U.S. patent application number 11/033805 was filed with the patent office on 2005-06-02 for carbodiimide-containing hardening type reactive particles, process for producing the same, and use of the same.
Invention is credited to Hashiba, Toshifumi, Hayakawa, Kazutoshi, Takahashi, Ikuo.
Application Number | 20050118424 11/033805 |
Document ID | / |
Family ID | 27764503 |
Filed Date | 2005-06-02 |
United States Patent
Application |
20050118424 |
Kind Code |
A1 |
Takahashi, Ikuo ; et
al. |
June 2, 2005 |
Carbodiimide-containing hardening type reactive particles, process
for producing the same, and use of the same
Abstract
A hardening type reactive particles which contain a carbodiimide
compound in such a way to have the reactive performance the
carbodiimide group inherently has only in the surface layer section
or both surface layer section and inside of the base particle,
without deforming shape of the base particle. The hardening type
reactive particles each comprising a base particle (A) of
thermoplastic resin having a functional group and carbodiimide
compound (B) impregnated only in the surface layer section or both
surface layer section and inside of the base particle, wherein the
base particle (A) and carbodiimide compound (B) are strong bonded
to each other by the crosslinking reaction taking place under
heating between the functional group in the former and carbodiimide
group in the latter, and a process for producing the same.
Inventors: |
Takahashi, Ikuo; (Chiba,
JP) ; Hashiba, Toshifumi; (Chiba, JP) ;
Hayakawa, Kazutoshi; (Chiba, JP) |
Correspondence
Address: |
WESTERMAN, HATTORI, DANIELS & ADRIAN, LLP
1250 CONNECTICUT AVENUE, NW
SUITE 700
WASHINGTON
DC
20036
US
|
Family ID: |
27764503 |
Appl. No.: |
11/033805 |
Filed: |
January 13, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11033805 |
Jan 13, 2005 |
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10386929 |
Mar 13, 2003 |
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6866934 |
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Current U.S.
Class: |
428/402 ;
427/222; 428/407 |
Current CPC
Class: |
C08K 9/04 20130101; Y10T
428/2982 20150115; C08J 3/12 20130101; Y10T 428/2995 20150115; C08J
2375/12 20130101; Y10T 428/2991 20150115; Y10T 428/2998 20150115;
Y10T 428/2996 20150115; Y10T 428/2993 20150115 |
Class at
Publication: |
428/402 ;
428/407; 427/222 |
International
Class: |
B32B 001/00; B32B
027/06; B32B 031/00; B05D 007/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 13, 2002 |
JP |
2002-68151 |
Claims
1-11. (canceled)
12. A process for producing the hardening type reactive particles
comprising two steps: the first step in which the base particle (A)
of thermoplastic resin having a functional group is mixed with the
carbodiimide compound (B) in the presence of at least one type of
solvent which dissolves (B) but not (A), selected from the group
consisting of water and organic solvents, to have the latter
impregnated only in the surface layer section or both surface layer
section and inside of the former; and the subsequent second step in
which the above mixture is thermally treated.
13. The process for producing the hardening type reactive particles
according to claim 12, wherein said base particle (A) is
morphologically truly or nearly spherical.
14. The process for producing the hardening type reactive particles
according to claim 13, wherein said base particle (A) is the one
prepared beforehand by suspension, emulsion, dispersion or seed
polymerization.
15. The process for producing the hardening type reactive particles
according to claim 12, wherein said base particle (A) is immersed
in a solution of the carbodiimide compound (B) dissolved in at
least one type of solvent selected from the group consisting of
water and organic solvents in said first step.
16. The process for producing the hardening type reactive particles
according to claim 15, wherein concentration of said carbodiimide
compound (B) in said solution is 5 to 60% by weight, determined by
the following formula: Solution concentration (% by
weight)=100.times.(whole solution-solvent)/whole solution.
17. The process for producing the hardening type reactive particles
according to claim 12, wherein said solvent is water, a mixture of
water and a lower alcohol, or toluene.
18. The process for producing the hardening type reactive particles
according to claim 12, wherein said base particle (A) is mixed with
said carbodiimide compound (B) in a ratio of 0.1 to 20 equivalents
of the carbodiimide group in said carbodiimide compound (B) to
equivalent of the functional group in said base particle (A).
19. The process for producing the hardening type reactive particles
according to claim 12, wherein said thermal treatment in the second
step is effected at 10 to 200.degree. C.
20. The process for producing the hardening type reactive particles
according to claim 12, wherein said thermal treatment in the second
step is effected for 1 to 24 hours.
21. The process for producing the hardening type reactive particles
according to claim 12, wherein said functional group is at least
one type of active hydrogen group selected from the group
consisting of hydroxyl, carboxyl, amino and thiol group.
22. The process for producing the hardening type reactive particles
according to claim 21, wherein said thermoplastic resin is one of
styrene-based polymer, (meth)acrylate-based polymer, a copolymer
produced by addition polymerization with another vinyl-based
polymer, polymer produced by hydrogen transfer polymerization,
polymer produced by polycondensation or polymer produced by
addition condensation.
23. The process for producing the hardening type reactive particles
according to claim 12, wherein said carbodiimide compound (B) has
an average molecular weight of 200 to 100,000.
24. The process for producing the hardening type reactive particles
according to claim 12, wherein said carbodiimide compound (B) has
at least one type of hydrophilic segment and is soluble in
water.
25. The process for producing the hardening type reactive particles
according to claim 24, wherein said hydrophilic segment is
represented by the chemical formula (1) with R.sup.1 and R.sup.3
being each at least one type of residue represented by one of the
chemical formulae (2) to (5).
26. The process for producing the hardening type reactive particles
according to claim 12, wherein at least one type of additive
selected from the group consisting of dispersant, antioxidant,
stabilizer and emulsifier is added to said first step, in addition
to the base particle (A) and carbodiimide compound (B).
27-33. (canceled)
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to carbodiimide-containing,
hardening type reactive particles, process for producing the same
and use of the same, more particularly hardening type reactive
particles each comprising a base particle (A) of thermoplastic
resin having a functional group and carbodiimide compound (B)
impregnated only in the surface layer section or both surface layer
section and inside of the base particle, and process for producing
the same and use of the same.
[0003] 2. Description of the Prior Art
[0004] Carbodiimides, having a structure of --N.dbd.C.dbd.N--, have
been widely used as a stabilizer for improving hydrolysis
resistance for compounds having an ester group or as a crosslinking
agent for resins, e.g., (meth)acrylic resin, having carboxyl group
reactive with carbodiimide group, where high reactivity of
carbodiimide group is generally utilized.
[0005] Various applicable areas have been proposed for carbodiimide
resins, e.g., paints, adhesives and coating agents, as disclosed by
Japanese Patent Application Laid-Open Nos. 10-60272 and 10-30024,
and they have been already commercialized in these areas.
[0006] However, most of the resins to be crosslinked with a
carbodiimide-containing composition are in the form of solution of
molten resin, paste or emulsion. Hardening of solid particles
themselves requires a great deal of time and is hence
difficult.
[0007] Production of polyolefin-based resin particles of
crosslinked structure by the reaction with a carbodiimide compound
in a melting/kneading machine or the like has been studied, as
disclosed by, e.g., Japanese Patent Application Laid-Open No.
2000-155441. However, no particles which can sufficiently satisfy
resistance to heat and chemicals have been developed.
[0008] Broadly speaking, the processes for producing polymer
particles fall into two general categories; (I) production of the
objective particles by crushing and classifying the resin produced
by, e.g., block or solution polymerization, as known, and (II)
production of adequate particles during a polymerization stage,
e.g., suspension, emulsion or dispersion polymerization, or seed
process based on these processes.
[0009] Production of hardened particles usually uses a
crosslinkable vinyl-based monomer or polymer to improve resistance
to heat and chemicals, or incorporate a crosslinkable monomer or
polymer other than a vinyl-based one, e.g., epoxy resin or the
like, to improve resistance to heat and solvents.
SUMMARY OF THE INVENTION
[0010] It is an object of the present invention to provide
hardening type reactive particles each comprising a base particle
of thermoplastic resin which contains a carbodiimide compound such
that the reactive performance the carbodiimide group inherently has
only in the surface layer section or both surface layer section and
inside of the base particle, without deforming shape of the base
particle.
[0011] The inventors of the present invention have found, after
having extensively studied to solve the problems involved in the
conventional techniques, that a thermoplastic resin particle having
a group reactive with carbodiimide group (e.g., hydroxyl, amino,
carboxyl or thiol group), when mixed and crosslinked with a
carbodiimide resin under heating in the presence of water or an
organic solvent which dissolves the carbodiimide resin but not the
particle, comes to show resistance both to heat and solvent, and to
be a functional reactive particle with at least one carbodiumide
group in the surface or both inside and in the surface. The present
invention is developed based on the above knowledge.
[0012] The first aspect of the present invention provides hardening
type reactive particles each comprising a base particle (A) of
thermoplastic resin having a functional group and carbodiimide
compound (B) impregnated only in the surface layer section or both
surface layer section and inside of the base particle, wherein the
base particle (A) and carbodiimide compound (B) are strongly bonded
to each other by the crosslinking reaction taking place under
heating between the functional group in the former and carbodiimide
group in the latter.
[0013] The second aspect of the present invention provides the
hardening type reactive particles of the first aspect, wherein the
base particle (A) has an average diameter of 0.01 to 10,000
.mu.m.
[0014] The third aspect of the present invention provides the
hardening type reactive particles of the first aspect, wherein the
base particle (A) is morphologically truly or nearly spherical.
[0015] The fourth aspect of the present invention provides the
hardening type reactive particles of the first aspect, wherein the
functional group is at least one type of active hydrogen group
selected from the group consisting of hydroxyl, carboxyl, amino and
thiol group.
[0016] The fifth aspect of the present invention provides the
hardening type reactive particles of the first aspect, wherein the
thermoplastic resin has 30 to 700 equivalents of the functional
groups.
[0017] The sixth aspect of the present invention provides the
hardening type reactive particles of the first aspect, wherein the
thermoplastic resin is one of styrene-based polymer,
(meth)acrylate-based polymer, a copolymer produced by addition
polymerization with another vinyl-based polymer, polymer produced
by hydrogen transfer polymerization, polymer produced by
polycondensation or polymer produced by addition condensation.
[0018] The seventh aspect of the present invention provides the
hardening type reactive particles of the first aspect, wherein the
carbodiimide compound (B) is the carbodiimide resin represented by
the chemical formula (1):
R.sup.1--Y--(R.sup.2N.dbd.C.dbd.N).sub.n--R.sup.2--Y--R.sup.3
(1)
[0019] (wherein, R.sup.1 and R.sup.3 are each hydrogen or an
organic residue of 1 to 40 carbon atoms, which is a compound having
a functional group reactive with isocyanate group left by the
functional group, and may be the same or different; R.sup.2 is an
organic residue which is a diisocyanate made from isocyanate group,
wherein the diisocyanates may be different; Y is a bond formed by
isocyanate group and a functional group reactive with isocyanate
group; "n" is an integer of 1 to 100, representing average degree
of polymerization; and each of R.sup.1--Y and Y--R.sup.3 may be
isocyanate group halfway in the reaction to be converted into the
carbodiimide).
[0020] The eighth aspect of the present invention provides the
hardening type reactive particles of the seventh aspect, wherein
the carbodiumide resin has 50 to 500 equivalents of the
carbodiumide (--NCN--) groups.
[0021] The ninth aspect of the present invention provides the
hardening type reactive particles of the seventh aspect, wherein
the carbodiimide resin has an average molecular weight of 200 to
100,000.
[0022] The tenth aspect of the present invention provides the
hardening type reactive particles of the seventh aspect, wherein
the carbodiimide resin has at least one type of hydrophilic segment
and is soluble in water.
[0023] The 11.sup.th aspect of the present invention provides the
hardening type reactive particles of the tenth aspect, wherein the
hydrophilic segment is represented by the chemical formula (1) with
R.sup.1 and R.sup.3 being each at least one type of residue
represented by one of the chemical formulae (2) to (5):
[0024] (i) a residue of alkyl sulfonate having at least one
reactive hydroxyl group, represented by:
R.sup.5--SO.sub.3--R.sup.4--OH (2)
[0025] (wherein, R.sup.4 is an alkylene group of 1 to 10 carbon
atoms; and R.sup.5 is an alkali metal),
[0026] (ii) a quaternary salt of a dialkylaminoalcohol residue
represented by:
(R.sup.6).sub.2--NR'-R.sup.7--OH (3)
[0027] (wherein, R.sup.6 is a lower alkyl group of 1 to 4 carbon
atoms; R.sup.7 is an alkylene or oxyalkylene group of 1 to 10
carbon atoms; and R' is a group derived from an agent for producing
a quaternary salt),
[0028] (iii) a quaternary salt of a dialkylaminoalkylamine residue
represented by:
(R.sup.6).sub.2--NR'-R.sup.7-NH.sub.2 (4)
[0029] (wherein, R.sup.6, R.sup.7 and R' are each the same as the
corresponding one in the formula (3)), and
[0030] (iv) a poly(alkylene oxide) residue capped with alkoxy group
at the terminals, having at least one reactive hydroxyl group,
represented by:
R.sup.8--(O--CHR.sup.9--CH.sub.2).sub.m--OH (5)
[0031] (wherein, R.sup.8 is a lower alkyl group of 1 to 4 carbon
atoms; R.sup.9 is hydrogen atom or methyl group; and "m" is an
integer of 2 to 30).
[0032] The 12.sup.th aspect of the present invention provides a
process for producing the hardening type reactive particles of one
of first to 11.sup.th aspects comprising two steps: the first step
in which the base particle (A) of thermoplastic resin having a
functional group is mixed with the carbodiumide compound (B) in the
presence of at least one type of solvent which dissolves (B) but
not (A), selected from the group consisting of water and organic
compounds, to have the latter impregnated only in the surface layer
section or both surface layer section and inside of the former; and
the subsequent second step in which the above mixture is thermally
treated.
[0033] The 13.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the base particle (A) is
morphologically truly or nearly spherical.
[0034] The 14.sup.th aspect of the present invention provides the
process of the 13.sup.th aspect, wherein the base particle (A) is
the one prepared beforehand by suspension, emulsion, dispersion or
seed polymerization.
[0035] The 15.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the base particle (A) is
immersed in a solution of the carbodiimide compound (B) dissolved
in at least one type of solvent selected from the group consisting
of water and organic solvents in said first step.
[0036] The 16.sup.th aspect of the present invention provides the
process of the 15.sup.th aspect, wherein concentration of the
carbodiimide compound (B) in the solution is 5 to 60% by weight,
determined by the following formula:
Solution concentration (% by weight)=100.times.(whole
solution-solvent)/whole solution.
[0037] The 17.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the solvent is water, a
mixture of water and a lower alcohol, or toluene.
[0038] The 18.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the base particle (A) is
mixed with the carbodiumide compound in a ratio of 0.1 to 20
equivalents of the carbodiimide group in the carbodiimide compound
(B) to equivalent of the functional group in the base particle
(A).
[0039] The 19.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the thermal treatment in
the second step is effected at 10 to 200.degree. C.
[0040] The 20.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the thermal treatment in
the second step is effected for 1 to 24 hours.
[0041] The 21.sup.st aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the functional group is at
least one type of active hydrogen group selected from the group
consisting of hydroxyl, carboxyl, amino and thiol group.
