U.S. patent application number 10/580652 was filed with the patent office on 2007-05-10 for multiple particle and composition having disperse system.
This patent application is currently assigned to Daicel Chemical Industries, Ltd.. Invention is credited to Hisayoshi Ito.
Application Number | 20070104951 10/580652 |
Document ID | / |
Family ID | 34631658 |
Filed Date | 2007-05-10 |
United States Patent
Application |
20070104951 |
Kind Code |
A1 |
Ito; Hisayoshi |
May 10, 2007 |
Multiple particle and composition having disperse system
Abstract
A multiple particle (e.g., a spherical particle) comprising an
organic solid component (A) containing a plurality of organic solid
materials (e.g., polymers) is produced by eluting a water-soluble
auxiliary component (B) containing at least an oligosaccharide (B1)
from a composition having a disperse system, in which a particulate
dispersed phase comprising the organic solid component (A) is
dispersed in a matrix comprising the auxiliary component (B). The
organic solid materials may be different in affinity relative to
the auxiliary component (B) from each other. The particle may have
a core-shell structure which comprises a core containing a first
organic solid material (e.g., a hydrophobic polymer) and a shell
containing a second organic solid material (e.g., a hydrophilic
polymer) immiscible with the first organic solid material. The
weight ratio of the organic solid component (A) relative to the
auxiliary component (B) may be about 55/45 to 1/99. The multiple
particle corresponding to the dispersed phase (e.g., a core-shell
particle) can be produced by a convenient process independently of
affinity between the dispersed phase and the matrix and
polymerization manner of the polymer.
Inventors: |
Ito; Hisayoshi; (Himeji-shi,
JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Daicel Chemical Industries,
Ltd.
Sakai-shi
JP
590-8501
|
Family ID: |
34631658 |
Appl. No.: |
10/580652 |
Filed: |
November 10, 2004 |
PCT Filed: |
November 10, 2004 |
PCT NO: |
PCT/JP04/16655 |
371 Date: |
September 25, 2006 |
Current U.S.
Class: |
428/402.2 |
Current CPC
Class: |
A61Q 19/00 20130101;
C08J 3/126 20130101; A61K 8/60 20130101; A61Q 1/02 20130101; A61K
8/8129 20130101; A61K 2800/412 20130101; A61K 8/0237 20130101; A61K
8/11 20130101; Y10T 428/2984 20150115 |
Class at
Publication: |
428/402.2 |
International
Class: |
B32B 9/00 20060101
B32B009/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 2003 |
JP |
2003-400821 |
Claims
1. A multiple particle which comprises a meltable organic solid
component (A), wherein the solid component (A) comprises a
plurality of organic solid materials each having a different
affinity relative to a water-soluble auxiliary component (B), and
the water-soluble auxiliary component (B) comprises at least an
oligosaccharide (B1).
2. A multiple particle according to claim 1, which comprises a
polymer component (A) containing a plurality of polymers, wherein
each of the polymers has a different affinity relative to the
auxiliary component (B).
3. A multiple particle according to claim 1, wherein the organic
solid materials form a polymer alloy.
4. A multiple particle according to claim 1, which has a core-shell
structure, wherein the core contains a first organic solid material
(A1) and the shell contains a second organic solid material
(A2).
5. A multiple particle according to claim 4, wherein the shell has
a thickness of 10 nm to 1 .mu.m.
6. A multiple particle according to claim 1, wherein at least one
of the organic solid materials is a non-addition polymerization
polymer.
7. A multiple particle according to claim 1, wherein the organic
solid component (A) comprises a first organic solid material (A1)
and a second organic solid material (A2) different in affinity
relative to the auxiliary component (B) from each other, and the
ratio (weight ratio) of the first organic solid material (A1)
relative to the second organic solid material (A2) is 30/70 to
99/1.
8. A multiple particle according to claim 1, wherein the organic
solid component (A) comprises a hydrophobic polymer (A1), and a
hydrophilic polymer (A2) having at least one hydrophilic group
selected from the group consisting of a hydroxyl group, a carboxyl
group, an amino group, an imino group, an ether group, an
oxyalkylene group, an ester group and an amide group.
9. A multiple particle according to claim 8, wherein the
hydrophilic polymer (A2) contains at least one member selected from
the group consisting of a vinyl acetate-series polymer, a polyvinyl
alcohol-series polymer, a polyester-series polymer, a
polyamide-series polymer, a polycarbonate-series polymer, a
polyurethane-series polymer and a cellulose derivative.
10. A multiple particle according to claim 1, which is a spherical
particle having an average particle size of 0.1 to 100 .mu.m, a
coefficient of variation of the average particle size of not more
than 60, and a length ratio of a major-axis relative to a minor
axis of 1.5/1 to 1/1.
11. A composition having a disperse system, which comprises a
matrix comprising a water-soluble auxiliary component (B)
containing at least an oligosaccharide (B1), and a particulate
dispersed phase comprising an organic solid component (A)
containing a plurality of organic solid materials, and dispersed in
the matrix.
12. A composition according to claim 11, wherein the organic solid
component (A) comprises a first organic solid material (A1) and a
second organic solid material (A2), and the first material (A1) and
the second material (A2) being immiscible with each other and
different in affinity relative to the auxiliary component (B) from
each other.
13. A composition according to claim 11, wherein the dispersed
phase is a spherical dispersed phase having an average particle
size of 0.1 to 100 .mu.m, a coefficient of variation of the average
particle size of not more than 60, and a length ratio of a major
axis relative to a minor axis of 1.5/1 to 1/1.
14. A composition according to claim 11, wherein the
oligosaccharide (B1) comprises at least a tetrasaccharide.
15. A composition according to claim 11, wherein the
oligosaccharide (B1) comprises at least one member selected from
the group consisting of a starch sugar, a galactooligosaccharide, a
coupling sugar, a fructooligosaccharide, a xylooligosaccharide, a
soybean oligosaccharide, a chitin oligosaccharide and a chitosan
oligosaccharide.
16. A composition according to claim 11, wherein the
oligosaccharide (B1) has a viscosity of not lower than 1 Pas when a
50% by weight aqueous solution of the oligosaccharide is measured
at a temperature of 25.degree. C. by a B-type viscometer.
17. A composition according to claim 11, wherein the auxiliary
component (B) comprises the oligosaccharide (B1) and a
water-soluble plasticizing component (B2) for plasticizing the
oligosaccharide (B1).
18. A composition according to claim 17, wherein the
oligosaccharide (B1) shows a melting point or softening point or is
decomposed at a temperature higher than each of heat distortion
temperatures of a plurality of organic solid materials constituting
the organic solid component (A), and the melting point or softening
point of the plasticizing component (B2) is not higher than the
heat distortion temperature of at least one of the organic solid
materials.
19. A composition according to claim 17, wherein the plasticizing
component (B2) comprises at least one member selected from the
group consisting of a saccharide and a sugar alcohol.
20. A composition according to claim 19, wherein the sugar alcohol
comprises at least one member selected from the group of
erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbitol,
dulcitol and mannitol.
21. A composition according to claim 17, wherein the ratio (weight
ratio) of the oligosaccharide (B1) relative to the plasticizing
component (B2) is 99/1 to 50/50.
22. A composition according to claim 17, wherein the organic solid
component (A) comprises a plurality of polymers, and each of the
polymers has a Vicat softening temperature defined by JIS K 7206 of
60 to 300.degree. C.; the oligosaccharide (B1) has a viscosity of 3
to 100 Pas when the viscosity is measured using a 50% by weight
aqueous solution of the oligosaccharide at a temperature of
25.degree. C. by a B-type viscometer; and the auxiliary component
(B) has a melt flow rate defined by JIS K 7210 of not less than 1
when measured at a temperature 30.degree. C. higher than the
minimum point of the Vicat softening temperatures of said
polymers.
23. A composition according to claim 11, wherein the ratio (weight
ratio) of the organic solid component (A) relative to the auxiliary
component (B) is 55/45 to 1/99.
24. A process for producing a multiple particle comprising an
organic solid component (A) containing a plurality of organic solid
materials, which comprises eluting an auxiliary component (B) from
a composition recited in claim 11.
Description
TECHNICAL FIELD
[0001] The present invention relates to a multiple particle (e.g.,
a multiple polymer particle) providing characteristics unachievable
in a particle (e.g., a polymer particle) formed from a single
component (e.g., a polymer), a dispersion composition for obtaining
the multiple particle, and a process for producing the multiple
particle. More specifically, the present invention also relates to
a multiple particle (e.g., a microcapsule) useful for various
fields such as a cosmetic, an image recording material (such as an
ink or a colored particle) used for an ink jet printer or other
means, a paint and varnish such as a powdered paint.
BACKGROUND ART
[0002] Heretofore, as a process for producing a polymer particle, a
mechanical pulverization (or crushing) method has been utilized,
which comprises, for example, crushing a polymer or polymer
composition coarsely by using a crushing machine or other means,
then pulverizing the crushed matter finely by using a jet mill or
other means, and classifying the resultant by an air classifier or
other means. In such a method, however, manufacturing machines are
expensive, and additionally, thus obtained particle is irregular in
shape and widely varies in particle size. In order to make the
polymer particle size uniform, the obtained particle should be
classified. However, unusable polymer particles in size are
produced in large quantities by classification, and are unfavorable
from an economical viewpoint. Further, spherical fine particles are
preferred from the viewpoint of blocking among particles,
dispersibility, flowability or others, however, it is impossible to
obtain spherical particles by mechanical pulverization (or
crushing) methods.
[0003] Moreover, Japanese Patent Application Laid-Open No.
176065/1998 (JP-10-176065A, Patent Document 1) discloses a process
for obtaining a spherical fine particle of a thermoplastic resin
(a), which comprises melt-kneading the thermoplastic resin (a) to
be powdered with other one or more of thermoplastic resin(s) (b) to
give a polymer composition comprising the resin (a) constituting
the dispersed phase and the resin (b) constituting the continuous
phase, and washing the polymer composition with a solvent incapable
of dissolving the resin (a) and capable of dissolving the resin
(b). In this process, however, it is necessary not only that the
dispersed phase and the continuous phase are immiscible with each
other, but also that an appropriate combination of the resin
constituting the continuous phase with the solvent is selected
depending on the kind of the resin of the dispersed phase.
Therefore, the combination of the resins should be limited to a
specific one, and in addition, the combination of the resin with
the solvent should be limited to a specific one. Moreover, in the
case where a fine particle comprising a plurality of resins is
produced by using this process, not only the combination of resins
constituting the dispersed phase and the combination of the resin
constituting the dispersed phase and the resin constituting the
continuous phase, but also the kind of the washing solvent or
others are highly limited. In particular, in such a system, it is
very difficult to obtain a multiple particle having a core-shell
structure. Furthermore, the resin constituting the continuous phase
is to be recovered in the end, or to be discarded in a dissolved
state, as it is not included in the resin fine particle as a final
product. However, recovery of the resin in the solution not only is
very difficult but also is a caused factor of increase in the
production cost of the polymer particle. Moreover, in the case of
discarding the resin solution directly as a waste fluid, adverse
effects on the environment cannot be ignored.
[0004] Japanese Patent Application Laid-Open No. 13816/1985
(JP-60-13816A, Patent Document 2) proposes a process for producing
a thermoplastic polymer particle, which comprises melting a
polyethylene glycol and a thermoplastic resin with stirring,
putting the molten mixture into water to solidify, and then
removing the polyethylene glycol from the resulting matter with
water. Japanese Patent Application Laid-Open No. 9433/1986
(JP-61-9433A, Patent Document 3) discloses a process for producing
a thermoplastic polymer particle, which comprises melting a
thermoplastic resin and a polyethylene oxide with stirring, then
cooling the molten mixture, and removing the polyethylene oxide
from the mixture with water. Japanese Patent Application Laid-Open
No. 165457/1997 (JP-9-165457A, Patent Document 4) discloses a
process for producing a polymer fine particle, which comprises
mixing a melt-formable and water-soluble polymer (such as a
polyvinyl alcohol-series polymer, a denatured starch, or a
polyethylene oxide) and a thermoplastic resin to give a melt-shaped
product, and then removing the water-soluble polymer from the
shaped product with water.
[0005] Even in these processes, however, since it is necessary that
a resin and a water-soluble polymer are immiscible with each other,
a selectable combination of the resins is limited, and in addition,
the particle size distribution of thus resulting polymer particle
is insufficient in uniformity. In particular, in the case of
forming a polymer particle comprising a plurality of resins, the
species of raw material to be used is highly limited because the
combination of the resin and the water-soluble polymer also exerts
a great influence on formation of the polymer particle. Further,
these water-soluble polymers having small solubilities to water
need a large amount of water for dissolution, and in addition,
significantly deteriorate productivity of polymer particles due to
the low velocity of dissolution. Furthermore, since such
water-soluble polymers are often derived from unnatural products, a
waste fluid containing such a water-soluble polymer dissolved
therein adversely affects on the environment.
[0006] On the other hand, as a process for obtaining a polymer fine
particle having a core-shell structure, a seeded emulsion
polymerization, comprising polymerization of a polymerizable
monomer after synthesizing a polymer fine particle as a core, is
most popularly practiced. For example, Japanese Patent Application
Laid-Open No. 70255/1995 (JP-7-70255A, Patent Document 5) discloses
a production process of a core-shell polymer having an alkyl
acrylate-series rubber-like core and a methyl methacrylate-series
glass-like shell.
