COMPOSITION DE TONER

TONER COMPOSITION

Abrégé français

Cette invention concerne une composition de toner qui comprend un agent formateur de couleur ainsi qu'un polymère au moins choisi dans le groupe comprenant A et B. A représente un polyesterimide non réticulé comprenant des unités ester E et des unités imide I spécifiques, tandis que B représente un polyesterimide réticulé comprenant les unités E et I ainsi que des unités de réticulation C. Cette composition possède une excellente fluidité à l'état fondu ainsi qu'une excellente capacité de fixation. Elle possède en outre d'excellentes propriétés anti-décalage et de résistance au blocage, et peut être électrifiée positivement.

Abrégé anglais

A toner composition which comprises a color former and at least one polymer
selected from the group consisting of A and B, is excellent in melt
flowability, fixability, anti-offset properties, and blocking resistance, and
can be positively electrified, wherein A is a noncross-linked polyesterimide
comprising specific ester units E and imide units I, and B is a cross-linked
polyesterimide comprising the units E and I and cross-linking units C.

Revendications

33
CLAIMS
1. A toner composition comprising a coloring agent and at least
one kind of polymer selected from the group consisting of A and B.
A : a non-crosslinked polyester imide
(i) comprising mainly an ester unit E represented by the following
formula (1) below and at least one kind of imide unit I selected from the
group consisting of units represented by the following formulas (2) and (3)
below, E and I are bonded through ester bond ;
(ii) having physical properties of
(a) a number-average molecular weight of from 2,000 to
10,000,
(b) a glass transition temperature of from 50 to 90°C and
(c) a softening temperature of from 90 to 160°C ;
(iii) satisfying the following formula (A-1)
0.01~a2/a1~0.60 (A-1)
(wherein a1 is the mol% of the ester unit E and a2 is the mol%
of the imide unit I based on the all units constituting the non-crosslinked
polyester imide A)
formula (1)
<IMG>
(wherein Ar1 is a bivalent aromatic hydrocarbon group having a
carbon number of from 6 to 12, and R1 is at least one kind of group selected
from the group consisting of an alkylene group, an oxyalkylene group and
a polyoxyalkylene group each having a carbon number of from 2 to 20)
formula (2) and (3)

34
<IMG>
<IMG>
(wherein Ar2 is a tri- or tetravalent aromatic hydrocarbon
group having a carbon number of from 6 to 12, R2 is an alkylene group
having a carbon number of from 2 to 12, and X is -CO- or -O-)
B : a crosslinked polyester imide
(iv) comprising mainly the above ester unit E, the above imide
unit I and at least one kind of crosslinking unit C selected from the group
consisting of units represented by the following formulas (4) and (5) below,
the above three units (E, I and C) are bonded together through ester bond,
(v) having physical properties of
(d) a glass transition temperature of from 50 to 90°C and
(e) a softening temperature of from 90 to 190°C,
(vi) satisfying the following formulas (B-1) and (B-2)
0.01~b2/b1~0.60 (B-1)
0.01~b3/b1~0.40 (B-2)
(wherein b1 is the mol% of the ester unit E, b2 is the mol% of
the imide unit I, and b3 is the mol% of the crosslinking unit C based on the
all units constituting the crosslinked polyester imide B).
formulas (4) and (5)
Ar3-(-CO-)r- (4)
R3-(-O-)q- (5)

35
(wherein Ar3 is an r-valent aromatic hydrocarbon group
having a carbon number of from 6 to 12, R3 is a q-valent aliphatic group
having a carbon number of from 3 to 9, and r and q are each 3 or 4)
2. A toner composition according to Claim 1, wherein the group
R1 in the above formula (1) is at least one kind of group selected from the
group consisting of an alkylene group and an oxyalkylene group each
having carbon number of from 2 to 6.
3. A toner composition according to Claim 1, wherein the group
Ar1 in the above formula (1) is at least one kind of group selected from
1,4-phenylene group and 1,3-phenylene group.
4. A toner composition according to Claim 1, wherein the group
R2 in the above formula (2) is an alkylene group having a carbon number of
from 2 to 6 and the group X is -O-.
5. A toner composition according to Claim 1, wherein the group
Ar2 in the above formula (2) is a benzene ring bonded to other atoms at 1, 2
and 4 positions which is represented by the following formula (Ar2-1).
<IMG>
6. A toner composition according to Claim 1, wherein the
non-crosslinked polyester imide A satisfies the following formula (A-2)
0.05 ~ a2/a1 ~ 0.50 (A-2)
(wherein the definitions of the terms a1 and a2 are same as
those described above).
7. A toner composition accooding to Claim 1, wherein the
crosslinking unit C is represented by the following formula (5-1)
R31-(-O-)3- (5-1)
(wherein R31 is a trivalent aliphatic group having a carbon
number of from 3 to 6).
8. A toner composition according to Claim 1, wherein the
crosslinked polyester imide B satisfies the following formulas (B-1-1) and
(B-2-1)

36
0.05 ~ b1/b1 ~ 0.50 (B-1-1)
0.03 ~ b3/b1 ~ 0.20 (B-2-1)
(wherein the definitions of the terms b1, b2 and b3 are same as
those described above).
9. A toner composition according to Claim 1, wherein the
non-crosslinked polyester imide A has a number-average molecular weight of
from 2,500 to 8,000.
10. A toner composition according to Claim 1, wherein the ratio of
the polymer in the toner composition is from 40 to 99% by weight.
11. A toner composition comprising a coloring agent and at least
one kind of polymer selected from the group consisting of A and B.
A : a non-crosslinked polyester imide
(i) comprising mainly an ester unit E represented by the following
formula (1-1) below and an imide unit I represented by the following
formula (2-1) below, E and I are bonded through ester bond;
(ii) having physical properties of
(a) a number-average molecular weight of from 2,000 to
10, 000,
(b) a glass transition temperature of from 55 to 85~C and
(c) a softening temperature of from 90 to 150~C ;
(iii) satisfying the following formula (A-2)
0.05 ~ a2/a1 ~ 0.50 (A-2)
(wherein a1 is the mol% of the ester unit E and a2 is the mol%
of the imide unit I based on the all units constituting the non-crosslinked
polyester imide A)
formula (1-1)
<IMG>
(wherein R11 is at least one kind of group selected from the
group consisting of an alkylene group and an oxyalkylene group each

37
having a carbon number of from 2 to 6)
formula (2-1)
<IMG>
(wherein R21 is an alkylene group having a carbon number of
from 2 to 5)
B : a crosslinked polyester imide
(iv) comprising mainly the above ester unit E represented by
formula (1-1), the above imide unit I represented by the formula (2-1) and
a crosslinking unit C represented by the following formula (5-1) below, the
above three units (E, I and C) are bonded through ester bond,
(v) having physical properties of
(d) a glass transition temperature of from 55 to 85~C and
(e) a softening temperature of from 110 to 160~C,
(vi) satisfying the following formulas (B-1-1) and (B-2-1)
0.05 ~ b2/b1 ~ 0.50 (B-1-1)
0.03 ~ b3/b1 ~ 0.20 (B-2-1)
(wherein b1 is the mol% of the ester unit E, b2 is the mol% of
the imide unit I, and b3 is the mol% of the crosslinking unit C based on the
all units constituting the crosslinked polyester imide B).
formula (5-1)
R31-(-O-)3- (5-1)
(wherein R31 is an aliphatic group having a carbon number of
from 3 to 6)
12. A toner composition according to Claim 11, wherein the ratio of
the above polymer in said toner composition is from 40 to 99% by weight.

