U.S. patent application number 12/573595 was filed with the patent office on 2010-04-15 for granular stabilizer for polymer and production process thereof.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Kenji Kimura, Kazuhiro Kitamura, Natsuko Sato.
Application Number | 20100093904 12/573595 |
Document ID | / |
Family ID | 41480131 |
Filed Date | 2010-04-15 |
United States Patent
Application |
20100093904 |
Kind Code |
A1 |
Kitamura; Kazuhiro ; et
al. |
April 15, 2010 |
GRANULAR STABILIZER FOR POLYMER AND PRODUCTION PROCESS THEREOF
Abstract
The present invention provides a granular stabilizer for a
polymer which is low-dusting and thus is easy to be handled. The
present invention relates to a granular stabilizer for a polymer,
comprising a compound shown by the formula (1): ##STR00001##
wherein R.sup.1s and R.sup.2s each independently represents a
hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a
cycloalkyl group having 5 to 8 carbon atoms; R.sup.3s each
independently represents a hydrogen atom or an alkyl group having 1
to 8 carbon atoms; and X represents a single bond, a sulfur atom,
an oxygen atom, an alkylidene group having 1 to 8 carbon atoms or a
cycloalkylidene group having 5 to 8 carbon atoms.
Inventors: |
Kitamura; Kazuhiro; (Osaka,
JP) ; Sato; Natsuko; (Osaka, JP) ; Kimura;
Kenji; (Funabashi-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W., SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
Tokyo
JP
|
Family ID: |
41480131 |
Appl. No.: |
12/573595 |
Filed: |
October 5, 2009 |
Current U.S.
Class: |
524/291 ;
252/182.18; 560/140 |
Current CPC
Class: |
C08K 5/134 20130101 |
Class at
Publication: |
524/291 ;
560/140; 252/182.18 |
International
Class: |
C08K 5/105 20060101
C08K005/105; C07C 69/017 20060101 C07C069/017; C09K 3/00 20060101
C09K003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 6, 2008 |
JP |
2008-259470 |
Dec 22, 2008 |
JP |
2008-325940 |
Dec 22, 2008 |
JP |
2008-325942 |
Claims
1. A granular stabilizer for a polymer, comprising a compound shown
by the formula (1): ##STR00012## wherein R.sup.1s and R.sup.2s each
independently represents a hydrogen atom, an alkyl group having 1
to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon
atoms; R.sup.3s each independently represents a hydrogen atom or an
alkyl group having 1 to 8 carbon atoms; and X represents a single
bond, a sulfur atom, an oxygen atom, an alkylidene group having 1
to 8 carbon atoms or a cycloalkylidene group having 5 to 8 carbon
atoms.
2. The granular stabilizer for a polymer according to claim 1,
wherein the granular stabilizer for a polymer has a weight of 1 mg
to 25 mg per particle, preferably 5 mg to 25 mg per particle.
3. The granular stabilizer for a polymer according to claim 1 or 2,
wherein the compound shown by the formula (1) is
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate or
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate.
4. The granular stabilizer for a polymer according to claim 1 or 2,
comprising 99.9 to 80% by weight of the compound shown by the
formula (1) and 0.1 to 20% by weight of a compound shown by the
formula (2) based on 100% by weight of the granular stabilizer for
a polymer, ##STR00013## wherein R.sup.1s and R.sup.2s each
independently represents a hydrogen atom, an alkyl group having 1
to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon
atoms; R.sup.3s each independently represents a hydrogen atom or an
alkyl group having 1 to 8 carbon atoms; and X represents a single
bond, a sulfur atom, an oxygen atom, an alkylidene group having 1
to 8 carbon atoms or a cycloalkylidene group having 5 to 8 carbon
atoms, ##STR00014## wherein R.sup.11 is a linear alkyl group having
1 to 30 carbon atoms or a branched alkyl group having 3 to 60
carbon atoms, to the alkyl group may be bonded a hydroxyl group, a
carboxyl group, an alkoxycarbonyl group having 2 to 30 carbon
atoms, or an alkylcarbonyloxy group having 2 to 30 carbon atoms,
and a methylene group contained in the alkyl group, the
alkoxycarbonyl group and the alkylcarbonyloxy group may be
substituted by a sulfur atom or an oxygen atom; and R.sup.12 is a
linear alkyl group having 1 to 30 carbon atoms, a branched alkyl
group having 3 to 30 carbon atoms, or an aralkyl group having 7 to
20 carbon atoms, to the alkyl group or the aralkyl group may be
bonded a hydroxyl group, a carboxyl group, an alkoxycarbonyl group
having 2 to 30 carbon atoms or an alkylcarbonyloxy group having 2
to 30 carbon atoms, and methylene groups contained in the alkyl
group, the aralkyl group, the alkoxycarbonyl group and the
alkylcarbonyloxy group may be substituted by a sulfur atom or an
oxygen atom.
5. The granular stabilizer for a polymer according to claim 4,
wherein the compound shown by the formula (2) is
octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, glycerin
monostearate, dimyristyl-3,3'-thiodipropionate or
distearyl-3,3'-thiodipropionate.
6. The granular stabilizer for a polymer according to any one of
claims 1 to 5, wherein the granular stabilizer for a polymer is in
the shape of a circular disc, an approximate sphere or an
approximate hemi-sphere.
7. A process for producing a granular stabilizer for a polymer,
comprising a compound shown by the formula (1): ##STR00015##
wherein R.sup.1s and R.sup.2s each independently represents a
hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a
cycloalkyl group having 5 to 8 carbon atoms; R.sup.3s each
independently represents a hydrogen atom or an alkyl group having 1
to 8 carbon atoms; and X represents a single bond, a sulfur atom,
an oxygen atom, an alkylidene group having 1 to 8 carbon atoms or a
cycloalkylidene group having 5 to 8 carbon atoms, wherein the
process comprises: a first step of melting the compound shown by
the formula (1), which has a melting point of T.sub.m.degree. C.; a
second step of solidifying the molten material obtained in the
first step at a temperature of T.sub.1.degree. C. wherein the
T.sub.1.degree. C. is a temperature lower than T.sub.m.degree. C.;
and a third step of heating the solidified material obtained in the
second step under an atmosphere at a temperature of T.sub.2.degree.
C. satisfying the formula (I): T.sub.1<T.sub.2.ltoreq.T.sub.m
(I)
8. The process for producing a granular stabilizer for a polymer
according to claim 7, wherein the molten material obtained in the
first step is solidified at a temperature of T.sub.1.degree. C.
satisfying the formula (II): 5<T.sub.1<T.sub.m-40 (II) in the
second step.
9. The process for producing a granular stabilizer for a polymer
according to claim 7 or 8, wherein the molten material obtained in
the first step is dropped on a plate to be solidified in the second
step.
10. The process for producing a granular stabilizer for a polymer
according to any one of claims 7 to 9, wherein the solidified
material obtained in the second step is further heated under an
atmosphere at a temperature of T.sub.2.degree. C. satisfying the
formula (III): T.sub.m-30<T.sub.2.ltoreq.T.sub.m (III) in the
third step.
11. The process for producing a granular stabilizer for a polymer
according to any one of claims 7 to 10, further comprising a fourth
step of cooling the heated material obtained in the third step at a
temperature less than T.sub.2.degree. C.
12. The process for producing a granular stabilizer for a polymer
according to claim 11, wherein the heated material is cooled under
an atmosphere at a temperature of T.sub.1.degree. C. satisfying the
formula (II): 5<T.sub.1<T.sub.m-40 (II) in the fourth
step.
13. A process for producing a granular stabilizer for a polymer,
comprising a compound shown by the formula (1): ##STR00016##
wherein R.sup.1s and R.sup.2s each independently represents a
hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a
cycloalkyl group having 5 to 8 carbon atoms; R.sup.3s each
independently represents a hydrogen atom or an alkyl group having 1
to 8 carbon atoms; and X represents a single bond, a sulfur atom,
an oxygen atom, an alkylidene group having 1 to 8 carbon atoms or a
cycloalkylidene group having 5 to 8 carbon atoms, wherein the
process comprises: a first step of melting the compound shown by
the formula (1) having a melting point of T.sub.m.degree. C.; a
second step of forming the molten material obtained in the first
step at a temperature of T.sub.1.degree. C. satisfying the formula
(I): T.sub.1<T.sub.m (I) and a third step of mixing the formed
material obtained in the second step with the solid compound shown
by the formula (1) at a temperature lower than T.sub.m.degree.
C.
14. The process for producing a granular stabilizer for a polymer
according to claim 13, wherein the molten material obtained in the
first step is formed at a temperature of T.sub.1.degree. C.
satisfying the formula (II): T.sub.m-50<T.sub.1<T.sub.m (II)
in the second step.
15. The process for producing a granular stabilizer for a polymer
according to claim 13 or 14, wherein, in the third step, the solid
compound shown by the formula (1) is mixed in an amount of 1 to 20%
by weight based on 100% by weight of the formed material obtained
in the second step.