[0007] In the seeded emulsion polymerization, however, it is
difficult to stably produce a particle having a particle size over
1 .mu.m and a narrow particle size distribution, further the
polymer available for the seed polymerization is limited to a
polymer obtained from a radical-polymerizable monomer. Therefore,
the seeded emulsion polymerization cannot be employed to a polymer
obtained by a condensation reaction, or a curing or crosslinking
reaction.
[0008] [Patent Document 1] JP-10-176065A (claim 1)
[0009] [Patent Document 2] JP-60-13816A
[0010] [Patent Document 3] JP-61-9433A
[0011] [Patent Document 4] JP-9-165457A
[0012] [Patent Document 5] JP-7-70255A (claim 1)
DISCLOSURE OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0013] It is therefore an object of the present invention to
provide a composition having a disperse system, which is capable of
producing a multiple particle (e.g., multiple polymer particle)
industrially with advantage by a convenient method even in the case
where the multiple particle (e.g., a multiple polymer particle)
comprises a plurality of organic solid materials (e.g., polymers),
independent of (i) miscibility or immiscibility between a dispersed
phase and a matrix, and (ii) solvent resistance; a process for
producing a multiple particle from the composition having a
disperse system; and the multiple particle.
[0014] It is another object of the present invention to provide a
composition having a disperse system, which is applicable for
various organic solid materials (e.g., polymers) irrespective of a
polymerization method and is useful for producing a multiple
particle (e.g., a multiple polymer particle) having a core-shell
structure; a process for producing the multiple particle; and the
multiple particle.
[0015] It is still another object of the present invention to
provide a composition having a disperse system, which is stably
capable of producing a multiple particle having a structure such as
a core-shell structure even in a large particle size; a process for
producing the multiple particle; and the multiple particle.
[0016] It is a further object of the present invention to provide a
composition having a disperse system, which is capable of narrowing
a particle size distribution and controlling (or adjusting) a
particle size of a multiple particle, and useful for obtaining a
spherical multiple particle; a process for producing the multiple
particle; and the multiple particle.
[0017] It is a still further object of the present invention to
provide a composition having a disperse system, which is capable of
reducing the burden on the environment due to a waste fluid or
other factors, and a process for producing a multiple particle from
the composition.
MEANS TO SOLVE THE PROBLEMS
[0018] The inventor of the present invention made intensive studies
to achieve the above objects and finally found that even in a
plurality of organic solid materials (e.g., polymers), a
particulate dispersed phase having a multiple (or composite)
structure (e.g., a core-shell structure) can be stably formed by
using, as a matrix of a composition having a disperse system, an
auxiliary component comprising at least an oligosaccharide, and
that a multiple particle (e.g., a multiple polymer particle)
combining characteristics of a plurality of organic solid materials
(e.g., polymers) can be obtained by further eluting or extracting
the auxiliary component with an aqueous medium or the like. The
present invention was accomplished based on the above findings.
[0019] That is, the multiple particle (or composite particle) of
the present invention comprises an organic solid component (e.g., a
polymer component) (A), and the organic solid component (A)
comprises a plurality of organic solid materials each having a
different affinity relative to a water-soluble auxiliary component
(B) comprising at least an oligosaccharide (B1). The plurality of
the organic solid materials (e.g., polymers) may form a polymer
alloy. Moreover, the multiple particle may have a core-shell
structure, wherein the core part (or core) contains a first organic
solid material (e.g., a polymer) (A1) and the shell part (or shell)
contains a second organic solid material (e.g., a polymer) (A2). In
the core-shell structure, the shell may have a thickness of not
more than 1 .mu.m (for example, about 10 nm to 1 .mu.m). At least
one organic solid material (e.g., a polymer) of the plurality of
the organic solid materials may be a polymer obtained by a
non-addition polymerization (or a non-addition polymerization
polymer). The organic solid component (A) may comprise a first
organic solid material (e.g., a polymer) (A1) and a second organic
solid material (e.g., a polymer) (A2) different in affinity
relative to the auxiliary component (B) from each other. The ratio
(weight ratio) of the first organic solid material (e.g., a
polymer) (A1) relative to the second organic solid material (e.g.,
a polymer) (A2) [(A1)/(A2)] may be about 30/70 to 99/1. The organic
solid component (A) may comprise a hydrophobic polymer (A1), and a
hydrophilic polymer (A2) having at least one hydrophilic group
selected from the group consisting of a hydroxyl group, a carboxyl
group, an amino group, an imino group, an ether group, an
oxyalkylene group, an ester group and an amide group. The
hydrophilic polymer (A2) may contain at least one member selected
from the group consisting of a vinyl acetate-series polymer (or
resin), a polyvinyl alcohol-series polymer (or resin), a
polyester-series polymer (or resin), a polyamide-series polymer (or
resin), a polycarbonate-series polymer (or resin), a
polyurethane-series polymer (or resin) and a cellulose derivative.
The multiple particle may be a spherical particle, and the
spherical particle may have an average particle size of 0.1 to 100
.mu.m, a coefficient of variation of the average particle size of
not more than 60, and a length ratio of a major axis relative to a
minor axis of 1.5/1 to 1/1.
[0020] The present invention also includes a composition having a
disperse system (or a dispersion composition), which comprises a
matrix comprising a water-soluble auxiliary component (B)
containing at least an oligosaccharide (B1), and a particulate
dispersed phase comprising an organic solid component (A)
containing a plurality of organic solid materials, and dispersed in
the matrix. In the dispersion composition, the organic solid
component (A) may comprise a first organic solid material (e.g., a
polymer) (A1) having a lower affinity relative to the auxiliary
component (B), and a second organic solid material (e.g., a
polymer) (A2) having a higher affinity relative to the auxiliary
component (B). The first organic solid material (A1) and the second
organic solid material (A2) may be immiscible with each other.
[0021] The oligosaccharide (B1) may comprise at least a
tetrasaccharide. The oligosaccharide (B1) may comprise at least one
member selected from the group consisting of a starch sugar, a
galactooligosaccharide, a coupling sugar, a fructooligosaccharide,
a xylooligosaccharide, a soybean oligosaccharide, a chitin
oligosaccharide and a chitosan oligosaccharide. The oligosaccharide
(B1) may have a viscosity of not lower than 1 Pass when a 50% by
weight aqueous solution of the oligosaccharide is measured at a
temperature of 25.degree. C. by a B-type viscometer. The auxiliary
component (B) may comprise the oligosaccharide (B1) and a
water-soluble plasticizing component (B2) for plasticizing the
oligosaccharide (B1). In the case of using the oligosaccharide (B1)
and the plasticizing component (B2) in combination, the
plasticizing component (B2) can effectively plasticize or soften
the oligosaccharide (B1) even when the oligosaccharide (B1) is a
thermally decomposable oligosaccharide. The oligosaccharide (B1)
may show a melting point or softening point or may be decomposed
(thermally decomposed) at a temperature (e.g., about 90 to
290.degree. C.) higher than each of heat distortion temperatures of
a plurality of organic solid materials (e.g. polymers) constituting
the organic solid component (A), and the melting point or softening
point of the plasticizing component (B2) may be not higher than the
heat distortion temperature of at least one (e.g., a polymer) of
the plurality of the organic solid materials. The plasticizing
component (B2) may comprise at least one member selected from the
group consisting of a saccharide (e.g., a monosaccharide, and a
disaccharide) and a sugar alcohol (e.g., erythritol,
pentaerythritol, arabitol, ribitol, xylitol, sorbitol, dulcitol and
mannitol). The ratio (weight ratio) of the oligosaccharide (B1)
relative to the plasticizing component (B2) [the oligosaccharide
(B1)/the plasticizing component (B2)] may be about 99/1 to 50/50.
In the dispersion composition, the organic solid component (A) may
comprise a plurality of polymers, each of the polymers may have a
Vicat softening temperatures defined by JIS K 7206 of 60 to
300.degree. C., and the oligosaccharide (B1) may have a viscosity
of 3 to 100 Pas when the viscosity is measured using a 50% by
weight aqueous solution of the oligosaccharide at a temperature of
25.degree. C. by a B-type viscometer. Moreover, the auxiliary
component (B) comprising the oligosaccharide (B1) and the
plasticizing component (B2) may have a melt flow rate defined by
JIS K 7210 of not less than 1 when measured at a temperature
30.degree. C. higher than the minimum point of the Vicat softening
temperatures of the plurality of polymers. The ratio (weight ratio)
of the organic solid component (A) relative to the auxiliary
component (B) [the organic solid component (A)/the auxiliary
component (B)] may be about 55/45 to 1/99.
[0022] The present invention further includes a process for
producing a multiple particle (e.g., a multiple polymer particle)
comprising an organic solid component (A) containing a plurality of
organic solid materials (e.g., polymers), which comprises eluting
an auxiliary component (B) from the dispersion composition.
[0023] Incidentally, in the present invention, the dispersion
composition may be a polymer composition forming a disperse system
containing an auxiliary component and an organic solid component
comprising a plurality of organic solid materials, and the term
"dispersion composition" is sometimes used synonymously with the
term "polymer composition" accordingly. Moreover, in the present
invention, an organic solid component comprising a plurality of
organic solid materials, or a multiple (or composite) matter of a
plurality of organic solid materials is sometimes simply referred
to as "an organic solid component"; a polymer component comprising
a plurality of polymers or a multiple (or composite) matter of a
plurality of polymers is sometimes simply referred to as "a polymer
component"; and a water-soluble auxiliary component is sometimes
simply referred to as "an auxiliary component". Incidentally, the
term "spherical" shape is not limited to a finely spherical shape,
and includes a shape having a length ratio of a major axis relative
to a minor axis of about 1.5/1 to 1/1.
[0024] Throughout this description, the meaning of the term
"organic solid component" includes not only a carbon-containing
organic compound but also a silicon-containing compound (e.g., a
silicone) as far as the compounds are in a solid form.
EFFECTS OF THE INVENTION
[0025] According to the present invention, since a water-soluble
auxiliary component comprising at least an oligosaccharide
constitutes a matrix of a dispersion composition, even in a
multiple particle comprising a plurality of organic solid
materials, a multiple particle corresponding to the dispersed phase
can be produced by a convenient method industrially with advantage
independently of (i) affinity (miscibility or immiscibility)
between a dispersed phase and a matrix, and (ii) solvent
resistance. Moreover, the present invention can be applied to
various polymers independent of the kind of polymerization method,
and a multiple particle having a core-shell structure or other
structure can be produced. Even when the particle size is large,
the multiple particle having a core-shell structure can be stably
produced. The present invention ensures to narrow the particle size
distribution and control the particle size of the multiple polymer
particle, and also ensures to obtain a spherical multiple particle.
Further, since the water-soluble auxiliary component is derived
from a natural product, the burden on the environment due to a
waste fluid or other factors can be reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a transmission electron micrograph of a multiple
polymer particle obtained in Example 2.
[0027] FIG. 2 is a transmission electron micrograph showing a
particle state after treating the multiple polymer particle of
Example 2 with tetrahydrofuran.
[0028] FIG. 3 is a transmission electron micrograph of a cross
section of the multiple polymer particle obtained in Example 2.
DETAILED DESCRIPTION OF THE INVENTION
[0029] [Dispersion Composition]
[0030] In the dispersion composition of the present invention, a
particulate dispersed phase comprising an organic solid component
(A) containing a plurality of organic solid materials is dispersed
in a matrix comprising a water-soluble auxiliary component (B)
containing at least an oligosaccharide (B1).
[0031] (A) Meltable Organic Solid Component
[0032] The combination of a plurality of organic solid materials is
not particularly limited to a specific one, and the materials may
be organic solid materials (e.g., polymers) being miscible with
each other, or may be organic solid materials (e.g., polymers)
being immiscible with each other. In the dispersed phase (or
multiple particle), for example, a plurality of organic solid
materials (e.g., polymers) being miscible with each other may form
a polymer alloy, or a plurality of organic solid materials (e.g.,
polymers) being immiscible with each other may form a phase
separation structure (e.g., an islands-in-the-sea structure, a
bicontinuous phase structure, and a core-shell structure (including
a multi-layered core-shell structure)].
[0033] A plurality of organic solid materials constituting the
organic solid component (A) may be combined by suitably selecting
from the below-mentioned materials (low molecular weight compounds,
and high molecular weight compounds).
[0034] As the meltable (or thermoplastic) organic solid component
(A), a component (water-insoluble component) immiscible with or
hydrophobic relative to the water-soluble auxiliary agent (or
component) (B) may be usually employed. The organic solid component
(A) is usually a solid at a room temperature (about 15 to
25.degree. C.), and may be a low molecular weight compound or a
high molecular weight compound (or a polymer or resin). The melting
point of the organic solid component (A) having a low molecular
weight may be about 40 to 280.degree. C. (preferably about 50 to
270.degree. C., and more preferably about 70 to 260.degree. C.), or
a compound having a relatively high melting point (about 100 to
260.degree. C.) may be used as the organic solid component (A).
