Polyperfluoroalkyl acrylate or polyvinyl perfluoroalkanoate; low

14 Pages·2013·1.65 MB·English

United States Patent [111 3,975,352
1191
1451 Aug. 17, 1976
Yoerger et al.
154] REPELLENT COMPOSITIONS AND 2,642,416 6/1953 Ahlbrecht et a1 ................ .. 260/835
ELEMENTS CONTAINING THE SAME 2,826,564 3/1958 Bovey et al. . . . . . . . . . . . . . . .. 260/895 H
2,839,513 7/1958 Ahlbrecht 8t :11... 260/895 H
1751 lnventors: William E. Yoerger, Rochester; 3.016.823 1/1962 Thurlow ......................... .. 96/33
John M. McCabe, Pittsford‘, John F. 3,677,178 7/1972 Gipe ............. .. 96/363
Wright, Rochester, all of N.Y. 3,775,115 11/1973 -Sorkin 01. al. 96/111
1731 Assignee: Eastman Kodak Company, 3,790,382 2/1974 Dahlman . . . . . , . . . . . . . . . . . . . . . . . . . .. 96/33
Rochester, N.Y.
Primary Examincr—Lewis T. Jacobs
1221 Filed: Mar. 13, 1975 Assistant Examiner-—H. H. Fletcher
Attorney, Agent, or Firm-J. R. Everett
1211 Appl. No.: 558,030
Related US. Application Data
157] ABSTRACT
1621 Division of Ser. No. 497,348, Aug. 13, 1974, Pat. No.
3,901,700, which is a division of Ser. No. 361,370, A repellent composition containing an oil of low vola
May 17, 1973, Pat. No. 3,859,090.
tility having a surface energy less than 27 dynes/cm.
and a solid ?uorinated polymer such as a polymer of a
1521 US. Cl ............................. .. 260/333 F; 96/1 R; fluoroalkyl acrylate. In accord with certain embodi
96/1 LY; 96/].5; 96/31; 96/33; 101/450;
ments of the invention, a resinous binder and/or a par
101/457; 106/2; 260/291 SB‘, 526/245
ticulate ?uorocarbon powder may be added tothe re
1511 Int. Cl.2 ...................... .. C08K 5/02; C08K 5/54 pellent composition. The repellent composition may
158] Field of Search ................ .. 260/338 F, 89.5 H,
be used to prepare an ink repellent surface for a “wa
260/29.l SB; 106/2
terless” lithoplate or as a coating on the surface of an
electrographic element from which a liquid developed
1561 References Cited
electrographic image is transferred.
UNlTED STATES PATENTS
2,592,069 4/1952 Reid ................................. ., 260/85.7 6 Claims, No Drawings
3,975,352
1 2
. As is apparent from the literature noted above, sev
REPELLlENT COMPOSITIONS AND ELEMENTS ._ eral repellent or abhesive compositions‘ havetbeen in
.Y ‘ CONTAINING THE SAME A vestigated and proposed previously for use in-electro
graphic and/or planographic elements and processes.
This is a division of application Ser. No.1 497,348, 5 However, subsequent research and testing has shown
?led Aug. 13, 1974, now U.S. Pat. ,No. 3,901,700, various problems‘ and defects which. may be encoun
issued Aug. 26, 1976, which, in; turnv is a division of tered when using these previously developed composi
application Ser. No. 361,370, ?led May 17, 1973, now tions.’ For example, the above repellent silicones and
U.S. Pat. No. 3,859,090, issued Jan. 7, 1975.' . repellent ?uorocarbon materials provide coatings hav
ing relatively soft surfaces that are subject to abrasion
Field of Invention
as well; "as contamination and smudging by electro
The present invention relates to a novel repellent graphic and-planographic developer apparatus and by
composition and various useful elementshparticularly,
developer and ink compositions. Such defects tend to
electrographic and/or planographic elements, (such as
destroy ‘lthe repellent-or abhesive characteristics of
lithoplates), bearing a coatingof such alrepellent com-_ these compositions thereby substantially decreasing the
position. \ _ e _, I‘ v " " ' ability of these materials to effectively transfer clean
developer or ink images. ‘ > ' '
Related'Art . . In addition, it'has been found that the abhesive sili
A great deal of work has been undertaken in the past
cone 'materi'als'such as described in U.SI Pat. No:
relating to the use of repellent compositions (or as they
2,990,278, U.S. 3,511,178 and German OLS No.