[0042] The 22.sup.nd aspect of the present invention provides the
process of the 21.sup.st aspect, wherein the thermoplastic resin is
one of styrene-based polymer, (meth)acrylate-based polymer, a
copolymer produced by addition polymerization with another
vinyl-based polymer, polymer produced by hydrogen transfer
polymerization, polymer produced by polycondensation or polymer
produced by addition condensation.
[0043] The 23.sup.rd aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the carbodiimide compound
(B) has an average molecular weight of 200 to 100,000.
[0044] The 24.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein the carbodiimide compound
(B) has at least one type of hydrophilic segment and is soluble in
water.
[0045] The 25.sup.th aspect of the present invention provides the
process of the 24.sup.th aspect, wherein the hydrophilic segment is
represented by the chemical formula (1) with R.sup.1 and R.sup.3
being each at least one type of residue represented by one of the
chemical formulae (2) to (5).
[0046] The 26.sup.th aspect of the present invention provides the
process of the 12.sup.th aspect, wherein at least one type of
additive selected from the group consisting of dispersant,
antioxidant, stabilizer and emulsifier is added to the first step,
in addition to the base particle (A) and carbodiimide compound
(B).
[0047] The 27.sup.th to 32.sup.nd aspects of the present invention
provide a crosslinking agent, stabilizer for improving hydrolysis
resistance, thermoplastic resin-hardening agent, adhesive agent,
coating material or paint, and reinforcing material for the
electric/electronic areas, respectively, which comprise the
hardening type reactive particles according to one of claims 1 to
11.
[0048] As described above, the present invention relates to
hardening type reactive particles each comprising a base particle
(A) of thermoplastic resin having a functional group and
carbodiimide compound (B) impregnated only in the surface layer
section or both surface layer section and inside of the base
particle, wherein the base particle (A) and carbodiimide compound
(B) are strongly bonded to each other by the crosslinking reaction
taking place under heating between the functional group in the
former and carbodiimide group in the latter, a process for
producing the same, and use of the same. The preferred embodiments
include the followings:
[0049] (1) The hardening type reactive particles of the first
aspect of the present invention, wherein the particles are
semi-hardened.
[0050] (2) The hardening type reactive particles of the first
aspect of the present invention, wherein the base particle ( ) is
non-spherical.
[0051] (3) The process for producing the hardening type reactive
particles of (2), wherein the base particle (A) is produced by
block polymerization, solution polymerization or dropping
method.
[0052] (4) The process of the 12.sup.th aspect of the present
invention for producing the hardening type reactive particles,
wherein the solvent is selected from the group consisting of
dimethylformamide (DMF), tetrahydrofuran (THF), methylethylketone
(MEK), methylisobutylketone (MIBK), acetone, N-methyl-2-pyrrolidone
(NMP), dichloromethane and tetrachloroethylene.
DETAILED DESCRIPTION OF THE INVENTION
[0053] The present invention is described below in detail for each
item.
[0054] 1. Hardening Type Reactive Particles
[0055] Each of the hardening type reactive particles of the present
invention comprises a base particle (A) of thermoplastic resin
having a functional group and carbodiimide compound (B) impregnated
only in the surface layer section or both surface layer section and
inside of the base particle, wherein the base particle (A) and
carbodiimide compound (B) are strongly bonded to each other by the
crosslinking reaction taking place under heating between the
functional group in the former and carbodiimide group in the
latter.
[0056] The hardening type reactive particle has a chemical
structure, conceptually illustrated below: 1
[0057] In the above chemical formula, "n" is random, and some (at
least one) of the carbodiimide groups in the polycarbodiimide
molecule are bonded to the particle inside or surface (surface
layer section). The one whose terminal R is a reactive group, e.g.,
isocyanate, is reactive with a terminal group.
[0058] Moreover, the carbodiimide group can be preferentially
bonded to the thermoplastic resin particle surface (surface layer
section) or crosslinked only on the particle surface (surface layer
section), as required, by selecting the carbodiimide resin
type.
[0059] The hardening type reactive particles may be hardened or
semi-hardened.
[0060] 2. Carbodiimide Compound (B)
[0061] The carbodiimide compound (B) for the hardening type
reactive particles of the present invention is the carbodiimide
resin (or poly carbodiimide) represented by the chemical formula
(1):
R.sup.1--Y--(R.sup.2--N.dbd.C.dbd.N).sub.n--R.sup.2--Y--R.sup.3
(1)
[0062] (wherein, R.sup.1 and R.sup.3 are each hydrogen or an
organic residue of 1 to 40 carbon atoms, which is a compound having
a functional group reactive with isocyanate group left by the
functional group, and may be the same or different; R.sup.2 is an
organic residue which is a diisocyanate left by isocyanate group,
where the diisocyanates may be different; Y is a bond formed by
isocyanate group and a functional group reactive with isocyanate
group; "n" is an integer of 1 to 100, representing average degree
of polymerization; and each of R.sup.1--Y and Y--R.sup.3 may be
isocyanate group halfway in the reaction to be converted into the
carbodiimide).
[0063] In more detail, R.sup.1 or R.sup.3 in the general formula
(1) is at least one type of segment composed of a residue
represented by a compound having a functional group or bond
reactive with isocyanate group.
[0064] The representative examples of the functional group or bond
include:
[0065] (a) hydroxide group --OH (including H.sub.2O)
[0066] (b) mercapto group --SH
[0067] (c) amino group --NH.sub.2
[0068] (d) carboxyl group --COOH
[0069] (e) isocyanate group --NCO
[0070] (f) urethane bond --NHCOO--
[0071] (g) urea bond --NHCONH--
[0072] (h) amide bond --NHCO--
[0073] (i) carbodiimide bond --NCN--
[0074] (j) dimerized isocyanate bond 2
[0075] More specifically, the representative compounds reactive
with isocyanate group include:
[0076] (a) compounds containing hydroxyl group (--OH): (i)
monovalent alcohols, e.g., methyl alcohol, ethyl alcohol, propyl
alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol and
tert-butyl alcohol; (ii) saturated or unsaturated glycols, e.g.,
ethylene glycol, propylene glycol, trimethylol propane,
pentaerythritol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol,
1,4-butanediol, neopentyl glycol, pentanediol, hexanediol,
octanediol, 1,4-butenediol, diethylene glycol, triethylene glycol
and dipropylene glycol; (iii) cellosolve; e.g., methyl cellosolve,
ethyl cellosolve and butyl cellosolve; (iv) (meth)acrylate-based
monomers, e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl
(meth)acrylate; (v) polyalkylene glycol (meth)acrylate-based
compounds, e.g., polyethylene glycol mono(meth)acrylate and
polypropylene glycol mono(meth)acrylate; (vi) various types of
hydroxyalkyl vinyl ethers, e.g., hydroxyethyl vinyl ether and
hydroxybutyl vinyl ether; (vii) various allyl compounds, e.g.,
allyl alcohol and 2-hydroxyethyl allyl ether; (viii) alkyl glycidyl
ethers, e.g., n-butyl glycidyl ether and 2-ethylhexyl glycidyl
ether; and (ix) high-molecular-weight compounds containing hydroxyl
group, e.g., polyethylene glycol and polypropylene glycol (these
compounds may be used either individually or in combination);
[0077] (b) compounds containing mercapto group: (i) aliphatic alkyl
mono-functional thiols, e.g., methanethiol, ethanethiol, n- and
iso-propanethiol, n- and iso-butanethiol, pentanethiol,
hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol
and cyclohexanethiol; (ii) aliphatic thiols having a heterocyclic
ring, e.g., 1,4-dithian-2-thiol, 2-(1-mercaptomethyl)-1,4-dithian,
2-(1-mercaptoethyl)-1,4-dithian, 2-(1-mercaptopropyl)-1,4-dithian,
2-(mercaptobutyl)-1,4-dithian, tetrahydrothiophene-2-thiol,
tetrahydrothiophene-3-thiol, pyrrolidine-2-thiol,
pyrrolidine-3-thiol, tetrahydrofuran-2-thiol,
tetrahydrofuran-3-thiol, piperidine-2-thiol, piperidine-3-thiol and
piperidine-4-thiol; (iii) aliphatic thiols having a hydroxy group,
e.g., 2-mercaptoethanol, 3-mercaptopropanol and thioglycerol; (iv)
compounds having a double bond, e.g., 2-mercaptoethyl
(meth)acrylate, 2-mercapto-1-carboxyethyl (meth)acrylate,
N-(2-mercaptoethyl)acrylamide,
N-(2-mercapto-1-carboxyethyl)acrylamide,
N-(2-mercaptoethyl)methacrylamide, N-(4-mercaptophenyl)acrylamide,
N-(7-mercaptonaphthyl)acrylamide and mono-2-mercaptoethylamide
maleate;
[0078] (v) aliphatic dithiols, e.g., 1,2-ethanedithiol,
1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol,
1,8-octanedithiol, 1,2-cyclohexanedithiol, ethylene glycol
bisthioglycolate, ethylene glycol bisthiopropionate, butanediol
bisthioglycolate, butanediol bisthiopropionate, trimethylolpropane
tristhioglycolate, trimethylolpropane tristhiopropionate,
pentaerythritol tetrakisthioglycolate, pentaerythritol
tetrakisthiopropionate, tris(2-mercaptoethyl)isocyanurate and
tris(3-mercaptopropyl)isocyanurate; (vi) aromatic dithiols, e.g.,
1,2-benzenedihiol, 1,4-benzenedihiol, 4-methyl-1,2-benzenedihiol,
4-butyl-1,2-benzenedihiol and 4-chloro-1,2-benzenedihiol; and (vii)
high-molecular-weight compounds containing mercapto group, e.g.,
modified polyvinyl alcohol containing mercapto group (these
compounds may be used either individually or in combination);
[0079] (c) compounds containing amino group: (i) aliphatic or
aromatic amine-containing compounds, e.g., ammonia, methylamine,
ethylamine, n-propylamine, isopropylamine, monoethanolamine,
n-propanolamine, isopropanolamine, aniline, cyclohexylamine,
n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine,
n-octylamine, n-nonylamine, n-decylamine, n-undecylamine,
n-dodecylamine, n-tridecylamine, n-tetradecylamine,
n-pentadecylamine, n-hexadecylamine, n-heptadecylamine,
n-octadecylamine, n-eicosylamine, aminomethyltrimethylsilane,
aminomethyltriethylsilane, aminomethyltripropylsilane,
aminoethyltrimethylsilane, aminoethyltriethylsilane,
aminoethyltripropylsilane, aminopropyltrimethylsilane,
aminopropyltriethylsilane, aminopropyltripropylsilane,
aminomethyltrimethoxysilane, aminomethyltriethoxysilane,
aminomethyltripropoxysilane, aminomethyldimethoxymethylsilane,
aminomethylmethoxydimethylsilane, aminomethyldiethoxymethylsilane,
aminomethylethoxydimethylsilane, aminomethyldimethoxyethylsilane,
aminomethylmethoxydiethylsilane, aminomethyldiethoxyethylsilane,
aminomethylethoxydiethylsilane, aminoethyldimethoxymethylsilane,
aminoethylmethoxydimethylsilane, aminoethyldiethoxymethylsilane,
aminoethylethoxydimethylsilane, aminoethyldimethoxyethylsilane,
aminoethylmethoxydiethylsilane, aminoethyldiethoxyethylsilane,
aminoethylethoxydiethylsilane, aminopropyldimethoxymethylsilane,
aminopropylmethoxydimethylsilane, aminopropyldiethoxymethylsilane,
aminopropylethoxydimethylsilane, aminopropyldimethoxyethylsilane,
aminopropylmethoxydiethylsilane, aminopropyldiethoxyethylsilane,
aminopropylethoxydiethylsilane, aminomethylphenyldimethylsilane,
diethylamine, diethanolamine, di-n-propanolamine,
di-isopropanolamine, N-methylethanolamine and N-ethylethanolamine;
(ii) alkylamino acrylates, e.g., dimethylaminoethyl acrylate,
diethylaminoethyl acrylate, dimethylaminomethyl acrylate,
diethylaminomethyl acrylate, adduct of diacrylate and diethylamine,
and adduct of trimethylolpropane triacrylate and diethylamine;
(iii) alkylaminoalkylvinyl ethers, e.g., (meth)acrylamide,
.alpha.-ethyl (meth)acrylamide, N-methyl (meth)acrylamide,
N-butoxymethyl (meth)acrylamide, diacetone (meth)acrylamide,
N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide,
N,N-dimethyl-p-styrenesul- foamide, N,N-dimethylaminoethyl
(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate,
N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl
(meth)acrylate, N-[2-(meth)acryloyloxyethyl]piperi- dine,
N-[2-(meth)acryloyloxyethylene]pyrrolidine,
N-[2-(meth)acryloyloxyet- hyl] morpholine,
4-(N,N-dimethylamino)styrene, 4-(N,N-diethylamino)styrene- ,
4-vinyl pyridine, 2-dimethylaminoethylvinyl ether,
2-diethylaminoethylvinyl ether, 4-dimethylaminobutylvinyl ether,
4-diethylaminobutylvinyl ether and 6-dimethylaminohexylvinyl ether;
and (iv) high-molecular-weight compounds containing amino group
(these compounds may be used either individually or in
combination);
[0080] (d) compounds containing carboxyl group: (i) saturated
aliphatic monocarboxylates, e.g., formic, acetic, propionic,
isovaleric and hexanoic acid; (ii) saturated aliphatic
dicarboxylates, e.g., oxalic, malonic and succinic acid; (iii)
organic carboxylic acids, e.g., 2-acryloyloxyethylsuccinic and
3-acryloyloxypropylphthalic acid; (iv) carbocyclic carboxylic
acids, e.g., benzoic, toluyl and salicylic acid; (v) heterocyclic
carboxylic acids, e.g., furancarboxylic, thiophenecarboxylic and
pyridinecarboxylic acid; (vi) various unsaturated mono- or
di-carboxylic or unsaturated dibasic acids, e.g., acrylic,
methacrylic, crotonic, itaconic, maleic and fumaric acid, and
monobutyl itaconate and monobutyl maleate; (vii) acid anhydrates
derived from carboxylic acid, e.g., acetic, succinic and phthalic
anhydride; and (viii) high-molecular-weight carboxylic acids, e.g.,
polyacrylic and polymethacrylic acid (these compounds may be used
either individually or in combination);
[0081] (e) compounds containing isocyanate group: (i) cyclohexyl
isocyanate, n-decyl isocyanate, n-undecyl isocyanate, n-dodecyl
isocyanate, n-tridecyl isocyanate, n-tetradecyl isocyanate,
n-pentadecyl isocyanate, n-hexadecyl isocyanate, n-heptadecyl
isocyanate, n-octadecyl isocyanate, n-eicosyl isocyanate, phenyl
isocyanate and naphthyl isocyanate; and (ii) isocyanate compounds
having 2 or more isocyanate groups, e.g., those used for
carbodiimidated resins (these compounds may be used either
individually or in combination); and
[0082] (f) to (j): compounds having a representative bonding group
reactive with an isocyanate group, which can be produced by
polymerization of the compound of (a) to (e), respectively, with a
varying isocyanate compound under heating in the presence or
absence of catalyst.
[0083] The representative compounds reactive with isocyanate group
are not limited to those compounds (a) to j). Any compound may be
used, so long as it has a functional group or bond reactive with
isocyanate group (e.g., acid anhydride and compound having a double
bond). They may be used either individually or in combination.