[0035] The organic solid component (A) having a low molecular
weight may include, for example, a wax or lipid, a stabilizer
(e.g., an antioxidant such as a hindered phenol-series, a hindered
amine-series or a phosphorus-series antioxidant, and an ultraviolet
ray absorbing agent or light stabilizer such as a
benzophenone-series or a salicylic acid-series ultraviolet ray
absorbing agent or a hindered amine-series light stabilizer), an
antistatic agent, a flame retardant, a lubricant, a nucleation
agent, a vulcanization accelerator, an antiaging agent, and a
vulcanizing agent. Examples of the wax or lipid may include an
aliphatic hydrocarbon-series wax (e.g., a polyolefinic wax such as
a polyethylene wax or a polypropylene wax, a paraffin-series wax,
and a microcrystalline wax), a plant- or animal-derived wax (e.g.,
a carnauba wax, a yellow bees wax, a shellac wax, and a montan
wax), a higher fatty acid ester (e.g., a glycerin fatty acid ester,
a diglycerin fatty acid ester, and a polyglycerin fatty acid
ester), a fatty acid amide (e.g., stearic acid amide, and erucic
acid amide), an alkylenebis fatty acid amide (e.g.,
methylenebisstearic acid amide, ethylenebisstearic acid amide, and
ethylenebishydroxystearic acid amide), a metal salt of a fatty acid
(e.g., a polyvalent metal salt of a higher fatty acid, such as
barium laurate, zinc laurate, calcium stearate, zinc stearate or
magnesium stearate). Incidentally, the wax or lipid may be also
used as a lubricant. These components may be used singly or in
combination.
[0036] According to the present invention, even in such an organic
solid component having a low molecular weight, a particle (in
particular a fine spherical particle) may be obtained by using in
combination with the water-soluble auxiliary agent (B). Therefore,
the present invention can improve in handleability of such an
organic solid component (A) having a low molecular weight.
[0037] As the organic solid component (A), a high molecular weight
compound (polymer or resin) is often used. Examples of the polymer
may include a thermosetting resin [for example, an epoxy polymer,
an unsaturated polyester polymer, a diallyl phthalate polymer, and
a silicone (e.g., a silicone rubber, and a silicone varnish)], and
usually include a thermoplastic resin, e.g., a condensation-series
thermoplastic resin [for example, a polyester-series polymer (e.g.,
an aromatic polyester-series polymer, and an aliphatic
polyester-series polymer), a polyamide-series polymer, a
polyurethane-series polymer, a poly(thio)ether series polymer
(e.g., a polyacetal-series polymer, a polyphenylene ether-series
polymer, a polysulfide-series polymer, and a polyether
ketone-series polymer), a polycarbonate-series polymer, a
polysulfone-series polymer, and a polyimide-series polymer], a
vinyl polymerization-type (or series) (additive polymerization-type
(or series)) thermoplastic resin [for example, a polyolefinic
polymer, a (meth)acrylic polymer, a styrenic polymer, and a
vinyl-series polymer (e.g., a halogen-containing polymer, a vinyl
ester-series polymer, and a vinyl alcohol-series polymer)], a
natural product-derived polymer such as a cellulose derivative, and
a thermoplastic silicone.
[0038] (1) Polyester-Series Polymer
[0039] The polyester-series polymer (or resin) may include, for
example, a polyester including a copolyester obtained by a
polycondensation of a dicarboxylic acid component and a diol
component; a polyester including a copolyester obtained by a
polycondensation of a hydroxycarboxylic acid; and a polyester
including a copolyester obtained by a ring opening polymerization
of a lactone. These polyester-series polymers may be used singly or
in combination.
[0040] The dicarboxylic acid component may include, for example, an
aromatic dicarboxylic acid [e.g., an aromatic dicarboxylic acid
having about 8 to 20 carbon atoms, such as terephthalic acid,
isophthalic acid, phthalic acid; an alkyl-substituted phthalic acid
such as methylterephthalic acid or methylisophthalic acid; a
naphthalenedicarboxylic acid (e.g., 2,6-naphthalenedicarboxylic
acid, 2,7-naphthalenedicarboxylic acid, and
1,5-naphthalenedicarboxylicacid); adiphenyldicarboxylic acid such
as 4,4'-diphenyldicarboxylic acid or 3,4'-diphenyldicarboxylic
acid; a diphenoxyethanedicarboxylic acid such as
4,4'-diphenoxyethanedicarboxylic acid; a diphenyl
ether-dicarboxylic acid such as diphenyl ether-4,4'-dicarboxylic
acid; a diphenylalkanedicarboxylic acid such as
diphenylmethanedicarboxylic acid or diphenylethanedicarboxylic
acid; or a diphenylketonedicarboxylic acid], an aliphatic
dicarboxylic acid (e.g., an aliphatic dicarboxylic acid having
about 2 to 40 carbon atoms, such as oxalic acid, succinic acid,
adipic acid, azelaic acid, sebacic acid, dodecanedioic acid,
hexadecanedicarboxylic acid, or dimeric acid), and an alicyclic
dicarboxylic acid (e.g., an alicyclic dicarboxylic acid having
about 8 to 12 carbon atoms, such as cyclohexanedicarboxylic acid,
hexahydrophthalic acid, hexahydroisophthalic acid,
hexahydroterephthalic acid, or himic acid). These dicarboxylic acid
components may be used singly or in combination.
[0041] Incidentally, the dicarboxylic acid component may also
include an ester-formable derivative, e.g., a lower alkyl ester
such as a dimethyl ester, an acid anhydride, and an acid halide
such as an acid chloride.
[0042] Examples of the diol component may include an aliphatic
C.sub.2-12diol (e.g., ethylene glycol, propylene glycol,
1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, and a
(poly)C.sub.2-4alkylene glycol (e.g., diethylene glycol and
dipropylene glycol)); and an alicyclic C.sub.6-12diol (e.g.,
cyclohexanediol, and cyclohexanedimethanol); an aromatic
C.sub.6-20diol (e.g., resorcinol, hydroquinone, naphthalenediol, a
bisphenol compound such as bisphenol A, F, or AD; and an adduct of
a bisphenol compound with an alkylene oxide). These diol components
may be used singly or in combination.
[0043] The hydroxycarboxylic acid may include, for example, an
aliphatic C.sub.2-6hydroxycarboxylic acid such as glycolic acid,
lactic acid, hydroxypropionic acid, hydroxybutyric acid, glyceric
acid, or tartronic acid; and an aromatic hydroxycarboxylic acid
such as hydroxybenzoic acid, or hydroxynaphthoic acid. These
hydroxycarboxylic acids may be used singly or in combination.
[0044] Examples of the lactone may include a C.sub.3-12lactone such
as propiolactone, butyrolactone, valerolactone, or caprolactone.
These lactones may be used singly or in combination. Among these
lactones, a C.sub.4-10lactone, in particular a caprolactone (e.g.,
.epsilon.-caprolactone), is preferred.
[0045] The polyester-series polymer may include an aromatic
polyester-series polymer, an aliphatic polyester-series polymer,
and others.
[0046] Examples of the aromatic polyester-series polymer may
include a polyester including a copolyester obtained by
polycondensation of the aromatic dicarboxylic acid (preferably, an
aromatic dicarboxylic acid having about 8 to 20 carbon atoms, such
as terephthalic acid, isophthalic acid, phthalic acid or a
naphthalenedicarboxylic acid) and the aliphaticdiol (preferably,
e.g., analiphaticC.sub.2-12diol such as ethylene glycol, propylene
glycol, 1,4-butanediol or 1,3-butanediol) or the alicyclic diol
(preferably, an alicyclic C.sub.6-20diol such as
cyclohexanedimethanol), and preferably include a polyester
including a copolyester having an alkylene arylate unit such as an
alkylene terephthalate or an alkylene naphthalate as a main unit
(e.g., not less than 50% by weight). The copolymerizable component
may include a polyC.sub.2-4alkylene glycol having a repeating
oxyalkylene unit of about 2 to 4 [e.g., a glycol compound
containing a poly(oxy-C.sub.2-4alkylene) unit such as diethylene
glycol], or an aliphatic dicarboxylic acid having about 6 to 12
carbon atoms (e.g., adipic acid, pimelic acid, suberic acid,
azelaic acid, and sebacic acid).
[0047] More specifically, as the aromatic polyester-series polymer,
there may be exemplified a polyalkylene terephthalate [e.g., a
polycycloalkanediC.sub.1-4alkylene terephthalate such as a
poly(1,4-cyclohexanedimethyleneterephthalate) (PCT); and a
polyC.sub.2-4alkylene terephthalate such as a polyethylene
terephthalate (PET) or a polybutylene terephthalate (PBT)], a
polyC.sub.2-4alkylene naphthalate corresponding to the polyalkylene
terephthalate (e.g., a polyethylene naphthalate), a polyethylene
terephthalate copolyester containing an ethylene terephthalate unit
as a main unit, and a polybutylene terephthalate copolyester
containing a butylene terephthalate unit as a main unit. The
aromatic polyester-series polymer may be a liquid crystalline
polyester.
[0048] Examples of the aliphatic polyester-series polymer may
include a polyester including a copolyester obtained by a
polycondensation of the aliphatic dicarboxylic acid component
(e.g., an aliphatic dicarboxylic acid having about 2 to 6 carbon
atoms, such as oxalic acid, succinic acid or adipic acid, and
preferably an aliphatic dicarboxylic acid having about 2 to 4
carbon atoms, such as oxalic acid or succinic acid) and the
aliphatic diol component (e.g., an aliphatic C.sub.2-6diol (a
C.sub.2-6alkanediol) such as ethylene glycol, propylene glycol,
1,4-butanediol, 1,3-butanediol, neopentyl glycol or hexanediol, and
preferably an aliphatic C.sub.2-4diol (a C.sub.2-4alkanediol) such
as ethylene glycol, 1,4-butanediol or neopentyl glycol), a
polyester including a copolyester of the aliphatic
hydroxycarboxylic acid (e.g., an aliphatic
C.sub.2-6hydroxycarboxylic acid such as glycolic acid, lactic acid,
hydroxypropionic acid or hydroxybutyric acid, and preferably an
aliphatic C.sub.2-4hydroxycarboxylic acid such as glycolic acid or
lactic acid), and a homopolylactone or copolylactone obtained by a
ring opening polymerization of the lactone (preferably, a
C.sub.4-10lactone such as caprolactone) with an initiator (a
bifunctional or trifunctional initiator, e.g., an active
hydrogen-containing compound such as an alcohol compound). The
copolymerizable component may include a polyC.sub.2-4alkylene
glycol having a repeating oxyalkylene unit of about 2 to 4 [e.g., a
glycol compound containing a poly(oxy-C.sub.2-4alkylene) unit such
as diethylene glycol], or an aliphatic dicarboxylic acid having
about 6 to 12 carbon atoms (e.g., adipic acid, pimelic acid,
suberic acid, azelaic acid, and sebacic acid).
[0049] More specifically, the aliphatic polyester-series polymer
may include, for example, a polyester-series polymer obtained by a
polycondensation of a dicarboxylic acid component and a diol
component (for example, a polyC.sub.2-6alkylene oxalate such as a
polyethylene oxalate, a polybutylene oxalate or a polyneopentylene
oxalate; a polyC.sub.2-6alkylene succinate such as a polyethylene
succinate, a polybutylene succinate or a polyneopentylene
succinate; and a polyC.sub.2-6alkylene adipate such as a
polyethylene adipate, a polybutylene adipate or a polyneopentylene
adipate), a polyhydroxycarboxylic acid-series polymer (e.g., a
homo- or copolymer of a hydroxyC.sub.2-10alkanecarboxylic acid,
such as a polyglycolic acid, a polylactic acid, or a lactic
acid-glycolic acid copolymer), and a polylactone-series polymer
[e.g., a polyC.sub.3-12lactone-series polymer such as a
polycaprolactone (e.g., "PCLH7", "PCLH4" and "PCLH1" manufactured
by Daicel Chemical Industries, Ltd.)]. The concrete examples of the
copolyester include a copolyester containing two kinds of
dicarboxylic acid components (e.g., a polyC.sub.2-4alkylene
succinate-adipate copolymer such as a polyethylene
succinate-adipate copolymer or a polybutylene succinate-adipate
copolymer), and a copolyester obtained from a dicarboxylic acid
component, a diol component and a lactone (e.g., a
polycaprolactone-polybutylene succinate copolymer).
[0050] The polyester-series polymer used in the present invention
may be a polyester-series polymer containing a urethane bond (for
example, an aliphatic polyester-series polymer containing a
urethane bond). The polyester-series polymer containing a urethane
bond preferably includes a polymer obtained by allowing the above
polyester-series polymer (e.g., a polyester diol having a low
molecular weight) to have a high molecular weight with a
diisocyanate compound (e.g., an aliphatic diisocyanate).
[0051] The diisocyanate compound may include an aromatic
diisocyanate (e.g., a phenylene diisocyanate, a tolylene
diisocyanate, and diphenylmethane-4,4'-diisocyanate), an
araliphatic diisocyanate compound (e.g., a xylylene diisocyanate),
an alicyclic diisocyanate compound (e.g., isophorone diisocyanate),
an aliphatic diisocyanate compound (e.g., trimethylene
diisocyanate, tetramethylene diisocyanate, pentamethylene
diisocyanate, hexamethylene diisocyanate, lysine diisocyanatemethyl
ester, and trimethylhexamethylene diisocyanate), and others. These
diisocyanate compounds may be used singly or in combination. Among
these diisocyanate compounds, the aliphatic diisocyanate compound,
e.g., hexamethylene diisocyanate, may be used.
[0052] Examples of the polyester-series polymer containing a
urethane bond (e.g., an aliphatic polyester-series polymer) may
include "BIONOLLE #1000" series, "BIONOLLE #3000" series and
"BIONOLLE #6000" series manufactured by Showa Highpolymer Co.,
Ltd.
[0053] (2) Polyamide-Series Polymer
[0054] The polyamide-series polymer (or resin) may include, for
example, an aliphatic polyamide-series polymer, an alicyclic
polyamide-series polymer, and an aromatic polyamide-series polymer,
and the aliphatic polyamide-series polymer is usually employed.
These polyamide-series polymers may be used singly or in
combination.