are sometimes called “abhesive”~ compositions)‘. Such 2,204,745 ‘present a difficult-toner fusion problem.
compositions are generally characterized by their abilé
when used as an abhesive coating for an electrophoto
ity to repel most other kinds of materials including solid
graphic element. That‘is, it has been found extremely
materials such as various natural and synthetic poly
difficult to obtain good adhesion between conventional
meric articles, for'example, sheets, blocks, ?laments 25
oleophilic electroscopic toner'materials and an abhe
and powders, and liquidimaterials such as aqueous
sive silicone surface. As a result, when such an electro
based and oil-base compositions, for example,- dye and‘
graphic element is used as a planographic printing
pigment-containing compositions, including inks, ‘lac
plate, the ink-receptive ‘image on the plate (which is
quers, paints, and variousliquid electrographic and
composed of the electroscopic toner) tends to deterio
30
photographic developing compositions. . . . v:.; _~ _ rate ‘rapidly and'is generally useful for the‘ production
For instance, U.S.-Pat. No. 3,247,825, issuedrApr.
of only a small number 'of clean, high quality copies.
26, 1966, describes a non-wettable insulator belt made
of Te?on, a trademark for poly(tetr.afluoroethylene-) ’_ - , SUMMARY OFI'l‘HE INVENTION
—.-containing_ materials manufactured by El. . duPont
*In accord with the’ present invention we have discov
Nemours‘ and Co., for use in an clectrographic imaging 35
' ered'a useful repellent composition comprising (a) an
process employing a printing ink composition. The
oil’of low volatility having a surface energy less than‘
non-wettable Te?on belt is used to transfer relatively
about 27 dynes/cm and selected from the group con
clean ink images electro'graphically formed’ on'the» belt
sisting of ?uorinated oils and poly(siloxane) oils' and
to a ‘receiving sheet. German‘ Offenle'gungschrift ( OL‘S)
(b‘) a solid '?uorinated polymer having at least one
No.‘2,204,745 datedAug. 17, 1972 (and referred to
repeating unit of the following formula:’
hereinbelow in greater detail) describes an electro
graphic lithographic process similar to' that of U.S.‘Pat‘.
No. 3,247,825. I‘ " ' I
In addition, U.S. Pat._ Nos. 2,990,278 issued 11116727, _
1961; 3,146,145 issued Aug. "25, 1964; 3,185,777is-l 45,
sued May 25, 1965; and 3,515,584 issued June 2,‘ 1970
describe 'various'typ'es of lubriciou's materials'useful in
wherein R‘ represents a member. selected from the
electrographic processes and elements because of the‘
group consisting of hydrogen and alkyl groups having
inability of dry or tacki?ed electro‘graph'ic toner pow
one to about four carbon atoms, and Y represents a
ders to adhere substantially to' such materials-Among
moiety having one of the ‘following formulas:
the various abhesive materials described in the above‘
patents are poly(tetra?uoroethylene) and other similar
?uorinated vinyl carbon materials, certain silicone'ma
terials, etc. . . 1 t ' ~ I 5-1; - '
There have also appeared a number of references in 55
the art to the use of abhesivezmaterials such‘ as ~fluoro
carbons and certain silicones as ink repellent back
ground areas of “waterless” lithographic printing sur
faces; that is, lithographic printing surfaces having
background areas repellent to both oil-based printing wherein n is 0 or 1 and R is a ?uorinated alkyl, includ
inks and aqueous-based dampening agents. Plano ing branched and straight chain alkyls as well as ?uo
graphic printing processes using such waterless printing roalkoxy substituted ?uorinated alkyls, having one to
surfaces do not require the use of a separate aqueous about 20 carbon atoms.
dampening agent. See British Pat. No. 1,146,618 dated in, accord witha preferred embodiment of the pre
Mar. 26, 1969; U.S. Pat. No. 3,511,178 issued May ,12, 6.5 sent invention, we incorporateva polymeric binder in
1970; U.S. Pat. No. 3,606,922 issued Sept. 21,. 1971; the vabove-described repellent composition to improve
U.S. Pat. No. 3,677,178 issued Jun/‘18,1972; German . its toughness and abrasion resistance and to reduce the
OLS No. 2,204,745 dated Aug: 17, 1972. amount of the substantially solid ?uorocarbon polymer
3,975,352
3 4
which :generally' is much moreexpensive than suitable printing plates and which used as the ink-accepting
polymeric binders. Suitable polymeric binders may image surface ‘of ‘the plate exhibits poor-wear“ proper
generally be-chosen from a variety of commercially ties, that is, e-xhibits'va tendency'to'rub off the plate
available-resins as will be described -in greater detail during the printing process.
