3.1. Compoziia cernelurilor.

Generaliti
There are probably as many different definitions of ink as there are types. Perhaps the simplest
description is that ink is a liquid or semi-liquid material used for writing, printing or drawing.
Chemists view it as a colloidal system of fine pigment particles dispersed in a solvent (Chem. Br.,
February 2003, p28). The pigment may or may not be coloured, and the solvent may be aqueous or
organic.
Modern ink formulations are rather more complex. In addition to the pigment, they contain many
other ingredients in varying levels. Collectively known as vehicle, these additional ingredients
include pH modifiers, humectants to retard premature drying, polymeric resins to impart binding and
allied properties, defoamer/antifoaming agents to regulate foam efficiency, wetting agents such as
surfactants to control surface properties, biocides to inhibit the fungal and bacterial growth that lead
to fouling, and thickeners or rheology modifiers to control ink application.
Over 90 per cent of inks are printing inks, in which colour is imparted by pigments rather than
the dyes used in writing inks. Pigments are insoluble, whereas dyes are soluble, though sometimes
these terms are used interchangeably in commercial literature. Ink pigments are both inorganic and
organic. Most red writing inks are a dilute solution of the red dye eosin. Blue colour can be obtained
with substituted triphenylmethane dyes. Many permanent writing inks contain iron sulfate and gallic
and tannic acids as well as dyes. Ballpoint ink is usually a paste containing 40 to 50 per cent dye.
Most white inks contain titanium dioxide as the pigment, as rutile and anatase in tetragonal
crystalline form. However, growing concerns over the known toxicity of heavy metals have led to the
replacement of many inorganic pigments such as chrome yellow, molybdenum orange and cadmium
red with organic pigments, which offer better light fastness and reduced toxicity. Furthermore, carbon
black now replaces spinel black, rutile black and iron black in nearly all black inks. In fact the ink
industry is the second largest consumer of carbon black.
Other inorganic materials such as clays serve as fillers or extenders, which primarily reduces the
cost of pigments, though some also improve ink properties. Metallic pigments like aluminium
powder (aluminium bronze) and copper-zinc alloy powder (gold bronze) are used in novel silver and
gold inks. Miscellaneous inorganic pigments provide luminescent and pearlescent effects.
Changes in ink chemistry over the years closely reflect developments in the instruments for ink
coating: the pen and the printing machine. The ballpoint pen, the felt-tip marker, and the fibre-tip pen
have led to inks containing solutions of dyes in water or organic solvents such as propylene glycol,
propyl alcohol, toluene or glyco-ethers. Other ingredients like resins, preservatives and wetting
agents

are

also added.
543.4 362
03.00.00inks depends on the
Similarly, theUTM
composition
of printing

Mod Coala

document.