[0055] Examples of the aliphatic polyamide-series polymer may
include a condensate (or condensed product) of an aliphatic diamine
component (a C.sub.4-10alkylenediamine such as
tetramethylenediamine or hexamethylenediamine) and an aliphatic
dicarboxylic acid component (e.g., a C.sub.4-20alkylenedicarboxylic
acid such as adipic acid, sebacic acid or dodecanedioic acid) (for
example, a polyamide 46, a polyamide 66, a polyamide 610, a
polyamide 612, a polyamide 1010, a polyamide 1012, and a polyamide
1212), a homo- or copolymer of a lactam (e.g., a C.sub.4-20lactam
such as .epsilon.-caprolactam or .omega.-laurolactam) or an
aminocarboxylic acid (e.g., a C.sub.4-20aminocarboxylic acid such
as .omega.-aminoundecanoic acid) (for example, a polyamide 6, a
polyamide 11, a polyamide 12, a polyamide 6/11, and a polyamide
6/12); and a copolyamide having these polyamide components
copolymerized therein (for example, a polyamide 66/11, and a
polyamide 66/12).
[0056] Further, the polyamide-series polymer may have
biodegradability. The biodegradable polyamide-series polymer may
include a polyester amide as a condensate of the aliphatic diamine
component (a C.sub.4-10alkylenediamine such as
tetramethylenediamine or hexamethylenediamine), the aliphatic
dicarboxylic acid component (e.g., a C.sub.4-20alkylenedicarboxylic
acid such as adipic acid, sebacic acid or dodecanedioic acid) and
the aliphatic diol component (e.g., a C.sub.2-12alkylene glycol
such as ethylene glycol, propylene glycol or butanediol).
[0057] (3) Polyurethane-Series Polymer
[0058] The polyurethane-series polymer (or resin) may be obtained
by a reaction between a diisocyanate compound and a polyol compound
(e.g., a diol compound) and, if necessary, a chain-extension agent.
As the diisocyanate compound, there may be exemplified an aliphatic
diisocyanate compound such as hexamethylene diisocyanate or
2,2,4-trimethylhexamethylene diisocyanate; an alicyclic
diisocyanate compound such as 1,4-cyclohexanediisocyanate or
isophorone diisocyanate; an aromatic diisocyanate compound such as
a phenylene diisocyanate, a tolylene diisocyanate,
diphenylmethane-4,4'-diisocyanate or 1,5-naphthalene diisocyanate;
an araliphatic diisocyanate compound such as a xylylene
diisocyanate; and others.
[0059] The polyol compound may include, for example, a polyester
polyol, a polyether polyol, and a polycarbonate polyol. Among the
polyol compounds, a diol compound (e.g., a polyester diol, a
polyether diol, and a polycarbonate diol) is particularly
preferred. These polyol compounds may be used singly or in
combination.
[0060] Examples of a compound available as the diol compound may
include a polyester diol (e.g., a polyester diol derived from a
C.sub.4-12aliphatic dicarboxylic acid component such as succinic
acid, adipic acid or azelaic acid, and a C.sub.2-12aliphatic diol
component such as ethylene glycol, propylene glycol, butanediol or
neopentyl glycol; a polyester diol derived from a C.sub.4-12lactone
component such as .epsilon.-caprolactone; and a polyester diol
derived from the aliphatic dicarboxylic acid component and/or the
aliphatic diol component, and the lactone component), a polyether
diol (e.g., a polyethylene glycol, a polypropylene glycol, a
polyoxyethylene-polyoxypropylene block copolymer, a
polytetramethylene glycol, and a bisphenol A-alkylene oxide
adduct), and a polyester ether diol (e.g., a polyester diol
obtained by using the polyether diol as part of a diol
component).
[0061] Further, as the chain-extension agent, there may be used a
C.sub.2-10alkylene glycol such as ethylene glycol or propylene
glycol, and in addition, a diamine compound [for example, an
aliphatic diamine compound (a linear or branched alkylenediamine
such as ethylenediamine, trimethylenediamine or
tetramethylenediamine; and a linear or branched
polyalkylenepolyamine such as diethylenetriamine,
triethylenetetramine, tetraethylenepentamine or
dipropylenetriamine), an alicyclic diamine compound (e.g.,
isophoronediamine), and an aromatic diamine compound (e.g.,
phenylenediamine, and xylylenediamine)]. These polyurethane-series
polymers may be used singly or in combination.
[0062] (4) Poly(thio)ether-Series Polymer
[0063] Examples of the poly(thio)ether-series polymer (or resin)
may include a polyalkylene glycol, a polyphenylene ether-series
polymer, and a polysulfide-series polymer (polythioether-series
polymer). The polyalkylene glycol may include a homo- or copolymer
of an alkylene glycol (e.g., a polyC.sub.2-4alkylene glycol) such
as a polypropylene glycol, a polytetramethylene ether glycol, or a
polyoxyethylene-polyoxypropylene block copolymer. These
poly(thio)ether-series polymers may be used singly or in
combination.
[0064] (5) Polycarbonate-Series Polymer
[0065] The polycarbonate-series polymer (or resin) may include, for
example, an aromatic polycarbonate containing a bisphenol compound
(e.g., bisphenol A) as a base unit, and an aliphatic polycarbonate
such as diethylene glycol bisallyl carbonate. These
polycarbonate-series polymers may be used singly or in
combination.
[0066] (6) Polysulfone-Series Polymer
[0067] Examples of the polysulfone-series polymer (or resin) may
include a polysulfone polymer obtained by polycondensation of a
dihalogenodiphenyl sulfone (e.g., dichlorodiphenyl sulfone) and a
bisphenol compound (e.g., bisphenol A or a metal salt thereof), a
polyether sulfone polymer, and a polyallyl sulfone polymer (brand
name: RADEL). These polysulfone-series polymers may be used singly
or in combination.
[0068] (7) Polyolefinic Polymer
[0069] The polyolefinic polymer (or resin) may include a homo- or
copolymer of an .alpha.-C.sub.2-6olefin, for example, a homo- or
copolymer of an olefin such as a polyethylene, a polypropylene, an
ethylene-propylene copolymer or a poly(methylpentene-1), and a
copolymer of an olefin and a copolymerizable monomer (e.g., an
ethylene-vinyl acetate copolymer, an ethylene-(meth)acrylic acid
copolymer, and an ethylene-(meth)acrylate copolymer). These
polyolefinic polymers may be used singly or in combination.
[0070] (8) (Meth)acrylic Polymer
[0071] As the (meth)acrylic polymer (or resin), there may be
mentioned a homo- or copolymer of a (meth)acrylic monomer [e.g.,
(meth)acrylic acid, a C.sub.1-18alkyl (meth)acrylate, a
hydroxyalkyl (meth)acrylate, a glycidyl (meth)acrylate, and
(meth)acrylonitrile], for example, a poly(meth)acrylate such as a
poly(methyl (meth)acrylate), a methyl methacrylate-(meth)acrylic
acid copolymer, a methyl methacrylate-acrylate-(meth)acrylic acid
copolymer, a methyl methacrylate-(meth)acrylate copolymer, and a
(meth)acrylate-styrene copolymer (e.g., an MS polymer). The
preferred (meth)acrylic polymer includes a poly(C.sub.1-5alkyl
(meth)acrylate), a methyl methacrylate-acrylate copolymer, a (meth)
acrylate-styrene copolymer (e.g., an MS polymer), and others. These
(meth)acrylic polymers may be used singly or in combination.
[0072] (9) Styrenic Polymer
[0073] Examples of the styrenic polymer (or resin) may include a
homo- or copolymer of a styrenic monomer (e.g., styrene,
.alpha.-methylstyrene, and vinyl toluene) (for example, a
polystyrene, a styrene-vinyl toluene copolymer, and a
styrene-.alpha.-methylstyrene copolymer), a copolymer of a styrenic
monomer and copolymerizable monomer(s) [for example, a copolymer
such as a styrene-acrylonitrile copolymer (an AS polymer), a
(meth)acrylate-styrene copolymer (e.g., an MS polymer), a
styrene-maleic anhydride copolymer, or a styrene-butadiene block
copolymer; a styrenic graft copolymer such as an
acrylonitrile-acrylate-styrene copolymer (an AAS polymer), an
acrylonitrile-chlorinated polyethylene-styrene copolymer (an ACS
polymer), or an acrylonitrile-vinyl acetate-styrene copolymer
(e.g., an AXS polymer); and a graft polymer obtained by a graft
polymerization of at least a styrenic monomer in the presence of a
rubber component, for example, a high impact polystyrene (HIPS, or
a rubber-grafted polystyrenic polymer), an
acrylonitrile-butadiene-styrene copolymer (an ABS polymer), and an
acrylonitrile-ethylene propylene rubber-styrene copolymer (an AES
polymer)]. These styrenic polymers may be used singly in
combination.
[0074] (10) Vinyl-Series Polymer
[0075] Examples of the vinyl-series polymer (or resin) may include
a homo- or copolymer of a vinyl-series monomer, or a copolymer of a
vinyl-series monomer and other copolymerizable monomer(s). The
vinyl-series monomer may include, for example, a halogen-containing
vinyl monomer [for example, a chlorine atom-containing vinyl
monomer (e.g., vinyl chloride, vinylidene chloride, and
chloroprene), and a fluorine atom-containing vinyl monomer (e.g.,
fluoroethylene)], and a vinyl carboxylate [for example, a vinyl
ester such as vinyl acetate, vinyl propionate, vinyl
crotonateorvinylbenzoate]. These vinyl-series polymers may be used
singly or in combination.
[0076] As the vinyl-series polymer, for example, there may be
mentioned a vinyl chloride-series polymer (e.g., a polyvinyl
chloride, a polyvinylidene chloride, a vinyl chloride-vinyl acetate
copolymer, and a vinylidene chloride-vinyl acetate copolymer), a
fluorocarbon polymer (e.g., a polyvinyl fluoride, a polyvinylidene
fluoride, a polychlorotrifuloroethylene, a
tetrafluoroethylene-hexafluoropropylene copolymer, a
tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and a
tetrafluoroethylene-ethylene copolymer), and a vinyl ester-series
polymer (e.g., a polyvinyl acetate; a vinyl acetate-series
copolymer such as an ethylene-vinyl acetate copolymer, a vinyl
acetate-vinyl chloride copolymer, or a vinyl acetate-(meth)acrylate
copolymer).
[0077] Moreover, the vinyl-series polymer may also include a
derivative of the vinyl ester-series polymer, for example, a vinyl
alcohol-series polymer (e.g., a polyvinyl acetal such as a
polyvinyl formal or a polyvinyl butyral; and a saponification
product of the vinyl acetate-series copolymer, e.g., an
ethylene-vinyl alcohol copolymer). Among these vinyl alcohol-series
polymers, the saponification product of the vinyl acetate-series
copolymer, in particular the ethylene-vinyl alcohol copolymer, is
preferred. In the saponification product of the vinyl
acetate-series copolymer, the degree of hydrophilicity may be
controlled by adjusting a proportion of a hydrophobic comonomer
unit (e.g., an ethylene unit in an ethylene-vinyl alcohol
copolymer). In the case of using the saponification product of the
vinylacetate-series copolymer as a hydrophilic polymer, the
proportion of the hydrophobic monomer unit may be adjusted to, for
example, about 10 to 40% by weight from the viewpoint of affinity
relative to the auxiliary component (B).
[0078] (11) Cellulose Derivative
[0079] Examples of the cellulose derivative may include a cellulose
ester compound (e.g., a cellulose acetate, and a cellulose
phthalate), a cellulose carbamate compound (e.g., a cellulose
phenylcarbamate), and a cellulose ether compound (e.g., a
cyanoethyl cellulose). These cellulose derivatives may be used
singly or in combination.
[0080] As the cellulose ester, for example, there may be mentioned
an organic acid ester of a cellulose (or an acyl cellulose), e.g.,
a cellulose acetate (an acetyl cellulose) such as a cellulose
diacetate or a cellulose triacetate, a cellulose propionate, a
cellulose butyrate, a cellulose acetate propionate, and a cellulose
acetate butyrate; an inorganic acid ester of a cellulose such as a
cellulose nitrate, a cellulose sulfate or a cellulose phosphate;
and a mixed acid ester of a cellulose such as a cellulose nitrate
acetate.
[0081] The cellulose ether may include, for example, an alkyl
cellulose (e.g., a C.sub.2-6alkyl cellulose such as an ethyl
cellulose, an isopropyl cellulose or a butyl cellulose), an aralkyl
cellulose (e.g., a benzyl cellulose), and a cyanoethyl
cellulose.
[0082] In view of biodegradability, it is preferred that the
substitution degree of the cellulose derivative is low. For
example, the average substitution degree is not more than 2.5,
preferably not more than 2 (e.g., about 0.1 to 2), and more
preferably not more than 1.5 (e.g., about 0.1 to 1.5).
