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2005

Modification of a single-solvent-based gravure ink for enhance

wettability and substrate adhesion
Wiphut Janjomsuke

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 Modification of a single-solvent-based gravure ink

for enhance wettability and substrate adhesion

By

Wiphut Janjomsuke

A thesis submitted in partial fulfillment of the

requirement for the degree of Master of Science in the

School of Print Media in the College

of Imaging Arts and Science of the

Rochester Institute of Technology

May 2005

Thesis Advisors: Professor Scott A. Williams

Professor Mary Anne Evans
 School of Print Media
Rochester Institute of Technology
Rochester, New York

Certificate of Approval

Master's Thesis Proposal

This is to certify that the Master 's Thesis of

has been approved by the Thesis Committee as satisfactory

for the thesis requirement for the Master of Science degree
at the convocation of

Thesis Committee:

Scott A. Williams
Primary Thesis Advisor

Mary Anne Evans

Secondary T hesis Advisor

Thesis Consultant

Twyla J. Cummings
Graduate Thesis Coordinator

Twyla J. Cummings
Graduate Program Coordinator

Patricia Sorce
Chair, SPM
Title of thesis :

Modification of a single-solvent-based gravure ink for enhance wettability and substrate

adhesion

I, Wiphut Janjomsuke, hereby grant permission to the Wallace Memorial Library of

R.I. T. to reproduce my thesis in whole or in part. Any reproduction will not be for

commercial use or profit.

Date:

Signature: Wiphut Janjomsuke

 Acknowledgements

I sincerely appreciate the efforts of those who helped me with this thesis. I would

like to thank the for their time, help, and patience with this thesis.
following persons

Dr. Scott A. Williams, for technical advice and helping in experimental planning;

Dr. Anne Evans, for technical advice, and Mr. Daniel

Dr. Twyla Cummings and Mary

Clark Application Laboratory for advice and helping in laboratory

of the Printing

equipment.

in
 Table of Contents

vii
List of Tables

VU1
List of Figures

x
Abstract

Introduction 1
Chapter 1 -

Theoretical Basis 4
Chapter 2 -
of Study
4
2.1 Surface Tension
2.2 Contact Angle
5
9
2.3 Viscosity
Newtonian 10
Viscosity
n
2.4 Ink Setting

Review Literature 12
Chapter 3 -
of

12
3.1 Introduction
Gravure Process What is Gravure? 12
Printing
-

Gravure 14
History of

Gravure Ink
15
3 .2

Gravure Inks 16
3.2. 1 Classification of

Publication Gravure Inks 16

Product Gravure Inks 17

Packaging and

Ink Components 18
3 .2.2

Colorants i8

Vehicles 21

Additives 23

Solvents 24

3.2.3 Ink Transfer and Drying Mechanisms 26

3.2.4 Single Solvent-based Gravure Ink 28

3.2.5 Surface Active Agents 29

iv
 the Research 31
Chapter 4 -
Statement of

Chapter 5 32
-

Methodology
32
5 1 Introduction
.

5.2 Ink Preparation 33

5.3 Characterization of the Physical Properties 33

Surface Measurement 34
Energy
Contact Angle Measurement 35

Measurement 37
Viscosity
Drawdown Test 37

Adhesion Test 38

5.4 Ink Formulation Modifications 39

The Effect of Ink Temperature 40

Surface Tension Modifications 41

Press Run Analysis 41

43
5.5 Data Analysis
44
5.6 Experiment Limitations

The Results 45
Chapter 6 -

45
6.1 Ink Component Experiments
Water and Propanol 46

Ethyl Acetate and Nitrocellulose 49

Dioctyl Phthalate 51
Ethyl Acetate and

Isopropanol Acetate 53
Ethyl Acetate and

the Ink Component Experiments

56
Summary of

57
6.2 Ink Formulation Experiments
58
Ink Preparation

Physical Properties
59

Surface Tension 59
60
Viscosity
61
Contact Angle
Temperature 62
The Effect of

The Effect of Pigment Type 64

Adhesion 66

Drawdown Test 66

Dots-on-substrate Test 67

Ink-on-ink Test 69

of the Ink Formulation Experiments 71

Summary
 '3
6.3 Surface Tension Modification
80
Summary of the Surface Tension Modification
81
6.4 Press Run Analysis

Conclusions 88
Chapter 7 -

Summary and

y3
Glossary

"5
Bibliography

vi
 List of Tables

Table 5.1. Single solvent-based ink components 33

Table 5.2. Ink formulations 40

Table 6.1. the ink component experiments 56

Summary of

Table 6.2. Substrate and chemical components surface tension

57

Table 6.3. Ink formulation surface tension at different pigments and solvents 59

Table 6.4. Inks viscosity at different types of solvents and pigments 60

different types of solvents and pigments 61

Table 6.5. Ink contact angle at

Table 6.6. Drawdown adhesion test at different types of solvents and pigments 66

Table 6.7. Dot adhesion test at different types of solvents and pigments 68

Table 6.8. Ink-on-ink Test (cyan pigment) 69

Table 6.9. Ink-on-ink Test (black pigment)

70

the Ink Formulation Experiments 72

Table 6.10. Summary on

information 74
Table 6.11. Surface active agent

ink different kinds of additives 77

Table 6. 12 Black ethyl acetate with

86
Table 6.13 New ink formulations dot area analysis

vn
 List of Figures

5
Figure 2.1. Contact angle

'
Figure 2.2. Adhesion and cohesion ratio

10
Figure 2.3. A concentric viscometer

(Copper Phthalocyanine) 19
Figure 3.1. Phthalocyanine molecule structures

Cellulose Nitrate molecule structure 22

Figure 3.2. Nitrocellulose or

Figure 3.3. Toluene and Xylene molecule structure 25

26
Figure 3.4. Ethyl Acetate Molecule Structure

tensiometer 35
Figure 5.1. Fisher Scientific surface

36
Figure 5.2. Contact angle measurement

37
Figure 5.3. Brookfield digital viscometer

42
Figure 5.4. Gravure proofing press

42
Figure 5.5. Engraved gravure cylinder

(black) 43
Figure 5.6. IT 8.7/3 test target

Iso-propanol
Figure 6. 1. Relation between the percentage of

and surface tension

46

of surface-active molecules 48
Figure 6.2. Adsorption

Figure 6.3. Relation between percentage of Nitrocellulose in ethyl acetate and

surface tension 49

vin
 50
Figure 6.4. Nitrocellulose on OPP film

Figure 6.5. Relation between percentage of DOP in ethyl acetate

52
and surface tension

Figure 6.6. DOP contact angle

53

Figure 6.7. Relation between percentage of isopropyl acetate in ethyl acetate

and surface tension

54

Figure 6.8. Relation between ethyl acetate-based ink and contact angle

and time at
32
C 62

Figure 6.9. Relation between black ethyl acetate-based ink contact angle and time

at different temperatures 63

Figure 6.10. Relation between ethyl acetate-based ink surface tension and temperature

at different types of pigments 65

Figure 6.11. Relation between ethyl acetate-based black ink contact angle

and temperature
68

ink dots 67
Figure 6.12. Fish eye effect on ethyl acetate-based

isopropyl acetate-based ink dots 69

Figure 6.13. Donut effect on

time at different types

Figure 6.14. Relation between ink contact angle and

'
of surfactants

(100% dot area, 5X magnified) 82

Figure 6.15. Ink appearance

(50% dot area, 5X magnified) 83

Figure 6.16. Ink appearance

(50% dot area, 20X magnified) 84

Figure 6.17. Ink appearance

(40% dot area, 5X magnified) 85

Figure 6.18. Ink appearance

86
Figure 6.19. Ink dot area

IX
 Abstract

types on C-type
ester-
In this research, the effect of solvent types and pigment

based gravure inks were studied. Three of the widely used solvent types and two of the

pigment types were used in this study. The characteristics of the modified inks were

investigated important physical properties of the inks: (i) surface

by measuring the most

(iv) substrate adhesion. The experiment

energy, (ii) contact angle, (iii) viscosity and

results showed that the ink properties changed significantly depending on the solvent

while pigment type variation had a negligible effect on the ink properties. From this
type,

in the ethyl-acetate-based ink. In

experiment, the most improved properties were obtained

order to further improve the ink properties without suppressing the advantage of this

small amounts of various aqueous additives and surfactants

were added to
solvent type,

find suitable formulations. From this stage of study, three ink formulations with suitable

and properties were achieved. These formulations were C-type ethyl-

printability wetting

acetate-based ink with one of the following surfactants; 0.8 percent of Zonyl FS-300, 0.1

percent of Zonyl FSJ, and 12 percent of hexane. The wetting and print performance

characteristics of these formulations were tested by practically using them in the pilot

press trials. The results from pilot press trials indicated that the new ink formulations

with low concentration aqueous surfactants may be used to minimize printing problems

such as and fish-eye effect. However, even the best performance formulation
pinholing
was found to have quite high temperature sensitivity and surface tension higher than the

lead to poor quality.

theoretical upper surface tension limit. These, unfortunately, printing

to find a better ink formulation with superior properties

Therefore, further study is needed

the printing problems.

that will overcome print quality difficulties and completely solve

XI
 Chapter 1

Introduction

Single-solvent (also called monosolvent) gravure ink is one of the inks that is

widely used in the food and beverage packaging industry in European countries,

especially in Italy and Scandinavia. Single-solvent gravure inks have the advantage of

lower in cost, environmentally friendly, and more cost-effective in terms of solvent

being

recyclability. The typical solvent tends to be an ester, such as isopropyl acetate or ethyl

acetate (Langhammer J. P., 1994). Ester-based inks are also more environmentally

inks in terms of the fulfillment of the

friendly than xylene/toluene solvent-based

requirement that highly volatile organic compounds not be emitted into the atmosphere

(Rochelli V., 2000).

Even though the single-solvent-based ink has many advantages as mentioned

disadvantages that cannot be overlooked. For example,

above, it also has some significant

the ethyl-acetate-based single-solvent ink has high solvent retention values and odor,

which are sensitive issues in food and beverage packaging industry and slow drying
very

rate when compared to the other packaging gravure inks. Of all the disadvantages, the

most critical is the limited control of ink surface energy. Improper ink surface energy

leads to several printing problems, for example screening, pinholing, and fish-eye effect
as well as the donut effect. it impossible to acquire data on
Industry confidentiality made

the existence of modified formulations that might solve the surface energy problem. As a

result, the solution to the problem of limited surface energy control of single-solvent

gravure inks is unclear even now. Therefore, the motivation for this research was to study

the effect of solvent types and pigment types on C-type ester-based gravure inks in order

to modify the single-solvent-based ink formulation with the enhanced ink wettability and

substrate adhesion.

To modify the single-solvent-based gravure ink, the researcher started with simple

C-type gravure ink. The basic ingredient in C-type ink is nitrocellulose. Plasticizer was

added to C-type ink to achieve special characteristics and to improve ink properties.

These combinations require solvents of the ester class, such as ethyl acetate, isopropyl

acetate, propyl acetate, and butyl acetate. In this research, ethyl acetate and dioctyl

phthalate were used as ink solvent and plasticizer, respectively.

In this research, experiments were divided into four major steps: (i) the physical

formulation modification, (iii) tension

property characterization, (ii) ink surface

modification, and (iv) press run analysis.

Initially, ink components, nitrocellulose (binder), dioctyl phthalate (plasticizer),

and isopropyl acetate (alternative solvent), were mixed with ethyl acetate. After mixing,

the physical properties of the mixed ink, including surface energy, contact angle,

adhesion force were investigated. Then, six ink formulations were created
viscosity, and

based on three of the widely used solvent types and two of the pigment types. The

solvents used in this experiment were (i) isopropyl acetate (ii) 50% propanol+50% ethyl

acetate, and the pigments used were phthalocyanine blue and

acetate and (iii) ethyl
Furnace black. The physical properties of these new ink formulations were measured in

order to find out the ink formulations with good wettability and substrate adhesion. Then,

the researcher tried to further modify the achieved ink formulations by adding small

amounts of various aqueous additives and surfactants, which are widely known to

improve the ink properties without suppressing the advantage of this solvent type. At this

step, the improved ink formulations were achieved. Finally, the wetting and print

performance characteristics of these formulations were tested by practically using them in

the pilot press trials.

Besides ink formulation modification experiments, the researcher also studied the

effect of temperature on ink wettability and drying rate. All ink formulation surface

20 40

tensions and contact angles were measured at different temperatures from C to C.

This test simulated ink drying rate and ink temperature sensitivity in press room

temperatures.

In Chapter 2, the theoretical basis of study is given. Review of literature and

statement of the research are presented in Chapter 3 and Chapter 4, respectively. The

experimental details are given in Chapter 5. In Chapter 6, the experimental data is

reported and discussed.