[0084] When R.sup.1 or R.sup.3 in the chemical formula (1) is a
residue represented by the compound of one of (a) to ( ) having the
functional group or bond, the bond Y is represented by:
[0085] (a') urethane bond --NHCOO--
[0086] (b') thiourethane bond --NHCSO--
[0087] (c') urea bond --NHCONH--
[0088] (d') amide bond --NHCO--
[0089] (e') carbodiimide bond --NCN--
[0090] (in the presence of a catalyst) or dimerized isocyanate bond
3
[0091] (f') allophanate
[0092] (g') burrette bond
[0093] (h') acylurea bond
[0094] (i') uretonimine bond
[0095] (j') trimerized isocyanate bond 4 5
[0096] The carbodiimide resin represented by the chemical formula
(1) has an average molecular weight of 200 to 100,000, preferably
500 to 50,000.
[0097] The isocyanates as the starting compounds for producing the
carbodiimide compound for the present invention include those
having per molecule at least 2 isocyanate groups, preferably one or
more isocyanates selected from bifunctional isocyanate,
hexamethylene diisocyanate (hereinafter sometimes referred to as
HDI), hydrogenated xylylene diisocyanate (H.sub.6XDI), xylylene
diisocyanate (XDI), 2,2,4-trimethylhexamethylene diisocyanate
(TMHDI), 1,12-diisocyanatedodecane (DDI), norbornane diisocyanate
(NBDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI) and
tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate
(IPDI), 2,4,6-triisopropylphenyl diisocyanate (TIDI),
4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate
(TDI) and hydrogenated tolylene diisocyanate (HTDI), among
others.
[0098] The first step for producing the carbodiimide compound for
the present invention is heating the above-described isocyanate in
the presence of a carbodiimidation catalyst.
[0099] The catalyst useful for the present invention is not
limited, so long as it can accelerate the carbodiimidation
reaction, but organophosphorus-based compounds are suitable, in
particular phospholene oxides for their activity.
[0100] More specifically, these phospholene oxides include
3-methyl-1-phenyl-2-phospholene-1-oxide,
3-methyl-1-ethyl-2-phospholene-1- -oxide,
1,3-dimethyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-oxide-
, 1-ethyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide and
a double-bond isomer thereof, of which
3-methyl-1-phenyl-2-phospholene-1-ox- ide is more suitable for its
industrial availability. Timing of incorporation of the
carbodiimidation catalyst is not limited, i.e., it may be
incorporated before, during or after the isocyanate is heated. It
is however preferable to incorporate the catalyst while the
reaction system is at a relatively low temperature for safety
considerations.
[0101] The first step for producing the carbodiimide compound for
the present invention is heating the above-described isocyanate in
the presence of a carbodiimidation catalyst, as described above.
The synthesis process may be effected in the presence or absence of
a solvent, or a solvent may be added while the reaction process is
proceeding. Whether a solvent is used or not, or its addition
timing, when used, can be selected depending on specific purposes
or objects of the carbodiimide compound.
[0102] The specific examples of the solvents useful for the present
invention include ketones, e.g., acetone, methylethylketone,
methylisobutylketone and cyclohexanone; esters, e.g., ethyl
acetate, butyl acetate, ethyl propionate and cellosolve acetate;
aliphatic or aromatic hydrocarbons, e.g., pentane, 2-methylbutane,
n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane,
2,3-dimethylbutane, heptane, n-octane, isooctane,
2,2,3-trimethylpentane, decane, nonane, cyclopentane,
methylcyclopentane, methylcyclohexane, ethylcyclohexane,
p-menthane, benzene, toluene, xylene and ethylbenzene; halogenated
hydrocarbons, e.g., carbon tetrachloride, trichloroethylene,
chlorobenzene and tetrabromoethane; ethers, e.g., ethyl ether,
dimethyl ether, trioxane and tetrahydrofuran; acetals, e.g.,
methylal and diethyl acetal; and sulfur- or nitrogen containing
organic compounds, e.g., nitropropene, nitrobenzene, pyridine,
dimethylformamide and dimethylsulfoxide. The solvent is not
limited, so long as it is not harmful to the isocyanate or
carbodiimide group during the synthesis process, and can be
selected, as required, for a specific purpose of the polymerization
process. These solvents may be used either individually or in
combination.
[0103] The following compounds may be used as diluents, in addition
to the above solvents, provided that the carbodiimide resin
terminal is capped with the hydrophilic segment, described later,
after completion of the synthesis process: water; alcohols, e.g.,
methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,
isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol,
3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl
alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol,
2-ethyl butanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol,
2-ethyl-1-hexanol, benzyl alcohol and cyclohexanol; and ether
alcohols, e.g., methyl cellosolve, ethyl cellosolve, isopropyl
cellosolve, butyl cellosolve and diethylene glycol monobutyl ether.
These may be used either individually or in combination. When used
as a diluent, the above compound is preferably used at a relatively
low temperature, because of high reactivity of the carbodiimide
group.
[0104] A water-soluble polycarbodiimide is preferably used as the
carbodiumide compound for the present invention, on account of
recent environmental considerations.
[0105] Such a polycarbodiimide has a hydrophilic segment which is
represented by, e.g., the chemical formula (1) with R.sup.1 or
R.sup.3 being at least one type of residue represented by one of
the chemical formulae (2) to (5).
[0106] (i) A residue of alkyl sulfonate having at least one
reactive hydroxyl group, represented by:
R.sup.5--SO.sub.3--R.sup.4--OH (2)
[0107] (wherein, R.sup.4 is an alkylene group of 1 to 10 carbon
atoms; and R.sup.5 is an alkali metal).
[0108] The alkyl sulfonates include sodium hydroxyethanesulfonate
and sodium hydroxypropanesulfonate, of which the latter is more
preferable. (ii) A quaternary salt of a dialkylaminoalcohol residue
represented by:
(R.sup.6).sub.2--NR'-R.sup.7--OH (3)
[0109] (wherein, R.sup.6 is a lower alkyl group of 1 to 4 carbon
atoms; R.sup.7 is an alkylene or oxyalkylene group of 1 to 10
carbon atoms; and R' is a group derived from an agent for producing
a quaternary salt).
[0110] The dialkylaminoalcohols include 2-dimethylaminoethanol,
2-diethylaminoethanol, 3-dimethylamino-1-propanol,
3-diethylamino-1-propanol, 3-diethylamino-2-propanol,
5-diethylamino-2-propanol and 2-(di-n-butylamino)ethanol, of which
2-dimethylaminoethanol is more preferable.
[0111] The agents for producing a quaternary salt include
dimethylsulfuric acid and methyl p-toluenesulfonate.
[0112] (iii) A quaternary salt of a dialkylaminoalkylamine residue
represented by:
(R.sup.6).sub.2--NR'--R.sup.7--NH.sub.2 (4)
[0113] (wherein, R.sup.6, R.sup.7 and R' are each the same as the
corresponding one in the formula (3)).
[0114] The dialkylaminoalkylamines include
3-dimethylamino-n-propylamine, 3-diethylamino-n-propylamine and
2-(diethylamino)ethylamine, of which 3-dimethylamino-n-propylamine
is more preferable.
[0115] The agents for producing a quaternary salt include
dimethylsulfuric acid and methyl p-toluenesulfonate.
[0116] (iv) A poly(alkylene oxide) residue sealed with alkoxy group
at the terminals, having at least one reactive hydroxyl group,
represented by:
R.sup.8--(O--CHR.sup.9--CH.sub.2).sub.m--OH (5)
[0117] (wherein, R.sup.8 is a lower alkyl group of 1 to 4 carbon
atoms; R.sup.9 is hydrogen atom or methyl group; and "m" is an
integer of 2 to 30).
[0118] The poly(alkylene oxides) include poly(ethylene
oxide)monomethyl ether, poly(ethylene oxide)monoethyl ether,
poly(ethylene oxide/propylene oxide)monomethyl ether and
poly(ethylene oxide/propylene oxide)monoethyl ether, of which
poly(ethylene oxide)monomethyl ether is more preferable.
[0119] 3. Base Particle (a) of Thermoplastic Resin and Method for
Producing the Same
[0120] The processes for producing the base particle (A) of
thermoplastic resin having a functional group for the present
invention include those for producing a thermoplastic resin having
a functional group reactive with carbodiimide group (e.g.,
hydroxyl, carboxyl, amino or thiol group) and particles thereof.
More specifically, they include:
[0121] (1) A process for producing the solution thermoplastic resin
by common block or solution polymerization, and particles thereof
by crushing and classifying the resin.
[0122] (2) A process for producing the thermoplastic resin by the
above polymerization process, and particles (including spherical
particles) thereof by dropping the polymer.
[0123] (3) A process for producing the thermoplastic resin and
particles (including spherical particles) thereof by emulsion or
suspension polymerization effected in an aqueous solution.
[0124] (4) A process for producing the thermoplastic resin and
particles (including spherical particles) thereof by the above
process (3) combined with a seed process or the like.
[0125] (5) A process for producing the thermoplastic resin and
particles (mainly spherical particles) thereof by dispersion
polymerization in a non-aqueous solvent or water-mixed solvent.
[0126] (6) A process for producing the thermoplastic resin and
particles thereof by the above process (5) combined with a seed
process or the like.
[0127] (7) Extrusion or the like to produce pellets, particles or
film-shaped articles of the thermoplastic resin.
[0128] (8) Injection molding or the like to produce formed articles
of the thermoplastic resin.
[0129] The processes for the present invention are not limited to
the above, and any process may be used so long as it produces the
composition and particles thereof which satisfy the necessary
conditions, e.g., quantity of the functional group in the
thermoplastic resin and particles thereof, particle size, and
thickness of the formed article.
[0130] In the process for producing the base particle (A) of
thermoplastic resin, the particles produced by one of the above
polymerization processes may have a crosslinked structure
beforehand, and can be used for producing the hardening type
reactive particles of the present invention.
[0131] The base particle (A) of thermoplastic resin for the present
invention is the one having a functional group reactive with
carbodiimide group. More specifically, it has an active hydrogen
group, e.g., hydroxyl (--OH), carboxyl (--COOH), amino (--NH.sub.2)
or thiol (--SH) group.
[0132] The base particle of thermoplastic resin has a
weight-average molecular weight of around 1,000 to 3,000,000, or
3,000 to 500,000 when it is spherical.
[0133] The thermoplastic resin is one of styrene-based polymer,
(meth)acrylate-based polymer, a copolymer produced by addition
polymerization with another vinyl-based polymer, polymer produced
by hydrogen transfer polymerization, polymer produced by
polycondensation and polymer produced by addition condensation.
[0134] The specific examples of the representative starting
copolymerizable monomers as the main component for the above
polymer include (i) styrenes, e.g., styrene, o-methyl styrene,
m-methyl styrene, p-methyl styrene, .alpha.-methyl styrene, p-ethyl
styrene, 2,4-dimethyl styrene, p-n-butyl styrene, p-tert-butyl
styrene, p-n-hexyl styrene, p-n-octyl styrene, p-n-nonyl styrene,
p-n-decyl styrene, p-n-dodecyl styrene, p-methoxystyrene, p-phenyl
styrene, p-chlorostyrene and 3,4-dichlorostyrene; (ii)
(meth)acrylate esters, e.g., methyl acrylate, ethyl acrylate,
n-butyl acrylate, isobutyl acrylate, propyl acrylate, hexyl
acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl
acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl
acrylate, phenyl acrylate, methyl .alpha.-chloroacrylate, methyl
methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl
methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl
methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl
methacrylate and stearyl methacrylate; (iii) vinyl esters, e.g.,
vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate;
(iv) (meth)acrylic acid derivatives, e.g., acrylonitrile and
methacrylonitrile; (v) vinyl ethers, e.g., vinyl methyl ether,
vinyl ethyl ether and vinyl isobutyl ether; (vi) vinyl ketones,
e.g., vinyl methylketone, vinyl hexylketone and
methylisopropenylketone; (vii) N-vinyl compounds, e.g., N-vinyl
pyrrole, N-vinyl carbazole, N vinyl indole and N-vinyl pyrrolidone;
and (viii) (meth)acrylate esters having a fluorine-containing alkyl
group, e.g., vinyl fluoride, vinylidene fluoride,
tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate
and tetrafluoropropyl acrylate. These compounds may be used either
individually or in combination.
[0135] The specific examples of the representative
radical-polymerizable monomers having carboxyl group as the
functional group reactive with carbodiimide group include various
unsaturated mono- and di-carboxylic acids and unsaturated dibasic
acids, e.g., acrylic, methacrylic, crotonic, itaconic, maleic and
fumaric acid, and monobutyl itaconate and monobutyl maleate. These
compounds may be used either individually or in combination.
[0136] The specific examples of the representative
radical-polymerizable monomers having hydroxyl group as the
functional group reactive with carbodiimide group include
(meth)acrylate-based monomers, e.g., 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and
4-hydroxybutyl (meth)acrylate; polyalkylene glycol
(meth)acrylate-based compounds, e.g., polyethylene glycol
mono(meth)acrylate and polypropylene glycol mono(meth)acrylate;
various types of hydroxyalkyl vinyl ethers, e.g., hydroxyethyl
vinyl ether and hydroxybutyl vinyl ether; and various allyl
compounds, e.g., allyl alcohol and 2-hydroxyethyl allyl ether.
These compounds may be used either individually or in
combination.
[0137] The specific examples of the representative polymers having
hydroxyl group include thermoplastic resins having hydroxyl group,
e.g., totally or partially saponified resins (e.g., polyvinyl
alcohol (PVA)), and saponified resins (e.g., acetate esters
composed of a copolymer of vinyl acetate and another vinyl
monomer). These polymers are also useful for the present
invention.
[0138] The specific examples of the representative
radical-polymerizable monomers or compounds having amino group as
the functional group reactive with carbodiumide group include
(meth)acrylamide, .alpha.-ethyl (meth)acrylamide, N-methyl
(meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone
(meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl
(meth)acrylamide, N,N-dimethyl-p-styrenesul- foamide,
N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl
(meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate,
N,N-diethylaminopropyl (meth)acrylate,
N-[2-(meth)acryloyloxyethyl]piperi- dine,
N-[2-(meth)acryloyloxyethylene]pyrrolidine,
N-[2-(meth)acryloyloxyet- hyl]morpholine,
4-(N,N-dimethylamino)styrene, 4-(N,N-diethylamino)styrene, 4-vinyl
pyridine, 2-dimethylaminoethylvinyl ether, 2-diethylaminoethylvinyl
ether, 4-dimethylaminobutylvinyl ether, 4-diethylaminobutylvinyl
ether and 6-dimethylaminohexylvinyl ether. These compounds may be
used either individually or in combination.
[0139] The specific examples of the representative
radical-polymerizable monomers or compounds having thiol (mercapto)
group as the functional group reactive with carbodiimide group
include those having a double bond, e.g., 2-propene-1-thiol,
3-butene-1-thiol, 4-pentene-1-thiol, 2-mercaptoethyl
(meth)acrylate, 2-mercapto-1-carboxyethyl (meth)acrylate,
N-(2-mercaptoethyl)acrylamide,
N-(2-mercapto-1-carboxyethyl)acrylamide,
N-(2-mercaptoethyl)methacrylamide, N-(4-mercaptophenyl)acrylamide,
N-(7-mercaptonaphthyl)acrylamide and mono-2-mercaptoethylamide
maleate; and compounds having a crosslinked structure between a
compound having at least 2 functional groups (e.g.,
tetramethylenedithiol, hexamethylenedithiol, octamethylenedithiol
or decamethylenedithiol) and monomer having a group reactive with
thiol (mercapto) group and --C.dbd.C-- double bond. These compounds
may be used either individually or in combination. Thermoplastic
resins having thiol (mercapto) group, e.g., modified polyvinyl
alcohol having thiol (mercapto) group, are also useful for the
present invention.
