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PREPARATION OF STYRENE ACRYLIC COPOLYMERS

AS TONER RESIN BY
SUSPENSION POLYMERIZATION

TANG BEE KIM

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

I wish to express my sincere gratitude and deepest appreciation to my supervisor


Professor Dr. Gan Seng Neon for his timely advice, guidance and constant encouragement
throughout the length of this work. I would also like to thank Professor Dr. Rosiyah Yahya
(co-supervisor) for her time and valuable assistance.
I would like to thank all the members of the Polymer group, both past and present
who have helped me directly or indirectly during this research. Financial and research
assistantship from the Jadi Imaging Technologies Sdn. Bhd. is also appreciated. Finally, I
am grateful to all the members of my family for their love, encouragement and support
throughout my education, without which this would not have been possible.

CONTENTS
ABSTRACT

III

ABSTRAK

ACKNOWLEDGEMENTS

VII

CONTENTS

VIII

LIST OF FIGURES

XIV

LIST OF TABLES

XIX

LIST OF ABBREVIATIONS

XXII

CHAPTER ONE: INTRODUCTION


1.1

Toner

1.2

Electrophotography

1.3

Conventional toner Manufacturing Process

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

Charge Control Agent (CCA)

1.4.5

Other Additives

Required Properties of toner

1.5.1

Glass Transition Temperature, Tg

10

1.5.2

Molecular Weight Distribution

10

1.5.3

Melt Viscosity

11

1.5.4
1.6

1.7

Particle Size Distribution

Prints Defects in Laser Printers

11
11

1.6.1

Banding

12

1.6.2

Repetitive Marks

12

1.6.3

Ghosting

13

Suspension Polymerization

14

1.7.1

Monomer to water volume ratio

16

1.7.2

Agitation speed

17

1.7.3

Type and concentration of stabilizer

17

1.7.4

Concentration of initiator

18

1.7.5

Reaction temperature

18

1.8

Free Radical Polymerization

18

1.9

Gel Effect

20

1.10

Selection of Monomers

20

1.11

Scope of Study

21

CHAPTER TWO: EXPERIMENTAL


2.1

2.2

Synthesis of Styrene Acrylic Copolymers

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

Low Molecular Weight Styrene Acrylic Copolymer

24

2.2.2

High Molecular Weight Styrene Acrylic Copolymer

25

Mixing of High Molecular Weight and Low Molecular Weight Styrene


Acrylic Copolymer

26

Preparation of raw toner by using Pilot Plant

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

Evaluation of Print Quality

29

2.7

Characterization of toner resins and toners

31

2.7.1

Determination of Glass Transition Temperature, Tg

31

2.7.2

Determination of Molecular Weight Distribution

31

2.7.3

Infrared IR Spectrum

32

2.7.4

Percentage of Conversion

32

2.7.5

Percentage of Tetrahydrofuran (THF) Insoluble Fraction

33

2.7.6

Melt Flow Index

33

2.7.7

Determination of Acid Number

34

2.7.8

Tribo-charge

36

2.7.9

Apparent Density

37

2.7.10

Flowability

37

2.7.11

Particle Size Distribution

38

2.7.12

Magnetic Content

38

2.7.13

Image Density (ID) and background density (BD)