16. The process for producing a granular stabilizer for a polymer
according to any one of claims 13 to 15, further comprising a step
of cooling the mixture obtained in the third step at a temperature
of T.sub.2 satisfying the formula (III): 5<T.sub.2<T.sub.1-30
(III).
17. The process for producing a granular stabilizer for a polymer
according to any one of claims 7 to 16, wherein the compound shown
by the formula (1) is
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate or
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate.
18. Use of the granular stabilizer for a polymer according to any
one of claims 1 to 6 for thermally stabilizing a thermoplastic
polymer.
19. A thermoplastic polymer composition, comprising 0.01 to 2 parts
by weight of the granular stabilizer for a polymer according to any
one of claims 1 to 6 based on 100 parts by weight of a
thermoplastic polymer.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present patent application claims priority to Japanese
Patent Application Nos. 2008-259470, 2008-325940, and 2008-325942,
herein incorporated by reference in their entirety.
[0003] The present invention relates to granular stabilizers for a
polymer and a production process thereof.
[0004] 2. Description of the Related Art
[0005] As a stabilizer for a polymer, which stabilizes a polymer
such as polybutadiene against heat and the like,
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate (hereinafter referred to as "a compound (1-1)"), shown by
the formula (1-1):
##STR00002##
is known (see JP-A No. 1-168643).
[0006] As a process for producing polybutadiene blended with a
stabilizer for a polymer, a process in which polymerization is
performed in a hydrocarbon medium, and a solution comprising the
polybutadiene after finishing the polymerization reaction is mixed
with a solution of a stabilizer for a polymer in a hydrocarbon
medium, followed by removal of the hydrocarbon medium, is generally
adopted (see JP-A No. 1-168643).
[0007] Also, as a process for producing the compound of the formula
(1-1), a process in which bisphenol and acrylic acid are reacted in
an organic medium, and the reaction mass is washed with water and
cooled to produce a crystal (see JP-A No. 1-168643), and a process
in which the organic medium is distilled away by evaporation from
the above-mentioned reaction mass, and methanol is added to the
resulting mass to produce a crystal (see JP-A No. 4-264051) are
disclosed.
SUMMARY OF THE INVENTION
[0008] The stabilizers for a polymer obtained by the processes
described above, however, are powdery crystals, and therefore, they
are difficult to be handled because of occurrence of dusting.
[0009] In order to solve the problem, the present inventors have
made painstaking studies. As a result, they have reached the
following inventions [1] to [19].
[1] A granular stabilizer for a polymer, comprising a compound
shown by the formula (1):
##STR00003##
wherein R.sup.1s and R.sup.2s each independently represents a
hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a
cycloalkyl group having 5 to 8 carbon atoms; R.sup.3s each
independently represents a hydrogen atom or an alkyl group having 1
to 8 carbon atoms; and X represents a single bond, a sulfur atom,
an oxygen atom, an alkylidene group having 1 to 8 carbon atoms or a
cycloalkylidene group having 5 to 8 carbon atoms. [2] The granular
stabilizer for a polymer according to [1], wherein the granular
stabilizer for a polymer has a weight of 1 mg to 25 mg per
particle, preferably 5 mg to 25 mg per particle. [3] The granular
stabilizer for a polymer according to [1] or [2], wherein the
compound shown by the formula (1) is [0010]
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate or
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate. [4] The granular stabilizer for a polymer according to
[1] or [2], comprising 99.9 to 80% by weight of the compound shown
by the formula (1) and 0.1 to 20% by weight of a compound shown by
the formula (2) based on 100% by weight of the granular stabilizer
for a polymer,
##STR00004##
[0010] wherein R.sup.1s and R.sup.2s each independently represents
a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a
cycloalkyl group having 5 to 8 carbon atoms; R.sup.3s each
independently represents a hydrogen atom or an alkyl group having 1
to 8 carbon atoms; and X represents a single bond, a sulfur atom,
an oxygen atom, an alkylidene group having 1 to 8 carbon atoms or a
cycloalkylidene group having 5 to 8 carbon atoms,
##STR00005##
wherein R.sup.11 is a linear alkyl group having 1 to 30 carbon
atoms or a branched alkyl group having 3 to 60 carbon atoms, to the
alkyl group may be bonded a hydroxyl group, a carboxyl group, an
alkoxycarbonyl group having 2 to 30 carbon atoms, or an
alkylcarbonyloxy group having 2 to 30 carbon atoms, and a methylene
group contained in the alkyl group, the alkoxycarbonyl group and
the alkylcarbonyloxy group may be substituted by a sulfur atom or
an oxygen atom; and R.sup.12 is a linear alkyl group having 1 to 30
carbon atoms, a branched alkyl group having 3 to 30 carbon atoms,
or an aralkyl group having 7 to 20 carbon atoms, to the alkyl group
or the aralkyl group may be bonded a hydroxyl group, a carboxyl
group, an alkoxycarbonyl group having 2 to 30 carbon atoms or an
alkylcarbonyloxy group having 2 to 30 carbon atoms, and methylene
groups contained in the alkyl group, the aralkyl group, the
alkoxycarbonyl group and the alkylcarbonyloxy group may be
substituted by a sulfur atom or an oxygen atom. [5] The granular
stabilizer for a polymer according to [4], wherein the compound
shown by the formula (2) is [0011]
octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, glycerin
monostearate, dimyristyl-3,3'-thiodipropionate or
distearyl-3,3'-thiodipropionate. [6] The granular stabilizer for a
polymer according to any one of [1] to [5], wherein the granular
stabilizer for a polymer is in the shape of a circular disc, an
approximate sphere or an approximate hemi-sphere. [7] A process for
producing a granular stabilizer for a polymer, comprising a
compound shown by the formula (1):
##STR00006##
[0011] wherein R.sup.1s and R.sup.2s each independently represents
a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a
cycloalkyl group having 5 to 8 carbon atoms; R.sup.3s each
independently represents a hydrogen atom or an alkyl group having 1
to 8 carbon atoms; and X represents a single bond, a sulfur atom,
an oxygen atom, an alkylidene group having 1 to 8 carbon atoms or a
cycloalkylidene group having 5 to 8 carbon atoms, wherein the
process comprises: a first step of melting the compound shown by
the formula (1), which has a melting point of T.sub.m.degree. C.; a
second step of solidifying the molten material obtained in the
first step at a temperature of T.sub.1.degree. C. wherein the
T.sub.1.degree. C. is a temperature lower than T.sub.m.degree. C.;
and a third step of heating the solidified material obtained in the
second step under an atmosphere at a temperature of T.sub.2.degree.
C. satisfying the formula (I):
T.sub.1<T.sub.2.ltoreq.T.sub.m (I)
[8] The process for producing a granular stabilizer for a polymer
according to [7], wherein the molten material obtained in the first
step is solidified at a temperature of T.sub.1.degree. C.
satisfying the formula (II):
5<T.sub.1<T.sub.m-40 (II)
in the second step. [9] The process for producing a granular
stabilizer for a polymer according to [7] or [8], wherein the
molten material obtained in the first step is dropped on a plate to
be solidified in the second step. [10] The process for producing a
granular stabilizer for a polymer according to any one of [7] to
[9], wherein the solidified material obtained in the second step is
further heated under an atmosphere at a temperature of
T.sub.2.degree. C. satisfying the formula (III):
T.sub.m-30<T.sub.2.ltoreq.T.sub.m (III)
in the third step. [11] The process for producing a granular
stabilizer for a polymer according to any one of [7] to [10],
further comprising a fourth step of cooling the heated material
obtained in the third step at a temperature less than
T.sub.2.degree. C. [12] The process for producing a granular
stabilizer for a polymer according to [11], wherein the heated
material is cooled under an atmosphere at a temperature of
T.sub.1.degree. C. satisfying the formula (II):
5<T.sub.1<T.sub.m-40 (II)
in the fourth step. [13] A process for producing a granular
stabilizer for a polymer, comprising a compound shown by the
formula (1):
##STR00007##
wherein R.sup.1s and R.sup.2s each independently represents a
hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a
cycloalkyl group having 5 to 8 carbon atoms; R.sup.3s each
independently represents a hydrogen atom or an alkyl group having 1
to 8 carbon atoms; and X represents a single bond, a sulfur atom,
an oxygen atom, an alkylidene group having 1 to 8 carbon atoms or a
cycloalkylidene group having 5 to 8 carbon atoms, wherein the
process comprises: a first step of melting the compound shown by
the formula (1) having a melting point of T.sub.m.degree. C.; a
second step of forming the molten material obtained in the first
step at a temperature of T.sub.1.degree. C. satisfying the formula
(I):
T.sub.1<T.sub.m (I)
and a third step of mixing the formed material obtained in the
second step with a solid compound shown by the formula (1) at a
temperature lower than T.sub.m.degree. C. [14] The process for
producing a granular stabilizer for a polymer according to [13],
wherein the molten material obtained in the first step is formed at
a temperature of T.sub.1.degree. C. satisfying the formula
(II):
T.sub.m-50<T.sub.1<T.sub.m (II)
in the second step. [15] The process for producing a granular
stabilizer for a polymer according to [13] or [14], wherein, in the
third step, the solid compound shown by the formula (1) is mixed in
an amount of 1 to 20% by weight based on 100% by weight of the
formed material obtained in the second step. [16] The process for
producing a granular stabilizer for a polymer according to any one
of [13] to [15], further comprising a step of cooling the mixture
obtained in the third step at a temperature of T.sub.2 satisfying
the formula (III):
5<T.sub.2<T.sub.1-30 (III).