Efectuat

Miron Cristina

Verificat

Cazac Viorica

Semnat

Data

type

of

printing

process

Analiza cernelurilor
specifically,
how the inktipografice cu efecte speciale

Litera

Coala
1

UTM
DTP-131

Coli
5

distribution rollers are arranged in the printing press. The major classes of printing processes are
lithography or the offset process, flexography, gravure printing, screen printing, letter press and
digital printing.
The principle of printing is illustrated by the simple stamp pad operation. Here we use a liquid
ink that wets the pad. A rubber type dipped in the pad gets wet with the ink, which is pressed against
the substrate, say paper, to produce the impression. Clearly, this ink should be a liquid while in the
pad and should dry fast on paper. The various printing processes differ in the way the type is
impregnated with the ink, although digital printing does not involve movable types. Each process
therefore demands an ink that differs in its viscosity and drying efficiency, which is possible by finetuning the composition.
A printing ink chemist is primarily interested in preparing a dispersion of pigment particles that
does not settle into clumps. Inorganic pigments can be easily dispersed by applying minimal force,
but most organic pigments require special milling techniques to produce sub-mm size particles for
stable dispersion. In general the colour of the ink arises from organic pigments; the particle size of
the pigment governs the colour intensity.
Milling is carried out in two stages: the primary mixing is done with an ordinary mixer and the
resultant pre-mix is subjected to secondary grinding in a ball mill or a roller mill. After the primary
mixing, the chemist adds chemicals called dispersants or grinding aids to prevent the fine pigment
particles from reaggregating during the grinding stage. The correct choice of dispersants, along with
the right grinding technique, is the key to obtaining a stable dispersion.
Dispersants stabilise the pigment particles by lowering the mechanical energy needed for
grinding. Two classes of compounds are used for this purpose: surfactants and polymers. These
compounds adsorb to the pigment particles and form a coating of varying composition and thickness.
The resulting modified particle surfaces either attract or repel each other - leading to flocculation or
stabilisation, respectively. Flocculation hampers dispersion, and stabilising forces are essential to
prevent the fine particles of pigment from settling. The size and shape of the pigment particles
dictates the colour intensity, shade and light fastness.
There is a growing tendency these days to exclude organic solvents from commercial products,
and inks are no exception. Strict regulations limit the use of volatile organic compounds (VOCs)
everywhere from paint to plastic manufacture. As a result, ink chemists have been forced to abandon
many efficient and time-tested recipes by replacing organic solvents with water. Water-based inks
have in turn introduced new classes of surfactants and polymers into ink chemistry.
An obvious disadvantage of using water as a medium is the increased surface tension of aqueous
inks, which makes wetting substrates such as paper or plastics more difficult. A two-pronged
approach has helped to alleviate this problem: special surfactants lower the surface tension of inks,
Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

2
UTM 543.4 346 00.00.00

while modifying the surfaces of substrates like plastic (eg the corona treatment) enhances the surface
energy, and so makes wetting easier. Surfactants have the downside of producing a stabilised foam.
Inks should have a viscosity (loosely called thickness) appropriate to the printing process. Some
inks have a butter-like consistency and others have intermediate viscosity. Various polymeric
thickening agents are added for this purpose. In this regard, ink chemists are interested in rheology,
the study of the relationship between the applied stress and the resulting deformation. Complex fluids
like inks show non-Newtonian behaviour, ie their viscosity changes when stirred, although by
themselves most of the raw materials in a typical ink composition show the opposite, Newtonian,
behaviour. Furthermore, most inks exhibit pseudoplasticity, which essentially means that they
become runnier when stirred or spread.
In the past, chemists fine-tuned the properties of solvent-borne inks by including polymers of
various molecular weights. These inks contained relatively little solid matter, ie were low solids
type, and required large amount of solvent to dissolve high molecular weight polymers. Modern
solvent-free inks are high solids types, incorporating monomeric and oligomeric polymer precursors
that can be polymerised in situ after applying the ink to the substrate, for example by UV light or a
high energy electron beam.
These inks contain easily polymerisable monomeric or oligomeric units mixed with an initiator
that produces radicals or ions on irradiation that will initiate the polymerisation process. Electron
beam inks do not require an externally added initiator because the electrons can themselves generate
radicals. Aside from being solvent-free, these inks cure instantly, giving fast printing speeds. Demand
for these inks is currently growing at about 10 per cent per year.
How fast the ink dries governs the speed of the printing process. Drying can involve the
absorption or penetration of liquid components into the substrate; evaporating the solvent at a certain
temperature; or chemical processes involving oxidation or polymerisation.
A newly developed ink that meets the requirements of a printing process and substrate will be
subjected to a number of quality control tests before being marketed. These tests vary with the end
application. Some of the tests are termed print quality, block resistance, scrubbing, light fastness,
bleeding, foamability, shear stability, gloss, water resistance, tape adhesion and drying in air. Print
quality tests how good is the print, block resistance tests the transfer of ink from a printed roll to an
unprinted surface and foamability indicates the extent of foam generation in an ink formulation, and
so on.
In addition to these properties, many speciality inks are designed for other specific end uses.
With some new thermochromic and photochromic inks heat and light are needed to produce colour,
while electronic ink requires an electric field to induce colour (see Box below and Chem. Br., July
2002, p22). Thermochromic inks help detect temperature changes in a moving part while electronic
Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