[0083] (12) Thermoplastic Elastomer
[0084] Examples of the thermoplastic elastomer may include a
polyamide-series elastomer [for example, a block copolymer
comprising a polyamide block (e.g., an aliphatic polyamide) as a
hard segment part and a polyether or polyester block having a low
glass transition temperature (e.g., an ether block such as a
polyoxyC.sub.2-4alkylene block such as a polyoxytetramethylene or
polyoxypropylene block; and an aliphatic polyester block) as a soft
segment part], a polyester-series elastomer [for example, a block
copolymer comprising a polyester block (e.g., an aromatic
crystalline polyester such as a polybutylene terephthalate, and a
liquid crystal polyester) as a hard segment part and the polyether
or polyester block as a soft segment part], a polyurethane-series
elastomer [for example, a block copolymer comprising a polyurethane
block as a hard segment part and the polyether or polyester block
as a soft segment part], a polystyrenic elastomer [for example, a
block copolymer comprising a polystyrene block and a diene or
olefin block, e.g., a styrene-butadiene-styrene (SBS) block
copolymer, a styrene-isoprene-styrene (SIS) block copolymer, a
styrene-ethylene-butylene-styrene block copolymer (SEBS), a
styrene-ethylene-propylene-styrene block copolymer (SEPS), and a
hydrogenated product of a random styrene-butadiene rubber (HSBR)],
a polyolefinic elastomer [for example, a polyolefin (e.g., a
polyethylene, and a polypropylene) as a hard segment part and a
rubber component (e.g., a blend comprising an ethylene-propylene
rubber (EPR), and an ethylene-propylene-diene rubber (EPDM)) as a
soft segment part], a polydiene-series elastomer (for example, a
syndiotactic 1,2-polybutadiene-series elastomer, a trans
1,4-polyisoprene-series elastomer, and a natural rubber-series
elastomer), a chlorine-series elastomer [for example, a
blend-formed elastomer comprising a highly polymerized or partially
crosslinked polyvinyl chloride (hard segment part) and a polyvinyl
chloride plasticized with a plasticizer (soft segment part), a
polyvinyl chloride-series elastomer such as a polymer alloy-formed
elastomer comprising a vinyl chloride polymer (hard segment part)
and a rubber or elastomer component (e.g., a soft segment part such
as a partially crosslinked nitrile rubber, a polyurethane-series
elastomer, or a polyester-series elastomer); and a chlorinated
polyethylene], and a fluorine-containing thermoplastic elastomer
[for example, an ABA block copolymer comprising a fluorocarbon
polymer (e.g., a tetrafluoroethylene-ethylene copolymer, and a
polyvinylidene fluoride (PVDF)) as a hard segment part and a
fluorine rubber (e.g., a vinylidene
fluoride-hexafluoropropylene-tetrafluoroethylene ternary copolymer)
as a soft segment part]. Incidentally, in the case where the
thermoplastic elastomer is a block copolymer, the block structure
is not particularly limited to a specific one, and may be a
triblock structure, a multiblock structure, a star-shaped block
structure, and others.
[0085] The heat distortion temperature of the polymer or resin
(e.g., a Vicat softening temperature defined by JIS K 7206) may be
selected from the range of 60 to 300.degree. C., and for example,
may be about 80 to 260.degree. C., preferably about 100 to
240.degree. C. (e.g., about 110 to 240.degree. C.), and more
preferably about 120 to 230.degree. C. (e.g., about 130 to
220.degree. C.).
[0086] A plurality of organic solid materials (e.g., polymers)
constituting the organic solid component (A) may be suitably
selected from the above-mentioned organic solid material (e.g., a
low molecular weight compound, and a high molecular weight
compound), and for example, may comprise 2 to 5 kinds, preferably 2
to 3 kinds (e.g., 2 kinds) of the organic solid materials.
[0087] In the present invention, a dispersion composition or
multiple polymer particle can be obtained by even using a polymer
derived from an addition-polymerizable monomer without limiting the
way of polymerization of the polymer, and a multiple polymer
particle having a structure such as a core-shell structure can be
obtained even in the case of using a polymer obtained by not a
seeded polymerization but a non-addition polymerization.
[0088] A plurality of organic solid materials constituting the
organic solid component (A) may have a different affinity from each
other relative to the water-soluble auxiliary component (B). Among
a plurality of the organic solid materials constituting the organic
solid component (A), at least one organic solid material may be an
organic solid material (e.g., a hydrophilic polymer) having a high
affinity relative to the auxiliary component. Along with formation
of the dispersion composition, the organic solid material (e.g., a
polymer) such as a hydrophilic polymer having a high affinity
relative to the auxiliary component tends to be located in the
neighborhood of the matrix in the dispersion composition, that is,
outside or outer layer of the dispersed phase.
[0089] Therefore, in the case where an organic solid material (A2)
having a higher affinity relative to the auxiliary component (B)
(e.g., an affinity polymer or a hydrophilic polymer) and an organic
solid material (A1) having a lower affinity relative to the
component (B) (e.g., a non-affinity polymer or a hydrophobic
polymer, a polymer having a lower affinity or hydrophilicity than
the polymer (A2), and a wax or lipid) are combined, a dispersed
phase (or a polymer particle) having a core-shell structure may be
formed which comprises a core including the organic solid material
(e.g., a polymer) (A1) and a shell covering the core and including
the organic solid material (A2). In such a combination of the
organic solid materials, as the miscibility between the organic
solid materials (A1) and (A2) is decreased (that is, immiscibility
is increased), a dispersed phase (or particle) having clearer
boundary between the core and the shell can be formed. That is,
depending on the miscibility between both materials (e.g.,
polymers), the core of the dispersed phase may be formed by the
organic solid material (A1) alone, or by a mixture of the organic
solid material (A1) and the organic solid material (A2), or others.
Incidentally, in the case of selecting a combination of organic
solid materials (e.g., polymers) having a high miscibility with
each other as a plurality of organic solid materials, a polymer
alloyed dispersed phase (or particle) can be obtained.
[0090] In the case where the dispersed phase (or multiple particle)
has a core-shell structure, the internal property and the surface
property of the dispersed phase (or multiple particle) can be
controlled by suitably selecting the kind of the organic solid
material (e.g., a polymer) constituting the core and the kind of
the organic solid material (e.g., a polymer) constituting the
shell, and various functions can be imparted to a desired layer
(the core or the shell) for any purpose. For example, the core may
comprise a polymer excellent in a mechanical property (such as
hardness) and the shell may comprise a polymer excellent in a
surface property (such as a sliding property or an antistatic
property), or heat weldability can be imparted to only the shell.
In addition, a multiple particle (e.g., a multiple polymer
particle) capable of effectively expressing properties or physical
properties of the organic solid material (e.g., a polymer) can be
obtained.
[0091] In a preferred embodiment, the organic solid component (A)
may comprise (A1) a first organic solid material (or composition)
having a lower affinity relative to the component (B), and (A2) a
second organic solid material (or composition) having a higher
affinity relative to the component (B). Examples of the material
(A1) may include a polymer having no affinity (e.g., a hydrophobic
or water-insoluble polymer), and a polymer having a lower affinity
or hydrophilicity compared with the polymer (A2) (such a polymer
having a lower affinity or hydrophilicity may be a hydrophilic
polymer). Examples of the material (A2) may include a polymer
having an affinity, or a hydrophilic polymer. The first organic
solid material (e.g., a polymer) (A1) and the second organic solid
material (e.g., a polymer) (A2) may be miscible with each other, or
immiscible with each other. In such a combination, the dispersed
phase may have a core-shell structure comprising a core containing
the first organic solid material (e.g., a polymer) (A1) and a shell
containing the second organic solid material (e.g., a polymer)
(A2).
[0092] The polymer having an affinity (or the hydrophilic polymer)
has a polar group, usually, a hydrophilic group (or a polar group)
such as a hydroxyl group, a carboxyl group, an amino group, an
imino group (--NH), an ether group, an oxyalkylene group (e.g., a
linear or branched polyoxyC.sub.2-4 alkylene group such as a
polyoxyethylene group or a polyoxypropylene group), an ester group
(or ester linkage), an amide group (or amide linkage), or a
urethane linkage (--NHC(.dbd.O)O--). The polymer having an affinity
may have the single polar group, or not less than two kinds of the
polar group.
[0093] Such a polymer having an affinity may include, among the
above-mentioned polymers, for example, a hydrophilic polymer such
as the vinyl acetate-series polymer, the polyvinyl alcohol-series
polymer, the polyester-series polymer, the polyamide-series
polymer, the polycarbonate-series polymer, the polyurethane-series
polymer, the (meth)acrylic polymer [for example, a (meth) acrylic
polymer having (meth) acrylic acid or an alkyl (meth)acrylate as a
constitutional unit], the cellulose derivative, or the
thermoplastic elastomer (e.g., a polyamide elastomer having a
polyC.sub.2-4oxyalkylene unit as a soft segment part, a polyester
elastomer, and a polyurethane elastomer). These hydrophilic
polymers may be used singly or in combination.
[0094] Among the combinations of the first and the second organic
solid materials, a combination of the first polymer and the second
polymer may include (a) a combination of different polymers, for
example, a combination of a hydrophobic polymer (A1) and a
hydrophilic polymer (A2), and (b) a combination of the same series
polymers, and others. The combination of the same series polymers
includes, for example, a combination of polymers different in
concentration of a polar group (such as a hydrophilic group) from
each other. Moreover, the combination of the first polymer and the
second polymer may be a combination of a hydrophilic polymer (A2)
having a hydrophilic group having a higher hydrophilicity (e.g., a
water-soluble group such as a carboxyl group, an amino group or an
imino group) and a hydrophilic polymer (A1) having a hydrophilic
group having a lower hydrophilicity (e.g., a hydroxyl group, an
ether group, an oxyalkylene group, an ester group, an amide group,
and a urethane linkage), and other combination. Among the first
polymers (A1), examples of the hydrophobic polymer may include the
polyolefinic polymer, the styrenic polymer, the hydrophobic
vinyl-series polymer (e.g., a vinyl chloride-series polymer, and a
fluororesin), and the thermoplastic elastomer (e.g., an olefinic
elastomer, and a styrenic elastomer) among the above-mentioned
thermoplastic resins. The hydrophobic polymer may be a polymer
having a nonpolar group. These hydrophobic polymers may be also
used singly or in combination.
[0095] Among the combinations of the first polymer and the second
polymer, the combination (a) may include a combination of an
olefinic elastomer or a styrenic elastomer (A1) with a
polyamide-series polymer, a polyester-series polymer, a
polyamide-series elastomer, a polyester-series elastomer or a
polyurethane-series elastomer (A2), and other combination.
Moreover, the combination (b) may include, for example, a
combination of an aliphatic polyester-series polymer (A1) [e.g., a
copolyester such as a polyC.sub.2-4alkylene succinate-adipate
copolymer; and a copolyester obtained from a dicarboxylic acid
component, a diol component and a lactone (e.g., a
polycaprolactone-polybutylene succinate copolymer)] and a homo- or
copolyester (A2) of a short-chained hydroxycarboxylic acid or a
lactone (e.g., a polylactic acid).
[0096] Moreover, in the case where the organic solid component (A)
comprises a biodegradable polymer [for example, a biodegradable
polyester-series polymer such as an aliphatic polyester-series
polymer (e.g., a polylactic acid-series polymer, and a
polyC.sub.3-12lactone-series polymer) or a polyester amide, a vinyl
alcohol-series polymer, and the above-mentioned cellulose
derivative], a polymer particle excellent in biodegradability can
be also obtained.
[0097] In the average molecular weight of each polymer constituting
the polymer component, the weight-average molecular weight or the
viscosity-average molecular weight may be, for example, not more
than 500,000 (e.g., about 10,000 to 500,000), preferably about
50,000 to 400,000 and more preferably about 10,000 to 350,000, in
terms of polystyrene by a gel-permeation chromatography.
Incidentally, with respect to a thermoplastic resin (such as a
cellulose derivative) with difficulty in molecular weight
measurement by a gel-permeation chromatography, the
viscosity-average molecular weight may be adopted. Incidentally,
the weight-average molecular weight of the polymer component (A)
may be also adjusted depending on a kneading time or a kneading
temperature of the polymer component.
[0098] In the organic solid component (A), the ratio (weight ratio)
of the first organic solid material (A1) relative to the second
organic solid (A2) maybe, for example, about 30/70 to 99/1,
preferably about 40/60 to 95/5, and more preferably about 45/55 to
90/10 (e.g., about 50/50 to 90/10).
[0099] Incidentally, to the organic solid component (e.g., a
polymer component) (A) may be added a compatibilizing agent as far
as formation of the dispersed phase is not inhibited.
[0100] (B) Water-Soluble Auxiliary Component
[0101] The water-soluble auxiliary component comprises at least an
oligosaccharide (B1). Moreover, in order to adjust a thermal fusing
property of the oligosaccharide, the water-soluble auxiliary
component may further comprise a plasticizing component (B2) for
plasticizing the oligosaccharide. By using the oligosaccharide (B1)
and the water-soluble plasticizing component (B2) in combination,
the viscosity of the water-soluble auxiliary component (B) can be
adjusted in kneading with the organic solid component (A).
Incidentally, the multiple particle (e.g., a multiple polymer
particle) may be obtained by forming a dispersion composition by
using the water-soluble auxiliary component in combination with the
organic solid component, and then suitably eluting or washing the
water-soluble auxiliary component from the dispersion
composition.
[0102] (B1) Oligosaccharide
[0103] The oligosaccharide (B1) is classified broadly into two
groups: a homooligosaccharide condensed by dehydration of 2 to 10
monosaccharide molecules through glycoside linkage(s), and a
heterooligosaccharide condensed by dehydration of 2 to 10 molecules
of at least not less than two kinds of monosaccharides and/or sugar
alcohols through glycoside linkage(s). The oligosaccharide (B1) may
include, for example, a disaccharide to a decasaccharide, and
usually, an oligosaccharide of a disaccharide to a hexasaccharide
is employed. The oligosaccharide is usually a solid at a room
temperature. Incidentally, these oligosaccharides may be an
anhydrate. Moreover, in the oligosaccharide, a monosaccharide may
bond (or link) with a sugar alcohol. Incidentally, the
oligosaccharide may be an oligosaccharide composition comprising a
plurality of sugar components. Such an oligosaccharide composition
is sometimes simply referred to as an oligosaccharide. These
oligosaccharides (or oligosaccharide compositions) may be used
singly or in combination.