38
13. A non-crosslinked polyester imide suitable for toner,
(i) comprising mainly an ester unit E represented by the
following formula (1) below and at least one kind of imide unit I selected
from the group consisting of units represented by the following formulas
(2) and (3) below, E and I are bonded through ester bond;
(ii) having physical properties of
(a) a number-average molecular weight of from 2,400 to
10, 000,
(b) a glass transition temperature of from 50 to 90~C and
(c) a softening temperature of from 90 to 160~C ;
(iii) satisfying the following formula (A-1)
0.0l ~ a2/a1 ~ 0.60 (A-1)
(wherein a1 is the mol% of the ester unit E and a2 is the mol%
of the imide unit I based on the all units constituting the non-crosslinked
polyester imide A)
formula (1)
<IMG>
(wherein Ar1 is a bivalent aromatic hydrocarbon group having
a carbon number of from 6 to 12, and R1 is at least one kind of group
selected from the group consisting of an alkylene group, an oxyalkylene
group and a polyoxyalkylene group each having a carbon number of from 2
to 20)
formula (2) and (3)
<IMG>

39
<IMG>
(wherein Ar2 is a tri- or tetravalent aromatic hydrocarbon group
having a carbon number of from 6 to 12, R2 is an alkylene group having a
carbon number of from 2 to 12, and X is -CO- or -O-)
14. A non-crosslinked polyester imide according to Claim 13,
wherein the group R1 in the above formula (1) is at least one kind of group
selected from the group consisting of an alkylene group and an
oxyalkylene group each having a carbon number of from 2 to 6 and the
group Ar1 is at least one kind of group selected from 1,4-phenylene group
and 1,3-phenylene group.
15. A non-crosslinked polyester imide according to Claim 13,
wherein the group R2 in the above formula (2) is an alkylene group having
a carbon number of from 2 to 5, X is -O- and Ar2 is a benzene ring bonded
to other atoms at 1, 2 and 4 positions which is represented by the following
formula (Ar2-1).
<IMG>
16. A non-crosslinked polyester imide suitable according to Claim
13, wherein the group R1 in the above formula (1) is at least one kind of
group selected from the group consisting of an alkylene group and an
oxyalkylene group each having a carbon number of from 2 to 6, the group
Ar1 is at least one kind of group selected from 1,4-phenylene and 1,
3-phenylene group, the group R2 in the above formula (2) is ethylene group,
X is -O- and Ar2 is a benzene ring bonded to other atoms at 1, 2 and 4
positions which is represented by the following formula (Ar2-1)
<IMG>

40
provided that the non-crosslinked polyester imide has a number-average
molecular weight of from 2,500 to 8,000, a glass transition temperature of
from 55 to 85~C and a softening temperature of from 95 to 130~C and
satisfies the following formula (A-2)
0.05 ~ a2/a ~ 0.50 (A-2)
(wherein the definitions of the terms a1 and a2 are same as those described
above).
17. A non-crosslinked polyester imide according to Claim 16,
wherein the alkylene group R1 having a carbon number of from 2 to 6 is
ethylene group, 1,2-propylene group or neopentylene group.
18. A crosslinked polyester imide suitable for toner,
(iv) comprising mainly an ester unit E represented by the following
formula (1) below, at least one kind of imide unit I selected from the
group consisting of units represented by the following formulas (2) and (3)
below, and at least one kind of crosslomking unit C selected from the
group consisting of units represented by the following formulas (4) and (5)
below, the above three units (E, I and C) are bonded together through
ester bond,
(v) having physical properties of
(d) a glass transition temperature of from 50 to 90~C and
(e) a softening temperature of from 90 to 190~C,
(vi) satisfying the following formula (B-1) and (B-2)
0.10 ~ b2/b1 ~ 0.60 (B-1)
0.01 ~ b3/b1 ~ 0.40 (B-2)
(wherein b1 is the mol% of the ester unit E, b2 is the mol% of
the imide unit I, and b3 is the mol% of the crosslinked unit C based on the
all units constituting the crosslinked polyester imide B )
formula (1)
<IMG>
(wherein Ar1 is a bivalent aromatic hydrocarbon group having

41
a carbon number of from 6 to 12, and R1 is at least one kind of group
selected from the group consisting of an alkylene group, an oxyalkylene
group and a polyoxyalkylene group each having a carbon number of from 2
to 20)
formula (2) and (3)
<IMG>
<IMG>
(wherein Ar2 is a tri- or tetravalent aromatic hydrocarbon
group having a carbon number of from 6 to 12, R2 is an alkylene group
having a carbon number of from 2 to 12, and X is -CO- or -O-)
formulas (4) and (5)
Ar3-(-CO-)r- (4)
R3-(-O-)q- (5)
(wherein Ar3 is an r-valent aromatic hydrocarbon group
having a carbon number of from 6 to 12, R3 is a q-valent aliphatic group
having a carbon number of from 3 to 9, and r and q are each 3 or 4)
19. A crosslinked polyester imide according to Claim 18, wherein
the group R1 in the above formula (1) is at least one kind of group selected
from the group consisting of an alkylene group and an oxyalkylene group
each having a carbon number of from 2 to 6 and Ar1 is at least one kind of
group selected from 1,4-phenylene group and 1,3-phenylene group.
20. A crosslinked polyester imide according to Claim 18, wherein

42
the group R2 in the above formula (2) is an alkylene group having a carbon
number of from 2 to 5, X is -O- and Ar2 is a benzene ring bonded to other
atoms at 1,2 and 4 positions which is represented by the following formula
(Ar2-1).
<IMG>
21. A crosslinked polyester imide according to Claim 18, wherein
the group R1 in the above formula (1) is at least one kind of group selected
from the group consisting of an alkylene group and an oxyalkylene group
each having a carbon number of from 2 to 6, and the group Ar1 is at least
one kind of group selected from 1,4-phenylene group and 1,3-phenylene
group, the group R2 in the above formula (2) is ethylene group, X is -O- and
Ar2 is a benzene ring bonded to other atoms at 1, 2 and 4 positions which is
represented by the following formula (Ar2-1),
<IMG>
the crosslinking unit C is represented by the following formula (5-1)
R31-(-O-)3- (5-1)
(wherein R31 is an aliphatic group having a carbon number of from 3 to 6),
provided that the polymer has a glass transition temperature of from 55 to
85~C and a softening temperature of from 110 to 160~C and satisfies the
following formulas (B-1-1) and (B-2-1)
0.05 ~ b2/b1 ~ 0.50 (B-1-1)
0.03 ~ b3/b1 ~ 0.20 (B-2-1)
(wherein the definitions of the terms b1, b2 and b3 are same as those
described above).
22. A crosslinked polyester imide according to Claim 21, wherein
the alkylene group R1 having a carbon number of from 2 to 6 is ethylene
group, 1,2-propylene group or neopentylene group.

Description

CA 02267551 1999-03-26
T-342/TS
1
DESCRIPTION
Toner Composition
Detailed Description of the Invention
Technical Field
The present invention relates to a toner composition useful for a
high speed copy machine and a full-color printer. More particularly, this
invention relates to a toner composition having excellent blocking
resistance, low-temperature fixability and melt-fluidity and useful for the
development of electrostatic image or magnetic latent image in
electrophotography or magnetic transfer printing, and to a polyester imide
resin giving said toner composition.
Background Arts
In an electrostatic photograph3r, i.e. a process for producing a
permanent sensible image by electrostatic charge, the electrostatic image
formed on a photoconductive semiconductor or an electrostatic recording
material is developed with a toner charged by frictional electrification and
the developed image is fixed. In a magnetic latent image, a latent image
on a magnetic drum is developed with a toner containing magnetic
material and fixed. The fixation is carried out by directly fusing the toner
image developed on a photoconductive photosensitive material or on an
electrostatic recording material or transi:erring the toner image on a paper
or a film and fusing the transferred image on a transfer sheet. The fusion
of the toner image is usually performed ~by the application of pressure and
heat. The heating process comprises a non-contact heating process using
an electric oven or flash light and a pressure-heating process using a
pressurizing roller, and the latter process is being mainly employed in
recent years requiring the speed-up and simplification of the fixing step.
The above methods are generally called .as "dry developing process".
The toner composition to be used in the dry developing process is
produced by sufficiently dispersing a binder resin as a base, a coloring

CA 02267551 1999-03-26
2
agent, a charge-controlling agent, magnetic powder and necessary other
additives by kneading the components in molten state and pulverizing the
kneaded mixture. The resin is a main component of the toner and exerts
substantial influence on the performance required for a toner. The binder
resin for toner is required to have good dispersibility of the coloring agent
and other additives in the melt-kneading process, pulverizability in the
crushing process and various properties such as fixability, offset resistance,
blocking resistance and electrical properties in the case of using as a toner.
Resins generally used as the binder resins are epoxy resins, polyester
resins, polystyrene resins, acrylic resins, etc., and polyester resins among
the above resins are attracting attention because the resins are fixable at
lower temperature, give fixed toner image having excellent resistance to
plasticizers for polyvinyl chloride resin a:nd have high transparency to cope
with the development of color copying technique.
JP-A 6-128367 (hereunder, JP-A means "Japanese Unexamined
Patent Publication)], JP-B 59-11902 (hereunder, JP-B means "Japanese
Examined Patent Publication) and JP-B 5-85901 describe polyester resins
having crosslinked structure introduced by using a tri- or higher-
functional monomer or a monomer having an unsaturated group as a
component for improving the offset resistance in the fixing step. However,
these polyester resins having branched or crosslinked structure have
lowered fluidity and are unsuitable for high-speed copying and color
copying use.
A polyester resin having a linear structure has been proposed as a
toner resin having high melt fluidity. Linear polyesters generally have a
problem that the Tg is lowered to deteriorate the storage stability and the
blocking resistance of the toner when the fluidity of the resin is improved
by lowering the melt-viscosity. Polyesters produced by using ethylene
oxide or propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane
(bisphenol A) as a diol component are described in the JP-A 2-269364, JP-
A 4-42l61, JP-A 5-9278 and JP-A 5-107F>05. These resins have relatively
high Tg and excellent melt-fluidity. However, ethylene oxide or
propylene oxide adduct of bisphenol A usually contains an adduct having a
structure containing two or more molecules of ethylene oxide or propylene