3
UTM 543.4 346 00.00.00

inks find application in various displays. Magnetic inks incorporate certain magnetic materials in the
ink and are used in printing cheque books for efficient screening by cashiers.
As these and many other examples show, ink is a more complex fluid than you might previously
have imagined. The paperless society that many people envisage for the future is still a long way off.
Meanwhile, ink chemistry should continue to preoccupy scientists for many years to come.
A colourful palette

Pigments are considered to be the chief constituent of an ink and contribute about 50 per cent of
its cost. A pigment is essentially any particulate solid - coloured, black, white or fluorescent - that
alters the appearance of an object by the selective absorption and/or scattering of light. It occurs as a
colloidal suspension in ink and retains a crystal or particulate structure throughout the colouring or
printing process.
Organic pigments in modern inks are identified by a Colour Index System number that reflects
the colour shade or hue, and structural and chronological details (order of synthesis) of the pigment.
For example the well-known blue pigment copper phthalocyanine blue is PB 15. The colour intensity
(strength) of a pigment increases as the particle size reduces, and the opacity peaks around a particle
size of 0.3?m.
Other speciality pigments are also in demand. Fluorescent pigments have a variety of
applications, such as in security inks to prevent forgery, in traffic light signals, poster boards and
advertising. Pearlescent pigments used in other inks reflect light in the same way as natural pearls.
However, instead of comprising multiple layers of calcium carbonate and protein, pearlescent
pigments contain flakes of mineral mica (lower refractive index) coated with layers of titanium
dioxide (higher refractive index).
Stabilising influences
Surfactants are surface active agents that lower the surface tension of the solvent in which they
dissolve. Surfactants have multiple functions in an ink formulation. Primarily they act as stabilising
agents for pigment dispersions. With the advent of water-based inks, they have an additional function
as wetting agents - keeping the surface tension of the aqueous medium low so that the ink interacts
favourably with the substrate. Careful choice of surfactants is often necessary to avoid problems with
ink foaming - the break in ink flow that sometimes occurs when bubbles form at a pen tip, for
example.
Foam is almost unavoidable during ink manufacture, and results from the release of various
gases, such as the adsorbed gas in pigment released at the dispersion stage, as well as from the air
introduced during mixing. Surfactants adsorb on the liquid-air interface in the foam and stabilise it,
thereby accelerating its formation.
Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

4
UTM 543.4 346 00.00.00

Foaming may be overcome by two approaches: it can be prevented by antifoaming agents and
cured by defoaming agents. These agents include various hydrophobic solids, fatty oils and some
special surfactants, which work by penetrating the liquid-air interface in the foam and slowing foam
formation.
In general surfactants are structures that contain a hydrophobic hydrocarbon chain and a polar
group. If the polar group is ionic, two classes of surfactants result: cationic and anionic. Ionic
surfactants are particularly good at stabilising foams, and ink chemists try to avoid them in an ink
formulation. Another class of zwitterionic surfactants contains both positive and negative groups in
the same molecule in addition to the hydrophobic group. In non-ionic surfactants, a block of ethylene
oxide groups usually imparts polarity.
Sodium dodecyl sulfate, SDS, is a well known anionic surfactant
CH3 (CH2)11 OSO3- Na+
Cetyl trimethyl ammonium bromide (CTAB) is a cationic surfactant
C16 H33 (CH3)3 N+ Br Dodecyl octaethyleneglycol monoether is a non-ionic surfactant
CH3 (CH2)11 (OCH2 CH2)8 OH
N-n -Dodecyl-N,N -dimethyl betaine is a zwitterionic surfactant
CH3 (CH2)11 N+ (CH3)2 CH2 COO-