 Chapter 2

Theoretical Basis of the Study

2.1 Surface Tension

Gravure printing process has the printing area etched below the image carrier

surface. The ink contained in the etched cells transfers to the substrate by various forces,

depending on what type of substrate is used. In the case of a porous substrate such as

the capillary force aids that help transferring the ink to the substrate.
paper, there are

Since there is no capillary action occurring in the case of non-porous substrates, such as

plastics and metal foils, the ink transfer process depends strongly on the surface energy

and surface tension relationships. In order to wet a substrate, the ink surface tension

should be at least 10 mN/m lower than the substrate surface energy (Thomson, B., 1998).

of the liquid is higher than that of the substrate, the surface will be
If the surface energy

the ink be poor, and it may even exhibit reticulation.

poorly wetted and the lay of will

is measure of how a substrate surface and ink will

Therefore, the surface tension a key

Intimate wetting promotes good print acceptance and adhesion.

interact to each other.

Surface tension is defined as the force acting along the surface of a liquid at right

angles to any line of unit length. In the older system of units, but one, which still prevails,

the force and unit length are expressed in dynes and centimeters respectively, and the unit
of measurement for surface tension is dynes/cm. In the SI system, the force is expressed

in the unit of length in a unit of measurement for

millinewtons (mN) and meters giving

Surface tension be based the force

surface tension of mN/m. can directly measured on

interface them upward from the liquid. The

needed to keep objects at an or pull

instruments by which such forces are measured are called tensiometers.

Du is the most to measure liquid

Nouy ring method one of popular methods

surface tension. In this method, the force required to detach a ring from a surface or

interface is suspending the ring from the arm of a balance or by using

measured either by

a torsion wire arrangement. The detachment force is related to the surface or interfacial

tension.

Surface tension measurements are good indicators of wettability, but they do not

produce precise numbers that can guarantee good adhesion or print acceptance. Contact

be measured with surface tension, to assure good adhesion and printed

angle must along

appearance.

2.2 Contact Angle

is the angle between the solid surface and the tangent to the liquid
A contact angle

surface at the angle of contact. Liquids having contact angles of less than 90 degrees tend

A contact angle of zero degree indicates that a liquid will completely

to wet surfaces.

while a contact angle of more than 90 degrees indicates the liquid beads
cover a surface,

on a surface. When a liquid comes into contact with another phase such as a solid,
up

forces of attraction will usually be set up between the two phases, the strength of which

determines what happens at the interface (Figure 2.1.). In gravure process, liquid is ink
and solid is the substrate (Figure 2.1.).

>

Air
h L/A

y Liquid

H
7 7
S/A
Solid

Figure 2.1. Contact angle

The various surface forces can be represented by surface tension acting in the

direction of the surfaces, equating the horizontal components of these tensions (Figure

2.1.).

S/A= S/L+
L/A COS (1)

this expression with the appropriate form of the Dupre equation

Combining

( ws/L
=
S/A + L/A
"

S/L )>

WS/L=
L/A (1 "

cos )

(2)

between solid phase and liquid phase. It equals the

ws/L is tne work of adhesion

work required to separate a unit area of the solid-liquid interfaces and forms a separate

liquid-air interface and a solid-air interface. L/A is the work of adhesion for a single

cross-
to the work required to pull apart a column of unit sectional
liquid and corresponds

area (Shaw, D.J., 1970).

Zero contact angle results when the forces of attraction between liquid and solid

to or greater than, those forces between liquid and air. A finite contact angle
are equal
results when the liquid adheres to the solid less than it coheres to itself. Contact angles of

zero to 90 degrees are taken to represent degrees of wetting, whereas angles of 90 to 1 80

2, adhesion and
degrees represent non-wetting (Thomson, B., 1998). From equation the

be liquid contact angle on a particular solid surface. The

cohesion ratio can calculated by

force of cohesion is defined as the force of attraction between molecules of the same

substance. The force of adhesion is defined as the force of attraction between different

substances.

2.5

2 &~-^~^

CO

sz 1.5
o
O
c
o
5. 1
__

< ..

0.5 '.,

"-...

30 60 90 120 150 180

Contact angle

Figure 2.2. Adhesion and cohesion ratio

a contact angle between zero and 90 degrees represents wetting. It

By definition,

liquid adhesion force is at least equal to or stronger than cohesion force

also means that

hand, nonwetting means that adhesion force is smaller than

(Figure 2.2.). On the other

liquid cohesion force.

The contact angle can be measured by recording an image of the liquid-solid

 tangential value of contact
interface using a projector or video camera and measuring the

angle. This is the simplest and most direct method, but putting a tangent to a curved

surface is subjective (Lyklema, J., 1991), more so since the profile can be optically

distorted.

If the forces between molecules in the solid and liquid interfaces are negligible,

the spherical shape of the liquid droplet is largely unaltered. On the other hand, if the

intermolecular forces of attraction are very strong, the liquid will be pulled onto the

surface and flattened out. The strength of the attractive forces causes the liquid and solid

to stick together. These are called adhesive forces, the phenomenon being called

adhesion. When the forces cause the liquid to spread, wetting is said to occur.

Conversely, nonwetting is the condition where zero or only partial spreading takes place

(Thomson, B., 1998).

are time-dependent.
Most of the contact angles for liquids, including printing inks,

The contact angle rate is a nonlinear function. The changing rate is dependent
changing

on both liquid and solid physical properties. Liquid properties, such as surface tension,

evaporation rate, temperature, liquid detergency, and solid properties, such as solid types,

foreign material on solid surface, and surface smoothness, are examples of factors that

influence the rate of contact angle change. Contact angle changing rate is an important

it determines how ink interacts with the specific substrate. An

factor for gravure ink, as

improper changing rate would cause printing defects (Fish-eye effect, donut effect).

The donut effect is defined as a printed dot that only prints on the circumference

in the center. Fish-eye effect is defined as a printed dot that has

of the cells leaving a void

thickness on the circumference. Deformed dots caused by the donut effect

higher ink film
increase the dot gain and mottle, which leads to a decrease in print quality (EPA, 2001).

Improper ink wettability and substrate adhesion are major causes of these effects.

2.3 Viscosity

is the internal resistance offered to the relative motion

Viscosity a measurement of

different the liquid. is important characteristic of gravure ink to

of parts of Viscosity the

be monitored and maintained on press. Viscosity must be controlled to ensure print

It influences printability,
uniformity and color consistency throughout the press run. also

drying speed, trapping, gloss, adhesion, and penetration (GAA, 2003).

The range of ink viscosities met with in gravure is generally between 15 to 25

Zahn No.2 25 C (Leach, R.H., 1988), which equals 20 to 50 mPa.s.

seconds Cup at

Viscosity depends on

The rheological characteristics of the ink

Speed of printing

Rate of evaporation of the solvent system

Shape and range of cell depths

The design parameters

Substrate properties

Since ink viscosity is such an important factor in the operation of the gravure

it requires an accurate fast method of viscosity measurement. Traditionally,

press,

flow cups for viscosity measurement of ink, which have near

printers have used

Newtonian flow. Today, automatic viscometry is widely used along with viscosity

for solvent from a header tank to be metered into the duct ink to
controllers which allow
replace solvent loss by evaporation (Leach, R.H., 1988).

Newtonian Viscosity

Gravure inks are defined as a near Newtionian liquid. In ideal or simple liquids

force liquid is to the amount of shear

the shearing applied to the directly proportional

Newtonian
strain (resistance) it produces (Shaw, D.J., 1970). Viscosity is described as

between two liquid in

shearing force
when the per unit area parallel planes of relative

motion is proportional to the viscosity gradient between the planes,

for studying the flow behavior

non-
Rotational methods are useful of
particularly

Newtonian liquids. In the an approximation to uniform

concentric viscometry technique,

rate of shear throughout the sample is achieved by shearing a thin film of the liquid

between concentric cylinders (Figure 2.3.). The outer cylinder can be rotated at a constant

rate and the shear stress measured in terms of the deflection of the inner cylinder, which

is suspended by a torsion wire (Figure 2.3.).

Figure 2.3. A concentric viscometer

10
2.4 Ink Setting

is the immediate buildup of viscosity the ink is applied to the paper;

Setting after

it promotes ink trapping in a multiple-color process. Setting is essential in

printing

sheetfed offset printing to avoid setoff. Setting is considered to be a physical

phenomenon, while drying is considered to be a chemical occurrence. For pasty inks,

the same time, and it is difficult to distinguish whether the

drying and setting occur at

increase in viscosity results from a physical phenomenon or from chemical behavior. For

liquid inks, other techniques are required to trap the second-down ink. The most effective

method used on gravure presses is to dry the film between each unit (Eldred, N. R. and

Scarlett, T., 1990).

11
 Chapter 3

Review of the Literature in the Field

3.1 Introduction

Gravure Printing Process

Gravure is a printing process that operates as one of the fastest and widest printing

processes in the world. Gravure is an intaglio printing process. There are four basic

components to each printing unit: an image carrier, the ink fountain, the doctor blade, and

the impression roller. The image carrier has the image cut or etched below the surface of

the image carrier, which is normally a chrome plated copper cylinder. This in-depth

variation enables different volumes of ink to be delivered from individual cells, giving

precise and repeatable control over tone and color produced on the prints. During

is immersed in the ink. As the image carrier rotates, ink fills

printing, the image carrier

cells and covers the surface of the

cylinder. The cylinder surface is wiped with a
the tiny

the non-image area clean while the ink remains in the recessed
doctor blade, leaving

is then brought into contact with the image carrier with the help of an
cells. The substrate

impression roll. At the point of contact, ink is drawn out of the cells onto the substrate by

action (Kasunich C.L., 1998).

capillary

12
 The term
"Intaglio"

is sometimes used to refer to all printing from engraved plates

including rotogravure, but today, intaglio plates are used to print currency, treasury bond,

some postage stamps and fine art reproductions. Intaglio plate printing uses very thick

to transfer images from to Rotogravure is the

ink, and requires great pressure plate paper.

most common form of the broad intaglio category (Eldred, N. R. and Scarlett, T., 1990).

electroplated with
The image carrier is usually made of a steel or aluminum core or base,

that the is below the surface of the

copper, and then etched or engraved so print area

cylinder. The entire cylinder is then chrome plated to increase the cylinder life (Thomson,

B., 1998).

Gravure is particularly suited to very long print runs where very high quality

is for a market share of 10-15%

reproduction required. Today, gravure printing accounts

in industrialized countries (Kipphan, H, 2003). A variety of substrates can be printed on

gravure process such as plastic film, metal film, paper, board, etc. Substrates are

form than sheet form. The simplicity of the process

commonly in continuous rather

makes automation and combination with

other converting processes possible, like

laminating, sheeting, folding, diecutting, and slitting (Thomson, B., 1998).

is used by all of the top ten publication companies,

In North America, gravure

count average of about 2.75 billion over the past five years. Seventy two
with a total copy

the standard magazine pages, 63% of the digest pages, and almost 100% of the
percent of

gravure printed. For the packaging market, a total of 6% of all

tabloid pages, are

product in the U.S. are gravure printed (Kasunich C.L., 1998).

packaging

13
History of Gravure

processes
Gravure printing is a very old process. For 1400 years, gravure printing

were produced by hand engraving tools. It was made by covering the plate with ink,

paper or other substrate on the plate to print. In the 16th

wiping the excess, and pressing

chemical was invented, whereby the image could be scratched into a

century etching

resistant on the metal surface and then engraved using sulfuric acid. This was a
coating

major step forward for the gravure process and high quality printing in general. By 1838,

the principles of photography were used in gravure plate making. In 1880, the first

tested in England by Karl Klic, and the first rotogravure presses

laboratory press was

were used at a plant called Rembrandt, from where the process quickly expanded

throughout the world (ERA, 2003). Carbon tissue continued to be the main method of

the process at this

producing gravure cylinders, using acid to etch away the cells, and

time required considerable skill to achieve the demanded result. Those involved in the

gravure process were committed to producing a work of art. In the late 1960s, electronic

was started and has become the main method for producing cylinders for the
engraving

gravure publication industry. Also, in the packaging and product gravure markets,

electronic engraving is the main method in the western world. However, worldwide

used method for producing gravure cylinders,

chemical etching is still the most widely

particularly in Asia.

There have been remarkable developments in this technology, including filmless

laser exposure techniques. As soon as gravure moved to electronic engraving, the process

it required was digital signals to drive the diamond engraving

no longer needed film, all

that gravure would become the first mass printing

heads. Therefore, it was natural

14
 (computer-to-image carrier).
process to produce the printing form from digital data only

In 1981 the industry started engraving directly from digital data, and has progressed

considerably since its early beginning.

The majority of the industry in Europe and the U.S. has moved to filmless

engraving. The advantages are so substantial that it has become the standard way of

cylinder production. Gravure has long since moved from an art form and craft skill to

being a computer controlled manufacturing process, ready to compete in the next century.

Outstanding print quality and high output consistency make gravure the ideal printing

process for a wide range of high circulation and high quality publication products.

(Kasunich C.L., 1998)

3.2 Gravure Inks

The gravure inking unit is the shortest inking unit from ink fountain onto the

substrate of all inking units used with conventional printing technologies. It consists only

ink that the printing plate directly with ink, and a doctor
of an feeding chamber supplies

blade. This is a closed system that permits the use of a very low viscosity ink (Thomson,

B., 1998).