In contrast, the waterless printing plates of-the pre
hereinafter. . - - 1 - ~ ' ' ' .> t
In accord with-another embodiment of the invention, sent invention eliminate or at least substantially reduce
the toughnessand abrasion resistanceof the repellent the above-noted ‘problems associated with waterless
compositions described above- may ,be further en-v printing vplates containing an abhesive silicone material.
hanced by incorporation therein of ‘a minor amount of For example, the repellent‘composition of the present
an inert, ?nely-divided ?uorocarbon powder. ' invention is much more compatible with conventional
The repellent composition of the present invention is electroscopic toner materials,’ i.e., conventional toner
particularly suitable as an abhesive composition for use materialsadhere well to the repellent composition of
in- the production of “waterless” printing plate- ele the invention when subjected to conventional toner
ments of the, type described hereinbefore._Thus, in ?xing techniques such as heat fusing or pressure and
accord with one embodiment of the invention, the heat fusing. Moreover, the repellent composition of the
above-described repellent composition is coated. on ‘a invention, especially that embodiment of the composi
support to form an unimaged waterless printing plate
tion which contains a polymeric binder, exhibits im
element. If desired, such waterless printing plate ele
proved toughness and abrasion resistance.
ments may have advantageously incorporated therein a
As indicated above, the repellent composition of the
light-sensitive interlayer such as a photocrosslinkable 20
present invention is also particularlyv useful in liquid
polymer, a photoconductive material, andv the like to
developed electrographic image transfer processes. In '
facilitate imaging the waterless printing plate element.
such processes,>it has been found-that the repellent
The repellent composition of the present invention is
compositions of . the present invention provide im
also particularly useful in liquid developed electro
proved transfer efficiency, i.e., more-complete transfer
graphic image transfer processes. In such processesa 25
of the liquid developed toner image is obtained. And,
wet, liquid-developed electrostatic charge image car
the repellent. coated surfaces on which them-original '
riedon a dielectric-surfaced support istransferred to a
liquid developed image is formed requires little or no
suitable receiving sheet. One such process is that re-‘
ferred to above in U.S.vPat. No. 3,247,825. In accord cleaning before it is ready for reuse. - ‘ > -
with the present invention, we have found that transfer 30 In addition to the foregoing advantages, it is apparent
of such wet, liquid-developed electrographicimages is ‘ that the repellent composition of the present invention
greatly enhanced by applying the repellent composition will be 'of special utility and‘ afford particular advan
described above as a surface layer on the-support prior tag'es'in any situation which may require the use of ‘a
to theformation and the liquid development of electro repellent coating ‘composition which ‘exhibits ‘good an
static charge images thereon. As a result, wet, liquid-I 35 titack and release properties. ' ’ '
developed images formed on such repellent coated The oil'component of the repellent composition of
surfaces are more completely transferred to receiving the‘ present invention maybe selected from a variety of
sheets. Also, the repellent coated surfaces require little ?ou'rinated oils and poly(siloxane) oils which are gen
or no cleaning after image transfer prior to formation erally readily available commercially. As indicated,
and development of a‘ subsequent image on the repel 40 these oils should have a low volatility so“ that they are
lent surface. ' not susceptible to evaporation from the resultant ele
m'ent under atmospheric pressure and normal room
DESCRIPTION OF THE PREFERRED ’
temperatures and should have a low surface energy less
EMBODIMENTS
than about 2‘7 dynes/cm. toenhance the abhesive prop
The repellent composition of the present invention, erties of the repellent composition. Among the various
as suggested above, provides a number of advantages. useful ?uorinated oils exhibiting the above-noted char
In the ?rst place, as indicated, this repellent composi acteristics are materials such as the per?uoroalkyl
tion is particularly useful in the production of waterless polyether polymeric ?uids commercially available-from
printing plate elements. . ' E.I. duPont Nemours and Co. under the tradename of
Waterless printing plates as recently developed in the
Krytox ?uids, particularly-Krytox .143 AC, 143 AD,
lithographic art have generally relied upon a poly(silox
and 143 “CZ ?uids,.and other similar per?uoro alkyl.
