U.S. patent application number 13/034067 was filed with the patent office on 2011-09-29 for conjugated diene polymer rubber, and conjugated diene polymer rubber composition.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Toru FUJII, Katsunari INAGAKI, Mayumi OSHIMA, Takuya SUDO.
Application Number | 20110237737 13/034067 |
Document ID | / |
Family ID | 44489186 |
Filed Date | 2011-09-29 |
United States Patent
Application |
20110237737 |
Kind Code |
A1 |
FUJII; Toru ; et
al. |
September 29, 2011 |
CONJUGATED DIENE POLYMER RUBBER, AND CONJUGATED DIENE POLYMER
RUBBER COMPOSITION
Abstract
A conjugated diene polymer rubber is provided that includes
component (A) and component (B) below, component (A) having a
content, with the total amount of component (A) and component (B)
as 100% by weight, of from 5% to 90% by weight, and component (B)
having a content of from 95% to 10% by weight, Component (A): a
conjugated diene polymer rubber component modified with a carbonyl
group- and substituted amino group-containing compound Component
(B): a conjugated diene polymer rubber component modified with a
compound represented by formula (IIa) below
(R.sup.21O).sub.mSi(R.sup.22A).sub.nR.sup.23.sub.4-m-n (IIa)
wherein m denotes a number from 1 to 3, n denotes a number from 1
to 3, m+n is from 2 to 4, R.sup.21 and R.sup.23 denote a
hydrocarbyl group, R.sup.22 denotes a hydrocarbylene group, A
denotes a substituted amino group or an optionally substituted
hydrocarbyloxy group, when there are a plurality of R.sup.21s the
plurality of R.sup.21s may be identical to or different from each
other, when there are a plurality of R.sup.22s the plurality of
R.sup.22s may be identical to or different from each other, when
there are a plurality of R.sup.23s the plurality of R.sup.23s may
be identical to or different from each other, and when there are a
plurality of As the plurality of As may be identical to or
different from each other.
Inventors: |
FUJII; Toru; (Chiba-shi,
JP) ; SUDO; Takuya; (Ichihara-shi, JP) ;
OSHIMA; Mayumi; (Yokohama-shi, JP) ; INAGAKI;
Katsunari; (Ichihara-shi, JP) |
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
Tokyo
JP
|
Family ID: |
44489186 |
Appl. No.: |
13/034067 |
Filed: |
February 24, 2011 |
Current U.S.
Class: |
524/526 ;
525/209; 525/236 |
Current CPC
Class: |
C08C 19/44 20130101;
C08F 236/04 20130101; C08K 5/548 20130101; C08F 279/02 20130101;
C08K 3/36 20130101; C08L 19/006 20130101; C08L 15/00 20130101; C08F
4/48 20130101; C08L 2666/08 20130101; C08F 236/04 20130101; C08L
15/00 20130101 |
Class at
Publication: |
524/526 ;
525/236; 525/209 |
International
Class: |
C08L 83/00 20060101
C08L083/00; C08L 9/00 20060101 C08L009/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 26, 2010 |
JP |
2010-041901 |
Feb 26, 2010 |
JP |
2010-041902 |
Claims
1. A conjugated diene polymer rubber comprising component (A) and
component (B) below, component (A) having a content, with the total
amount of component (A) and component (B) as 100% by weight, of
from 5 to 90% by weight, and component (B) having a content of from
95 to 10% by weight, component (A): a conjugated diene polymer
rubber component modified with a carbonyl group- and substituted
amino group-containing compound component (B): a conjugated diene
polymer rubber component modified with a compound represented by
formula (IIa) below
(R.sup.21O).sub.mSi(R.sup.22A).sub.nR.sup.23.sub.4-m-n (IIa)
wherein m denotes a number from 1 to 3, n denotes a number from 1
to 3, m+n is from 2 to 4, R.sup.21 and R.sup.23 denote a
hydrocarbyl group, R.sup.22 denotes a hydrocarbylene group, A
denotes a substituted amino group or an optionally substituted
hydrocarbyloxy group, when there are a plurality of R.sup.21s the
plurality of R.sup.21s may be identical to or different from each
other, when there are a plurality of R.sup.22s the plurality of
R.sup.22s may be identical to or different from each other, when
there are a plurality of R.sup.23s the plurality of R.sup.23s may
be identical to or different from each other, and when there are a
plurality of As the plurality of As may be identical to or
different from each other.
2. The rubber according to claim 1, wherein the carbonyl group- and
substituted amino group-containing compound is a compound
represented by formula (Ia) below, ##STR00011## wherein Z.sup.1 and
Z.sup.2 denote a substituted amino group-containing group, a
hydrogen atom, an optionally substituted hydrocarbyl group, or an
optionally substituted hydrocarbyloxy group, at least one of
Z.sup.1 and Z.sup.2 is a substituted amino group-containing group,
or Z.sup.1 and Z.sup.2 are bonded to each other and denote a group
in which a substituted amino group-containing ring structure is
formed by Z.sup.1, Z.sup.2, and the carbonyl carbon.
3. The rubber according to claim 2, wherein at least one of Z.sup.1
and Z.sup.2 of formula (Ia) is a group represented by formula (Ib)
below, * T .sub.pR.sup.4--NR.sup.5.sub.2 (Ib) wherein p denotes 0
or 1, T denotes an oxygen atom or --NR.sup.6-- (R.sup.6 denotes a
hydrocarbyl group or a hydrogen atom), R.sup.4 denotes a
hydrocarbylene group, R.sup.5 denotes a hydrocarbyl group that may
contain a nitrogen atom and/or an oxygen atom (the two R.sup.5s may
be identical to or different from each other), a group having 2 to
20 carbon atoms in which the two R.sup.5s form a single group and
are bonded to the nitrogen atom via a double bond, or a divalent
group having 2 to 20 carbon atoms in which the two R.sup.5s are
bonded to each other, and * represents a bonding position.
4. The rubber according to claim 1, wherein the carbonyl group- and
substituted amino group-containing compound is a compound
represented by formula (I-3) below, ##STR00012## wherein R.sup.5
denotes a hydrocarbyl group that may contain a nitrogen atom and/or
an oxygen atom (the two R.sup.5s may be identical to or different
from each other), a group having 2 to 20 carbon atoms in which the
two R.sup.5s form a single group and are bonded to the nitrogen
atom via a double bond, or a divalent group having 2 to 20 carbon
atoms in which the two R.sup.5s are bonded to each other, q denotes
an integer from 1 to 10, T denotes an oxygen atom or --NR.sup.6--
(R.sup.6 denotes a hydrocarbyl group or a hydrogen atom), and
R.sup.8 denotes an optionally substituted hydrocarbyl group or a
hydrogen atom.
5. The rubber according to claim 1, wherein the compound
represented by formula (IIa) is a
[3-(dialkylamino)propyl]trialkoxysilane.
6. The rubber according to claim 1, wherein component (A) and/or
component (B) comprise a constituent unit based on a
silicon-containing monomer.
7. The rubber according to claim 6, wherein the silicon-containing
monomer is a monomer represented by formula (X) below, ##STR00013##
wherein X.sup.1, X.sup.2, and X.sup.3 denote an optionally
substituted hydrocarbyl group or a group represented by formula
(Xa) below, and at least one of X.sup.1, X.sup.2, and X.sup.3 is a
group represented by formula (Xa) below, ##STR00014## wherein R'
and R'' denote a hydrocarbyl group having 1 to 6 carbon atoms that
may contain at least one atom selected from the group consisting of
a nitrogen atom, an oxygen atom, and a silicon atom, a silyl group,
a substituted silyl group, or a divalent group having 2 to 12
carbon atoms in which R' and R'' are bonded to each other, and *
represents a bonding position.
8. The rubber according to claim 1, wherein the conjugated diene
polymer rubber has a vinyl bond content, with the conjugated
diene-based constituent unit content as 100% by mole, of not less
than 20% by mole and not more than 70% by mole.
9. A conjugated diene polymer rubber composition comprising the
conjugated diene polymer rubber according to claim 1 and a filler,
the filler having a content of from 10 to 150 parts by weight per
100 parts by weight of the conjugated diene polymer rubber.
Description
TECHNICAL FIELD
[0001] The present invention relates to a conjugated diene polymer
rubber, and a conjugated diene polymer rubber composition.
BACKGROUND ART
[0002] In recent years, with the growing concern over environmental
problems the demand for good fuel economy for automobiles has been
becoming stronger, and there is also a demand for excellent fuel
economy for rubber composition used for automobile tires. As a
rubber composition for automobile tires, a polymer rubber
composition comprising a conjugated diene polymer rubber such as
polybutadiene rubber or a butadiene-styrene copolymer rubber and a
filler such as carbon black or silica, etc. is used.
[0003] For example, as a conjugated diene polymer rubber, a rubber
composition employing a polymer rubber formed by modifying with a
dialkylamino group-containing acrylamide one terminus of a polymer
rubber formed by copolymerizing butadiene and styrene using an
alkyllithium as a polymerization initiator (see e.g. JP-A 1-217047
(JP-A denotes a Japanese unexamined patent application
publication)), as a conjugated diene polymer rubber, a rubber
composition employing a polymer rubber formed by modifying with a
dialkylamino group-containing alkoxysilane one terminus of a
polymer formed by copolymerizing butadiene and styrene using an
alkyllithium as a polymerization initiator (see e.g. JP-A 63-186748
and JP-A 2005-290355), etc. have been proposed as polymer
compositions having good fuel economy.
DISCLOSURE OF THE INVENTION
[0004] However, the rubber composition employing the
above-mentioned conventional conjugated diene polymer rubber is not
always fully satisfactory in terms of abrasion resistance.
[0005] Under such circumstances, it is an object of the present
invention to provide a conjugated diene polymer rubber that can
give a conjugated diene polymer rubber composition having excellent
abrasion resistance and a conjugated diene polymer rubber
composition containing the conjugated diene polymer rubber and a
filler.
[0006] A first aspect of the present invention relates to a
conjugated diene polymer rubber comprising component (A) and
component (B) below, component (A) having a content, with the total
amount of component (A) and component (B) as 100% by weight, of
from 5 to 90% by weight, and component (B) having a content of from
95 to 10% by weight, component (A): a conjugated diene polymer
rubber component modified with a carbonyl group- and substituted
amino group-containing compound component (B): a conjugated diene
polymer rubber component modified with a compound represented by
formula (IIa) below,
(R.sup.21O).sub.mSi(R.sup.22A).sub.nR.sup.23.sub.4-m-n (IIa)
wherein m denotes a number from 1 to 3, n denotes a number from 1
to 3, m+n is from 2 to 4, R.sup.21 and R.sup.23 denote a
hydrocarbyl group, R.sup.22 denotes a hydrocarbylene group, A
denotes a substituted amino group or an optionally substituted
hydrocarbyloxy group, when there are a plurality of R.sup.21s the
plurality of R.sup.21s may be identical to or different from each
other, when there are a plurality of R.sup.22s the plurality of
R.sup.22s may be identical to or different from each other, when
there are a plurality of R.sup.23s the plurality of R.sup.23s may
be identical to or different from each other, and when there are a
plurality of As the plurality of As may be identical to or
different from each other.
[0007] A second aspect of the present invention relates to a
conjugated diene polymer rubber composition comprising the
conjugated diene polymer rubber and a filler.
MODE FOR CARRYING OUT THE INVENTION
Conjugated Diene Polymer Rubber
[0008] The conjugated diene polymer rubber of the present invention
is a diene polymer rubber comprising component (A) and component
(B) below, component (A) having a content, with the total amount of
component (A) and component (B) as 100% by weight, of from 5 to 90%
by weight, and component (B) having a content of from 95 to 10% by
weight.
Component (A)
[0009] Component (A) is a conjugated diene polymer rubber component
that is modified with a carbonyl group- and substituted amino
group-containing compound.
[0010] A conjugated diene polymer rubber component in component (A)
contains a conjugated diene based monomer unit (conjugated unit).
Examples of the conjugated diene include 1,3-butadiene, isoprene,
1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and
one or more types thereof may be used. The conjugated diene is
preferably 1,3-butadiene or isoprene.
[0011] The conjugated diene polymer rubber component of component
(A) may further comprise, in addition to the conjugated diene-based
constituent unit (conjugated diene unit), a constituent unit based
on another monomer. Examples of said other monomer include an
aromatic vinyl, a vinylnitrile, and an unsaturated carboxylic acid
ester. Examples of the aromatic vinyl include styrene,
.alpha.-methylstyrene, vinyltoluene, vinylnaphthalene,
divinylbenzene, trivinylbenzene, and divinylnaphthalene. Examples
of the vinylnitrile include acrylonitrile, and examples of the
unsaturated carboxylic acid ester include methyl acrylate, ethyl
acrylate, methyl methacrylate, and ethyl methacrylate. Among them,
an aromatic vinyl is preferable, and styrene is more
preferable.
[0012] In order to increase strength the conjugated diene polymer
of component (A) preferably contains an aromatic vinyl-based
constituent unit (aromatic vinyl unit), and the content of the
aromatic vinyl unit, relative to 100% by weight of the total amount
of the conjugated diene unit and the aromatic vinyl unit, is
preferably at least 10% by weight (the content of the conjugated
diene unit being no greater than 90% by weight), and more
preferably at least 15% by weight (the content of the conjugated
diene unit being no greater than 85% by weight). Furthermore, from
the viewpoint of fuel economy, the content of the aromatic vinyl
unit is preferably no greater than 50% by weight (the content of
the conjugated diene unit being at least 50% by weight), and more
preferably no greater than 45% by weight (the content of the
conjugated diene unit being at least 55% by weight).
[0013] In order to improve abrasion resistance and fuel economy,
the conjugated diene polymer rubber component of component (A)
preferably contains a constituent unit based on a
silicon-containing monomer.
[0014] The silicon-containing monomer is preferably a monomer
represented by formula (X) below,
##STR00001##
wherein X.sup.1, X.sup.2, and X.sup.3 denote an optionally
substituted hydrocarbyl group or a group represented by formula
(Xa) below, and at least one of X.sup.1, X.sup.2, and X.sup.3 is a
group represented by formula (Xa) below,
##STR00002##
wherein R' and R'' denote a hydrocarbyl group having 1 to 6 carbon
atoms that may contain at least one atom selected from the group
consisting of a nitrogen atom, an oxygen atom, and a silicon atom,
a silyl group, a substituted silyl group, or a divalent group
having 2 to 12 carbon atoms in which R' and R'' are bonded to each
other, and * denotes a bonding position.
[0015] In the present specification, the hydrocarbyl group denotes
a hydrocarbon residue. The substituted hydrocarbyl group (the
hydrocarbyl group containing a substituent) denotes a group in
which at least one hydrogen atom of the hydrocarbon residue is
replaced by a substituent. The hydrocarbyloxy group denotes a group
in which the hydrogen atom of a hydroxy group is replaced by a
hydrocarbyl group, and the substituted hydrocarbyloxy group (the
hydrocarbyloxy group containing a substituent) denotes a group in
which at least one hydrogen atom of a hydrocarbyloxy group is
replaced by a substituent. The substituted silyl group denotes a
group in which at least one hydrogen atom of a silyl group is
replaced by a substituent.
[0016] In formula (X), X.sup.1, X.sup.2, and X.sup.3 denote an
optionally substituted hydrocarbyl group or a group represented by
formula (Xa) below, and at least one of X.sup.1, X.sup.2, and
X.sup.3 is a group represented by formula (Xa) above.
[0017] Examples of the hydrocarbyl groups denoted by X.sup.1,
X.sup.2, and X.sup.3 include an alkyl group such as a methyl group,
an ethyl group, an n-propyl group, an isopropyl group, an n-butyl
group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a
neopentyl group, an isopentyl group, or an n-hexyl group; a
cycloalkyl group such as a cyclohexyl group; an aryl group such as
a phenyl group, a methylphenyl group, or an ethylphenyl group; and
an aralkyl group such as a benzyl group. The hydrocarbyl group is
preferably an alkyl group.
[0018] The number of carbon atoms of the hydrocarbyl groups denoted
by X.sup.1, X.sup.2, and X.sup.3 is preferably from 1 to 4, and
more preferably 1 or 2.
[0019] Examples of the substituted hydrocarbyl groups denoted by
X.sup.1, X.sup.2, and X.sup.3 include an alkoxyalkyl group such as
a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group,
or an ethoxyethyl group.
[0020] The substituted hydrocarbyl group is preferably an
alkoxyalkyl group, and more preferably an alkoxyalkyl group having
2 to 4 carbon atoms.
[0021] The number of carbon atoms of the substituted hydrocarbyl
groups denoted by X.sup.1, X.sup.2, and X.sup.3 is preferably from
1 to 4.
[0022] R' and R'' of formula (Xa) are hydrocarbyl groups having 1
to 6 carbon atoms that may contain at least one atom selected from
the group consisting of a nitrogen atom, an oxygen atom, and a
silicon atom, silyl groups, substituted silyl groups, or divalent
groups having 2 to 12 carbon atoms in which R' and R'' are bonded
to each other.
[0023] Examples of the hydrocarbyl group having 1 to 6 carbon atoms
denoted by R' and R'' include an alkyl group such as a methyl
group, an ethyl group, an n-propyl group, an isopropyl group, an
n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl
group, a neopentyl group, an isopentyl group, or an n-hexyl group;
a cycloalkyl group such as a cyclohexyl group; and a phenyl group.
It is preferably an alkyl group, more preferably an alkyl group
having 1 to 4 carbon atoms, and yet more preferably a methyl group,
an ethyl group, an n-propyl group, or an n-butyl group.
[0024] Examples of the nitrogen atom-containing hydrocarbyl group
denoted by R' and R'' include a dialkylaminoalkyl group such as a
dimethylaminomethyl group, a dimethylaminoethyl group, a
dimethylaminopropyl group, or a diethylaminoethyl group.
[0025] Examples of the oxygen atom-containing hydrocarbyl group
denoted by R' and R'' include an alkoxyalkyl group such as a
methoxymethyl group, a methoxyethyl group, a methoxypropyl group,
an ethoxymethyl group, or an ethoxyethyl group. It is preferably an
alkoxyalkyl group, and more preferably an alkoxyalkyl group having
2 to 4 carbon atoms.
[0026] Examples of the silicon atom-containing hydrocarbyl group
denoted by R' and R'' include a trialkylsilylalkyl group such as a
trimethylsilylmethyl group.