[17] The process for producing a granular stabilizer for a polymer
according to any one of [7] to [16], wherein the compound shown by
the formula (1) is
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate or
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate. [18] Use of the granular stabilizer for a polymer
according to any one of [1] to [6] for thermally stabilizing a
thermoplastic polymer. [19] A thermoplastic polymer composition,
comprising 0.01 to 2 parts by weight of the granular stabilizer for
a polymer according to any one of [1] to [6] based on 100 parts by
weight of a thermoplastic polymer.
[0012] The granular stabilizer for a polymer of the invention is
low-dusting and is therefore easy to be handled.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The granular stabilizer for a polymer of the invention
comprises a compound shown by the formula (1):
##STR00008##
(hereinafter sometimes referred to as "a compound (1)".
[0014] In the formula (1), R.sup.1s and R.sup.2s each independently
represents a hydrogen atom, an alkyl group having 1 to 8 carbon
atoms, or a cycloalkyl group having 5 to 8 carbon atoms. Here,
examples of the alkyl group include a methyl group, an ethyl group,
an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl
group, a t-butyl group, an n-pentyl group, an i-pentyl group, a
t-pentyl group, a 2-ethylhexyl group, and the like. Examples of the
cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a
cyclooctyl group, 3-methylcyclopentyl group, a 4-methylcyclopentyl
group, a 3-methylcyclohexyl group, and the like.
[0015] R.sup.3s each independently represents a hydrogen atom or an
alkyl group having 1 to 8 carbon atoms. Specific examples of the
alkyl group in R.sup.3 include the alkyl groups exemplified in
R.sup.1.
[0016] X represents a single bond, a sulfur atom, an oxygen atom,
an alkylidene group having 1 to 8 carbon atoms, or a
cycloalkylidene group having 5 to 8 carbon atoms.
[0017] Here, examples of the alkylidene group include a methylene
group, an ethylidene group, a propylidene group, a butylidene
group, and the like. Examples of the cycloalkylidene group include
a cyclopentylidene group, a cyclohexylidene group, and the
like.
[0018] The compound (1) has a melting point of usually 70 to
220.degree. C., and preferably 100 to 140.degree. C.
[0019] Examples of the compound (1) include [0020]
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate, [0021]
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
methacrylate,
2-(2-hydroxy-3,5-di-t-pentylbenzyl)-4,6-di-t-pentylphenyl acrylate,
2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxyphenyl)ethyl]pheny- l
acrylate, 2,4-di-t-butyl-6-(3,5-di-t-butyl-2-hydroxybenzyl)phenyl
acrylate, [0022]
2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxyphenyl)ethyl]phenyl
methacrylate, [0023]
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate, [0024]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methyl-
phenyl acrylate,
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
methacrylate, [0025]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-methylphenyl)propyl]-4-methylphenyl
acrylate,
2-t-butyl-6-(3-t-butyl-5-ethyl-2-hydroxybenzyl)-4-ethylphenyl
acrylate, [0026]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-propylphenyl)ethyl]-4-propylphenyl
acrylate, [0027]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-isopropylphenyl)ethyl]-4-isopropyl
phenyl acrylate, and the like.
[0028] Preferable examples thereof include [0029]
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate, [0030]
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl
acrylate, [0031]
2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxyphenyl)ethyl]phenyl
acrylate, [0032]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methylphenyl
acrylate, [0033]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-methylphenyl)propyl]-4-methylphenyl
acrylate, [0034]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-propylphenyl)ethyl]-4-propylphenyl
acrylate, [0035]
2-t-butyl-6-[1-(3-t-butyl-2-hydroxy-5-isopropylphenyl)ethyl]-4-isopropylp-
henyl acrylate, and the like.
[0036] Particularly preferable examples include [0037]
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate and 2-t-butyl-6-(3-t-butyl
2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate.
[0038] The compound (1) can be produced according to a process
described in, for example, JP-A Nos. 59-144733, 1-168643 or
4-264051, U.S. Pat. Nos. 4,525,514, 4,562,281 and 4,365,032, or the
like.
[0039] The compound (1) may be used as a mixture of multiple
different kinds of the compounds (1).
[0040] The granular stabilizer for a polymer of the invention
comprises the compound (1).
[0041] In one embodiment of the invention, the granular stabilizer
for a polymer comprises usually 95% by weight or more, preferably
99% by weight or more of the compound (1), and particularly
preferably, the stabilizer comprises the compound (1) alone.
[0042] In another embodiments of the invention, the granular
stabilizer for a polymer comprises a compound shown by the formula
(2):
##STR00009##
(hereinafter sometimes referred to as "a compound (2)") in addition
to the compound (1).
[0043] In the formula (2), R.sup.11 is a linear alkyl group having
1 to 30 carbon atoms such as a methyl group, an ethyl group, an
n-propyl group, an n-butyl group, an n-pentyl group, an n-octadecyl
group or an n-tetradecyl group; or a branched alkyl group having 3
to 30 carbon atoms such as an i-propyl group, an i-butyl group, a
t-butyl group, an i-pentyl group, a t-pentyl group or a
2-ethylhexyl group.
[0044] A hydroxyl group, a carboxyl group, an alkoxycarbonyl group
having 2 to 30 carbon atoms or an alkylcarbonyloxy group having 2
to 30 carbon atoms may be bonded to the alkyl group. Also, the
methylene group contained in the alkyl group, the alkoxycarbonyl
group and the alkylcarbonyloxy group may be substituted by a sulfur
atom or an oxygen atom.
[0045] Examples of the R.sup.11 include a group shown by the
following formula:
##STR00010##
in addition to the alkyl groups as described above.
[0046] Examples of R.sup.12 include a linear alkyl group having 1
to 30 carbon atoms such as a methyl group, an ethyl group, an
n-propyl group, an n-butyl group, an n-pentyl group, an n-octadecyl
group or an n-tetradecyl group; a branched alkyl group having 3 to
30 carbon atoms such as an i-propyl group, an i-butyl group, a
t-butyl group, an i-pentyl group, a t-pentyl group or a
2-ethylhexyl group; or an aralkyl group having 7 to 20 carbon atoms
such as a benzyl group, a phenylethyl group or a phenylpropyl
group.
[0047] A hydroxyl group, a carboxyl group, an alkoxycarbonyl group
having 2 to 30 carbon atoms, or an alkylcarbonyloxy group having 2
to 30 carbon atoms may be bonded to the alkyl group and the aralkyl
group. Also, the methylene group contained in the alkyl group may
be substituted by a sulfur atom or an oxygen atom. Examples of
R.sup.12 include a 2,3-di-hydroxypropyloxy group,
--CH.sub.2CH.sub.2SCH.sub.2CH.sub.2COOC.sub.12H.sub.25,
--CH.sub.2CH.sub.9SCH.sub.2CH.sub.2COOC.sub.14H.sub.29,
--CH.sub.2CH.sub.2SCH.sub.2CH.sub.2COOC.sub.18H.sub.37, an aralkyl
group shown by the following formula:
##STR00011##
and the like.
[0048] The compound (2) has preferably a melting point lower than
that of the compound (1). The compound (2) having a melting point
lower than that of the compound (1) is preferable because the
resulting granular stabilizer for a polymer is difficult to cause
blocking upon transportation or storage thereof; in other words,
the resulting stabilizer has good anti-blocking properties.
[0049] The compound (2) having a melting point of 30.degree. C. or
more is preferable, because the resulting granular stabilizer for a
polymer has good form stability. The compounds (2) having a melting
point of not less than 40.degree. C. and less than 80.degree. C.,
especially not less than 45.degree. C. and less than 70.degree. C.,
are particularly preferable.
[0050] The preferable compound (2) is particularly at least one
compound selected from the group consisting of phenol antioxidants,
sulfur antioxidants and antistatic agents.