ane) elastomeric surface to provide an abhesive surface polyether?uids available fromv Montecatini Edison Co.
which is repellent to both conventional aqueous damp
under the tradename of Fomblin ?uids. Generally these
ening agents and to lithographic oil-based printing inks.
per?uoro alkyl polyethers are polymers having as a
One problem with these poly(siloxane) surfaces is their 55
repeating unit thereof the- following per?uorinated
tendency to easily abrade which may result in scum
ming of the copy sheets which are to be printed from moiety: ' ' 1 '
such a litho plate.
In addition, waterless printing plates having a con
ventional poly(siloxane) abhesive surface and which 60
are imaged by'electrophotographic processes are not
readily compatible with conventional electrophot'o
graphic developer compositions. This‘ is because con
ventional electrophotographic developer compositions
including both conventional liquid and dry developer 65 wherein-n vis an integerv of about 25 to about 50 and
materials typically do not ‘adhere well to abhesive wherein R2 represents‘ a ?uorine atom or a per?uori
poly(siloxane) surfaces. Accordingly, the electroscopic nated alkyl group having from I to about 4 carbon
toner image formed'on the surface of suchv waterless
atoms. '
3,975,352
5
Still other low surface energy ?uorinated oils useful
in the present invention are copolymers of tri?uoroni
trosomethane and tetra?uoroethylene. Other useful
?uids are the poly(perfluoroalkylene triazines) as de
scribed in US. Pat. No. 3,489,727.
The low surface energy poly(siloxane) oils useful in
the present invention exhibit the same general charac 1,1.
teristics as the above-described ?uorinated oils. That is,
these poly(siloxane) oils have a surface energy less wherein n and y in Formulas Vl-X are integers greater
than about 27 dynes/cm and low volatility under atmo- " than 3.
spheric pressure and normal room temperature condi _ The term low volatility?as used ‘herein is de?ned to
tions. Such poly(siloxane) oils are well-known and mean an oil having a boilingv point at' l mm.Hg which is
readily available commercially. These poly(siloxane) greater than 100°C. -
oils are generally characterized by the presence of the Preferred low surface energy ?uorinated oils and
' following repeating unit in their polymeric structural 15 poly(siloxane) oils useful in the repellent compositions
chain: of the present invention generally have a viscosity less
than about 5000 centistokesat 38°C., preferably within
the range of from about 50 to about 1000 centistokes.
The amount of the low surface energy ?uorinated oil or
20 poly(siloxane) oil contained in the repellent composi
tions of the present invention may vary over a consider
able range. Generally, amounts of low surface energy
oil within the range of from about 1 to about 40% by
wherein R3 and R", which may be the same-or different’, weight, preferably about 2.5 to about 30% by weight,
represent an alkyl having 1 to 4 carbon atoms‘, phenyl', 25 based on the total weight of the repellent composition
are useful. Although larger amounts than this may be
or halogenated alkyl or phenyl. g‘ _ ' ' \ ‘
Representative of preferred poly(siloxane) oils'are used, it is generally found that repellent compositions
the following materials: dimethyl poly(siloxaneffluid; containing amounts of the oil in excess of about 40% by
alkylaryl poly(siloxane) fluid available from Dow Cor’ weight are so soft that they are difficult to utilize in
ning under the tradename DC. 230; ?uorinated poly( 30 most applications; however, in certain situations where
siloxane) ?uids believed‘ to have the following struc waxy compositions and appreciable amounts of the oil
component can be tolerated, amounts in excess of 40%
tural formula: 7 Y I ' ’ I ' " ‘ by weight of the low surface energy oil could be used.
Amounts of the low surface energy component less
35 than about 1 weight percent based on the total weight
of the repellent composition could also be utilized in
accord with the present invention. However, it will be
appreciated that when such small amounts of the oil
component are employed, the useful effects provided
- ‘40 by the oil component may be so slight as to be largely
unnoticed in most applications.
The solid ?uorinated polymers useful in the present
available commercially from Dow Corning under- the invention are characterized by the presence of at least
tradename F.S. 1265; and a ‘series of various‘ other one repeating unit in the polymer having formula 1
poly(siloxane) fluids believed to have‘ the structural 45 shown hereinabove. Typically, these ‘?uorinated poly
formulas noted hereinbelow as VII-X: mers, whether homopolymers. or copolymers, have a
VII.
