Note: Descriptions are shown in the official language in which they were submitted.
~74~386
_l_
SELF-FIXINC LIQUID ELECTROGRAPHIC DEVELOPERS
m e present lnventlon relates to ~elr_
fixing liguid electro~tatlc image de~eloper~ comprising
as a dlspersed component, a compatlble blend o~ at
least one polyester blnder and at lea~t one polye~ter
plastlclzer, to image~ formed ~rom such developer~,
and to methods of formlng images with such developers.
Electrographlc imaglng and development
processes have been extenslvely described in both
the patent and other llterature. Cenerally, these
processes have in common the step~ of formlng an
electrostatlc charge image, often called an electro-
static latent image, on an lnsulatlng sur~ace, such
as a photoconductive lnsulating layer coated on a
conductive ~upport. m- electrostatic latent image
i8 then rendered vl~lble by a development step ln which
the charge image_bearing ~urface 18 brought into
contact with a suitable electrostatlc image developer
compositlon which deposits toner particle on either
the charged or uncharged lmage areas. After development,
the visible image i8 either heat_flxed dlrectly to the
electrostatlc charge_bearing sur~ace or lt 18
transferred to another surface such as paper where
lt 18 there heat-~ixed.
Llquid developer compositions of the type
de~cribed ln U.8. Patent No. 4,202,785 are very
useful for developlng latent electrostatlc images.
m ese developer~ comprl~e a stable dl perslon o~
dlsper~ed componQnts and dl~olved component~ in an
electrically ~nsulating carrler ll~uld. The dlspersed
component~ include charged p~rtlcle~, ~nown a~ toner
partlcle~, comprl~lng ~ colorant or pigment, ~uch a~
carbon black, generally a~ociated wlth a thermo_
plastlc re~ln blnder. The dl~solved component~
_2-
include optional organic liquids from previous steps
ln the preparation of the liquid developer, as well
as optional charge control agents.
Liquid developers containing polyester
resin binders such as those disclosed in the afore-
mentloned U.S. Patent No. 4,202,785 as well as
developers containing other polyester resin binders are
particularly useful. As noted in the said U.S. patent,
however, the polyesters are fixed to receiving surfaces
by the application of heat. Heat_fixable polyesters
having very high glass transition temperatures (Tg),
(i.e., above 150C) thus require higher fixing
temperatures as well as careful selection of the
receiving support to avoid support distortion or
charring.
In the published patent literature, various
llquid toner formulations having self-fixing qualities
are reported. For example, U.S. Patent 3,954,640
reports the use of low Tg linear addition polymers
to give liquid developers and lnks that become fixed
to a substrate with little or no carrier evaporation
in the a~sence of heat. It ls essential to this
patent that the polymer Tg be no higher than 35C.
m e patent further discloses the use of monomeric
plasticizers as optional components that are miscible
in the carrier. ~ The purpose of the plasticizer is to
ad~ust the ability of the carrier to disperse the
polymer resin.
U.K. Patent 1,110,225 describes a liquid
developer which is sald to be self_fixing upon removal
of the carrier liquid ~ollowing deposition of the
toner particles. To achieve such self_fixing, the
patent discloses the use of liquid alkyd resins which,
because of their unsaturated chemical bond linkages,
cure in air upon removal of the carrier liquid. Toner
particles containing oxidizing type unsaturated alkyd
~74~386
resins in combination with certain phenol modified pen-
taerythritol ester resins are also noted in UK Patent
897,903.
Also from the patent literature, the use of
certain plasticizers is reported in liquid toner formu-
lations for purposes entirely unrelated to selffixing.
Thus, for example, it is reported that toner adhesion
to a substrate can be achieved by tack modification;
that i6, through the addition of modifying agents, a
resin binder can be rendered suitably tacky to adhere
to a surface of choice. According to Smith et al US
Patent 3,939,085 issued February 17~ 1976, the addition
of monomeric plasticizers to toner resins produces a
toner composition which has low adhesion for an image-
forming surface and high adhesion for a copy surface.The adhesion differential facilitates transfer of toner
images from the imageforming surface to the copy where
the tacky quality is lost by curing. From the teach-
ings of this patent, therefore, it would appear that
the use of plasticizers will not produce a toner which
self-fixes to an image-forming surface.