CA 02267551 1999-03-26
3
oxide based on the OH group of bisphenol A, and the Tg-improving effect is
not sufficient because the aliphatic ether structure results in the lowering
of Tg. Furthermore, the polyester easily releases the alkylene oxide by
the acid treatment condition used in a sewage treatment or by acid rain
when the polyester is wasted and left outdoors to bring dangers of the
release of bisphenol A which has recently been attracting attention as a
troublesome "environmental hormone".
Accordingly, there is no polyester resin free from environmental
problems as a binder resin for toner and satisfying the required melt
fluidity, low-temperature fixability, offset resistance and blocking
resistance at present.
JP-B 8-l0358 discloses an attempt to introduce an imide structure
into a resin for toner taking consideration of an aliphatic imide and a
positive-charge imparting property introduced by the imide, however, the
compound is added or copolymerized to a conventional resin in a small
amount as an agent for controlling the electric charge.
JP-A 7-160046 and JP-A 8-628!6 describe a toner containing a
polyester imide resin produced by the melt-polycondensation of a flexible
diaminoalkane (Jeffamin, product of Te~;aco Chemical Co.) and trimellitic
anhydride.
A polyester imide resin prepared by the polycondensation of
Jeffamin and pyromellitic anhydride is described in JP-A 7-181738.
In addition to the above, crosslinked polyester imide resins
produced by introducing an unsaturated group together with Jeffamin and
optionally reacting with a free radical :initiator are disclosed in JP-A 7
160047, JP-A 7-2l9273 and JP-A 7-333907.
All of these resins have poor handling performance in the
manufacture of the resins because of t)ze use of the diamine (Jeffamin)
which is viscous at ordinary temperature. Furthermore, since a polyester
imide resin produced by the polycondensation of Jeffamin and an acid
anhydride has extremely high hygroscop:icity, electric charge accumulation
is insufficient under high temperature ~~nd humidity conditions to cause
fixability problem in the case of evaluating the resin as a toner, supposedly,
because of the presence of ether bond in t;he imide-constituting component.

CA 02267551 1999-03-26
4
Further, the synthesis of Jeffamin necessitates a considerably large
number of steps to raise the production cost in comparison with the
performance improvement as a toner, and the use of the resin as a toner
resin meeting the cost is difficult.
An object of the present invention is to provide a new toner
composition.
Another object of the present invention is to provide a toner
composition having excellent melt-fluidii~y, fixability, offset resistance and
blocking resistance and capable of applying positive static charge.
A further object of the present i~avention is to provide a polyester
imide as a binder resin for toner for giving the above toner composition.
Still another object of the present invention is to provide a toner
composition containing a polyester imi.de having high glass transition
temperature (Tg) and low melt-fusion temperature.
Still further object of the present invention is to provide a new
binder resin for toner having improved characteristics of a polyester resin
as a binder resin for toner.
Still further object of the present invention is to provide a toner
composition useful as a dry-type toner applicable to hot-roll fixing process,
flash fixing process, etc.
The other objects and advantages of the present invention will be
clarified by the following descriptions.
Disclosure of the Invention
According to the present invention, the objects and advantages of
the present invention can be attained by a toner composition comprising a
coloring agent and at least one kind of polymer selected from the group
consisting of A and B.
A : a non-crosslinked polyester imide
(i) comprising mainly an ester unit E represented by the following
formula (1) below and at least one kind of imide unit I selected from the
group consisting of units represented by the following formulas (2) and (3)
below, E and I are bonded through ester bond ;
(ii) having physical properties of

CA 02267551 1999-03-26
(a) a number-average molecular weight of from 2,000 to
10, 000,
(b) a glass transition temperature of from 50 to 90~C and
(c) a softening temperature of from 90 to l60~C ;
5 (iii) satisfying the following forrrmla (A-1)
O.Olca2/a1~0.60 (A-1)
(wherein al is the mol% of the ester unit E and a2 is the mol%
of the imide unit I based on the all unii;s constituting the non-crosslinked
polyester imide A)
formula (1)
0 O
- ~-~l-C-p~Rl-Q- (1)
(wherein Arl is a bivalent aromatic hydrocarbon group having a
carbon number of from 6 to 12, and Rl is at least one kind of group selected
- from the group consisting of an alkylene group, an oxyalkylene group and
a polyoxyalkylene group each having a <;arbon number of from 2 to 20)
formula (2) and (3)
~ ..
Ic
0
-c-A \ j N- RZ-x - (2)
II
0
0 0
II II
c ,c
-X-Rz-N~C/A \C/N-_R2-X-
(3)
(wherein Ar2 is a tri- or tetravalent aromatic hydrocarbon
group having a carbon number of from. 6 to 12, R? is an alkylene group

CA 02267551 1999-03-26
6
having a carbon number of from 2 to 12, and X is -CO- or -O-)
B : a crosslinked polyester imide
(iv) comprising mainly the above ester unit E, the above imide
unit I and at least one kind of crosslinkiag unit C selected from the group
consisting of units represented by the fol:Lowing formulas (4) and (5) below,
the above three units (E, I and C) are bonded together through ester bond,
(v) having physical properties of
(d) a glass transition temperature of from 50 to 90~C and
(e) a softening temperature of from 90 to 190~C,
(vi) satisfying the following formulas (B-1) and (B-2)
0.01cb2/bW0.60 (B-1)
0.01~bs/b1~0.40 (B-2)
(wherein bi is the mol% of th.e ester unit E, bz is the mol% of
the imide unit I, and bs is the mol% of the crosslinking unit C based on the
all units constituting the crosslinked pol~,~ester imide B).
formulas (4) and (5)
Ar 3-(-CO-)r- (4)
R3-(-O-)q- (5)
(wherein Ar3 is an r-valent aromatic hydrocarbon group
having a carbon number of from 6 to 12, R3 is a q-valent aliphatic gr oup
having a carbon number of from 3 to 8, and r and q are each 3 or 4)
Best Mode for Carrying out the Invention
The toner composition of the present invention contains a coloring
agent and a polymer selected from the group of A and B.
The polymer A is a polyester im.ide resin composed mainly of an
ester unit E expressed by the above formula (1) and an imide unit I
selected from the group consisting of t:he units expressed by the above
formulas (2) and (3). These units are not bonded through ether bond but
bonded through ester bond.

CA 02267551 1999-03-26
7
In the above formula (1), Arl i:~ an aromatic hydrocarbon group
having a carbon number of from 6 to 12. Such aromatic hydrocarbon
groups are, for example, 1,4-phenylene group, 1,3-phenylene group, 1,2-
phenylene group, 2,6-naphthylene group, 2,7-naphthylene group and 4,4'-
biphenylene groups. Two or more kincls of these groups may be used in
combination. 1,4-Phenylene group and 1,3-phenylene group are
preferable among the above exemplified groups. These are groups
usually derived from aromatic dicarboxylic acid components.
In the case of using 1,4-phenyle:ne group in combination with 1,3
phenylene group, the amount of 1,4-ph.enylene group is 50 to 80 mol%,
preferably 60 to 70 mol% based on the total groups.
The group R1 is selected from the group consisting of alkylene
groups, oxyalkylene groups and polyo~;yalkylene groups each having a
carbon number of from 2 to 20.
Examples of such alkylene groups are ethylene group, 1,2-
propylene group, trimethylene group, tetramethylene group,
hexamethylene group, neopentylene g;roup (2,2-dimethyl-1,3-propylene
group) and the groups expressed by the following formulas (R1-1) and
(R1-2).
- GH2~ CHz - (R1-1)
CH3
(Rl-2)
CH3
Two or more kinds of these groups may be used in combination.
Alkylene groups having a carbon number of from 2 to 6 are preferable, and
ethylene group, 1,2-propylene group and neopentylene group are
especially preferable among the above groups.
Such oxyalkylene groups are, for example, oxydiethylene group
and trioxyethylene group. Oxydiethyle:ne group is preferable between the
exemplified groups.
Such polyoxyalkylene groups are, for example, a polyoxyethylene