.cH, .
CH“ VIII.
CH3
fluorine content of at least about 40% based on the
60 total molecular weight of the polymer. These polymers
exist in solid form at normal temperature (i.e., 25°C)
and'pressure (1 atmosphere) conditions whereas the
?uorinated low surface energy oils described herein
IX.
above are liquid at 25°C. and 1 atmosphere. Best re
sults have generally been obtained in accord with the
invention wherein R of formula ll and Ill above con
tains a perfluorinated terminal carbon atom, i.e.,
_CF3.
3,975,352
7 8
Representative solid ?uorinated polymers which may
be employed in the present invention are substantially
solid polymeric fluorocarbons having repeating units 5
shown in formulas Xl-XV hereinbelow:
four-(inv- - X'
‘wherein X is an integer of 1 to about 18.
As indicated above both ?uorinated homopolymers
and copolymers may be used as the solid ?uorinated
polymer in the present invention. For example, copoly
. ‘l in mers containing two or more different repeating units
such as those shown in formulas Xl-XV above may be
CF, used. Alternatively, copolymers containing both ?uori
nated repeating units such as those described above
and non-?uorinated units, for example, repeating units
of alkyl acrylates and methacrylates such as methyl
methacrylate, may be employed. Typically, the solid
25
?uorinated polymers vused in the’ present invention
contain at least about 30 repeating units.
‘The solid ?uorinated polymers used in the present
invention are readily available commercially and ac
cordinglyildescription of their preparation is deemed
30
unnecessary. These materials are available under a
variety of tradenames from numerous chemical suppli
ers. Exemplary of useful commercially available mate
rials are the following: poly(l,l-dihydroper?uorobutyl
35 acrylate) and poly( 3-per?uoromethoxy- l , l ~dihy
droperfluoropropyl acrylate) sold by the Minnesota
Mining and Manufacturing Co., NyeBar Type C ?uoro
polymers sold by the William F. Nye lnc. Co., and
' X111. ?uoro polymers sold by the B1. duPont Nemours Co.
under the tradename Zepel 2979 polymers and TLF
2916 Fabric ?uoridizer polymers. If additional infor‘
mation is desired concerning the preparation and man
ufacture; of materials representative of the above
describedsolid ?uorinated polymers, reference may be
45 made to US. Pat. Nos. 2,592,069 issued Apr. 8, 1952
and 2,642,416 issued June 16, 1953.
The relative amount of the solid ?uorinated polymers
used in the repellent composition of the present inven
tion may vary considerably. As will be apparent, the
amount of solid ?uorinated polymer will depend, at
least in part, upon the specific low surface energy oil
which is used. In addition, the amount of the ?uori
nated polymer will vary depending upon whether a
polymeric binder is incorporated-in the‘ repellent com
55 position as described hereinabove. Typically, useful
repellent compositions in accord with the present in
vention comprise from about 5 to about 98% by weight
of the solid ?uorinated polymer component, and pref
erably from about 5 to about 30 percent by weight of
0 60 said solid ?uorinated polymer.
As indicated hereinbefore, and in accord with a pre
ferred embodiment of the invention, we may employ a
resinous binder together with the low surface energy oil
and solid ?uorinated polymer in the repellent composi
65 tions of the present invention. The binder resin pro
vides added toughness and abrasion resistance to the
resultant repellent composition. In addition, the binder
resin, especially those selected from the preferred class
3,975,352
10
of binder resins described hereinbelow,‘ ‘significantly throughout the repellent composition. Typically, these
reduces the amount of the more‘ expensive‘solid ?uorii ?uorocarbon ?ller particles have aniaverage particle
nated polymer used in the repellent'compositions of the’ size of less than'about 1 micron.
