 1.50 89
Experimental Example 6.cndot.14 Binder aqueous solution 6 (Example
6) 1.30 94 Experimental Example 7.cndot.15 Binder aqueous solution
7 (Example 7) 1.71 94 Experimental Example 8.cndot.16 Binder
aqueous solution 8 (Example 8) 2.18 94 Comparative Experimental
Binder aqueous solution 101 (Comparative 0.054 72 Example 1.cndot.4
Example 1) Comparative Experimental Binder aqueous solution 102
(Comparative 0.15 49 Example 2.cndot.5 Example 2) Comparative
Experimental Binder aqueous solution 103 (Comparative 0.83 58
Example 3.cndot.6 Example 3)
[0285] From Table 2, in a case of the binder aqueous solutions 1 to
8 obtained in Examples 1 to 8, the tan .delta. of the slurry for
measurement showed a value larger than 1, and the capacity
retention rate in the charge/discharge test was 80% or more. This
is considered to be due to the fact that the binder having tan
.delta.>1 under the measurement conditions in the first
invention was excellent in the dispersibility of the conductive
assistant, and therefore the battery using this binder was able to
maintain good battery characteristics even after 20 cycles of
charge and discharge.
[0286] On the other hand, in a case of the binder aqueous solutions
101 to 103 obtained in Comparative Examples 1 to 3, the tan .delta.
of the slurry for measurement was 1 or less, and the capacity
retention rate in the charge/discharge test was less than 80%. This
is considered to be due to the fact that the dispersibility of the
conductive assistant was insufficient with the binder having tan
.delta..ltoreq.1 under the measurement conditions in the first
invention, and therefore the battery using this binder could not
sufficiently transmit electrons.
Example 9
[0287] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 280 parts by mass of ion exchange water, 4 parts by mass
(0.06 mol) of acrylic acid (manufactured by Toagosei Co., Ltd.),
and 36 parts by mass (0.76 mol) of 2-hydroxyethyl acrylate
(manufactured by Osaka Organic Chemical Industry Ltd.), followed by
heating under a nitrogen stream until the internal temperature
reached 77.degree. C. Next, 0.31 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
(trade name: VA-057, manufactured by FUJIFILM Wako Pure Chemical
Corporation) were added thereto, and the obtained solution was
reacted at 77.degree. C. for 4 hours. After the reaction was
complete, the reaction solution was cooled to room temperature, and
an aqueous solution prepared by adding 40 parts by mass of ion
exchange water to 4.6 parts by mass of pentylamine (manufactured by
FUJIFILM Wako Pure Chemical Corporation) was added dropwise to
obtain a binder aqueous solution 9 (solid content: 14%).
Examples 10 to 34
[0288] Binder aqueous solutions 10 to 34 were obtained in the same
manner as in Example 9, except that each of amines shown in Table 3
below was used instead of 4.6 parts by mass of pentylamine.
TABLE-US-00009 TABLE 3 Amount Number used Degree of of basic Amine
(parts neutralization Molecular functional value Example Amine name
by mass) (%) weight groups (meq./g) Example 9 Pentylamine 4.60 95
87.16 1 11.5 Example 10 Octylamine 6.82 95 129.24 1 7.7 Example 11
Dibutylamine 6.82 95 129.24 1 7.7 Example 12 Benzylamine 5.65 95
107.15 1 9.3 Example 13 Aniline 4.91 95 93.13 1 10.7 Example 14
Ethanolamine 3.22 95 61.08 1 16.4 Example 15
N,N-diethylethanolamine 6.18 95 117.19 1 8.5 Example 16
Benzyltrimethylammonium hydroxide 8.82 95 167.25 1 6.0 Example 17
Tetrabutylammonium hydroxide 13.68 95 259.47 1 3.9 Example 18
Tetrabutylphosphonium hydroxide 14.58 95 276.44 1 3.6 Example 19
Diazabicycloundecene 8.03 95 152.24 1 6.6 Example 20
Diisopropylethylamine 6.82 95 129.30 1 7.7 Example 21
Tris(2-cyanoethyl)amine 9.29 95 176.22 1 5.7 Example 22
Bis(2-cyanoethyl)amine 6.49 95 123.16 1 8.1 Example 23
3-Aminopropionitrile 3.70 95 70.09 1 14.3 Example 24
3-Methoxypropylamine 4.70 95 89.14 1 11.2 Example 25
3-Aminotriazole 4.43 95 84.08 1 11.9 Example 26 3,5-Diaminotriazole
5.23 95 99.10 2 20.2 Example 27 4-Dimethylaminopyridine 6.44 95
122.17 2 16.4 Example 28 JEFFAMINE (registered trademark) D-400
11.80 95 (400) 2 4.5 Example 29 JEFFAMINE (registered trademark)
ED-600 16.13 95 (600) 2 3.3 Example 30 Polyethyleneimine 2.27 95
43.07 .asterisk-pseud.per 1 23.2 monomer unit Example 31
Ethylenediamine 1.58 95 60.10 2 33.3 Example 32 1,2-Propanediamine
1.95 95 74.12 2 27.0 Example 33 N-Methyl-1,3-propanediamine 2.32 95
88.15 2 22.7 Example 34 Tris(2-aminoethyl)amine 1.93 95 146.23 4
27.4
Example 35
[0289] To a 1000 mL separable flask equipped with a stirrer, a
cooling pipe, a thermometer, and a nitrogen introduction pipe were
added 320 parts by mass of ion exchange water, 20 parts by mass
(0.28 mol) of acrylic acid (manufactured by Toagosei Co., Ltd.), 20
parts by mass (0.43 mol) of 2-hydroxyethyl acrylate (manufactured
by Osaka Organic Chemical Industry Ltd.), and 0.19 parts by mass
(0.0013 mol) of N,N-methylenebisacrylamide (manufactured by
FUJIFILM Wako Pure Chemical Corporation), followed by heating under
a nitrogen stream until the internal temperature reached 77.degree.