Gravure inks are rapid-drying fluid inks that

have the proper viscosity to be drawn

action from the engraved wells in the cylinder or plate (Bruno, H.M., 2000)
by capillary

liquid ink (n=0 Pa.s, even as low as 0.01 Pa.s in publication

Gravure process uses a .05-0.5

which can fill the image forming cells of the gravure cylinder at high
gravure printing)

and high contact pressure, (1.5-5 MPa) compared to flexographic and offset
print speed,

2003).
printing (0.1-2 MPa) (Kipphan, H,

15
 From a process point of view, gravure inks are simpler in composition and

manufacture, compared to offset inks. Although additives, such as plasticizers, are

packaging use, the

inks
required to impart flexibility to ink films, particularly for flexible

are essentially simple liquids. This is reflected in their flow behavior, which usually

approximates Newtonian liquid behavior (Thomson, B., 1998).

3.2.1 Classification of Gravure Inks

A classification system is used to distinguish the various ink types and to assist

the printer in selecting the proper ink solvent. However, it cannot encompass all the

variations used in the gravure market. By product types

technologies, and technology

inks can be divided into two groups: publication gravure inks

printed by gravure, gravure

types and packaging/product gravure inks.

Publication Gravure Inks

Publication gravure inks are printed on paper for the production of magazines,

inserts, and other similar work. The primary

newspaper supplements, catalogs, advertising

inks are for the reproduction of text and pictures. The resins used in
use of the publication

and require modification to improve film toughness and

these inks are relatively brittle,

are not suited for work requiring high heat resistance. These inks are
adhesion. They

available in practically any color, including metallics and fluorescents (GAA, 2003).

of aliphatic
A-Type ink refers to an ink with a solvent composed primarily

Group VII inks. A-Type ink

hydrocarbon (GAA, 2003). A-type inks are also called

publication newspaper and board.

includes

16
 B-Type ink refers to ink containing toluene, which is a very volatile, flammable,

aromatic hydrocarbon (GAA, 1991). B-Type ink contains higher aromatic content.

Coated paper is a application for this type of ink (Gravure Technical Association, 1975).

In North America, there are two types of publication gravure ink classified by

solvent systems: high aromatic (greater than 90% toluene) solvent systems, and 60% of

toluene and 40% of aliphatic solvent systems (GAA, 2003).

Packaging and Product Gravure Inks

for printing packaging and product application are

Typically, ink systems utilized

chosen on the basis of the resins and solvents in the formulation. Other factors to be

considered include their flexibility and ability to adhere to the substrate, the

specifications of the end product, and product resistance (GAA, 2003).

C-Type inks. The basic ingredient in C-Type ink is nitrocellulose. Many other

resins and plasticizers may be added to a C-type ink to achieve special characteristics.

combinations require solvents of the ester class, such as ethyl acetate, isopropyl
These

propyl acetate, and butyl acetate. From the ketone class, acetone or methyl ethyl
acetate,

ketone can be used. This ink type can be mixed with limited amounts of aromatic and

diluents to C-
hydrocarbons that are not true solvents, but act as minimize solvent cost.

Type inks are typically used for packaging printing on foil, paper, and films, such as

coated and uncoated paper, and metallized paper.

polypropylene, polyester, paperboard,

this type of ink are excellent heat and scuff resistance for surface print
Advantages of

flexibility, and lamination performance required in many

applications to good adhesion,

reverse print applications (GAA, 2003).

17
 E-type inks. Vehicle systems, which are normally thinned with alcohol, are

designated as E-type. The n-propanol and

alcohols commonly used are ethyl alcohol,

isopropyl amounts of ethyl

alcohol. Many E-type inks benefit from the addition of small

acetate, or normal propyl acetate, to the solvent blends. Nitrocellulose is the most

common resin in E-type inks. E-type inks include a variety of inks and lacquers, and

some dye inks. They are often used on paper and paperboard, polypropylene and polyester

specialty-coated papers
films, shellac or nitrocellulose primed foil, pouch stock, and many

boards. low is required. C-Type and E-

and They are often chosen where residual odor

type of inks are the dominant group used in packaging gravure (GAA, 2003).

3.2.2 Ink Components

Gravure inks are principally made up of four components:

colorants (pigments, dyes),

vehicles (binder),

additives, and

carrier substances (solvent).

Colorants

Colorants are divided into two groups: pigments and dyes. Pigments, both organic

are colored particles that are insoluble in solvents and vehicles. The majority
and inorganic,

pigments utilized in gravure ink formulations are based on Azo, Phthalocyanine,

of the

and Quinacridone chemistry.

Dioxazine, Triphenylmethane,

used in gravure yellow and magenta ink such as

Azo pigments are normally
 nitrogen atoms
Pigment Yellow 1 3. Azo, which means organic compound containing two

double bond formed aromatic amine with

with (-N=N-), are by the reaction of a primary

nitrous acid. This forms a diazonium salt which reacts with a coupler to form the pigment

or sodium salt. Metallized azo pigments contain one or more acid groups in the molecule,

which react with a metal salt to render the pigment insoluble. The most commonly used

salts are barium, calcium, and strontium. Non-metallized azo pigments contain no acid

groups in the molecule, and do not require metallization to completely form the pigment

that produces an insoluble particle (GAA, 2003).

Phthalocyanines are a of light-fast organic pigments with four isoindole

group

four to form a Included are

groups, linked by nitrogen atoms conjugated chain.

phthalocyanine (blue-green), copper phthalocyanine (blue), chlorinated copper

phthalocyanine (green), and sulfonated copper phthalocyanine (green). The structure of

phthalocyanine is shown in Figure 3.1 (Parker, 2003).

molecule structures (Copper Phthalocyanine)

Figure 3.1. Phthalocyanine

19
 crystals.
Pigments consist of molecules that are cross-linked with one another as

Normally, pigments have a particle size of 0.1-2 microns (Eldred, N. R. and Scarlett, T.,

1990). The particle size of the pigment is determined during the manufacturing of the

pigment. Groups of individual particles form clusters of particles called agglomerates and

aggregates (GAA, 2003). A pigment particle can consist of several million molecules.

Only around 10% of the molecules lie on the surface, and it is only theses molecules and

a few underneath that can absorb light. Pigments disperse light. They have a wide

absorption band and are therefore not as pure as dyes, which possess narrower absorption

bands (Kipphan, H., 2003). Pigments impart color to the printing ink, either by

or in combination with other components such as metals, various micas or

themselves,

other raw materials.

in gravure except of a fluorescent type, are soluble in the

Dyes, not normally used

liquid portion of the ink and can be either synthetic or natural in origin. Most dyes are

transparent and have limited resistant and lightfastness properties.

very

Pigment always required a vehicle for binding them to the substrate, while dyes in

most applications connect themselves directly to the substrate surface (GAA, 2003). Dye

that almost every molecule can absorb photons,

molecules are surrounded by solvents so

which lead to higher color intensity and more luminous colors. However, Dyes are

known to have limited light-fastness (Kipphan, H, 2003).

20
Vehicles

Vehicles, ingredients
or binders, act as the glue that keeps the colorant and other

evenly dispersed in the liquid ink and adheres it to the substrate. They perform many

functions; encapsulating the pigment particles, allowing the particles to break down, and

developing the color, strength, gloss, and transparency of the ink. Vehicles also carry the

colorant through the printing process and deposit it on the substrate. It consists essentially

of a resin dissolved in a volatile solvent. Binders can be a single resin or a complex

combination of resins and additives. Resins are classified either as film formers or non-

film formers. Film formers are polymers capable of forming a continuous and totally

flexible film, either with or without the presence of a plasticizing agent. They aid in

adhesion, and impart such properties as toughness and chemical resistance (GAA, 2003).

Resins are non-crystalline solid material of high molecular weight. Resins used in

hardness, in
printing inks contribute to the properties of gloss, adhesion, and printability

the ink. Resin can be classified into two types, natural resin (such as Rosin, shellac, Gum

arabic) and synthetic resin (such as Alkyd resin, Polystyrene resins, Polyamide resin,

Vinyl resins).

Nitrocellulose, polyamide resins, and acrylic resins are some of the more widely

used gravure ink for paper, polymer films, foil and board. These resins are usually in

combination with other resins. Nitrocellulose has excellent scratch, heat and rubber

resistance. Nitrocellulose (cellulose nitrate) is made by treating purified cellulose with

excess nitric and sulphuric acids.

21
 CH2ON02

0N02 ONO- "

ONO,~^T^

ON02 -U^

ono2

Figure 3.2. Nitrocellulose or Cellulose Nitrate molecule structure

(-
Polyamide resins are a large family of polymers that include the amide grouping

CO-NH-) in the main polymer chain. The largest class of polyamides is the nylon group

of polymers that has high molecular weight and poor solubility. Advantages of polyamide

resins are excellent compatibility with shellac, rosin, maleic, phenolic, and ketone resins

that have a, high gloss resistance to fats and grease. When incorporated into gravure inks

they create excellent adhesion to difficult substrates such as polyethylene, polypropylene,

polystyrene.

Acrylic resins are based upon monomers of acrylic acid (CH2=CH-COOH) and

methacrylic acid. Acrylic resins can be found in almost any solvent system used in

is large. Acrylic resins are chemical

printing inks because the
modern range of acrylic so

inertness that have very good light fastness and resistance to yellowing. Most types are

soluble in gravure ink solvents, but grades are available that are soluble in alcohols and

high distillates.
both low and boiling aliphatic

Resins capable of forming a film without any additives are considered internally

plasticized. Certain polyamides and vinyl resins have this function. Conversely,

nitrocellulose and certain acrylics are brittle polymers that will not form a film without

the addition of a proper plasticizer. Acrylics, polyamide, shellac, vinylidine chloride, and

22
 are
vinyl chloride are examples of common film forming resins. Non-forming resins

do form a
natural or synthetic polymers that are exceedingly hard or very brittle, and not

continuous flexible film even with the addition of plasticizers. Non-film forming resins

are used in inks to increase gloss, to improve adhesion to certain stocks, and to produce

higher ink solids (GAA, 2003).

Plasticizers are solvents or lower molecular weight polymers that

non-evaporating

remain in the vehicle after the solvent has evaporated. Plasticizers affect flexibility,

product resistance, lubricity, glueability, heat resistance, adhesion, printability, gloss,

2003). Solvent-type in the film and impart

odor, and blocking (GAA, plasticizers remain

flexibility by partially dissolving the resin. These plasticizers include sulfonamides,

citrates, phthalates and phosphates. Polymeric plasticizers increase flexibility by

softening the chemical bonds of the resins. These changes in surface tension are a

consequence of the polymer-plasticizer interactions. Plasticizers are capable of moderate

hydrogen bonding based on their solubility parameters (Sakellariou and Rowe, 1995).

Interaction of the plasticizer with the polymer reduces polymer-polymer interactions and

allows for greater polymer chain mobility that results in a slightly altered surface

configuration. It is also possible that some plasticizer molecules are present at the surface

of the polymer film (Panzer, 1973).

Additives

Additives, or modifiers, are added to the ink influence drying, flow behavior, and

are added during the formulation process that includes neutral

abrasion resistance. They

pigments, waxes, plasticizers, viscosity

modifiers, and slip agents (Kipphan, H, 2003).

23
Typical additives include:

Wax -
to improves rub resistance and lower the coefficient of friction

Siloxanes and Silicones -

to improve release characteristics or lower

coefficient of friction (COF)

Surfactants -

to reduce surface tension for improved grinding efficiency and

substrate wetting on-non-porous substrates

Crosslinkers -
to improve heat and product resistance

Corrosion inhibitors -
to prevent galvanic cell formation in water-based ink

Bacteriocides -

to prevent fungi and mold growth in aqueous systems

Optical brighteners -

for appearance or security

Defoamersor antifoams -

to minimize or eliminate foam in aqueous systems.

(GAA, 2003)

Solvents

the low viscosity

particularly important in They
gravure. ensure of
Solvents are

the ink and also change the pigment concentration/optical ink density (Kipphan, H,

2003). Carrier substances, or solvents, serve two purposes: to dissolve the resin and to

adjust viscosity. They are classified as active, latent or incompatible, diluent based on

their ability to dissolve the resin in specific ink. Ink formulators and printers select

the system, press speed, trapping, cost, and toxicity of the solvent.
solvents based on resin

dissolves a resin or polymer by itself. Diluent are usually added to

An active solvent

of ink. Latent solvents do not dissolve a resin but become active in the
reduce viscosity

presence of an active solvent.

Solvent are particularly important in gravure. Completely

24
different solvents have to be used for publication gravure and packaging gravure. This is

mainly because of the very varied requirements of individual packaging (GAA, 2003).

The most important solvents for publication gravure are toluene, xylene, and

petroleum spirits. Toluene, a petrochemical product, is a colorless flammable liquid that

is an ideal solvent for gravure ink. Pure toluene is derived from the fractional distillation

of light coal tar oil or catalytic of petrochemicals. Toluene does an excellent job
cracking

dissolving the binders which surround the pigments, can be regained to a great extent in

reclamation systems, dries with comparatively little expenditure of energy, and is

available at a reasonable price. Xylene is closely related to toluene from a chemical

aspect. It is also derived from petroleum and dries more slowly than toluene,

Xylene is rarely in except in

approximately half time of toluene. used gravure printing

gravure proofing and sheetfed gravure inks (Kipphan, H., 2003).