CA 02267551 1999-03-26
8
group and a polyoxypropylene group. The molecular weight of the
polyoxyalkylene group is usually from 500 to l0,000.
Two or more kinds of the above alkylene groups, oxyalkylene
groups and polyoxyalkylene groups each having a carbon number of from 2
to 20 may be used in combination. These groups are usually derived from
diol components.
The ester groups E expressed by the above formula (1) are
preferably those of the formula (1) wherein, e. g. Arl is 1, 4-phenylene
group,
1, 3-phenylene group or their combination and R1 is ethylene group, l, 2-
propylene group, neopentylene group; oxydiethylene group or their
combination.
Especially, when Rl is an oxyalk.ylene group, it is preferably used
in combination with an alkylene group. In this case, the content of such
oxyalkylene group is preferably 10 to 9fl mol%, more preferably 20 to 85
mol%, especially 30 to 80 mol%, based on the alkylene group.
The groups Arl may be those, in addition to the above-mentioned
groups, derived from a relatively small amount of other carboxylic acid
component. The following acids are examples of these other dicarboxylic
acid components.
Aromatic dicarboxylic acid such as phthalic acid, phthalic
anhydride, Biphenyl ether dicarboxylic acid and diphenylsulfone
dicarboxylic acid; aliphatic dicarboxylic acid such as succinic acid, fumaric
acid and adipic acid; alicyclic dicarboxylic acid such as
cyclohexanedicarboxylic acid and norbornene-2,3-dicarboxylic acid. The
ratio of these other dicarboxylic acid components is preferably 30 mol% or
less, more prefer ably 20 mol% or less, especially 10 mol% or less based on
the total acid component constituting the ester unit E.
The group Rl may contain groups derived from diol components
other than the groups cited above to an extent not to deteriorate the
physical properties of the product. Examples of such other diol
component are bisphenol A, bisphenol S, bisphenol Z, hydroquinone, 1,4-
benzenediol and l, 3-benzenediol. The addition amount of such other diol
component is preferably 40 mol% or less, more preferably 30 mol% or less
based on the diol components constituting the ester unit E.

CA 02267551 1999-03-26
9
The above ester unit E may cont~~in a small amount of unit derived
from hydroxycarboxylic acids such as hydroxybenzoic acid and
hydroxycaproic acid. The ratio of such unit is preferably 30 mol% or less,
more preferably 20 mol% or less, especially 10 mol% or less based on the
ester unit E.
In the formulas (2) and (3), the group Ar2 is a tri- or tetravalent
aromatic hydrocarbon group having a carbon number of from 6 to 12, R2 is
an alkylene group having a carbon number of from 2 to 12, and X is -CO- or
-O-.
Examples of the group Ar2 consisting of a tri- or tetravalent
aromatic hydrocarbon group having a carbon number of from 6 to 12 are a
benzene ring bonded to other atoms at 1,2 and 4 positions and expressed
by the following formula (Ar2-1)
(Ar2-1)
and a benzene ring bonded to other atoms at 1,2,4 and 5 positions and
expressed by the following formula (Ar2-2).
(Ar2-2)
These groups are derived from trimellitic acid or its anhydride and
pyromellitic acid or its anhydride, respecaively.
Examples of the group R2 consisting of an alkylene group having a
carbon number of from 2 to 12 are ethylene group, 1,2-propylene group,
1.3-propylene group, 1,4-tetramethylene group and hexamethylene group.
Among the above groups, an alkylene group having a carbon number of
from 2 to 6 such as ethylene group and 1,3-propylene group is preferable
and ethylene group is especially preferable. These are groups usually
derived from aliphatic amino alcohol or ;aliphatic aminocarboxylic acid.
The group X is -CO- or -O-.
Preferable examples of the imide unit I expressed by the above

CA 02267551 1999-03-26
formula (2) are those of the formula (:?) wherein Ar2 is a benzene ring
bonded to other atoms at l, 2 and 4 positions, R2 is an alkylene group
having a carbon number of from 2 to 6 and X is -0- or -CO-.
Preferable examples of the imide unit I expressed by the above
5 formula (3) are those of the formula (3) wherein Ar2 is a benzene ring
bonded to other atoms at 1,2,4 and 5 positions, R2 is an alkylene group
having a carbon number of from 2 to 6 and X is -O- or -CO-.
Concrete examples of the imide unit I are those expressed by the
following formulas.
10 , o il
c~~~N-Rzy~ (2-1)
~c
II
0
0
a II
II ~c o
-c jN-Rz'-c (2-2)
c
II
0
0 0
II a
c c
o R~~ N~ ~ /N RZC-o- (3-1)
C C
It II
0 0
0 0
o ~ I~ o
-c-'R~~ Nw ~ /N-~~~-c- (3 2)
c c
n n
0 0
In the above formulas, R''1 is an alkylene group having a carbon
number of from 2 to 6, especially preferably ethylene group.
Especially preferable imide unit, I is composed solely of the unit
expressed by the above formula (2-1).
Introduction of the above imide unit I randomly or in the form of
blocks into a polymer chain containing the above ester unit E by ester
bond gives an amorphous polymer and contributes to the improvement of
the storage stability by raising the Tg which is insufficient by the single
use of a polyester resin composed solely of the above ester unit while
keeping excellent melt-fluidity of the polyester resin composed solely of the

CA 02267551 1999-03-26
11
above ester unit. Furthermore, the obt;~ined polymer can be applied to a
positive-charge developing process which is difficult to be achieved by the
use of conventional polyesters.
The above polyester imide resin ~~ preferably has a Tg of 50 to 90~C
and a softening temperature of 90 to 1E>0~ for the use of the resin as a
binder resin for toner. The Tg is the rise temperature of the inflection
point determined by differential scanning calorimetry at a temperature
increasing rate of 20~C/min. The softening temperature is measured by
charging 1 gram of a sample into a Koka flow tester under a load of 30 kg,
slowly raising the temperature from room temperature at a temperature
increasing rate of 3~C/min and determining the temperature when 50% of
the charged sample is extruded in molten state through a nozzle having a
diameter of 1 mm and a land length of 10 mm.
When the Tg of the above polyester imide A is lower than 50~C, the
blocking resistance becomes insufficient, and a Tg higher than 90 ~C
results in poor low-temperature fixabilit;y. The value of Tg is preferably
between 55~C and 85~C. When the sofi;ening temperature is lower than
90 ~C , the offset resistance become: insufficient, and a softening
temperature higher than 160~C causes the lowering of the fluidity of the
resin. The softening temperature is preferably between 90~C and 150~C .
The polyester imide A having the above-mentioned thermal characteristics
gives the toner composition of the present invention producible at a low
cost, having excellent fixability caused by the low melt-fluidity and
excellent blocking resistance even at a high temperature, and exhibiting
excellent storage stability compared with conventional binder resins for
toner.
The molecular weight of the above polyester imide A is preferably
adjusted to give the polymer satisfying the above thermal characteristics.
The number-average molecular weight is preferably in the range of from
2,000 to 20,000, more preferably from 2;,000 to 10,000, particularly from
2,000 to 8,000, and especially preferably from 2,500 to 5,000 depending
upon the kinds of the constituent units.
The above polyester imide resin A satisfies the following formula
(A-1).