[0051] Examples of the compound (2) include phenol antioxidants
such as octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate
(melting point: 50 to 55.degree. C., Irganox 1076, which is a
registered trademark of Ciba Specialty Chemicals); sulfur
antioxidants such as dilauryl-3,3'-thiodipropionate (melting point:
40 to 42.degree. C.), dimyristyl-3,3'-thiodipropionate (melting
point: 49 to 54.degree. C.), distearyl-3,3'-thiodipropionate
(melting point: 65 to 67.degree. C.), and
tetrakis(3-dodecylthiopropionic acid)pentaerythrityl ester (melting
point: about 46.degree. C.); and antistatic agents such as glycerin
monostearate (melting point: 65 to 70.degree. C.), glycerin
monocaprate (melting point: 46.degree. C.), glycerin monolaurate
(melting point: 57.degree. C.), and citric acid fatty acid
monoglyceride (melting point: 59.degree. C.); and the like.
[0052] The compound (2) may be used as a mixture of multiple
different kinds of the compounds (2).
[0053] The preferable compound (2) is particularly [0054]
octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, glycerin
monostearate, dimyristyl-3,3'-thiodipropionate and
distearyl-3,3'-thiodipropionate, especially [0055]
octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate.
[0056] In an embodiment in which the granular stabilizer for a
polymer of the invention comprises the compound (2), the granular
stabilizer for a polymer comprises the compound (1) in an amount of
preferably 99.9 to 80% by weight, more preferably 99.7 to 90% by
weight, and particularly preferably 99.5 to 95% by weight, based on
100% by weight of the granular stabilizer for a polymer.
[0057] Also, the stabilizer comprises the compound (2) in an amount
of preferably 0.1 to 20% by weight, more preferably 0.3 to 10% by
weight, and particularly preferably 0.5 to 5% by weight, based on
100% by weight of the granular stabilizer for a polymer.
[0058] As a process for producing the granular stabilizer for a
polymer of the invention, examples thereof include a process
comprising a first step of melting the compound (1) having a
melting point of T.sub.m.degree. C.; a second step of solidifying
the molten material obtained in the first step at a temperature of
T.sub.1.degree. C. in which T.sub.1.degree. C. is a temperature
less than T.sub.m.degree. C.; and a third step of heating the
solidified material obtained in the second step under an atmosphere
at a temperature of T.sub.2.degree. C. satisfying the formula
(I):
T.sub.1<T.sub.2.ltoreq.T.sub.m (I).
[0059] The first step is a step of melting the compound (1).
Specifically, the compound (1) is heated at a temperature of a
melting point of the compound (1), T.sub.m.degree. C., or more to
melt it. The temperature at which the compound (1) is heated to
melt it is not particularly limited so long as the temperature is
T.sub.m.degree. C. or more, and the temperature range is preferably
from T.sub.m.degree. C. to (T.sub.m+50).degree. C., more preferably
from (T.sub.m+5).degree. C. to (T.sub.m+40).degree. C., and
particularly preferably from (T.sub.m+10).degree. C. to
(T.sub.m+30).degree. C.
[0060] The second step is a step of solidifying (cooling) the
molten material obtained in the first step at a temperature of
T.sub.1.degree. C. in which T.sub.1.degree. C. is a temperature
less than T.sub.m.degree. C.
[0061] Preferably, the solidifying temperature, T.sub.1.degree. C.
is within a range shown by the formula (II):
5<T.sub.1<T.sub.m-40 (II).
[0062] More preferably, the solidifying temperature,
T.sub.1.degree. C. is within a range shown by the formula
(II)':
10<T.sub.1<T.sub.m-50 (II)'.
[0063] The solidifying temperature more than 5.degree. C. is
preferable because the crystallization is easily promoted when the
solidified material is reheated in the subsequent third step,
whereas the solidifying temperatures less than (T.sub.m-40).degree.
C. are also preferable because the shape can be retained upon
solidification. The solidifying time is not particularly limited,
and the temperature is preferably kept for 1 minute or more, and
particularly preferably for 2 minutes or more immediately after the
temperature reaches the above-mentioned temperature range. The
solidifying time is preferably 24 hours or less from the viewpoint
of productivity.
[0064] The solidification methods are not particularly limited, and
include, for example, a method in which a molten compound (1) is
sprayed or dropped on a plate (preferably a heat-exchangeable plate
made of a metal such as stainless steel) which is cooled to,
preferably, a predetermined temperature (T.sub.1.degree. C.),
thereby cooling and solidifying the molten compound (1) in the
shape of a sphere or approximate hemisphere; a method in which a
molten compound (1) is connectively extruded onto a belt which is
cooled to, preferably, a predetermined temperature (T.sub.1.degree.
C.), thereby cooling and solidifying the molten compound (1) in the
shape of a bar, plate or the like; and the like.
[0065] The plate on which the molten compound (1) is sprayed or
dropped is usually a heat-exchangeable plate which is cooled to a
temperature of about 0 to 60.degree. C., and the plate includes
stainless steel belts cooled with water or the like, stainless
steel belts cooled with cool air or the like, stainless steel
plates cooled with water or the like, stainless steel plates cooled
with cool air or the like, and the like.
[0066] The surface of the plate on which the molten material is
dropped is usually flat and smooth.
[0067] When the belt is used as the plate, the molten material may
be cooled while moving the belt, and when the solidification is
performed on a stationary plate, the solidified material may be
taken out from the plate after the solidification.
[0068] Examples of the method for spraying or dropping the molten
compound (1) specifically include methods in which the molten
compound (1) is dropped, for example, through a dropping tube,
methods in which the molten compound (1) is filled in a Rolldrop
granulator, a Rotoform granulator or the like, and then the
compound is dropped, and the like.
[0069] The Rolldrop granulators refer to granulators having usually
a rotating drum with protrusions, and a mechanism in which a molten
material is scraped by the tips of the protrusions, and the molten
material scraped is chopped on a plate with centrifugal force
obtained by rotation of the rotating drum and/or force of
gravity.
[0070] The Rotoform granulators refer to granulators having usually
a cylindrical part with holes, a molten material being held inside
of the cylindrical part, and having a mechanism in which the molten
material is dropped from the holes on the plate.
[0071] It is particularly preferable to drop the molten material by
using the Rotoform granulators.
[0072] The belts used for connectively extruding the molten
compound (1) are preferably belts composed of a metal heat
exchangeable plate such as a stainless steel plate, which is cooled
to a predetermined temperature (T.sub.1.degree. C.), and include
specifically stainless steel belts cooled with water or the like,
stainless steel belts cooled with cool air or the like, and the
like.
[0073] The methods for connectively extruding the molten compound
(1) include specifically methods in which the compound is extruded
through a strip former into a bar, or methods in which the compound
is extruded through a double roll feeder or an overflow feeder into
a plate, and the like.
[0074] The extruded material in the shape of a bar, plate or the
like can be granulated as described below.
[0075] In the second step, the dropped material or connectively
extruded material is usually cooled and solidified on the plate,
and at that time, crystals of the compound (1), and the like may be
added thereto as seed crystals to solidify it.
[0076] When the belt is used as the plate, the molten material may
be cooled while moving the belt, and when the solidification is
performed on a stationary plate, the solidified material may be
taken out from the plate after the solidification.
[0077] The third step is a step of heating the solidified material
obtained in the second step under an atmosphere at a temperature of
T.sub.2.degree. C. satisfying the formula (I):
T.sub.1<T.sub.2.ltoreq.T.sub.m (I).
When the solidified material is reheated within such a temperature
range, the crystallization can be caused in a short time, thus
resulting in obtaining a stabilizer which does not cause
blocking.
[0078] As the phenomenon causes more easily, the reheating
temperature, T.sub.2 preferably satisfies the formula (III):
T.sub.m-30<T.sub.2.ltoreq.T.sub.m (III),
more preferably satisfies the formula (III)':
T.sub.m-20<T.sub.2.ltoreq.T.sub.m-5 (III)'.
[0079] Also, with respect to the reheating time, the solidified
material obtained in the second step may be heated so long as it
dose not flow, and the reheating time is preferably not less than 1
minute and within 10 hours. The time is more preferably from not
less than 2 minutes and within 5 hours, because the solidified
material can be crystallized in a short time, and the time is
further more preferably from not less than 5 minutes and within 30
minutes from the viewpoint of productivity.
[0080] The reheating may be performed by using the same metal plate
or belt such as the stainless steel plate or belt as used in the
second step, or may be performed by using a metal plate or belt
separately prepared. Also, when the spherical or hemispherical
compound (1) is reheated, it is preferably reheated so that the
particles are not contacted with each other, from the viewpoint of
blocking. The shape which has been given upon cooling can be
maintained in this manner.
[0081] The process for producing the granular stabilizer for a
polymer of the invention comprises a fourth step of cooling the
heated material obtained in the third step at a temperature less
than T.sub.2.degree. C., as occasion demands.
[0082] The cooling temperature, T.sub.1.degree. C. in the fourth
step is preferably within a range shown by the formula (II):
5<T.sub.1<T.sub.m-40 (II)
[0083] The cooling temperature, T.sub.1.degree. C. is more
preferably within a range shown by the formula (II)'
10<T.sub.1<T.sub.m-50 (II)'.