,CH,
,CH,

S^ 'CH,,

Toluene Xylene

Figure 3.3. Toluene and Xylene molecule structure

The most important solvents for gravure package printing are ethanol, ethyl

water (Kipphan, H, 2003). Ethanol, or ethyl alcohol, is not used as pure

acetate, and

printing inks. The water, or

combination of ethanol with ester
solvent in commercial

Ethyl acetate is one of the best low boiling solvents for nitrocellulose
solvent is common.

25
 It usually combines with
that is created by esterification of acetic acid with ethyl alcohol.

a small amount of alcohol to increase its characteristics. Ethyl acetate is extensively used

in gravure inks manufacturing and in lacquer formulation as a fast drying solvent.

f ! H
n u

HC 0
X
\ H/ \
H H

Figure 3.4. Ethyl Acetate Molecule Structure

3.2.3 Ink Transfer and Drying Mechanisms

The inks allows the recessed cells of the gravure cylinder to be

fluidity of gravure

filled rapidly. The inking system is a short time and distance between the ink tank and the

cylinder. Gravure ink requires fast drying time and quick transfer to the substrate, and

volatile solvents such as toluene can be used. Other important factors

therefore highly

that affect gravure ink transfer are

the wetting properties of the printing substrate

the surface properties of the material involved

the properties of the paper

the viscosity of the ink

the printing pressure

the printing speed

the shape of the cells and their filling level (Kipphan, H, 2003)

The for gravure inks are evaporation for non-porous (plastic and
drying processes

26
metal) stocks, coupled with absorption for porous (paper and board) stock (Thomson, B.,

1998).

In the process of evaporation, the solvent component evaporates leaving behind

in is affected by the
pigment entrapped resin at the surface of the substrate. Drying speed

evaporation rate of the solvents used to adjust viscosity. Drying speed is also affected by

the affinity of the resin for the solvents. Generally, the greater the affinity of the resin for

the solvents, the slower the rate of solvent release (Leach, R.H., 1988). It has been

calculated that the drying rate of an evaporation drying ink is approximately proportional

to the square of the ink-film thickness (Young L.C., 1973). However, the evaporation

heat transfer
process is assisted by supplying heat energy to the ink by one of these

methods, conduction, convection and radiation. Each type of ink requires a very careful

balance of properties if the characteristics of the ink are to meet the requirements of the

gravure process and the end use of the printing article.

be considered the first of the printing ink

The absorption drying process can

After adding printing ink to the substrate, the ink is slowly absorbed into
drying methods.

the fibers of the substrate. Surface tension will cause some of that liquid to be drawn into

in the surface structure. The network of narrow channels between fiber and
the openings

the particles of mineral loading makes most papers extremely porous materials, and the

attraction of the ink into paper surface provides the simplest physical method of
capillary

1973). For this to occur, the substrate must be as absorbent as

drying (Young L.C.,

but not so absorbent as to cause the ink to be absorbed through to the other side
possible,

or to cause the vehicle to be absorb too much

of the substrate and cause strike-through,

substrate and produce

show-through. The absorption drying process
into the fiber of the

27
is (Todd R.E., 1994). Although
also referred to as the penetration drying process

into the
the initial drying removing the liquid
component
absorption assists process by

from the gives a lower

stock, it also removes pigment and resin substrate surface, and

optical density and saturation (Todd R.E., 1994).

For non-porous substrate especially plastic films, corona treatment is an effective

way to improve ink transfer. The material being treated is exposed to an electrical

discharge, resulting in a chemically activated surface. Corona treatment increases

substrate surface energy and improve adhesion bond between ink and substrate.

3.2.4 Single Solvent-based Gravure Ink

Since the ink used for gravure printing has a low viscosity, the ink in the cells can

run out and be transferred on to the substrate on high speed web presses. This low

high proportion of solvent with a low boiling

viscosity is a principle achieved by using a

point in the ink. (Kipphan, H, 2003). As described in the ink components section,

gravure inks are classified on the basis of the resins and solvents in the formulation.

Gravure inks are also classified by how many solvents are used in the formulation. Single

solvent based ink, and multiple solvent-based inks can be found in both publication and

packaging/product categories.

Single solvent-based gravure ink is widely used in European countries especially,

Scandinavia countries where the solvent tends to be ester type such as ethyl
Italy and

been widely for food and beverage

(Langhammer, J. P., 1994). It has also used
acetate

The of a single solvent-based ink are they are easy to

packaging industry.
advantages

Solvent recovery reduces printing costs and causes less

recover and recycle.

28
environmental problems due to the avoidance emissions of VOCs in the atmosphere.

However, ethyl acetate based single solvent ink has a high total solvent retention values,

and odor, which is very sensitive issue in food and beverage packaging industry. During

printing process, ethyl acetate based inks have a slower drying rate than other packaging

inks and it is difficult to adjust viscosity during the press run.

3.2.5 Surface Active Agents

Solvent-based ink formulations with their naturally lower surface tensions, wet

readily and transfer well onto most substrates, even though they may have higher

coefficients of spreading on select substrates. Single solvent-based inks have inherent

flow, leveling. Single solvent-based inks

problems of surface wetting, foaming and and

require alcohols and surface active to lower their surface tensions to acceptable levels for

transfer, spreading and adhesion.

Surface active agents or surfactants have the ability to reduce surface tension.

There are four types of surfactant; anionic surfactant, cationic surfactant, nonionic

and amphoteric surfactant. These are classified by the ionic charge of the
surfactant,

surface part of the molecule. Anionic surfactants have a negative molecular

acting

cationic positive, and nonionics no charge. Amphoterics have both positive and
charge,

Anionics and nonionic surfactants provide most of industrial

negative charges.

often-
surfactants requirements. Selection of surfactants is based on specific needs and

mixed surfactants are used. In general, surfactants with a smaller (lighter) molecule mass

adsorbed
(short hydrophobic tail) diffuse more rapidly to the interface, and are vertically

at the interface. This causes a compressive force to act on the surface thereby reducing

29
surface energy or surface tension. Nonionic surfactants with ethylene oxide groups

surfactants are slower and

usually diffuse very rapidly to the surface while fluorinated

more effective at equilibrium. Most surfactants at higher concentrations exert strong

molecular attractions between adjacent molecules that cause strong surface films, the

strength of which, determines the surface properties of the surfactants solutions.

30
 Chapter 4

Statement of the Research

Single-solvent gravure inks have the advantage of being lower in cost,

environmentally friendly, and more cost-effective in terms of solvent recyclability.

However, limited surface energy control of these formulas represents a significant

disadvantage.

Therefore, the researcher proposed to investigate formulation modification of

single-solvent gravure inks that provide substantial surface energy modification to the ink

without an adverse impact on the print quality. Surface energy modification was
causing

Additional then
using intrinsic formulation
components. components were
first explored

investigated that imparted surface energy control without affecting the aforementioned

advantages.

31
 Chapter 5

Methodology

5.1 Introduction

The influence of organic additives and surfactants in ethyl- acetate-based gravure

ink had been observed. Single-solvent-based gravure inks were created and evaluated

surface tension, viscosity, contact angle, and drawdown adhesion measurements.

using

The best performance ink formulations were printed in a gravure proofing press and

analyzed by imaging analysis software.

The focus of this investigation was a C-type single-solvent-based gravure ink

listed in Table 5.1 (Leach, R.H., 1988). This type of ester-based ink was simple,

contained ester solvents, and was based on plasticized nitrocellulose. Polypropylene and

cellulose film packaging printings are typical application for this type of ink. Ester-based

inks are used in the European flexible packaging market and in the
gravure widely

and direct recyclability

product gravure industry, due to their consistent printing quality

of the solvent. Ester-based inks are also more environmentally friendly than

xylene/toluene solvent-based inks in terms of the fulfillment of the requirement that

volatile organic compounds not

be emitted into the atmosphere.
highly

32
 Table 5.1 Single solvent-based ink components

Components Samples used WT%

Pigments Carbon Black, 9.5%

Phthalocyanine Bluel5:3
Binder Nitrocellulose 14.0 %

Plasticizers Dioctyl phthalate 5.5%

Solvent Ethyl acetate 70.0 %

Additive Polyethylene wax 1.0%

Total 100.0 %

5.2 Ink Preparation

listed in Table a
The ink, as 5.1, was prepared by mixing the components using

variable hi-speed Caframo mixer model BDC3030 located in the Print Science

Laboratory in the School of Print Media. Fourteen part of nitrocellulose (Aldrich, 11%

Nitration, Lot no. 03021TG) was dissolved into 70 part of ethyl acetate (Sigma-Aldrich,

99.5%, batch no. 00655HC). One part of polyethylene wax (Microthene, F-532) was

incorporated a Sonic Dismembrator (Fisher Scientific).

by mixing ultrasonication
using

After adding 5.5 parts of Dioctyl phthalate (Aldrich, 99%, batch no.l0513MC), 9.5 parts of

pigment was dispersed in the formula. There were two pigments used; Sunfast

phthalocyanine blue 15: 3 powder pigment from SunChemical, and carbon black pigment

ball-milling machine (Tru-Square Metal product,

from Kremers Pigments Inc. Finally, a

Model A) was used to mill the inks for better dispersion.

5.3 Characterization of the Physical Properties

inks were characterized using physical properties

The single-solvent-based

energy (surface tension),

contact angle, viscosity, and
measurements including surface

adhesion force.

33
Surface Energy Measurement

Single component experiments were set

up to investigate the variation of surface

of each chemical component with ethyl acetate. To study the properties of each
energy

chemical component, the following experiments were designed:

1 Water
. and propanol mixed compound experiment;

2. Ethyl acetate and nitrocellulose mixed compound experiment;

3. Ethyl acetate and dioctyl phthalate mixed compound experiment; and,

4. Ethyl acetate and isopropanol acetate mixed compound experiment.

Fisher Scientific surface tensiometer (model Surface Tensiomat 21) was used in

this experiment (Figure 5.1). This tensiometer employs the du Noiiy ring method

a diameter platinum-iridium ring. Surface tension was directly measured by a force

using

necessary to separate the platinum-iridium ring from liquid. After setting the surface

tension scale to zero, the platinum-iridium ring was set into the tensiometer and put onto

the mixed liquid. Surface tension was measured at the point that the ring separates from

10"3

the liquid surface in the unit of dyne per centimeter, which is equal to newtons per

meter. This measurement was repeatedly performed from 0 percent to 100 percent of the

This experiment determined the relationship between surface

component by weight.

tension and the percentage of each chemical component mixed with ethyl acetate by

weight.

34
 Figure 5.1 Fisher Scientific
. surface tensiometer

The surface energy of the substrate, which was untreated oriented polypropylene

(Exxonmobil Chemical, Bicor LTSC), was measured by a dyne pen (Enercon). This pen

was drawn across the treated surface of the substrate. If the liquid did not break into

droplets after two seconds, then the researcher would assume that the surface energy of

the material was at least higher than the value shown on the dyne pen.

Contact Angle Measurement

Contact angles on polymer films were measured by pipetting one droplet

160 formulation the substrate. The droplet was observed

(approximately 1) of each onto

located in the Printing Applications

using the Image Pro-Plus image
analysis system

the contact angle was determined. A camera model DVC with lens
Laboratory (PAL) and

light sources (Fostec) was used to capture pictures of a droplet of

model (Olympus), and

the liquid on the substrate surface from the time the droplet contacted the substrate

surface until the time the liquid droplet was absorbed by the substrate (Figure 5.2). The

determined the angle made between a liquid droplet and the solid
contact angle was by

35
interface. It was measured through the liquid to the tangent drawn to its surface. Polymer

films were washed once with distilled water and dried at room temperature. This was

repeatedly measured and averaged. Analysis was performed in triplicate.

1139
Figure 5.2. Contact angle measurement

There were three tests used for contact angle measurements; contact angle test at

contact angle test at different temperature, and time-dependent test.

constant temperature,

A contact angle test at constant temperature was implemented to study the wettability of

ink formulation on the specific substrate at constant temperature. A

the solvent and

20 40

contact angle test was also implemented at different temperature (from C to C) to

and to simulate how temperature in

study the ink droplet
thermodynamic property

pressroom affects ink wettability. A time-dependent test was conduced to measure the

of droplet contact angle against the substrate surface. The time scale was set
changing

time the droplet contacted the substrate surface until 20 seconds. The time
from the

multi-frame capture function on the

dependent test was implemented by using

Capture rate was set at one second per

frame. This test simulated the ink
microscope.

OPP substrate at various temperatures. Results, from this test, leaded to

leveling rate on

the discovery of ink temperature sensitivity.

36
Viscosity Measurement

The Brookfield digital viscometer model DV-I+ and standard spindles model LV

were used in this experiment (Figure 5.3). This type of viscometer measures viscosity by

force liquid The principle of the

measuring the shear of a sample at given shear rate.

operation was to drive a spindle, which was immersed in the test liquid, through a

calibrated spring. The liquid resistance against the spindle was measured by the spring

deflection. Viscosity appears in units of centipoise, which are shown as "cP", or

milliPascal-seconds (mPa.s) in SI units. All liquid viscosity was measured by LV spindle

#3 at 100 rpm revolution.