present invention. In general, the resinous binder 'may The‘ repellent composition of the present invention,
be any hydrophobic, ?lm-forming polymeric: material. as will'be apparent, has utility in and of itself as a self
Materials of this type include silicone resins, Qthe supporting film. As such, the composition may be
poly(acrylic ester) and poly(methacrylic ester) resins, coated out and dried to'iform useful self-supporting
and ?uorinated hydrocarbon ‘resins, ‘and mixtures of
?lms. ' ‘ '
the foregoing materials. Representative'exam‘ples of More generally,'however, the repellent composition
various individual members ‘of these binder materials of the present invention finds application when coated
include the following resinous materials: poly(methyl-‘ on a suitable supporting element. The particular sup
methacrylate ) , poly( n-butylmethacrylate ) ,' poly( isobu port on which the repellent composition may be coated
tylymethacrylate), copolymers of nébutyl methacrylate is not ‘critical and may be selected with regard to the
and‘isobutyl methacrylate, copolymers of vinylidene particular use for which the resultant element is in
?uoride and hexa?uoropropylene, copolymers of vinyl tended. For example, various supports which may be
idene ?uoride and tri?uorochloroethylene, copolymers used‘ include wood; paper; metals; plastics; including
of vinylidene fluoride and‘ tetra?uoroethylene, terpoly natural and synthetic resins; ‘laminates; and multilay
mers of vinylidene ?uori'de, hexa?uoropropylene, land ered supports such as various metal coated plastic sup
tetra?uoroethylene. poly(vinylidene fluoride), and the ports and various light-sensitive elements comprising a
like. Such materials as those‘ indicated immediately base, a suitable light-sensitive layer(s), and any neces
above have been described in‘the' prior art and are sary or desired intermediate subbing layers.
commercially available from a number of manufactur The particular process by which the repellent compo
sition of the present invention is coated on a suitable
ers. ' ~ -' ‘ >
The ?uorinated hydrocarbon resins are especially support is not critical to the present invention. A vari
preferred for use as the binder're'sin (if 'one is used) in 25 ety of different coating methods are well known in the
the repellent compositions of the invention. These pre4 art including such methods as spray-coating, dip-coat
ferred ?uorinated hydrocarbon resins are readily com ing, and the like. Moreover, the repellent composition
patible with the other components‘ ofthe vrepellent of the present invention maybe coated either in the
compositions of the invention-and, in addition, appear form of-a dispersion or as a substantially homogeneous
to enhance the repellent properties of the resultant solution. Typically, the repellent compositions of the
present composition are coated from organic solvent
composition. ' ' 7 ' > ' ‘_
When a binder resin is ‘used in the present invention, solution or dispersion. A variety of different organic
the amount employed in the'repellent'composition may solvents may be utilized in the coating operation in
vary considerably. Typically, the resinous binder is cluding such organic solvents as acetone, methylethyl
present in an amount varying from 1 to about 85v weight 35 ketone; ethyl acetate, dimethylacetamide, halogenated
percent of the repellent composition. Typically, if the hydrocarbon solvents such as methylene chloride, and
resinous'binder component is not one of the preferred various ?uorinatedv hydrocarbon solvents such as
?uorinated hydrocarbon ' resinous binders‘ indicated Freon, a trademark of E.I. duPont for a group of halo
hereinabove, the amount thereof which may be‘ advan genated'hydrocarbons containing one or more ?uorine
tageously utilized in the present invention is reduced atoms such. as, 1,1,2-trichloro-l,2,2-tri?uoroethane,
and generally lies within the'range of from 5 to about and the like. Mixtures of‘these various organic'solvents
30 weight percent of the repellent composition.‘ How and other conventional solvent materials may also be
ever, when one of the preferred resinous binder com
used. - ~
ponents is used the amount thereof which can be effec Theithickness of the resultant repellent compositions
tively employed in accord with the preferred‘ embodi 45 of the present invention (when coated and dried to
ment of the present - invention is considerably in eliminate or substantially reduce any residual disper
creased. In such case, the amount of the binder compo sion or solvent liquid) may vary over a wide range.