US Patent ~,839,032 issued October 1, 1974,
relates to the use of carrier-soluble monomeric and
polymeric plasticizing agents for the toner binder
resin. The use of carrier-soluble plasticizers, how-
ever, is undesirable as they tend to le&ch out of the
binder resin into the carrier, thus negating any poten-
tial benefit from ther use. Furthermore, this document
does not teach that its toners are self-fixing.
In &ccordance with the presnet invention, a
self-fixing liquid electrographic developer is provided
exhibitng, in its broadest aspects, several significant
advantages. The developer is self-fixing without
resort to tacky low-T binder polymers. The self-
fixing property, moreover, is exhibited specifically on
an electrostatic image-bearing surface without fear
~L~7~86
of unwanted transfer to other surfaces. Furthermore,
the liquid developer exhibi~ its self-fixing property
immediately upon extraction o~ the image-bearing
surface or element from the liquid development region,
in contrast to the prior art methods relying upon
further chemical reaction of included curing agents
having unsaturated chemical groups.
These and other advantages are achieved
with a liquid electrographic developer composition
which self-fixes to an electrostatic image-forming
surface.
According to the present invention there is
provided a liquid electrostatic image developer
composition comprising an electrically insulating
organic carrier liquid contain~ng, as a dispersed
constituent, a plurality of toner particles comprising
a compatible blend of at least one polyester resln and
at least one polyester plasticizer, characterized in
that the plasticizer is substantially free of curable
groups and i~ substantially insoluble in the carrier
liquid.
Self_fixing in the context of the present
invention denotes the quality of forming a rub
resistant image on an electrostatic image-bearing
surface without resort to externally applied heat.
me self-fixing property, moreover, is substantially
immediate, after the image_bearing surface is treated
in and removed from the liquid developer, and any
residual carrier evaporated to dryness. To determine
whether a particular developer meets the sel~-~ixing
criteria of the present invention one can employ a
simple test to determine rub resistance. The rub
test comprise~ the appllcatlon of a 700 gram wei pted
olelc acid soaked patch approxlmately 5 mm in diameter
to a toner_bearing image and oscillating a portion of
the image back and forth underneath the absorbent
~7~386
5--
patch. Oleic acid is chosen to simulate natural finger
oil. Rub resistance is determined as a range A to B,
wherein A is the number of oscillatory cycles (a cycle
being one movement of the patch back and forth) lt takes
to first interrupt the toner image integrity while B
represents the number of cycles necessary to completely
remove the sub~ected portion of the image by such
rubbing. Specific toner images prepared in accordance
with the present invention, exhibit an A value of from
1 to 9 cycles and a ~ value of from 2 to 12 cycles
whereas control images having no polyester plasticizer
are completely removed (B) in one cycle. In the
practice of this inventlon, higher A_B values are,
of course, likely to be obtained depending on such
factors as the materials used in the compatible blend
of resin and plasticizer, as well as the nature of the
surface to which the blend is self_fixed.
In the practice of the present invention,
a compatible blend Or at least one polyester resin
and at least one polyester plasticizer is used. The
plasticizer i8 specifically free of curable groups,
in contrast to prlor art materials such as alkyd resins
that rely on further chemlcal reaction of curable groups
to fix. The plasticizer, moreover, is substantially
insoluble in the carrier liquid 80 as to prevent
leaching Or the plasticizer into the carrier~ A
compatible blend in this regard, refers to the ability
of the re~in and plasticizer to form a non_hazy solid
solution of one in the other.
The ratio of components in the compatible
blend varies widely in accordance with the user
need~. A useful wei p t ratio of plasticizer to resin
is in the range from 0.2 to 1Ø A preferred ratio
is in the range from 0.25 to 0.5.
1~74~3~i
Many polyester reslns are useful ~n the
practice of the present invention. Typical polyesters
include repeating diol units and diacid recurring
units well known to those skilled in the art.
Representative polyesters are disclosed, for example
in U.K. Patent 1,528,950. m is patent discloses a
redi~persible liquid developer in which the polyester
binder comprises disulphonamido groups.