[0027] Examples of the substituted silyl group denoted by R' and
R'' include a trialkylsilyl group such as a trimethylsilyl group, a
triethylsilyl group, or a t-butyldimethylsilyl group. The
substituted silyl group is preferably a trialkylsilyl group, and
more preferably a trimethylsilyl group.
[0028] Examples of the divalent group having 2 to 12 carbon atoms
in which R' and R'' are bonded to each other include an alkylene
group such as a methylene group, an ethylene group, a trimethylene
group, a tetramethylene group, a pentamethylene group, or a
hexamethylene group; an alkenylene group such as a group
represented by --CH.dbd.CH--CH.dbd.CH--; a nitrogen-containing
group such as a group represented by
--CH.sub.2CH.sub.2--NH--CH.sub.2--, a group represented by
--CH.dbd.CH--N.dbd.CH--, a group represented by
--CH.sub.2CH.sub.2--N.dbd.CH--, a group represented by
--CH.sub.2CH.sub.2CH.sub.2--NH--, a group represented by
--CH.dbd.CHCH.dbd.N--, or a group represented by
--CH.sub.2CH.sub.2--NH--CH.sub.2CH.sub.2--; and an
oxygen-containing group such as a group represented by
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2-- or a group represented by
--CH.sub.2CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2CH.sub.2--.
[0029] R' and R'' are preferably alkyl groups, alkoxyalkyl groups,
substituted silyl groups or a divalent group in which R' and R''
are bonded to each other, and are more preferably alkyl groups.
[0030] As the group represented by formula (Xa), an acyclic amino
group and a cyclic amino group can be cited.
[0031] Examples of the acyclic amino group include a dialkylamino
group such as a dimethylamino group, a diethylamino group, a
di(n-propyl)amino group, a di(isopropyl)amino group, a
di(n-butyl)amino group, a di(sec-butyl)amino group, a
di(tert-butyl)amino group, a di(neopentyl)amino group, or an
ethylmethylamino group; a dialkoxyalkylamino group such as a
di(methoxyethyl)amino group, a di(ethoxymethyl)amino group, or
di(ethoxyethyl)amino group; and a di(trialkylsilyl)amino group such
as a di(trimethylsilyl)amino group.
[0032] Examples of the cyclic amino group include a
1-polymethyleneimino group such as a 1-aziridinyl group, a
1-azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group,
a 1-hexamethyleneimino group, a 1-heptamethyleneimino group, a
1-octamethyleneimino group, a 1-decamethyleneimino group, or a
1-dodecamethyleneimino group. Furthermore, examples of the cyclic
amino group also include a 1-pyrrolyl group, a 1-imidazolidinyl
group, a 1-imidazolyl group, a 4,5-dihydro-1-imidazolyl group, a
1-pyrazolidinyl group, a 1-pyrazolyl group, a 1-piperazinyl group,
and a morpholino group.
[0033] The group represented by formula (Xa) is preferably an
acyclic amino group, and more preferably a dialkyl amino group.
[0034] At least one of X.sup.1, X.sup.2, and X.sup.3 of formula (X)
is a group represented by formula (Xa). It is preferable that two
or more of X.sup.1, X.sup.2, and X.sup.3 are a group represented by
formula (Xa), and it is more preferable that two of X.sup.1,
X.sup.2, and X.sup.3 are a group represented by formula (Xa).
[0035] With regard to the compound represented by formula (X), as
compounds in which one of X.sup.1 to X.sup.3 is an acyclic amino
group represented by formula (Xa) and two thereof are a hydrocarbyl
group or a substituted hydrocarbyl group there can be cited a
(dialkylamino)dialkylvinylsilane, a
{di(trialkylsilyl)amino}dialkylvinylsilane, and a
(dialkylamino)dialkoxyalkylvinylsilane.
[0036] Examples of the (dialkylamino)dialkylvinylsilane include
(dimethylamino)dimethylvinylsilane,
(ethylmethylamino)dimethylvinylsilane,
(diethylamino)dimethylvinylsilane,
(ethyl-n-propylamino)dimethylvinylsilane,
(ethylisopropylamino)dimethylvinylsilane,
di(n-propyl)aminodimethylvinylsilane,
(diisopropylamino)dimethylvinylsilane,
(n-butyl-n-propylamino)dimethylvinylsilane,
di(n-butyl)aminodimethylvinylsilane,
(dimethylamino)diethylvinylsilane,
di(tert-butyl)aminodimethylvinylsilane,
(dimethylamino)diethylvinylsilane,
(ethylmethylamino)diethylvinylsilane,
(diethylamino)diethylvinylsilane,
(ethyl-n-propylamino)diethylvinylsilane,
(ethylisopropylamino)diethylvinylsilane,
di(n-propyl)aminodiethylvinylsilane,
(diisopropylamino)diethylvinylsilane,
(n-butyl-n-propylamino)diethylvinylsilane,
di(n-butyl)aminodiethylvinylsilane,
di(tert-butyl)aminodiethylvinylsilane,
(dimethylamino)dipropylvinylsilane,
(ethylmethylamino)dipropylvinylsilane,
(diethylamino)dipropylvinylsilane,
(ethyl-n-propylamino)dipropylvinylsilane,
(ethylisopropylamino)dipropylvinylsilane,
di(n-propyl)aminodipropylvinylsilane,
(diisopropylamino)dipropylvinylsilane,
(n-butyl-n-propylamino)dipropylvinylsilane,
di(n-butyl)aminodipropylvinylsilane,
di(tert-butyl)aminodipropylvinylsilane,
(dimethylamino)dibutylvinylsilane,
(ethylmethylamino)dibutylvinylsilane,
(diethylamino)dibutylvinylsilane,
(ethyl-n-propylamino)dibutylvinylsilane,
(ethylisopropylamino)dibutylvinylsilane,
di(n-propyl)aminodibutylvinylsilane,
(diisopropylamino)dibutylvinylsilane,
(n-butyl-n-propylamino)dibutylvinylsilane,
di(n-butyl)aminodibutylvinylsilane and
di(tert-butyl)aminodibutylvinylsilane.
[0037] Examples of the {di(trialkylsilyl)amino}dialkylvinylsilane
include {di(trimethylsilyl)amino}dimethylvinylsilane,
{di(t-butyldimethylsilyl)amino}dimethylvinylsilane,
{di(trimethylsilyl)amino}diethylvinylsilane, and
{di(t-butyldimethylsilyl)amino}diethylvinylsilane.
[0038] Examples of the (dialkylamino)dialkoxyalkylvinylsilane
include [0039] (dimethylamino)dimethoxymethylvinylsilane, [0040]
(dimethylamino)dimethoxyethylvinylsilane, [0041]
(dimethylamino)diethoxymethylvinylsilane, [0042]
(dimethylamino)diethoxyethylvinylsilane, [0043]
(diethylamino)dimethoxymethylvinylsilane, [0044]
(diethylamino)dimethoxyethylvinylsilane, [0045]
(diethylamino)diethoxymethylvinylsilane, and [0046]
(diethylamino)diethoxyethylvinylsilane.
[0047] With regard to the compound represented by formula (X), as a
compound in which two of X.sup.1 to X.sup.3 are acyclic amino
groups represented by formula (Xa) and one thereof is a hydrocarbyl
group or a substituted hydrocarbyl group there can be cited a
bis(dialkylamino)alkylvinylsilane, a
bis{di(trialkylsilyl)amino}alkylvinylsilane, a
bis(dialkylamino)alkoxyalkylvinylsilane, etc.
[0048] Examples of the bis(dialkylamino)alkylvinylsilane include
bis(dimethylamino)methylvinylsilane,
bis(ethylmethylamino)methylvinylsilane,
bis(diethylamino)methylvinylsilane,
bis(ethyl-n-propylamino)methylvinylsilane,
bis(ethylisopropylamino)methylvinylsilane,
bisdi(n-propyl)aminomethylvinylsilane,
bis(diisopropylamino)methylvinylsilane,
bis(n-butyl-n-propylamino)methylvinylsilane,
bisdi(n-butyl)aminomethylvinylsilane,
bis(dimethylamino)ethylvinylsilane,
bis(ethylmethylamino)ethylvinylsilane,
bis(diethylamino)ethylvinylsilane,
bis(ethyl-n-propylamino)ethylvinylsilane,
bis(ethylisopropylamino)ethylvinylsilane,
bisdi(n-propyl)aminoethylvinylsilane,
bis(diisopropylamino)ethylvinylsilane,
bis(n-butyl-n-propylamino)ethylvinylsilane,
bis(di(n-butyl)amino)ethylvinylsilane,
bis(dimethylamino)propylvinylsilane,
bis(ethylmethylamino)propylvinylsilane,
bis(diethylamino)propylvinylsilane,
bis(ethyl-n-propylamino)propylvinylsilane,
bis(ethylisopropylamino)propylvinylsilane,
bisdi(n-propyl)aminopropylvinylsilane,
bis(diisopropylamino)propylvinylsilane,
bis(n-butyl-n-propylamino)propylvinylsilane,
bisdi(n-butyl)aminopropylvinylsilane,
bis(dimethylamino)butylvinylsilane,
bis(ethylmethylamino)butylvinylsilane,
bis(diethylamino)butylvinylsilane,
bis(ethyl-n-propylamino)butylvinylsilane,
bis(ethylisopropylamino)butylvinylsilane,
bisdi(n-propyl)aminobutylvinylsilane,
bis(diisopropylamino)butylvinylsilane,
bis(n-butyl-n-propylamino)butylvinylsilane, and
bisdi(n-butyl)aminobutylvinylsilane.
[0049] Examples of the bis{di(trialkylsilyl)amino}alkylvinylsilane
include bis{di(trimethylsilyl)amino}methylvinylsilane,
bis{di(t-butyldimethylsilyl)amino}methylvinylsilane,
bis{di(trimethylsilyl)amino}ethylvinylsilane, and
bis{di(t-butyldimethylsilyl)amino}ethylvinylsilane.
[0050] Examples of the bis(dialkylamino)alkoxyalkylvinylsilane
include [0051] bis(dimethylamino)methoxymethylvinylsilane, [0052]
bis(dimethylamino)methoxyethylvinylsilane, [0053]
bis(dimethylamino)ethoxymethylvinylsilane, [0054]
bis(dimethylamino)ethoxyethylvinylsilane, [0055]
bis(diethylamino)methoxymethylvinylsilane, [0056]
bis(diethylamino)methoxyethylvinylsilane, [0057]
bis(diethylamino)ethoxymethylvinylsilane, and [0058]
bis(diethylamino)ethoxyethylvinylsilane.
[0059] Examples of the bis(dialkylamino)alkoxyalkylvinylsilane
include [0060] bis(dimethylamino)methoxymethylvinylsilane, [0061]
bis(dimethylamino)methoxyethylvinylsilane, [0062]
bis(dimethylamino)ethoxymethylvinylsilane, [0063]
bis(dimethylamino)ethoxyethylvinylsilane, [0064]
bis(diethylamino)methoxymethylvinylsilane, [0065]
bis(diethylamino)methoxyethylvinylsilane, [0066]
bis(diethylamino)ethoxymethylvinylsilane, and [0067]
bis(diethylamino)ethoxyethylvinylsilane.
[0068] With regard to the compound represented by formula (X), as
compounds in which three of X.sup.1 to X.sup.3 are acyclic amino
groups represented by formula (Xa) there can be cited a
tri(dialkylamino)vinylsilane, etc.
[0069] Examples thereof include tri(dimethylamino)vinylsilane,
tri(ethylmethylamino)vinylsilane, tri(diethylamino)vinylsilane,
tri(ethylpropylamino)vinylsilane, tri(dipropylamino)vinylsilane,
and tri(butylpropylamino)vinylsilane.
[0070] With regard to the compound represented by formula (X),
examples of compounds in which two of X.sup.1 to X.sup.3 are cyclic
amino groups represented by formula (Xa) and one thereof is a
hydrocarbyl group or a substituted hydrocarbyl group include
bis(1-piperidinyl)methylvinylsilane,
bis(hexamethyleneimino)methylvinylsilane,
bis(4,5-dihydro-1-imidazolyl)methylvinylsilane, and
bis(morpholino)methylvinylsilane.
[0071] In order to improve abrasion resistance and fuel economy,
the content of the constituent unit based on a silicon-containing
monomer (monomer unit based on silicon-containing monomer) in the
conjugated diene polymer rubber component of component (A) is
preferably not less than 0.001 mmol/g and not more than 0.1 mmol/g
per unit weight of component (A). It is more preferably not less
than 0.002 mmol/g and not more than 0.07 mmol/g. It is yet more
preferably not less than 0.003 mmol/g and not more than 0.05
mmol/g.
[0072] It is thought that the constituent unit based on a monomer
represented by formula (X) turns into a structure represented by
formula (Xb) below in a polymer rubber. Furthermore, with regard to
the constituent unit based on a monomer represented by formula (X),
a group represented by formula (Xa) may become a hydroxy group as a
result of hydrolysis, etc.
##STR00003##
[0073] The conjugated diene polymer rubber component of component
(A) is modified with a carbonyl group- and substituted amino
group-containing compound (hereinafter, also called compound
(I)).
[0074] The substituted amino group of compound (I) is a group in
which one or more hydrogen atoms on the amino group are replaced by
a substituent; examples thereof include a dialkylamino group such
as a dimethylamino group, a diethylamino group, a di(n-propyl)amino
group, a di(isopropyl)amino group, a di(n-butyl)amino group, a
di(sec-butyl)amino group, a di(tert-butyl)amino group, a
di(neopentyl)amino group, or an ethylmethylamino group; an
aralkylamino group such as a benzylamino group; an arylamino group
such as a phenylamino group; a diarylamino group such as a
diphenylamino group; an alkylideneamino group such as an
ethylideneamino group, a 1-methylethylideneamino group, a
2-methylpropylideneamino group, or a 1,3-dimethylbutylideneamino
group, and a cyclic amino group such as a 1-aziridinyl group, a
1-azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group,
a 1-hexamethyleneimino group, a 1-heptamethyleneimino group, a
1-pyrrolyl group, a 1-imidazolidinyl group, a 1-imidazolyl group, a
4,5-dihydro-1-imidazolyl group, a 1-pyrazolidinyl group, a
1-pyrazolyl group, a 1-piperazinyl group, or a morpholino
group.
[0075] As compound (I), formula (Ia) below may be cited,
##STR00004##
wherein Z.sup.1 and Z.sup.2 denote a substituted amino
group-containing group, a hydrogen atom, an optionally substituted
hydrocarbyl group, or an optionally substituted hydrocarbyloxy
group, at least one of Z.sup.1 and Z.sup.2 is a substituted amino
group-containing group, or Z.sup.1 and Z.sup.2 are bonded to each
other and denote a divalent group in which a substituted amino
group-containing ring structure in which Z.sup.1 and Z.sup.2 are
bonded is formed by Z.sup.1, Z.sup.2, and the carbonyl carbon.
[0076] As the substituted amino group-containing group, a
substituted amino group, a hydrocarbyl group containing a
substituted amino group as a substituent, and a hydrocarbyloxy
group containing a substituted amino group as a substituent can be
cited.
[0077] Examples of the substituted amino group include the
above-mentioned substituted amino groups. Examples thereof further
include an amino group containing a substituted amino
group-containing group as a substituent and an amino group
containing a hydrocarbyloxy group-containing group as a
substituent.
[0078] Examples of the amino group containing a substituted amino
group-containing group as a substituent include a
(dialkylaminoalkyl)amino group such as a (dimethylaminomethyl)amino
group, a (dimethylaminoethyl)amino group, a
(dimethylaminopropyl)amino group, a (diethylaminopropyl)amino
group, or a (dipropylaminopropyl)amino group; and a
bis(dialkylaminoalkyl)amino group such as a
bis(dimethylaminoethyl)amino group or a
bis(dimethylaminopropyl)amino group.
[0079] Examples of the amino group containing a hydrocarbyloxy
group-containing group as a substituent include an
(alkoxyalkyl)amino group such as a (methoxymethyl)amino group, a
(methoxyethyl)amino group, a (methoxypropyl)amino group, or an
(ethoxymethyl)amino group; an (aryloxyalkyl)amino group such as a
(phenoxymethyl)amino group or a (phenoxyethyl)amino group; and an
(aralkyloxyalkyl)amino group such as a (benzyloxymethyl)amino group
or a (benzyloxyethyl)amino group.
[0080] As the hydrocarbyl group containing a substituted amino
group as a substituent, a hydrocarbyl group containing a
hydrocarbyl-substituted amino group as a substituent can be cited.
Examples of the hydrocarbyl group containing a
hydrocarbyl-substituted amino group as a substituent include a
dialkylaminoalkyl group such as a dimethylaminomethyl group, a
dimethylaminoethyl group, or a dimethylaminopropyl group; and a
dialkylaminoaryl group such as a dimethylaminophenyl group or a
diethylaminophenyl group.
[0081] As the hydrocarbyloxy group containing a substituted amino
group as a substituent, a hydrocarbyloxy group containing a
hydrocarbyl-substituted amino group as a substituent can be cited.
Examples of the hydrocarbyloxy group containing a
hydrocarbyl-substituted amino group as a substituent include a
dialkylaminoalkoxy group such as a dimethylaminomethoxy group, a
dimethylaminoethoxy group, or a dimethylaminopropoxy group.
[0082] As the substituted amino group-containing group, a group
represented by formula (Ib) below can be cited preferably,
* T .sub.pR.sup.4--NR.sup.5.sub.2 (Ib)
wherein p denotes 0 or 1, T denotes an oxygen atom or --NR.sup.6--
(R.sup.6 denotes a hydrocarbyl group or a hydrogen atom), R.sup.4
denotes a hydrocarbylene group, R.sup.5 denotes a hydrocarbyl group
that may contain a nitrogen atom and/or an oxygen atom (the two
R.sup.5s may be identical to or different from each other), a group
having 2 to 20 carbon atoms in which the two R.sup.5s form a single
group and are bonded to the nitrogen atom via a double bond, or a
divalent group having 2 to 20 carbon atoms in which the two
R.sup.5s are bonded to each other, and * represents a bonding
position.
[0083] In the present specification, a hydrocarbylene group denotes
a divalent hydrocarbon residue.
[0084] In formula (Ib), p denotes 0 or 1.