38

CHAPTER THREE: RESULTS AND DISCUSSION


3.1

Synthesis of Low Molecular Weight Styrene Acrylic Copolymer


3.1.1

Series 1: Different monomer ratios at constant initiator


concentration

3.1.2

39

Series 2: Different concentration of initiator at constant


monomer ratio

3.2

39

Synthesis of High Molecular Weight Styrene Acrylic Copolymer

45
48

3.2.1

Series 3: Different monomer ratio at constant AA, initiator and


cross-linking agent concentration

3.2.2

Series 4: Different Concentration of Cross-linking Agent at


constant monomer ratio and initiator concentration

3.3

48

54

Mixing High Molecular Weight and Low Molecular Weight Styrene Acrylic
Copolymers

59

3.4

Properties Results of toner

63

3.5

Comparison between the synthesized toner resin and commercial

3.6

toner resins

77

Comparison between the synthesized toner and commercial toner

78

CHAPTER FOUR: CONCLUSION


4.1

Summary

82

4.2

Presentations at Conferences/Seminars

83

4.3

Suggestions of Future Works

84

REFERENCES

85

APPENDIX
A

Machines used to produce raw toner

Instruments used for sample characterization

DSC profiles of toner resins and toners

TGA profiles of toners

GPC profiles of toner resins and toners

Particle Size Distribution Data Sheet

Calculation of Acid Number of High Molecular Weight Styrene Acrylic


Copolymers and Blended Resins

Calculation of Percentage of THF Insoluble Fraction of High Molecular Weight


Styrene Acrylic Copolymers and Blended Resins

Estimation of Tg by using Fox equation and Gordon-Taylor equation

Test Print Images of M09-FT

Test Print Images of M10-FT

Test Print Images of M11-FT

Test Print Images of commercial toner A

LIST OF FIGURES

CHAPTER ONE: INTRODUCTION


Figure 1.1

SEM photograph of (a) chemically produced toner and (b) conventional


toner

Figure 1.2

Basic principle of electrophotography

Figure 1.3

Diagram of the manufacturing process for conventional toner

Figure 1.4

Image with banding defect

Figure 1.5

Image with repetitive marks

Figure 1.6

Image with positive ghosting defect

Figure 1.7

Schematic diagram of the stages of dispersion in suspension polymerization

Figure 1.8

Thermal decomposition of benzoyl peroxide

CHAPTER TWO: EXPERIMENTAL


Figure 2.1

Apparatus for synthesis Styrene Acrylic Copolymer (A: mechanical stirrer,


B: condenser, C: thermometer, D: reactor flask with detachable lid, E:
heater controller, F: water bath)

Figure 2.2

Process to produce raw toner

Figure 2.3

Test images

CHAPTER THREE: RESULTS AND DISCUSSION


Figure 3.1

DSC thermogram of L20-TR, L21-TR, L22-TR, L15-TR and L16-TR at the


heating rate of 10oC/min

Figure 3.2

Comparison of Tgs of Styrene Acrylic Copolymers obtained from


experimental and calculation by Fox equation and Gordon-Taylor equation

(k=0.3445)
Figure 3.3

FT-IR spectra of L20-TR, L22-TR and L16-TR

Figure 3.4

DSC thermogram of L23-TR, L24-TR, L25-TR, L18-TR and L16-TR at the


heating rate of 10oC/min

Figure 3.5

DSC thermogram of H22-TR, H15-TR, H16-TR, H17-TR and H23-TR at


the heating rate of 10oC/min

Figure 3.6

Comparison of Tgs of Styrene Acrylic Copolymers obtained from


experimental and calculation by Fox equation and Gordon-Taylor equation
(k=0.5461)

Figure 3.7

FT-IR spectra of H22-TR, H16-TR and H23-TR

Figure 3.8

Plausible cross-linking reaction to form cross-linked Styrene Acrylic


Copolymer

Figure 3.9

DSC thermogram of H17-TR, H18-TR and H19-TR at the heating rate of


10oC/min

Figure 3.10

GPC profiles of H18-TR, L18-TR and M10-TR

Figure 3.11

Comparison of GPC chromatogram of Blended Resins at different blending


ratios

Figure 3.12

DSC thermogram of M08-TR, M09-TR, M10-TR, M11-TR and M12-TR at


the heating rate of 10oC/min

Figure 3.13

M09-FT (A: under magnification 40X, B: under magnification 100X)

Figure 3.14

M10-FT (A: under magnification 40X, B: under magnification 100X)

Figure 3.15

M11-FT (A: under magnification 40X, B: under magnification 100X)

Figure 3.16

TGA curves of M09-FT, M10-FT and M11-FT at the heating rate of


30oC/min

Figure 3.17

Example of test images template (A: text target, B: black page uniformity,
C: image and background density target)