Preferred polyester resins of the invention
include ionic poiyesters comprlsing recurring diol
units and recurring ionic diacid units. Representative
preferred polyester binders have recurring diol units
of the formula:
_ 0 G - 0- _
wherein:
Gl represents straight or branched chain
alkylene ha~ing Z to 12 carbon atoms or,
~ubstituted or unsubstituted, cycloalkylene
cycloalkylenebis(oxyalkylene) or cycloalkylene-
dialkylene; d have up to 35 mole percent
(based on the total moles of diacid units) of
ionic diacid units of the formula:
P 11
t C A C t
wherein:
A represents sulphoarylene, sulphoaryloxy-
arylene, sulphocyclohexylene, arylsulphonyl_
imino, sulphonylarylene, iminobis(sulphonyl-
arylene), sulphoaryloxysulphonylarylene and
sulphoaralkylarylene or the alkali metal or
ammonlum salts thereof.
~i7~886
--7--
5uch preferred polyester resin~ include, for example,
the polyester ionomer resins disclosea in U.S. Patent
4,202,785.
In general, useful polyester resin-~ of the
present invention have a glass transition temperature
~Tg) of from 40C to 100C. Polyester resins having
a Tg in the aforementioned preferred range can be
self-fixed to smooth_surfaced dielectric coated
receiving elements, as well as ordinary support
surfaces, such as photoconductive co~ted paper or
film elements, without dif~iculty.
Materials having a Tg above 150C can also
be used.
The glass transition temperatures can be
determined by conventional methods, such as differential
scanning calorimetry (DSC).
Useful polyester re~ins have an inherent
viscosity of 0.01 to 0.65, preferably 0.16 to 0.~1.
Polyester resins havlng inherent viscosities in the
preferred range are compatible with the preferred
charge control agent~, optionally used in the liquid
electrographic developers of the present lnvention.
Inherent viscositie~ of the polyesters are measured
in a 1:1 by weight solution of phenol:chlorobenzene at
25C at a concentration of 0.25 gram per 100 ml of
solution.
The p1asticizers employed in the compatible
blend of resin snd plasticizer are chosen from among
a variety of commercially availsble polyester
pla8ticizerg hsving ~ Tg below -40C, preferably
within the range from about -45C to about
-70C. In selecting suitable msterial, the
criteria of compatibility with the polyester binder
is usually first employed to screen potentislly
~i7~386 .
-- 8 --
useful materials. From smong these materials that
satisfy the compatibility criteria, one then excludes
plasticizers having curable chemic~l groups such as
oil-modified polyester plasticizers or epoxidized
5 oils. Of the eligible plasticizers, ones are chosen
that are insoluble in the electrically insulating
carrier liquid as defined below.
~ 1~74~386
_9_
plasticizers, ones are chosen that are insoluble in the
electrically insulating carrier liquid as defined below.
Representative useful polyester plasticizers
that are insoluble in commonly employed isoparaffinic
hydrocarbon carrier liquids such as that sold under
the trade mark 'Isopar' G are listed in the following
table by Trade Mar~ and commercial source.
TABLE I
Plasticizer Commercial Source
10 'San~icizer' 429 Monsanto Chemical Co.
'Santicizer' 409 Monsanto Chemical Co.
'Paraplex' C_25 Rohm and Haas Co.
'Paraplex' G_41 Rohm and Haas Co.
'Paraplex' G_57 Rohm and Haas Co.
15 'Paraplex' G_31 Rohm and Haas Co.
'Paraplex' G-40 Rohm and Haas Co.
'Eastman' NP_10 Eastman Koda~ Co.
Preferred polyester plasticizers include
those sold under the Trade Marks 'Santicizer' 429,
'Paraplex' G_25, 'Paraplex' G_41 and 'Paraplex' G-57.
'Santicizer' 429, typifying the preferred materials,
has the following physical properties:
Acidity 4.0 meq/100 gm max
Refractive Index
at 25C 1.460 to 1.470
Speclflc Gravity
25/25C . 1.080 to 1.110
Density (25C)
ca. lbs./gal. 9.1
. Flash point 288C
Fire point 310C
Insoluble ln water at 25C
Tg -56C
1~74~3~6
-10
Preferred polyester plasticizers comprlse
repeating alkylene diol units having 2 to 6 carbon
~toms such as diol units derived from ethylene glycol
or butylene diol, and repeating aliphatic diacid units
having 3 to 10 carbon atoms such ag diacid units derived
11'74886
from malonic acid, succinic acid or adipic acid. A
particularly preferred polyester plasticizer comprises
an acetate terminated adipic acid-butylene glycol
polyester.
m e polystyrene equivalent molecular weight
of the preferred polyester plasticizers rangeæ from
7000 to 9000 as determined by gel permeation
chromatography.