BMOHIHD

o o
Figure 5.3. Brookfield digital viscometer

Drawdown test

was implemented in this research for visual

The K-bar drawdown testing

for the adhesion test. This experiment

comparisons between two formulations and used

would appear on a specified

substrate. In this test, K-bar number 4
simulated how the ink

37
 0.0004"

(Diversified Enterprises OPP substrate were used to a wet ink

Inc.) and apply

film thickness on OPP substrate which

approximately equaled the ink film thickness on

gravure press. This experiment also aided in comparing different inks on the basis of

hues, lightness, and pigment textures. The efficiency of wetting each ink formulation was

visually analyzed.

5.75"

Dot-on-substrate test was also demonstrated by using Pipette (Fisher

Scientific, Fisherbrand). A pipette tip was filled up with ink and dots were created by

tapping the pipette tips on OPP substrate. This test applied approximately one millimeter

diameter of ink dot on the substrate. The pipette test simulates how ink transfer from

gravure ink cell to the substrate. These printed dots were visually observed by using a

digital microscope and tested using an adhesion test.

Adhesion Test

drawdown test, dots-on-

There were three adhesion tests in this research; a

substrate test, and ink-on-ink test. The drawdown test was used for the K-bar drawdown

ink film force on the substrate. The dot-on-substrate test

samples to evaluate dry adhesion

the dot samples to evaluate the printed dot adhesion force and the ink
was used on

cohesion force on the substrate. Dot adhesion force on dry ink film was evaluated by

the ink-on-ink test on the samples previously used in the drawdown test
implementing

and the dot-on-substrate test.

Drawdown and dot samples from drawdown tests were used to evaluate the bond

ink to the printed substrate, compared to the bond of the ink to the pressure-

of the

sensitive tape (Flexography, 1980). To perform an adhesion test, it is necessary to use a

38
 The test was implemented
pressure-sensitive tape (3M 610 or similar) and a rubber roller.

at least twenty-four hours after the print run when the drawdown test is performed. Ink

adhesion is likely to get better after aging because additives tend to rise to the surface

during additional ink setting time (Flexographic Ink, 1998).

To perform this test, the printed sample was fastened on a flat surface with an

adhesive tape. After the sample was secured, a one-inch by six-inch pressure-sensitive

tape was applied on the cross direction width of the substrate. If there were air bubbles on

the to remove them. During the test, the angle

tape, a rubber-covered roller was used

The
approximately be 150 degrees.
presence
between the tape and substrate was kept at

of ink residues on the tape was evaluated to consider the presence of adhesion problems

(ASTM F 2252-03). For a drawdown sample, a digital scanner (Epson, model Perfection

to scan the tape with black filter at 300 dpi. The grayscale images of the
4870) was used

The
using Pro-Plus image
ink analysis system. result
tape were measured the residues by

was the percentage of the ink residue on the adhesion tape. For ink dots samples, dot

the percentage of dot on the tape, out of the total dots on the
residues were calculated by

substrate.

5.4 Ink Formulation Modifications

Ink formulation modifications were performed by changing the ink solvent with

50 percent propanol mixed with 50 percent of ethyl acetate. In

isopropyl acetate and

pigments were used to determine effects of the pigment types on

addition, two types of

ink formulations were created (Table 5.2). Each ink

ink properties. Six types of

contact angle, and adhesion force was measured

formulation surface tension, viscosity,

39
 constant
and compared to other ink formulations. The contact angle was measured at

temperature, variable temperature

(20
C to
40
C), and time dependent test. All ink

using the digital

microscope.
formulations dots were magnified and
visually observed

From these results, the best performance ink formulations were chosen.

Table 5.2. Ink formulations

Formulation Solvents % Pigments %

1 Ethyl acetate 70 Phthalocyanine blue 9.5

2 Isopropyl acetate 70 Phthalocyanine blue 9.5

Propanol 35
3 Phthalocyanine blue 9.5
Ethyl acetate 35

4 Ethyl acetate 70 Furnace Black 9.5

5 Isopropyl acetate 70 Furnace Black 9.5

Propanol 35
6 Furnace Black 9.5
Ethyl acetate 35

The Effect of Ink Temperature

In this study, the effect of temperature on surface tensions and contact angles

were tested in order to simulate ink leveling rate and ink temperature sensitivity in

All ink formulation surface tensions and contact angles

gravure pressroom condition.

20 40

different temperatures from C to C. This temperature range

were measured at

the extreme of printing condition that might be encountered in

was selected to represent

the industry (EPA, 2001).

40
Surface Tension Modifications

Surface tension modification of the chosen ink was also to be accomplished using

novel additives and surfactants. These components were organic class additives and

surfactants. The wetting and print performance characteristics of these formulations were

tested on a pilot press run using the analytical method described in this research. The

modifications were implemented by applying each surfactant from 0.01 percent to one

percent by weight to the ink formulation except hexane, a linear alkane co-solvent.

Hexane was added to the ink from five to 50 percent by weight. Each modified ink

formulation surface tension and viscosity was measured.

The adjustments to control surface energy had to be made without affecting the

print image quality. Print quality among other factors depends on the shape of the

halftone dots on a substrate. For liquid inks, maintaining ink surface tension was critical.

Low surface tension results in excessive ink spreading over the substrate causing

High surface tension was the cause of

significant dot gain and foaming problem.

pinholing (or missing dots) problem.

Press run Analysis

the best performance ink formulations, pilot press runs were

After discovering

press (J.M. Heaford) (Figure 5.4) with standard IT8.7/3

implemented by gravure proofing

engraved cylinder (Figure 5.5), and OPP substrate.

test target

41
 Figure 5.4. Gravure proofing press

Figure 5.5. Engraved gravure cylinder

Each modified ink formulation printed area in IT8.7/3 test target were captured

the digital image system (Figure 5.6). These images were visually
and magnified by

the 100 percent dot area (B5), 50 percent dot area (F5), and 40 percent dot
compared at

captured dot area images were analyzed actual dot area

area (F4). Additionally,

percentage compared to the original ink formulation using Pro-Plus image analysis

software.

42
 13

12

11

10

1
i J Wlmt
ABCDEFGHIJKLMN

Figure 5.6. 1T8.7/3 test target (black)

Each experiment was implemented and replicated to ensure its consistency and

reliability. The mixed chemical compounds that were used in these experiments were

Therefore, experiments were made at the standard temperature

highly volatile solvents.

and humidity, so that variation in temperature and humidity would have no significant

influence on the wetting properties.

5.5 Data Analysis

The measurements were analyzed to determine the effect of ink components on

ink physical properties statistical methods. An analysis of variance (ANOVA) test

using

was applied to prove and to determine the variables from the above experiments.

Throughout the analysis of the test data, a confidence interval ( ) of 95 percent was used.

43
5.6 Experimental Limitations

There were several experimental limitations in this research. This study was

basically a non-press investigation and only two pigments were investigated on a press

trial. It would be interesting to observe another pigment effect on the wettability and

substrate adhesion of the ink formulation to make a strong conclusion.

In the real world, gravure press usually run at very high speed which means ink

needs only several microseconds to transfers from gravure cell to substrate and then dry.

Therefore, a high-speed digital video microscopy system would be necessary for

measuring these properties to make a strong conclusion.

It would be interesting to investigate gravure ink behavior on a multi-color

gravure press. For example, it would be valuable to study the behavior of ink dot on dry

ink film compared to ink dot on substrate, or ink property differences between a

continuous high-speed press run and a low-speed press case. This study evaluated the ink

physical properties on C-type ink only; results may differ with other ink types.

44
 Chapter 6

The Results

6.1 Ink Component Experiments

Ink component experiments were designed to study the properties associated with

each ink chemical component. Initially, the water and propanol mixed compound

experiment was designed as a fundamental experiment and was implemented to

demonstrate the technique, as well as for calibration of the surface tensiometer and

viscometer.

Experiments were also designed to determine how ink components like

plasticizer, additive, and vehicle would influence ink solvent physical properties. In these

nitrocellulose, dioctyl phthalate (DOP), n-

ethyl acetate mixed with and
experiments,

ink components surface tension and viscosity. In

propanol were set up to evaluate using

addition, contact angle measurements were implemented to evaluate surface interactions.

Gravure ink surface tension had to be at least 10 mN/m lower than substrate

surface energy to allow the ink to appropriately wet a specific substrate. OPP, the only

substrate that was used throughout this research, had a surface energy of 36 mN/m with

and 31 mN/m without corona treatment. This would, therefore, set the
corona treatment,

upper limit of the newly created ink formulation surface tension to be at least 21 mN/m or

45
lower.

Because ethyl acetate has nine times the evaporation rate of water (ethyl acetate

has a comparative evaporation rate at

7.468, while distilled water is at only 0.82;

(Sunchemical, 2001), ink viscosity had to be monitored and had to be consistent during

the experiments.
Viscosity was controlled by adjusting the ink solvent percentage.

Water and Propanol

80.0 -

70.0 1

__
60.0 V
E
c
O
50.0 \
co
c
^
CD
40.0
1-

0>
o 30.0
ro
t

Co 20.0

10.0

0.0
0 10 20 30 40 50 60 70 80 90 100

% of n-Propanol by weight

Figure 6.1. Relation between the percentage of n-propanol and surface tension.

Surface Tension

Figure 6. 1 shows that in this experiment, water surface tension was nonlinearly

decreased with the addition of n-propanol. Pure distilled water and n-propanol surface

tension is 72.6 mN/m and 21.4 mN/m at 20 C, respectively (Thompson B., 1998, p. 180).

The results in Figure 6.1 reaffirmed the published values. Surface tension decreased more

by weight. After adding 20 percent or

than 50 percent by adding 10 percent of n-propanol

46
more of n-propanol into water, surface tension slightly decreased (decreasing by only 26

percent in comparison to pure n-propanol surface tension).

Water has a high surface tension because of its strong intermolecular bonds.

Water is best described as a polar molecule, in which there is a partial separation of

charge to give positive and negative poles. The attraction force between a positively

charged hydrogen atom on one water molecule and the negatively charged oxygen atom

on another gives rise to an intermolecular bond. The hydrogen bond is another major

intermolecular bond in water. Typically this occurs where the partially positively charged

hydrogen atom lies between partially negatively charged oxygen and nitrogen atoms.

Water contains by far the densest hydrogen bonding of any solvent with almost as many

hydrogen bonds as there are covalent bonds (Chaplin, M.). Water surface tension is

relatively strong compared to hydrocarbon products such as alcohol and ethyl acetate,

which have weaker hydrogen bonding because of their hydrocarbon components.

Hydrocarbons have strong covalent bonds between atoms and weaker intermolecular

bonds. A minor force of that attraction between molecules in hydrocarbon liquid is van

der Waal's force, which is much weaker than a hydrogen bond.

like propanol is soluble in both water and oil solvents.

A short-chain fatty alcohol

The hydrocarbon part of the molecule, rectangles in Figure 6.2, is responsible for its

the polar part (-OH group), the circles in Figure 6.2, has sufficient
solubility in oil, while

a short-length nonpolar hydrocarbon chain into aqueous solution

affinity to water to drag

it. At the air-liquid interface, alcohol is able to locate hydrophillic head group in the
with

liquid phase and allow the hydrocarbon part to escape into the air. This situation is the

most energy-stable state.

47
 AIR

1 1
1 1 hydrophillic part

H ;U fS M.j
Ob
-.
("S r
OO^o o ^ ,U

\ 'v__y \
hydrophobic part
Q

^
WATER M

Figure 6.2. Adsorption of surface-active molecules.

Viscosity

The viscosity of the water and n-propanol mixed liquid was too low to measure by

the Brookfield method. However, it was expected to be between the viscosity of water

25
and n-propanol, which are 0.89 and 2.07 mPa.s at C, respectively.

Contact Angle

The average of the contact angle of a water droplet on polycarbonate film was

64.3 degrees at
25
C. Water did not wet the polycarbonate film well because of its high

25

surface tension (72 mN/m at

25
C) compared to the polycarbonate film (39 mN/m at

C). On the other hand, the n-propanol contact angle on polycarbonate film was very

zero degrees. Therefore, n-propanol completely wet the polycarbonate

small, approaching

film because its surface tension was lower than the substrate surface energy (21 mN/m at

25
C). The water contact angle on OPP substrate was almost constant during the

experiment time (20 seconds) due to the slow evaporation rate of the water and its high

surface tension.

48
Ethyl Acetate and Nitrocellulose

Surface Tension

Nitrocellulose is one of the most

widely used vehicles in gravure ink used on

packaging. In this research, the formulation specified a 14 percent nitrocellulose by

weight. Nitrocellulose had no significant impact on ethyl acetate surface tension (Figure

6.3) based on statistical analysis at a 95 percent confidence interval. The ethyl acetate

23.9
surface tension at zero percent of nitrocellulose was 23.5 mN/m at C. Increasing the

nitrocellulose to 20 percent, which is the solubility limit, increased surface tension of the

23.9
mixture liquid by only 1.7 mN/m at C.

30.0 :

28.0
c

co 22.0

20.0
0% 5% 10% 15% 20%0

% of Nitrocellulose

Figure 6.3. Relation between percentage of nitrocellulose in ethyl acetate

and surface tension.