CA 02267551 1999-03-26
12
0.01 s az/al S 0.60 (A-1)
wherein al is the mol% of the ester unit E and az is the mol% of the imide
unit I based on the total unit constituting a non-crosslinked polyester
imide A.
When the value of a2 in the above formula (A-1) is smaller than
0.01, the Tg becomes low and blocking trouble is liable to occur in the case
of using the resin as a toner. Conversely, the az value larger than 0.60
gives high softening temperature to cause poor fixability in the case of
evaluating as a toner and shifts th.e non-offset region to a high
temperature side. The preferable ratio of al to a2 satisfies the following
formula (A-2), more preferably the following formula (A-3).
0.05 c az/ai c 0.50 (A-2)
O.lOSaz/ais0.40 (A-3)
The polymer B is a crosslinked polyester imide resin composed
mainly of the ester unit E expressed by the above formula (1), the imide
unit I selected from the group consisting of the units expressed by the
above formulas (2) and (3), and a crosslinking unit C selected from the
group consisting of the above formulas (4) and (5). These units are
bonded not through ether bond but through ester bond.
The units same as the above-mentioned units can be used as the
ester unit E and the imide unit I.
The crosslinking unit C is selected from the group consisting of the
above formulas (4) and (5).
In the above formula (4), the group Ar3 is an r-valent aromatic
hydrocarbon group having a carbon number of from 6 to 12. Examples of
such aromatic hydrocarbon group are t:he benzene ring bonded to other
atoms at 1, 2 and 4 positions and expree,sed by the above formula (Ar2-1)
and a benzene ring bonded to other atoms at 1, 2, 4 and 5 positions and
expressed by the above formula (Ar2-2). These groups are derived from
trivalent or tetravalent aromatic polybasic carboxylic acids or their
anhydrides.
The value of r is 3 or 4.
In the above formula (5), the group R3 is a q-valent aliphatic group
having a carbon number of from 3 to 9. These groups are usually derived

CA 02267551 1999-03-26
13
from polyhydric aliphatic alcohols having 3 or more valences. Examples
of polyhydric aliphatic alcohol component giving such aliphatic groups are
glycerol, pentaerythritol, trimethylolpropane, trimethylolethane and
tris(2-hydroxyethyl) isocyanurate. Two or more kinds of the above
compounds may be used in combination. Among the above examples,
aliphatic groups having a carbon number of from 3 to 6 such as glycerol,
pentaerythritol and trimethylolpropane are preferable and, above all,
glycerol and pentaerythritol are more preferable.
The value of q is 3 or 4.
The crosslinking unit C is preferably composed of the unit
expressed by the above formula (5).
The above polyester imide satisfies the following formula (B-1).
O.Olsb2/b150.60 (B-1)
In the formula, bi is the mol% of the ester unit E and b2 is the mol% of the
imide unit I based on the total unit con~,tituting the crosslinked polyester
imide B.
When the ratio b2/bi is smaller than 0.01, the Tg of the polymer
becomes low and blocking trouble is liable to occur in the case of using the
resin as a toner. Conversely, the ratio bz/bi larger than 0.60 gives high
softening temperature to cause poor fixability in the case of evaluating as
a toner and shifts the non-offset region to a high temperature side. The
ratio of bi to bz preferably satisfies the following formula (B-1-1), more
preferably the following formula (B-1-2).
0.05cb2/b1~0.50 (B-1-1)
0.10~b2/bl S 0.40 (B-1-2)
Furthermore, the above polyester imide B satisfies the following
formula (B-2).
0.0l ~ba/b i ~ 0.40 (B-2)
In the formula, the definition of bi is same as above and bs is the mol% of
the crosslinking unit C.
The ratio of bs/bi smaller than 0.01 lowers the softening
temperature of the polymer, decreases t:he storage modulus G' within the
temperature range of from 150 to 200~C measured by using a rheometer
while varying the temperature from the softening temperature of the resin

CA 02267551 1999-03-26
14
to 200~C, and causes offset-resistance problem in the case of evaluating the
resin as a toner. When the ratio is larger than 30%, the softening
temperature is raised to deteriorate the fixability in the evaluation of the
resin as a toner and the production of the resin becomes difficult. The
ratio of bs to bi preferably satisfies the following formula (B-2-1), more
preferably the following formula (B-2-2).
0.03~b3/b1s0.20 (B-2-1)
0.05cbs/b1~0.15 (B-2-2)
The above polyester imide preferably has a Tg of 50 to 90~C and a
l0 softening temperature of 90 to 190~C for the use of the polymer as a binder
resin for toner. The influence of Tg in this case is same as the case of the
above polyester imide A. The offset resistance becomes insufficient when
the softening temperature is lower than 90~C, and the fluidity of the resin
is lowered when the temperature is higher than 190~C. The softening
temperature is preferably from 100 to 1f30, more preferably from 1l0 to
160. The polyester imide B having the above thermal characteristics
gives the toner composition of the present invention producible at a low
cost, having excellent fixability caused by low melt-fluidity and excellent
blocking resistance even at a high temperature and exhibiting excellent
storage stability compared with conventional binder resin for toner.
The above polymers A and B ma.y contain other units functioning
as a thermal stabilizer, oxidation stabilizer, photo-stabilizer, pigment
dispersing agent, dye-fixing improving agent, flame-retardant, etc., in the
polymer chain in small amounts, e.g. not; more than 20 mol% based on the
total polymer. For example, the compounds shown as the following
formulas (Other-1), (Other-2) and (Othf~r-3) can be used as the fixation
improving agent and a dispersing agent; for coloring agent, and a flame
retardant. The above polymer can lbe imparted with the objective
performance of each agent by adding and reacting the agent in the
production of the polymer.

CA 02267551 1999-03-26
0 0
H3C.,0 O.C~;f3
(Other-1)
sa3Ha
0 0
Hj C~p ~~ ~H:~ (Other-2)
10 $~3P~~ ~4
CH3
(Other-3)
O
There is no particular restriction. on the method for producing the
polyester imides A and B in the present invention, and conventional
production processes in the field can be used.
For example, the polymer may be produced by reacting the imide-
constituting raw materials, synthesizing an imide unit and subjecting the
unit to the esterification to form the ester unit E and the simultaneous
dehydrative condensation; or reacting the raw materials of the imide unit
to form an amidocarboxylic acid as an irnide precursor and subjecting the
acid to the esterification to form the ester unit E simultaneously with
dehydrative condensation; or charging the raw materials for the ester unit
and the raw materials for the imide unit into a single reaction system and
carrying out the formation of the imide unit I simultaneously with the
formation of the ester unit E. These methods can be properly used in the
present invention.
The esterification process for the production of the ester unit E can
be carried out, for example, by the direct polymerization process using the
dicarboxylic acid component and each glycol component as raw materials,
the transesterification polymerization process to use a dicarboxylic acid
ester and each glycol component as raw materials, etc.

CA 02267551 1999-03-26
16
The imide unit I can be producE~d by the reaction of an aromatic
polybasic carboxylic acid component with an amino alcohol component or
an aminocarboxylic acid component. Examples of such aromatic
polybasic carboxylic component are trimellitic anhydride and pyromellitic
anhydride. Trimellitic anhydride is preferable between the above
compounds because of the formation of a polyester imide having higher
amorphousness.
The amino alcohol component is, for example, ethanolamine, 2
aminopropanol and 3-aminopropanol. Fahanolamine is preferable among
the above compounds because it has high reactivity, gives a polyester
imide having higher amorphousness similar to the above and is easily
removable at the latter stage of polymerization owing to its low boiling
point even if the compound is left in the :system as an unreacted material .
The aminocarboxylic acid component is, for example, a
aminocarboxylic acids, r -aminocarboxylic acids, b -aminocarboxylic
acids and ~ -aminocarboxylic acids. ~ -Aminocarboxylic acids are
preferable among the above compounds owing to good handleability to
enable the use as a toner resin at a low cost.
The ester unit E can be produced by reacting an aromatic
dicarboxylic acid component with a viol component. The aromatic
dicarboxylic acid component is, for example, terephthalic acid, isophthalic
acid, 2,6-naphthalenedicarboxylic acid and their alkyl esters.
Terephthalic acid and isophthalic acid are preferable among the above
compounds to enable the use as a toner resin at a low cost.
The diol component is, for example, alkylene glycols such as
ethylene glycol, propylene glycol and 2 ,2-dimethyl-1,3-propylene glycol;
oxyalkylene glycols such as diethylene ;;lycol and triethylene glycol; and
polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene
glycol and polytetraethylene glycol. Among the above compounds,
ethylene glycol and 2-dimethyl-1,3-propylene glycol are preferable because
these compounds do not lower the Tg of t:he resultant toner, and diethylene
glycol is also preferable because it gives a toner having improved melt-
fluidity.
A concrete example of the process for producing the polymer A

CA 02267551 1999-03-26
17
comprises the mixing of a trivalent or tetravalent aromatic polybasic
carboxylic acid component such as trimellitic anhydride and an aliphatic
amino alcohol such as ethanolamine as raw materials for constructing the
imide unit I and a diol component such as ethylene glycol which is a raw
material for constructing the ester unit E, the reaction of the above
components at l00 ~C or below to form an amidocarboxylic acid, the
incorporation of the system with an aronnatic dicarboxylic acid component
such as terephthalic acid as the remaining raw material component for
constructing the ester unit E optionally together with an oxyalkylene
glycol component and/or a polyalkylene glycol component, and the
dehydration and polycondensation of the components. The amounts of
the diol component and the tri- or tetravalent polybasic aromatic
carboxylic acid component are usually 0..0l to 0.90 mol% and 0.99 to 0.10
mol% based on the aromatic dicarboxylic acid component, respectively,
and the amount of the amino alcohol. is equivalent to the polybasic
aromatic carboxylic acid component.
The imide unit I and the ester unit E of the polymer B can be
produced by the methods described above.
The crosslinking unit C can be derived from a trivalent or
tetravalent aromatic polybasic carboxylic acid component and a trivalent
or tetravalent polyhydric aliphatic alcohol component.
A concrete example of the production process of the polymer B
comprises the preparatory charging and mixing of a trivalent or
tetravalent aromatic polybasic carbo:~ylic acid component such as
trimellitic anhydride and an aliphatic amino alcohol such as ethanolamine
as raw materials for constructing the iraide unit I and a diol component
such as ethylene glycol which is a raw material for constructing the ester
unit E, the reaction of the above components at 100~C or below, the
incorporation of the system with an aronnatic dicarboxylic acid component
as the remaining raw material component for constructing the ester unit E
and an aromatic polybasic carboxylic acid or a polyhydric aliphatic alcohol
component constructing the crosslinkin~; unit C optionally together with
an oxyalkylene glycol component and/or a polyalkylene glycol component,
and the polycondensation of the components.