As the concentration of surfactants increases in a solution, some of the physical properties of the
solution will change sharply at a concentration called the critical micelle concentration (CMC), (see
Fig). Above CMC, the surfactant molecules come together to form spherical aggregates (micelles) in
which the core is populated with hydrophobic chains and the corona by polar groups. The average
number of surfactant molecules in each micelle structure is known as the aggregation number, which
is about 60 in the case of SDS micelles.
Surfactants aggregate on the surface layers at the liquid-air and the solid-liquid interfaces. In the
former case, the surface tension of the liquid reduces and in the latter case the solid (pigment)-liquid
Coala
UTM 543.4 362
5
Mod Coala document. Semnat
Data
UTM 543.4 346 00.00.00

interface is modified. Either way, the net result is to make the application of the ink to its substrate
(eg paper) easier.
Multi-task polymers
Polymers have multiple functions in fine-tuning the properties of an ink. In the past, naturally
occurring polymer resins found use in inks and coatings, but modern inks contain many synthetic
polymers. One of the main functions of polymers in ink is to serve as dispersants, either alone or
coupled with surfactants. They also help to adjust viscosity and to modify rheological properties.
Other important functions include aiding film formation and improving the mechanical and specific
properties of inks, such as washability and abrasion resistance.
Nitrocellulose based polymers were the main player in solvent-borne inks, but polyacrylates are
most familiar in modern water-borne inks. Various polyacrylate homopolymers and copolymers are
widely used, although other classes such as polyurethanes and polyesters are useful in imparting
specific properties. Basic properties like the glass transition temperature - at which the polymer
transforms from a glassy or hard state to a flexible state - must be controlled to achieve the
appropriate blocking resistance (causing ink to adhere only to its substrate) and minimum film
forming temperature (MFFT).
The reactivity of polymers with other components in the ink decides the final properties of the
ink coating. For example, polymer-surfactant interactions detract from fine properties like viscosity
and dispersion stability, affecting the applicability and colour strength of the ink.
Ink ingredients

Pigments (organic and inorganic)

Dispersants (surfactants and polymers)

Resins or polymers improve binding, rheology and mechanical properties

Humectants retard premature drying

Defoamers and antifoaming agents

Wetting agents enhance contact with the substrate

pH modifiers (usually amine derivatives)

Biocides and bacteriostats

https://www.chemistryworld.com/news/ink-chemistry/1013163.article
UTM 543.4 362
Mod Coala

document.

Semnat

Data

Coala

6
UTM 543.4 346 00.00.00

Caracteristicile specifice fiecrui tip de cerneal sunt date de propriet ile materiilor prime
utilizate n reeta de preparare.
Pentru toate felurile de cerneal, principiul de baz este acelai.
Orice sistem convenional de cerneal este format din patru componeni, ai anume:
- binder;
- solvent;
- colorant;
- ageni auxiliari
Binderul reprezint baza n care se formeaz cerneala. Acesta are rolul de a nconjura particulele
de colorant, dar i de a asigura aderena cernelii la substrat. n funcie de aplica ie, binderul este
special indicat pentru hrtie, plastic, sticl sau metal. Particulele de binder pot fi rigide sau elastice,
astfel nct s permit deformarea sau nu. n general se utilizeaz n varianta rigid care, n timpul
procesrii, se va dizolva.
Solventul are rolul de a dizolva binderul, transformndu-l din forma rigid ntr-o mas vscoas,
utilizabil n procesul serigrafic. Dar exist foarte multe tipuri de substrat care nu rezist atacului
solvenilor. n acest caz, solventul este utilizat doar pentru a mari aderena la substrat a cernelii.
Solvenii difer ntre ei prin puterea de dizolvare i prin viteza de evaporare. Solvenii cu
volatilitate ridicat se numesc diluani iar cei cu viteza mic de evaporare se numesc ntrzietori.
Viteza de evaporare a solventului din compoziia cernelii, n procesul de polimerizare a acesteia,
depinde att de volatilitatea solventului ct i de natura binderului.
Colorantul este substana responsabil de culoarea cernelii. n industria cernelurilor serigrafice,
acetia pot fi colorani sau pigmeni. Doar n situaii speciale se utilizeaz ageni de colorare, care au
proprieti limitate n ceea ce privete strlucirea, luciul i transparena.
Agenii auxiliari sunt utilizai pentru a da cernelurilor proprieti speciale. Printre acetia se
numr: ageni de curgere, aditivi pentru luciu sau mtuire, aditivi pentru vscozitate, promotori de
aderen.
3.2. Compoziia cernelurilor fosforescente
Phosphorus
Atomic Number: 15
Symbol: P
Atomic Weight: 30.973762
Discovery: Hennig Brand, 1669 (Germany)

Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

7
UTM 543.4 346 00.00.00

Electron Configuration: [Ne] 3s2 3p3

Word Origin: Greek: phosphoros: light-bearing, also, the ancient name given the planet Venus
before sunrise.
Properties: The melting point of phosphorus (white) is 44.1C, boiling point (white) is
280C, specific gravity (white) is 1.82, (red) 2.20, (black) 2.25-2.69, with a valence of 3 or 5. There
are four allotropic forms of phosphorus: two forms of white (or yellow), red, and black (or violet).
White phosphorus exhibits a and b modifications, with a transition temperature between the two
forms at -3.8C. Ordinary phosphorus is a waxy white solid. It is colorless and transparent in its pure
form. Phosphorus is insoluble in water, but soluble in carbon disulfide. Phosphorus burns
spontaneously in air to its pentoxide. It is highly poisonous, with a lethal dose of ~50 mg. White
phosphorus should be stored under water and handled with forceps.
It causes severe burns when in contact with skin. White phosphorus is converted to red
phosphorus when exposed to sunlight or heated in its own vapor to 250C. Unlike white phosphorus,
red phosphorus does not phosphoresce in air, although it still requires careful handling.
Uses: Red phosphorus, which is relatively stable, is used to make safety matches, tracer bullets,
incendiary devices, pesticides, pyrotechnic devices, and many other products. There is a high demand
for phosphates for use as fertilizers. Phosphates are also used to make certain glasses (e.g., for
sodium lamps). Trisodium phosphate is used as a cleaner, water softener, and scale/corrosion
inhibitor. Bone ash (calcium phosphate) is used to make chinaware and to make monocalcium
phosphate for baking powder. Phosphorus is used to make steels and phosphor bronze and is added to
other alloys. There are many uses for organic phosphorus compounds. Phosphorus is an essential
element in plant and animal cytoplasm. In humans, it is essential for proper skeletal and nervous
system formation and function.
Element Classification: Non-Metal
Isotopes: Phosphorus has 22 known isotopes. P-31 is the only stable isotope.
Density (g/cc): 1.82 (white phosphorus)
Melting Point (K): 317.3
Boiling Point (K): 553
Appearance: white phosphorus is a waxy, phosphorescent solid
Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

8
UTM 543.4 346 00.00.00

Atomic Radius (pm): 128

Atomic Volume (cc/mol): 17.0
Covalent Radius (pm): 106
Ionic Radius: 35 (+5e) 212 (-3e)
Specific Heat (@20C J/g mol): 0.757
Fusion Heat (kJ/mol): 2.51
Evaporation Heat (kJ/mol): 49.8
Pauling Negativity Number: 2.19
First Ionizing Energy (kJ/mol): 1011.2
Oxidation States: 5, 3, -3
Lattice Structure: Cubic
Lattice Constant (): 7.170
CAS Registry Number: 7723-14-0
Phosphorus Trivia:
Hennig Brand isolated phosphorus from urine. He kept his process a secret, choosing

instead to sell the process to other alchemists. His process became more widely known when it was
sold to the French Academy of Sciences.
Brand's technique was replaced by Carl Wilhelm Scheele's method of extracting

phosphorus from bones.

Phosphorus is the sixth most common element in the human body.

Phosphorus is the seventh most common element in the Earth's crust.

Phosphorus is the eighteenth most common element in seawater.