49
Viscosity
long-
Nitrocellulose did have a significant effect on liquid viscosity because of its

chain molecular structure (Figure 3.2). Because of the long-chain structure, more force is

required to move liquid molecules. That means increased shear stress at the same shear

rate. Therefore, viscosity, which is the proportion of shear stress by shear rate, was

increased by adding more nitrocellulose. The viscosity of pure ethyl acetate was 0.43

24.5
mPa.s at C. The viscosity of the mixed liquid at 20 percent nitrocellulose

23.9
concentration was 246 mPa.s at C.

Contact Angle

Nitrocellulose had a significant influence on the ethyl acetate contact angle. The

contact angle of pure ethyl acetate approached zero degrees on the OPP substrate,

meaning that ethyl acetate completely wet the OPP substrate. The addition of five percent

of nitrocellulose increased the contact angle to 41 degrees. However, adding more

nitrocellulose until it saturated did not increase the contact angle above 44 degrees

23
(Figure 6.4) at C. This was because nitrocellulose has no significant effect on ethyl

acetate surface tension.

Figure 6.4. Nitrocellulose on OPP film.

50
 The nitrocellulose contact angle
changing rate was observed. The contact angle of

nitrocellulose mixed with ethyl acetate was almost constant

during the experiment (20

seconds). Its contact angle was 44 degrees at the beginning, decreased to 41 degrees after

one second, with no change until the end of the experiment.

Ethyl Acetate and Dioctyl Phthalate

Surface Tension

Dioctyl phthalate (DOP) is a colorless, oily liquid. It is an organic ester compound

made by heating acids and alcohol in the presence of a catalyst. In this experiment, it was

used as a plasticizer, and was added to about six percent in the ink formulation.

DOP had the effect of increasing the ethyl acetate surface tension (Figure 6.5).

Surface tension at zero percent of DOP, that is the surface tension of pure ethyl acetate,

23.5
was 23.5 mN/m at C. Surface tension increased by 1 .5 mN/m at 10 percent and by

2.6 mN/m at 50 percent concentration. Surface tension increased up to 32.7 mN/m at

23.5
C, which is the surface tension value of pure DOP. These changes in surface

tension are a consequence of the solvent-plasticizer interactions. Plasticizers are capable

of moderate hydrogen bonding based on their solubility parameters (Sakellariou and

Rowe, 1995).

51
 c
o
tn
c:

0
O
CD
t
___>

CO
22.0

20.0
0% 20% 40% 60% 80% 100%

% of Dioctyl Phthalate by weight

Figure 6.5. Relation between percentage of DOP in Ethyl acetate and surface tension.

DOP has a significant effect on increasing surface tension and solves certain

printing problems such as brittleness. However, DOP is toxic to human and is unsafe for

the environment (National Library of Medicine, 2004). Five percent of DOP was the

maximum amount used in the formulation and that concentration did not significantly

increase the liquid surface tension (Figure 6.5).

Viscosity

The viscosity experiment showed that DOP also has a significant effect on ethyl

acetate viscosity. At 10 percent concentration, the mixture liquid viscosity was 20 mPa.s.

to 55 50 percent concentration. Pure DOP viscosity was 74

Viscosity increased mPa.s at

22
mPa.s at C.

52
Contact Angle

The ethyl acetate and DOP solution wet the OPP substrate at five percent

concentration. The surface tension of the solution was higher than the surface energy of

the substrate (33 mN/m at 23.5 C). In the contact angle experiment, the researcher

observed that pure DOP had a

relatively high contact angle decreasing rate (Figure 6.6)

due to its weak intermolecular force. The contact angle between its droplets on the

substrate was 53 degrees, and it continued to decrease keep decreasing to 26 degrees in

less than two seconds.

60

50

CD 40
___

U>
(_

30

< 20

10 j

o
o 0.5 1.5

time (s)

Figure 6.6. DOP contact angle.

Ethyl Acetate and Isopropyl Acetate

Surface Tension

Isopropyl acetate was used as co-solvent in the ink formulations. It was also used

as an alternative solvent in the ink formulation experiments because of its similar

53
chemical properties and low surface tension 3.0 lower than that of
(approximately mN/m

ethyl acetate; see Figure 6.7).

26.0

_.
25.0
E:

1 24.0

c
o 23.0
'v>
c
CD
4
22.0
CD
u
CD

21.0
if)

20.0
0% 20% 40% 60% 80% 100%

% of Isopropyl Acetate

Figure 6.7. Relation between percentage of isopropyl acetate in ethyl acetate

and surface tension.

Isopropyl acetate had a significant effect on ethyl acetate surface tension (Figure

6.7). Ethyl acetate surface tension decreased approximately 1.2 mN/m at 10 percent

concentration, and 2. 1 mN/m at 40 percent concentration. Pure isopropyl acetate surface

25
tension was 22.0 mN/m at C. Isopropyl acetate had a lower surface tension because it

has a larger hydrocarbon group (CH3COOCHCH3CH3) than ethyl acetate

(CH3COOCHCH3)

54
Viscosity

Ethyl acetate and isopropyl acetate mixed liquid viscosity could not be measured

by the Brookfield method. However, it is expected that isopropyl acetate would have no

significant effect on ethyl acetate

viscosity because both liquids have almost the same

physical properties. Introduction

According to to Colloid and Surface Chemistry by
25
Shaw, D. J., the viscosity both ethyl acetate and isopropyl acetate is 0.4 mPa.s at C.

Contact Angle

Both the ethyl acetate and isopropyl acetate contact angles were very small and

approached zero degrees. The solutions completely wetted the OPP substrate. Since the

surface tension of these solvents was significantly lower than the substrate surface

energy, complete wetting was expected and observed.

55
Summary of the Ink Component Experiments

The results of the ink component experiments are summarized in Table 6.1 DOP

caused the greatest increase in surface tension. Isopropyl acetate caused the greatest

decrease in surface tension. Nitrocellulose caused the greatest increase in viscosity and

contact angle.

Table 6.1. Summary of the Ink Component Experiments

Name Ink component Surface tension Viscosity Contact angle

Nitrocellulose binder no change increased increased

Dioctyl
plasticizer increased increased increased
phthalate

Isopropyl alternative
decreased no change no change
acetate solvent

From these results, the researcher cannot rely on the ink components to vary the

surface wetting properties of C-type ethyl-acetate-based ink.

56
6.2 Ink Formulation Experiments

Information on substrate and chemical component surface tension is shown in

Table 6.2. Untreated OPP surface tension was

approximately five mN/m lower than

corona-charge-treated OPP (Table 6.2). Ethyl acetate has the highest surface tension and

isopropyl acetate has the lowest surface tension among solvents used in the experiments

at the same temperature. There are about three mN/m differences between ethyl acetate

and isopropyl acetate, which are both in the same ester group. This is because isopropyl

acetate has a larger hydrocarbon group than ethyl acetate. However, pure propanol could

not be used as a solvent in this experiment, because it could not dissolve nitrocellulose.

Instead, 50 percent of propanol by weight mixed with ethyl acetate solution was used.

Table 6.2. Substrate and chemical components surface tension.

Types Names Surface tension ( y )

at 23.9 C

Substrates Untreated OPP 31.0

Treated OPP 36.0

Ink solvents Ethyl acetate 25.8

Isopropyl acetate 22.1

50:50 Ethyl acetate/propanol 23.9

Propanol 23.0

There were two types of pigments used in this research. These were Furnace

Black (or and phthalocyanine blue 15:3. The former is the common black
carbon black)

pigment used in gravure and other printing technology. Carbon blacks are manufactured

57
by thermal oxidative dissociation of hydrocarbons such as mineral oils or natural gases. It

has good physical properties for inks (light fastness, resistance to solvents, chemical

stability, and heat stability) and provides good black color due to the small particle size.

However, it was difficult to disperse as it has very small particles with a correspondingly

large surface area. Phthalocyanine pigment is also widely used in the printing ink

industry. It has good

printing properties, but phthalocyanine pigments possess small

primary particles that have a

tendency to flocculate (because of a low surface energy),

creating a loss of color strength.

Ink Preparation

From the ink component experiments, the effects of each ink component on the

physical properties of particular solvents were studied. Ink formulation experiments were

implemented to study ink physical properties. Six types of inks were prepared based on

three types of solvents (ethyl acetate, isopropyl acetate, and 50 percent propanol mixed

with ethyl acetate) and two types of pigments (Furnace black, and phthalocyanine blue)

(Table 5.2). These inks were kept in a sealed container after being created due to the high

evaporation rate of the solvent.

Contact angle, surface tension, and adhesion tests were used to determine ink

was measured and monitored to ensure ink and

physical properties. Viscosity wettability

the sets of ink were used in the K-bar drawdown test and dot-on-
printability. Finally,

substrate test. The printed area and dots from drawdown tests were magnified and

digital microscopy to observe dot appearance.

captured
by

58
Physical Properties

Surface Tension

The experiment started

by creating six types of ink according to the ink

formulation in Table 5.1 and measuring surface tension, viscosity, contact angle, and

adhesion for each type of ink formulation. The parameters in this experiment were

pigment type and solvent type. Table 6.3 shows information on ink formulation surface

tension with two different types of pigments and three types of solvents implemented in

the experiments.

Table 6.3. Ink formulation surface tension with different pigments and solvents.

Formulation Solvent type Pigment type Surface tension (mN/m)

1 ethyl acetate phthalocyanine blue 26.9

2 isopropyl acetate phthalocyanine blue 25.9

3 propanol/ phthalocyanine blue 25.8

ethyl acetate

4 ethyl acetate Furnace Black 27.2

5 isopropyl acetate Furnace Black 26.0

6 propanol/ Furnace Black 25.8

ethyl acetate

There was no significant difference in surface tension between the black and cyan

pigments (Table 6.3). The differences were within the experimental error of 1 mN/m.

Ethyl-acetate-based ink had the strongest surface tension and propanol mixed with ethyl-

acetate-based ink had the weakest surface tension. The inks had about two mN/m higher

tension than the pure solvent. This is due to the ability of both pigments and binder
surface

59
to increase ink cohesion.

Viscosity

The viscosity of each ink formulation was measured

by the Brookfield viscometer

for consistency and quality control. Table 6.4 shows results for the different ink
viscosity

types. The differences were within the experimental error of 1%. The type of pigment

had a significant influence on ink viscosity for the same solvent. Black inks had higher

viscosity than cyan inks at the same concentration. The type of solvent used in the ink

formulation had no significant influence on ink viscosity. However, viscosity of any ink

formulation in this research had to be consistent. Therefore, all ink formulations,

regardless of type of pigment and solvent used, had to have a viscosity adjustment by

adding or reducing the amount of solvent until their viscosity values were in the range

25
between 100-170 mPa.S at C.

Table 6.4. Ink viscosity with different types of solvents and pigments.

Formulation Solvent type Pigment type Viscosity (mPa.s)

1 ethyl acetate phthalocyanine blue 98.7

2 isopropyl acetate phthalocyanine blue 152.4

3 propanol/ phthalocyanine blue 165.3

ethyl acetate

4 ethyl acetate Furnace Black 328.0

5 isopropyl acetate Furnace Black 278.0

6 propanol/ Furnace Black 246.5

ethyl acetate

60
Contact Angle

Each ink formulation contact angle was measured to evaluate wettability of the

solvent and ink formulation on the specific substrate. Pigment types had no significant

impact on the ink contact angle (Table 6.5). The estimated of experimental error is 5

degrees. Solvent type had a significant impact on ink contact angle. These results were

affirmed in the surface tension test (Table 6.3). The lower the ink surface tension, the

lower the contact angle.

Table 6.5. Ink contact angle with different types of solvents and pigments.

Formulation Solvent type Pigment type Contact angle (degrees)

1 Ethyl acetate phthalocyanine blue 75.0

2 isopropyl acetate phthalocyanine blue 70.3

3 propanol/ phthalocyanine blue 65.1

Ethyl acetate

4 Ethyl acetate Furnace Black 79.7

5 isopropyl acetate Furnace Black 70.4

6 propanol/ Furnace Black 67.4

Ethyl acetate

61
The Effect of Temperature

The contact angle changing rate test was implemented by using

ethyl-acetate-

32
based black ink. The ink contact angle was measured for 20 seconds at C constant

temperature. The camera was set at two seconds per frame.

70 !

65

CD

TO
- 60
o

o
O
55

50
10 15 20

Time (s)

32
Figure 6.8. Relation between ethyl-acetate-based ink contact angle and time at C.

The ink contact angle was 67 degrees at the beginning of the experiment at t=0.

The contact angle drastically decreased to 54 degrees within six seconds. For the

the experiment, the contact angle decreased only another two

remaining 14 seconds of

degrees to 52 degrees at
32
C (Figure 6.8). The ink contact angle had a higher initial rate

of change due to the solvent detergency effect. The ink solvent removed foreign material

on the substrate surface when the ink made contact with the substrate. Then, the contact

rate decreased as the ink solvent evaporated and the ink started to dry.
angle changing

62
 B 26 0
i
33 0
36 0
? 38 0
t
CD
c

o
-2

cr
O
O

70.0
0 0.5 1 1.5 2 2.5 3 3.5

Time (s)

Figure 6.9. Relation between black ethyl-acetate-based ink contact angle and time

at different temperatures.