CA 02267551 1999-03-26
18
In the case of using the trivalent or tetravalent aromatic polybasic
carboxylic acid component such as trimellitic anhydride as a crosslinking
unit C, it may be mixed in the stage of charging.
In the case of using trimellitic anhydride in the imide unit I and
the crosslinking unit C, trimellitic anhydride is used in excess of
ethanolamine in terms of charging ratio (molar ratio), and the molar
amount of trimellitic anhydride is preferably 1 to 3 times, more preferably
1 to 2 times that of ethanolamine.
The polyester imides A and B can be used as a mixture with other
crosslinked or non-crosslinked binder resin for toner in the present
invention. The other binder resin for toner to be used by mixing with the
polymer A is, for example, the above polymer B, a bisphenol-type polyester
resin, a polyester resin free from bisphenol component and a crosslinked
styrene-acrylic resin. The other binder resin for toner to be used by
mixing with the polymer B is, for example, the above polymer A, a
bisphenol-type polyester resin, a polyester resin other than the bisphenol-
type resin and a non-crosslinked styrene-acrylic resin. The use of the
polymers as a mixture with other resins is effective for increasing the
physical properties of the above polymers A and B such as Tg and storage
modulus and further improving the physical properties as a binder resin.
Accordingly, the physical properties such as offset resistance is further
improved in the case of evaluating the ~~esin as a toner. The amount of
the polymer A or B is preferably 10 to 90% by weight, more preferably 20
to 80% by weight based on the total binder resin.
For example, when the above poJlymer B is to be used by blending
with other binder resin consisting of a polypropylene terephthalate having
a molecular weight of 2, 500 and a molecular weight distribution of 2.0, the
ratio of the polymer B is preferably 10 to 50% by weight, more preferably
20 to 40% by weight, especially 25 to 35% by weight. The resultant
mixture (composition) has a number-average molecular weight of 3,000 to
5,000 and a molecular weight distribution of 10 to 20, and exhibits
balanced properties as a binder resin for vtoner, i.e. a Tg of 60 to 70~C and
a
softening temperature of 1l5 to 125~C.
The polyester imide A and B in the present invention is properly

CA 02267551 1999-03-26
19
mixed as a binder resin for toner with adlditives such as a color developing
agent, a static charge regulator, a wax and a surface-treating agent to
form a toner composition.
The amount of the binder resin in the toner composition depends
upon the process for forming the latent image such as the
electrophotographic process or magnetic process and is about 40 to 99% by
weight, preferably 50 to 99% by weight.
The color-developing agent is e.g. a coloring agent such as pigment
and dye. The pigment is, for example, a carbon black such as furnace
black Raven 5250, Raven 5750, Raven 1250 and Raven 1255
manufactured by Columbian Carbon Japan Ltd. and a magnetite such as
MAPICO BLACKS manufactured by Columbian Magnetite Co., or other
equivalent black pigment. The amount, of the color-developing agent is
generally 1 to 50% by weight, preferably 1 to 30% by weight based on the
toner.
Conventional cyan, magenta, blue, red, green, brown or yellow
pigment or their mixture can be used as the color pigment other than black
pigment in an amount same as the above-mentioned amount of the black
pigment.
Conventional charge controlling agent can be used as the charge
controlling agent. Representative examples of the agent are azo-based
metal complex, nigrosine pigment, ammonium salt-based agent and fatty
acid metal salt agent and the amount of the agent is generally 1 to 15% by
weight, preferably 1 to 10% by weight based on the toner.
Conventional surface-treating agent can be used as the surface-
treating agent. Representative examples of the agent are hydrophobic
silica, alumina, titanium oxide and ultrafine resin particles and the
amount of the agent is generally 0.1 to 1C1% by weight, preferably 0.1 to 7%
by weight.
Conventional wax can be used as the wax. Representative
examples of the wax are polypropylene, polyethylene (molecular weight:
1,000 to l0,000) and higher fatty acid salt. The amount of the wax is
generally 0.5 to 10% by weight, preferably 1 to 5% by weight based on the
toner.

CA 02267551 1999-03-26
The above toner composition can. be prepared in the form of toner
particles having an average particle diameter of from 7 to 20 ~c m
measured by a Coulter counter by the conventional crushing, pulverization
and classification processes after the addition of the above additives.
5 The toner composition of the present invention may further
contain a small amount, e.g. not more titian 20% by weight (based on the
total composition) of a heat-stabilizer, an oxidation stabilizer, a light
stabilizer, a pigment dispersing agent, a dye-fixing promoting agent, a
flame-retardant and a dye as necessary.
Effect of the Invention
The toner composition of the present invention has especially
excellent melt-fluidity, fixability and ofiaet resistance and high blocking
resistance because of the use of the above polyester imide resin having
high Tg and low softening~temperature as the binder resin. Accordingly,
the toner composition is extremely useful for electrophotographic printer,
magnetic printer, etc.
Especially, the polyester imide to be used in the present invention
has a characteristic feature to enable the use as a binder resin of a toner
for a positively charged printing system in contrast with conventional
polyester resins restricted to the use in negatively charged printing system
owing to the characters of the polymer. Since the polyester imide to be
used in the present invention contains a specific imide unit, it is easily
imparted with positively charging property compared with conventional
polyester resins and is usable as a toner for a positively charged printing
system.
~The present invention is explained in more details by the following
examples, which do not restrict the scope of the invention. The term
"part" in the examples means "parts by weight".
The reduced viscosity ( ~ sp/C) of the polymer was measured by
using a phenol/l, l,2,2-tetrachloroethane mixture (weight ratio: 6/4) at
35~C and a polymer concentration of 1.2 g/dl.
The Tg of the polymer was determined by the following method

CA 02267551 1999-03-26
21
using a differential scanning calorimeter DSC220 (product of Seiko
Instruments Inc.). The polymer was heated to 200 at a temperature
increasing rate of 20~C/min, quenched with dry ice and measured by the
differential scanning calorimeter at a temperature increasing rate of 20~
/min. The temperature at the intersection of the base line and the
tangential line of the heat-absorption curve near the Tg was determined
on the chart and defined as Tg.
The softening temperature wa.s measured by "KOKA FLOW
TESTER" (manufactured by Shimadzu Corp.) using a nozzle of lmm ~ X
lOmm under a load of 30 kgf. The sample was heated at a temperature
increasing rate of 3 ~C /min and the temperature was defined as the
softening temperature when 1/2 of 1 grim of the sample was melted and
flowed out through the nozzle.
The average molecular weights (Mw and Mn) were determined in
terms of standard polystyrene by dissolving 20 mg each of the samples in
10 ml of THF and measuring the molecular weights by Shodex "GPC
system-11" having four columns "Shodex KF-80M" for GPC connected in
series using THF as the developing solvent.
The polyester imide resin was subjected to the following toner
tests (1) to (3) and evaluated as a resin for toner binder.
(1) Simplified flxability test
The generation of offset phenomenon consisting of the adhesion of
a resin or a toner composition to a roller was examined by using a
conventional hot-roller-type flxability tester. The examination was
carried out on two cases, i.e. the generation of print blot caused by the
deposition of the toner on a hot roller in the form of toner powder without
melting the polymer at a roller temperature of 160~C (cold offset) and the
generation of print blot caused by the adhesion of molten polymer to the
hot roller without being fixed to a test printing paper at a roller
temperature of 200~C (hot offset). The generation of offset phenomenon
is shown by the mark X and the absence of the phenomenon is shown by
0.
(2) Fixing ratio test
The printing density of a printed matter obtained by the simplified