The compatible blend of resin and plasticizer
defined above is formed in a variety of ways that
facilitate the formation of small particles, preferably
of submicron size (l.e., 0.01 to 1.0 micron average
particle size). A preferred method of forming the
blend comprises preparing a concentrated solution of the
plasticizer and resin in a common solvent such as
'Solvesso' 100 (the trade mark for an alkylated aromatic
having a ma~or aromatic component and a boiling range
of from 150_185C sold by Humble Oil & Refining Co.,
U.S.A.). me concentrated solution ls thereafter mixed
with a large excess Or the liquid carrier to precipitate
particles of the plasticizer_resin blend in working
developer concentration strength~.
The carrier liquid employed according to the
present invention is selected from a varlety of
materials that satiæfy the plasticizer insolubility
criteria. These materlals should be electrically
insulating and have a fairly low dielectric
constant.
Useful carrier liquids have a dielectric
constant of less than 3, and a volume resistivity
greater than 101 ohmlcm. Suitable carrier liqulds
include halogenated hydrocarbon solvents, for example,
fluorinated lower alkanes, such as trichloromono_
fluoromethane and trlchlorotrifluoroethane, having
a boiling range typically from 2C to 55C. Other
~ 4
-12-
hydrocarbon solvents which are useful include iso-
paraffinic hydrocarbons having a boiling range of
from 145 to 185 C, such as Isopar G~, or
cyclohydrocarbons, such as cyclohexane. Additional
S carrier liquids which are useful include polysilox-
anes, odorlesæ mineral spirits and octane.
In general, useful working-strength devel-
opers of the present invention contain from 0.005
to 5 percent by weight of the plasticizer-resin
blend. These developers contain from 99.999 to 90
percent by weight of the liquid carrier vehicle.
Although it is possible to use the liquid
developers of the present invention without further
addenda, it is often desirable to incorporate such
addenda as charge-control agents, waxes and dis-
persing agents for the wax or colorants in the
developer.
If a colorless image is desired, it i8
unnecessary to add any colorant. For example, the
developer may be used to form a colorless hydropho-
bic image in a lithographic printing process. In
such case, the resultant developer composition con-
sists essentially of the liquid carrier behicle and
the plasticizer-resin blend particles of the pres-
ent invention.
In accordance with a preferred embodimentof the present invention, however, colorants such
as carbon black pigments are also included in the
liquid developer defined. In this regard, it has
been determined that images formed from toners com-
prising polyester resin binder and colorants
exhibit a tendency to crack in a pattern resembling
that of the bed of a dried lake, the so-called
adobe pattern. This tendency is significantly
reduced and often eliminated with the presently
defined blend of resin-plasticizer. Accordingly,
the present invention contemplates the use of
~'
~'74~3a6
-13-
colorant-containing developers to produce self-
fixing and crack-resistant visible images. Useful
results are obtained from virtually any of a wide
variety of known dyes or pigment materials. Par-
ticularly good results are obtained by using vari-
ous kinds of carbon black pigments.
A representative list of colorants are
found, for example, in Researc _ sclosure, Vol.
109, May, 1973, in an article entitled "Electropho~
tographic Elements, Materials and Processes".
The colorant concentration, when colorant
is present, varies widely with a useful concentra-
tion range, by weight of the total dispersed con-
stituents, being 10 to 90 percent. A preferred
concentration range is from 35 to 45 percent.
Waxes and dispersing agents for the wax are
also included as optional dispersed components in
the present developers. Suitable waxes and dispers-
lng agents include those described in Canadian
Serial No. 397,476 by Alexandrovich and Upson filed
March 3, 1982, which describes liquid electrographic
developers comprising an electrically insulating
organic carrier liquid containing dispersed con-
stituents and dissolved constituents, said dissolved
constituents comprising an electrically insulating
organic dispersing liquid which forms a solution
with said carrier liquid, said dispersed constitu-
ents comprising at least one thermoplaætic resin and
wax particles, and characterized in that said devel-
oper also contains a dispersing agent for said waxparticles which is insoluble in said solution of
carrier liquid and dispersing liquid, but soluble in
said dispersing liquid alone. Preferably, the wax
particles are a polyolefin wax, carnauba wax, an
ester wax or an amide wax. The dispersing liquid
used with these waxes is preferably an alkylated
~.~7~386
-14-
aromatic liquid when the carrier liquid is an iso-
paraffinic hydrocarbon.