[0085] In formula (Ib), T denotes an oxygen atom or --NR.sup.6--
(R.sup.6 denotes a hydrocarbyl group or a hydrogen atom). Examples
of the hydrocarbyl group denoted by R.sup.6 include an alkyl group
such as a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, a sec-butyl group, or a
tert-butyl group; an aryl group such as a phenyl group, a
methylphenyl group, an ethylphenyl group, or a naphthyl group; and
an aralkyl group such as a benzyl group.
[0086] The number of carbon atoms of the hydrocarbyl group denoted
by R.sup.6 is preferably from 1 to 10, and more preferably from 1
to 4.
[0087] The hydrocarbyl group denoted by R.sup.6 is preferably an
alkyl group, more preferably an alkyl group having 1 to 4 carbon
atoms, and yet more preferably a methyl group or an ethyl
group.
[0088] R.sup.6 is preferably a hydrogen atom or an alkyl group,
more preferably a hydrogen atom or an alkyl group having 1 to 4
carbon atoms, yet more preferably a hydrogen atom, a methyl group,
or an ethyl group, and yet more preferably a hydrogen atom or a
methyl group.
[0089] R.sup.4 in formula (Ib) denotes a hydrocarbylene group, and
examples of the hydrocarbylene group include an alkylene group such
as a methylene group, an ethylene group, a trimethylene group, a
tetramethylene group, a pentamethylene group, or a hexamethylene
group; an arylene group such as a phenylene group, a tolylene
group, or a xylylene group; and an aralkylene group.
[0090] The number of carbon atoms of R.sup.4 of formula (Ib) is
preferably from 1 to 10, and more preferably from 2 to 4.
[0091] R.sup.5 of formula (Ib) denotes a hydrocarbyl group that may
contain a nitrogen atom and/or an oxygen atom (the two R.sup.5s may
be identical to or different from each other), a group having 2 to
20 carbon atoms in which the two R.sup.5s form a single group and
are bonded to the nitrogen atom via a double bond, or a divalent
group having 2 to 20 carbon atoms in which the two R.sup.5s are
bonded to each other.
[0092] Examples of the hydrocarbyl group denoted by R.sup.5 include
an alkyl group such as a methyl group, an ethyl group, an n-propyl
group, an isopropyl group, a n-butyl group, a sec-butyl group, or a
tert-butyl group; an aryl group such as a phenyl group, a
methylphenyl group, or an ethylphenyl group; and an aralkyl group
such as a benzyl group. The number of carbon atoms of the
hydrocarbyl group denoted by R.sup.5 is preferably from 1 to 10,
more preferably from 1 to 6, and yet more preferably from 1 to
4.
[0093] Examples of the nitrogen atom-containing hydrocarbyl group
denoted by R.sup.5 include a dialkylaminoalkyl group such as a
dimethylaminomethyl group, a dimethylaminoethyl group, a
dimethylaminopropyl group, or a diethylaminoethyl group. The number
of carbon atoms of the nitrogen atom-containing hydrocarbyl group
denoted by R.sup.5 is preferably from 3 to 10, more preferably from
3 to 6, and yet more preferably from 3 to 4.
[0094] Examples of the oxygen atom-containing hydrocarbyl group
denoted by R.sup.5 include an alkoxyalkyl group such as a
methoxymethyl group, a methoxyethyl group, a methoxypropyl group,
an ethoxymethyl group, or an ethoxyethyl group; an oxacycloalkyl
group such as an oxiranyl group or a tetrahydrofuranyl group; and
an oxacycloalkylalkyl group such as a glycidyl group or a
tetrahydrofurfuryl group. The number of carbon atoms of the oxygen
atom-containing hydrocarbyl group denoted by R.sup.5 is preferably
from 2 to 10, more preferably from 2 to 6, and yet more preferably
from 2 to 4.
[0095] In the present specification, the oxacycloalkyl group
denotes a group in which CH.sub.2 on the alicyclic ring of a
cycloalkyl group is replaced by an oxygen atom, and the
oxacycloalkylalkyl group denotes a group in which a hydrogen atom
of an alkyl group is replaced by an oxacycloalkyl group.
[0096] As the single group denoted by the two R.sup.5s in which
they bond to the nitrogen atom via a double bond, a divalent group
that may contain at least one atom selected from the group
consisting of a nitrogen atom and an oxygen atom can be cited.
Examples thereof include an ethylidene group, a propylidene group,
a butylidene group, a 1-methylethylidene group, a
1-methylpropylidene group, a 1,3-dimethylbutylidene group, a
benzylidene group, and a 4-N,N-dimethylaminobenzylidene group. The
number of carbon atoms of the single group denoted by the two
R.sup.5s in which they bond to the nitrogen atom via a double bond
is from 2 to 20, preferably from 2 to 12, and more preferably from
2 to 8.
[0097] Examples of the divalent group having 2 to 20 carbon atoms
in which the two R.sup.5s are bonded to each other include an
alkylene group such as an ethylene group, a trimethylene group, a
tetramethylene group, a pentamethylene group, or a hexamethylene
group; an alkenylene group such as a group represented by
--CH.dbd.CH--CH.dbd.CH--; a nitrogen-containing group such as a
group represented by --CH.sub.2CH.sub.2--NH--CH.sub.2--, a group
represented by --CH.dbd.CH--N.dbd.CH--, a group represented by
--CH.sub.2CH.sub.2--N.dbd.CH--, a group represented by
--CH.sub.2CH.sub.2CH.sub.2--NH--, a group represented by
--CH.dbd.CHCH.dbd.N--, or a group represented by
--CH.sub.2CH.sub.2--NH--CH.sub.2CH.sub.2--; and an
oxygen-containing group such as a group represented by
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2-- or a group represented by
--CH.sub.2CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2CH.sub.2--. The
number of carbon atoms of the divalent group in which the two
R.sup.5s are bonded to each other is preferably from 2 to 12, and
more preferably from 2 to 8.
[0098] As the optionally substituted hydrocarbyl group denoted by
Z.sup.1 and Z.sup.2 of formula (Ia), a hydrocarbyl group and a
hydrocarbyl group containing a hydrocarbyloxy group as a
substituent can be cited. Examples of the hydrocarbyl group include
an alkyl group such as a methyl group, an ethyl group, an n-propyl
group, an isopropyl group, or an n-butyl group; a cycloalkyl group
such as a cyclohexyl group; an aryl group such as a phenyl group, a
methylphenyl group, or an ethylphenyl group; an aralkyl group such
as a benzyl group; an alkenyl group such as a vinyl group, a
1-propenyl group, an allyl group, an isopropenyl group, a crotyl
group, an isocrotyl group, or a methallyl group; and an alkynyl
group such as a propargyl group.
[0099] Examples of the hydrocarbyl group containing a
hydrocarbyloxy group as a substituent include an alkoxyalkyl group
such as a methoxymethyl group, a methoxyethyl group, a
methoxypropyl group, or an ethoxymethyl group; an aryloxyalkyl
group such as a phenoxymethyl group or a phenoxyethyl group; and an
aralkyloxyalkyl group such as a benzyloxymethyl group or a
benzyloxyethyl group.
[0100] The optionally substituted hydrocarbyl group is preferably a
hydrocarbyl group, and more preferably a hydrocarbyl group having 1
to 4 carbon atoms. The hydrocarbyl group is preferably an alkyl
group or an alkenyl group.
[0101] As the optionally substituted hydrocarbyloxy group denoted
by Z.sup.1 and Z.sup.2 of formula (Ia), a hydrocarbyloxy group and
a hydrocarbyloxy group containing a hydrocarbyloxy group as a
substituent can be cited.
[0102] Examples of the hydrocarbyloxy group include an alkoxy group
such as a methoxy group, an ethoxy group, an n-propoxy group, an
isopropoxy group, or a butoxy group; an aryloxy group such as a
phenoxy group, a methylphenoxy group, or an ethylphenoxy group; and
an aralkyloxy group such as a benzyloxy group.
[0103] Examples of the hydrocarbyloxy group containing a
hydrocarbyloxy group as a substituent include an alkoxyalkoxy group
such as a methoxymethoxy group, a methoxyethoxy group, a
methoxypropoxy group, or an ethoxymethoxy group; an aryloxyalkoxy
group such as a phenoxymethoxy group or a phenoxyethoxy group; and
an aralkyloxyalkoxy group such as a benzyloxymethoxy group or a
benzyloxyethoxy group.
[0104] The optionally substituted hydrocarbyloxy group is
preferably a hydrocarbyloxy group, and more preferably a
hydrocarbyloxy group having 1 to 4 carbon atoms. The hydrocarbyloxy
group is preferably an alkoxy group.
[0105] Examples of the divalent group in which Z.sup.1 and Z.sup.2
of formula (Ia) are bonded to each other and a substituted amino
group-containing ring structure in which Z.sup.1 and Z.sup.2 are
bonded is formed by Z.sup.1, Z.sup.2, and the carbonyl carbon
include a group represented by
--CH.sub.2CH.sub.2CH.sub.2--N(C.sub.6H.sub.5)--, a group
represented by
--CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2--N(CH.sub.3)--, a group
represented by --N(CH.sub.3)--CH.sub.2CH.sub.2--N(CH.sub.3)--, a
group represented by
--CH.sub.2--N(CH.sub.2CH.sub.3)--CH.sub.2CH.sub.2CH.sub.2--, and a
group represented by --CH.sub.2CH.sub.2C(.dbd.O)--NH--.
[0106] Examples of compounds represented by formula (Ia) include
carboxylic acid amide compounds and carboxylic acid ester
compounds.
[0107] Examples of the carboxylic acid amide compound include a
formamide compound such formamide, N,N-dimethylformamide, or
N,N-diethylformamide;
an acetamide compound such as N,N-dimethylacetamide,
N,N-diethylacetamide, aminoacetamide,
N,N-dimethyl-N',N'-dimethylaminoacetamide,
N,N-dimethylaminoacetamide, N,N-dimethyl-N'-ethylaminoacetamide,
N,N-dimethylaminoacetamide, or N-phenyldiacetamide; a propionamide
compound such as propionamide or N,N-dimethylpropionamide; a
pyridylamide compound such as 4-pyridylamide or
N,N-dimethyl-4-pyridylamide; a benzamide compound such as
benzamide, N,N-dimethylbenzamide, N',N'-(p-dimethylamino)benzamide,
N',N'-(p-diethylamino)benzamide,
N,N-dimethyl-N',N'-(p-dimethylamino)benzamide, or
N,N-dimethyl-N',N'-(p-diethylamino)benzamide; a pyridylamide
compound such as N,N-dimethyl-4-pyridylamide; and a phthalamide
compound such as N,N,N',N'-tetramethylphthalamide or
N,N,N',N'-tetraethylphthalamide.
[0108] Examples of the carboxylic acid ester compounds include
an N,N-dialkylaminomethyl acetate such as N,N-dimethylaminomethyl
acetate or N,N-diethylaminomethyl acetate; an N,N-dialkylaminoethyl
acetate such as N,N-dimethylaminoethyl acetate or
N,N-diethylaminoethyl acetate; an N,N-dialkylaminopropyl acetate
such as N,N-dimethylaminopropyl acetate or N,N-diethylaminopropyl
acetate; and an N,N-dialkylaminoethylbenzoate such as
N,N-dimethylaminoethylbenzoate or
N,N-diethylaminoethylbenzoate.
[0109] As a preferred compound represented by formula (Ia), a
compound in which at least one of Z.sup.1 and Z.sup.2 is a group
represented by formula (Ib) can be cited.
[0110] Examples of the compound include a compound represented by
formula (I-1) below and a compound represented by formula (I-2)
below, for which p of formula (Ib) is 0,
##STR00005##
wherein r denotes 1 or 2, R.sup.5.sub.2N-- is a substituent on the
benzene ring, R.sup.5 denotes a hydrocarbyl group that may contain
a nitrogen atom and/or an oxygen atom (the two R.sup.5s may be
identical to or different from each other), a group having 2 to 20
carbon atoms in which the two R.sup.5s form a single group and are
bonded to the nitrogen atom via a double bond, or a divalent group
having 2 to 20 carbon atoms in which the two R.sup.5s are bonded to
each other, and R.sup.7 denotes a hydrocarbyl group or a hydrogen
atom,
##STR00006##
wherein s denotes 1 or 2, t denotes a number from 0 to 2,
R.sup.5.sub.2N-- denotes a substituent on a benzene ring, and
R.sup.5 denotes a hydrocarbyl group that may contain a nitrogen
atom and/or an oxygen atom (the two R.sup.5s may be identical to or
different from each other), a group having 2 to 20 carbon atoms in
which the two R.sup.5s form a single group and are bonded to the
nitrogen atom via a double bond, or a divalent group having 2 to 20
carbon atoms in which the two R.sup.5s are bonded to each
other.
[0111] r of formula (I-1) denotes 1 or 2, s of formula (I-2)
denotes 1 or 2, and t denotes a number from 0 to 2.
[0112] R.sup.5.sub.2N-- of formula (I-1) and formula (I-2) is a
substituent on a benzene ring. When r, s, and t are 2, it means
that two R.sup.5.sub.2N-s are bonded to a benzene ring. The
definition, examples, and preferred groups for R.sup.5 are the same
as the definition, examples, and preferred groups described for
R.sup.5 of formula (Ib).
[0113] R.sup.5.sub.2N-- of formula (I-1) and formula (I-2) is
preferably a dialkylamino group. The alkyl groups of the
dialkylamino group are preferably alkyl groups having 1 to 4 carbon
atoms.
[0114] R.sup.7 of formula (I-1) denotes a hydrogen atom or a
hydrocarbyl group. Examples of the hydrocarbyl group include an
alkyl group such as a methyl group, an ethyl group, an n-propyl
group, an isopropyl group, an n-butyl group, a sec-butyl group, or
a tert-butyl group; an aryl group such as a phenyl group, a
methylphenyl group, or an ethylphenyl group; and an aralkyl group
such as a benzyl group.
[0115] Examples of the compound represented by formula (I-1)
include a dialkylamino-substituted benzaldehyde compound such as
4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, or
3,5-bis(dihexylamino)benzaldehyde; a dialkylamino-substituted
acetophenone compound such as 4-dimethylaminoacetophenone or
4-diethylaminoacetophenone; a heterocyclic group-substituted
acetophenone compound such as 4'-(1-imidazolyl)acetophenone,
4'-(1-pyrazolyl)acetophenone, or, 4-morpholinoacetophenone.
[0116] Examples of the compound represented by formula (I-2)
include dimethylaminobenzophenone, compound such as
3-dimethylaminobenzophenone, 3-diethylaminobenzophenone, or
4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, or
4,4'-bis(dimethylamino)benzophenone,
4,4'-bis(diethylamino)benzophenone; a heterocyclic
group-substituted benzophenone compound such as
4'-(imidazol-1-yl)benzophenone, 4'-(1-pyrazolyl)benzophenone,
4-morpholinobenzophenone.
[0117] As a preferred compound of formula (Ia) in which at least
one of Z.sup.1 and Z.sup.2 is a group represented by formula (Ib),
a compound represented by formula (I-3) below for which p of
formula (Ib) is 1 can be cited,
##STR00007##
wherein R.sup.5 denotes a hydrocarbyl group that may contain a
nitrogen atom and/or an oxygen atom (the two R.sup.5s may be
identical to or different from each other), a group having 2 to 20
carbon atoms in which the two R.sup.5s form a single group and are
bonded to the nitrogen atom via a double bond, or a divalent group
having 2 to 20 carbon atoms in which the two R.sup.5s are bonded to
each other, q denotes an integer from 1 to 10, T denotes an oxygen
atom or --NR.sup.6-- (R.sup.6 denotes a hydrocarbyl group or a
hydrogen atom), and R.sup.8 denotes an optionally substituted
hydrocarbyl group or a hydrogen atom.
[0118] The definition, examples, and preferred groups for R.sup.5
of formula (I-3) are the same as the definition, examples, and
preferred groups described for R.sup.5 of formula (Ib). In formula
(I-3), R.sup.5 is more preferably a group for which
--NR.sup.5.sub.2 is an acyclic amino group, yet more preferably an
alkyl group, an oxacycloalkyl group, or an oxacycloalkylalkyl
group, and yet more preferably an alkyl group.
[0119] q of formula (I-3) denotes a number from 1 to 10. It is
preferably a number from 2 to 4.
[0120] T of formula (I-3) denotes an oxygen atom or --NR.sup.6--
(R.sup.6 denotes a hydrocarbyl group or a hydrogen atom), and the
definition, examples, and preferred groups for R.sup.6 are the same
as the definition, examples, and preferred groups described for
R.sup.6 of formula (Ib). In formula (I-3), R.sup.6 is more
preferably a hydrogen atom.
[0121] R.sup.8 of formula (I-3) denotes an optionally substituted
hydrocarbyl group or a hydrogen atom. Examples of the hydrocarbyl
group include an alkyl group such as a methyl group, an ethyl
group, an n-propyl group, an isopropyl group, an n-butyl group, a
sec-butyl group, or a tert-butyl group; an aryl group such as a
phenyl group, a methylphenyl group, or an ethylphenyl group; and an
aralkyl group such as a benzyl group. The hydrocarbyl group is
preferably an alkyl group, and more preferably an alkyl group
having 1 to 4 carbon atoms.
[0122] Examples of the substituted hydrocarbyl group denoted by
R.sup.8 of formula (I-3) include an alkoxyalkyl group such as a
methoxymethyl group, a methoxyethyl group, an ethoxymethyl group,
or an ethoxyethyl group.
[0123] The substituted hydrocarbyl group is preferably an
alkoxyalkyl group, and more preferably alkoxyalkyl group having 2
to 4 carbon atoms.
[0124] Examples of the compound represented by formula (I-3)
include acrylamide compounds (T: NH, R.sup.8: H) below. [0125]
N-(2-dimethylaminoethyl)acrylamide, [0126]
N-(2-diethylaminoethyl)acrylamide, [0127]
N-(3-dimethylaminopropyl)acrylamide, [0128]
N-(3-diethylaminopropyl)acrylamide, [0129]
N-(4-dimethylaminobutyl)acrylamide, [0130]
N-(4-diethylaminobutyl)acrylamide, [0131]
N-(3-di(glycidyl)aminopropyl)acrylamide, [0132]
N-(3-di(tetrahydrofurfuryl)aminopropyl)acrylamide, and [0133]
N-(3-morpholinopropyl)acrylamide.