[0084] The cooling temperature more than 5.degree. C. is preferable
from the viewpoint of productivity, and the cooling temperature
less than (T.sub.m-40).degree. C. is also preferable because the
shape can be maintained when it is cooled. The cooling time is not
particularly limited, and the temperature is preferably kept for 1
minute or more immediately after the temperature reaches the
above-mentioned temperature range from the viewpoint of formation
of a shape.
[0085] In the second step, when the molten compound (1) is
connectively extruded into a bar, plate or the like, and it is
cooled and solidified, the bar, plate or the like is pulverized in
a known method before, during or after the third step or the fourth
step and if necessary the obtained particles are size-selected,
whereby desired particles can be made.
[0086] Examples of the method for pulverizing the bar, plate or the
like specifically include a method for pulverizing it with a
rotating roller using a breaker roller, and the like.
[0087] Examples of the size-selection method include, for example,
a method in which the bar is cut into flakes through a strip
granulator, a method in which the plate is pulverized through a
breaker roller to give irregularly-shaped pieces and they are
passed through a sieve, and the like.
[0088] In another embodiment of the invention, the process for
producing the granular stabilizer for a polymer of the invention
comprises:
a first step of melting a compound (1) having a melting point of
T.sub.m.degree. C.; a second step of forming the molten material
obtained in the first step at a temperature of T.sub.1.degree. C.
satisfying the formula (I):
T.sub.1<T.sub.m (I)
and a third step of mixing the formed material obtained in the
second step with a solid compound (1) at a temperature less than
T.sub.m.degree. C.
[0089] The first step is a step of melting the compound (1).
Specifically, the compound (1) is heated at a temperature of a
melting point of compound (1), T.sub.m.degree. C. or more to melt
the compound (1). The temperature at which the compound (1) is
heated and molten is not particularly limited so long as the
temperature is T.sub.m.degree. C. or more, and the temperature is
preferably within a range of T.sub.m.degree. C. to
(T.sub.m+50).degree. C., more preferably (T.sub.m+5).degree. C. to
(T.sub.m+40).degree. C., particularly preferably
(T.sub.m+10).degree. C. to (T.sub.m+30).degree. C.
[0090] The second step is a step of forming the molten material
obtained in the first step at a temperature of T.sub.1.degree. C.
satisfying the formula (I):
T.sub.1<T.sub.m (I).
[0091] The forming temperature, T.sub.1.degree. C. is preferably
within a range shown by the formula (II):
T.sub.m-50<T.sub.1<T.sub.m (II).
[0092] The forming temperature, T.sub.1.degree. C. is more
preferably within a range shown by the formula (II)':
T.sub.m-40<T.sub.1<T.sub.m (II)'.
[0093] The forming temperature more than (T.sub.m-50).degree. C. is
preferable because the crystallization can be easily promoted, and
the forming temperature less than T.sub.m.degree. C. is also
preferable because the formed shape can be maintained.
[0094] The time during which the molten material is maintained at
the forming temperature is preferably not less than 1 minute and
within 1 hour, and more preferably not less than 1 minute and
within 30 minutes. From the viewpoints of promotion of subsequent
crystallization and efficiency of productivity, the time is further
more preferably not less than 2 minutes and within 30 minutes.
[0095] The forming methods are not particularly limited, and
include, for example, a method in which a molten compound (1) is
sprayed or dropped on a plate (preferably a heat-exchangeable plate
made of a metal such as stainless steel) which is cooled to,
preferably, a predetermined temperature (T.sub.1.degree. C.),
thereby cooling and solidifying the molten compound (1) in the
shape of a particle such as a sphere or approximate hemisphere; a
method in which a molten compound (1) is connectively extruded onto
a belt which is cooled to, preferably, a predetermined temperature
(T.sub.1.degree. C.), thereby cooling and solidifying the molten
compound (1) in the shape of a bar, plate or the like to form; and
the like.
[0096] The plate on which the molten compound (1) is sprayed or
dropped is usually a heat-exchangeable plate which is cooled to a
temperature of about 0 to 60.degree. C., and the plate includes
stainless steel belts cooled with water or the like, stainless
steel belts cooled with cool air or the like, stainless steel
plates cooled with water or the like, stainless steel plates cooled
with cool air or the like, and the like.
[0097] The surface of the plate on which the molten material is
dropped is usually flat and smooth.
[0098] When the belt is used as the plate, the molten material may
be cooled while moving the belt, and when the solidification is
performed on a stationary plate, the solidified material may be
taken out from the plate after the solidification.
[0099] Examples of the method for spraying or chopping the molten
compound (1) specifically include methods in which the molten
compound (1) is dropped, for example, through a dropping tube,
methods in which the molten compound (1) is filled in a Rolldrop
granulator, a Rotoform granulator or the like, and then the
compound is dropped, and the like.
[0100] The Rolldrop granulators refer to granulators having usually
a rotating drum with protrusions, and a mechanism in which a molten
material is scrapped by the tips of the protrusions, and the molten
material scraped is dropped on a plate with centrifugal force
obtained by rotation of the rotating drum and/or force of
gravity.
[0101] The Rotoform granulators refer to granulators having usually
a cylindrical part with holes, a molten material being held inside
of the cylindrical part, and having a mechanism in which the molten
material is dropped from the holes on the plate.
[0102] It is particularly preferable to drop the molten material by
using the Rotoform granulators.
[0103] The belts used for connectively extruding the molten
compound (1) are preferably belts composed of a metal heat
exchangeable plate such as a stainless steel plate, which is cooled
to a predetermined temperature (T.sub.1.degree. C.), and include
specifically stainless steel belts cooled with water or the like,
stainless steel belts cooled with cool air or the like, and the
like.
[0104] The methods for connectively extruding the molten compound
(1) include specifically methods in which the compound is extruded
through a strip former into a bar, or methods in which the compound
is extruded through a double roll feeder or an overflow feeder into
a plate, and the like.
[0105] The extruded materials in the shape of a bar, plate or the
like can be granulated as described below.
[0106] The third step is a step of mixing the formed material
obtained in the second step with the solid compound (1) at a
temperature of less than T.sub.m.degree. C., preferably
T.sub.1.degree. C. or less.
[0107] The methods for mixing the formed material obtained in the
second step with the solid compound (1) are not particularly
limited, and include, for example, a method in which the solid
compound (1) is placed on the metal plate or belt, to which the
formed material obtained by dropping the molten material is added,
and they are mixed; a method in which the solid compound (1) is
placed on the metal plate or belt, to which the formed material
obtained by extruding the molten material is added; a method in
which the solid compound (1) is sprinkled over the formed material
obtained by dropping or connectively extruding the molten material;
a method in which any of the above-mentioned procedures are
simultaneously performed; and the like.
[0108] The mixing in the third step of the invention also includes
a case in which the formed material is brought into contact with
the solid compound (1), as illustrated above, and this contacting
method is particularly preferable.
[0109] The solid compound (1) used in the third step includes, for
example, crystalline powder of compound (1), particularly powder
having an endotherm peak at 110 to 130.degree. C. when the
temperature is elevated at a rate of 10.degree. C./minute in a
differential scanning calorimeter (DSC), and having an average
particle size of 10 .mu.m to 100 .mu.m. Specifically, compounds (1)
described in JP-A Nos. 1-168643, 4-264051, and the like, and
commercially available compounds (1) (for example, Sumilizer
(registered trademark) GM, GS (Sumitomo Chemical Co., Ltd.), and
the like) may be directly used.
[0110] The average particle size referred herein means a 50%
particle size (median size) when a particle seize distribution
measured by using a laser diffraction particle size distribution
measuring device is integrated from the finer particle side in
terms of a volume.
[0111] In the third step, the solid compound (1) is mixed with the
formed material obtained in the second step in an amount of
preferably 1 to 20% by weight, and more preferably 5 to 10% by
weight, based on 100% by weight of the formed material. The amount
of the solid compound (1) of 5% by weight or more is preferable,
because the crystallization is promoted, and the amount of 10% by
weight or less is also preferable because dusting tends to be
inhibited.
[0112] When there is a solid compound (1) which was not contained
in the mixture of the formed material obtained in the third step
and the solid compound (1), the occurrence of dusting can be
inhibited by removing the solid compound from the system by using a
sieve, or the like.
[0113] Further, the mixture obtained in the third step is
preferably treated in a step in which the mixture is cooled at a
temperature (T.sub.2) less than T.sub.1.degree. C. (hereinafter
sometimes referred to as "a cooling step"). The cooling
temperature, T.sub.2.degree. C. in the cooling step is preferably
within a range shown by the formula (III):
5<T.sub.2<T.sub.1-30 (III).
[0114] The cooling temperature, T.sub.2.degree. C. is more
preferably within the range shown by the formula (III)':
10<T.sub.2<T.sub.1-40 (III)'.