[0140] When 2 or more functional groups, e.g., carboxyl, hydroxyl,
amino and thiol (mercapto) group, are to be incorporated, the
above-described monomers having a varying reactive group may be
combined with each other to produce a multi-functional copolymer.
Moreover, multi-functional polymer particles containing
carbodiimide group can be produced by adjusting carbodiimide resin
content or reaction temperature.
[0141] For radical polymerization to produce the thermoplastic
resin for the present invention, a known radical polymerization
initiator may be used.
[0142] The specific examples of the representative radical
polymerization initiators include peroxides, e.g., benzoyl
peroxide, cumene hydroperoxide, t-butyl hydroperoxide; persulfates,
e.g., sodium persulfate and ammonium persulfate; and azo-based
compounds, e.g., azobisisobutylonitrile, azobismethylbutylonitrile
and azobisisovaleronitrile. These compounds may be used either
individually or in combination.
[0143] For production of the thermoplastic resin particles reactive
with carbodiimide group, various synthesis/polymerization processes
described above may be employed; they may be synthesized in the
absence of solvent, e.g., block polymerization, or in the presence
of solvent, e.g., solution polymerization.
[0144] The specific examples of the representative polymerization
solvents include water; alcohols, eg., methanol, ethanol,
1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol,
tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol,
2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol,
1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl
butanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol,
2-ethyl-1-hexanol, benzyl alcohol and cyclohexariol; and ether
alcohols, e.g., methyl cellosolve, ethyl cellosolve, isopropyl
cellosolve, butyl cellosolve, and diethylene glycol monobutyl
ether; ketones, e.g., acetone, methylethylketone,
methylisobutylketone and cyclohexanone; esters, e.g., ethyl
acetate, butyl acetate, ethyl propionate and cellosolve acetate;
aliphatic or aromatic hydrocarbons, e.g., pentane, 2-methylbutane,
n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane,
2,3-dimethylbutane, heptane, n-octane, isooctane,
2,2,3-trimethylpentane, decane, nonane, cyclopentane,
methylcyclopentane, methylcyclohexane, ethylcyclohexane,
p-menthane, dicyclohexane, benzene, toluene, xylene and
ethylbenzene; halogenated hydrocarbons, e.g., carbon tetrachloride,
trichloroethylene, chlorobenzene and tetrabromoethane; ethers,
e.g., ethyl ether, dimethyl ether, trioxane and tetrahydrofuran;
acetals, e.g., methylal and diethyl acetal; fatty acids, e.g.,
formic, acetic and propionic acid; and sulfur- or nitrogen
containing organic compounds, e.g., nitropropene, nitrobenzene,
dimethyl amine, monoethanolamine, pyridine, dimethylformamide and
dimethylsulfoxide. The solvent is not limited, and can be selected,
as required, for a specific purpose of the polymerization process.
These solvents may be used either individually or in
combination.
[0145] A specific polymerization may incorporate, as required, one
or more additives, e.g., polymer dispersant, stabilizer, emulsifier
and surfactant, for production of the particles.
[0146] The specific examples of the representative additives are
cited. The dispersants and stabilizers include various hydrophilic
and hydrophobic ones, such as polystyrene derivatives, e.g.,
polyhydroxystyrene, polystyrenesulfonic acid, vinyl
phenyl/(meth)acrylate ester copolymer, styrene/(meth)acrylate ester
copolymer and styrene/vinyl phenyl/(meth)acrylate ester copolymer;
poly(meth)acrylic acid and derivatives thereof, e.g.,
poly(meth)acrylic acid, poly(meth)acrylamide, polyacrylonitrile,
polyethyl (meth)acrylate and polybutyl (meth)acrylate; polyvinyl
alkyl ether derivatives, e.g., polymethyl vinyl ether, polyethyl
vinyl ether, polybutyl vinyl ether and polyisobutyl vinyl ether;
cellulose and derivatives thereof, e.g., cellulose, methyl
cellulose, cellulose acetate, cellulose nitrate, hydroxymethyl
cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and
carboxymethyl cellulose; polyvinyl acetate and derivatives thereof
e.g., polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, and
polyvinyl acetate; nitrogen-containing polymer derivatives, e.g.,
polyvinyl pyridine, polyvinyl pyrrolidone, polyethyleneimine and
poly-2-methyl-2-oxazoline; halogenated polyvinyl derivatives, e.g.,
polyvinyl chloride and polyvinylidene chloride; and polysiloxane
derivatives, e.g., polydimethyl siloxane. These may be used either
individually or in combination.
[0147] The emulsifiers (surfactants) useful for the present
invention include anionic emulsifiers, including alkyl sulfate
ester salts, e.g., sodium lauryl sulfate, alkyl benzenesulfonates,
e.g., sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonates,
fatty acid salts, alkyl phosphates, and alkylsulfosuccinates;
cationic emulsifiers, including alkylamine salts, quarternary
ammonium salts, alkyl betaine, and amine oxide; nonionic
emulsifiers, including polyoxyethylene alkyl ether, polyoxyethylene
alkyl allyl ether, polyoxyethylene alkyl phenyl ether,
sorbitan/fatty acid ester, glycerin/fatty acid ester and
polyoxyethylene/fatty acid ester. These may be used either
individually or in combination.
[0148] When the resin or its particles are produced, a small
quantity of crosslinking agent may be incorporated, depending on
their purposes.
[0149] The specific examples of the representative crosslinking
agents include aromatic divinyl compounds, e.g., divinyl benzene
and divinyl naphthalene, ethylene glycol diacrylate, ethylene
glycol dimethacrylate, triethylene glycol dimethacrylate,
tetraethylene glycol dimethacrylate, 1,3-butylene glycol
dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane
trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol
diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, pentaerythritol dimethacrylate,
pentaerythritol tetramethacrylate, glycerol acryloxydimethacrylate,
N,N-divinyl aniline, divinyl ether, divinyl sulfide and divinyl
sulfone. These may be used either individually or in
combination.
[0150] 4. Process for Producing the Hardening Type Reactive
Particles
[0151] The hardening type reactive particles of the present
invention are produced first by producing a thermoplastic resin
having a functional group reactive with carbodiimide group or its
particles, and reacting the resin or particles with a carbodiimide
resin under heating in the presence of a solvent which dissolves
the carbodiimide resin but not the thermoplastic resin or
particles, to obtain the semi-hardening to hardening type reactive
particles without deforming shape of the particles. More
specifically, the process comprises two steps: the first step in
which the base particle (A) of the thermoplastic resin having a
functional group is mixed with the carbodiimide compound (B) in the
presence of at least one type of solvent which dissolves (B) but
not (A), to have the latter impregnated only in the surface layer
section or both surface layer section and inside of the former; and
the subsequent second step in which the above mixture is thermally
treated. This produces the semi-hardening to hardening type
reactive particles.
[0152] The first step may incorporate, as required, an adequate
additive, e.g., dispersant, antioxidant, stabilizer or emulsifier,
in addition to the base particle (A) and carbodiimide compound (B).
The specific examples of the representative additives are
described. The dispersants, stabilizers and emulsifiers useful for
the process are similar to those described earlier. On the other
hand, the antioxidants useful for the process include those based
on phenyl, sulfur, phosphorus, amine, hydroquinone and
hydroxylamine. These may be used either individually or in
combination.
[0153] The thermoplastic resin particles having a functional group
reactive with the carbodiimide group in the carbodiimide compound
(i.e., carbodiimide resin) contain the functional group preferably
at 30 to 700 equivalents, more preferably 50 to 700 equivalents,
still more preferably 80 to 700 equivalents. The particles
containing the functional group at above 700 equivalents may have
deteriorated crosslinking capacity, because of an excessive
distance between the molecules. When the semi-hardened particles
are to be produced, however, the functional group may be present at
above 700 equivalents.
[0154] The thermoplastic resin particle having a functional group
is not limited, so long as it has active hydrogen group reactive
with the carbodiimide group, e.g., hydroxyl, carboxyl, amino or
thiol group. The particularly preferable thermoplastic resin
particles are those having carboxyl or hydroxyl group.
[0155] The thermoplastic resin particles having a functional group
are preferably truly or nearly spherical. However, the
non-spherical ones are acceptable.
[0156] The thermoplastic resin particles preferably have a diameter
of 0.01 to 10,000 .mu.m, more preferably 0.01 to 1,000 .mu.m, still
more preferably 0.1 to 700 .mu.m.
[0157] Even when the thermoplastic resin is a film-shape
composition, it can be crosslinkable when film thickness is in the
above range. The films can be the hardening type reactive
particles, and hence semi-hardened to hardened.
[0158] Content of the polycarbodiimide varies depending on the
required carbodiimide group remaining after the crosslinking step.
As a measure, it may be incorporated at 0.1 to 20 equivalents per
equivalent of the functional group in the thermoplastic resin
particle, preferably 0.5 to 8 equivalents, more preferably 1 to 6
equivalents.
[0159] Thermal treatment temperature at which the reaction mixture
is heated for the reaction varies depending on type of the solvent
used. However, it is in a range from 10 to 200.degree. C.,
preferably 15 to 150.degree. C., more preferably 20 to 130.degree.
C.
[0160] Crosslinking time is not limited, so long as it allows the
crosslinking reaction to be almost completed. It largely varies
depending on type and content of the carbodiimide resin used, type
of the functional group in the resin (particle), viscosity and
concentration of the solution, and so on. It is however around 1 to
24 hours at 40.degree. C., preferably 6 to 24 hours.
[0161] The solvent which dissolves the carbodiimide resin but not
the thermoplastic resin or its particles is at least one type of
solvent selected from the group consisting of water and organic
solvents. It may be adequately selected in consideration of type
and content of the carbodiimide resin used, type of the
thermoplastic resin (or particle) and type of the functional group
it contains, purpose of the hardening type reactive particles, and
so on.
[0162] The specific examples of the representative solvents include
water; alcohols, e.g., methanol, ethanol, 1-propanol, 2-propanol,
1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol,
1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl
alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl-1-pentanol,
4-methyl-2-pentanol, 2-ethyl butanol, 1-heptanol, 2-heptanol,
3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol and
cyclohexanol; and ether alcohols, e.g., methyl cellosolve, ethyl
cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene
glycol monobutyl ether; ketones, e.g., acetone, methylethylketone,
methylisobutylketone and cyclohexanone; esters, e.g., ethyl
acetate, butyl acetate, ethyl propionate and cellosolve acetate;
aliphatic or aromatic hydrocarbons, e.g., pentane, 2-methylbutane,
n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane,
2,3-dimethylbutane, heptane, n-octane, isooctane,
2,2,3-trimethylpentane, decane, nonane, cyclopentane,
methylcyclopentane, methylcyclohexane, ethylcyclohexane,
p-menthane, dicyclohexane, benzene, toluene, xylene and
ethylbenzene; halogenated hydrocarbons, e.g., carbon tetrachloride,
trichloroethylene, chlorobenzene and tetrabromoethane; ethers,
e.g., ethyl ether, dimethyl ether, trioxane and tetrahydrofuran;
acetals, e.g., methylal and diethyl acetal; fatty acids, e.g.,
formic, acetic and propionic acid; and sulfur- or nitrogen
containing organic compounds, e.g., nitropropene, nitrobenzene,
dimethyl amine, monoethanolamine, pyridine, dimethylformamide and
dimethylsulfoxide. The more preferable solvents are water, lower
alcohols (e.g., methanol and ethanol), a mixture of water and lower
alcohol, toluene, dimethylformamide (DMF), tetrahydrofuran (THF),
methylethylketone (MEK), methylisobutylketone (MIBK), acetone,
N-methyl pyrrolidone (NMP), dichloromethane and
tetrachloroethylene. The still more preferable ones are water,
lower alcohols (e.g., methanol and ethanol), a mixture of water and
lower alcohol (e.g., methanol and ethanol) and toluene. The solvent
is not limited, and can be selected, as required, for a specific
purpose of the polymerization process. These solvents may be used
either individually or in combination.
[0163] The hardening type reactive particles are produced by mixing
and reacting, under heating, a thermoplastic resin particle having
a group reactive with carbodiimide group (e.g., hydroxyl, amino,
carboxyl or thiol group) with a carbodiimide resin in the presence
of water or an organic solvent which dissolves the carbodiimide
resin but not the particle. The hardening type reactive particles
show performance effects of improved resistance to heat and
solvents as the crosslinked particles, and excellent glueability
and adhesion as the reactive particles.
[0164] Therefore, the thermoplastic resin can be hardened, have
reacted carbodiimide group inside and on the surface, and hence
have improved glueability and adhesion to another substance.
Moreover, use of water-soluble poly carbodiimide improves
dispersibility of the particles, and allows a dye or pigment having
a reactive group to react with the carbodiimide to produce the fast
color.
[0165] The hardening type reactive particles, keeping the above
performances and being reactive crosslinked particles, can go into
various areas, e.g., crosslinking agent, stabilizer for improving
hydrolysis resistance, hardening agent for thermoplastic resins,
adhesive agent, coating agent, paint, reinforcing material and aid
for automobile and electric/electronic industries, and furniture
and building materials. They are also applicable to spacers for
liquid crystals, or the like.
[0166] In the process for producing the hardening type reactive
particles, the carbodiimide resin can be bonded directly and simply
to the spherical particles synthesized by emulsion, suspension or
dispersion polymerization, or the like. Therefore, the resultant
particles can be also used as those of core/shell structure.
Moreover, they can be hardened with the carbodiimide resin
solution, allowing the unreacted, residual carbodiimide resin to be
reused repeatedly. These features make the process more
economically advantageous.
EXAMPLES
[0167] The present invention is described in more detail by
EXAMPLES and COMPARATIVE EXAMPLES, which by no means limit the
present invention, wherein "part(s)" and "water" mean part(s) by
weight and distilled water, respectively, unless otherwise
stated.
[0168] [Synthesis of Carbodiimide Compound]
[0169] Synthesis of the carbodiimide Compounds for the present
invention is described before EXAMPLES and COMPARATIVE
EXAMPLES.
Synthesis Example 1
[0170] 1200 g of 4,4'-dicyclohexylmethane diisocyanate (hereinafter
sometimes referred to as HMDI) was reacted with 6 g of a
carbodiimidation catalyst (3-methyl-1-phenyl-2-phopholene-1-oxide,
which was used as the carbodiimidation catalyst in all SYNTHESIS
EXAMPLES) at 180.degree. C. for 21 hours, to produce 1027.3 g of
4.4'-dicyclohexylmethane carbodiimide resin with isocyanate group
at the terminal (degree of polymerization: 6). Then, toluene was
added to the above product, to produce the carbodiimide resin
solution (resin concentration: 50% by weight). It contained the
carbodiimide at 262 equivalents.
Synthesis Example 2
[0171] 1000 g of 4,4'-dicyclohexylmethane diisocyanate (HMDI) was
reacted with 106 g of cyclohexyl isocyanate in the presence of 11.1
g of the carbodiimidation catalyst at 180.degree. C. for 36 hours,
to produce 919.4 g of the carbodiimide resin with cyclohexyl group
at the terminal (degree of polymerization: 10). Then, toluene was
added to the above product, to produce the carbodiimide resin
solution (resin concentration: 50% by weight). It contained the
carbodiimide at 217 equivalents.
