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AS TONER RESIN BY
SUSPENSION POLYMERIZATION
FACULTY OF SCIENCE
UNIVERSITI OF MALAYA
KUALA LUMPUR
2012
ABSTRACT
Toner resins are polymeric materials used in the manufacturing of toners to be used
in the photocopy machines and LaserJet printers. The popular commercial resins are the
styrene acrylic copolymers. A typical toner resin has a bimodal molecular weight
distribution, having one fraction of lower molecular weight and another of higher molecular
weight, so that it can impart good fixing and offset properties to provide the performance of
a good toner.
This research project describes the synthesis of toner resins by suspension
polymerization, using poly(vinyl alcohol) and benzoyl peroxide as a colloid stabilizer and
initiator respectively, in an aqueous medium to produce the copolymers in the form of tiny
beads. Three series of experiments were carried in the study: (i) synthesis of low molecular
weight styrene acrylic copolymers, (ii) synthesis of high molecular weight styrene acrylic
copolymers and (iii) blending the both high and low molecular weight copolymers at
different ratios to obtain the desired properties.
Gel permeation chromatography (GPC) was used to study molecular weight
distribution (MWD); melt flow index (MFI) reflected the flow ability of resin; Differential
Scanning Calorimetry (DSC) was used to study the thermal properties; and acid number
(AN) to quantify the amount of acidic groups in the resin.
The effects of monomer ratio, concentration of initiator and concentration of
crosslinking agent on the properties of high and low molecular weight resins had been
investigated. The desired glass transition temperature of toner resin was obtained by
varying the monomer ratio. By increasing the concentration of initiator, the number average
of molecular weight of resin tends to shift to lower molecular weight presumably due to the
excess free radicals that could lead to more chain termination and chain transfer reactions.
The addition of cross-linking agent leads to gel formation. The percentage of
tetrahydrofuran (THF) insoluble fraction has increased as the concentration of cross-linking
agent was increased. The properties of synthesized toner resins were compared to those of
selected commercial resins.
The synthesized resins after blend at different ratios have glass transition
temperature in the range of 56-69oC; MFI in the range of 13 55 g/10 min; AN in the range
of 2.5 - 3.4 mg KOH/g; Mw in the range of 7.00 x 103 3.20 x 103 Daltons (1 Daltons =
1.66 x 10-27 kg) with 9 - 14% of tetrahydrofuran (THF) insoluble fraction. Three of the
synthesized resins with desired properties had been tested in a lab scale production of toner.
Print test had been carried out to evaluate the print quality. Image density of the test images
are in the range of 1.33 - 1.58 which is comparable to commercial toner, while background
density is around 0.12-0.13 which is slightly higher than commercial toner.
ABSTRAK
Resin toner adalah polymer yang digunakan untuk membuat toner bagi mesin
fotokopi dan alat pencetak laserjet. Resin komersial yang paling popular adalah kopolimer
stirena akrilik. Resin toner biasanya mempunyai taburan berat molekul bimodal tinggi
dengan bahagian berat molekul rendah. Ini dapat memberi sifat penetapan dan
pengimbangan agar menjadi toner yang baik.
Projek ini melibatkan sintesis resin toner dengan kaedah pempolimeran ampaian.
Penstabil koloid yang digunakan dalam pempolimeran adalah poli(vinil alkohol), manakala
pemula adalah benzoil peroksida. Pelarut dalam proses pempolimeran ampaian adalah air
suling. Tiga siri eksperimen telah dijalankan sepanjang kajian: (i) sintesis kopolimer stirena
akrilik berberat molekul rendah, (ii) sintesis kopolimer stirena akrilik berberat molekul
tinggi, (iii) Pencampuran kedua-dua kopolimer stirena akrilik dengan berat molekul rendah
dan berat molekul tinggi. Nisbah antara kopolimer dengan berat molekul rendah dan tinggi
telah dicampur untuk mendapat sifat-sifat yang dikehendaki.
Kromatograf Penelapan Gel (GPC) telah digunakan untuk mengkaji taburan berat
molekul; Alat Indeks Aliran Leburan (MFI) menunjukkan keupayaan aliran resin;
Kalorimetri Pengimbasan Pembeza (DSC) telah digunakan untuk mengkaji sifat-sifat
terma resin; Nombor asid (AN) untuk jumlah kumpulan berasid dalam resin toner. Kesankesan bagi nisbah monomer, kepekatan pemula dan kepekatan penyilangan ejen pada sifatsifat resin dengsan berat molekul rendah dan tinggi telah dikaji. Sifat-sifat resin toner yang
disintesis dan resin toner komersial telah dibandingkan.
Resin yang disintesis yang telah dicampur pada nisbah berbeza mempunyai suhu
peralihan kaca, Tg dalam lingkungan 56 - 69oC; MFI dalam lingkungan 13 55 g/10 min;
AN dalam lingkungan 2.5 - 3.4 mg KOH/g; Mw dalam lingkungan 7.00 x 103 3.20 x 103
Daltons (1 Daltons = 1.66 x 10-27 kg) dengan mengandungi 9 - 14 % yang tidak larut dalam
THF. Tiga resin yang disintesis yang mempunyai sifat-sifat yang dikehendaki telah diuji
untuk menghasilkan toner dalam skala makmal. Tiga siri ujian cetakan telah dijalankan
untuk menilai mutu cetakan dengan kaedah membandingkan mutu cetakan toner komersial.
Kepadatan imej yang diperolehi daripada imej yang diuji adalah dalam lingkungan 1.33
1.58, nilai ini adalah sebanding dengan toner komersial. Kepadatan latar belakang adalah
dalam lingkungan 0.12 0.13, nilai ini adalah lebih tinggi daripada toner komersial.