[0115] The cooling temperature more than 5.degree. C. of is
preferable from the viewpoint of productivity, and the cooling
temperature less than (T.sub.1-30).degree. C. is also preferable
because the shape can be maintained upon cooling. The cooling time
is not particularly limited, and it is preferable to keep the
temperature for 1 hour or more immediately after the temperature
reaches the above-mentioned temperature range from the viewpoint of
formation of a shape.
[0116] In the second step, when the molten compound (1) is
connectively extruded to form a bar, plate or the like, the bar,
plate or the like is pulverized in a known method before, during or
after the third step and if necessary the obtained particles are
size-selected, whereby desired particles can be made.
[0117] Examples of the method for pulverizing the bar, plate or the
like specifically include a method for pulverizing it with a
rotating roller using a breaker roller, and the like.
[0118] Examples of the method for size-selecting include, for
example, a method in which the bar is cut into flakes through a
strip granulator, a method in which the plate is pulverized through
a breaker roller to give irregularly-shaped pieces and they are
passed through a sieve, and the like.
[0119] In an embodiment in which the granular stabilizer for a
polymer of the invention comprises the compound (2), the process
for producing the granular stabilizer for a polymer of the
invention includes, for example, a process comprising a melting
step in which 99.9 to 80% by weight of the compound (1) and 0.1 to
20% by weight of the compound (2), based on 100% by weight of the
composition are melted; and a forming step in which the molten
material obtained in the melting step is solidified to give
particles, and the like.
[0120] The specific melting step includes, for example, a method in
which the compound (1) and the compound (2) are mixed in the weight
ratio described above in a vessel, the mixture is heated to a
temperature equal to or more than the melting point of the compound
(1), specifically about 120.degree. C. to about 160.degree. C., and
stirred it to melt it; a method in which the compound (1) and the
compound (2) are previously mixed through a Banbury mixer, and the
like before they are added in a vessel, and then they are molten; a
method in which the compound (2) having a lower melting point is
previously heated and stirred to melt it, to which the compound (1)
is added, and they are molten, and the like.
[0121] For the forming step, a method in which the molten material
obtained in the melting step is sprayed or dropped in the shape of
a droplet on, for example, a board, preferably a heat exchangeable
plate such as a stainless steel plate, which can be cooled, and the
like can be adopted.
[0122] Specifically, examples of the method include a method in
which the molten material obtained in the melting step is dropped,
for example, from a dropping tube, a step in which the molten
material is filled in a Rolldrop granulator, a Rotoform granulator
or the like, and then it is dropped therefrom, and the like.
[0123] Here, the Rolldrop granulators refer to granulators having
usually a rotating drum with protrusions, and a mechanism in which
a molten material is scraped by the tips of the protrusions, and
the molten material scraped is dropped on a plate with centrifugal
force obtained by rotation of the rotating drum and/or force of
gravity.
[0124] The Rotoform granulators refer to granulators having usually
a cylindrical part with holes, a molten material being held inside
of the cylindrical part, and having a mechanism in which the molten
material is dropped from the holes on the plate.
[0125] It is particularly preferable to drop the molten material by
using the Rotoform granulators.
[0126] The plate is usually a heat-exchangeable plate which is
cooled to a temperature of about 0 to 60.degree. C., and the plate
includes stainless steel belts cooled with water or the like,
stainless steel belts cooled with cool air or the like, stainless
steel plates cooled with water or the like, stainless steel plates
cooled with cool air or the like, and the like.
[0127] The surface of the plate on which the molten material is
dropped is usually flat and smooth.
[0128] When the belt is used as the plate, the molten material may
be cooled while moving the belt, and when the solidification is
performed on a stationary plate, the solidified material may be
taken out from the plate after the solidification.
[0129] In the present invention, the granular composition usually
can be obtained as a granular composition having an endotherm peak
within a temperature range of (a melting point of the compound (1)
.+-.10.degree. C.) in a short time such as about 10 seconds to 10
minutes after cooling.
[0130] The granular stabilizers for a polymer of the invention are
particles in the shape of a plate, a flake, a bar, a disc, an
approximate sphere, an approximate hemisphere, or the like. The
granular stabilizers for a polymer in the shape of a disc, an
approximate sphere or an approximate hemisphere can be obtained by
dropping the molten material comprising compound (1). When the
particle size is small, spherical particles are obtained, and when
the size is larger, hemispherical particles are obtained because
the molten material becomes flat due to its own weight.
[0131] When the granular stabilizers for a polymer are in the shape
of a sphere, the particle size is usually from 1 mm to 5 mm, and
when the stabilizers are in the shape of an approximate hemisphere,
the particle size is from 1 mm to 4 mm, and the height is from 1 mm
to 4 mm. From the viewpoint of dispersibility in a thermoplastic
polymer, when the stabilizers are in the shape of a sphere, the
particle size is preferably from 1 mm to 4 mm, and when the
stabilizers are in the shape of an approximate hemisphere, the
particle size is preferably from 2 mm to 4 mm and the height is
preferably from 1 mm to 3 mm.
[0132] The granular stabilizers for a polymer of the invention have
a weight of one particle of the granular stabilizer for a polymer
of, for example 1 mg to 25 mg, preferably 5 mg to 25 mg, and more
preferably 6 mg to 20 mg. The weights within the above-mentioned
range are preferable, because dusting is inhibited, and there is a
tendency that the particles are difficult to agglomerate with each
other.
[0133] To control the weight of the granular stabilizer for a
polymer, when the molten material is dropped using the dropping
tube in the solidification step, an amount of the dropping molten
material may be adjusted by adjusting a size of holes, a viscosity
of the molten material, and the like, when the Rolldrop granulator
is used, an amount of the molten material scrapped by the tips of
the protrusions may be adjusted, and when the Rotoform granulator
is used, the amount of the dropping molten material may be
controlled by adjusting a size of holes, a viscosity of the molten
material, and the like.
[0134] When the molten material is connectively extruded in the
solidification step, the extruded, solidified material in the shape
of a plate or bar may be cut or pulverized so that the pieces are
within the above-mentioned weight range.
[0135] The granular stabilizers for a polymer of the invention are
crystalline particles. That is, the granular stabilizers for a
polymer of the invention have an endotherm peak at a range of,
preferably (a melting point of the compound (1).+-.10.degree. C.)
when the temperature is elevated at a rate of 10.degree. C./minute
in a differential scanning calorimeter (DSC), more preferably, they
have an endotherm peak within a range of 110 to 140.degree. C.
[0136] The granular stabilizers for a polymer of the invention are
low-dusting, and easy to be handled. The stabilizers can be
dissolved in a hydrocarbon medium such as pentane, hexane,
cyclopentane, or cyclohexane while dusting hardly occurs, and then
the solution may be added to a thermoplastic polymer. In addition,
even if the stabilizers are stored for a long period of time,
blocking (agglomeration) does not occur, in other words, blocking
resistance is good.
[0137] Further, when the granular stabilizer for a polymer of the
invention is added to a thermoplastic polymer such as polypropylene
during melt-kneading, the granular stabilizer for a polymer
exhibits excellent dispersibility like conventional powdery
granular stabilizers for a polymer, even if the granular stabilizer
is in the shape of a particle. The dispersibilities of the compound
(1) and the compound (2) if present in the obtained thermoplastic
polymer composition are almost the same as the dispersibilities
thereof in a thermoplastic polymer composition comprising the
powdery compound (1) or a thermoplastic polymer composition
obtained by separately adding the compound (1) and the compound (2)
to a thermoplastic polymer and melt-kneading the mixture.
[0138] Here, examples of the thermoplastic polymer include
polypropylene resins such as an ethylene-propylene copolymer,
polyethylene resins (high density polyethylene (HD-PE), low density
polyethylene (LD-PE), linear low density polyethylene (LLDPE), and
the like), a methylpentene polymer, an ethylene-ethyl acrylate
copolymer, an ethylene-vinyl acetate copolymer, polystyrenes
(polystyrene such as poly(p-methyl styrene) or poly(.alpha.-methyl
styrene), an acrylonitrile-styrene copolymer, an
acrylonitrile-butadiene-styrene copolymer, a special acrylic
rubber-acrylonitrile-styrene copolymer, an
acrylonitrile-chlorinated polyethylene-styrene copolymer, a
styrene-butadiene copolymer, and the like), chlorinated
polyethylene, polychloroprene, a chlorinated rubber, polyvinyl
chloride, polyvinylidene chloride, a methacrylic resin, an
ethylene-vinyl alcohol copolymer, a fluorocarbon resin, polyacetal,
a grafted polyphenylene-ether resin, a polyphenylene-sulfide resin,
polyurethane, polyamide, polyester resins (for example,
polyethylene terephthalate, polybutyrene terephthalate, and the
like), polycarbonate, polyacrylate, polysulfone, polyether ether
ketone, polyether sulfone, an aromatic polyester resin, a
di-allylphthalate prepolymer, a silicone resin, 1,2-polybutadiene,
polyisoprene, a butadiene/acrylonitrile copolymer, an
ethylene-methyl methacrylate copolymer, and the like. Among these,
the polyethylene resins, polypropylene resins and polystyrenes are
particularly preferable because of their good forming
processability, and the polypropylene resins,
acrylonitrile-butadiene-styrene copolymers and styrene-butadiene
copolymers are especially preferable.