CA 02267551 1999-03-26
22
fixability test was measured beforehand. A piece of Sekisui cellophane
adhesive tape was applied to the measm.~ed part of the printed matter and
rubbed 20 strokes with a roller under a load of 1 kg. The tape was peeled
off, the printing density of the peeled part was measured and the ratio of
the printing densities before and after the application of the tape was
defined as the fixing ratio (%). The painting density was measured by
using a reflection densitometer.
(3) Blocking property test
A powdery specimen was filled in a container, left at rest for 1
week in an atmosphere of 45~C and dropped from the container on a 20
mesh sieve. The case absolutely free from powdery specimen on the sieve
is shown by the mark ~, the mark D shows the case that the lump of the
powdery specimen left on the sieve is crushed and passed through the
sieve by knocking the sieve, and the mark X is the case that the lump of
the powdery specimen is left on the sieve even by knocking the sieve.
Examples 1 to 3 and Comparative Example 1
Aminoethanol, trimellitic anhydride and propylene glycol were
charged into a reaction vessel provided with a stirring apparatus and a
distillation system having a rectifying; column in respectively specific
amounts described in the Table l, the <~tmosphere in the reaction vessel
was substituted with nitrogen gas at ordinary temperature, and the vessel
was heated at 50 ~C under atmospheric pressure. After reacting the
components for 30 minutes, dimethyl terephthalate and diethylene glycol
were added to the system in respectively specific amounts described in the
Table 1, the system was further incorporated with 4 parts of tetrabutyl
titanate and the reaction vessel was heated to 200~C under atmospheric
pressure. After keeping the vessel at the reaction temperature (200~C)
for 3 hours, the vessel was heated to 220"C and the reaction was continued
for 1.5 hours. At the point, 36 parts of water and 560 parts of methanol
were distilled out from the system. Tree reaction was further continued
for 1 hour at 240~C under atmospheric pressure in nitrogen gas stream,
for 15 minutes in low vacuum of about 20 mmHg and finally for 120
minutes in high vacuum of 1 mmHg or below to obtain a transparent

CA 02267551 1999-03-26
23
pale-yellow non-crosslinked polyester im:ide resin.
The measured results of the number-average molecular. weight,
the Tg and the softening temperature of the polymer produced by the
above method are shown in the Table 1.
Five (5) parts by weight of carbon black and 1 part of a charge-
controlling agent were added to 94 parts by weight of the above polyester
imide resin and the mixture was kneaded with a twin-screw extruder in
molten state. The obtained pellets were crushed with a jet mill and
classified with a classifier to obtain a toner composition having particle
diameters of from 10 to 15 a m.
The toner composition was evaluated by the above methods and
the results are also described in the Table 1.
Table 1
Example 1 2 3 Comparative
ts/mol Exam le 1
Charged DMT 1940/100 1910/1001940/100 l940/100
raw TMA 384/20 1!2/10 384/20 -
material ethanolamine122/20 61/10 122/20 -
PG 1522 1522 1522 1522
2o DEG 637/60 637/60 739/70 637/60
Resin Mn 7900 ~ 900 7500 8000
propertiesTg(C) 65 59 61 48
Softening 148 l44 138 150
temp. (C)
Toner test(1)
Simplified
flxability ~ 0
Cold offset
(2) Fixing 95 95 99 95
ratio (%)
(3) Blocking0 ~ ~ X
ro ert
DMT : Dimethyl terephthalate
TMA : Trimellitic anhydride
PG : Propylene glycol
DEG : Diethylene glycol
The polyester imide resin to be used in the present invention has

CA 02267551 1999-03-26
24
low softening temperature for high Tg and excellent offset property,
fixability and blocking resistance owing to the introduction of an aromatic
imide group and exhibits balanced characteristics as a binder resin for
toner.
Example 4
A reaction vessel furnished with a stirring apparatus and a
distillation system having a rectifying column was charged with 122 parts
(20 mol) of aminoethanol, 480 parts (25 mol) of trimellitic anhydride and
1522 parts of propylene glycol, the space in the reaction vessel was
substituted with nitrogen gas at ordinary temperature and the vessel was
heated at 50 ~C under atmospheric pressure. After reacting the
components for 30 minutes, the system was charged with 1940 parts (100
mol) of dimethyl terephthalate, 637 parts (60 mol) of diethylene glycol and
4 parts of tetrabutyl titanate and the reaction vessel was heated to 200~C
under atmospheric pressure. The system was maintained at the reaction
temperature (200~C) for 3 hours, heated to 220~C and reacted for 1.5 hours.
At the point, 36 parts of water and 560 p;~rts of methanol were distilled out
from the system. The reaction was further continued for 1 hour at 240~C
ZO under atmospheric pressure in nitrogen gas stream, for 15 minutes in low
vacuum of about 20 mmHg and finally for 120 minutes in high vacuum of 1
mmHg or below to obtain a transparent pale-yellow crosslinked polyester
imide resin.
The measured results of the number-average molecular weight,
the Tg and the softening temperature of the polymer produced by this
process are shown in the Table 2.
Comparative Example 2
A reaction vessel furnished with a stirring apparatus and a
distillation system having a rectifying column was charged with 1522
parts of propylene glycol, 1940 parts of dimethyl terephthalate and 4 parts
of tetrabutyl titanate, the space in the reaction vessel was substituted
with nitrogen gas at ordinary temperature and the vessel was heated at
200~C under atmospheric pressure. The system was maintained at the

CA 02267551 1999-03-26
reaction temperature (2000 for 3 hours, heated to 220 and reacted for
1.5 hours. At the point, 36 parts of water and 560 parts of methanol were
distilled out from the system. The reacaion was further continued for 1
hour at 240~C under atmospheric pressure in nitrogen gas stream, for 15
5 minutes in low vacuum of about 20 mmHg and finally for 120 minutes in
high vacuum of 1 mmHg or below to obtain a colorless transparent non-
crosslinked polyester resin.
The measured results of the number-average molecular weight,
the Tg and the softening temperature of the polymer produced by this
l0 process are shown in the Table 2.
Example 5
A transparent yellow blend pol;~mer was produced by the melt
extrusion kneading of 40 parts of the polyester imide resin obtained by the
15 Example 4 and 60 parts of the polyester resin obtained by the
Comparative Example 2 using a twin-screw extruder (PCM30
manufactured by Ikegai Corp.) at a cylinder temperature of 170~C.
The measured results of the number-average molecular weight,
the Tg and the softening temperature of the blend polymer produced by
20 this process are shown in the Table 2.
Pellets were produced by adding 5 parts by weight of carbon black
and 1 part of a charge controlling agent 'to 94 parts by weight of polyester
(imide) resins of the above Examples 4 and 5 and the Comparative
Example 2 and kneading the mixture by a twin-screw extruder in molten
25 state. The obtained pellets were crushed with a jet mill and classified
with a classifier to obtain toners having particle diameter of 10 to 15 a m.
The toners were evaluated by the above methods and the results
are shown in the Table 2.

CA 02267551 1999-03-26
26
Table 2
Example 4 Comparative5
ts/mol E xam le
2
Charged DMT 1940/l00 1940 Mixture of 40
pts.
raw TMA 480/25 - of the polymer
of
material ethanolaminel22/20 - Example 4 and
60
PG 1522 1522 pts. of the
DEG 637I60 - polymer of
Comparative
Exam le 2
Resin Mn 6800 2500 3500
propertiesTg(C) 65 61 63
Softening 146 l10 l23
temp. (C)
Toner (1) Simplified
test;
fixability
Cold offsetO O O
Hot offset O
(2) Fixing 95 95 95
ratio(%)
(3) BlockingO X O
ro erty
The polyester imide resin for goner to be used in the present
invention has low softening temperature for high Tg and excellent offset
property, fixability and blocking resistance owing to the introduction of an
aromatic imide group and exhibits balanced characteristics as a binder
resin for toner.
Examples 6 to 13
Aminoethanol, trimellitic anhydride and propylene glycol were
charged into a reaction vessel provided with a stirring apparatus and a
distillation system having a rectifying column in respectively specific
amounts described in the Table 3, the atmosphere in the reaction vessel
was substituted with nitrogen gas at ordinary temperature and the vessel
was heated at 50~C under atmospheric pressure. After reacting for 30
minutes, dimethyl terephthalate, diethylene glycol and a polyhydric diol
were added to the system in respectively specific amounts described in the