[0134] Examples of the compound represented by formula (I-3)
include methacrylamide compounds (T: NH, R.sup.8: CH.sub.3) below.
[0135] N-(2-dimethylaminoethyl)methacrylamide, [0136]
N-(2-diethylaminoethyl)methacrylamide, [0137]
N-(3-dimethylaminopropyl)methacrylamide, [0138]
N-(3-diethylaminopropyl)methacrylamide, [0139]
N-(4-dimethylaminobutyl)methacrylamide, [0140]
N-(4-diethylaminobutyl)methacrylamide, [0141]
N-(3-di(glycidyl)aminopropyl)methacrylamide, [0142]
N-(3-di(tetrahydrofurfuryl)aminopropyl)methacrylamide, and [0143]
N-(3-morpholinopropyl)methacrylamide.
[0144] Examples of the compound represented by formula (I-3)
include methacrylamide compounds (T: O, R.sup.8: H) below. [0145]
2-dimethylaminoethyacrylate, [0146] 2-diethylaminoethylacrylate,
[0147] 3-dimethylaminopropylacrylate, [0148]
3-diethylaminopropylacrylate, [0149] 4-dimethylaminobutylacrylate,
[0150] 4-diethylaminobutylacrylate, [0151]
3-di(glycidyl)aminopropylacrylate, and [0152]
3-di(tetrahydrofurfuryl)aminopropylacrylate.
[0153] Examples of the compound represented by formula (I-3)
include methacrylamide compounds (T: O, R.sup.8: CH.sub.3) below.
[0154] 2-dimethylaminoethyl methacrylate, [0155]
2-diethylaminoethyl methacrylate, [0156] 3-dimethylaminopropyl
methacrylate, [0157] 3-diethylaminopropyl methacrylate, [0158]
4-dimethylaminobutyl methacrylate, [0159] 4-diethylaminobutyl
methacrylate, [0160] 3-di(glycidyl)aminopropylmethacrylate, and
[0161] 3-di(tetrahydrofurfuryl)aminopropylmethacrylate.
[0162] The compound represented by formula (I-3) is preferably an
acrylamide compound (T: NH, R.sup.8: H) or a methacrylamide
compound (T: NH, R.sup.8: CH.sub.3), more preferably an
N-(3-dialkylaminopropyl)acrylamide or an
N-(3-dialkylaminopropyl)methacrylamide, and yet more preferably
N-(3-dimethylaminopropyl)acrylamide,
N-(3-diethylaminopropyl)acrylamide,
N-(3-dimethylaminopropyl)methacrylamide, or
N-(3-diethylaminopropyl)methacrylamide.
[0163] With regard to the compound represented by formula (Ia), as
the compound in which Z.sup.1 and Z.sup.2 form a group in which
Z.sup.1 and Z.sup.2 are bonded to each other and a substituted
amino group-containing ring structure is formed by Z.sup.1,
Z.sup.2, and the carbonyl carbon, a compound represented by formula
(I-4) below and a compound represented by formula (I-5), which is
described later, can be cited.
##STR00008##
wherein g denotes a number from 0 to 10, R.sup.9 denotes an
optionally substituted hydrocarbyl group, R.sup.10, R.sup.11, and
R.sup.12 denote a hydrogen atom or a hydrocarbyl group, and the
plurality of R.sup.12s may be identical to or different from each
other.
[0164] R.sup.9 of formula (I-4) denotes an optionally substituted
hydrocarbyl group. Examples of the hydrocarbyl group denoted by
R.sup.9 include an alkyl group such as a methyl group, an ethyl
group, an n-propyl group, an isopropyl group, an n-butyl group, a
sec-butyl group, or a tert-butyl group; an aryl group such as a
phenyl group, a methylphenyl group, an ethylphenyl group, or a
naphthyl group; and an aralkyl group such as a benzyl group. The
number of carbon atoms of the hydrocarbyl group is preferably from
1 to 20.
[0165] Examples of the substituted hydrocarbyl group denoted by
R.sup.9 of formula (I-4) include a dialkylaminoalkyl group such as
a dimethylaminoethyl group or a diethylaminoethyl group; and an
alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl
group, an ethoxymethyl group, or an ethoxyethyl group. The number
of carbon atoms of the substituted hydrocarbyl group is preferably
from 1 to 20.
[0166] R.sup.9 of formula (I-4) is preferably a hydrocarbyl group,
and more preferably an alkyl group or an aryl group.
[0167] R.sup.10 and R.sup.11 of formula (I-4) denote a hydrogen
atom or a hydrocarbyl group. Examples of the hydrocarbyl group
include an alkyl group such as a methyl group, an ethyl group, an
n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl
group, or a tert-butyl group; an aryl group such as a phenyl group,
a methylphenyl group, an ethylphenyl group, or a naphthyl group;
and an aralkyl group such as a benzyl group. The number of carbon
atoms of the hydrocarbyl group is preferably from 1 to 20.
[0168] R.sup.10 and R.sup.11 of formula (I-4) are preferably
hydrogen atoms, alkyl groups, or aryl groups, and more preferably
hydrogen atoms.
[0169] g of formula (I-4) denotes a number from 0 to 10. It is
preferably a number from 2 to 7.
[0170] R.sup.12 of formula (I-4) denotes a hydrogen atom or a
hydrocarbyl group. Examples of the hydrocarbyl group include an
alkyl group such as a methyl group, an ethyl group, an n-propyl
group, an isopropyl group, an n-butyl group, a sec-butyl group, or
a tert-butyl group.
[0171] R.sup.12 of formula (I-4) is preferably a hydrogen atom or
an alkyl group, and more preferably a hydrogen atom.
[0172] Examples of the compound of formula (I-4) include a
.beta.-propiolactam compound such as N-methyl-.beta.-propiolactam,
N-(tert-butyl)-.beta.-propiolactam, or
N-phenyl-.beta.-propiolactam;
a 2-pyrrolidone compound such as 1-methyl-2-pyrrolidone,
1-phenyl-2-pyrrolidone, 1-(p-methylphenyl)-2-pyrrolidone,
1-(p-methoxyphenyl)-2-pyrrolidone, 1-benzyl-2-pyrrolidone,
1-naphthyl-2-pyrrolidone, 1-phenyl-5-methyl-2-pyrrolidone,
1-(tert-butyl)-5-methyl-2-pyrrolidone, or
1-(tert-butyl)-3,3-dimethyl-2-pyrrolidone; a 2-piperidone compound
such as 1-(tert-butyl)-2-piperidone, 1-phenyl-2-piperidone,
1-(p-methylphenyl)-2-piperidone, or 1-naphthyl-2-piperidone; an
.epsilon.-caprolactam compound such as
N-methyl-.epsilon.-caprolactam, N-ethyl-.epsilon.-caprolactam,
N-(n-propyl)-.epsilon.-caprolactam, N-phenyl-.epsilon.-caprolactam,
N-(p-methoxyphenyl)-.epsilon.-caprolactam, or
N-benzyl-.epsilon.-caprolactam; and a .omega.-laurolactam compound
such as N-phenyl-.omega.-laurolactam.
[0173] The compound represented by formula (I-4) is preferably a
2-pyrrolidone compound or an .epsilon.-caprolactam compound, more
preferably a 1-hydrocarbyl-substituted 2-pyrrolidone or an
N-hydrocarbyl-substituted .epsilon.-caprolactam, and yet more
preferably a 1-alkyl-substituted 2-pyrrolidone, a
1-aryl-substituted 2-pyrrolidone, an N-alkyl-substituted
.epsilon.-caprolactam, or an N-aryl-substituted
.epsilon.-caprolactam.
##STR00009##
wherein h denotes a number from 0 to 10, R.sup.13 and R.sup.14
denote an optionally substituted hydrocarbyl group, R.sup.15
denotes a hydrogen atom or a hydrocarbyl group, and the plurality
of R.sup.15s may be identical to or different from each other.
[0174] R.sup.13 and R.sup.14 of formula (I-5) denote an optionally
substituted hydrocarbyl group. Examples of the hydrocarbyl group
denoted by R.sup.13 and R.sup.14 include an alkyl group such as a
methyl group, an ethyl group, an n-propyl group, an isopropyl
group, an n-butyl group, a sec-butyl group, or a tert-butyl group;
an aryl group such as a phenyl group, a methylphenyl group, an
ethylphenyl group, or a naphthyl group; and an aralkyl group such
as a benzyl group. The number of carbon atoms of the hydrocarbyl
group is preferably from 1 to 20.
[0175] Examples of the substituted hydrocarbyl group denoted by
R.sup.13 and R.sup.14 of formula (I-5) include a dialkylaminoalkyl
group such as a dimethylaminoethyl group or a diethylaminoethyl
group; and an alkoxyalkyl group such as a methoxymethyl group, a
methoxyethyl group, an ethoxymethyl group, or an ethoxyethyl group.
The number of carbon atoms of the substituted hydrocarbyl group is
preferably from 1 to 20.
[0176] R.sup.13 and R.sup.14 of formula (I-5) are preferably
hydrocarbyl groups, more preferably alkyl groups or aryl groups,
and yet more preferably alkyl groups.
[0177] h of formula (I-5) denotes a number from 0 to 10. It is
preferably a number from 2 to 7.
[0178] R.sup.15 of formula (I-5) denotes a hydrogen atom or a
hydrocarbyl group. Examples of the hydrocarbyl group include an
alkyl group such as a methyl group, an ethyl group, an n-propyl
group, an isopropyl group, an n-butyl group, a sec-butyl group, or
a tert-butyl group.
[0179] R.sup.15 of formula (I-5) is preferably a hydrogen atom or
an alkyl group, and more preferably a hydrogen atom.
[0180] Examples of the compound represented by formula (I-5)
include a 1,3-hydrocarbyl-substituted 2-imidazolidinone such as
1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone,
1,3-di(n-propyl)-2-imidazolidinone,
1,3-di(tert-butyl)-2-imidazolidinone, or
1,3-diphenyl-2-imidazolidinone.
[0181] The compound represented by formula (I-5) is preferably a
1,3-substituted 2-imidazolidinone, more preferably a
1,3-hydrocarbyl-substituted 2-imidazolidinone, and yet more
preferably a 1,3-dialkyl-2-imidazolidinone. The
1,3-dialkyl-2-imidazolidinone is preferably
1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, or
1,3-di(n-propyl)-2-imidazolidinone, and more preferably
1,3-dimethyl-2-imidazolidinone.
Component (B)
[0182] Component (B) is a conjugated diene polymer rubber component
modified with a compound represented by formula (IIa) below,
(R.sup.21O).sub.mSi(R.sup.22A).sub.nR.sup.23.sub.4-m-n (IIa)
wherein m denotes a number from 1 to 3, n denotes a number from 1
to 3, m+n is from 2 to 4, R.sup.21 and R.sup.23 denote a
hydrocarbyl group, R.sup.22 denotes a hydrocarbylene group, A
denotes a substituted amino group or an optionally substituted
hydrocarbyloxy group, when there are a plurality of R.sup.21s the
plurality of R.sup.21s may be identical to or different from each
other, when there are a plurality of R.sup.22s the plurality of
R.sup.22s may be identical to or different from each other, when
there are a plurality of R.sup.23s the plurality of R.sup.23s may
be identical to or different from each other, and when there are a
plurality of As the plurality of As may be identical to or
different from each other.
[0183] A conjugated diene polymer rubber component in component (B)
contains a conjugated diene unit. Examples of the conjugated diene
include 1,3-butadiene, isoprene, 1,3-pentadiene,
2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and one or more
types thereof may be used. The conjugated diene is preferably
1,3-butadiene or isoprene.
[0184] The conjugated diene polymer rubber component of component
(B) may further comprise, in addition to the conjugated diene-based
constituent unit (conjugated diene unit), a constituent unit based
on another monomer. Examples of said other monomer include an
aromatic vinyl, a vinylnitrile, and an unsaturated carboxylic acid
ester. Examples of the aromatic vinyl include styrene,
a-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene,
trivinylbenzene, and divinylnaphthalene. Examples of the
vinylnitrile include acrylonitrile, and examples of the unsaturated
carboxylic acid ester include methyl acrylate, ethyl acrylate,
methyl methacrylate, and ethyl methacrylate. Among them, an
aromatic vinyl is preferable, and styrene is more preferable.
[0185] In order to increase the strength, the conjugated diene
polymer of component (B) preferably contains an aromatic vinyl
unit, and the content of the aromatic vinyl unit, relative to 100%
by weight of the total amount of the conjugated diene unit and the
aromatic vinyl unit, is preferably at least 10% by weight (the
content of the conjugated diene unit being no greater than 90% by
weight), and more preferably at least 15% by weight (the content of
the conjugated diene unit being no greater than 85% by weight).
Furthermore, from the viewpoint of fuel economy, the content of the
aromatic vinyl unit is preferably no greater than 50% by weight
(the content of the conjugated diene unit being at least 50% by
weight), and more preferably no greater than 45% by weight (the
content of the conjugated diene unit being at least 55% by
weight).
[0186] In order to improve abrasion resistance and fuel economy,
the conjugated diene polymer rubber component of component (B)
preferably contains a constituent unit based on a
silicon-containing monomer. The silicon-containing monomer is
preferably a monomer represented by formula (X). The monomer
represented by formula (X) is as explained for component (A).
[0187] In order to improve abrasion resistance and fuel economy,
the content of the constituent unit based on a silicon-containing
monomer in the conjugated diene polymer rubber component of
component (B) is preferably not less than 0.001 mmol/g and not more
than 0.1 mmol/g per unit weight of component (B). It is more
preferably not less than 0.002 mmol/g and not more than 0.07
mmol/g. It is yet more preferably not less than 0.003 mmol/g and
not more than 0.05 mmol/g.
[0188] The conjugated diene polymer rubber component of component
(B) is modified with the above-mentioned compound represented by
formula (IIa) (hereinafter, also called compound (II)).
[0189] m of formula (IIa) denotes a number from 1 to 3. It is
preferably a number from 2 to 3, and more preferably 3.
[0190] n of formula (IIa) denotes a number from 1 to 3. It is
preferably a number from 1 to 2, and more preferably 1. m+n is a
number from 2 to 4, preferably from 3 to 4, and more preferably
4.
[0191] R.sup.21 and R.sup.23 of formula (IIa) denote a hydrocarbyl
group. Examples of the hydrocarbyl group include an alkyl group
such as a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, a sec-butyl group, or a
tert-butyl group; an aryl group such as a phenyl group, a
methylphenyl group, an ethylphenyl group, or a naphthyl group; and
an aralkyl group such as a benzyl group. The hydrocarbyl group is
preferably an alkyl group.
[0192] The number of carbon atoms of the hydrocarbyl group denoted
by R.sup.21 and R.sup.23 is preferably from 1 to 4, more preferably
from 1 to 3, and yet more preferably 1 or 2.
[0193] R.sup.22 of formula (IIa) denotes a hydrocarbylene group.
Examples of the hydrocarbylene group include an alkylene group such
as a methylene group, an ethylene group, a trimethylene group, a
tetramethylene group, a pentamethylene group, or a hexamethylene
group; an arylene group such as a phenylene group, a tolylene
group, or a xylylene group; and an aralkylene group. The
hydrocarbylene group is preferably a straight-chain alkylene
group.
[0194] The number of carbon atoms of R.sup.22 of formula (Ib) is
preferably from 1 to 10, and more preferably from 2 to 4.
[0195] A of formula (IIa) denotes a substituted amino group or an
optionally substituted hydrocarbyloxy group. As the substituted
amino group, a group represented by formula (IIb) can be cited. As
the optionally substituted hydrocarbyloxy group, a group
represented by formula (IIc), which is described later, can be
cited.
##STR00010##
wherein R.sup.24 and R.sup.25 denote a hydrocarbyl group that may
contain at least one atom selected from the group consisting of a
nitrogen atom, an oxygen atom, and a silicon atom, a substituted
silyl group, a group having 2 to 20 carbon atoms in which R.sup.24
and R.sup.25 form a single group and are bonded to the nitrogen
atom via a double bond, or a divalent group having 2 to 20 carbon
atoms in which R.sup.24 and R.sup.25 are bonded to each other, and
* represents a bonding position.
[0196] Examples of the hydrocarbyl group denoted by R.sup.24 and
R.sup.25 include an alkyl group such as a methyl group, an ethyl
group, an n-propyl group, an isopropyl group, an n-butyl group, a
sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl
group, an isopentyl group, or an n-hexyl group; a cycloalkyl group
such as a cyclohexyl group; an aryl group such as a phenyl group, a
methylphenyl group, or an ethylphenyl group; and an aralkyl group
such as a benzyl group. It is preferably an alkyl group.
[0197] The number of carbon atoms of the hydrocarbyl group denoted
by R.sup.24 and R.sup.25 is preferably from 1 to 10, more
preferably from 1 to 6, and yet more preferably from 1 to 4.
[0198] Examples of the nitrogen atom-containing hydrocarbyl group
denoted by R.sup.24 and R.sup.25 include a dialkylaminoalkyl group
such as a dimethylaminomethyl group, a dimethylaminoethyl group, a
dimethylaminopropyl group, or a diethylaminoethyl group.
[0199] The number of carbon atoms of the nitrogen atom-containing
hydrocarbyl group denoted by R.sup.24 and R.sup.25 is preferably
from 3 to 10, more preferably from 3 to 6, and yet more preferably
from 3 to 4.
[0200] Examples of the oxygen atom-containing hydrocarbyl group
denoted by R.sup.24 and R.sup.25 include an alkoxyalkyl group such
as a methoxymethyl group, a methoxyethyl group, a methoxypropyl
group, an ethoxymethyl group, or an ethoxyethyl group; an
oxacycloalkyl group such as an oxiranyl group or a
tetrahydrofuranyl group; and an oxacycloalkylalkyl group such as a
glycidyl group or a tetrahydrofurfuryl group. It is preferably an
oxacycloalkyl group or an oxacycloalkylalkyl group.
[0201] The number of carbon atoms of the oxygen atom-containing
hydrocarbyl group denoted by R.sup.24 and R.sup.25 is preferably
from 2 to 10, more preferably from 2 to 6, and yet more preferably
from 2 to 4.
[0202] Examples of the silicon atom-containing hydrocarbyl group
denoted by R.sup.24 and R.sup.25 include a trialkylsilylalkyl group
such as a trimethylsilylmethyl group.