[0104] Examples of the disaccharide may include a
homooligosaccharide such as a trehalose (e.g.,
.alpha.,.alpha.-trehalose, .beta.,.beta.-trehalose, and
.alpha.,.beta.-trehalose), kojibiose, nigerose, maltose,
isomaltose, sophorose, laminaribiose, cellobiose or gentiobiose;
and a heterooligosaccharide such as lactose, sucrose, palatinose,
melibiose, rutinose, primeverose or turanose.
[0105] As the trisaccharide, there may be mentioned a
homooligosaccharide such as maltotriose, isomaltotriose, panose or
cellotriose; a heterooligosaccharide such as manninotriose,
solatriose, melezitose, planteose, gentianose, umbelliferose,
lactosucrose or raffinose; and others.
[0106] Examples of the tetrasaccharide may include a
homooligosaccharide such as maltotetraose or isomaltotetraose; and
a heterooligosaccharide such as stachyose, cellotetraose,
scorodose, lychnose, or a tetraose having a sugar or sugar alcohol
attached to a reducing end of panose.
[0107] Among these tetrasaccharides, the tetraose having a
monosaccharide or sugar alcohol attached to a reducing end of
panose is disclosed in, for example, Japanese Patent Application
Laid-Open No.215892/1998 (JP-10-215892A), and may include a
tetraose having a monosaccharide (such as glucose, fructose,
mannose, xylose or arabinose) or a sugar alcohol (such as sorbitol,
xylitol or erythritol) attached to a reducing end of panose.
[0108] The pentasaccharide may include a homooligosaccharide such
as maltopentaose or isomaltopentaose; and a heterooligosaccharide
such as a pentaose having a disaccharide attached to a reducing end
of panose. The pentaose having a disaccharide attached to a
reducing end of panose is also disclosed in, for example, Japanese
Patent Application Laid-Open No. 215892/1998 (JP-10-215892A), and
may include a pentaose having a disaccharide (such as sucrose,
lactose, cellobiose or trehalose) attached to a reducing end of
panose.
[0109] Examples of the hexasaccharide may include a
homooligosaccharide such as maltohexaose or isomaltohexaose.
[0110] The oligosaccharide preferably comprises at least a
tetrasaccharide from the viewpoint of a melt-kneading property with
the organic solid component.
[0111] The oligosaccharide may be an oligosaccharide composition
produced by decomposition of a polysaccharide. The oligosaccharide
composition usually contains a tetrasaccharide. The oligosaccharide
composition may include, for example, a starch sugar (a
saccharification product of a starch (or a saccharified starch)), a
galactooligosaccharide, a coupling sugar, a fructooligosaccharide,
a xylooligosaccharide, a soybean oligosaccharide, a chitin
oligosaccharide, and a chitosan oligosaccharide.
[0112] For example, the starch sugar is an oligosaccharide
composition obtained by making an acid or glucoamylase or the like
act on a starch, and may be a mixture of an oligosaccharide
obtained by bonding a plurality of glucoses to each other. The
starch sugar may include, for example, a reduced
starch-saccharified manufactured by Towa Chemical Industry Co.,
Ltd. (brand name "PO-10", the tetrasaccharide content is not less
than 90% by weight).
[0113] The galactooligosaccharide is an oligosaccharide composition
obtained by making .beta.-galactosidase or the like act on lactose,
and may be a mixture of galactosyllactose and a
galactose-(glucose).sub.n ("n" denotes an integer of 1 to 4).
[0114] The coupling sugar is an oligosaccharide composition
obtained by making cyclodextrin synthetase (CGTase) act on a starch
and sucrose, and may be a mixture of a (glucose)n-sucrose ("n"
denotes an integer of 1 to 4).
[0115] The fructooligosaccharide is an oligosaccharide composition
obtained by making fructofuranosidase act on sucrose, and may be a
mixture of a sucrose-(fructose) ("n" denotes an integer of 1 to
4).
[0116] Concerning these oligosaccharide compositions, in order to
inhibit rapid decrease of the viscosity in melt-kneading, the
content of the trisaccharide or the tetrasaccharide (in particular,
the tetrasaccharide) in the oligosaccharide composition may be, for
example, not less than 60% by weight (about 60 to 100% by weight),
preferably not less than 70% by weight (about 70 to 100% by
weight), more preferably not less than 80% by weight (about 80 to
100% by weight), and particularly not less than 90% by weight
(about 90 to 100% by weight).
[0117] The oligosaccharide may be a reducing-type (maltose-type),
or a non-reducing type (trehalose-type). The reducing-type
oligosaccharide is preferred because of excellence in heat
resistance.
[0118] The reducing-type oligosaccharide is not particularly
limited to a specific one as far as the oligosaccharide has a free
aldehyde group or ketone group to exhibit a reducing property. For
example, the reducing-type oligosaccharide may include a
disaccharide suchaskojibiose, nigerose, maltose, isomaltose,
sophorose, laminaribiose, cellobiose, gentiobiose, lactose,
palatinose, melibiose, rutinose, primeverose or turanose; a
trisaccharide such as maltotriose, isomaltotriose, panose
cellotriose, manninotriose or solatriose; a tetrasaccharide such as
maltotetraose, isomaltotetraose, cellotetraose or lychnose; a
pentasaccharide such as maltopentaose or isomaltopentaose; and a
hexasaccharide such as maltohexaose or isomaltohexaose.
[0119] Since the oligosaccharide is generally a natural
polysaccharide derivative, or a product derived from a natural
product being manufactured by reducing the derivative, use of the
oligosaccharide can reduce in the burden on the environment.
[0120] The flowability of the organic solid component and that of
the auxiliary component may be the same, or different. In order to
effectively disperse the organic solid component and the auxiliary
component by kneading, it is desirable that the oligosaccharide has
a high viscosity. More specifically, in the case where the
viscosity of the 50% by weight aqueous solution of the
oligosaccharide is measured at a temperature of 25.degree. C. by
using a B-type viscometer, the viscosity is not lower than 1 Pas
(e.g., about 1 to 500 Pas), preferably not lower than 2 Pas (e.g.,
about 2 to 250 Pas, and in particular about 3 to 100 Pas), more
preferably not lower than 4 Pas (e.g., about 4 to 50 Pas), and
particularly not lower than 6 Pas (e.g., about 6 to 50 Pas), and it
is preferred to use an oligosaccharide having a high viscosity.
[0121] Moreover, the melting point or softening point of the
oligosaccharide (B1) is preferably higher than the heat distortion
temperature of each organic solid material (e.g., a polymer)
constituting the organic solid component (e.g., a polymer
component) (A) (e.g., a melting point or softening point of the
organic solid component (A), and a Vicat softening temperature
defined by JIS K 7206). Incidentally, depending on the kind or
species of the oligosaccharide [e.g., in the case of a starch sugar
such as a reduced starch-saccharified], the oligosaccharide
sometimes decomposed (thermally decomposed) without showing a
melting point or softening point. In such a case, the decomposition
temperature may be considered as the "melting point or softening
point" of the oligosaccharide (B1).
[0122] The temperature difference between the melting point or
softening point of the oligosaccharide (B1) and the heat distortion
temperature of each organic solid material (e.g., a polymer)
constituting the organic solid component (A) is, for example, not
less than 1.degree. C. (e.g., about 1 to 80.degree. C.), preferably
not less than 10.degree. C. (e.g., about 10 to 70.degree. C.), and
more preferably not less than 15.degree. C. (e.g., about 15 to
60.degree. C.). The melting point or softening point of the
oligosaccharide (B1) may be selected from the range of 70 to
300.degree. C. depending on the kind of the organic solid component
(A) and other factor(s), and may be, for example, about 90 to
290.degree. C., preferably about 100 to 280.degree. C. (e.g., about
110 to 270.degree. C.), and more preferably about 120 to
260.degree. C. (e.g., about 130 to 260.degree. C.). Incidentally,
an anhydride of an oligosaccharide generally has a high melting
point or softening point. For example, in the case of a trehalose,
the melting point of the dehydrate is 97.degree. C. and that of the
anhydride is 203.degree. C. In the case where the melting point or
softening point of the oligosaccharide is higher than the heat
distortion temperature of each organic solid material (e.g., a
polymer) constituting the organic solid component (A), the
oligosaccharide can be not only prevented from rapid deterioration
of the viscosity in melt-kneading but also inhibited from thermal
degradation.
[0123] (B2) Water-Soluble Plasticizing Component
[0124] The water-soluble plasticizing component (B2) is enough to
just express a phenomenon that the oligosaccharide (B1) hydrates to
turn into a syrup state, and may include, for example, a
saccharide, and a sugar alcohol. These plasticizing components may
be used singly or in combination.
[0125] (a) Saccharide
[0126] As the saccharide, a monosaccharide and/or a disaccharide is
usually employed for plasticizing the oligosaccharide (B1)
effectively. These saccharides may be used singly or in
combination.
[0127] Examples of the monosaccharide may include a triose, a
tetrose, a pentose, a hexose, a heptose, an octose, a nonose, and a
decose. These compounds may be an aldose or ketose compound, a
dialdose compound (for example, a compound which is a saccharide
derivative and has aldehyde groups in both ends of the carbon
chain, such as tetraacetylgalacto-hexodialdose, ido-hexodialdose or
xylo-pento-dialdose), a monosaccharide having a plurality of
carbonyl groups (e.g., an aldoalko-ketose such as osone or onose),
a monosaccharide having a methyl group (e.g., a methyl sugar such
as altromethylose), a monosaccharide having an acyl group (in
particular, e.g., a C.sub.2-4acyl group such as acetyl group) (for
example, an acetylated product of the above-mentioned aldose
compound, e.g., an acetylated product such as a pentaacetylated
product of an aldehyde glucose), a saccharide having an introduced
carboxyl group (e.g., a saccharic acid or a uronic acid), a
thiosugar, an amino sugar, a deoxy sugar, or others.
[0128] Concrete examples of such a monosaccharide may include a
tetrose (e.g., erythrose, and threorose), a pentose (e.g.,
arabinose, ribose, lyxose, deoxyribose, and xylose), and a hexose
(e.g., allose, altrose, glucose, mannose, gulose, idose, galactose,
fructose, sorbose, fucose, rhamnose, talose, galacturonic acid,
glucuronic acid, mannuronic acid, and glucosamine).
[0129] Moreover, the monosaccharide may be a cyclic isomer having a
cyclic structure formed through a hemiacetal linkage. It is not
necessary that the monosaccharide has an optical activity (or
rotatory polarization), and the monosaccharide maybe any one of
D-form, L-form, or DL-form. These monosaccharides may be used
singly or in combination.
[0130] The disaccharide is not particularly limited to a specific
one as far as the disaccharide can plasticize the oligosaccharide
(B1). For example, among the above-mentioned disaccharides, there
may be exemplified a disaccharide having a low melting point or low
softening point (e.g., gentiobiose, melibiose, and trehalose
(dehydrate)), and a disaccharide corresponding to a homo- and
heterodisaccharide of the above-mentioned monosaccharide (e.g., an
aldobiouronic acid such as glucuronoglucose in which glucuronic
acid binds to glucose through an .alpha.-1,6-glycoside
linkage).
[0131] The saccharide is preferably a reducing sugar in terms of
having an excellent thermal stability. Examples of such a
saccharide include a free monosaccharide, and in addition, a
reducing sugar having a low melting point or low softening point
(e.g., gentiobiose, and melibiose) among the disaccharides.
[0132] (b) Sugar Alcohol
[0133] As the sugar alcohol, a linear (or chain) sugar alcohol such
as an alditol (glycitol) or a cyclic sugar alcohol such as an
inositol may be used, and usually, the linear sugar alcohol may be
employed. These sugar alcohols may be used singly or in
combination.
[0134] Examples of the linear sugar alcohol may include a tetrytol
(e.g., threitol, and erythritol), a pentitol [e.g.,
pentaerythritol, arabitol, ribitol (adonitol), xylitol, and
lyxitol], a hexitol [e.g., sorbitol, mannitol, iditol, gulitol,
talitol, dulcitol (galactitol), allo-dulcitol (allitol), and
altritol], a heptitol, an octitol, a nonitol, a decitol, and a
dodecitol.
[0135] Among these sugar alcohols, the preferred sugar alcohol
includes erythritol, pentaerythritol, arabitol, ribitol, xylitol,
sorbitol, dulcitol and mannitol. The sugar alcohol often comprises
at least one sugar alcohol selected from the group consisting of
erythritol, pentaerythritol and xylitol.
[0136] The plasticizing component (B2) may be a liquid (or in a
syrup state) at a room temperature (e.g., about 15 to 20.degree.
C.), and from the viewpoint of handleability and others, the
plasticizing component (B2) is usually a solid in many cases. In
the case where the auxiliary component (B) comprises the
oligosaccharide (B1) and the plasticizing component (B2), the
plasticizing component (B2) can effectively plasticize or soften
the oligosaccharide (B1) even when the oligosaccharide (B1) is a
thermally decomposable oligosaccharide not having a clear melting
point or softening point.