Synthesis Example 3
[0172] 1200 g of m-tetramethylxylylene diisocyanate (hereinafter
sometimes referred to as TMXDI) was reacted with 24 g of the
carbodiimidation catalyst at 180.degree. C. for 26 hours, to
produce 1003.3 g of m-tetramethylxylylene carbodiimide with
isocyanate group at the terminal (degree of polymerization: 10).
Then, toluene was added to the above product, to produce the
carbodiumide resin solution (resin concentration: 50% by weight).
It contained the carbodiimide at 224 equivalents.
Synthesis Example 4
[0173] 1300 g of m-tetramethylxylylene diisocyanate (TMXDI) was
reacted with 26 g of the carbodiimidation catalyst at 180.degree.
C. for 40 hours, to produce 1068.5 g of m-tetramethylxylylene
carbodiimide with isocyanate group at the terminal (degree of
polymerization: 80). Then, toluene was added to the above product,
to produce the carbodiimide resin solution (resin concentration:
50% by weight). It contained the carbodiimide at 203
equivalents.
Synthesis Example 5
[0174] 1200 g of 2,6-tolylene diisocyanate (TDI) was reacted with
55.2 g of methanol at 50.degree. C. for 1 hour, and then in the
presence of 12 g of the carbodiimidation catalyst at 85.degree. C.
for 6 hours in 989.7 g of toluene, to produce the carbodiimide
resin with methyl group at the terminal (degree of polymerization:
7) in the solution (resin concentration: 50% by weight). It
contained the carbodiimide at 164 equivalents.
Synthesis Example 6
[0175] 1000 g of 4,4'-diphenylmethane diisocyanate (hereinafter
referred to as MDI) was reacted with 238 g of phenyl isocyanate in
the presence of 2.5 g of the carbodiimidation catalyst at
70.degree. C. for 5 hours in 1018 g of toluene, to produce the
carbodiimide resin (degree of polymerization: 5) in the solution
(resin concentration: 50% by weight). It contained the carbodiimide
at 204 equivalents.
[0176] [Synthesis of Water-Soluble Carbodiimide Compound]
Synthesis Example 7
[0177] 800 g of 4,4'-dicyclohexylmethane diisocyanate (HMDI) was
reacted with 4 g of a carbodiimidation catalyst at 180.degree. C.
for 21 hours, to produce 4.4'-dicyclohexylmethane carbodiimide
resin with isocyanate group at the terminal (degree of
polymerization: 6). Next, 684.8 g of the carbodiimide resin was
reacted with 488.5 g of polyoxyethylene monomethyl ether having a
degree of polymerization m of 12 at 140.degree. C. for 6 hours.
Then, 782.2 g of distilled water was slowly added to the reaction
effluent, to produce the light, yellowish, transparent carbodiimide
resin solution (resin concentration: 60% by weight). It contained
the carbodiimide at 448 equivalents.
Synthesis Example 8
[0178] 800 g of m-tetramethylxylylene diisocyanate (TMXDI) was
reacted with 16 g of the carbodiimidation catalyst at 180.degree.
C. for 20 hours, to produce m-tetramethylxylylene carbodiimide
resin with isocyanate group at the terminal (degree of
polymerization: 5). Next, 679.8 g of the resultant carbodiimide
resin was reacted with 177.1 g of sodium hydroxypropanesulfonate at
100.degree. C. for 24 hours. Then, 571.3 g of distilled water was
slowly added to the reaction effluent, to produce the yellowish
brown, transparent carbodiimide resin solution (resin
concentration: 60% by weight). It contained the carbodiimide at 314
equivalents.
Synthesis Example 9
[0179] 800 g of m-tetramethylxylylene diisocyanate (TMXDI) was
reacted with 16 g of the carbodiimidation catalyst at 180.degree.
C. for 26 hours, to produce m-tetramethylxylylene carbodiimide
resin with isocyanate group at the terminal (degree of
polymerization: 10). Next, 668.9 g of the resultant carbodiimide
resin was reacted with 333.9 g of polyoxyethylene monomethyl ether
at 140.degree. C. for 6 hours. Then, 668.5 g of distilled water was
slowly added to the reaction effluent, to produce the yellowish
brown, transparent carbodiimide resin solution (resin
concentration: 60% by weight). It contained the carbodiimide at 336
equivalents.
Synthesis Example 10
[0180] 800 g of 2,6-tolylene diisocyanate (TDI) was reacted
preliminarily with 441.4 g of polyoxyethylene monomethyl ether
(degree of polymerization (m): 8) at 50.degree. C. for 1 hour, and
then in the presence of the presence of 8 g of the carbodiimidation
catalyst at 85.degree. C. for 6 hours, to produce the carbodiimide
resin with the sealed terminals (degree of polymerization: 7).
Then, 709.6 g of distilled water was slowly added to the reaction
effluent, to produce the lightly yellowish, transparent
carbodiimide resin solution (resin concentration: 60% by weight).
It contained the carbodiimide at 265 equivalents.
Synthesis Example 11
[0181] 700 g of 2,6-tolylene diisocyanate (TDI) was reacted
preliminarily with 418.4 g of polyoxyethylene monomethyl ether
(degree of polymerization m: 4) at 50.degree. C. for 1 hour, and
then in the presence of the presence of 7 g of the carbodiimidation
catalyst at 85.degree. C. for 6 hours, to produce the carbodiimide
resin with the sealed terminals (degree of polymerization: 3).
Then, 657.1 g of distilled water was slowly added to the reaction
effluent, to produce the lightly yellowish, transparent
carbodiimide resin solution (resin concentration: 60% by weight).
It contained the carbodiimide at 327 equivalents. The carbodiimide
compounds prepared in SYNTHESIS EXAMPLES are summarized in Table
1.
1TABLE 1 Degree of Carbodiimide polymerization SYNTHESIS
Diisocyanate as the of the Starting material for NCN EXAMPLES
starting compound carbodiimide terminal sealing segment equivalents
Solvent SYNTHESIS HMDI 6 Not used (isocyanate) 262 Toluene EXAMPLE
1 SYNTHESIS HMDI 10 Cyclohexyl isocyanate 217 Toluene EXAMPLE 2
SYNTHESIS TMXDI 10 Not used (isocyanate) 224 Toluene EXAMPLE 3
SYNTHESIS TMXDI 80 Not used (isocyanate) 203 Toluene EXAMPLE 4
SYNTHESIS TDI 7 Methanol 164 Toluene EXAMPLE 5 SYNTHESIS MDI 5
Phenyl isocyanate 204 Toluene EXAMPLE 6 SYNTHESIS HMDI 6
Polyoxyethylene 448 Water EXAMPLE 7 monomethyl ether SYNTHESIS
TMXDI 5 Sodium 314 Water EXAMPLE 8 hydroxypropanesulfonate
SYNTHESIS TMXDI 10 Polyoxyethylene 336 Water EXAMPLE 9 monomethyl
ether SYNTHESIS TDI 7 Polyoxyethylene 265 Water EXAMPLE 10
monomethyl ether SYNTHESIS TDI 3 Polyoxyethylene 327 Water EXAMPLE
11 monomethyl ether
[0182] [Particle Example 1, Prepared on a Trial Basis]
Comparative Example 1
[0183] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 18 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C.
2 Styrene 60.0 parts Methacrylic acid 40.0 parts Methanol 100.0
parts Azobis-2-methylbutylonitrile (ABNE) 1.0 part
[0184] The resultant reactive polymer solution was left to cool and
collected on a stainless tray. It was then dried at 60.degree. C.
for around 24 hours in a drier, to produce the resin containing
carboxyl group. It was crushed and classified by known machines
into the particles.
[0185] These particles had a volume-average particle diameter of 41
.mu.m, determined by a particle size distribution analyzer
(Nikkiso's Microtrack 9320HRA). They had the smallest particle
diameter of 0.1 .mu.m and largest particle diameter of 78 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 1 particles.
[0186] [Particle Example 2, Prepared on a Trial Basis]
Comparative Example 2
[0187] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 18 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C.
3 Styrene 50.0 parts Acrylic acid 50.0 parts Methanol 100.0 parts
Azobis-isobutylonitrile (AIBN) 3.0 parts
[0188] The resultant reactive polymer solution was left to cool and
collected on a stainless tray. It was then dried at 60.degree. C.
for around 24 hours in a drier, to produce the resin containing
carboxyl group. It was crushed and classified by known machines
into the particles.
[0189] These particles had a volume-average particle diameter of
164 .mu.m, determined by a particle size distribution analyzer
(Nikkiso's Microtrack 9320HRA). They had the smallest particle
diameter of 6.5 .mu.m and largest particle diameter of 1020 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 2 particles.
[0190] [Particle Example 3, Prepared on a Trial Basis]
Comparative Example 3
[0191] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 18 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C.
4 Methyl methacrylate 50.0 parts Acrylic acid 50.0 parts Methanol
100.0 parts Azobis-isobutylonitrile (AIBN) 4.0 parts
[0192] The resultant reactive polymer solution was left to cool and
collected on a stainless tray. It was then dried at 60.degree. C.
for around 24 hours in a drier, to produce the resin containing
carboxyl group. It was crushed and classified by known machines
into the particles.
[0193] These particles had a volume-average particle diameter of
282 .mu.m, determined by a particle size distribution analyzer
(Nikkiso's Microtrack 9320HRA). They had the smallest particle
diameter of 95 .mu.m and largest particle diameter of 710 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 3 particles.
[0194] [Particle Example 4, Prepared on a Trial Basis]
Comparative Example 4
[0195] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 18 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C.
5 Styrene 30.0 parts Acrylic acid 70.0 parts Methanol 100.0 parts
Azobis-isobutylonitrile (AIBN) 2.0 parts
[0196] The resultant reactive polymer solution was left to cool and
collected on a stainless tray. It was then dried at 60.degree. C.
for around 24 hours in a drier, to produce the resin containing
carboxyl group. It was crushed and classified by known machines
into the particles.
[0197] These particles had a volume-average particle diameter of 73
.mu.m, determined by a particle size distribution analyzer
(Nikkiso's Microtrack 9320HRA). They had the smallest particle
diameter of 61 .mu.m and largest particle diameter of 211 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 4 particles.
[0198] [Particle Example 5, Prepared on a Trial Basis]
Comparative Example 5
[0199] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 18 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C.
6 Acrylic acid 100.0 parts Methanol 100.0 parts
Azobis-isobutylonitrile (AIBN) 3.0 parts
[0200] The resultant reactive polymer solution was left to cool and
collected on a stainless tray. It was then dried at 60.degree. C.
for around 24 hours in a drier, to produce the resin containing
carboxyl group. It was crushed and classified by known machines
into the particles.
[0201] These particles had a volume-average particle diameter of 24
.mu.m, determined by a particle size distribution analyzer
(Nikkiso's MICROTRACK 9320HRA). They had the smallest particle
diameter of 1.1 .mu.m and largest particle diameter of 65 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 5 particles.
[0202] [Particle Example 6, Prepared on a Trial Basis]
Comparative Example 6
[0203] Coarse particles of polyvinyl alcohol (Kuraray's PVA-210,
partly saponified, 88% by mol) were crushed and classified by known
machines into the fine particles.
[0204] These particles had a volume-average particle diameter of 48
.mu.m, determined by a particle size distribution analyzer
(Nikkiso's MICROTRACK 9320HRA). They had the smallest particle
diameter of 1.2 .mu.m and largest particle diameter of 103 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 6 particles.
[0205] [Particle Example 7, Prepared on a Trial Basis]
Comparative Example 7
[0206] Coarse particles of polyvinyl alcohol (Kuraray's PVA-117,
totally saponified) were crushed and classified by known machines
into the fine particles.
[0207] These particles had a volume-average particle diameter of 21
.mu.m, determined by a particle size distribution analyzer
(Nikkiso's MICROTRACK 9320HRA). They had the smallest particle
diameter of 1.2 .mu.m and largest particle diameter of 74 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 7 particles.
[0208] [Particle Example 8, Prepared on a Trial Basis]
Comparative Example 8
[0209] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 18 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C.
7 Styrene 90.0 parts Acrylic acid 10.0 parts THF 100.0 parts
Azobis-isobutylonitrile (AIBN) 2.0 parts
[0210] The resultant reactive polymer solution was left to cool and
collected on a stainless tray. It was then dried at 60.degree. C.
for around 24 hours in a drier, to produce the resin containing
carboxyl group. It was crushed and classified by known machines
into the particles.
[0211] These particles had a volume-average particle diameter of 71
.mu.m, determined by a particle size distribution analyzer
(Nikkiso's MICROTRACK 9320HRA). They had the smallest particle
diameter of 4.2 .mu.m and largest particle diameter of 229 .mu.m,
determined by SEM analysis. These particles were named COMPARATIVE
EXAMPLE 8 particles.
[0212] These PARTICLE EXAMPLES 1 to 8, prepared on a trial basis,
are summarized in Table 2.