Figure 3.18

Example of test images template (A & B: tone reproduction, line edge


raggedness and resolution test target, C: gray page uniformity)

Figure 3.19

Example of test images template (A: thermal banding target, B & C:


monochrome toner yield)

Figure 3.20

DSC thermogram of of M10-TR, commercial resin A, commercial resin B,


commercial resin C and commercial resin D at the heating rate of
10oC/min

Figure 3.21

Microscope pictures of (a) M10-FT and (b) Commercial toner A

APPENDIX A: Machines used to produce raw toner


Figure A.1

Henschel Mixer (A: Sample container with cooling jacket, B: Power button)

Figure A.2

Extruder

Figure A.3

Crusher

Figure A.4

Jet mill and Classifier

Figure A.5

Blender (A: Sample container, B: timer, C: speed controller)

APPENDIX B: Instruments used for sample characterization


Figure B.1

Mettler Toledo Differential Scanning Calorimeter 822e

Figure B.2

Gel Permeation Chromatography (GPC)

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

(a) Instrument for tribocharge determination (A: tribometer, B: electrometer,


C: sample cell which held by tribometer)

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

CILAS 1064 particle size analyzer

Figure B.8

Tectron Ag. 916 Fluxmeter

Figure B.9

QUIKDens 100 Densitometer

APPENDIX C: DSC profiles of toner resins and toners


Figure C.1

DSC profile of L20-TR

Figure C.2

DSC profile of L21-TR

Figure C.3

DSC profile of L22-TR

Figure C.4

DSC profile of L15-TR

Figure C.5

DSC profile of L16-TR

Figure C.6

DSC profile of L23-TR

Figure C.7

DSC profile of L24-TR

Figure C.8

DSC profile of L25-TR

Figure C.9

DSC profile of L18-TR

Figure C.10

DSC profile of H22-TR

Figure C.11

DSC profile of H15-TR

Figure C.12

DSC profile of H16-TR

Figure C.13

DSC profile of H17-TR

Figure C.14

DSC profile of H23-TR

Figure C.15

DSC profile of H18-TR

Figure C.16

DSC profile of H19-TR

Figure C.17

DSC profile of M08-TR

Figure C.18

DSC profile of M09-TR

Figure C.19

DSC profile of M10-TR

Figure C.20

DSC profile of M11-TR

Figure C.21

DSC profile of M12-TR

Figure C.22

DSC profile of Commercial Resin A

Figure C.23

DSC profile of Commercial Resin B

Figure C.24

DSC profile of Commercial Resin C

Figure C.25

DSC profile of Commercial Resin D

APPENDIX D: TGA profiles of toners


Figure D.1

TGA curve of M09-FT

Figure D.2

TGA curve of H10-FT

Figure D.3

TGA curve of M11-FT

Figure D.4

TGA curve of magnetite pigment

Figure D.5

TGA curve of charge control agent

APPENDIX E: GPC profiles of toner resins and toners


Figure E.1

GPC profile of L18-TR

Figure E.2

GPC profile of H18-TR

Figure E.3

GPC profile of high molecular weight fraction of M10-TR

Figure E.4

GPC profile of low molecular weight fraction of M10-TR

Figure E.5

GPC profile of high molecular weight fraction of M10-FT

Figure E.6

GPC profile of low molecular weight fraction of M10-FT

APPENDIX F: Particle Size Distribution Data Sheet


Figure F.1

Particle size distribution of M09-FT

Figure F.2

Particle size distribution of M10-FT

Figure F.3

Particle size distribution of M11-FT

LIST OF TABLES

CHAPTER ONE: INTRODUCTION


Table 1.1

Classification of print quality defects

CHAPTER TWO: EXPERIMENTAL


Table 2.1

Series 1 - Different monomer ratios at constant initiator concentration

Table 2.2

Series 2 - Different concentrations of initiator at constant monomer ratio

Table 2.3

Series 3 - Different monomer ratios at constant AA, initiator and CLA


concentration

Table 2.4

Series 4 - Different concentrations of cross-linking agent (CLA) at constant


monomer ratio and initiator concentration

Table 2.5

Formulation to produce raw toner

Table 2.6

Formulation to produce toner

CHAPTER THREE: RESULTS AND DISCUSSION


Table 3.1

FT-IR spectral peak area ratio of1601 cm-1/1724 cm-1 bands in the
Styrene Acrylic Copolymers