C. Next, 0.31 parts by mass of
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate
(trade name: VA-057, manufactured by FUJIFILM Wako Pure Chemical
Corporation) were added thereto, and the obtained solution was
reacted at 77.degree. C. for 4 hours. After the reaction was
complete, the reaction solution was cooled to room temperature, an
aqueous solution prepared by adding 40 parts by mass of ion
exchange water to 18.5 parts by mass of 48% sodium hydroxide
aqueous solution (manufactured by Toagosei Co., Ltd.) was added
dropwise, and then an aqueous solution prepared by adding 40 parts
by mass of ion exchange water to 3.6 parts by mass of pentylamine
(manufactured by FUJIFILM Wako Pure Chemical Corporation) was added
dropwise to obtain a binder aqueous solution 35 (solid content:
11%).
Examples 36 to 39
[0290] Binder aqueous solutions 36 to 39 were obtained in the same
manner as in Example 35, except that each of the amines shown in
Table 4 below was used instead of 3.6 parts by mass of
pentylamine.
TABLE-US-00010 TABLE 4 Number of Degree of basic Amine Amount used
neutralization (%) Molecular functional value Example Concomitant
amine name (parts by mass) Amine NaOH weight groups (meq./g)
Example 35 Pentylamine 0.73 15 80 87.16 1 11.5 Example 36
3-Methoxypropylamine 0.74 15 80 89.14 1 11.2 Example 37
3-Aminotriazole 0.70 15 80 84.08 1 11.9 Example 38
3,5-Diaminotriazole 0.83 15 80 99.10 2 20.2 Example 39 JEFFAMINE
(registered trademark) ED-600 2.55 15 80 (600) 2 3.3
Experimental Example 17
[0291] (1) Preparation of Slurry Composition and Production of
Electrode for Lithium Secondary Battery
[0292] An electrode for a lithium secondary battery was produced in
the same manner as in (1) Preparation of slurry composition and (2)
Production of electrode for lithium secondary battery in
Experimental Example 9, except that the binder aqueous solution 9
obtained in Example 9 was used instead of the binder aqueous
solution 1.
[0293] (2) Bend Resistance Test
[0294] The electrode produced in (1) was cut out to a size of 10
mm.times.100 mm and set in a mandrel tester (BEVS1603 cylindrical
bending tester). Then, the diameter of the mandrel rod around which
the electrode was wound was gradually reduced from 32 mm, and the
diameter at which the electrode cracked (mandrel diameter) was
measured. The case where the mandrel diameter was 2 mm to 6 mm was
evaluated as A; the case where the mandrel diameter was 7 mm to 9
mm was evaluated as B; the case where the mandrel diameter was 10
mm to 12 mm was evaluated as C; and the case where the mandrel
diameter was 13 mm or more was evaluated as D.
[0295] (3) Production of Coin Cell Battery
[0296] A coin cell battery was produced in a glove box filled with
argon. Here, a coin cell battery consisting of the electrode
obtained in (1), a lithium foil electrode, a solution of 2% by mass
of vinylene carbonate (VC) added to ethylene carbonate
(EC)/dimethyl carbonate (DMC) (volume ratio=1:1) containing 1 M
LiPF.sub.6, and a separator was assembled.
[0297] (4) Charge/Discharge Test
[0298] A charge/discharge test was carried out using the coin cell
battery produced in (3), under the same conditions as those
described in (4) Charge/discharge test of Experimental Example
9.
Experimental Examples 18 to 42
[0299] The bend resistance test and the charge/discharge test were
carried out in the same manner as in Experimental Example 17,
except that each of the binder aqueous solutions 10 to 34 obtained
in Examples 10 to 34 was used instead of the binder aqueous
solution 9.
[0300] Table 4 shows the evaluation results obtained in the bend
resistance test in Experimental Examples 17 to 42 and the capacity
retention rates obtained in the charge/discharge test in
Experimental Examples 17 to 42.