8 TABLE 2 Functional Equivalents group of the in the functional
particle group Starting compounds used PARTICLE Carboxyl 215/COOH
Styrene and methacrylic acid EXAMPLE 1 PARTICLE Carboxyl 144/COOH
Styrene and acrylic acid EXAMPLE 2 PARTICLE Carboxyl 144/COOH
Methyl methacrylate and EXAMPLE 3 acrylic acid PARTICLE Carboxyl
103/COOH Styrene and acrylic acid EXAMPLE 4 PARTICLE Carboxyl
72/COOH Acrylic acid EXAMPLE 5 PARTICLE Hydroxyl 56/OH PVA EXAMPLE
6 PARTICLE Hydroxyl 44/OH PVA EXAMPLE 7 PARTICLE Carboxyl 720/COOH
Styrene and acrylic acid EXAMPLE 8
Example 1
[0213] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
9 PARTICLE EXAMPLE 1, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 78.0 parts SYNTHESIS
EXAMPLE 1 Toluene 52.0 parts
[0214] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 2
[0215] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
55.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
10 PARTICLE EXAMPLE 1, prepared on a trial basis 7.0 parts
Carbodiimide resin solution prepared in 56.0 parts SYNTHESIS
EXAMPLE 2 Toluene 84.0 parts
[0216] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 3
[0217] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
11 PARTICLE EXAMPLE 1, prepared on a trial basis 10.0 parts
Carbodiimide resin solution prepared in 84.0 parts SYNTHESIS
EXAMPLE 3 Toluene 56.0 parts
[0218] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 4
[0219] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
65.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
12 PARTICLE EXAMPLE 1, prepared on a trial basis 10.0 parts
Carbodiimide resin solution prepared in 56.0 parts SYNTHESIS
EXAMPLE 4 Toluene 84.0 parts
[0220] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 5
[0221] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
45.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
13 PARTICLE EXAMPLE 1, prepared on a trial basis 10.0 parts
Carbodiimide resin solution prepared in 60.0 parts SYNTHESIS
EXAMPLE 5 Toluene 90.0 parts
[0222] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 6
[0223] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
14 PARTICLE EXAMPLE 1, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 60.0 parts SYNTHESIS
EXAMPLE 6 Toluene 90.0 parts
[0224] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 7
[0225] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
15 PARTICLE EXAMPLE 1, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 28.0 parts SYNTHESIS
EXAMPLE 7 Methanol 77.0 parts Water 66.0 parts
[0226] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiumide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 8
[0227] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
55.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
16 PARTICLE EXAMPLE 1, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 48.0 parts SYNTHESIS
EXAMPLE 8 Methanol 58.0 parts Water 39.0 parts
[0228] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 9
[0229] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
17 PARTICLE EXAMPLE 1, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 52.0 parts SYNTHESIS
EXAMPLE 9 Methanol 62.0 parts Water 41.0 parts
[0230] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 10
[0231] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
40.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
18 PARTICLE EXAMPLE 1, prepared on a trial basis 7.0 parts
Carbodiimide resin solution prepared in 43.0 parts SYNTHESIS
EXAMPLE 10 Methanol 52.0 parts Water 35.0 parts
[0232] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 11
[0233] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
35.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
19 PARTICLE EXAMPLE 1, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 62.0 parts SYNTHESIS
EXAMPLE 11 Methanol 43.0 parts Water 18.0 parts
[0234] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 12
[0235] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
20 PARTICLE EXAMPLE 2, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 72.0 parts SYNTHESIS
EXAMPLE 1 Toluene 48.0 parts
[0236] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 13
[0237] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
21 PARTICLE EXAMPLE 2, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 76.0 parts SYNTHESIS
EXAMPLE 2 Toluene 114.0 parts
[0238] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 14
[0239] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
55.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
22 PARTICLE EXAMPLE 2, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 78.0 parts SYNTHESIS
EXAMPLE 3 Toluene 52.0 parts
[0240] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 15
[0241] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
65.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
23 PARTICLE EXAMPLE 2, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 46.0 parts SYNTHESIS
EXAMPLE 4 Toluene 69.0 parts
[0242] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 16
[0243] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
40.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
24 PARTICLE EXAMPLE 2, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 54.0 parts SYNTHESIS
EXAMPLE 5 Toluene 81.0 parts
[0244] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 17
[0245] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
45.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
25 PARTICLE EXAMPLE 2, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 46.0 parts SYNTHESIS
EXAMPLE 6 Toluene 69.0 parts
[0246] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 18
[0247] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
55.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
26 PARTICLE EXAMPLE 2, prepared on a trial basis 3.0 parts
Carbodiimide resin solution prepared in 32.0 parts SYNTHESIS
EXAMPLE 7 Water 158.0 parts
[0248] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiumide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 19
[0249] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
27 PARTICLE EXAMPLE 2, prepared on a trial basis 3.0 parts
Carbodiimide resin solution prepared in 43.0 parts SYNTHESIS
EXAMPLE 8 Water 87.0 parts
[0250] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 20
[0251] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
65.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
28 PARTICLE EXAMPLE 2, prepared on a trial basis 3.0 parts
Carbodiimide resin solution prepared in 58.0 parts SYNTHESIS
EXAMPLE 9 Water 117.0 parts
[0252] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 21
[0253] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
30.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
29 PARTICLE EXAMPLE 2, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 62.0 parts SYNTHESIS
EXAMPLE 10 Water 61.0 parts
[0254] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 22
[0255] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
25.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
30 PARTICLE EXAMPLE 2, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 95.0 parts SYNTHESIS
EXAMPLE 11 Water 48.0 parts
[0256] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 23
[0257] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
31 PARTICLE EXAMPLE 3, prepared on a trial basis 4.0 parts
Carbodiimide resin solution prepared in 72.0 parts SYNTHESIS
EXAMPLE 1 Toluene 48.0 parts
[0258] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 24
[0259] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
32 PARTICLE EXAMPLE 3, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 84.0 parts SYNTHESIS
EXAMPLE 4 Toluene 56.0 parts
[0260] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 25
[0261] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
33 PARTICLE EXAMPLE 3, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 70.0 parts SYNTHESIS
EXAMPLE 6 Toluene 105.0 parts
[0262] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 26
[0263] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
45.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
34 PARTICLE EXAMPLE 3, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 52.0 parts SYNTHESIS
EXAMPLE 7 Water 103.0 parts
[0264] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 27
[0265] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
20.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
35 PARTICLE EXAMPLE 3, prepared on a trial basis 5.0 parts
Carbodiimide resin solution prepared in 62.0 parts SYNTHESIS
EXAMPLE 10 Water 61.0 parts
[0266] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 28
[0267] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
36 PARTICLE EXAMPLE 4, prepared on a trial basis 3.0 parts
Carbodiimide resin solution prepared in 122.0 parts SYNTHESIS
EXAMPLE 1 Toluene 81.0 parts
[0268] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 29
[0269] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
65.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
37 PARTICLE EXAMPLE 4, prepared on a trial basis 4.0 parts
Carbodiimide resin solution prepared in 78.0 parts SYNTHESIS
EXAMPLE 4 Toluene 52.0 parts
[0270] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 30
[0271] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
38 PARTICLE EXAMPLE 4, prepared on a trial basis 4.0 parts
Carbodiimide resin solution prepared in 80.0 parts SYNTHESIS
EXAMPLE 6 Toluene 120.0 parts
[0272] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 31
[0273] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
39 PARTICLE EXAMPLE 4, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 72.0 parts SYNTHESIS
EXAMPLE 7 Water 143.0 parts
[0274] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 32
[0275] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
40.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
40 PARTICLE EXAMPLE 4, prepared on a trial basis 4.0 parts
Carbodiimide resin solution prepared in 85.0 parts SYNTHESIS
EXAMPLE 10 Water 85.0 parts
[0276] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 33
[0277] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
55.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
41 PARTICLE EXAMPLE 5, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 84.0 parts SYNTHESIS
EXAMPLE 2 Toluene 126.0 parts
[0278] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 34
[0279] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
65.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
42 PARTICLE EXAMPLE 5, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 124.0 parts SYNTHESIS
EXAMPLE 3 Toluene 83.0 parts
[0280] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 35
[0281] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
43 PARTICLE EXAMPLE 5, prepared on a trial basis 3.0 parts
Carbodiimide resin solution prepared in 109.0 parts SYNTHESIS
EXAMPLE 5 Toluene 73.0 parts
[0282] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 36
[0283] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
44 PAETICLE EXAMPLE 5, prepared on a trial basis 2.0 parts
Cafbodiimide resin solution prepared in 68.0 parts SYNTHESIS
EXAMPLE 6 Toluene 102.0 parts
[0284] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed an absorption
band peak assigned to carbodiimide group at a wavelength of around
2150 (1/cm), determined by a Fourier transform infrared
spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Example 37
[0285] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
105.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
45 PARTICLE EXAMPLE 6, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 112.0 parts SYNTHESIS
EXAMPLE 1 Toluene 75.0 parts
[0286] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 38
[0287] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
110.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
46 PARTICLE EXAMPLE 6, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 128.0 parts SYNTHESIS
EXAMPLE 3 Toluene 85.0 parts
[0288] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 39
[0289] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
100.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
47 PARTICLE EXAMPLE 6, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 94.0 parts SYNTHESIS
EXAMPLE 5 Toluene 63.0 parts
[0290] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 40
[0291] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
100.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
48 PARTICLE EXAMPLE 7, prepared on a trial basis 3.0 parts
Carbodiimide resin solution prepared in 134.0 parts SYNTHESIS
EXAMPLE 5 Toluene 89.0 parts
[0292] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Example 41
[0293] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
95.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
49 PARTICLE EXAMPLE 7, prepared on a trial basis 2.0 parts
Carbodiimide resin solution prepared in 112.0 parts SYNTHESIS
EXAMPLE 6 Toluene 112.0 parts
[0294] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
These particles showed an absorption band peak assigned to
carbodiimide group at a wavelength of around 2150 (1/cm),
determined by a Fourier transform infrared spectrometer (Shimadzu
Corp.'s FT-IR8200PC).
Comparative Example 9
[0295] A 300 mL flask was charged with the mixture of the following
composition all at once. However, PARTICLE EXAMPLE 8 was dissolved
in toluene.
50 PARTICLE EXAMPLE 8, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 30.0 parts SYNTHESIS
EXAMPLE 1 Toluene 120.0 parts
Comparative Example 10
[0296] A 300 mL flask was charged with the mixture of the following
composition all at once. However, PARTICLE EXAMPLE 8 was dissolved
in toluene.
51 PARTICLE EXAMPLE 8, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 24.0 parts SYNTHESIS
EXAMPLE 2 Toluene 96.0 parts
Comparative Example 11
[0297] A 300 mL flask was charged with the mixture of the following
composition all at once. However, PARTICLE EXAMPLE 8 was dissolved
in toluene.
52 PARTICLE EXAMPLE 8, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 24.0 parts SYNTHESIS
EXAMPLE 3 Toluene 96.0 parts
Comparative Example 12
[0298] A 300 mL flask was charged with the mixture of the following
composition all at once. However, PARTICLE EXAMPLE 8 was dissolved
in toluene.
53 PARTICLE EXAMPLE 8, prepared on a trial basis 10.0 parts
Carbodiimide resin solution prepared in 22.0 parts SYNTHESIS
EXAMPLE 4 Toluene 88.0 parts
Comparative Example 13
[0299] A 300 mL flask was charged with the mixture of the following
composition all at once. However, PARTICLE EXAMPLE 8 was dissolved
in toluene.
54 PARTICLE EXAMPLE 8, prepared on a trial basis 10.0 parts
Carbodiimide resin solution prepared in 22.0 parts SYNTHESIS
EXAMPLE 5 Toluene 88.0 parts
Comparative Example 14
[0300] A 300 mL flask was charged with the mixture of the following
composition all at once. However, PARTICLE EXAMPLE 8 was dissolved
in toluene.
55 PARTICLE EXAMPLE 8, prepared on a trial basis 10.0 parts
Carbodiimide resin solution prepared in 22.0 parts SYNTHESIS
EXAMPLE 6 Toluene 88.0 parts
Comparative Example 15
[0301] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
56 PARTICLE EXAMPLE 8, prepared on a trial basis 6.0 parts
Carbodiimide resin solution prepared in 25.0 parts SYNTHESIS
EXAMPLE 7 Methanol 95.0 parts Water 31.0 parts
[0302] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed a trace quantity
of absorption band peak assigned to carbodiimide group at a
wavelength of around 2150 (1/cm), determined by a Fourier transform
infrared spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Comparative Example 16
[0303] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
57 PARTICLE EXAMPLE 8, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 23.0 parts SYNTHESIS
EXAMPLE 8 Methanol 88.0 parts Water 29.0 parts
[0304] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed a trace quantity
of absorption band peak assigned to carbodiimide group at a
wavelength of around 2150 (1/cm), determined by a Fourier transform
infrared spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Comparative Example 17
[0305] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
65.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
58 PARTICLE EXAMPLE 8, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 25.0 parts SYNTHESIS
EXAMPLE 9 Methanol 95.0 parts Water 31.0 parts
[0306] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed a trace quantity
of absorption band peak assigned to carbodiimide group at a
wavelength of around 2150 (1/cm), determined by a Fourier transform
infrared spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Comparative Example 18
[0307] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
35.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
59 PARTICLE EXAMPLE 8, prepared on a trial basis 10.0 parts
Carbodiimide resin solution prepared in 25.0 parts SYNTHESIS
EXAMPLE 10 Methanol 95.0 parts Water 31.0 parts
[0308] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed a trace quantity
of absorption band peak assigned to carbodiimide group at a
wavelength of around 2150 (1/cm), determined by a Fourier transform
infrared spectrometer (Shimadzu Corp.'s FT-IR8200PC).
Comparative Example 19
[0309] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
30.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
60 PARTICLE EXAMPLE 8, prepared on a trial basis 8.0 parts
Carbodiimide resin solution prepared in 25.0 parts SYNTHESIS
EXAMPLE 11 Methanol 95.0 parts Water 31.0 parts
[0310] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles. These particles showed a trace quantity
of absorption band peak assigned to carbodiimide group at a
wavelength of around 2150 (1/cm), determined by a Fourier transform
infrared spectrometer (Shimadzu Corp.'s FT-IR8200PC).
[0311] EXAMPLES 1 to 41 are summarized in Table 3, and COMPARATIVE
EXAMPLES 1 to 19 in Table 4.
61TABLE 3 Content of Solution concentration carbodiimide (% by
weight) Starting diisocyanate (equivalents), Reaction (Total
solution - compound for (NCN/functional temperature Solvent)/Total
solution .times. EXAMPLES carbodiimidation group) (.degree. C.)
Solvents 100 1 HMDI 4 50 Toluene 34.1 2 HMDI 4 55 Toluene 23.8 3
TMXDI 4 60 Toluene 34.7 4 TMXDI 3 65 Toluene 25.3 5 TDI 4 45
Toluene 25.0 6 MDI 4 50 Toluene 24.1 7 HMDI 4 50 Water/methanol, 11
mixture 8 TMXDI 4 55 Water/methanol, 22.7 mixture 9 TMXDI 4 60
Water/methanol, 22.5 mixture 10 TDI 3 40 Water/methanol, 24.1
mixture 11 TDI 3 35 Water/methanol, 34.4 mixture 12 HMDI 4 50
Toluene 32.8 13 HMDI 5 60 Toluene 22.1 14 TMXDI 5 55 Toluene 32.6
15 TMXDI 2 65 Toluene 25.2 16 TDI 3 40 Toluene 24.5 17 MDI 2 45
Toluene 25.2 18 HMDI 2 55 Water 11.4 19 TMXDI 4 60 Water 21.8 20
TMXDI 5 65 Water 21.3 21 TDI 4 30 Water 32.8 22 TDI 5 25 Water 41.9
23 HMDI 5 60 Toluene 32.3 24 TMXDI 6 70 Toluene 32.4 25 MDI 5 50
Toluene 22.2 26 HMDI 5 45 Water 21 27 TDI 4 20 Water 32.8 28 HMDI 8
60 Toluene 31.1 29 TMXDI 5 65 Toluene 32.1 30 MDI 5 50 Toluene 21.6
31 HMDI 5 50 Water 20.7 32 TDI 5 40 Water 31.6 33 HMDI 7 55 Toluene
20.8 34 TMXDI 10 65 Toluene 30.6 35 TDI 8 50 Toluene 31.1 36 MDI 6
50 Toluene 20.9 37 HMDI 6 105 Toluene 30.7 38 TMXDI 8 110 Toluene
30.7 39 TDI 6 100 Toluene 30.8 40 TDI 6 100 Toluene 31 41 MDI 6 95
Toluene 25.7
[0312]
62TABLE 4 Content of Solution concentration carbodiimide (% by
weight) Starting diisocyanate (equivalents), Reaction (Total
solution - COMPARATIVE compound for (NCN/functional temperature
Solvent)/Total solution .times. EXAMPLES carbodiimidation group)
(.degree. C.) Solvents 100 1 No carbodiimide was contained -- -- --
2 in the particle 3 4 5 6 7 8 9 HMDI 5 -- Toluene 14.6 10 HMDI 5
Toluene 15.6 11 TMXDI 5 Toluene 15.6 12 TMXDI 4 Toluene 17.5 13 TDI
5 Toluene 17.5 14 MDI 4 Toluene 17.5 15 HMDI 4 60 Water/methanol,
13.4 mixture 16 TMXDI 4 60 Water/methanol, 14.9 mixture 17 TMXDI 4
65 Water/methanol, 14.5 mixture 18 TDI 4 35 Water/methanol, 15.5
mixture 19 TDI 4 30 Water/methanol, 14.5 mixture
[0313] (Evaluation test 1)
[0314] A 300 mL flask was charged with 1 g of the particles
prepared in each of EXAMPLES 1 to 41 and COMPARATIVE EXAMPLES 1 to
19, water and 100 mL of an organic solvent described in Table 5 or
6. Each of the resultant was stirred at normal temperature for 30
minutes. Then, it was visually observed to confirm its resistance
to solvents, and also analyzed by an SEM (Hitachi's S-2150) to
confirm the particle shape. The evaluation results in Tables 5 and
6.