nent may be as high as about 85 weightlpercent-of the Coatings having a thickness in the range of from about
repellent composition and preferably lies within the 0.1 micron to about 500 microns or more are useful,
range of from 50 to about 80v weight percent thereof. 50 with a coating thickness within the range of from about
Optionally, in accord with another embodiment of 0.2 microns to about 200 microns suitable for most
the invention the toughness and abrasion resistance of
applications. . I w >
the repellent composition of the present invention- may As. noted hereinabove, the repellent compositions of
be further enhanced '- by incorporation; of a. minor the present invention are especially useful in the pro
amount of inert, solid, particulate fluorocarbon powder 55 duction of waterless planographic printing plates. Such
in the repellent composition. For example,>particulate plates are especially desirable because they eliminate
?uorocarbon material sold as F E?‘ TEFLON powder by' _ the need for the aqueous dampening agent required in
E.l. duPont Nemoursland Co. may be incorporated in conventional lithographic printing processes. That is,
the repellent compositions of the invention in amounts these compositions effectively repel or remain substan
up to about 40 percent by weight, preferably from 5 to tially non-wettable by oil-based liquidssuch as conven
about 30 percent by weight, based ‘on the total dry tional planographic oil-base printing inks without the
weight of the resulting repellent coating. The particu addition of an aqueous. dampening agent. -
late ?uorocarbon powder acts as an a'ntiadhesive (or -To use the repellent compositions of the present
abhesive) ?ller ‘material for the repellent composition invention is a typical waterless printing process, one
of the invention. This material, if‘ used in the repellent 65 simply forms an oleophilic image on the surface of a
composition -of the invention, retains its particulate planographic printing element which has been over
form within the repellent composition-and appears as coated with the repellent composition of the present
discrete, ?nely-divided particles uniformly distributed invention. Because the repellent composition of the
3,975,352
1 1
present invention is substantially nonwettable by and chargevimyage directlythereon. In other instances, a
repels generally. all oil-based compositions, many mate photoconductive element may be used to electrophoto
graphically provide an_ electrostatic charge image
rials will be more oleophilic than the repellent compo
sition of the present invention and can be employed as formed on the repellent surface of a‘ separate electro
the oleophilic imaging material to which conventional graphic receivingelement. In the latter case, the photo'
oil-based printing inks will preferentially adhere. Once conductive element may be reused and the repellent
an oleophilic image is formed on the surface of a print surface-coated electrographic element used in the pre
ing element bearing the repellent composition of the sent invention functions as a receiving sheet on which
present invention, the element, thus imaged. is ready an electrostatic charge pattern is formed or transferred.
for use as a printing plate. Accordingly, it may beaf In another embodiment of the invention an electro
?xed to conventional planographic printing apparatus graphic toner particle image, rather than an electro
to produce the desired number,of copies. (Of course, static charge image as discussed above, may be trans
because plates bearing the repellent compositionsof ferred to a repellent surface electrographic receiving
element. For example, using conventional electropho
the present invention do not require the use of aqueous
dampening agents which are conventionally employed tographic techniques a toner particle image may vbe
in planographic printing apparatus, one can eliminate formed on a reusable photoconductive element and
the aqueous dampening agent when waterless plates of then transferred in imagewise manner to a repellent
surfaced electrographic receiving element.
the present invention are run on conventional printing
apparatus.) The formation of an ink-receptive image physically
Oleophilic images may be formed on waterless print 20 adhered to the ‘repellent surface of the electrographic
ing plates employing the repellent compositions of the element is accomplished according to the present in
present invention by any number of methods. For: ex vention throughv the use of an electrostatic developer
comprising ?nely-divided oleophilic electroscopic
ample, an element comprising a suitable support over
coated with the repellent composition of the present .marking particles. Both. dry and liquid electrostatic
invention‘ may be imaged simply by removing the repel developers which contain such marking particles may
lent overcoating of the present invention in the image
be used._ I . . , _ .
The electrographic elements typicallyv used in the
areas to expose the surface of the support. In such case,
the exposed surface of the support serves as the oleo present invention either as an independent element
philic image areas, preferentially receiving conven from-which an electrostatic charge image may be trans
tional printing inks, whereas the surface areas of the 30 ferred or as a base on which a layer of ‘the repellent
element which comprise the repellent composition of composition described herein may be applied are com
the present invention, repel printing ink and serve as prised of -a support, typically transparent, such as a
po,ly(e_thylene terephthalate), cellulose acetate or the
non-image, non-ink receptive background areas. ~ '
To facilitate imaging printing elements of vthe present like ‘photographic film supports, typically having
invention, a light sensitive layer may be incorporated in 35 coated thereon a conductive coating which maybe
the element. For example, a photocrosslinkablepoly transparent such as vacuum evaporated nickel, cuprous
mer material may be incorporated in the-element in a iodide, a conducting polymer as described, for exam
manner similar to that described in Gipe, US. Pat. No. ple, in US. Pat. No. 3,007,901 and similar materials.