The relationship between the ethyl-acetate-based ink contact angle and time at

different temperatures is shown in Figure 6.9. Four sets of data were collected at different

(26 33 36 38
temperatures C, C, C, and C). These temperatures simulated press-room

conditions and were selected to represent the extreme of printing condition that might be

encountered in the industry. This result can be achieved with any type of solvent used in

ink formulations.

The experiment results showed that the ink contact angle of C-type ethyl-acetate-

based ink has significant effect on the contact angle changing rate with temperature. The

initial contact angles decreased with increasing temperature (Figure 6.9). The time zero,

38

surface tension at
26
C was 79 degrees, compared with 73.5 degrees at C. At the

high temperature, ink had a lower contact angle, which resulted in better substrate

adhesion (unreported data). The ink leveling rate of C-type ethyl-acetate-based ink may

63
have a high temperature sensitivity. Contact angle decreased with increased temperature

as cohesive forces decreased due to an increase of molecular thermal activity.

Contact angle curves at any temperature were found to decrease nonlinearly. At

high temperature ink had faster leveling rate compared to that of low temperature (Figure

6.9). This was related to the ink leveling rate of the solvent, which was the main

component in the formulation and ink detergency effect. Foreign material on the substrate

surface was removed by the ink solvent when the ink contacted with the substrate.

However, ink leveling rate is faster with

increasing temperature but still measurable. The

temperature does not have as an effect on ink leveling as the chemical modification

reported below.

The Effect of Pigment Type

The influence of pigment type on ink surface tension and contact angle was also

studied. Ethyl-acetate-based black and blue inks were created at the same concentration.

20 40
Both ink surface tensions were measured at different temperatures from C to C.

The ink contact angle was measured at various temperatures (Figure 6.10).

This experiment shows that the surface tension was inversely proportional to the

ink temperature (i.e., the higher the ink temperature, the lower the surface tension).

Pigment type had no significant impact on the relationship between surface tension and

temperature. Both inks had approximately identical surface tension curves, which were

20 40

decreased at the same rate from 26.9 mN/m at C to 24.0 mN/m at C. In general,

surface tension decreased with increased temperatures as cohesive forces decreased with

an increase of molecular thermal activity.

64
 28.0 r
|
27.0 I
26.0 |
z
E. 25.0 |
c

_:
24.0 j
v
o
23.0 |
3 22.0
c.

21.0

20.0
15.0 20.0 25.0 30.0 35.0 40.0 45.0

Temperature (C)

Figure 6.10. Relation between ethyl acetate-based ink surface tension and temperature

at different types of pigments

The researcher found that ink temperatures have a significant influence on ink

contact angle (Figure 6.1 1). Ethyl- acetate-based black ink was tested to determine the

26 38
effect of temperature on the ink contact angle over a temperature range from C to

C.

82

<D
78 !
_r

to

Tj 76 j
<-
c:
o
O 74 \

72
[
:

70 [
25 30 35 40

Temperature (C)

Figure 6.11. Relation between ethyl-acetate-based black ink contact angles

and temperature.

65
 The ethyl-acetate-based ink contact angle was 79 degrees at
26
C. The contact

38
angle decreased to 74 degrees at C. The higher the ink temperature, the lower the ink

contact angle. At higher temperatures ink molecules have higher energy and reduced

intermolecular forces.

Adhesion Tests

The adhesion tests were performed: a drawdown test, a dots-on-substrate test, and

ink-on-ink test. These tests were designed to study how ink components (solvents and

pigments) effect ink adhesion and dot appearance on OPP substrate.

Drawdown Test

The drawdown test was designed to determine the dry ink film adhesion force by

measuring the ink residue area picked off. The result is shown in percentage of ink picked

off. Drawdown test results are shown in Table 6.6.

Table 6.6. Drawdown adhesion test at different type of solvents and pigments.

Formulation Solvent type Pigment type Percentages of ink Substrate

residue (%) picked off

1 ethyl acetate phthalocyanine blue 10% Yes

2 isopropyl acetate phthalocyanine blue 30% No

3 propanol/ phthalocyanine blue 10% No

ethyl acetate

4 ethyl acetate Furnace Black 70% Yes

5 isopropyl acetate Furnace Black 50% No

6 propanol/ Furnace Black 10% no

ethyl acetate

66
 The researcher observed that dry ethyl-acetate-based ink film as well as the top

layer of OPP The ink film

substrate was picked off. adhesion force was so strong that it

overcame the substrate inter layer bond. On the other hand, isopropyl-acetate-based ink

and propanol/ethyl-acetate-based ink film did not pick off with the substrate layer. This

means that ethyl-acetate-based black ink had the strongest adhesion force and isopropyl-

acetate-based ink had the weakest adhesion force (Table 6.6). Results were identical

regardless of the pigment variation. Ethyl acetate has the highest evaporation rate and

better heat transfer which leads to better substrate adhesion. Regardless of solvent type,

black ink has slightly stronger adhesion force than cyan ink. Isopropyl-acetate-based ink

had weakest adhesion force regardless of pigment type.

Dots-on-substrate Test

The dots-on-substrate test was similar to the drawdown test. Instead of testing

drawdown adhesion, this test measured dot adhesion. The result is shown in terms of

percentage of ink residue on the testing tape (Table 6.7). Propanol mixed solvent-based

ink had the highest percentage of ink residue, and ethyl-acetate-based ink had no ink

residue on the testing tape for any pigment type. The researcher observed that no

substrate was picked off during this test, indicating the lower the percentage, the stronger

the ink film adhesion. Ethyl-acetate-based ink had the strongest adhesion force, and

propanol mixed solvent-based had the weakest ink adhesion force.

67
 Table 6.7. Dot adhesion test with different types of solvents and pigments.

Formulation Solvent type Pigment type Percentages of ink Substrate

residue (%) picked off

1 ethyl acetate phthalocyanine blue 0% no

2 isopropyl acetate phthalocyanine blue 10% no

3 propanol/ phthalocyanine blue 50% no

ethyl acetate

4 ethyl acetate Furnace Black 0% no

5 isopropyl acetate Furnace Black 13% no

6 propanol/ Furnace Black 25% no

ethyl acetate

The researcher also observed that ethyl-acetate-based ink dots had printing faults

referred to as the fish eye effect (Figure 6.12). Isopropyl-acetate-based ink dots had no

ink in the center of the dot (Figure 6. 1 3). This effect is called the donut effect. These

effects occurred because the ink surface tension was higher than the substrate surface

energy.

Cyan dots Black dots

Figure 6.12. Fish eye effect on ethyl-acetate-based ink dots.

68
 ,..Mi|liillSs|i-M ,

-fe. ..__?:..____

Figure 6.13. Donut effect on isopropyl-acetate-based ink dots.

Ink-on-ink Test

The ink-on-ink test was a combination of the drawdown test and the dots-on-

substrate test. The ink dot adhesion force was measured in terms of percentage of ink

residue on the testing tape. Different types of ink dots were printed on all three types of

ink drawdown. This test showed which combination of inks had the best ink adhesion and

cohesion forces. Ink residue measurements were visually evaluated. This test was

implemented on one type of pigment at a time.

Table 6.8. Ink-on-ink Test (Cyan pigment).

Percentages of ink residue by dots

Ethyl acetate Isopropyl acetate 50:50 propanol/

ethyl acetate

Ethyl acetate
1 % 5% 8.3%

o
Isopropyl acetate
4% 2% 8%
1:

Q
Propanol/ethyl
33% 7.5% 7.5%
acetate

69
 Table 6.9. Ink-on-ink Test (Black pigment).

Percentages of ink residue by dots

Ethyl acetate Isopropyl acetate 50:50 propanol/

ethyl acetate

Ethyl acetate
20% 0% 15%
c

o
-a Isopropyl acetate
0% 0% 0%
03

Q
Propanol/ethyl
0% 0% 0%
acetate

From these results, pigment type had a significant influence on the substrate

adhesion of the ink. For the cyan ink-on-ink test, it was observed that no layer of the

substrate was picked off. So, the lower the ink residue percent, the stronger the ink

adhesion force. Ethyl-acetate-solvent-based ink drawdown with ethyl-acetate -based ink

dots created the lowest ink residue percentages. This is because ethyl-acetate-based ink

has better ink wettability than the others. Propanol mixed solvent-based ink drawdown

with ethyl-acetate-based ink dots created the highest ink residue percentage (Table 6.8).

Surprisingly, the black ink-on-ink test had completely opposite results from the

cyan ink test. Ethyl acetate solvent-based ink drawdown with ethyl-acetate-based ink dots

created the highest ink residue percentage (Table 6.9). The researcher observed that

ethyl-acetate-based ink dots on ethyl-acetate-based ink drawdown had a layer of the

substrate picked off. These results might be due to the black pigment having better heat

adsorption than the cyan pigment, which leads to better ink setting and substrate

adhesion.

Magnified images of ink dots showed that only ethyl-acetate-based ink dots had a

70
thicker ink film on the boundary than in the center of the dots, the phenomenon known as

the fish eye effect (Figure 6.13). This is caused by the ink reticulating on the surface of

the substrate and is seen as small holes in solid areas of print. In some cases, dots were

only printed on the circumference of the cells with a void in the center, this is referred to

as the donut effect (Figure 6.12). This problem has some possible causes: long leveling

rate ink, high evaporation rate or high surface tension.

Summary of the Ink Formulation Experiments

The result indicated that C-type ethyl-acetate-based ink had the strongest adhesion

force independent of pigment type (Table 6.10). The ink film adhesion force was so strong

that it overcame the substrate inter-layer bond. However, ethyl-acetate-based ink dots on

oriented polypropylene exhibited a fish-eye effect due to the ink's high surface tension

and longer leveling rate, which leads to a decrease in print quality. Improper ink

wettability and substrate adhesion are major causes of the fish-eye effect.

The researcher also discovered that C-type ethyl-acetate-based ink had high

temperature sensitivity regardless of pigment type. The results indicated that C-type

ethyl-acetate-based ink may have a leveling rate which may be substantially faster with

38
higher temperatures (from
20
C to C). This temperature range is commonly

encountered in the industry. Therefore, controlling ink temperature might be one possible

in the gravure system.

way to gain print quality improvement and cost reductions printing

71
 Table 6.10. Summary of Ink Formulation Experiments.

Formulation Solvent type Pigment Surface Viscosity Contact Substrate

type tension angle adhesion

1 ethyl acetate Blue lowest strong

2 isopropyl acetate Blue weak

3 propanol/ Blue lowest lowest weak

ethyl acetate

4 ethyl acetate Black highest highest highest strong

5 isopropyl acetate Black weak

6 propanol/ Black lowest weak

ethyl acetate

72
6.3 Surface Tension Modifications

Different types of additives were added to inks based on ethyl-acetate, which was

a polar organic solvent. The surfactants that performed best were defined by the ability to

lower the surface tension of the ink to the upper limit (21 mN/m) or lower to make

appropriate ink adhesion to the substrate.

Surface tension modifications were implemented by using 12 different types of

additives to ethyl-acetate-based black ink by only 0.01 to one percent by weight, except

for hexane, which is a low-surface-tension linear alkane. Hexane was added to the ink

formulation by five to 50 percent by weight. All surface active agents (surfactants) used

in this experiment were aqueous-based surfactants (Table 6.1 1). For each modified ink

formulation the surface tension and viscosity were measured (Table 6.12). Information on

surfactants used in this modification is shown in Table 6.11.

73
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76
 Table 6.12. Black ethyl acetate ink with different kinds of additives.

Surface
Surface tension Viscosity Tension
Additives name
(mPa.s)1
modification
capability (mN/m)2

Without additive -

145.5 25.8

Zonyl FSA no significant change -

-

Zonyl FSO no significant change -

-

2.0 mN/m decreased

Zonyl FSJ 137.0 23.8
at 0.1 % concentration

Zonyl FSP no significant change - -

1.5 mN/m decreased

Zonyl FS-300 140.5 24.3
at 0.8% concentration

Lanawet D-50 no significant change

- -

Silwet L-7500 no significant change

- -

Silwet L-7608 no significant change

- -

Triton X- 114 no significant change

- -

Niaproof
-

no significant change
-

Hexane 5% 0.7 mN/m decreased 155.0 25.1

Hexane 10% 1.5 mN/m decreased 165.4 24.3

Hexane 12% 2.1 mN/m decreased 170.7 22.5

Hexane 20% 3.0 mN/m decreased 203.2 21.7

Hexane 50% 5.0 mN/m decreased 246.9 20.8

77
 From this experiment, three additives that lower the ink surface tension with no

effect on ink viscosity were discovered: two types of surfactants and one type of co-

solvent (0.8 percent of Zonyl FS-300, 0.1 percent of Zonyl FSJ, and 12 percent of

hexane). These surfactants lowered the ink surface tension to 23.8, 24.3, and 22.5 mN/m

respectively. Zonyl FS-300 is a nonionic fluorosurfactant. Zonyl FSJ is an anionic

fluorosurfactant. Both surfactants are manufactured

by DuPont company (Table 6.1 1).