63 TABLE 5 Water Methanol Ethanol Toluene DMF Solvents Visual SEM
Visual SEM Visual SEM Visual SEM Visual SEM Test 1 observation
analysis observation analysis observation analysis observation
analysis observation analysis EXAMPLE 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 2
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 3 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 4 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 5 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 6
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 7 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 8 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 9 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 10
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 11 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 12 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 13 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 14
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 15 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 16 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 17 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 18
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 19 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 20 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 21 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 22
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 23 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 24 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 25 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 26
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 27 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 28 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 29 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 30
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 31 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 32 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 33 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 34
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 35 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 36 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 37 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 38
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 39 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 40 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 EXAMPLE 41
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 Dichloro- THF MEK NMP Acetone methane Solvents
Visual SEM Visual SEM Visual SEM Visual SEM Visual SEM Test 1
observation analysis observation analysis observation analysis
observation analysis observation analysis EXAMPLE 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 2
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 3 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 4 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 5 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 6
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 7 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 8 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 9 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 10
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 11 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 12 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 13 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 14
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 15 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 16 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 17 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 18
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 19 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 20 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 21 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 22
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 23 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 24 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 25 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 26
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 27 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 28 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 29 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 30
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 31 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 32 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 33 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 34
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 35 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 36 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 37 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 38
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 39 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 40 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 EXAMPLE 41
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle.: Dispersed .DELTA.: Partly dispersed
x: Dissolved 1: Particle retaining shape of the base particle 0:
Particle no longer retaining shape of the base particle F: Particle
dissolved before it was synthesized
[0315]
64 Water Methanol Ethanol Toluene DMF Solvents Visual SEM Visual
SEM Visual SEM Visual SEM Visual SEM Test 1 observation analysis
observation analysis observation analysis observation analysis
observation analysis COMPARATIVE .smallcircle. 1 x 0 x 0
.smallcircle. 1 x 0 EXAMPLE 1 2 .smallcircle. 1 x 0 x 0
.smallcircle. 1 x 0 3 .smallcircle. 1 x 0 x 0 .smallcircle. 1 x 0 4
.smallcircle. 1 x 0 x 0 .smallcircle. 1 x 0 5 .DELTA. 0 x 0 x 0
.smallcircle. 1 x 0 6 .DELTA. 0 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 7 * * .smallcircle. 1 .smallcircle.
1 .smallcircle. 1 .smallcircle. 1 8 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 x 0 x 0 9 F 10 F 11 F 12 F 13 F 14 F 15
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 x 0 x 0 16
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 x 0 x 0 17
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 x 0 x 0 18
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 x 0 x 0 COMPARATIVE
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 x 0 x 0 EXAMPLE 19
Dichloro- THF MEK NMP Acetone methane Solvents Visual SEM Visual
SEM Visual SEM Visual SEM Visual SEM Test 1 observation analysis
observation analysis observation analysis observation analysis
observation analysis COMPARATIVE x 0 x 0 x 0 x 0 .smallcircle. 1
EXAMPLE 1 2 x 0 x 0 x 0 x 0 .smallcircle. 1 3 x 0 x 0 x 0 x 0 x 0 4
x 0 x 0 x 0 x 0 .smallcircle. 0 5 x 0 x 0 x 0 x 0 .smallcircle. 0 6
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 7 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 8 x 0 x 0 x 0 x 0 x 0 9 F 10 F 11 F
12 F 13 F 14 F 15 x 0 x 0 x 0 x 0 x 0 16 x 0 x 0 x 0 x 0 x 0 17 x 0
x 0 x 0 x 0 x 0 18 x 0 x 0 x 0 x 0 x 0 COMPARATIVE x 0 x 0 x 0 x 0
x 0 EXAMPLE 19 .smallcircle.: Dispersed .DELTA.: Partly dispersed
x: Dissolved 1: Particle retaining shape of the base particle 0:
Particle no longer retaining shape of the base particle *: Normal
temperature .smallcircle., Elevated temperature x F: Particle
dissolved before it was synthesized
[0316] 1 g of the particles prepared in each of EXAMPLES 1 to 41
and COMPARATIVE EXAMPLES 1 to 19, put on an aluminum Petri dish,
was cured for 1 hour in a drier kept at 180.degree. C., to confirm
the residual particles on the dish. The residual particles were
analyzed by an SEM (Hitachi's S-2150) to confirm their shape. The
evaluation results are given in Table 7.
65 TABLE 7 Visual SEM Test 2 observation analysis EXAMPLE 1
.smallcircle. 2 EXAMPLE 2 .smallcircle. 2 EXAMPLE 3 .smallcircle. 2
EXAMPLE 4 .smallcircle. 2 EXAMPLE 5 .smallcircle. 2 EXAMPLE 6
.smallcircle. 2 EXAMPLE 7 .smallcircle. 2 EXAMPLE 8 .smallcircle. 2
EXAMPLE 9 .smallcircle. 2 EXAMPLE 10 .smallcircle. 2 EXAMPLE 11
.smallcircle. 2 EXAMPLE 12 .smallcircle. 2 EXAMPLE 13 .smallcircle.
2 EXAMPLE 14 .smallcircle. 2 EXAMPLE 15 .smallcircle. 2 EXAMPLE 16
.smallcircle. 2 EXAMPLE 17 .smallcircle. 2 EXAMPLE 18 .smallcircle.
2 EXAMPLE 19 .smallcircle. 2 EXAMPLE 20 .smallcircle. 2 EXAMPLE 21
.smallcircle. 2 EXAMPLE 22 .smallcircle. 2 EXAMPLE 23 .smallcircle.
2 EXAMPLE 24 .smallcircle. 2 EXAMPLE 25 .smallcircle. 2 EXAMPLE 26
.smallcircle. 2 EXAMPLE 27 .smallcircle. 2 EXAMPLE 28 .smallcircle.
2 EXAMPLE 29 .smallcircle. 2 EXAMPLE 30 .smallcircle. 2 EXAMPLE 31
.smallcircle. 2 EXAMPLE 32 .smallcircle. 2 EXAMPLE 33 .smallcircle.
2 EXAMPLE 34 .smallcircle. 2 EXAMPLE 35 .smallcircle. 2 EXAMPLE 36
.smallcircle. 2 EXAMPLE 37 .smallcircle. 2 EXAMPLE 38 .smallcircle.
2 EXAMPLE 39 .smallcircle. 2 EXAMPLE 40 .smallcircle. 2 EXAMPLE 41
.smallcircle. 2 COMPARATIVE .DELTA. 1 EXAMPLE 1 COMPARATIVE x 0
EXAMPLE 2 COMPARATIVE x 0 EXAMPLE 3 COMPARATIVE x 0 EXAMPLE 4
COMPARATIVE x 0 EXAMPLE 5 COMPARATIVE .smallcircle. 2 EXAMPLE 6
COMPARATIVE .smallcircle. 2 EXAMPLE 7 COMPARATIVE x 0 EXAMPLE 8
COMPARATIVE F EXAMPLE 9 COMPARATIVE F EXAMPLE 10 COMPARATIVE F
EXAMPLE 11 COMPARATIVE F EXAMPLE 12 COMPARATIVE F EXAMPLE 13
COMPARATIVE F EXAMPLE 14 COMPARATIVE .DELTA. 1 EXAMPLE 15
COMPARATIVE .DELTA. 1 EXAMPLE 16 COMPARATIVE .DELTA. 1 EXAMPLE 17
COMPARATIVE .DELTA. 1 EXAMPLE 18 COMPARATIVE .DELTA. 1 EXAMPLE 19
.smallcircle.: Particle retaining its shape .DELTA.: Particle
dissolved to some extent x: Particle dissolved into a plate shape
2: Particle retaining its original shape 1: Particle deformed 0:
Particle no longer retaining its particular shape F: Particle
dissolved before it was synthesized
Spherical Particle Syntheis Example 1
Comparative Example 20
[0317] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
80.degree. C., after dissolved oxygen was purged with nitrogen, to
prepare the styrene/methacrylate copolymer particle solution.
66 Styrene 48.2 parts Methacrylic acid 20.6 parts Methanol 162.0
parts Ethanol 40.5 parts Water 67.5 parts
Azobis-2-methylbutylonitrile (ABNE) 3.1 part 15% by weight of
methanol solution of PVP 8K-120) 82.0 parts
[0318] These particles had a volume-average particle diameter of
1.9 .mu.m, determined by particle size distribution analysis. They
were truly spherical, having a smallest particle diameter of 0.29
.mu.m and a largest particle diameter of 3.69 .mu.m, determined by
SEM analysis. Part of the particle solution was treated by around 3
to 5 cycles of washing with a water/methanol (3/7) mixed solution
and filtration by a vacuum filtration unit, and dried under a
vacuum to prepare the crosslinked particles. A portion of these
particles were named COMPARATIVE EXAMPLE 20 particles.
Spherical Particle Syntheis Example 2
Comparative Example 21
[0319] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
80.degree. C., after dissolved oxygen was purged with nitrogen, to
prepare the styrene/acrylate copolymer particle solution.
67 Styrene 48.2 parts Acrylic acid 20.6 parts Methanol 162.0 parts
Ethanol 54.0 parts Water 54.0 parts Azobis-2-methylbutylonitrile
(ABNE) 3.1 parts Styrene/methacrylate copolymer resin solution 60.0
parts (The styrene/methacrylate copolymer resin solution was a 40%
by weight methanol solution of styrene/2-hydroxyethyl methacrylate
(2/8).
[0320] These particles had a volume-average particle diameter of
12.9 .mu.m, determined by particle size distribution analysis. They
were truly spherical, having a smallest particle diameter of 5.9
.mu.m and a largest particle diameter of 37 .mu.m, determined by
SEM analysis. Part of the particle solution was treated by around 3
to 5 cycles of washing with a water/methanol (3/7) mixed solution
and filtration by a vacuum filtration unit, and dried under a
vacuum to prepare the crosslinked particles. A portion of these
particles were named COMPARATIVE EXAMPLE 21 particles.
Spherical Particle Syntheis Example 3
Comparative Example 22
[0321] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
70.degree. C., after dissolved oxygen was purged with nitrogen, to
prepare the styrene/methacrylate copolymer particle solution.
68 Styrene 44.7 parts Methacrylic acid 24.1 parts Methanol 94.5
parts Ethanol 87.8 parts Water 87.8 parts Azobis-isobutylonitrile
(AIBN) 8.1 parts Styrene/methacrylate copolymer resin solution 80.0
parts (The styrene/methacrylate copolymer resin solution was a 40%
by weight methanol solution of styrene/2-hydroxyethyl methacrylate
(1/9).
[0322] These particles had a volume-average particle diameter of
10.5 .mu.m, determined by particle size distribution analysis. They
were truly spherical, having a smallest particle diameter of 5.8
.mu.m and a largest particle diameter of 31 .mu.m, determined by
SEM analysis. Half of the particle solution was treated by around 3
to 5 cycles of washing with a water/methanol (3/7) mixed solution
and filtration by a vacuum filtration unit, and dried under a
vacuum to prepare the crosslinked particles. These particles were
named COMPARATIVE EXAMPLE 22 particles.
Spherical Particle Syntheis Example 4
Comparative Example 23
[0323] A 500 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
62.degree. C., after dissolved oxygen was purged with nitrogen, to
prepare the styrene/methacrylate copolymer particle solution.
69 Styrene 61.9 parts Methacrylic acid 6.9 parts Methanol 90.3
parts Azobis-isobutylonitrile (AIBN) 1.6 parts Styrene/methacrylate
copolymer resin solution 90.7 parts (The styrene/methacrylate
copolymer resin solution was a 40% by weight methanol solution of
styrene/2-hydroxyethyl methacrylate (1/9).
[0324] These particles had a volume-average particle diameter of
7.6 .mu.m, determined by particle size distribution analysis. They
were truly spherical, having a smallest particle diameter of 3.2
.mu.m and a largest particle diameter of 13.2 .mu.m, determined by
SEM analysis. The particle solution was treated by around 3 to 5
cycles of washing with methanol and filtration by a vacuum
filtration unit, and dried under a vacuum to prepare the
crosslinked particles. These particles were named COMPARATIVE
EXAMPLE 23 particles.
[0325] SYNTHESIS EXAMPLES 1 to 4 to prepare the spherical particles
are summarized in Table 8.
70 TABLE 8 Functional group in the Equivalents of the Starting
compounds particle functional group used SPHERICAL Carboxyl
287/COOH Styrene and PARTICLE methacrytic acid EXAMPLE 1 SPHERICAL
Carboxyl 240/COOH Styrene and acrylic PARTICLE acid EXAMPLE 2
SPHERICAL Carboxyl 246/COOH Styrene and PARTICLE methacrylic acid
EXAMPLE 3 SPHERICAL Carboxyl 860/COOH Styrene and PARTICLE
methacrylic acid EXAMPLE 4
Example 42
[0326] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
40.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
71 Particles prepared in SPHERICAL PARTICLE 5.0 parts SYNTHEISIS
EXAMPLE 1 Carbodiimide resin solution prepared in 65.0 parts
SYNTHESIS EXAMPLE 7 Methanol 109.2 parts Water 20.8 parts
[0327] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
Example 43
[0328] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
25.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
72 Particles prepared in SPHERICAL PARTICLE 8.0 parts SYNTHEISIS
EXAMPLE 1 Carbodiimide resin solution prepared in 37.0 parts
SYNTHESIS EXAMPLE 10 Methanol 62.2 parts Water 11.8 parts
[0329] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
Example 44
[0330] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
45.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
73 Particle solution prepared in SPHERICAL PARTICLE 30.0 parts
SYNTHEISIS EXAMPLE 2 Carbodiimide resin solution prepared in 74.7
parts SYNTHESIS EXAMPLE 7 Methanol 67.2 parts Water 37.3 parts
[0331] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
Example 45
[0332] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
45.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
74 Particle solution prepared in SPHERICAL PARTICLE 30.0 parts
SYNTHEISIS EXAMPLE 2 Carbodiimide resin solution prepared in 65.5
parts SYNTHESIS EXAMPLE 8 Methanol 78.6 parts Water 52.4 parts
[0333] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
Example 46
[0334] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
75 Particles prepared in SPHERICAL PARTICLE 8.0 parts SYNTHEISIS
EXAMPLE 3 Carbodiimide resin solution prepared in 68.2 parts
SYNTHESIS EXAMPLE 1 Toluene 102.3 parts
[0335] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
Example 47
[0336] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
76 Particles prepared in SPHERICAL PARTICLE 8.0 parts SYNTHEISIS
EXAMPLE 3 Carbodiimide resin solution prepared in 58.2 parts
SYNTHESIS EXAMPLE 3 Toluene 135.8 parts
[0337] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
Example 48
[0338] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
30.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
77 Particles prepared in SPHERICAL PARTICLE 10.0 parts SYNTHEISIS
EXAMPLE 3 Carbodiimide resin solution prepared in 66.4 parts
SYNTHESIS EXAMPLE 6 Toluene 99.6 parts
[0339] Next, the solution was treated by around 3 to 5 cycles of
washing with toluene and filtration by a vacuum filtration unit,
and dried under a vacuum to prepare the crosslinked particles.