[0137] The melting point or softening point of the plasticizing
component (B2) is usually not higher than the heat distortion
temperature of at least one organic solid material (or each organic
solid material) among a plurality of organic solid materials (e.g.,
polymers) constituting the organic solid component (A) (for
example, not higher than a melting point or softening point of the
organic solid component (A), and a Vicat softening temperature
defined by JIS K 7206). Incidentally, some plasticizing components
are molten at a temperature lower than the actual melting point
when coexisting with the oligosaccharide while having a high
melting point (e.g., a melting point of not lower than 200.degree.
C.). For example, pentaerythritol exerts a plasticizing effect on
the oligosaccharide and melts at a temperature (e.g., at about 160
to 180.degree. C.) lower than the actual melting point (260.degree.
C.). The plasticizing component having such a high melting point
cannot be singly utilized because of being not molten at the heat
distortion temperature of the organic solid component (e.g., a
polymer component). However, such a plasticizing component can be
utilized effectively in combination with the oligosaccharide.
Incidentally, in the plasticizing component exerting a plasticizing
effect on the oligosaccharide (e.g., pentaerythritol) at a
temperature lower than the actual melting point, the temperature at
which a plasticizing effect on the oligosaccharide is exerted may
be regarded as the melting point or softening pointw of the
plasticizing component (B2).
[0138] The melting point or softening point of the auxiliary
component (B) may be not higher or lower than the heat distortion
temperature of each organic solid material (e.g., a polymer)
constituting the organic solid component (A). It is sufficient that
each organic solid material (e.g., a polymer) constituting the
organic solid component (A) and the auxiliary component (B) are
molten or soften at least at a kneading temperature (or fabrication
temperature). For example, the temperature difference between the
melting point or softening point of the auxiliary component (B) and
the heat distortion temperature of each organic solid material
(e.g., a polymer) constituting the organic solid component (A) may
be selected from the range of 0 to 100.degree. C. For example, the
temperature difference may be about 3 to 80.degree. C. (e.g., about
3 to 55.degree. C.), preferably about 5 to 60.degree. C. (e.g.,
about 5 to 45.degree. C.), and more preferably about 5 to
40.degree. C. (e.g., about 10 to 35.degree. C.). Incidentally, in
the case where the temperature difference between the melting point
or softening point of the auxiliary component (B) and the heat
distortion temperature of each organic solid material (e.g., a
polymer) constituting the organic solid component (A) is small
(e.g., in the case where the temperature difference is about 0 to
20.degree. C.), there is an advantage that the dispersion shape can
be fixed in a short time by an auxiliary component (B) (e.g., a
sugar component) having a high solidification rate.
[0139] Further, the melt flow rate of the auxiliary component (B)
(e.g., an auxiliary component comprising the oligosaccharide (B1)
and the plasticizing component (B2)) may be, for example, not less
than 1 (e.g., about 1 to 40), preferably not less than 5 (e.g.,
about 5 to 30), and more preferably not less than 10 (e.g., about
10 to 20) when measured the melt flow rate defined by JIS K 7210 at
a temperature 30.degree. C. higher than the heat distortion
temperature of each organic solid material (e.g., a polymer)
constituting the organic solid component (A) [e.g., at a
temperature 30.degree. C. higher than the lowest temperature of a
melting point or softening point of the organic solid component (A)
and the Vicat softening temperature (the melting point or softening
point, the Vicat softening temperature)].
[0140] In the auxiliary component (B), the ratio (weight ratio) of
the plasticizing component (B2) is selected from the range that the
plasticizing component can plasticize the oligosaccharide (B1)
efficiently without localizing by aggregation or other reason
accompanying melt-kneading. For example, the ratio of the
oligosaccharide (B1) relative to the plasticizing component (B2)
[the oligosaccharide (B1)/the plasticizing component (B2)] may be
selected from 99/1 to 50/50, and may be preferably about 95/5 to
60/40 and more preferably about 90/10 to 70/30.
[0141] The ratio (weight ratio) of the organic solid component (A)
relative to the auxiliary component (B) may be selected depending
on the kinds or viscosities of the organic solid component and the
auxiliary component, the miscibility between the organic solid
component and the auxiliary component, or other factor(s), and is
not particularly limited to a specific one. The ratio (the organic
solid component (A)/the auxiliary component (B)] may be usually
selected from the range that formability (or moldability) of the
dispersion composition is not impaired, and may be, for example,
about 55/45 to 1/99, preferably about 50/50 to 5/95 and more
preferably about 45/55 to 10/90.
[0142] In the present invention, the dispersion composition or the
composition may contain, if necessary, various additives, for
example, other additive such as a filler (e.g., a particulate
filler, and a fibrous filler such as a glass fiber), a plasticizer
or a softener, an agent for imparting photodegradable property
(e.g., an anatase-type titanium oxide), a lubricant, a stabilizer
(e.g., a heat stabilizer, an antioxidant, an ultraviolet ray
absorbing agent, and a weather (light) stabilizer), an
ultraviolet-scattering agent (e.g., a powder of a metal oxide such
as titanium oxide, zirconium oxide, zinc oxide, or iron oxide), a
dispersing agent, a flame retardant, an antistatic agent, a
coloring agent [for example, a dye such as an oil-soluble organic
dye; an inorganic or organic. pigment (e.g., including a
ferromagnetic material such as a ferromagnetic metal (powder) such
as iron, cobalt, or nickel; a ferromagnetic alloy (powder) such as
a magnetite or a ferrite; or a ferromagnetic metal oxide (powder)
such as magnetic iron oxide)], a charge control agent (e.g., a
positive charge control agent such as a nigrosin dye, a
triphenylmethane-series dye, a quaternary ammonium salt, a
guanidine compound, an imidazole compound, or an amine-series
compound; and a negative charge control agent such as a metal
complex of salicylic acid, a metal complex of an azo dye, a copper
phthalocyanine dye, a nitroimidazole derivative, or a urea
derivative), a superplasticizer (or an agent for imparting
fluidization), a wax [for example, an olefinic wax such as a
polyethylene wax, an ethylene copolymer wax, or a polypropylene
wax; a paraffin wax; a higher fatty acid or a derivative thereof
(e.g., a salt, a polyhydric alcohol ester, and an amide); and an
ester-series wax], or a crosslinking agent. Incidentally, the
additive may be contained in any of the dispersed phase (e.g., each
organic solid material constituting the organic solid component
(A)) and the matrix constituting the dispersion composition.
[0143] The additive may be selected depending on applications of
the multiple particle (e.g., a multiple polymer particle) or
others. For example, in an application of a cosmetic (e.g., a
foundation, a face powder, and a blusher), the ultraviolet ray
absorbing agent (e.g., a benzophenone-series absorbing agent, a
cinnamic acid-series absorbing agent, a p-aminobenzoic acid-series
absorbing agent, a salicylic acid-series absorbing agent, a
dibenzoylmethane-series absorbing agent, urocanic acid or an ester
thereof, .beta.-isopropyl-furanone, and .beta.-carotene), the
ultraviolet-scattering agent, the coloring agent, and others may be
used. In an application of image recording material such as a
toner, for example, the charge control agent, the superplasticizer,
the wax, the coloring agent, and others may be used. Moreover, in
an application of paint and varnish, or the like, for example,
there may be used the crosslinking agent, the weather (light)
stabilizer, the ultraviolet ray absorbing agent, the
superplasticizer, and the coloring agent.
[0144] In these additives, the amount of-each additive may be an
effective amount, and for example, the total amount of the
additives may be selected from the range of about 0 to 100 parts by
weight relative to 100 parts by weight of the organic solid
component. For example, the total amount of the additives may be
about 0 to 50 parts by weight (e.g., about 0 to 30 parts by
weight), preferably about 0.05 to 20 parts by weight (e.g., about
0.1 to 20 parts by weight), and more preferably about 0.1 to 10
parts by weight (e.g., about 0.5 to 10 parts by weight), relative
to 100 parts by weight of the organic solid component.
[0145] In the dispersion composition of the present invention, the
average particle size of the dispersed phase is not particularly
limited to a specific one, and may be selected from the range of
about 0.1 .mu.m to 1 mm (e.g., about 0.1 to 800 .mu.m) as usage.
For example, the average particle size may be, for example, about
0.1 to 500 .mu.m, preferably about 0.1 to 100 .mu.m (e.g., about
0.5 to 80 .mu.m), more preferably about 0.2 to 50 .mu.m (e.g.,
about 0.5 to 50 .mu.m), and particularly about 1 to 40 .mu.m (e.g.,
about 1 to 20 .mu.m). Moreover, the average particle size of the
dispersed phase may be, for example, about 0.1 to 10 .mu.m (e.g.,
about 0.2 to 5 .mu.m), and preferably about 0.5 to 3 .mu.m (e.g.,
about 0.5 to 2 .mu.m).
[0146] In the present invention, the particle size of the dispersed
phase can be uniformized and the particle size distribution of the
particle size can be narrowed. The coefficient (%) of variation of
the average particle size in the dispersed phase ([the standard
deviation of the particle size/the average particle
size].times.100) may be, for example, not more than 60 (e.g., about
5 to 60), and more preferably not more than 50 (e.g., about 10 to
50).
[0147] In the dispersion composition of the present invention, it
is sufficient that the configuration (or shape) of the dispersed
phase is a particle shape. For example, the configuration (or
shape) of the dispersed phase may be a spherical shape, an
elliptical shape, a polyhedral shape, a prismatic shape, a columnar
(or cylindrical) shape, a rod-like shape, and an amorphous shape,
and others. The preferred shape of the disperse phase is a
spherical shape (e.g., a finely spherical shape). The spherical
dispersion composition (or spherical particle) is not limited to a
finely spherical shape, and for example, includes a shape having a
length ratio of a major axis relative to a minor axis of, e.g.,
about 1.5/1 to 1/1. The length ratio of the major axis relative to
the minor axis [the major axis/the minor axis] may be preferably
about 1.3/1 to 1/1 (e.g., about 1.2/1 to 1/1), and more preferably
about 1.1/1 to 1/1.
[0148] In the case where the dispersed phase has a core-shell
structure, the thickness of the shell may be appropriately
controlled as usage by suitably adjusting the proportion of the
organic solid material constituting the shell relative to the
organic solid material constituting the core, the combination of
these organic solid materials, the affinity relative to the
auxiliary component, and others. The thickness of the shell may be
selected from the wide range of not more than 5 .mu.m, for example,
from about 10 nm to 5 .mu.m. The thickness of the shell may be
preferably not more than 1 .mu.m (e.g., about 10 nm to 1 .mu.m),
and more preferably about 20 to 800 nm (e.g., about 30 to 500
nm).
[0149] The dispersion composition may be prepared by kneading a
plurality of organic solid materials constituting the organic solid
component (A) with the auxiliary component (B), and usually, the
kneaded composition is often shaped (or molded) to prepare a
preliminary shaped article. The kneading operation may be carried
out by using a conventional kneading machine (e.g., a uniaxial or
biaxial screw extruder, a kneader, and a calender roll). Moreover,
in advance of kneading, each of components may be preliminarily
converted into a powder form by a machine such as a freeze grinder
or maybe preliminarily kneaded by a Henschel mixer, a tumbler
mixer, a ball mill or others.
[0150] Examples of the shaping (or molding) method may include an
extrusion molding, an injection molding, a blow molding, and a
calender molding. In view of productivity or easiness of
processing, an extrusion molding or an injection molding is usually
applied. The shape of the preliminary shaped article (or dispersion
composition) is not particularly limited to a specific one, and may
be a zero-dimensional shape (e.g., a particle shape, and a pellet
shape), a one-dimensional shape (e.g., a strand shape, and a rod or
bar shape), a two-dimensional shape (e.g., a plate shape, a sheet
shape, and a film shape), a three-dimensional shape (e.g., a
tubular shape, and a block shape), and others. Considering the
elution property (or elution capability)of the auxiliary component,
it is desirable to process (or shape) the dispersion composition
into a strand shape, a rod or bar shape, a sheet shape., or a film
shape.
[0151] The water-soluble auxiliary component maybe eluted from the
kneaded matter, and the water-soluble auxiliary component is
usually eluted by shaping (or molding) after kneading.
[0152] Incidentally, it is possible to appropriately set the
kneading temperature or processing (or shaping) temperature (or
fabrication temperature) depending on a raw material to be used
(e.g., the organic solid component and the auxiliary component).
For example, the kneading temperature or processing temperature is
about 90 to 300.degree. C., preferably about 110 to 260.degree. C.
(e.g., about 170 to 250.degree. C.), more preferably about 140 to
240.degree. C. (e.g., about 170 to 240.degree. C.), and
particularly about 170 to 230.degree. C. (e.g. , about 180 to
220.degree. C.). In order to avoid thermal decomposition of the
auxiliary component (the oligosaccharide and the plasticizing
component), the kneading temperature or processing temperature may
be set to a temperature not higher than 230.degree. C. Moreover,
the kneading time may be, for example, selected from the range of
10 seconds to one hour, and is usually about 30 seconds to 45
minutes, and preferably about 1 to 30 minutes (e.g., 1 to 10
minutes).
[0153] The molten mixture (e.g., a kneaded matter, and a
preliminary shaped article) obtained by kneading and/or processing
(or fabrication) may be suitably cooled, if necessary. By cooling
the molten mixture in such a way, even in the case where the
organic solid component (A) (e.g., at least one member out of a
plurality of organic solid materials) and the auxiliary component
(B) are miscible with each other in the molten state, a dispersed
phase can be formed due to differences in surface tension and
solidification rate such as crystallization rate between the
organic solid component and the auxiliary component along with
cooling.