[0203] The number of carbon atoms of the silicon atom-containing
hydrocarbyl group denoted by R.sup.24 and R.sup.25 is preferably
from 4 to 10, more preferably from 4 to 6, and yet more preferably
4.
[0204] Examples of the substituted silyl group denoted by R.sup.24
and R.sup.25 include a trialkylsilyl group such as a trimethylsilyl
group, a triethylsilyl group, or a t-butyldimethylsilyl group; and
a trialkoxysilyl group such as a trimethoxysilyl group. It is
preferably a trialkylsilyl group.
[0205] The number of carbon atoms of the substituted silyl group
denoted by R.sup.24 and R.sup.25 is preferably from 3 to 10, more
preferably from 3 to 6, and yet more preferably 3.
[0206] As the single group denoted by the R.sup.24 and R.sup.25 in
which they bond to the nitrogen atom via a double bond, a divalent
group that may contain at least one atom selected from the group
consisting of a nitrogen atom and an oxygen atom can be cited.
Examples thereof include an ethylidene group, a propylidene group,
a butylidene group, a 1-methylethylidene group, a
1-methylpropylidene group, a 1,3-dimethylbutylidene group, a
benzylidene group, and a 4-N,N-dimethylaminobenzylidene group. The
number of carbon atoms of the single group denoted by the two
R.sup.24 and R.sup.25 in which they bond to the nitrogen atom via a
double bond is from 2 to 20, preferably from 2 to 12, and more
preferably from 2 to 8.
[0207] Examples of the divalent group having 2 to 20 carbon atoms
in which the R.sup.24 and R.sup.25 are bonded to each other include
an alkylene group such as a methylene group, an ethylene group, a
trimethylene group, a tetramethylene group, a pentamethylene group,
or a hexamethylene group; an alkenylene group such as a group
represented by --CH.dbd.CH--CH.dbd.CH--; a nitrogen-containing
group such as a group represented by
--CH.sub.2CH.sub.2--NH--CH.sub.2--, a group represented by
--CH.dbd.CH--N.dbd.CH--, a group represented by
--CH.sub.2CH.sub.2--N.dbd.CH--, a group represented by
--CH.sub.2CH.sub.2CH.sub.2--NH--, a group represented by
--CH.dbd.CHCH.dbd.N--, or a group represented by
--CH.sub.2CH.sub.2--NH--CH.sub.2CH.sub.2--; and an
oxygen-containing group such as a group represented by
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2-- or a group represented by
--CH.sub.2CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2CH.sub.2--. The
number of carbon atoms of the divalent group in which the R.sup.24
ad R.sup.25 are bonded to each other is preferably from 2 to 12,
and more preferably from 2 to 8.
[0208] As the group represented by formula (IIb), an acyclic amino
group and a cyclic amino group can be cited.
[0209] Examples of the acyclic amino group include a dialkylamino
group such as a dimethylamino group, a diethylamino group, a
di(n-propyl)amino group, a di(isopropyl)amino group, a
di(n-butyl)amino group, a di(sec-butyl)amino group, a
di(tert-butyl)amino group, a di(neopentyl)amino group, or an
ethylmethylamino group; a di(alkoxyalkyl)amino group such as a
di(methoxymethyl)amino group, a di(methoxyethyl)amino group, a
di(ethoxymethyl)amino group, or a di(ethoxyethyl)amino group; and a
di(trialkylsilyl)amino group such as a di(trimethylsilyl)amino
group or a di(t-butyldimethylsilyl)amino group. Further examples
thereof include a di(oxacycloalkyle) amino group such as
di(oxiranyl)amino group or a di(tetrahydrofuranyl)amino group; and
a di(oxacycloalkylalkyl)amino group such as a di(glycidyl)amino
group or a di(tetrahydrofurfuryl)amino group. Yet further examples
thereof include an ethylideneamino group, a
1-methylpropylideneamino group, a 1,3-dimethylbutylideneamino
group, a 1-methylethylideneamino group, and a
4-N,N-dimethylaminobenzylideneamino group.
[0210] Examples of the cyclic amino group include a
1-polymethyleneimino group such as a 1-aziridinyl group, a
1-azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group,
a 1-hexamethyleneimino group, a 1-heptamethyleneimino group, a
1-octamethyleneimino group, a 1-decamethyleneimino group, or a
1-dodecamethyleneimino group. Furthermore, examples of the cyclic
amino group also include a 1-pyrrolyl group, a 1-imidazolidinyl
group, a 1-imidazolyl group, a 4,5-dihydro-1-imidazolyl group, a
1-pyrazolidinyl group, a 1-pyrazolyl group, a 1-piperazinyl group,
and a morpholino group.
*--O--R.sup.26 (IIc)
wherein R.sup.26 denotes a hydrocarbyl group that may contain at
least one atom selected from the group consisting of a nitrogen
atom, an oxygen atom, and a silicon atom, and * represents a
bonding position.
[0211] Examples of the hydrocarbyl group denoted by R.sup.26
include an alkyl group such as a methyl group, an ethyl group, an
n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl
group, a tert-butyl group, an n-pentyl group, a neopentyl group, an
isopentyl group, or an n-hexyl group; a cycloalkyl group such as a
cyclohexyl group; an aryl group such as a phenyl group, a
methylphenyl group, or an ethylphenyl group; and an aralkyl group
such as a benzyl group. It is preferably an alkyl group.
[0212] The number of carbon atoms of the hydrocarbyl group denoted
by R.sup.26 is preferably from 1 to 10, more preferably from 1 to
6, and yet more preferably from 1 to 4.
[0213] Examples of the nitrogen atom-containing hydrocarbyl group
denoted by R.sup.26 include a dialkylaminoalkyl group such as a
dimethylaminomethyl group, a dimethylaminoethyl group, a
dimethylaminopropyl group, or a diethylaminoethyl group.
[0214] The number of carbon atoms of the nitrogen atom-containing
hydrocarbyl group denoted by R.sup.26 is preferably from 3 to 10,
more preferably from 3 to 6, and yet more preferably from 3 to
4.
[0215] Examples of the oxygen atom-containing hydrocarbyl group
denoted by R.sup.26 include an alkoxyalkyl group such as a
methoxymethyl group, a methoxyethyl group, a methoxypropyl group,
an ethoxymethyl group, or an ethoxyethyl group; an oxacycloalkyl
group such as an oxiranyl group or a tetrahydrofuranyl group; and
an oxacycloalkylalkyl group such as a glycidyl group or a
tetrahydrofurfuryl group. It is preferably an alkoxyalkyl group, an
oxacycloalkyl group, or an oxacycloalkylalkyl group.
[0216] The number of carbon atoms of the oxygen atom-containing
hydrocarbyl group denoted by R.sup.26 is preferably from 2 to 10,
more preferably from 2 to 6, and yet more preferably from 2 to
4.
[0217] Examples of the silicon atom-containing hydrocarbyl group
denoted by R.sup.26 include a trialkylsilylalkyl group such as a
trimethylsilylmethyl group.
[0218] The number of carbon atoms of the silicon atom-containing
hydrocarbyl group denoted by R.sup.26 is preferably from 4 to 10,
more preferably from 4 to 6, and yet more preferably 4.
[0219] The substituted hydrocarbyl group denoted by R.sup.26 is
preferably an alkoxyalkyl group, an oxacycloalkyl group, or an
oxacycloalkylalkyl group.
[0220] Examples of the group represented by formula (IIc) include
an alkoxy group such as a methoxy group, an ethoxy group, an
n-propoxy group, an isopropoxy group, a sec-butoxy group, or a
tert-butoxy group; a phenoxy group; a dialkylaminoalkoxy group such
as a dimethylaminomethoxy group, or a diethylaminomethoxy group;
and a trialkylsiloxy group such as a trimethylsiloxy group or a
t-butyldimethylsiloxy group. Examples further include a
1,2-oxiranylalkoxy group such as a 1,2-oxiranylpropoxy group, a
1,2-oxiranylbutoxy group, and a 1,2-oxiranylpentyloxy group.
[0221] The group denoted by A of formula (IIa) is preferably a
substituted amino group, more preferably an acyclic amino group,
and yet more preferably a dialkylamino group, a
di(oxacycloalkyl)amino group, a di(oxacycloalkylalkyl)amino group,
or a di(trialkylsilyl)amino group.
[0222] As compound (II) for which A of formula (IIa) is a group
represented by formula (IIb), the following compounds for which
formula (IIb) is an acyclic amino group such as a dialkylamino
group, a di(alkoxyalkyl)amino group, a di(oxacycloalkyl)amino
group, or a di(oxacycloalkylalkyl)amino group can be cited.
[0223] Examples of the compound in which formula (IIb) is a
dialkylamino group include [0224]
[3-(dialkylamino)propyl]trialkoxysilanes such as [0225]
[3-(dimethylamino)propyl]trimethoxysilane, [0226]
[3-(diethylamino)propyl]trimethoxysilane, [0227]
[3-(ethylmethylamino)propyl]trimethoxysilane, [0228]
[3-(dimethylamino)propyl]triethoxysilane, [0229]
[3-(diethylamino)propyl]triethoxysilane, and [0230]
[3-(ethylmethylamino)propyl]triethoxysilane; [0231]
[3-(dialkylamino)propyl]alkyldialkoxysilanes such as [0232]
[3-(dimethylamino)propyl]methyldimethoxysilane, [0233]
[3-(diethylamino)propyl]methyldimethoxysilane, [0234]
[3-(ethylmethylamino)propyl]methyldimethoxysilane, [0235]
[3-(dimethylamino)propyl]ethyldimethoxysilane, [0236]
[3-(diethylamino)propyl]ethyldimethoxysilane, [0237]
[3-(ethylmethylamino)propyl]ethyldimethoxysilane, [0238]
[3-(dimethylamino)propyl]methyldiethoxysilane, [0239]
[3-(diethylamino)propyl]methyldiethoxysilane, [0240]
[3-(ethylmethylamino)propyl]methyldiethoxysilane, [0241]
[3-(dimethylamino)propyl]ethyldiethoxysilane, [0242]
[3-(diethylamino)propyl]ethyldiethoxysilane, and [0243]
[3-(ethylmethylamino)propyl]ethyldiethoxysilane; and [0244]
[3-(dialkylamino)propyl]dialkylalkoxysilanes such as [0245]
[3-(dimethylamino)propyl]dimethylmethoxysilane, [0246]
[3-(diethylamino)propyl]dimethylmethoxysilane, [0247]
[3-(dimethylamino)propyl]diethylmethoxysilane, [0248]
[3-(diethylamino)propyl]diethylmethoxysilane, [0249]
[3-(dimethylamino)propyl]dimethylethoxysilane, [0250]
[3-(diethylamino)propyl]dimethylethoxysilane, [0251]
[3-(dimethylamino)propyl]diethylethoxysilane, and [0252]
[3-(diethylamino)propyl]diethylethoxysilane.
[0253] Examples of the compound in which formula (IIb) is a
di(alkoxyalkyl)amino group include [0254]
{3-[di(alkoxyalkyl)amino]propyl}trialkoxysilanes such as [0255]
{3-[di(methoxymethyl)amino]propyl}trimethoxysilane, [0256]
{3-[di(ethoxymethyl)amino]propyl}trimethoxysilane, [0257]
{3-[di(methoxyethyl)amino]propyl}trimethoxysilane, [0258]
{3-[di(ethoxyethyl)amino]propyl}trimethoxysilane, [0259]
{3-[di(methoxymethyl)amino]propyl}triethoxysilane, [0260]
{3-[di(ethoxymethyl)amino]propyl}triethoxysilane, [0261]
{3-[di(methoxyethyl)amino]propyl}triethoxysilane, and [0262]
{3-[di(ethoxyethyl)amino]propyl}triethoxysilane; [0263]
{3-[di(alkoxyalkyl)amino]propyl}alkyldialkoxysilanes such as [0264]
{3-[di(methoxymethyl)amino]propyl}methyldimethoxysilane, [0265]
{3-[di(ethoxymethyl)amino]propyl}methyldimethoxysilane, [0266]
{3-[di(methoxyethyl)amino]propyl}methyldimethoxysilane, [0267]
{3-[di(ethoxyethyl)amino]propyl}methyldimethoxysilane, [0268]
{3-[di(methoxymethyl)amino]propyl}ethyldimethoxysilane, [0269]
{3-[di(ethoxymethyl)amino]propyl}ethyldimethoxysilane, [0270]
{3-[di(methoxyethyl)amino]propyl}ethyldimethoxysilane, [0271]
{3-[di(ethoxyethyl)amino]propyl}ethyldimethoxysilane, [0272]
{3-[di(methoxymethyl)amino]propyl}methyldiethoxysilane, [0273]
{3-[di(ethoxymethyl)amino]propyl}methyldiethoxysilane, [0274]
{3-[di(methoxyethyl)amino]propyl}methyldiethoxysilane, [0275]
{3-[di(ethoxyethyl)amino]propyl}methyldiethoxysilane, [0276]
{3-[di(methoxymethyl)amino]propyl}ethyldiethoxysilane, [0277]
{3-[di(ethoxymethyl)amino]propyl}ethyldiethoxysilane, [0278]
{3-[di(methoxyethyl)amino]propyl}ethyldiethoxysilane, and [0279]
{3-[di(ethoxyethyl)amino]propyl}ethyldiethoxysilane; and [0280]
{3-[di(alkoxyalkyl)amino]propyl}dialkylalkoxysilanes such as [0281]
{3-[di(methoxymethyl)amino]propyl}dimethylmethoxysilane, [0282]
{3-[di(ethoxymethyl)amino]propyl}dimethylmethoxysilane, [0283]
{3-[di(methoxyethyl)amino]propyl}dimethylmethoxysilane, [0284]
{3-[di(ethoxyethyl)amino]propyl}dimethylmethoxysilane, [0285]
{3-[di(methoxymethyl)amino]propyl}diethylmethoxysilane, [0286]
{3-[di(ethoxymethyl)amino]propyl}diethylmethoxysilane, [0287]
{3-[di(methoxyethyl)amino]propyl}diethylmethoxysilane, [0288]
{3-[di(ethoxyethyl)amino]propyl}diethylmethoxysilane, [0289]
{3-[di(methoxymethyl)amino]propyl}dimethylethoxysilane, [0290]
{3-[di(ethoxymethyl)amino]propyl}dimethylethoxysilane, [0291]
{3-[di(methoxyethyl)amino]propyl}dimethylethoxysilane, [0292]
{3-[di(ethoxyethyl)amino]propyl}dimethylethoxysilane, [0293]
{3-[di(methoxymethyl)amino]propyl}diethylethoxysilane, [0294]
{3-[di(ethoxymethyl)amino]propyl}diethylethoxysilane, [0295]
{3-[di(methoxyethyl)amino]propyl}diethylethoxysilane, and [0296]
{3-[di(ethoxyethyl)amino]propyl}diethylethoxysilane.
[0297] Examples of the compound in which formula (IIb) is a
di(oxacycloalkyl) amino group include compounds in which formula
(IIa) is a di(oxiranyl)amino group such as [0298]
{3-[di(oxiranyl)amino]propyl}trimethoxysilane, [0299]
{3-[di(oxiranyl)amino]propyl}triethoxysilane, [0300]
{3-[di(oxiranyl)amino]propyl}methyldimethoxysilane, [0301]
{3-[di(oxiranyl)amino]propyl}ethyldimethoxysilane, [0302]
{3-[di(oxiranyl)amino]propyl}methyldiethoxysilane, [0303]
{3-[di(oxiranyl)amino]propyl}ethyldiethoxysilane, [0304]
{3-[di(oxiranyl)amino]propyl}dimethylmethoxysilane, [0305]
{3-[di(oxiranyl)amino]propyl}diethylmethoxysilane, [0306]
{3-[di(oxiranyl)amino]propyl}dimethylethoxysilane, and [0307]
{3-[di(oxiranyl)amino]propyl}diethylethoxysilane; and compounds in
which formula (IIb) is a di(tetrahydrofuranyl)amino group such as
[0308] {3-[di(tetrahydrofuranyl)amino]propyl}trimethoxysilane,
[0309] {3-[di(tetrahydrofuranyl)amino]propyl}triethoxysilane,
[0310] {3-[di(tetrahydrofuranyl)amino]propyl}methyldimethoxysilane,
[0311] {3-[di(tetrahydrofuranyl)amino]propyl}ethyldimethoxysilane,
[0312] {3-[di(tetrahydrofuranyl)amino]propyl}methyldiethoxysilane,
[0313] {3-[di(tetrahydrofuranyl)amino]propyl}ethyldiethoxysilane,
[0314] {3-[di(tetrahydrofuranyl)amino]propyl}dimethylmethoxysilane,
[0315] {3-[di(tetrahydrofuranyl)amino]propyl}diethylmethoxysilane,
[0316] {3-[di(tetrahydrofuranyl)amino]propyl}dimethylethoxysilane,
and [0317]
{3-[di(tetrahydrofuranyl)amino]propyl}diethylethoxysilane.
[0318] Examples of the compound in which formula (IIb) is a
di(alkylene oxide alkyl)amino group include compounds in which
formula (IIb) is a di(glycidyl)amino group such as [0319]
{3-[di(glycidyl)amino]propyl}trimethoxysilane, [0320]
{3-[di(glycidyl)amino]propyl}triethoxysilane, [0321]
{3-[di(glycidyl)amino]propyl}methyldimethoxysilane, [0322]
{3-[di(glycidyl)amino]propyl}ethyldimethoxysilane, [0323]
{3-[di(glycidyl)amino]propyl}methyldiethoxysilane, [0324]
{3-[di(glycidyl)amino]propyl}ethyldiethoxysilane, [0325]
{3-[di(glycidyl)amino]propyl}dimethylmethoxysilane, [0326]
{3-[di(glycidyl)amino]propyl}diethylmethoxysilane, [0327]
{3-[di(glycidyl)amino]propyl}dimethylethoxysilane, and [0328]
{3-[di(glycidyl)amino]propyl}diethylethoxysilane; and Compounds in
which formula (IIb) is a di(tetrahydrofurfuryl)amino group such as
[0329] {3-[di(tetrahydrofurfuryl)amino]propyl}trimethoxysilane,
[0330] {3-[di(tetrahydrofurfuryl)amino]propyl}triethoxysilane,
[0331]
{3-[di(tetrahydrofurfuryl)amino]propyl}methyldimethoxysilane,
[0332] {3-[di(tetrahydrofurfuryl)amino]propyl}ethyldimethoxysilane,
[0333] {3-[di(tetrahydrofurfuryl)amino]propyl}methyldiethoxysilane,
[0334] {3-[di(tetrahydrofurfuryl)amino]propyl}ethyldiethoxysilane,
[0335]
{3-[di(tetrahydrofurfuryl)amino]propyl}dimethylmethoxysilane,
[0336] {3-[di(tetrahydrofurfuryl)amino]propyl}diethylmethoxysilane,
[0337] {3-[di(tetrahydrofurfuryl)amino]propyl}dimethylethoxysilane,
and [0338]
{3-[di(tetrahydrofurfuryl)amino]propyl}diethylethoxysilane.