Unfortunately, none of the surfactants lowered the ink surface tension below the upper

surface tension limit (21 mN/m).

0)

c
o
O

45.0

40.0
4 6 10

time (s)

Figure 6.14. Relation between ink contact angle and time with different types of
surfactants.

The contact angle of each new ink formulation and the original formulation were

measured as a function of time. The contact angles were measured at the time was first

dropped and then second for 20 seconds. Modified ink contact angle changing rates
every

were compared with that of the original ink formulation (Figure 6.14). The original ink

78
formulation had the highest contact angle compared to modified formulations.
any

Formulation with FSJ had the lowest contact angle at any time (Figure 6.14). This was

because ink formulation with FSJ had the lowest surface tension. The original ink contact

angle changing rate was modeled to a nonlinear function. The original ink changing rate

was -0.74 degrees per second. FS-300, and FSJ have angle changing rate at -0.71, -0.60,

and -0.59 degrees per seconds respectively. The original ink had the fastest contact angle

changing rates, and the modified ink with FSJ surfactant had slowest contact angle

changing rate.

79
Summary of the Surface Tension Modification

The results from surface tension modifications indicated that even though the

surfactant amount added into the formulations in this experiment was much lower than

one percent
by weight, the surfactant-added ink formulations showed relevant

improvement of properties when compared to the original one. These were

1 . Original ink formulation (table 4.1) with 12 percent of hexane (Sigma-Aldrich),

2. Original ink formulation with 0.8 percent of Zonyl FS-300 (DuPont),

3. Original ink formulation with 0.01 percent of Zonyl FSJ (DuPont).

The results indicated that these modified ink formulations lowered surface tension

from 1.5 to 2.1 mN/m, and lowered the contact angle from 4 to 14 degrees compared to

the original ink formulation. The leveling rate was very fast with the modified

formulation than with the conventional formulation.

80
6.4 Press Run Analysis

Following the discovery of the best

performing ink formulations, pilot press runs

were implemented using a gravure IT8.7/3 test target-

proofing press with a standard

engraved cylinder, and OPP substrate. Black ink formulations the inks
were only types of

used in this press run.

For each modified ink formulation, printed areas in standard test targets were

captured and magnified

by digital microscopy. These images were visually compared at

the 100 percent dot area (Figure 6.15), 50 percent dot area (Figure 6.16 and Figure 6.17),

and 40 percent dot area (Figure 6.18).

81
 3; j?

Sli/*'

:. .';:,.-.

I'

'
:
/ .... ;/_. __ i

Original adding Zonyl FS-300

r :*
.> - v f \5 ":*:I.H;.K
.
: "fF *

' " ' '','

:. .
'
'''"'.".''. '

-FFFFF ::'Vi;\j

;,.
',.
-;'.

!.____

adding FSJ adding hexane 12%

Figure 6.15. Ink appearance (100% dot area)

82
? a a^a a A a -

a^A'AAA a a wj -15

a a-a^aa
^ ^>
a^#
: a^A^a^a,
r aya; 6iA^2^__i
-
aYaYA *01*I*

Vv Av
A^rArA A AAv A
AA~ *
__^* #***<
A
-

A A
* "
4

Original adding Zonyl FS-300

*I*1*_^a*_*V.*V_A*W'V

a *W*A <

!?_[*_.*__*_.__*__**' # W A,__*__A__*_|_*A*A

adding FSJ adding hexane 12%

Figure 6.16. Ink appearance (50% dot area)

83
Original adding Zonyl FS-300

FFiFjFr ;...:v,:,.

^spr __#.
*F.'

:~
uvt
;=.
.!'F;

'
I 'il * '

adding FSJ adding hexane 1 2%

Figure 6.17. Ink appearance (50% dot area, 20X magnified)

84
 ^,W,VA
# # <p # '
$:$
#
## # # # ;?!?-
4 #
& V *. V # 4 . 6 6 $

> .*_v.
* <> _
^.ad^ a.
> ; a ,
a 0 , *>A $ , #.
h #. >A*, m
'

Original adding Zonyl FS-300

# # 4 # # ^;#;# . #

A 41 <*t# A U # # # #

^__V_^W^V^_Wy_W___WAWZ& ,

adding FSJ adding hexane 12%

Figwre (5.7S . /ny. appearance (40% dot area, 5X magnified)

85
 The gravure-printed test targets printed on the OPP substrates using each ink

formulation were captured and the actual dot area was analyzed by imaging analysis

software. Analysis results are shown and compared with the gravure cylinder dot area

(Table 6.13).

Table 6.13. New ink formulations dot area analysis.

Additives Concentration Cylinder dot area (magnified)

by weight
100%
40% 50% 50%

(5X) (5X) (20 X) (5X)

Zonyl FS-300 38.18% 48.58 % 46.63 % 93.20 %

0.8%

Zonyl FSJ 0.1 % 39.51 % 47.89 % 48.34 % 97.06 %

Hexane 12.0 % 38.25 % 45.00 % 43.55 % 91.49%

Without additives -
27.51 % 31.65% 34.22 % 88.40 %

97
100 93 Zonyl FSJ Zonyl FS-300
91 88
Hexane 1 without additive

75

49 48 45
50
32

25

0
100% dot area 50% dot area

Figure 6.19. Ink dot area.

86
 Modified ink formulation images printed on the OPP substrate, generated less of

images. These proven

the donut effect compared to original results were mathematically

dot inks to formulation value

by comparing the actual area value of modified the original

at 100, 50, and 40 percent dot area. The measured dot area of all the modified ink

formulations more closely compared with the actual percent dot area than the unmodified

ink. Ink with Zonyl FSJ had the closest percent dot area to the cylinder dot area, the ideal

dot area. Ink with Zonyl FS-300 and 12 percent of hexane had better results than the

original formulation. It was found that the modified ink exhibited better wetting and a

greater adhesion to the substrate. Even though modified ink formulations could not

the donut effect, the effect was reduced compared to the

completely remove significantly

original captured images. All the modified inks had higher surface tension than preset

upper limit (21 mN/m). Therefore, it can be concluded from these results that the new ink

formulations with low-concentration aqueous surfactants could be used to minimize

problems such as pinholing, screening, donut effect, and fish-eye effect without
printing

suppressing the original ink properties.

87
 Chapter 7

Summary and Conclusions

In this research, the ink formulation modification of C-type single-solvent-based

gravure ink was proposed under laboratory-controlled conditions. The main findings of

this thesis research are the reduction of inherent print defects through an enhanced

leveling rate resulting from a modification to the existing formula, and the discovery of a

sensitivity of the formula to temperature.

Print defects reduction

In this study, black C-type (nitrocellulose) single-solvent-based gravure ink,

which is commonly used in the gravure flexible packaging industry, was used on a

gravure press with a standard IT8/7.3 test-target-engraved cylinder and a

proofing

pigmented oriented polypropylene test substrate. The results indicated that C-type single-

additive, on oriented polypropylene generated a printing

solvent-based ink, without an

defect called the donut effect, defined by a dot that prints only on the circumference of

in the center. Deformed dots caused by the donut effect increase

the cells leaving a void

dot which leads to a decrease in print quality. Improper ink

the gain and mottle,

and substrate adhesion are major

causes of the donut effect. The size of the
wettability

88
donut dot digital image analysis system. The result
effect and structure was analyzed by a

was represented in terms of the actual printed percent dot area compared with the ideal

percent dot area (engraved cylinder dot area). The results from this experiment showed

that ink formulation, without an additive, produced only 32 percent dot area as compared

to the ideal 50 percent dot area and 88 percent dot area as compared to the 100 percent

dot area (solid area). This problem was solved by adding smalls amount of aqueous-based

surface active agents (surfactants) into the ink formulation. The aqueous-based

surfactants used in this study are chemicals that are widely used in the paint and coatings

industry. From the experiment, two aqueous-based surfactants and one co-solvent,

selected from 1 1 surfactants and the one co-solvent, were found to have the ability to

reduce the donut effect without interfering with the advantages of the ink. These two

successful surfactants and the solvent were Zonyl FSJ, Zonyl FS-300, and hexane,

respectively. Even though the surfactant amount added into the formulations in this

experiment was much lower than one percent by weight, the surfactant-added formulation

showed relevant improved properties when compared to the original one. The results

by far faster with the modified formulation than with

indicated that the leveling rate was

the conventional formulation. In fact, the leveling rate was so fast that it was completed

time the camera acquire the first image (less than 0.5 seconds). This compares to
by the

about two second with the original formula, which is an improvement of the leveling rate

These results also supported the finding that all modified ink formulation
by 400 percent.

images printed on the pigmented oriented polypropylene substrate generated a smaller

donut effect compared to images printed using the original ink formulation at any percent

dot area.

89
 Results from the digital image analysis system showed that all modified ink

formulations had better actual percent dot area than the non-modified formulation. Ink

Zonyl FSJ best in terms dot

with showed the performance of having the closest percent

area to the cylinder dot area (the ideal dot area). At the ideal 100 percent dot area (solid

area), the image printed using the ink formulation with Zonyl FSJ had a 97 percent

measured dot area while the image printed using ink without surfactants had a 88 percent

dot area. This improved dot area percentage might be due to the fact that the modified

inks had stronger adhesion force and faster ink leveling than the original ink based on the

adhesion, contact angle, and surface tension test data (unreported data). Even though

modified ink formulations could not completely remove the donut effect, the effect was

significantly reduced compared to the original captured images, leading to a print quality

improvement. Therefore, it can be concluded from these results that the new ink

formulations with low-concentration aqueous surfactants could be used to minimize

problems such as pinholing, screening, donut effect, and fish-eye effect without
printing

suppressing the original ink properties.

Temperature sensitivity

It is noteworthy to point out that the C-type ethyl-acetate-based ink formulations

were discovered to have high temperature sensitivity. In this study, the effect of

temperature on surface tensions and contact angles were

tested in order to simulate ink

ink temperature sensitivity in gravure pressroom condition. The test was

leveling rate and

20 40

done in the temperature range of C to C. This temperature range was selected to

represent the extreme of printing condition that might be encountered in the industry

90
 the improved C-type ink
(EPA, 2001). The results showed that all ethyl-acetate-based

formulations reported here had high temperature sensitivity as was observed with the ink

higher
modification experiment, the ink leveling rate was substantially faster with

temperatures. Print defects, such as the donut effect, seem to remain at the high

temperature (EPA, 2001). The reason for this contradiction would be the subject for

further study.

The experiment results also showed that the ink surface tension of the C-type

ethyl-acetate-based ink has the same temperature sensitivity regardless of pigment type.

The ink found to decrease four increasing temperature

surface tension was by mN/m with

20
of about C. The decrease of surface tension can be explained in terms of the

molecular thermal activity increment and a decrease of intermolecular force (cohesion)

with increasing temperature. From the temperature dependency experiment, it was clear

that ink temperature might have a significant influence on ink leveling, which leads to

degradation of print quality. Therefore, controlling ink temperature might be one possible

quality improvement and cost reductions in the gravure printing system.

way to gain print

It is noteworthy to point out that this study is basically a non-press investigation,

investigated on a proofing press trial. It would be necessary

and only two pigments were

to observe another pigment effect on the wettability and substrate adhesion of the ink

formulations to make a conclusion. It would be interesting to investigate gravure

strong

ink behavior on a multi-color gravure press. For example, it would be valuable to study

film to ink dot on or ink property

the behavior of ink dot on dry ink compared substrate,

differences between a continuous high-speed press run and a low-speed press case. This

study evaluated the ink physical properties on C-type ink only; results may differ with

91
other ink types. As mentioned above, even though the donut effect was substantially

decreased by the new ink formulations, the surface tension of the best performing ink

formulations was still higher than the theoretical upper surface tension limit. Therefore,

this study needs to be continued to find a better ink formulation that can overcome this

print quality difficulty and completely solve this printing problem.

92
 Glossary

Adhesion the intermolecular attraction between different types of substances

Cohesion the force of attraction by which the molecules of a solid or liquid tend to

remain together

Contact angle a definite angle of liquid contact with the solid surface

Detergency the theory and practice of dirt removal from solid surfaces

Donut effect a printing defect defined as a printed dot that only print on the

circumference of the dot with a void in the center.

Ester The compound formed by the elimination of water and the bonding of an alcohol

and an organic acid.

dot that has higher ink film

Fish-eye effect a printing defect defined as a printed

thickness on the circumference

93
Hydrophilic Having an affinity for, attracting, adsorbing, or absorbing water.

Hydrophobic Lacking an affinity for, repelling, or

failing to adsorb or absorb water

Surface tension the property of liquids that gives surfaces a

slightly elastic and
quality

enables them to form into separate drops.

Van der Waal's force an attractive force between two atoms or non-polar molecules,

which arise because a

fluctuating dipole moment in one molecule induces a dipole

moment in the other, and the two dipole moments then interact. Also known as

dispersion force; London force; van der Waal's attraction.

Viscosity A measurement of the internal resistance offered to the relative motion of

different parts of the liquid

Wettability The ability of any solid surface to be wetted when in contact with a liquid; t

hat is, the surface tension of the liquid is reduced so that the liquid spreads over

the surface.

94
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