CA 02267551 1999-03-26
27
Table 3, the system was further incorporated with 60 parts of tetrabutyl
titanate and the reaction vessel was heated to 200 under atmospheric
pressure. After keeping the vessel at the reaction temperature (200~C)
for 8 hours, the vessel was heated to 230"C and the reaction was continued
for 2 hours. At the point, 550 parts of water and 9120 parts of methanol
were distilled out from the system. The system was evacuated from 760
mmHg to 5 mmHg spending 1 hour and i;he reaction was further continued
for 1.5 hour in high vacuum of 3 mmH~; or below to obtain a crosslinked
polyester imide resin.
The obtained polymer was a transparent pale-yellow polymer
insoluble in THF and the measurement of the molecular weight was
impossible.
The measured results of the number-average molecular weight,
the Tg and the softening temperature of the produced polymer are shown
in the Table 3 and the Table 4.
Table 3
Example 6 7 8 9
arts/mol
Charged DMT 29100/10029100/10029100/10029l00/100
raw TMA 5910/20.58790/30.55910/20.55910/20.5
material ethanolamine1830/20 N745/30 l830/20 l830/20
PG 22830 :e2830 22830 22830
DEG 9550I60 '3550/60 9550/60 9550/60
lycerol 1380/10 1380/10 2072/l5 -
trimethylol- - - l006/5
ro ane
pentaerythritol_ _ _ _
Resin Tg (C) 63 67 61 62
propertiesSoftening
temperature1?9 158 l58 150
(C )

CA 02267551 1999-03-26
28
Table 4
Example 10 11 12 13
arts/mol
Charged DMT 29100/10029100/10029l00/10029l00/100
raw TMA 5910/20.55910/20.55910/20.55910/20.5
material ethanolamine1830/20 1830/20 1830/20 l830/20
PG 22830 N2830 22830 22830
DEG 9550/60 '550/60 9550/60 9550/60
lycerol - - - 691/5
trimethylol2013/l0 - - -
ro ane
pentaerythritol- 2021/5 2042/10 511/2.5
Resin Tg (C) 59 57 57 57
propertiesSoftening
temperaturel44 151 157 153
(C )
Reference Example 1
A reaction vessel furnished with a stirring apparatus and a
distillation system having a rectifying column is charged with 1522 parts
of propylene glycol, 1940 parts of dimei;hyl terephthalate and 4 parts of
tetrabutyl titanate, the atmosphere in the reaction vessel was substituted
with nitrogen gas at ordinary temperature and the vessel was heated to
200~C under atmospheric pressure. The vessel was maintained at the
reaction temperature (200~C) for 3 hours and heated at 220~C and the
reaction was continued for 1.5 hours. A.t the point, 36 parts of water and
560 parts of methanol were distilled out from the system. The reaction
was further continued for 1 hour at 240"C under atmospheric pressure in
nitrogen gas stream, for 15 minutes in law vacuum of about 20 mmHg and
for 120 minutes in high vacuum of 1 rnmHg or below to obtain a non-
crosslinked polyester resin as the final product.
The obtained polymer was colorless and transparent and had a
number-average molecular weight of 2500, a Tg of 61~C and a softening
temperature of 110~C.
Examples 14 to 17

CA 02267551 1999-03-26
29
The polyester imide resins obtained by the Examples 6 to 8 and
the polyester resin obtained by the Reference Example 1 were subjected to
the extrusion kneading under melting at specific compositional ratios
shown in the following Table 5 using a twin-screw extruder (PCM30
manufactured by Ikegai Corp.) at a c~~linder temperature of 230 to
obtain a composition.
The obtained blend polymer (composition) was yellow and
transparent. The number-average molecular weights, the glass
transition temperatures and the softening temperatures are shown in the
l0 Table 5.
Five (5) parts by weight of carbon black and 1 part of a charge
controlling agent were added to 94 parts by weight of each of the above
compositions and the mixture was kneaded with a twin screw extruder in
molten state. The obtained pellets were crushed with a jet mill and
classified with a classifier to obtain toners having particle diameters of
from 10 to 15 ,u m.
The toners were evaluated by the aforementioned methods. The
results are shown in the Table 5.

CA 02267551 1999-03-26
Table 5
Example Reference 14 15 16 1'7
ts/mol Exam lp '
a 1
Polymer - 30 40 - -
of
5 Exam le
6
Polymer - - - 40 -
of
Exam le
7
Polymer - - - - 40
of
Exam le
8
Polymer 100 70 60 60 60
of
10 Reference
Exam le
1
Resin Mn 2500 3020 - - -
properties'__ 61 61 61 63 61
Tg(C) .
Softening 110 119 l24 125 123
temp. (C)
Toner test(1) Simplified
15 Viability
Cold offset O O O O O
Hot offset X O O O O
(2) Fixing 99 95 95 95 95
ratio(%)
(3) BlockingX O O O O
20 ro ert
Examples 18 to 20
Aminoethanol, a polybasic carboxylic acid anhydride and ethylene
glycol were charged into a reaction vessel provided with a stirring
25 apparatus and a distillation system having a rectifying column in
respectively specific amounts described in the Table 6, the atmosphere in
the reaction vessel was substituted with nitrogen gas at ordinary
temperature and the vessel was heated at 50 ~C under atmospheric
pressure. After reacting for 30 minutes, dimethyl terephthalate,
30 diethylene glycol or neopentyl glycol and glycerol were added to the system
in respectively specific amounts described in the Table 6, the system was
further incorporated with 60 parts of tel;rabutyl titanate and the reaction
vessel was heated to 200'C under atmospheric pressure. After keeping
the vessel at the reaction temperature (2000 for 8 hours, the vessel was

CA 02267551 1999-03-26
31
heated to 230'C and the reaction was continued for 2 hours. Water and
methanol were distilled out at the point. The system was evacuated from
760 mmHg to 5 mmHg spending 1 hour and the reaction was further
continued for 1.5 hours in high vacuum of 3 mmHg or below to obtain a
crosslinked polyester imide resin as the i:inal product.
The obtained polymer was pale yellow and transparent and
insoluble in THF and the measurement of the molecular weight was
impossible.
The measured results of the number-average molecular weight,
the Tg and the softening temperature of the produced polymer are shown
in the Table 6.
Table 6
Example 18 19 20
arts/mol
Charged DMT 29100/100 388/100 388/100
raw TMA 5910/20 79/20 -
material p~ - - 45/10
ethanolamine 1830/20 24/20 24/20
EG 13950 186 l86
2o DEG 9550/60 - l27/60
neo ent 1 lycol- 42/20 -
1 cerol 2763/20 18/10 l8/10
Resin Tg (C) 58 76 55
propertiesSoftening
temperature 143 137 146
(C)
PMA : Pyromellitic anhydride
Examples 21 and 22
Aminoethanol, trimellitic anhydride and ethylene glycol were
charged into a reaction vessel provided with a stirring apparatus and a
distillation system having a rectifying' column in respectively specific
amounts described in the Table 7, the atmosphere in the reaction vessel
was substituted with nitrogen gas at ordinary temperature and the vessel
was heated at 50~C under atmospheric pressure. After reacting for 30
minutes, dimethyl terephthalate, dimenhyl isophthalate and diethylene

CA 02267551 1999-03-26
32
glycol or neopentyl glycol were added to t;he system in respectively specific
amounts described in the Table 7, the system was further incorporated
with 4 parts of tetrabutyl titanate and l;he reaction vessel was heated to
200 ~C under atmospheric pressure. t~fter keeping the vessel at the
reaction temperature (200~C) for 3 hours, the vessel was heated to 220~C
and the reaction was continued for 1.5 hours. At the point, 36 parts of
water and 560 parts of methanol were distilled out from the system. The
reaction was further continued for 1 hour at 240~C in nitrogen gas stream
under atmospheric pressure, for 15 minutes in low vacuum of about 20
mmHg and then for 120 minutes in high vacuum of 1 mmHg or below to
obtain a pale yellow transparent non-crosslinked polyester imide resin as
the final product.
The measured results of the number-average molecular weight,
the Tg and the softening temperature of the polymers obtained by the
above process are shown in the Table 7.
Table 7
Example 2I 22
arts/mol
Charged raw DMT 20370/70 2'72/'70
material DMI 8730/30 1l6/30
TMA 3030I10 20I5
ethanolamine ~~ 15/10 6/5
EG l3950 186
DEG 1590/10 -
neo entyl lycol- 21/10
Resin Tg (C) 55 63
properties Softening
temperature 110 l19
(C)
DMI : Dimethyl isophthalate