Optionally, the developers of the present
invention include various charge control agent~ to
enhance uniform charge polarity on the developer toner
particles.
Various charge control agents have been
described heretofore in the liquid developer art.
Examples of such charge control agents may be found
in U.S. Patent No. 3,788,995 which describes various
polymeric charge control agents. Other useful charge
control agents include phosphonate materials
described in U.S. Patent No. 4,170,56~ and quaternary
ammonium polymers descrlbed in U.S. Patent No. 4,229,513.
Various optional non_polymeric charge control
agents are also employed such as the metal salts
described in U.S. Patent No. 3,417,019. Other charge
control agents known in the liquid developer art may also
be employed.
A partial listing of preferred representative
polymeric charge control agents for use in the present
invention includes poly(styrene-co-lauryl methacrylate_
co_sulphoethyl methacrylate), poly(vinyltoluene_co_
lauryl methacrylate-co-lithium methacrylate_co_meth_
acrylic acid), poly(styrene_co_lauryl methacrylate_co_
lithium sulphoethyl methacrylate), poly(~inyltoluene_co_
lauryl methacrylate-co_lithium methacrylate), poly-
(styrene-co-lauryl methacrylate_co_lithium methacrylate),
poly(t_butylstyrene_co_lauryl methacrylate_co-lithium
methacrylate, poly(t_butylstyrene_co_lithium meth_
acrylate), or poly~vinyl toluene_co_lauryl methacrylate-
co_methacryloyloxyethyl trimethylammonium p_toluene
~ulphonate).
1~174~386
The amount of charge-control agent used will
vary depending upon the particular charge-control
agent and its compatibility with the other component6
of the developer. It is uæually desirable to employ
an amount of charge-control agent within the range of
from 0.01 to 10.0 weight percent based on the total
weight of a working-strength liquid developer compo-
sition. The charge-control agent may be added in the
liquid developer simply by dissolving or dispersing
the charge-control agent in the liquid carrier
vehicle at the time concentrates of the components
are combined with the liquid carrier vehicle to form
a working-strength developer.
Various techniques are employed to prepare a
working-strength developer comprising the aforemen-
tioned plasticizér-binder blend. For example, as
disclosed in US Patent 4,202,785 by Hartman issued
May 13, 1980, one or more developer concentrates are
prepared for each of the developer components (a con-
centrate ls a concentrated solution or dispersion ofone or more developer components in a suitable elec-
trically insulating liquid vehicle not necessarily
the developer carrier liquid). The concentrates are
then admixed in a preselected sequence, the admixture
slurried with the carrier liquid to dilute the compo-
nents, and the slurry homogenized to form the
working-strength developer.
The present liquid developer~ are employed
to develop electrostatic charge patterns carried by
various types of elements. Such elements are either
photoconductive themselves, i.e., image-forming sur-
faces, or adapted to receive charge images, i.e.,
image-receiving surfaces, as disclosed in US Patent
3,519,819 issued July 7, 1970. For example, the
developers may be used with photoconductive film ele-
ments containing arylmethane photoconductor composi-
,~
1JL7~886
tions such as those disclosed in US Patent 4,301,226issued November 17, 1981.
The following examples are included for a
further understanding of the invention.
Examples:
Preparation of Liquid Developer
The following illustrates the preparation of
liquid developers in accordance with the present
invention. Various concentrates, each containing
separate developer components in Solvesso 100~
alkylated aromatic liquid, were prepared. Concen-
trates containing dispersed (insoluble) components in
the Solvesso 100~ were solvent ball-milled. The
Solvesso 100~ concentrates included the following in
approximately 10%-by-weight concentrations:
(A) colorantl and charge-control polymer,
(B) polyester resin2,
(C) auxiliary charge-control polymer,
(D) wax3 and disper~ing agent~ and
(E) polyester platicizer5.
Raven 1255~ carbon black available from Cit-
ies Service Company
2 polytneopentyl-4-methylcyclohexene-1,2-dica -
boxylate-co-terephthalate-co-5-(N-potassio-~-
toluene sulphonamidosulphonyl)isophthalate]
3 Shamrock Chemicals Corporation S-394~ poly-
ethylene wax
Elvax 210~, an ethylene/vinylacetate copoly-
mer available from duPont
5 Santicizer 429~ polyester plasticizer
available from Monsanto Chemical Co.