[0339] Examples of the compound in which formula (IIb) is a
trialkylsilyl group include [0340]
{3-[di(trialkylsilyl)amino]propyl}trialkoxysilanes such as [0341]
{3-[di(trimethylsilyl)amino]propyl}trimethoxysilane, [0342]
{3-[di(t-butyldimethylsilyl)amino]propyl}trimethoxysilane, [0343]
{3-[di(trimethylsilyl)amino]propyl}triethoxysilane, and [0344]
{3-[di(t-butyldimethylsilyl)amino]propyl}triethoxysilane; [0345]
{3-[di(trialkylsilyl)amino]propyl}alkyldialkoxysilanes such as
[0346] {3-[di(trimethylsilyl)amino]propyl}methyldimethoxysilane,
[0347]
{3-[di(t-butyldimethylsilyl)amino]propyl}methyldimethoxysilane,
[0348] {3-[di(trimethylsilyl)amino]propyl}methyldiethoxysilane, and
[0349]
{3-[di(t-butyldimethylsilyl)amino]propyl}methyldiethoxysilane; and
[0350] {3-[di(trialkylsilyl)amino]propyl}dialkylalkoxysilanes such
as [0351] {3-[di(trimethylsilyl)amino]propyl}dimethylmethoxysilane,
[0352]
{3-[di(t-butyldimethylsilyl)amino]propyl}dimethylmethoxysilane,
[0353] {3-[di(trimethylsilyl)amino]propyl}dimethylethoxysilane, and
[0354]
{3-[di(t-butyldimethylsilyl)amino]propyl}dimethylethoxysilane.
[0355] Furthermore, examples of the compound (II) which A of
formula (IIa) is a group represented by formula (IIb) include the
following compounds in which formula (IIb) is an acyclic amino
group such as a 1-piperidinyl group, a 1-hexamethyleneimino group,
a 1-imidazolyl group, a 4,5-dihydro-1-imidazolyl group, a
1-piperazinyl group, or a morpholino group.
[0356] Examples of the compound in which formula (IIb) is a
1-piperidino group include [0357]
3-(1-piperidino)propyltrimethoxysilane, [0358]
3-(1-piperidino)propyltriethoxysilane, [0359]
3-(1-piperidino)propylmethyldimethoxysilane, [0360]
3-(1-piperidino)propylethyldimethoxysilane, [0361]
3-(1-piperidino)propylmethyldiethoxysilane, and [0362]
3-(1-piperidino)propylethyldiethoxysilane.
[0363] Examples of the compound in which formula (IIb) is a
1-hexamethyleneimino group include [0364]
3-(1-hexamethyleneimino)propyltrimethoxysilane, [0365]
3-(1-hexamethyleneimino)propyltriethoxysilane, [0366]
3-(1-hexamethyleneimino)propylmethyldimethoxysilane, [0367]
3-(1-hexamethyleneimino)propylethyldimethoxysilane, [0368]
3-(1-hexamethyleneimino)propylmethyldiethoxysilane, and [0369]
3-(1-hexamethyleneimino)propylethyldiethoxysilane.
[0370] Examples of the compound in which formula (IIb) is a
1-imidazolyl group include [0371]
N-(3-trimethoxysilylpropyl)imidazole, and [0372]
N-(3-triethoxysilylpropyl)imidazole.
[0373] Examples of compounds in which formula (IIb) is a
4,5-dihydro-1-imidazolyl group include [0374]
N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole, and [0375]
N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.
[0376] Examples of the compound in which formula (IIb) is a
1-piperazinyl group include [0377]
3-(1-piperazinyl)propyltrimethoxysilane, [0378]
3-(1-piperazinyl)propyltriethoxysilane, [0379]
3-(1-piperazinyl)propylmethyldimethoxysilane, [0380]
3-(1-piperazinyl)propylethyldimethoxysilane, [0381]
3-(1-piperazinyl)propylmethyldiethoxysilane, and [0382]
3-(1-piperazinyl)propylethyldiethoxysilane.
[0383] Examples of the compound in which formula (IIb) is a
morpholino group include [0384] 3-morpholinopropyltrimethoxysilane,
[0385] 3-morpholinopropyltriethoxysilane, [0386]
3-morpholinopropylmethyldimethoxysilane, [0387]
3-morpholinopropylethyldimethoxysilane, [0388]
3-morpholinopropylmethyldiethoxysilane, and [0389]
3-morpholinopropylethyldiethoxysilane.
[0390] Examples of the compound (II) in which A of formula (IIa) is
a group represented by formula (IIc) include the following
compounds in which R.sup.26 of formula (IIc) is an alkyl group or
an oxacycloalkylalkyl group.
[0391] The following compounds in which formula (IIc) is an alkyl
group: [0392] 3-(alkoxy)propyltrialkoxysilanes such as [0393]
3-(methoxy)propyltrimethoxysilane, [0394]
3-(ethoxy)propyltrimethoxysilane, [0395]
3-(n-propoxy)propyltrimethoxysilane, [0396]
3-(isopropoxy)propyltrimethoxysilane, [0397]
3-(n-butoxy)propyltrimethoxysilane, [0398]
3-(sec-butoxy)propyltrimethoxysilane, and [0399]
3-(tert-butoxy)propyltrimethoxysilane.
[0400] Compounds in which formula (IIc) is an oxacycloalkylalkyl
group: [0401] 2-glycidoxyalkyltrialkoxysilanes such as [0402]
2-glycidoxyethyltrimethoxysilane, [0403]
3-glycidoxypropyltrimethoxysilane, [0404]
2-glycidoxyethyltriethoxysilane, and [0405]
3-glycidoxypropyltriethoxysilane.
Tetrahydrofurfuryloxyalkyltrialkoxysilanes such as [0406]
2-tetrahydrofurfuryloxyethyltrimethoxysilane, [0407]
3-tetrahydrofurfuryloxypropyltrimethoxysilane, [0408]
2-tetrahydrofurfuryloxyethyltriethoxysilane, and [0409]
3-tetrahydrofurfuryloxypropyltriethoxysilane.
[0410] Compound (II) is preferably a
[3-(dialkylamino)propyl]trialkoxysilane, and more preferably [0411]
[3-(dimethylamino)propyl]trimethoxysilane, [0412]
[3-(diethylamino)propyl]trimethoxysilane, [0413]
[3-(dimethylamino)propyl]triethoxysilane, or [0414]
[3-(diethylamino)propyl]triethoxysilane.
Conjugated Diene Polymer Rubber
[0415] The conjugated diene polymer rubber comprises the
above-mentioned component (A) and component (B), component (A)
having a content, with the total amount of component (A) and
component (B) as 100% by weight, of from 5 to 90% by weight, and
component (B) having a content of from 95 to 10% by weight. In
order to improve abrasion resistance, the content of component (A)
is preferably not less than 10% by weight (the content of component
(B) being not more than 90% by weight), more preferably not less
than 15% by weight (the content of component (B) being not more
than 85% by weight), and yet more preferably not less than 20% by
weight (the content of component (B) being not more than 80% by
weight). In order to improve fuel economy, the content of component
(A) is preferably not more than 80% by weight (the content of
component (B) being not less than 20% by weight), more preferably
not more than 70% by weight (the content of component (B) being not
less than 30% by weight), and yet more preferably not more than 50%
by weight (the content of component (B) being not less than 50% by
weight).
[0416] In order to increase the strength, the conjugated diene
polymer preferably contains an aromatic vinyl unit in component (A)
or/and (B), and the content of the aromatic vinyl unit, relative to
100% by weight of the total amount of the conjugated diene unit and
the aromatic vinyl unit, is preferably at least 10% by weight (the
content of the conjugated diene unit being no greater than 90% by
weight), and more preferably at least 15% by weight (the content of
the conjugated diene unit being no greater than 85% by weight).
Furthermore, from the viewpoint of fuel economy, the content of the
aromatic vinyl unit is preferably no greater than 50% by weight
(the content of the conjugated diene unit being at least 50% by
weight), and more preferably no greater than 45% by weight (the
content of the conjugated diene unit being at least 55% by
weight).
[0417] In order to improve abrasion resistance and fuel economy,
the conjugated diene polymer rubber component preferably contains a
constituent unit based on a silicon-containing monomer in component
(A) and/or component (B), more preferably contains a constituent
unit based on a silicon-containing monomer in component (A), yet
more preferably contains a constituent unit based on a
silicon-containing monomer in component (A) and component (B). The
silicon-containing monomer is preferably a monomer represented by
formula (X).
[0418] In order to improve abrasion resistance and fuel economy,
the content of the constituent unit based on a silicon-containing
monomer in the conjugated diene polymer rubber is preferably not
less than 0.001 mmol/g and not more than 0.1 mmol/g per unit weight
of component (B). It is more preferably not less than 0.002 mmol/g
and not more than 0.07 mmol/g. It is yet more preferably not less
than 0.003 mmol/g and not more than 0.05 mmol/g.
[0419] In order to improve fuel economy, the vinyl bond content
(proportion of conjugated diene-based 1,2-addition constitutional
unit) of the conjugated diene polymer of the present invention,
with the content of the conjugated diene unit as 100% by mol, is
preferably no greater than 80% by mol, and more preferably no
greater than 70% by mol. Furthermore, from the viewpoint of grip
properties, it is preferably at least 10% by mol, more preferably
at least 15% by mol, yet more preferably at least 20% by mol, and
particularly preferably at least 40% by mol. The vinyl bond content
may be obtained by IR spectroscopy from the absorption intensity at
around 910 cm.sup.-1, which is an absorption peak of a vinyl
group.
[0420] In order to increase strength, the Mooney viscosity
(ML.sub.1+4) of the conjugated diene polymer of the present
invention is preferably not less than 10, and more preferably not
less than 20. Furthermore, in order to improve processability, it
is preferably not more than 200, and more preferably not more than
150. The Mooney viscosity (ML.sub.1+4) is measured at 100.degree.
C. in accordance with JIS K6300 (1994).
[0421] In order to improve fuel economy, the molecular weight
distribution of the conjugated diene polymer rubber is preferably 1
to 5, and more preferably 1 to 2. The molecular weight distribution
is obtained by measuring number-average molecular weight (Mn) and
weight-average molecular weight (Mw) by a gel permeation
chromatograph (GPC) method, and dividing Mw by Mn.
Method for Producing Conjugated Diene Polymer Rubber
[0422] As a preferred method for producing the conjugated diene
polymer rubber of the present invention, a method in which
component (A) and component (B) are separately prepared, and
component (A) and component (B) are mixed by a known method (a
method in which melt mixing is carried out by means of a known
kneader such as a roll or a Banbury, a method in which solution
mixing is carried out in a hydrocarbon solvent, etc.) can be cited.
Furthermore, a production method including step (c-1), step (c-2),
and step (c-3) below can also be cited.
Step (c-1): a step of polymerizing a monomer component including a
conjugated diene in a hydrocarbon solvent by an alkali metal
catalyst, thus giving a polymer having an alkali metal derived from
the catalyst in at least one conjugated diene-based monomer
unit-containing polymer chain terminus. Step (c-2): a step of
reacting the alkali metal-containing polymer terminus of the
polymer obtained in step (c-1) with a carbonyl group- and
substituted amino group-containing compound (compound (I)), the
amount of compound (I) used being not less than 0.05 mol and not
more than 0.9 mol per mole of the alkali metal of the alkali metal
catalyst used in step (c-1). Step (c-3): a step of reacting the
alkali metal-containing polymer terminus of the polymer having an
alkali metal in at least one polymer terminus with a compound
represented by formula (IIa) below (compound (II)) after step (c-2)
is completed, the amount of compound (II) used satisfying
expression (i) below.
X(II).ltoreq.y.gtoreq.X(I).times.(10/90) (i)
[0423] X (I): amount of compound (I) used in step (c-2) (units:
mol)
[0424] X (II): amount of compound (II) used in step (c-3) (units:
mol)
[0425] y: value for m in formula (IIa)
(R.sup.21O).sub.mSi(R.sup.22A).sub.nR.sup.23.sub.4-m-n (IIa)
wherein m denotes a number from 1 to 3, n denotes a number from 1
to 3, m+n is from 2 to 4, R.sup.21 and R.sup.23 denote a
hydrocarbyl group, R.sup.22 denotes a hydrocarbylene group, A
denotes a substituted amino group or an optionally substituted
hydrocarbyloxy group, when there are a plurality of R.sup.21s the
plurality of R.sup.21s may be identical to or different from each
other, when there are a plurality of R.sup.22s the plurality of
R.sup.22s may be identical to or different from each other, when
there are a plurality of R.sup.23s the plurality of R.sup.23s may
be identical to or different from each other, and when there are a
plurality of As the plurality of As may be identical to or
different from each other.
[0426] Examples of the alkali metal catalyst that may be used in
(c-1) include an alkali metal, an organoalkali metal compound, a
complex between an alkali metal and a polar compound, an oligomer
having an alkali metal, etc.
[0427] Examples of the alkali metal include lithium, sodium,
potassium, rubidium, and cesium.
[0428] Examples of the organoalkali metal compound include
ethyllithium, n-propyllithium, iso-propyllithium, n-butyllithium,
sec-butyllithium, t-octyllithium, n-decyllithium, phenyllithium,
2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium,
cyclohexyllithium, 4-cyclopentyllithium,
dimethylaminopropyllithium, diethylaminopropyllithium,
t-butyldimethylsilyloxypropyllithium, N-morpholinopropyllithium,
lithium hexamethyleneimide, lithium pyrrolidide, lithium
piperidide, lithium heptamethyleneimide, lithium
dodecamethyleneimide, 1,4-dilithio-2-butene, sodium naphthalenide,
sodium biphenylide, and potassium naphthalenide.
[0429] Examples of the complex between an alkali metal and a polar
compound include a potassium-tetrahydrofuran complex and a
potassium-diethoxyethane complex.
[0430] Examples of the oligomer having an alkali metal include the
sodium salt of a-methylstyrene tetramer.
[0431] Among them, an organolithium compound or an organosodium
compound is preferable, and an organolithium compound or
organosodium compound having 2 to 20 carbon atoms is more
preferable.
[0432] The hydrocarbon solvent used in step (c-1) is a solvent that
does not deactivate the organoalkali metal compound catalyst, and
examples thereof include an aliphatic hydrocarbon, an aromatic
hydrocarbon, and an alicyclic hydrocarbon. Specific examples of the
aliphatic hydrocarbon include propane, n-butane, iso-butane,
n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene,
trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, and
2-hexene. Specific examples of the aromatic hydrocarbon include
benzene, toluene, xylene, and ethylbenzene, and specific examples
of the alicyclic hydrocarbon include cyclopentane and cyclohexane.
They may be used on their own or in a combination of two or more
types. Among them, a hydrocarbon having 2 to 12 carbon atoms is
preferable.
[0433] In step (c-1), monomer containing a conjugated diene are
polymerized to produce a conjugated diene polymer having at a
polymer chain terminus an alkali metal originating from the
above-mentioned alkali metal catalyst. Examples of the conjugated
diene include 1,3-butadiene, isoprene, 1,3-pentadiene,
2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and they may be used
on their own or in a combination of two or more types. Among them,
from the viewpoint of ready availability, 1,3-butadiene and
isoprene are preferable.
[0434] In step (c-1), polymerization may be carried out using the
conjugated diene and another monomer. Examples of said other
monomer include an aromatic vinyl, a vinylnitrile, and an
unsaturated carboxylic acid ester. Specific examples of the
aromatic vinyl include styrene, -methylstyrene, vinyltoluene,
vinylnaphthalene, divinylbenzene, trivinylbenzene, and
divinylnaphthalene. Specific examples of the vinylnitrile include
acrylonitrile, and specific examples of the unsaturated carboxylic
acid ester include methyl acrylate, ethyl acrylate, methyl
methacrylate, and ethyl methacrylate. Among them, an aromatic vinyl
is preferable, and styrene is more preferable.
[0435] The amount of aromatic vinyl used, with the total amount of
conjugated diene and aromatic vinyl used as 100% by weight, is not
less than 0% by weight (the amount of conjugated diene used being
not more than 100% by weight); in order to improve strength it is
preferably not less than 10% by weight (the amount of conjugated
diene used being not more than 90% by weight), and more preferably
not less than 15% by weight (the amount of conjugated diene used
being not more than 85% by weight). In order to improve fuel
economy, the amount of aromatic vinyl used is preferably not more
than 50% by weight (the amount of conjugated diene used being not
less than 50% by weight), and more preferably not more than 45% by
weight (the amount of conjugated diene used being not less than 55%
by weight).
[0436] In step (c-1), in order to improve abrasion resistance and
fuel economy of the conjugated diene polymer rubber obtained, it is
preferable to use a silicon-containing monomer as one of the
monomer components and carry out polymerization of the monomer
components including the conjugated diene and the
silicon-containing monomer in the hydrocarbon solvent by means of
the alkali metal catalyst, thus giving a polymer having a
catalyst-derived alkali metal on at least one terminus of a polymer
chain containing a conjugated diene-based monomer unit and a
constituent unit based on a silicon-containing monomer. The
silicon-containing monomer is preferably a monomer represented by
formula (X) above.
[0437] In order to improve abrasion resistance and fuel economy,
the amount of silicon-containing monomer used, per g of monomer
components used for polymerization, is preferably not less than
0.001 m mmol, more preferably not less than 0.002 mmol, and yet
more preferably not less than 0.003 mmol. The amount used is
preferably not more than 0.1 mmol, more preferably not more than
0.07 mmol, and yet more preferably not more than 0.05 mmol.