[0139] Here, the polypropylene resin means a polyolefin containing
a structural unit derived from propylene, and specifically includes
a crystalline propylene homopolymer, a propylene-ethylene random
copolymer, a propylene-.alpha.-olefin random copolymer, a
propylene-ethylene-.alpha.-olefin copolymer, and a polypropylene
block copolymer composed of a propylene homopolymer component or a
copolymer component mainly comprising propylene and a copolymer
compound of propylene, and ethylene and/or .alpha.-olefin, and the
like.
[0140] In the present invention, when a polypropylene resin is used
as the thermoplastic polymer, the polypropylene resin may be used
alone or as a mixture of two or more kinds thereof.
[0141] The .alpha.-olefin refers to usually an .alpha.-olefin
having 4 to 12 carbon atoms, and includes, for example, 1-butene,
1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and
the like, and 1-butene, 1-hexene and 1-octene are more
preferable.
[0142] The propylene-.alpha.-olefin random copolymer includes, for
example, a propylene-1-butene random copolymer, a
propylene-1-hexene random copolymer, a propylene-1-octene random
copolymer, and the like.
[0143] The propylene-ethylene-.alpha.-olefin copolymer includes,
for example, a propylene-ethylene-1-butene copolymer, a
propylene-ethylene-1-hexene copolymer, a
propylene-ethylene-1-octene copolymer, and the like.
[0144] In the polypropylene block copolymer composed of a propylene
homopolymer component or a copolymer component mainly comprising
propylene, and a copolymer component of propylene, and ethylene
and/or .alpha.-olefin, the copolymer component mainly comprising
propylene includes, for example, a propylene-ethylene copolymer
component, a propylene-1-butene copolymer component, and a
propylene-1-hexene copolymer component; and the copolymer component
of propylene, and ethylene and/or .alpha.-olefin includes, for
example, a propylene-ethylene copolymer component, a
propylene-ethylene-1-butene copolymer component, a
propylene-ethylene-1-hexene copolymer component, a
propylene-ethylene-1-octene copolymer component, a
propylene-1-butene copolymer component, a propylene-1-hexene
copolymer component, a propylene-1-octene copolymer component, and
the like. The content of the ethylene and/or the .alpha.-olefin
having 4 to 12 carbon atoms in the copolymer component of
propylene, and ethylene and/or .alpha.-olefin is usually from 0.01
to 20% by weight.
[0145] The polypropylene block copolymer composed of a propylene
homopolymer component or a copolymer component mainly comprising
propylene and a copolymer component comprising propylene, and
ethylene and/or .alpha.-olefin includes, for example, a
propylene-ethylene block copolymer, a
(propylene)-(propylene-ethylene) block copolymer, a
(propylene)-(propylene-ethylene-1-butene) block copolymer, a
(propylene)-(propylene-ethylene-1-hexene) block copolymer, a
(propylene)propylene-1-butene) block copolymer, a
(propylene)-(propylene-1-hexene) block copolymer, a
(propylene-ethylene)-(propylene-ethylene-1-butene) block copolymer,
a (propylene-ethylene)-(propylene-ethylene-1-hexene) block
copolymer, a (propylene-ethylene)-(propylene-1-butene) block
copolymer, a (propylene-ethylene)-(propylene-1-hexene) block
copolymer, a (propylene-1-butene)-(propylene-ethylene) block
copolymer, a (propylene-1-butene)-(propylene-ethylene-1-butene)
block copolymer, a
(propylene-1-butene)-(propylene-ethylene-1-hexene) block copolymer,
a (propylene-1-butene)-(propylene-1-butene) block copolymer, a
(propylene-1-butene)-(propylene-1-hexene) block copolymer, and the
like.
[0146] In the present invention, when the polypropylene resin is
used as the thermoplastic polymer, the crystalline propylene
homopolymer, and the polypropylene block copolymer composed of a
propylene homopolymer component or a copolymer component mainly
comprising propylene, and a copolymer component comprising
propylene, and ethylene and/or .alpha.-olefin having 4 to 12 carbon
atoms are preferable. The polypropylene block copolymer composed of
a propylene homopolymer component or a copolymer component mainly
comprising propylene, and a copolymer component comprising
propylene, and ethylene and/or .alpha.-olefin having 4 to 12 carbon
atoms is more preferable.
[0147] The granular stabilizer for a polymer of the invention
usually may be blended with the thermoplastic polymer in an amount
of 2 parts by weight or less based on 100 parts by weight of the
thermoplastic polymer. Specifically, the stabilizer may be blended
with the thermoplastic polymer in an amount of not less than 0.01
part by weight and not more than 2 parts by weight, preferably not
less than 0.01 part by weight and not more than 1 part by weight.
Preferably the amount is 2 parts by weight or less, because a
bleeding phenomenon in which the stabilizer is bled on the surface
of the thermoplastic polymer composition desirably tends to be
inhibited.
EXAMPLE
[0148] The present invention will be described in more detail by
means of Examples and Comparative Examples, but the present
invention is not limited thereto.
[0149] In the following examples and comparative examples, as a
compound (1),
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate (hereinafter referred to as "a compound (1-1)". melting
point: 119.degree. C.) was used. As a compound (2), glycerin
monostearate (hereinafter sometimes referred to as "a compound
(i)", an antistatic agent having a melting point of 65 to
70.degree. C.), dimyristyl-3,3'-thiodipropionate (hereinafter
sometimes referred to as "a compound (ii)", a sulfur antioxidant
having a melting point of 49 to 54.degree. C.),
distearyl-3,3'-thiodipropionate (hereinafter sometimes referred to
as "a compound (iii)", a sulfur antioxidant having a melting point
of 65 to 67.degree. C.) or
octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl) propionate
(hereinafter sometimes referred to as "a compound (iv)", a phenol
antioxidant, Irganox 1076 which is a registered trademark of Ciba
Specialty Chemicals, having a melting point of 55.degree. C.).
[0150] The properties of granular stabilizers for a polymer were
measured and evaluated as follows:
(Blocking Resistance Test)
[0151] A granular stabilizer for a polymer, 50 g was weighed, and
it was put in a cylindrical case having a cross-sectional area of
28.3 cm.sup.2 to which a 2 kg of weight was put (71 g/cm.sup.2).
The case was maintained in a thermostatic chamber at 40.degree. C.
under a moisture of 80% for 7 days as it was, and then it was
returned to room temperature (about 25.degree. C.). After the
pressure was removed from the case, the blocking state of the
granular stabilizer for a polymer was evaluated.
Good: The granular stabilizer for a polymer was not agglomerated,
and it spontaneously returned to the original state when it was
taken out from the case. Poor: The granular stabilizer for a
polymer was agglomerated, and it did not returned to the original
state.
(Method for Measuring Particle Size)
[0152] The obtained granular stabilizer for a polymer was measured
with a slide caliper, and the scale on the jaw part in the
horizontal direction was read as a particle size and the scale in
the vertical direction was read as a height. The same measurement
procedure was repeated 10 times per each sample, and the average
values are defined as a particle size (width) and a height.
(Method for Measuring Weight of One Particle of Granular Stabilizer
for Polymer)
[0153] One particle of the obtained granular stabilizer for a
polymer was measured by using a precision balance manufactured by
Mettler-Toledo International Inc. The same measurement was repeated
20 times per each sample, and the average value was defined as a
weight of one particle of the granular stabilizer for a
polymer.
(Differential Scanning Calorimetric Analysis)
[0154] The temperature of the granular stabilizer for a polymer was
elevated at a rate of 10.degree. C./minutes and an endotherm peak
(.degree. C.) was measured by using a differential scanning
calorimeter (DSC) (DSC-60A manufactured by Shimadzu
Corporation).
Comparative Example 1
[0155] A four-neck flask equipped with a thermometer, a stirrer,
and a condenser was charged with 494.8 g (1.0 mole) of
2,2'-ethylidenebis(4,6-di-t-pentylphenol), 72.1 g (1.0 mole) of
acrylic acid, 400 g of n-heptane, and 212.5 g (2.1 moles) of
triethyl amine, and the inside of the vessel was replaced by
nitrogen. Then, 107.3 g (0.7 mole) of phosphorous oxychloride was
added dropwise to the vessel, while the mixture was stirred. After
the addition was finished, the mixture was kept at 80.degree. C.
for 1 hour, and then, 500 g of water was added thereto, and it was
washed with water at 60.degree. C. and was separated into two
layers. The oil layer part was repeatedly washed with water and
separated until the layer became neutral, and the oil layer was
cooled to 5.degree. C. with stirring to precipitate crystals. The
stirring was further continued at the same temperature, and after
the crystals were precipitated, the crystals were filtered, washed
with cool n-heptane, dried under reduced pressure to give 235.6 g
of a white crystalline powdery compound (1-1) having a melting
point of 119.degree. C. The obtained powder had an average particle
size (median size: 50% particle size when a particle size
distribution measured by using a Shimadzu laser diffraction
particle size distribution measuring device SALD2200, using an ion
exchanged water mixed with a slight amount of a neutral detergent
as a dispersion medium, was integrated from the finer particle side
in terms of a volume) of 65.0 .mu.m. The obtained powder had a
weight of one particle of <1.0 mg, and an endotherm peak at
120.5.degree. C. The result of the blocking resistance test of the
powder is shown in Table 1. Also, the powder was extremely
dusting.