TABLE-US-00011 TABLE 5 Amine Mandrel Capacity Experimental value
diameter retention Example Example Amine name (meq./g) evaluation
rate (%) Experimental Example 9 Pentylamine 9.9 B 94 Example 17
Experimental Example 10 Octylamine 7.7 B 92 Example 18 Experimental
Example 11 Dibutylamine 7.7 B 91 Example 19 Experimental Example 12
Benzylamine 9.3 B 90 Example 20 Experimental Example 13 Aniline
10.7 B 89 Example 21 Experimental Example 14 Ethanolamine 16.4 A 91
Example 22 Experimental Example 15 N,N-diethylethanolamine 8.5 A 91
Example 23 Experimental Example 16 Benzyltrimethylammonium
hydroxide 6.0 A 85 Example 24 Experimental Example 17
Tetrabutylammonium hydroxide 3.9 A 84 Example 25 Experimental
Example 18 Tetrabutylphosphonium hydroxide 3.6 A 82 Example 26
Experimental Example 19 Diazabicycloundecene 6.6 B 90 Example 27
Experimental Example 20 Diisopropylethylamine 7.7 A 92 Example 28
Experimental Example 21 Tris(2-cyanoethyl)amine 5.7 B 97 Example 29
Experimental Example 22 Bis(2-cyanoethyl)amine 8.1 B 97 Example 30
Experimental Example 23 3-Aminopropionitrile 14.3 C 98 Example 31
Experimental Example 24 3-Methoxypropylamine 11.2 A 93 Example 32
Experimental Example 25 3-Aminotriazole 11.9 A 97 Example 33
Experimental Example 26 3,5-Diaminotriazole 20.2 A 98 Example 34
Experimental Example 27 4-Dimethylaminopyridine 16.4 B 90 Example
35 Experimental Example 28 JEFFAMINE D-400 4.5 A 96 Example 36
Experimental Example 29 JEFFAMINE ED-600 3.3 A 87 Example 37
Experimental Example 30 Polyethyleneimine 23.2 D 95 Example 38
Experimental Example 31 Ethylenediamine 33.3 D 86 Example 39
Experimental Example 32 1,2-Propanediamine 27.0 D 86 Example 40
Experimental Example 33 N-Methyl-1,3-propanediamine 22.7 D 84
Example 41 Experimental Example 34 Tris(2-aminoethyl)amine 27.4 D
86 Example 42
Experimental Examples 43 to 47
[0301] The bend resistance test and the charge/discharge test were
carried out in the same manner as in Experimental Example 17,
except that each of the binder aqueous solutions 35 to 39 obtained
in Examples 35 to 39 was used instead of the binder aqueous
solution 9.
[0302] Table 6 shows the evaluation results obtained in the bend
resistance test in Experimental Examples 43 to 47 and the capacity
retention rates obtained in the charge/discharge test in
Experimental Examples 43 to 47.
TABLE-US-00012 TABLE 6 Capacity Amine Mandrel retention
Experimental value diameter rate Example Example Concomitant amine
name (meq./g) evaluation (%) Experimental Example 35 Pentylamine
11.5 B 94 Example 43 Experimental Example 36 3-Methoxypropylamine
11.2 A 93 Example 44 Experimental Example 37 3-Aminotriazole 11.9 A
92 Example 45 Experimental Example 38 3,5-Diaminotriazole 20.2 A 93
Example 46 Experimental Example 39 JEFFAMINE 3.3 A 86 Example 47
(registered trademark) ED-600
[0303] From Table 5, in a case of the electrodes (Experimental
Examples 17 to 34) using the binder aqueous solutions 9 to 29
obtained in Examples 9 to 29, the mandrel diameter evaluation was A
to C, the bend resistance was high, and the capacity retention rate
was 80% or more. It is considered that the hydrophobic group of the
amine used for neutralization lowered the glass transition point of
the binder to make the binder flexible, thereby increasing the bend
resistance. In addition, it is considered that good battery
characteristics were maintained since the structure was similar to
that of the first invention.
[0304] In addition, from Table 6, in a case of the electrodes
(Experimental Examples 43 to 47) using the binder aqueous solutions
35 to 39 obtained in Examples 35 to 39, the mandrel diameter
evaluation was A to B, the bend resistance was high, and the
capacity retention rate was 85% or more. Therefore, it is
considered that the bend resistance was improved because the effect
of reducing the glass transition point of the binder is exhibited
as in the electrodes of Experimental Examples 17 to 34, even in a
case where the molar ratios of the monomer of (i) to the monomer of
(ii) and the presence or absence of the crosslinking structure are
different.
[0305] On the other hand, in a case of the electrodes (Experimental
Examples 38 to 42) using the binder aqueous solutions 30 to 34
obtained in Examples 30 to 34, the mandrel diameter evaluation was
D and the bend resistance was deteriorated. It is considered that
polyvalent amines having a high amine value had a short distance
between the neutralizing amines, and therefore the binder became
rigid, the electrode became hard, and the bend resistance
deteriorated.
* * * * *