[0438] The polymerization in step (c-1) may be carried out in the
presence of an agent for regulating the vinyl bond content of the
conjugated diene unit, an agent for regulating the distribution in
the conjugated diene polymer chain of the conjugated diene unit and
a constituent unit based on a monomer other than the conjugated
diene (hereafter, generally called `regulators`), etc. Examples of
such agents include an ether compound, a tertiary amine, and a
phosphine compound. Specific examples of the ether compound include
cyclic ethers such as tetrahydrofuran, tetrahydropyran, and
1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl
ether; aliphatic diethers such as ethylene glycol dimethyl ether,
ethylene glycol diethyl ether, ethylene glycol dibutyl ether,
diethylene glycol diethyl ether, and diethylene glycol dibutyl
ether; and aromatic ethers such as diphenyl ether and anisole.
Specific examples of the tertiary amine include triethylamine,
tripropylamine, tributylamine,
N,N,N',N'-tetramethylethylenediamine, N,N-diethylaniline, pyridine,
and quinoline. Specific examples of the phosphine compound include
trimethylphosphine, triethylphosphine, and triphenylphosphine. They
may be used on their own or in a combination of two or more
types.
[0439] The polymerization temperature in step A is preferably from
25.degree. C. to 100.degree. C., more preferably from 35.degree. C.
to 90.degree. C., and yet more preferably from 50.degree. C. to
80.degree. C. The polymerization time is preferably from 10 minutes
to 5 hours.
[0440] In step (c-2), the amount of compound (I) used in the
reaction between the polymer prepared in step (c-1) and compound
(I) is preferably from 0.05 to 0.9 mol per mol of the alkali metal
of alkali metal catalyst used in step (c-1). In order to improve
abrasion resistance, the amount of the compound (I) is more
preferably more than 0.1 mol, yet more preferably more than 0.15
mol, particularly preferably more than 0.2 mol. In order to improve
fuel economy, the amount of the compound (I) is more preferably
less than 0.8 mol, and yet more preferably less than 0.7 mol,
particularly preferably less than 0.5 mol.
[0441] In step (c-2), the temperature at which the polymer prepared
in step (c-2) and the compound (I) are reacted is preferably from
25.degree. C. to 100.degree. C., more preferably from 35.degree. C.
to 90.degree. C., and yet more preferably from 50.degree. C. to
80.degree. C. The contact time is preferably 60 sec to 5 hours, and
more preferably from 15 min to 1 hour.
[0442] In step (c-3), the amount of compound (II) used in the
reaction between the polymer having an alkali metal in at least one
polymer terminus and compound (II) is preferably an amount that
satisfies relationship (i) below. In order to improve abrasion
resistance, it is more preferably an amount that satisfies
relationship (ii) below, yet more preferably an amount that
satisfies relationship (iii) below, and particularly preferably an
amount that satisfies relationship (iv) below. In order to improve
fuel economy, it is more preferably an amount that satisfies
relationship (v) below, yet more preferably an amount that
satisfies relationship (vi) below, yet more preferably an amount
that satisfies relationship (vii) below, and particularly
preferably an amount that satisfies relationship (viii) below.
X(II).times.y.gtoreq.X(I).times.(10/90) (i)
X(II).times.y.gtoreq.X(I).times.(20/80) (ii)
X(II).times.y.gtoreq.X(I).times.(30/70) (iii)
X(II).times.y.gtoreq.X(I).times.(50/50) (iv)
X(I).times.(95/5).gtoreq.X(II) (v)
X(I).times.(90/10).gtoreq.X(II) (vi)
X(I).times.(85/15).gtoreq.X(II) (vii)
X(I).times.(80/20).gtoreq.X(II) (viii) [0443] X (I): amount of
compound (I) used in step (c-2) (units: mol) [0444] X (II): amount
of compound (II) used in step (c-3) (units: mol) [0445] y: value
for m in formula (IIa)
[0446] In step (c-3), the temperature at which the polymer having
an alkali metal in at least one polymer terminus and compound (II)
are reacted is preferably from 25.degree. C. to 100.degree. C., and
more preferably from 35.degree. C. to 90.degree. C. It is yet more
preferably from 50.degree. C. to 80.degree. C. The reaction time is
preferably from 60 seconds to 5 hours, more preferably from 5
minutes to 1 hour, and yet more preferably from 15 minutes to 1
hour.
[0447] In the production method of the conjugated diene polymer
rubber, a coupling agent may be added to the hydrocarbon solution
of the conjugated diene polymer as necessary from initiation of
polymerization of monomer by an alkali metal catalyst to
termination of polymerization. Examples of the coupling agent
include a compound represented by formula (III) below,
R.sup.31.sub.aML.sub.4-a (III)
wherein R.sup.10 denotes an alkyl group, an alkenyl group, a
cycloalkenyl group, or an aromatic residue, M denotes a silicon
atom or a tin atom, L denotes a halogen atom or a hydrocarbyloxy
group, and a denotes an integer of 0 to 2.
[0448] Here, the aromatic residue denotes a monovalent group in
which a hydrogen bonded to an aromatic ring is removed from an
aromatic hydrocarbon.
[0449] Examples of the coupling agent of formula (III) include
silicon tetrachloride, methyltrichlorosilane,
dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride,
methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin,
tetramethoxysilane, methyltrimethoxysilane,
dimethoxydimethylsilane, methyltriethoxysilane,
ethyltrimethoxysilane, dimethoxydiethylsilane,
diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane,
and diethoxydiethylsilane.
[0450] From the viewpoint of processability of the conjugated diene
polymer, the amount of coupling agent added is preferably not less
than 0.03 mol per mol of the alkali metal originating from the
alkali metal catalyst, and more preferably not less than 0.05 mol.
Furthermore, from the viewpoint of fuel economy, it is preferably
not more than 0.4 mol, and more preferably not more than 0.3
mol.
[0451] The conjugated diene polymer rubber may be recovered from
the hydrocarbon solution of the conjugated diene polymer rubber by
a known recovery method such as, for example, (1) a method in which
a coagulant is added to the hydrocarbon solution of the conjugated
diene polymer or (2) a method in which steam is added to the
hydrocarbon solution of the conjugated diene polymer. The
conjugated diene polymer thus recovered may be dried by a known
dryer such as a band dryer or an extrusion dryer.
A Conjugated Diene Polymer Rubber Composition
[0452] The conjugated diene polymer rubber of the present invention
may be used in a conjugated diene polymer rubber composition by
combining another polymer component, an additive, etc.
therewith.
[0453] Examples of another polymer component include conventional
styrene-butadiene copolymer rubber, polybutadiene rubber,
butadiene-isoprene copolymer rubber, and butyl rubber. Examples
further include natural rubber, an ethylene-propylene copolymer,
and an ethylene-octene copolymer. These polymer components may be
used in a combination of two or more types.
[0454] In the case where another polymer component is combined with
the conjugated diene polymer rubber of the present invention, from
the viewpoint of fuel economy, the amount of conjugated diene
polymer of the present invention is preferably not less than 10
parts by weight, and more preferably not less than 20 parts by
weight per 100 parts by weight of the total amount of polymer
components combined (including the amount of conjugated diene
polymer combined).
[0455] As the additive, a known additive may be used, and examples
thereof include a vulcanizing agent such as sulfur; a vulcanization
accelerator such as a thiazole-based vulcanization accelerator, a
thiuram-based vulcanization accelerator, a sulfenamide-based
vulcanization accelerator, or a guanidine-based vulcanization
accelerator; a vulcanization activator such as stearic acid or zinc
oxide; an organic peroxide; a filler such as silica, carbon black,
calcium carbonate, talc, alumina, clay, aluminum hydroxide, or
mica; a silane coupling agent; an extender oil; a processing aid;
an antioxidant; and a lubricant.
[0456] Examples of the silica include dry silica (anhydrous silicic
acid), wet silica (hydrated silicic acid), colloidal silica,
precipitated silica, calcium silicate, and aluminum silicate. One
type thereof may be used on its own, or two or more types thereof
may be used in combination. The BET specific surface area of the
silica is preferably from 50 to 250 m.sup.2/g. The BET specific
surface area is measured in accordance with ASTM D1993-03. As a
commercial product, product names VN3, AQ, ER, and RS-150
manufactured by Tosoh Silica Corporation, product names Zeosil
1115MP and 1165MP manufactured by Rhodia, etc. may be used.
[0457] Examples of the carbon black include furnace black,
acetylene black, thermal black, channel black, and graphite. With
regard to the carbon black, channel carbon black such as EPC, MPC,
or CC; furnace carbon black such as SAF, ISAF, HAF, MAF, FEF, SRF,
GPF, APF, FF, CF, SCF, or ECF; thermal carbon black such as FT or
MT; and acetylene carbon black can be cited as examples. One type
thereof may be used or two or more types thereof may be used in
combination.
[0458] The nitrogen adsorption specific surface area (N.sub.2SA) of
the carbon black is preferably from 5 to 200 m.sup.2/g, and the
dibutyl phthalate (DBP) absorption of the carbon black is
preferably from 5 to 300 mL/100 g. The nitrogen adsorption specific
surface area is measured in accordance with ASTM D4820-93, and the
DBP absorption is measured in accordance with ASTM D2414-93. As a
commercial product, product names SEAST 6, SEAST 7HM, and SEAST KH
manufactured by Tokai Carbon Co., Ltd., product names CK 3 and
Special Black 4A manufactured by Degussa, Inc., etc. may be
used.
[0459] Examples of the silane coupling agent include
vinyltrichlorosilane, vinyltriethoxysilane,
vinyltris(.beta.-methoxyethoxy)silane,
.epsilon.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
N-(.beta.-aminoethyl)-.gamma.-aminopropylmethyldimethoxysilane,
N-phenyl-.gamma.-aminopropyltrimethoxysilane,
.gamma.-chloropropyltrimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
bis(3-(triethoxysilyl)propyl)disulfide,
bis(3-(triethoxysilyl)propyl)tetrasulfide,
.gamma.-trimethoxysilylpropyldimethylthiocarbamyl tetrasulfide, and
.gamma.-trimethoxysilylpropylbenzothiazyl tetrasulfide. One type
thereof may be used or two or more types thereof may be used in
combination. As a commercial product, product names Si69 and Si75
manufactured by Degussa, Inc., etc. may be used.
[0460] When a conjugated diene polymer rubber is formed by
combining a filler with the conjugated diene polymer rubber of the
present invention, the amount of filler combined, relative to 100
parts by weight of the conjugated diene polymer of the present
invention combined, is preferably from 10 to 150 parts by weight.
From the viewpoint of abrasion resistance and strength, the amount
combined is more preferably not less than 20 parts by weight, and
yet more preferably not less than 30 parts by weight. From the
viewpoint of reinforcement being enhanced, it is more preferably
not more than 120 parts by weight, and yet more preferably not more
than 100 parts by weight.
[0461] When a conjugated diene polymer rubber is formed by
combining a filler from the viewpoint of fuel economy, it is
preferable to use silica as a filler. The amount of silica combined
is preferably not less than 50 parts by weight relative to 100
parts by weight of the total amount of fillers combined, and more
preferably not less than 70 parts by weight.
[0462] Examples of the extender oil include an aromatic mineral oil
(viscosity-gravity constant (V.G.C. value) from 0.900 to 1.049), a
naphthenic mineral oil (V.G.C. value from 0.850 to 0.899), and a
paraffinic mineral oil (V.G.C. value from 0.790 to 0.849). The
polycyclic aromatic content of the extender oil is preferably less
than 3% by weight, and more preferably less than 1% by weight. The
polycyclic aromatic content is measured in accordance with British
Institute of Petroleum method 346/92. Furthermore, the aromatic
compound content (CA) of the extender oil is preferably not less
than 20% by weight. Two or more types of extender oils may be used
in combination.
[0463] Examples of the vulcanization accelerator include
thiazole-based vulcanization accelerators such as
2-mercaptobenzothiazole, dibenzothiazyl disulfide, and
N-cyclohexyl-2-benzothiazylsulfenamide; thiuram-based vulcanization
accelerators such as tetramethylthiuram monosulfide and
tetramethylthiuram disulfide; sulfenamide-based vulcanization
accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide,
N-t-butyl-2-benzothiazolesulfenamide,
N-oxyethylene-2-benzothiazolesulfenamide,
N-oxyethylene-2-benzothiazolesulfenamide, and
N,N'-diisopropyl-2-benzothiazolesulfenamide; and guanidine-based
vulcanization accelerators such as diphenylguanidine,
diorthotolylguanidine and orthotolylbiguanidine. The amount thereof
used is preferably 0.1 to 5 parts by weight relative to 100 parts
by weight of rubber component, and more preferably 0.2 to 3 parts
by weight.
[0464] As a method for producing a conjugated diene polymer rubber
by combining another polymer component, an additive, etc. with the
conjugated diene polymer of the present invention, a known method
such as, for example, a method in which the components are kneaded
by means of a known mixer such as a roll or Banbury mixer can be
used.
[0465] With regard to kneading conditions, when an additive other
than a vulcanizing agent or a vulcanization accelerator is
combined, the kneading temperature is preferably from 50.degree. C.
to 200.degree. C. and more preferably from 80.degree. C. to
190.degree. C., and the kneading time is preferably from 30 sec to
30 min and more preferably from 1 min to 30 min. When a vulcanizing
agent or a vulcanization accelerator is combined, the kneading
temperature is preferably not more than 100.degree. C., and more
preferably from room temperature to 80.degree. C. A composition in
which a vulcanizing agent or a vulcanization accelerator is
combined is preferably used after carrying out a vulcanization
treatment such as press vulcanization. The vulcanization
temperature is preferably from 120.degree. C. to 200.degree. C.,
and more preferably from 140.degree. C. to 180.degree. C.
[0466] The conjugated diene polymer rubber composition of the
present invention have excellent fuel economy. The grip properties
are also good.
[0467] The conjugated diene polymer rubber and the conjugated diene
polymer rubber composition of the present invention are used for
tires, shoe soles, flooring materials, vibration-proofing
materials, etc., and are particularly suitably used for tires.
[0468] In accordance with the present invention, there can be
provided a conjugated diene polymer rubber that can give a
conjugated diene polymer rubber composition having excellent
abrasion resistance and a conjugated diene polymer rubber
composition containing the conjugated diene polymer rubber and a
filler.
EXAMPLES
[0469] The present invention is explained below by reference to
Examples.
[0470] `Normal temperature` in the Examples means 25.degree. C.
[0471] Physical properties were evaluated by the following
methods.
1. Mooney Viscosity (ML.sub.1+4)
[0472] The Mooney viscosity of a polymer was measured at
100.degree. C. in accordance with JIS K6300 (1994).
2. Vinyl Bond Content (Units: % by Mol)
[0473] The vinyl bond content of a polymer was determined by IR
spectroscopy from the absorption intensity at around 910 cm.sup.-1,
which is an absorption peak of a vinyl group.
3. Styrene Unit Content (Units: % by Weight)
[0474] The styrene unit content of a polymer was determined from
refractive index in accordance with JIS K6383 (1995).
4. Molecular Weight Distribution (Mw/Mn)
[0475] Weight-average molecular weight (Mw) and number-average
molecular weight (Mn) were measured under conditions (1) to (8)
below by a gel permeation chromatograph (GPC) method, and the
molecular weight distribution (Mw/Mn) of a polymer was
determined.
(1) Instrument: HLC-8020 manufactured by Tosoh Corporation (2)
Separation column: GMH-XL (2 columns in tandem) manufactured by
Tosoh Corporation (3) Measurement temperature: 40.degree. C. (4)
Carrier: tetrahydrofuran (5) Flow rate: 0.6 mL/min (6) Amount
injected: 5 .mu.L (7) Detector: differential refractometer (8)
Molecular weight standard: standard polystyrene 5. Abrasion
resistance (units: mg/1,000 rotations)
[0476] A ring-shaped vulcanized molded body is used as a test
piece; the amounts abraded under conditions of a load of 10 pounds
and a test piece rotational speed of 300 rpm for from 500 to 1,500
rotations, from 1,500 to 2,500 rotations, and from 2,500 to 3,500
rotations are measured using an Akron abrasion tester (Ueshima
Seisakusho Co., Ltd.), and the average value thereof is calculated.
The smaller this value, the better the abrasion resistance.
6. Fuel Economy
[0477] A strip-shaped test piece having a width of 1 or 2 mm and a
length of 40 mm was stamped out from a sheet-shaped vulcanized
molding and used for testing. The loss tangent (tan .delta.
(70.degree. C.)) at 70.degree. C. of the test piece was measured
using a viscoelastometer (Ueshima Seisakusho Co., Ltd.) under
conditions of a strain of 1% and a frequency of 10 Hz. The smaller
this value, the better the fuel economy.
Example 1
Preparation of Component (A)
[0478] A 20 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 10.2 kg of
industrial hexane (density 680 kg/m.sup.3), 604 g of 1,3-butadiene,
196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of
ethylene glycol diethyl ether. Subsequently, 14.65 mmol of
n-butyllithium was charged as an n-hexane solution, and
polymerization was started.
[0479] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 906 g, and the amount of
styrene supplied was 294 g.
[0480] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 11.40 mmol of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0481] 20 mL of a hexane solution containing 0.70 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0482] Following this, to the polymerization reaction solution thus
obtained were added 8.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 4.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), thus giving a polymer
solution (hereinafter, called solution (A1)) in which component (A)
was dissolved.
Preparation of component (B)
[0483] A 20 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 10.2 kg of
industrial hexane (density 680 kg/m.sup.3), 604 g of 1,3-butadiene,
196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of
ethylene glycol diethyl ether. Subsequently, 14.99 mmol of
n-butyllithium was charged as an n-hexane solution, and
polymerization was started.
[0484] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 906 g, and the amount of
styrene supplied was 294 g.
[0485] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 11.40 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0486] 20 mL of a hexane solution containing 0.70 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0487] Following this, to the polymerization reaction solution thus
obtained were added 8.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 4.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), thus giving a polymer
solution (hereinafter, called solution (B1)) in which component (B)
was dissolved.
(Preparation of Polymer Rubber)
[0488] 50 parts by weight of solution (A1) and 50 parts by weight
of solution (B1) were mixed, and the mixed solution thus obtained
was evaporated at normal temperature for 24 hours and further dried
under reduced pressure at 55.degree. C. for 12 hours, thus giving a
polymer rubber. The results of evaluation of the polymer rubber are
given in Table 1. `Normal temperature` in the Examples means
25.degree. C.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0489] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 1.