Example 1
[0156] The powdery compound (1-1) obtained in Comparative Example 1
was heated and stirred in a vessel until the temperature reached
140.degree. C. to melt the compound, and then the molten compound
(1-1) was dropped on an aluminum plate having a temperature of
25.degree. C., which was cooled to 50.degree. C. to give a
solidified material. The solidified material was kept at about
25.degree. C. for 1.5 hours, and then was heated again in a dryer
having a temperature of 110.degree. C. for 5 minutes. The compound
was taken out from the dryer and cooled to 25.degree. C. again to
give
2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl
acrylate in the shape of an approximate hemisphere having a
particle size of 3.3 mm and a height of 2 mm. The obtained granular
stabilizer for a polymer had a weight of one particle of 16.2 mg,
and an endotherm peak at 120.5.degree. C. The result of the
blocking resistance test of the granular stabilizer for a polymer
is shown in Table 1. The granular stabilizer for a polymer was not
dusting, and was easy to be handled.
Reference Example 1
[0157] The molten compound (1-1) was obtained in the same manner as
in Example 1. Then, the molten compound (1-1) was dropped onto an
aluminum plate having a temperature of 25.degree. C., which was
cooled at room temperature (about 25.degree. C.) until the molten
material was solidified to give 513.3 g of a compound (1-1) having
a particle size of 3.6 mm and a height of 2.2 mm. The obtained
granular stabilizer for a polymer had a weight of one particle of
15.5 mg and it had an endotherm peak at 20.6.degree. C., which was
derived from a glass transition temperature, but did not have an
endotherm peak at 120.degree. C. The result of the blocking
resistance test of the granular stabilizer for a polymer is shown
in Table 1. The granular stabilizer for a polymer was not dusting,
and was easy to be handled.
TABLE-US-00001 TABLE 1 Particle Endotherm size/height Weight peak
Blocking (mm) (mg/particle) (.degree. C.) resistance Example 1
3.3/2 16.2 120.5 Good Comparative 65.0 .mu.n* <1.0 120.5 Good
Example 1 Reference 3.6/2.2 15.5 20.6 Poor Example 1 *Median size
according to laser diffraction particle size distribution
measurement
Example 2
[0158] The compound (1-1) obtained in Comparative Example 1 was
heated and stirred at 140.degree. C. to give a molten compound
(1-1). After that, the molten material was dropped on an aluminum
plate on which the compound (1-1) obtained in Comparative Example 1
was placed under an atmosphere of 110.degree. C., over which 54.9 g
of the compound (1-1) obtained in Comparative Example 1 was
sprinkled. Subsequently, it was kept at 110.degree. C. for 5
minutes, and cooled it at room temperature (about 25.degree. C.) to
give a compound (1-1) in the shape of an approximate hemisphere
having a particle size of 3.5 mm and a height of 2.3 mm. The
obtained granular stabilizer for a polymer had a weight of one
particle of 15.9 mg, and an endotherm peak at 120.5.degree. C.
Then, the blocking resistance test was performed. The compound was
not dusting after the production, and was easy to be handled.
Example 3
[0159] The procedure was performed in the same manner as in Example
2 except that the amount of the compound (1-1) obtained in
Comparative Example 1 which was sprinkled over the molten compound
(1-1) was changed to 27.5 g to give approximately hemispherical
particles having a particle size of 3.3 mm and a height of 2.1 mm.
The obtained granular stabilizer for a polymer had a weight of one
particle of 17.3 mg, and an endotherm peak at 120.5.degree. C. The
results of the dusting and the block resistance are shown in Table
2.
Example 4
[0160] The procedure was performed in the same manner as in Example
2 except that the amount of the compound (1-1) obtained in
Comparative Example 1 which was sprinkled over the molten compound
(1-1) was changed to 5.5 g to give approximately hemispherical
particles having a particle size of 3.3 mm and a height of 2.1 mm.
The obtained granular stabilizer for a polymer had a weight of one
particle of 16.8 mg, and an endotherm peak at 120.5.degree. C. The
results of the dusting and the block resistance are shown in Table
2.
Reference Example 2
[0161] The procedure was performed in the same manner as in Example
2 except that the compound (1-1) obtained in Comparative Example 1
which was sprinkled over the molten compound (1-1) was not added to
give an approximately hemispherical particles having a particle
size of 3.2 mm and a height of 2.0 mm. The particles, however, were
very soft, and a small amount of deposits on the aluminum plate
were observed. The obtained granular stabilizer for a polymer had a
weight of one particle of 15.9 mg, and had an endotherm peak at
20.6.degree. C., which derived from the grass transition
temperature, but does not have an endotherm peak approximately at
120.degree. C. The results of the dusting and the block resistance
are shown in Table 2.
Reference Example 3
[0162] The procedure was performed in the same manner as in Example
2 except that the compound (1-1) obtained in Comparative Example 1
was not added to the molten compound (1-1), but the molten compound
(1-1) which was obtained by heating and stirring at 140.degree. C.
was dropped under an atmosphere of 25.degree. C., and then was
cooled to give approximate hemispherical particles having a
particle size of 3.2 mm and a height of 2.1 mm. The particles,
however, were very soft, and a small amount of deposits on the
aluminum plate were observed. The obtained granular stabilizer for
a polymer had a weight of one particle of 14.5 mg, and had an
endotherm peak at 20.6.degree. C., which derived from the grass
transition temperature, but does not have an endotherm peak
approximately at 120.degree. C. The results of the dusting and the
block resistance are shown in Table 2.
TABLE-US-00002 TABLE 2 Amount of the crystalline powdery compound
(1-1) added Blocking (parts by weight)* Dusting resistance Example
2 10 Good Very good Example 3 5 Good Very Good Example 4 1 Good
Good Comparative -- Heavy Very good Example 1 dusting Reference --
Good Poor Example 2 Reference -- Good Poor Example 3 *Based on 100
parts by weight of the compound (1-1) in a solution
Example 5
[0163] Melting Step: A melting tank was charged with the compound
(1) and the compound (iv) in a weight ratio of 10:1, and the
mixture was heated at 145.degree. C. to give a molten material.
Forming Step The molten material obtained in the above step was
dropped on a stainless steel plated which was cooled with cooling
water having a temperature of 30.degree. C. to give approximately
hemispherical granular stabilizer for a polymer having an average
particle size of 5.0 mm, an average height of 1.5 mm, and an
average particle weight of 13.6 mg (granular composition a). The
granular composition a was not dusting.
[0164] The particle size, weight and endotherm peak (DSC analysis)
of this granular composition were measured according to the
above-mentioned methods.
Example 6
[0165] A granular stabilizer for a polymer (granular composition b)
was obtained in the same manner as in Example 5 except that the
weight ratio of the compound (1) and the compound (iv) were mixed
in a weight ratio of 100:1. The results are summarized in Table 3.
The granular composition b showed an endotherm peak at 120.degree.
C. according to DSC.
TABLE-US-00003 TABLE 3 Example 5 Example 6 Granular composition in
the a b shape of a particle Particle size/height (mm) 5.0/1.5
3.2/2.0 Weight of one particle (mg) 13.6 15.4 Dusting Not observed
Not observed Anti-blocking properties* Good Good *Anti-blocking
properties
[0166] About 10 particles of the obtained granular composition was
applied with a load of 73.6 g/cm.sup.2 in a constant temperature
and moisture chamber having a temperature of 40.degree. C. and a
moisture of 80% RH, which was allowed to stand for one week. The
state was visually observed, and confirmed whether the particles of
the granular composition agglomerated with each other or not.
Good: There was no agglomeration. Somewhat poor: The agglomeration
which was collapsed with an impact was observed. Poor: Melting or
heavy agglomeration, which was not collapsed even if impact was
applied thereto, was observed.
Example 7
[0167] A granular composition can be obtained in the same manner as
in Example 6 except that the compound (i) is used as a compound
(2).
Example 8
[0168] A granular composition can be obtained in the same manner as
in Example 6 except that the compound (ii) is used as a compound
(2).
Example 9
[0169] A granular composition can be obtained in the same manner as
in Example 6 except that the compound (iii) is used as a compound
(2).
INDUSTRIAL APPLICABILITY
[0170] The granular stabilizer for a polymer of the present
invention is low-dusting and therefore is easy to be handled.
* * * * *