Example 49
[0340] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
60.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
78 Particle solution prepared in SPHERICAL PARTICLE 30.0 parts
SYNTHEISIS EXAMPLE 3 Carbodiimide resin solution prepared in 63.8
parts SYNTHESIS EXAMPLE 8 Methanol 76.6 parts Water 51.1 parts
[0341] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
Example 50
[0342] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
30.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
79 Particle solution prepared in SPHERICAL PARTICLE 40.0 parts
SYNTHEISIS EXAMPLE 3 Carbodiimide resin solution prepared in 57.5
parts SYNTHESIS EXAMPLE 10 Methanol 56.4 parts Water 1.2 parts
[0343] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
Comparative Example 24
[0344] A 300 mL flask was charged with the mixture of the following
composition all at once. However, the particles were dissolved.
80 Particles prepared in SPHERICAL PARTICLE 10.0 parts SYNTHEISIS
EXAMPLE 4 Carbodiimide resin solution prepared in 30.5 parts
SYNTHESIS EXAMPLE 5 Toluene 122.1 parts
Comparative Example 25
[0345] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
50.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
81 Particles prepared in SPHERICAL PARTICLE 10.0 parts SYNTHEISIS
EXAMPLE 4 Carbodiimide resin solution prepared in 43.3 parts
SYNTHESIS EXAMPLE 7 Methanol 72.8 parts Water 13.9 parts
[0346] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
Comparative Example 26
[0347] A 300 mL flask was charged with the mixture of the following
composition all at once, and heated for around 15 hours in a flow
of nitrogen with stirring by an agitator in an oil bath kept at
30.degree. C., to prepare the carbodiimide-containing, crosslinked
particle solution.
82 Particles prepared in SPHERICAL PARTICLE 10.0 parts SYNTHEISIS
EXAMPLE 4 Carbodiimide resin solution prepared in 20.6 parts
SYNTHESIS EXAMPLE 10 Methanol 77.5 parts Water 24.9 parts
[0348] Next, the solution was treated by around 3 to 5 cycles of
washing with a water/methanol (3/7) mixed solution and filtration
by a vacuum filtration unit, and dried under a vacuum to prepare
the crosslinked particles.
[0349] EXAMPLES 42 to 50 are summarized in Table 9, and COMPARATIVE
EXAMPLES 20 to 26 in Table 10.
83TABLE 9 Solution Content of concentration carbodiimide (% by
weight) Starting diisocyanate (equivalents) Reaction (Total
solution - compound for (NCN/functional temperature Solvent)/Total
EXAMPLES carbodiimidation group) (.degree. C.) Solvents solution
.times. 100 42 HMDI 5 40 Water/methanol, 22.0 mixture 43 TDI 3 25
Water/methanol, 25.4 mixture 44 HMDI 4 45 Water/methanol, 24.3
mixture 45 TMXDI 5 45 Water/methahol, 20.0 mixture 46 HMDI 4 50
Toluene 23.6 47 TMXDI 4 60 Toluene 18.4 48 MDI 4 30 Toluene 24.5 49
TMXDI 5 60 Water/methanol, 20.0 mixture 50 TDI 4 30 Water/methanol,
27.4 mixture
[0350]
84TABLE 10 Solution Content of concentration (% by carbodiimide
weight) Starting diisocyanate (equivalents) Reaction (Total
solution - COMPARATIVE compound for (NCN/functional temperature
Solvent)/Total EXAMPLES carbodiimidation group) (.degree. C.)
Solvents solution .times. 100 20 No carbodiimide was contained --
-- -- 21 in the particle 22 23 24 TDI 8 -- Toluene 15.5 25 HMDI 5
50 Water/methanol, 25.7 mixture 26 TDI 4 30 Water/methanol, 16.8
mixture
[0351] (Evaluation Test 3)
[0352] A 300 mL flask was charged with 1 g of the particles
prepared in each of EXAMPLES 42 to 50 and COMPARATIVE EXAMPLES 20
to 26, water and 100 mL of an organic solvent described in Table
11. Each of the resultant mixtures was stirred at normal
temperature for 30 minutes. Then, it was observed to confirm its
resistance to solvents, and also analyzed by an SEM (Hitachi's
S-2150) to confirm the particle shape. The evaluation results in
Table 11.
85 TABLE 11 Water Methanol Ethanol Toluene DMF Solvents Visual SEM
Visual SEM Visual SEM Visual SEM Visual SEM Test 3 observation
analysis observation analysis observation analysis observation
analysis observation analysis EXAMPLE 42 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
EXAMPLE 43 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 EXAMPLE 44 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
EXAMPLE 45 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 EXAMPLE 46 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
EXAMPLE 47 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 EXAMPLE 48 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
EXAMPLE 49 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 EXAMPLE 50 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
COMPARATIVE .smallcircle. 1 x 0 x 0 .DELTA. 0 x 0 EXAMPLE 20
COMPARATIVE .smallcircle. 1 x 0 x 0 .DELTA. 0 x 0 EXAMPLE 21
COMPARATIVE .smallcircle. 1 x 0 x 0 .smallcircle. 1 x 0 EXAMPLE 22
COMPARATIVE .smallcircle. 1 .smallcircle. 1 .smallcircle. 1 x 0 x 0
EXAMPLE 23 COMPARATIVE F EXAMPLE 24 COMPARATIVE .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 x 0 x 0 EXAMPLE 25 COMPARATIVE
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 x 0 x 0 EXAMPLE 26
Dichloro- THF MEK NMP Acetone methane Solvents Visual SEM Visual
SEM Visual SEM Visual SEM Visual SEM Test 3 observation analysis
observation analysis observation analysis observation analysis
observation analysis EXAMPLE 42 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 EXAMPLE 43
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 EXAMPLE 44 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 EXAMPLE 45
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 EXAMPLE 46 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 EXAMPLE 47
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 EXAMPLE 48 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 EXAMPLE 49
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 EXAMPLE 50 .smallcircle. 1 .smallcircle. 1
.smallcircle. 1 .smallcircle. 1 .smallcircle. 1 COMPARATIVE x 0 x 0
x 0 x 0 x 0 EXAMPLE 20 COMPARATIVE x 0 x 0 x 0 x 0 x 0 EXAMPLE 21
COMPARATIVE x 0 x 0 x 0 x 0 .DELTA. 0 EXAMPLE 22 COMPARATIVE x 0 x
0 x 0 x 0 x 0 EXAMPLE 23 COMPARATIVE F EXAMPLE 24 COMPARATIVE x 0 x
0 x 0 x 0 x 0 EXAMPLE 25 COMPARATIVE x 0 x 0 x 0 x 0 x 0 EXAMPLE 26
.smallcircle.: Dispersed .DELTA.: Partly dispersed x: Dissolved 1:
Particle retaining shape of the base particle 0: Particle no longer
retaining shape of the base particle *: Normal temperature
.smallcircle., Elevated temperature x F: Particle dissolved before
it was synthesized
[0353] (Evaluation Test 4)
[0354] 1 g of the particles prepared in each of EXAMPLES 42 to 50
and COMPARATIVE EXAMPLES 20 to 26, put on an aluminum Petri dish,
was cured for 1 hour in a drier kept at 180.degree. C., to confirm
the residual particles on the dish. The residual particles were
analyzed by an SEM (Hitachi's S-2150) to confirm their shape. The
evaluation results are given in Table 12.
86 TABLE 12 Visual SEM Test 4 observation analysis EXAMPLE 42
.smallcircle. 2 EXAMPLE 43 .smallcircle. 2 EXAMPLE 44 .smallcircle.
2 EXAMPLE 45 .smallcircle. 2 EXAMPLE 46 .smallcircle. 2 EXAMPLE 47
.smallcircle. 2 EXAMPLE 48 .smallcircle. 2 EXAMPLE 49 .smallcircle.
2 EXAMPLE 50 .smallcircle. 2 COMPARATIVE x 0 EXAMPLE 20 COMPARATIVE
x 0 EXAMPLE 21 COMPARATIVE .DELTA. 1 EXAMPLE 22 COMPARATIVE x 0
EXAMPLE 23 COMPARATIVE F EXAMPLE 24 COMPARATIVE .DELTA. 1 EXAMPLE
25 COMPARATIVE .DELTA. 1 EXAMPLE 26 .smallcircle.: Particle
retaining its shape .DELTA.: Particle dissolved to some extent x:
Particle dissolved into a plate shape 2: Particle retaining its
original shape 1: Particle deformed 0: Particle no longer retaining
its particular shape F: Particle dissolved before it was
synthesized
[0355] (Evaluation Test 5)
[0356] A 5% by weight particle solution was prepared by dissolving
0.5 g of the particles prepared, in each of EXAMPLES 1 to 50 and
COMPARATIVE EXAMPLES 1 to 26 in 9.5 g of a water/methanol (3/7)
solution. Then, a small quantity of the solution was spread on
slide glass (Corning's) coated with a silane coupling agent
containing amino group, and thermally treated for 30 minutes in a
drier kept at 150.degree. C. Next, the coated slide glass was
immersed in a THF bath (5 L) for 20 minutes, and then naturally
dried to observe the slide glass surface conditions. The slide
glass having deposits on the surface was analyzed by an SEM to
confirm the particle shape again. The evaluation results are given
in Table 13.
87 TABLE 13 Test 2 Visually observed SEM analysis deposits EXAMPLE
1 .smallcircle. Particle retaining its original shape EXAMPLE 2
.smallcircle. Particle retaining its original shape EXAMPLE 3
.smallcircle. Particle retaining its original shape EXAMPLE 4
.smallcircle. Particle retaining its original shape EXAMPLE 5
.smallcircle. Particle retaining its original shape EXAMPLE 6
.smallcircle. Particle retaining its original shape EXAMPLE 7
.smallcircle. Particle retaining its original shape EXAMPLE 8
.smallcircle. Particle retaining its original shape EXAMPLE 9
.smallcircle. Particle retaining its original shape EXAMPLE 10
.smallcircle. Particle retaining its original shape EXAMPLE 11
.smallcircle. Particle retaining its original shape EXAMPLE 12
.smallcircle. Particle retaining its original shape EXAMPLE 13
.smallcircle. Particle retaining its original shape EXAMPLE 14
.smallcircle. Particle retaining its original shape EXAMPLE 15
.smallcircle. Particle retaining its original shape EXAMPLE 16
.smallcircle. Particle retaining its original shape EXAMPLE 17
.smallcircle. Particle retaining its original shape EXAMPLE 18
.smallcircle. Particle retaining its original shape EXAMPLE 19
.smallcircle. Particle retaining its original shape EXAMPLE 20
.smallcircle. Particle retaining its original shape EXAMPLE 21
.smallcircle. Particle retaining its original shape EXAMPLE 22
.smallcircle. Particle retaining its original shape EXAMPLE 23
.smallcircle. Particle retaining its original shape EXAMPLE 24
.smallcircle. Particle retaining its original shape EXAMPLE 25
.smallcircle. Particle retaining its original shape EXAMPLE 26
.smallcircle. Particle retaining its original shape EXAMPLE 27
.smallcircle. Particle retaining its original shape EXAMPLE 28
.smallcircle. Particle retaining its original shape EXAMPLE 29
.smallcircle. Particle retaining its original shape EXAMPLE 30
.smallcircle. Particle retaining its original shape EXAMPLE 31
.smallcircle. Particle retaining its original shape EXAMPLE 32
.smallcircle. Particle retaining its original shape EXAMPLE 33
.smallcircle. Particle retaining its original shape EXAMPLE 34
.smallcircle. Particle retaining its original shape EXAMPLE 35
.smallcircle. Particle retaining its original shape EXAMPLE 36
.smallcircle. Particle retaining its original shape EXAMPLE 37
.smallcircle. Particle retaining its original shape EXAMPLE 38
.smallcircle. Particle retaining its original shape EXAMPLE 39
.smallcircle. Particle retaining its original shape EXAMPLE 40
.smallcircle. Particle retaining its original shape EXAMPLE 41
.smallcircle. Particle retaining its original shape EXAMPLE 42
.smallcircle. Spherical particle EXAMPLE 43 .smallcircle. Spherical
particle EXAMPLE 44 .smallcircle. Spherical particle EXAMPLE 45
.smallcircle. Spherical particle EXAMPLE 46 .smallcircle. Spherical
particle EXAMPLE 47 .smallcircle. Spherical particle EXAMPLE 48
.smallcircle. Spherical particle EXAMPLE 49 .smallcircle. Spherical
particle EXAMPLE 50 .smallcircle. Spherical particle COMPARATIVE x
-- EXAMPLE 1 COMPARATIVE x -- EXAMPLE 2 COMPARATIVE x -- EXAMPLE 3
COMPARATIVE x -- EXAMPLE 4 COMPARATIVE x -- EXAMPLE 5 COMPARATIVE x
-- EXAMPLE 6 COMPARATIVE x -- EXAMPLE 7 COMPARATIVE x -- EXAMPLE 8
COMPARATIVE F EXAMPLE 9 COMPARATIVE F EXAMPLE 10 COMPARATIVE F
EXAMPLE 11 COMPARATIVE F EXAMPLE 12 COMPARATIVE F EXAMPLE 13
COMPARATIVE F EXAMPLE 14 COMPARATIVE .smallcircle. Deformed
particle EXAMPLE 15 COMPARATIVE .smallcircle. Deformed particle
EXAMPLE 16 COMPARATIVE .smallcircle. Deformed particle EXAMPLE 17
COMPARATIVE .smallcircle. Deformed particle EXAMPLE 18 COMPARATIVE
.smallcircle. Deformed particle EXAMPLE 19 COMPARATIVE x -- EXAMPLE
20 COMPARATIVE x -- EXAMPLE 21 COMPARATIVE x -- EXAMPLE 22
COMPARATIVE x -- EXAMPLE 23 COMPARATIVE F EXAMPLE 24 COMPARATIVE
.smallcircle. Deformed particle EXAMPLE 25 COMPARATIVE
.smallcircle. Deformed particle EXAMPLE 26 .smallcircle.: Deposits
observed x: No deposits observed (particle dissolved) F: Particle
dissolved before it was synthesized
[0357] It is apparent from the results of EXAMPLES and COMPARATIVE
EXAMPLES (given in Tables 1 to 13) that the particles prepared in
each of EXAMPLES 1 to 50 show improved resistance to heat and
solvents as the crosslinked particles, and excellent glueability
and adhesion as the reactive particles.
[0358] On the other hand, the particles prepared in each of
COMPARATIVE EXAMPLES 1 to 19 show little effects of resistance to
heat and solvents as the crosslinked particles, and those prepared
in each of COMPARATIVE EXAMPLES 20 to 26 show little effects of
glueability and adhesion as the reactive particles.
[0359] It is apparent, based on these results, that the novel
carbodiimide-containing resin particles of the present invention
have excellent effects of resistance to heat and solvents, and
glueability and adhesion.
[0360] Advantage of the Invention
[0361] The hardening type reactive particles of the present
invention are each comprising a base particle (A) of thermoplastic
resin having a functional group and carbodiimide compound (B)
impregnated only in the surface layer section or both surface layer
section and inside of the base particle, wherein the base particle
(A) and carbodiimide compound (B) are strongly bonded to each other
by the crosslinking reaction taking place under heating between the
functional group in the former and carbodiimide group in the
latter. As such, they show excellent performances in resistance to
heat and solvents, and glueability and adhesion.
[0362] The hardening type reactive particles, keeping the above
performances and being reactive crosslinked particles, can go into
various areas, e.g., crosslinking agent, stabilizer for improving
hydrolysis resistance, hardening agent for thermoplastic resins,
adhesive agent, coating agent, paint, reinforcing material and aid
for automobile and electric/electronic industries, furniture and
building materials, and spacers for liquid crystals.
* * * * *