Preselected portions of each concentrate were
admixed with sufficient Isopar G~ isopar~ffinic
hydrocarbon carrier liquid and the resulting diluted
mixture homogenized to form 1 liter of a working-
strength de~eloper containing 1 part (0.7 gram)
colorant per liter. The concentrations of the other
~74~386
-17-
components, by parts, were as follows:
Colorant 1 part
Charge control polymer 1.2 parts
Polyester resin 1.2 parts
Auxiliary charge control polymer 0.175 part
Wax 0.25 part
Dispersing agent 0.125 part
Plasticizer X
where X represented varied concentrations of plasticizer
in five different developers as shown in Examples 1 to 5.
ExamPles 1 to 5
The developers prepared as above for
plasticizer concentrations X=0, 0.25, 0.375, 0.50 and
1.0 were employed to form toned images on a photo_
conductive recording film element without application
of heat to fix the images. The film element comprises
a film support, an electrically conducting layer
overlying the suppsrt and a photoconductive layer
overlying the conductlve layer.
m e resulting images were observed on a
microfiche viewer screen at 24X magnification and
the presence or non_presence of image cracking noted.
Images of varied density for each developer were also
sub~ected to the olelc acid rub test described above
to assess their self-fixlng qualities. Results are
shown in Table II.
.. .
` 117~86
-18-
TABLE II
X Imaze Ima~e Oleic Acid
ExamPle (parts) DensitY Crackin~ Rub (A_B) CYcles
l(control) 0 1.1 Yes l*
5- 0 0.7 Yes l*
2 0.25 1.2 No 3-5
0.25 0.8 No 1_2
3 0.375 1.2 No 5_11
0.375 0.8 No 3_6
10 4 0.5 1.3 No 4_8
0.5 0.8 No 2_4
1.0 1.4 No 1_2
1.0 0.9 No 1-2
*represented complete removal after one rub.
15 Exam~les 6 and 7
Two developers were prepared as above
having the followlng concentration of components
Colorant 1 part
Charge control polymer 1.2 parts
Polyester resin 1.2 parts
Auxiliary charge control polymer 0.1 part
Plasticizer X
The developers were employed to form images as in
Examples 1 to 5 and the images assessed for olelc acid
rub resistance. m e results are shown in Table III.
TABLE III
X Image Oleic Acid
Exa le t arts)DensitY R~b (A_B)
6 control 0 1.8
1.0
7 0.5 2.2 9-25
1.2 4_8
i
1174~86
-19_
Exam~les 8 to 10
Three developers were prepared and employed
to form images as above. In each developer, carbon
black was replaced with the colorant shown below:
5 Example 8
Cyan Blue GTNF
(American Cyanamid) 1 part
Charge control polymer 0.9 part
Polyester resin 1 part
Auxiliary charge control polymer 0.1 part
Plasticizer 0.5 part
Example 9
'Sunfast' Quinacridone
(Sun Chemicals Co.) 1 part
Charge control polymer 0.8 part
Polyester resin 1 part
Auxillary charge control polymer 0.1 part
Plast~clzer 0.5 part
Example 10
Lemon Metallic Yellow
(Sun Chemical Co.) 1 part
Charge control polymer 1 part
Polyester resin 1 part
Auxlliary charge control polymer 0.2 part
Plasticizer 0.5 part
Each of the developers was noted to exhibit
~elf_fixing.
Exam~les ll to 15
The followlng developer~ were prepared and
employed to form images a~ ln above Examples 1_5:
Colorant 1 part
Charge control polymer 1.4 parts
Polye-qter re~ln 1.2 parts
Auxlllary charge control polymer 0.2 part
Plasticlzer X
~ li74~386
-20-
Five developers were prepared with values of X equal
to 0, 0.125, 0.25, 0.50 and 1.0, m e cracking Or
the images, if any, was noted as in Examples 1_5 and
reported below in Table IV by severity.
TABLE rv
X
ExamPle (Parts) Toner Crackin~
11 control 0 Very heavy
12 0.125 Moderate to heavy
13 0.25 Slight, pinhole type
14 0.50 None
1.0 None