An early form of matches used white phosphorus in the match head. This practice gave rise
to a painful and debilitating deformation of the jawbone known as 'phossy jaw' to workers when
over-exposed to white phosphorus.
http://chemistry.about.com/od/elementfacts/a/phosphorus.htm
Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

9
UTM 543.4 346 00.00.00

Pigmenii fosforesceni
Allureglow SUA utilizeaza o serie de pigmeni fosforescent pe baz de cost eficient si unic grad
premium de stroniu aluminat, care revolutioneaza acum lumea de fotoluminiscenta. Avantajele
acestor cristale includ luminozitatea; luminozitatea este mult mai mare dect orice alt form de
cristal. Acest lucru se datoreaz faptului c cristalele sunt fabricate pentru a patentat Formularea
noastr, folosind numai materii prime de calitate premium i metodele noastre de procesare sunt
proiectate pentru a se obine puritatea maxim a produsului finit cu numai mcinarea minim a
cristalelor.
Pigmentul folosit n produsele noastre sunt considerate a fi o premier mondial n a avea
performane superioare a unui compus de tip stroniu, care poate fi furnizat sub form de ap sau pe
baz de solvent i dispersat n vopsele, cerneluri, acoperiri, glazuri ceramice i extrudate n cele mai
multe materiale plastice i rini . Pigmentul dovada de ap nu-i pierde luciul n ap sau n
formulrile pe baz de ap. Exist o gam larg de dimensiuni de particule disponibile, care permit
utilizarea sa n aplicaii unde sunt necesare particule foarte fine sau n cazul n care dimensiunile mari
ale particulelor sunt potrivite. Doar s ne anunai ce cererea dumneavoastr este i vom recomanda
cea mai potrivita de pigment size.Crystal apariia n lumina zilei este o culoare verde pal; Cu toate
acestea cerul albastru nostru, violet i alb va avea o culoare albicioas lumina zilei. Nivelul de
culoare lumina zilei variaz datorit dimensiunilor particulelor i grade.Due de performan la chimie
si cristal structura unica a pigmenilor noastre, atunci cnd sunt formulate corect, luminozitatea
inerent poate fi multiplicat n mod semnificativ. Acest lucru a permis produsele care urmeaz s fie
dezvoltate, care depesc toate standardele cele mai stricte pentru emisii, cum ar fi recentul 6-1 RSregula New York pentru marcajele de cale fosforescent, OMI ieire pentru, ASTM, ISO i PSPA.
Allureglow USA fotoluminiscente Pigmente (de asemenea, cunoscut sub numele de strlucire n
pigmentii nchis) sunt lider n industrie, n fiecare aspect msurabil. Aceti pigmeni absorb lumina de
la lumina soarelui, lumina zilei ecranat, sau lumin artificial, iar apoi emit aceast energie de lumin
ca lumina vizibil atunci cnd este plasat n ntuneric. Gama de pigmen i includ galben / verde i
aqua / pigmeni de strlucire albastru, care sunt standardul industriei. Acestea nu sunt elemente de
noutate, dar pigmeni de nalt performan concepute pentru aplicaii comerciale i de siguran .
clase speciale de la fel de mici ca 5 microni pn la fosforescent nisip granulatie de 450 microni sunt
disponibile pentru a satisface orice cerin. Exist o gam larg de culori disponibile, de asemenea.
Pigmenii sunt disponibile pentru aplicaii pe baz de ap precum i aplica ii pe baz de solvent sau
ulei.
Allureglow SUA UV sau de securitate Pigmente (pigmen i de lumin neagr, de asemenea,
cunoscut sub numele de pigmeni invizibile), care sunt utilizate pe scar larg n eforturile de
securitate i de combatere a contrafacerii n ntreaga lume. Thery sunt de asemenea disponibile pentru
efecte speciale applicatons.
Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

10
UTM 543.4 346 00.00.00

Toi pigmeni noastre sunt non-radioactive, nepericuloase i in conformitate cu regulamentul.

Coala

UTM 543.4 362

Mod Coala

document.

Semnat

Data

11
UTM 543.4 346 00.00.00