ACKNOWLEDGEMENTS
CONTENTS
ABSTRACT
III
ABSTRAK
ACKNOWLEDGEMENTS
VII
CONTENTS
VIII
LIST OF FIGURES
XIV
LIST OF TABLES
XIX
LIST OF ABBREVIATIONS
XXII
Toner
1.2
Electrophotography
1.3
1.4
Components of a toner
1.5
1.4.1
Binder Resins
1.4.2
Colorant
1.4.3
Magnetic Additives
1.4.4
1.4.5
Other Additives
1.5.1
10
1.5.2
10
1.5.3
Melt Viscosity
11
1.5.4
1.6
1.7
11
11
1.6.1
Banding
12
1.6.2
Repetitive Marks
12
1.6.3
Ghosting
13
Suspension Polymerization
14
1.7.1
16
1.7.2
Agitation speed
17
1.7.3
17
1.7.4
Concentration of initiator
18
1.7.5
Reaction temperature
18
1.8
18
1.9
Gel Effect
20
1.10
Selection of Monomers
20
1.11
Scope of Study
21
2.2
22
2.1.1
Materials
22
2.1.2
Apparatus
22
2.1.3
Suspension polymerization
23
Formulations
24
2.3
2.4
2.5
2.2.1
24
2.2.2
25
26
26
2.4.1
Materials
26
2.4.2
Procedures
27
2.4.3
Formulation
28
Preparation of toner
28
2.5.1
Materials
28
2.5.2
Procedures
29
2.5.3
Formulation
29
2.6
29
2.7
31
2.7.1
31
2.7.2
31
2.7.3
Infrared IR Spectrum
32
2.7.4
Percentage of Conversion
32
2.7.5
33
2.7.6
33
2.7.7
34
2.7.8
Tribo-charge
36
2.7.9
Apparent Density
37
2.7.10
Flowability
37
2.7.11
38
2.7.12
Magnetic Content
38
2.7.13
38
3.1.2
39
3.2
39
45
48
3.2.1
3.2.2
3.3
48
54
Mixing High Molecular Weight and Low Molecular Weight Styrene Acrylic
Copolymers
59
3.4
63
3.5
3.6
toner resins
77
78
Summary
82
4.2
Presentations at Conferences/Seminars
83
4.3
84
REFERENCES
85
APPENDIX
A
LIST OF FIGURES
Figure 1.2
Figure 1.3
Figure 1.4
Figure 1.5
Figure 1.6
Figure 1.7
Figure 1.8
Figure 2.2
Figure 2.3
Test images
Figure 3.2
(k=0.3445)
Figure 3.3
Figure 3.4
Figure 3.5
Figure 3.6
Figure 3.7
Figure 3.8
Figure 3.9
Figure 3.10
Figure 3.11
Figure 3.12
Figure 3.13
Figure 3.14
Figure 3.15
Figure 3.16
Figure 3.17
Example of test images template (A: text target, B: black page uniformity,
C: image and background density target)
Figure 3.18
Figure 3.19
Figure 3.20
Figure 3.21
Henschel Mixer (A: Sample container with cooling jacket, B: Power button)
Figure A.2
Extruder
Figure A.3
Crusher
Figure A.4
Figure A.5
Figure B.2
Figure B.3
Ray-ran Melt Flow Indexer (A: specified weight load, B: Automatic Flow
Rate Timer, C: Temperature Controller, D: Heater and Insulation)
Figure B.4
Figure B.5
Apparatus for Apparent Density Test (A: funnel, B: density cup, C: flowmeter
funnel)
Figure B.6
The Flotest Tester (A: funnel, B: sample container, C: flow disc with holes of
various diameters)
Figure B.7
Figure B.8
Figure B.9
Figure C.2
Figure C.3
Figure C.4
Figure C.5
Figure C.6
Figure C.7
Figure C.8
Figure C.9
Figure C.10
Figure C.11
Figure C.12
Figure C.13
Figure C.14
Figure C.15
Figure C.16
Figure C.17
Figure C.18
Figure C.19
Figure C.20
Figure C.21
Figure C.22
Figure C.23
Figure C.24
Figure C.25
Figure D.2
Figure D.3
Figure D.4
Figure D.5
Figure E.2
Figure E.3
Figure E.4
Figure E.5
Figure E.6
Figure F.2
Figure F.3
LIST OF TABLES
Table 2.2
Table 2.3
Table 2.4
Table 2.5
Table 2.6
FT-IR spectral peak area ratio of1601 cm-1/1724 cm-1 bands in the
Styrene Acrylic Copolymers
Table 3.2
Table 3.3
Table 3.4
FT-IR spectral peak area ratio of1601 cm-1/1724 cm-1 bands in the
Styrene Acrylic Copolymers
Table 3.5
Table 3.6
Table 3.7
Table 3.8
Table 3.9
Table 3.10
Table 3.11
Table 3.12
Table 3.13
Table 3.14
Table 3.15
Table 3.16
Table G.2
Table H.2
Table I.2
Table I.3
Table I.4
Table I.5
Table I.6
LIST OF ABBREVIATIONS
AA
Acrylic Acid
AN
Acid Number
BA
Butyl Acrylate
BD
Background density
BPO
Benzoyl Peroxide
CCA
CLA
Cross-linking Agent
CPT
DSC
GPC
ID
Image Density
MFI
Mn
Mw
Mp
Mz
Polydispersity Index
MWD
Tg