Table 3.2

Effect of varying monomer ratios at constant initiator concentration

Table 3.3

Effect of varying initiator concentration at constant monomer ratio

Table 3.4

FT-IR spectral peak area ratio of1601 cm-1/1724 cm-1 bands in the
Styrene Acrylic Copolymers

Table 3.5

Effect of varying monomer ratio at constant AA, initiator and cross-linking


agent concentration

Table 3.6

Effect of varying cross-linking agent concentration at constant monomer


ratio and initiator concentration

Table 3.7

Effect of blending High Molecular Weight and Low Molecular Weight


Copolymers at different ratios

Table 3.8

Properties Results for toners

Table 3.9

Percentage weight loss of toners at different temperature region obtained


from TGA at the heating rate of 30oC/min

Table 3.10

Thermal decomposition temperature of toners obtained from TGA at the


heating rate of 30oC/min

Table 3.11

Image density values of the three print test images

Table 3.12

Background density values of the three print test images

Table 3.13

Properties of the synthesized toner resin and commercial toner resins

Table 3.14

Properties of the synthesized toner and a commercial toner

Table 3.15

Image density values of M10-FT and Toner A

Table 3.16

Background density values of M10-FT and Toner A

APPENDIX G: Calculation of Acid Number of High Molecular Weight Styrene


Acrylic Copolymers and Blended Resins
Table G.1

Calculation of Acid Number of High Molecular Weight Styrene Acrylic


Copolymers

Table G.2

Calculation of Acid Number of Blended Resins

APPENDIX H: Calculation of Percentage of THF Insoluble Fraction of High


Molecular Weight Styrene Acrylic Copolymers and Blended Resins
Table H.1

Calculation of Percentage of THF Insoluble Fraction of High Molecular


Weight Styrene Acrylic Copolymers

Table H.2

Calculation of Percentage of THF Insoluble Fraction of Blended Resins

APPENDIX I: Estimation of Tg by using Fox equation and Gordon-Taylor equation


Table I.1

Estimation of Tg of Low Molecular Weight Styrene Acrylic Copolymers by


using Fox equation

Table I.2

Estimation of Tg of High Molecular Weight Styrene Acrylic Copolymers by


using Fox equation

Table I.3

Calculation of fitting factor, k of Low Molecular Weight Styrene Acrylic


Copolymers by using Gordon-Taylor equation

Table I.4

Calculation of fitting factor, k of High Molecular Weight Styrene Acrylic


Copolymers by using Gordon-Taylor equation

Table I.5

Estimation of Tg of Low Molecular Weight Styrene Acrylic Copolymers by


using Gordon-Taylor equation

Table I.6

Estimation of Tg of High Molecular Weight Styrene Acrylic Copolymers by


using Gordon-Taylor equation

LIST OF ABBREVIATIONS

AA

Acrylic Acid

AN

Acid Number

BA

Butyl Acrylate

BD

Background density

BPO

Benzoyl Peroxide

CCA

Charge Control Agent

CLA

Cross-linking Agent

CPT

Chemically Produced Toner

DSC

Differential Scanning Calorimetry

GPC

Gel Permeation Chromatography

ID

Image Density

MFI

Melt Flow Index

Mn

Number Average Molecular Weight

Mw

Weight Average Molecular Weight

Mp

Peak Value for Molecular Weight Distribution

Mz

Z-average Molecular Weight

Polydispersity Index

MWD

Molecular Weight Distribution

Tg

Glass Transition Temperature

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