[0154] The cooling temperature may be at least about 10.degree. C.
lower than the heat distortion temperature of each organic solid
material (e.g., a polymer) constituting the organic solid component
(A) or the melting point or softening point of the auxiliary
component (B), and for example, may be about 10 to 100.degree. C.
lower than the above temperature (the heat distortion temperature
of the organic solid material (e.g., a polymer), or the melting
point or softening point of the auxiliary component), preferably
about 15 to 80.degree. C. lower than the above temperature, and
more preferably about 20 to 60.degree. C. lower than the above
temperature. Specifically, for example, the cooling temperature may
be selected from the range of 5 to 150.degree. C. depending on the
kind of the organic solid material or the auxiliary component, and
may be, for example, about 10 to 120.degree. C. (e.g., about 10 to
60.degree. C.), preferably about 15 to 100.degree. C. (e.g., about
15 to 50.degree. C.), and more preferably about 20 to 80.degree. C.
(e.g., about 20 to 40.degree. C.). The cooling time may be suitably
set according to the kind of the organic solid component or the
auxiliary component, the cooling temperature, and others, and may
be selected, for example, from the broad range of 30 seconds to 20
hours. For example, the cooling time may be about 45 seconds to 10
hours, preferably about one minute to 5 hours (e.g., about one
minute to one hour), and more preferably about 1.5 to 30
minutes.
[0155] Moreover, by adjusting the miscibility between the organic
solid component and the auxiliary component, the kneading
conditions (e.g., the kneading time, and the kneading temperature),
the processing temperature and the cooling conditions (e.g., the
cooling time, and the cooling temperature), the average particle
size of the dispersed phase (or particle) may be changed or the
width of the particle size distribution may be further
narrowed.
[0156] Thus obtained dispersion composition has a phase separation
structure in which the auxiliary component (B) forms a continuous
phase of an islands-in-the-sea structure and the organic solid
component (A) forms an independent dispersed phase thereof.
Therefore, the auxiliary component can be quickly eluted or
extracted to give the dispersed phase (the phase of the organic
solid component) as a multiple particle (e.g., a multiple polymer
particle).
[0157] [Production Process of Multiple Particle]
[0158] According to the present invention, a multiple particle
(e.g., a multiple polymer particle) which comprises the organic
solid component (A) corresponding to the dispersed phase and
containing a plurality of organic solid materials (e.g., polymers)
is produced by eluting the water-soluble auxiliary component (B)
constituting a matrix from the dispersion composition.
[0159] The elution (or washing) of the water-soluble auxiliary
component (B) may be carried out by using an aqueous solvent, for
example, water, and a water-soluble solvent [e.g., an alcohol
compound (e.g., methanol, ethanol, propanol, isopropanol, and
butanol), and an ether compound (e.g., a cellosolve, and a butyl
cellosolve)]. These aqueous solvents may be used singly or in
combination. The preferred elution solvent is water because of the
low burden on the environment and the industrial cost
reduction.
[0160] The elution of the auxiliary component (B) may be conducted
by a conventional method, for example, by immersing and dispersing
the dispersion composition (or preliminary shaped article) in the
aqueous medium, and eluting or washing the auxiliary component from
the dispersion composition (or moving over the auxiliary component
to the phase of the aqueous solvent). In the case where the
dispersion composition (or preliminary shaped article thereof) is
immersed in the aqueous medium, the water-soluble auxiliary
component forming the matrix of the dispersion composition is
gradually eluted and the dispersed phase (particle) is dispersed in
the mixture obtained by the elution. In order to accelerate the
dispersion and elution of the auxiliary component, stirring or
other means may be suitably conducted.
[0161] The auxiliary component may be eluted, for example, under an
applied pressure, and usually, can be eluted under an atmospheric
pressure (e.g., about 1.times.10.sup.5 Pa) or a reduced pressure.
Moreover, the elution temperature of the auxiliary component may be
appropriately established depending on the organic solid component
and the auxiliary component. The elution temperature of the
auxiliary component is usually a temperature lower than the melting
point or softening point of the organic solid material, and is, for
example, about 10 to 100.degree. C., preferably about 25 to
90.degree. C., and more preferably 30 to 80.degree. C. (e.g., about
40 to 80.degree. C.). Since the water-soluble auxiliary component
of the present invention is easily soluble in water, a large amount
of water is not required. Moreover, since the viscosity of the
resultant mixture is low, the obtained particle can be easily
collected.
[0162] The multiple particle may be collected from a dispersion
liquid containing the dispersed particle by a conventional
separation (collecting) method, e.g., filtration and
centrifugation. It is desirable that the obtained shaped article
has substantially no residual auxiliary component. However, for
example, in view of cost reduction of the washing process, the
multiple particle may have a small amount of the residual auxiliary
component. The small amount of the auxiliary component in the
multiple particle does not significantly affect the obtained
particle and has a high safety because the auxiliary component is a
compound derived from a natural product (including a food product
or a food additive). Incidentally, the proportion of the auxiliary
component (B) in the particle may be, for example, not more than 3%
by weight.
[0163] Incidentally, the auxiliary component eluted or extracted
with the solvent may be collected by a conventional separation
means (e.g., distillation, concentration, recrystallization, and
drying (freeze drying)).
[0164] The multiple particle (e.g., a multiple polymer particle) of
the present invention corresponds to the dispersed phase of the
dispersion composition, and the configuration (or shape), the
average particle size and the coefficient of variation of the
average particle size of the particle may be selected from the same
range as the above-mentioned dispersed phase. Moreover, the length
ratio of the major axis relative to the minor axis in the particle
may be also selected from the same range as the above-mentioned
dispersed phase. Incidentally, the configuration (or shape) or size
of the particle is retained that of the intact dispersed phase
unless the organic solid component (A) is eluted in the elution
solvent (aqueous solvent). Incidentally, if necessary, the particle
size of the multiple particle may be made uniform by a means such
as classification.
INDUSTRIAL APPLICABILITY
[0165] Since the multiple particle (e.g., a multiple polymer
particle) of the present invention comprises a plurality of organic
solid materials (e.g., polymers), various functions unobtainable
from a particle comprising a single component (e.g., a single
polymer component) can be imparted to the multiple particle,
depending on properties of the organic solid materials (e.g.,
polymers). For example, in the case of using a plurality of organic
solid materials (e.g., polymers) different in refraction index
difference from each other, a high light scattering effect is
obtained, and therefore, the multiple particle may be utilized in
an application of a cosmetic (e.g., a foundation, a face powder, a
blusher, and an eye shadow). Moreover, the multiple particle having
a core-shell structure may be applied for a variety of applications
by utilizing a difference between a surface property and an
internal property thereof. Further, the multiple particle may be
also utilized for an image-recording material such as an ink
(including a polymer ink) or a colored toner used for an ink jet
printing or others, and a paint and varnish or a coating agent
(e.g., a powdered paint, or a coating material for slurry
painting). Incidentally, the multiple particle may be used for
improving the mix aptitude to other fine particle (e.g., an
inorganic fine particle), or may be used as an antiblocking agent
(e.g., an antiblocking agent for a shaped article), a spacer (e.g.,
a spacer for a liquid crystal), an additive for sheet or film, an
abrasive for chemical and mechanical polishing (CMP) of
semiconductor, and others.
[0166] Moreover, the multiple polymer particle obtained by using a
biodegradable polymer component is useful for a raw material or
additive in a fine chemical field such as an agricultural chemical,
a medicine (or a pharmaceutical), a paint and varnish (e.g., a
powdered paint, and a ship bottom paint), a coating agent or an
adhesive agent because of being excellent in biodegradability.
Further, the multiple polymer particle may be also utilized as an
additive to a film or sheet for agriculture, forestry and
fisheries, civil engineering, and construction; a material for
sanitary goods (e.g., a disposable diaper); a medical material
requiring biodegradation and bioabsorbability; or a sustained
release material requiring sustained release.
EXAMPLES
[0167] The following examples are intended to describe this
invention in further detail and should by no means be interpreted
as defining the scope of the invention.
Examples 1 to 6
[0168] In each Examples, a polymer composition comprising a
thermoplastic resin component and a water-soluble auxiliary
component in the formulation shown in Table 1 was melt-kneaded at a
preset temperature of 200.degree. C. for 5 minutes by using a
brabender (manufactured by Toyo Seiki Seisaku-sho, Ltd.,
laboplastmill), and then cooled to prepare a dispersion
composition. The obtained dispersion composition was immersed in
hot water of 60.degree. C. to give a suspension of the polymer
particle. The insoluble matter was separated from the suspension
with a membrane (pore size: 0.45 .mu.m) made of a polyvinylidene
fluoride to collect the fine particle of the polymer.
[0169] For reference, FIG. 1 shows a transmission electron
micrograph (1000 magnifications) of a multiple polymer particle
obtained in Example 2. Moreover, FIG. 2 shows a transmission
electron micrograph (1000 magnifications) representing a particle
state after treating the multiple polymer particle obtained in
Example 2 with tetrahydrofuran.
[0170] Incidentally, components used in Examples and evaluation
methods of the obtained fine particle are described below. The
results are shown in Table 1.
[0171] (Polymer Component)
[0172] Polymer 1: Polystyrene polymer (manufactured by Toyo Styrene
Co., Ltd., "GPPS HRM63C")
[0173] Polymer 2: Styrene-butadiene-styrene block copolymer (SBS
polymer) (manufactured by JSR Corporation, "TR2003")
[0174] Polymer 3: Polyamide 12 polymer (manufactured by
Daicel-Degussa Ltd., "DIAMID L1640")
[0175] Polymer 4: Polybutylene succinate-polycaprolactone copolymer
(manufactured by Daicel Chemical Industries, Ltd., "CELLGREEN
CBS17X")
[0176] Polymer 5: Polylactic acid (manufactured by Mitsui
Chemicals, Inc., "LACEA H-100PL")
[0177] (Water-soluble auxiliary component)
[0178] (B1) Oligosaccharide: Starch sugar (manufactured by Towa
Chemical Industry Co., Ltd., reduced saccharification product of a
starch "PO-10", a viscosity of a 50% by weight aqueous solution
measured at 25.degree. C. by a B-type viscometer: 6.5 Pas)
[0179] (B2) Plasticizing component: Sugar alcohol (manufactured by
Towa Chemical Industry Co., Ltd., "Marinecrystal D(-)mannitol")
[0180] (Structural Observation of Multiple Polymer Particle)
[0181] A Polymer fine particle was mixed with a chemically reactive
adhesive of epoxy polymer-series (manufactured byKonishi Co. ,Ltd.,
"BONDQUICK5") tomakeamassive product containing the polymer
particle dispersed therein, and the massive product was cut to a
thickness of about 0.05 .mu.m to 0.2 .mu.m by a microtome to give
an ultrathin section. Thereafter, the polymer particle in the
ultrathin section was stained with a coloring matter capable of
staining the Polymer component (A) and the Polymer component (B)
distinctively (e.g., osmic acid, and ruthenic acid), and was
observed about the structure by using a transmission electron
microscope. For reference, FIG. 3 shows a transmission electron
micrograph of the state (the cross section of the particle) after
staining the multiple polymer particle obtained in Example 2.
[0182] (Average Particle Size of Polymer Particle)
[0183] The collected resinous fine particle was dried, and then the
configuration (or shape) of the fine particle was observed by using
a scanning electron microscope. Moreover, the appropriate amount of
the dry Polymer fine particle was dispersed in pure water again to
prepare a suspension. Then, the number average particle size of the
resinous fine particle was determined by using a laser diffraction
particle size analyzer (manufactured by Shimadzu Corporation,
"SALD-2000J"). Further, concerning the resinous fine particle, the
standard deviation and the coefficient of variation relative to 100
particles selected at random were calculated.
[0184] [Table 1] TABLE-US-00001 TABLE 1 Polymer Polymer Number
average (A1) (A2) (B1) (B2) particle size Particle Particle Shell
thickness [parts] [parts] [parts] [parts] [.mu.m] shape structure
[.mu.m] EX. 1 Polymer 1 Polymer 3 75 25 7.2 Finely Core-shell <1
20 20 spherical shape Ex. 2 Polymer 2 Polymer 3 75 25 14 Finely
Core-shell <1 20 20 spherical shape Ex. 3 Polymer 2 Polymer 3 75
25 11 Finely Core-shell <1 30 10 spherical shape Ex. 4 Polymer 2
Polymer 4 75 25 5.8 Finely Core-shell <1 20 20 spherical shape
Ex. 5 Polymer 1 Polymer 5 75 25 6.4 Finely Core-shell <1 20 20
spherical shape Ex. 6 Polymer 4 Polymer 5 75 25 6.3 Finely
Core-shell <1 20 20 spherical shape (In Table, "parts" means
"parts by weight")
[0185] In each of Examples 1 to 6, core-shell finely spherical
multiple polymer particle s comprising the thermoplastic resin (A)
as the shell were obtained. The shell thickness of each obtained
particle was not more than 1 .mu.m. Moreover, from FIG. 3, in a
core-shell finely spherical multiple polymer particle containing
the polyamide 12 polymer as the shell and the
styrene-butadiene-styrene block copolymer as the nucleus (core), it
was confirmed that the butadiene part of the styrene-butadiene
block copolymer forming the core was stained with osmic acid and
observed black by a transmission electron microscope and that the
polyamide 12 polymer formed the shell. This is clear in view of the
fact that treatment of the polymer particle shown in FIG. 1 with
tetrahydrofuran, which dissolves a styrene-butadiene-styrene block
copolymer, induces exudation of the styrene-butadiene-styrene
copolymer due to collapse of the shell comprising the polyamide
polymer and makes the shell a broken state, as shown in FIG. 2.
* * * * *