Example 2
[0490] The procedure of Example 1 was repeated except that a mixed
solution was prepared with the amount of solution (A1) as 60 parts
by weight and the amount of solution (B1) as 40 parts by weight.
The results of evaluation of the polymer rubber and the vulcanized
sheet are given in Table 1.
Example 3
[0491] The procedure of Example 1 was repeated except that a mixed
solution was prepared with the amount of solution (A1) as 70 parts
by weight and the amount of solution (B1) as 30 parts by weight.
The results of evaluation of the polymer rubber and the vulcanized
sheet are given in Table 1.
TABLE-US-00001 TABLE 1 Example Example Example 1 2 3 Mooney
viscosity -- 54 55 56 Vinyl bond content % by mol 58 58 58 Styrene
unit content % by weight 25 25 25 Molecular weight -- 1.23 1.22
1.18 distribution Abrasion resistance mg/ 290 280 290 Loss 1,000
rotations Fuel economy -- 0.158 0.165 0.187 tan .delta. (70.degree.
C. )
Example 4
Preparation of Polymer Rubber
[0492] A 30 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 15.3 kg of
industrial hexane (density 680 kg/m.sup.3), 912 g of 1,3-butadiene,
288 g of styrene, 9.1 mL of tetrahydrofuran, and 6.36 mL of
ethylene glycol diethyl ether. Subsequently, 21.25 mmol of
n-butyllithium was charged as an n-hexane solution, and
polymerization was started.
[0493] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 1,368 g, and the amount of
styrene supplied was 432 g.
[0494] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 4.63 mmol
(0.22 mol per mol of n-butyllithium) of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0495] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 13.88 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0496] 20 mL of a hexane solution containing 1.12 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0497] To the polymerization reaction solution were added 12.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 6.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), and the
polymerization reaction solution was subsequently evaporated at
normal temperature for 24 hours and further dried under reduced
pressure at 55.degree. C. for 12 hours, thus giving a polymer
rubber. The results of evaluation of the polymer rubber are given
in Table 2.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0498] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 2.
Comparative Example 1
Preparation of Polymer Rubber
[0499] A 20 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 10.2 kg of
industrial hexane (density 680 kg/m.sup.3), 547 g of 1,3-butadiene,
173 g of styrene, 6.07 mL of tetrahydrofuran, and 4.12 mL of
ethylene glycol diethyl ether. Subsequently, 13.31 mmol of
n-butyllithium was charged as an n-hexane solution, and
polymerization was started.
[0500] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied throughout the polymerization
was 821 g, and the amount of styrene supplied was 259 g.
[0501] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 11.25 mmol of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0502] 20 mL of a hexane solution containing 1.12 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0503] To the polymerization reaction solution were added 8.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 4.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), and the
polymerization reaction solution was subsequently evaporated at
normal temperature for 24 hours and further dried under reduced
pressure at 55.degree. C. for 12 hours, thus giving a polymer
rubber. The results of evaluation of the polymer rubber are given
in Table 2.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0504] 100 parts by weight of the polymer thus obtained, 78.4 parts
by weight of silica (product name: Ultrasil VN3-G, manufactured by
Degussa, Inc.), 6.4 parts by weight of a silane coupling agent
(product name: Si69, manufactured by Degussa, Inc.), 6.4 parts by
weight of carbon black (product name: Diablack N339, manufactured
by Mitsubishi Chemical Corporation), 47.6 parts by weight of an
extender oil (product name: X-140, manufactured by Kyodo Sekiyu),
1.5 parts by weight of an antioxidant (product name: Antigene 3C,
manufactured by Sumitomo Chemical Co., Ltd.), 2 parts by weight of
stearic acid, 2 parts by weight of zinc oxide, 1 part by weight of
a vulcanizing accelerator (product name: Soxinol CZ, manufactured
by Sumitomo Chemical Co., Ltd.), 1 part by weight of a vulcanizing
accelerator (product name: Soxinol D, manufactured by Sumitomo
Chemical Co., Ltd.), 1.5 parts by weight of a wax (product name:
Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial Co.,
Ltd.), and 1.4 parts by weight of sulfur were kneaded by means of a
Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 2.
Comparative Example 2
Preparation of Polymer Rubber
[0505] A 5 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 2.55 kg of
industrial hexane (density 680 kg/m.sup.3), 137 g of 1,3-butadiene,
43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.06 mL of
ethylene glycol diethyl ether. Subsequently, 3.56 mmol of
n-butyllithium was charged as an n-hexane solution, and
polymerization was started.
[0506] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 2.5 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied throughout the polymerization
was 205 g, and the amount of styrene supplied was 65 g.
[0507] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 2.81 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0508] 20 mL of a hexane solution containing 0.17 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0509] To the polymerization reaction solution were added 1.8 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 0.9 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), and the
polymerization reaction solution was subsequently evaporated at
normal temperature for 24 hours and further dried under reduced
pressure at 55.degree. C. for 12 hours, thus giving a polymer
rubber. The results of evaluation of the polymer rubber are given
in Table 2.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0510] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 2.
TABLE-US-00002 TABLE 2 Comparative Comparative Example Example
Example 4 1 2 Mooney -- 45 41 66 viscosity Vinyl bond % by mol 57
57 55 content Styrene unit % by weight 24 24 24 content Molecular
-- 1.15 1.09 1.23 weight distribution Abrasion mg/ 310 340 360
resistance 1,000 rotations Loss Fuel economy -- 0.165 0.210 0.141
tan .delta. (70.degree. C. )
Example 5
Preparation of Component (A)
[0511] A 20 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 10.2 kg of
industrial hexane (density 680 kg/m.sup.3), 604 g of 1,3-butadiene,
196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of
ethylene glycol diethyl ether. Subsequently, 8.54 mmol of
bis(diethylamino)methylvinylsilane and 14.49 mmol of n-butyllithium
were charged as an n-hexane solution, and polymerization was
started.
[0512] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 906 g, and the amount of
styrene supplied was 294 g. Furthermore, the amount of
bis(diethylamino)methylvinylsilane charged per monomer unit weight
charged and supplied to the polymerization reactor was 0.0043
mmol.
[0513] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 12.20 mmol of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0514] 20 mL of a hexane solution containing 0.74 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0515] Following this, to the polymerization reaction solution thus
obtained were added 8.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 4.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), thus giving a polymer
solution (hereinafter, called solution (A2)) in which component (A)
was dissolved.
Preparation of Component (B)
[0516] A 20 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 10.2 kg of
industrial hexane (density 680 kg/m.sup.3), 604 g of 1,3-butadiene,
196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of
ethylene glycol diethyl ether. Subsequently, 8.54 mmol of
bis(diethylamino)methylvinylsilane and 14.31 mmol of n-butyllithium
were charged as an n-hexane solution, and polymerization was
started.
[0517] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 906 g, and the amount of
styrene supplied was 294 g. Furthermore, the amount of
bis(diethylamino)methylvinylsilane charged per monomer unit weight
charged and supplied to the polymerization reactor was 0.0043
mmol.
[0518] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 12.20 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0519] 20 mL of a hexane solution containing 0.74 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0520] Following this, to the polymerization reaction solution thus
obtained were added 8.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 4.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), thus giving a polymer
solution (hereinafter, called solution (B2)) in which component (B)
was dissolved.
(Preparation of Polymer Rubber)
[0521] 10 parts by weight of solution (A2) and 90 parts by weight
of solution (B2) were mixed, and the mixed solution thus obtained
was evaporated at normal temperature for 24 hours and further dried
under reduced pressure at 55.degree. C. for 12 hours, thus giving a
polymer rubber. The results of evaluation of the polymer rubber are
given in Table 3.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0522] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 3.
Example 6
[0523] The procedure of Example 5 was repeated except that a mixed
solution was prepared with the amount of solution (A2) as 25 parts
by weight and the amount of solution (B2) as 75 parts by weight.
The results of evaluation of the polymer rubber and the vulcanized
sheet are given in Table 3.
Example 7
[0524] The procedure of Example 5 was repeated except that a mixed
solution was prepared with the amount of solution (A2) as 50 parts
by weight and the amount of solution (B2) as 50 parts by weight.
The results of evaluation of the polymer rubber and the vulcanized
sheet are given in Table 3.
Example 8
[0525] The procedure of Example 5 was repeated except that a mixed
solution was prepared with the amount of solution (A2) as 70 parts
by weight and the amount of solution (B2) as 30 parts by weight.
The results of evaluation of the polymer rubber and the vulcanized
sheet are given in Table 3.
TABLE-US-00003 TABLE 3 Exam- Exam- Exam- Example ple 5 ple 6 ple 7
8 Mooney -- 41 37 38 31 viscosity Vinyl bond % by mol 56 56 56 56
content Styrene unit % by weight 25 25 25 25 content Molecular --
1.21 1.19 1.17 1.15 weight distribution Abrasion mg/ 230 210 210
220 resistance 1,000 rotations Loss Fuel economy -- 0.127 0.123
0.126 0.13 tan .delta. (70.degree. C. )
Example 9
Preparation of Component (A)
[0526] A 20 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 10.2 kg of
industrial hexane (density 680 kg/m.sup.3), 604 g of 1,3-butadiene,
196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of
ethylene glycol diethyl ether. Subsequently, 12.2 mmol of
bis(diethylamino)methylvinylsilane and 15.72 mmol of n-butyllithium
were charged as an n-hexane solution, and polymerization was
started.
[0527] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 906 g, and the amount of
styrene supplied was 294 g. Furthermore, the amount of
bis(diethylamino)methylvinylsilane charged per monomer unit weight
charged and supplied to the polymerization reactor was 0.0061
mmol.
[0528] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 12.20 mmol of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0529] 20 mL of a hexane solution containing 0.74 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0530] Following this, to the polymerization reaction solution thus
obtained were added 8.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 4.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), thus giving a polymer
solution (hereinafter, called solution (A3)) in which component (A)
was dissolved.
Preparation of Component (B)
[0531] A 20 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 10.2 kg of
industrial hexane (density 680 kg/m.sup.3), 604 g of 1,3-butadiene,
196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of
ethylene glycol diethyl ether. Subsequently, 12.2 mmol of
bis(diethylamino)methylvinylsilane and 14.84 mmol of n-butyllithium
were charged as an n-hexane solution, and polymerization was
started.
[0532] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 3 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 906 g, and the amount of
styrene supplied was 294 g. Furthermore, the amount of
bis(diethylamino)methylvinylsilane charged per monomer unit weight
charged and supplied to the polymerization reactor was 0.0061
mmol.
[0533] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 12.20 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0534] 20 mL of a hexane solution containing 0.74 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0535] Following this, to the polymerization reaction solution thus
obtained were added 8.0 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 4.0 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), thus giving a polymer
solution (hereinafter, called solution (B3)) in which component (B)
was dissolved.
(Preparation of Polymer Rubber)
[0536] 20 parts by weight of solution (A3) and 80 parts by weight
of solution (B3) were mixed, and the mixed solution thus obtained
was evaporated at normal temperature for 24 hours and further dried
under reduced pressure at 55.degree. C. for 12 hours, thus giving a
polymer rubber. The results of evaluation of the polymer rubber are
given in Table 4.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0537] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 4.
Example 10
[0538] The procedure of Example 9 was repeated except that a mixed
solution was prepared with the amount of solution (A3) as 50 parts
by weight and the amount of solution (B3) as 50 parts by weight.
The results of evaluation of the polymer rubber and the vulcanized
sheet are given in Table 4.
Example 11
[0539] The procedure of Example 9 was repeated except that a mixed
solution was prepared with the amount of solution (A3) as 75 parts
by weight and the amount of solution (B3) as 25 parts by weight.
The results of evaluation of the polymer rubber and the vulcanized
sheet are given in Table 4.
TABLE-US-00004 TABLE 4 Example Example Example 9 10 11 Mooney
viscosity -- 53 48 44 Vinyl bond content % by mol 57 57 57 Styrene
unit content % by weight 24 24 25 Molecular weight -- 1.21 1.18
1.15 distribution Abrasion resistance mg/ 250 240 240 Loss 1,000
rotations Fuel economy -- 0.109 0.104 0.103 tan .delta. (70.degree.
C. )
Example 12
Preparation of Polymer Rubber
[0540] A 5 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 2.55 kg of
industrial hexane (density 680 kg/m.sup.3), 137 g of 1,3-butadiene,
43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.09 mL of
ethylene glycol diethyl ether. Subsequently, 1.97 mmol of
bis(diethylamino)methylvinylsilane and 3.56 mmol of n-butyllithium
were charged as an n-hexane solution, and polymerization was
started.
[0541] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 2.5 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 205 g, and the amount of
styrene supplied was 65 g. Furthermore, the amount of
bis(diethylamino)methylvinylsilane charged per monomer unit weight
charged and supplied to the polymerization reactor was 0.0044
mmol.
[0542] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 0.42 mmol
(0.12 mol per mol of n-butyllithium) of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0543] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 2.39 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0544] 20 mL of a hexane solution containing 0.17 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0545] To the polymerization reaction solution were added 1.8 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 0.9 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), and the
polymerization reaction solution was subsequently evaporated at
normal temperature for 24 hours and further dried under reduced
pressure at 55.degree. C. for 12 hours, thus giving a polymer
rubber. The results of evaluation of the polymer rubber are given
in Table 5.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0546] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 5.
Example 13
Preparation of Polymer Rubber
[0547] A 5 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 2.55 kg of
industrial hexane (density 680 kg/m.sup.3), 137 g of 1,3-butadiene,
43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.12 mL of
ethylene glycol diethyl ether. Subsequently, 1.97 mmol of
bis(diethylamino)methylvinylsilane and 3.54 mmol of n-butyllithium
were charged as an n-hexane solution, and polymerization was
started.
[0548] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 2.5 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 205 g, and the amount of
styrene supplied was 65 g. Furthermore, the amount of
bis(diethylamino)methylvinylsilane charged per monomer unit weight
charged and supplied to the polymerization reactor was 0.0044
mmol.
[0549] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 0.70 mmol
(0.20 mol per mol of n-butyllithium) of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0550] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 2.11 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0551] 20 mL of a hexane solution containing 0.17 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0552] To the polymerization reaction solution were added 1.8 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 0.9 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), and the
polymerization reaction solution was subsequently evaporated at
normal temperature for 24 hours and further dried under reduced
pressure at 55.degree. C. for 12 hours, thus giving a polymer
rubber. The results of evaluation of the polymer rubber are given
in Table 5.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0553] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 5.
Example 14
Preparation of Polymer Rubber
[0554] A 5 L capacity stainless polymerization reactor was washed,
dried, flushed with dry nitrogen, and charged with 2.55 kg of
industrial hexane (density 680 kg/m.sup.3), 137 g of 1,3-butadiene,
43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.09 mL of
ethylene glycol diethyl ether. Subsequently, 1.97 mmol of
bis(diethylamino)methylvinylsilane and 3.68 mmol of n-butyllithium
were charged as an n-hexane solution, and polymerization was
started.
[0555] Copolymerization of 1,3-butadiene and styrene was carried
out at a stirring speed of 130 rpm and a polymerization reactor
internal temperature of 65.degree. C. for 2.5 hours while
continuously supplying the monomers to the polymerization reactor.
The amount of 1,3-butadiene supplied was 205 g, and the amount of
styrene supplied was 65 g. Furthermore, the amount of
bis(diethylamino)methylvinylsilane charged per monomer unit weight
charged and supplied to the polymerization reactor was 0.0044
mmol.
[0556] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 1.41 mmol
(0.38 mol per mol of n-butyllithium) of
N-(3-dimethylaminopropyl)acrylamide was added thereto, and stirring
was carried out for 15 minutes.
[0557] Following this, the polymerization reaction solution thus
obtained was stirred at a stirring speed of 130 rpm, 1.41 mmol of
3-diethylaminopropyltriethoxysilane was added thereto, and stirring
was carried out for 15 minutes.
[0558] 20 mL of a hexane solution containing 0.17 mL of methanol
was added to the polymerization reaction solution, and the
polymerization reaction solution was stirred for a further 5
minutes.
[0559] To the polymerization reaction solution were added 1.8 g of
2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate (product name: Sumilizer GM, manufactured by Sumitomo
Chemical Co., Ltd.) and 0.9 g of pentaerythritol
tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D,
manufactured by Sumitomo Chemical Co., Ltd.), and the
polymerization reaction solution was subsequently evaporated at
normal temperature for 24 hours and further dried under reduced
pressure at 55.degree. C. for 12 hours, thus giving a polymer
rubber. The results of evaluation of the polymer rubber are given
in Table 5.
(Preparation of Rubber Composition and Vulcanized Sheet)
[0560] 100 parts by weight of the polymer rubber thus obtained,
78.4 parts by weight of silica (product name: Ultrasil VN3-G,
manufactured by Degussa, Inc.), 6.4 parts by weight of a silane
coupling agent (product name: Si69, manufactured by Degussa, Inc.),
6.4 parts by weight of carbon black (product name: Diablack N339,
manufactured by Mitsubishi Chemical Corporation), 47.6 parts by
weight of an extender oil (product name: X-140, manufactured by
Kyodo Sekiyu), 1.5 parts by weight of an antioxidant (product name:
Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.), 2 parts
by weight of stearic acid, 2 parts by weight of zinc oxide, 1 part
by weight of a vulcanizing accelerator (product name: Soxinol CZ,
manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of a
vulcanizing accelerator (product name: Soxinol D, manufactured by
Sumitomo Chemical Co., Ltd.), 1.5 parts by weight of a wax (product
name: Sunnoc N, manufactured by Ouchi Shinko Chemical Industrial
Co., Ltd.), and 1.4 parts by weight of sulfur were kneaded by means
of a Labo Plastomill to prepare a rubber composition. The rubber
composition thus obtained was molded into a sheet using a 6 inch
roll, and the sheet was vulcanized by heating at 160.degree. C. for
45 minutes, thus giving a vulcanized sheet. The results of
evaluation of the physical properties of the vulcanized sheet are
given in Table 5.
TABLE-US-00005 TABLE 5 Example Example Example 12 13 14 Mooney
viscosity -- 62 54 55 Vinyl bond content % by mol 57 58 57 Styrene
unit content % by weight 24 24 24 Molecular weight -- 1.26 1.19
1.24 distribution Abrasion resistance mg/ 260 240 230 Loss 1,000
rotations Fuel economy -- 0.127 0.129 0.126 tan .delta. (70.degree.
C. )
* * * * *