3,677,178 issued July 18, 1972;.and US. Pat. No. The conducting support may then be overcoated with
3,511,178 issued‘ May 12, 1970. As described in the 40 a photoconductive layer. If desired, it’may be useful to
aforementioned Gipe U.S. Pat., the light sensitive ma insert various subbing interlayer(s) between the con
ductive support and the photoconductive layer, for
terial may be incorporated as an interlayer between a
suitable support and an overcoat of the repellent com example an adhesive interlayer and/or a barrier layer.
position of the present invention; or the repellent com The photoconductive layer may be comprisedof a
position of the present invention may be used as an binder and a photoconductor. Of course, polymeric
interlayer overcoated by a suitable light sensitive top photoconductors such as substituted and unsubstituted
polyvinyl.carbazoles and certain va'cu‘umv deposited
coat. In such case, the repellent composition ‘of'the
present invention is substituted for the abhesive poly( photoconductive.materials such as 'selenium'can be
siloxane) coating employed in the aforementioned pa used without. a separate binder. ‘In addition to. poly
tent publications incorporated herein by reference 50 meric photoconductors a wide varier of photoconduc
tive substances can be used in the elements of vthis
theArse tos.u ggeste. d earlier herein- , waterless pri. nting ele invention. Typical photoconductive materials include
organic, organo-metallic, and inorganic photoconduc
ments bearing therepellent or abhesive composition of
the present invention may be imaged electrograph tive materials. Useful organic photoconductive materi
ically. In such case, an electrographic element bearing 55 als include organic amine photoconductors, polyarylal
a- coating of the repellent composition described herein kane photoconductors, and diarylamino-substituted
chalcones, etc. A partial listing of publications describ
is employed. - =
In accordance with a preferred embodiment of the ing these and other organic photoconductive materials -
is listed below and hereby incorporated by reference
present invention, an ' electrographic image may be
formed on a suitable electrographic element bearing a 60 thereto: [.15. Pat. Nos. 3,139,338; 3,139,339;
repellent coating of the present invention by a variety 3,140,946; 3,141,770; 3,148,982; 3,155,503;
of well—known electrographic techniques. A preferred 3,180,730; 3,240,597; 3,257,202; 3,257;303;
electrographic imaging method is the electrophoto 3,257,504; 6,265,496; - 3,265,497; 3,274,000.
graphic process. If an electrophotographic process is 3,527,602; . ‘3,526,501; - 3,542,544; 3,533,786;
utilized to form an electrographic image, it is generally 65 3,542,546; 3,421,891 and Belgium Pat. No. 728,563.
Representative vorgano-metallic photoconductive
advantageous to sandwich a’ photoconductive layer
between the support and the repellent surface layer of materials are the organic derivatives .of Group [Va and
the electrographic element and form an electrostatic Va metals such as those having at least one amino-aryl
3,975,352
13 14
rene-butadiene copolymers, silicone resins; styrene
group attached to the metal atom. Exemplary organo
alkyd resins; silicone alkyd resins, soya-alkyl resins;
metallic compounds are the triphenyl-p~dialk
poly(vinyl chloride); poly(vinylidene chloride); vinyli
ylaminophenyl derivatives of silicone, germanium, tin
dene chloride-acrylonitrile copolymers; poly(vinyl ace
and lead and the tri-p-dialkylaminophenyl derivatives
tate); vinyl acetate-vinyl chloride copolymers; poly(vi
of arsenic, antimony, phosphorous and bismuth. The
organo-metallic or organic photoconductor materials nyl acetals), such as poly(vinyl butyral); polyacrylic
used in the photoconductive composition are generally and methacrylic esters, such as poly( methyl methacryl
ate), poly(n-butylmethacrylate), poly(isobutyl metha
present in an amount equal to at least about one weight
percent of the photoconductive composition. The crylate),retc.; polystyrene; nitrated polystytrene; poly
upper limit of the amount of organo-metallic organic 0 methylstyrene; iso-butylene polymers; polyesters, such
photoconductive substance present can widely vary in as poly(ethylene alkylenebisaryloxyalkylene tere
accordance with usual practice. Generally the photo phthalate); phenol formaldehyde resins; ketone resins;
polyamides; polycarbonates; polythiocarbonates; etc.
conductive composition contains less than about 99
weight percent of an organic or organo-metallic photo Methods of making resins of this type have been de
conductor material. A preferred weight range for an .... 5 scribed in the art, for example, styrenealkyd resins can
organic or organo-metallic photoconductive substance be prepared by the method described in U.S. Pat. Nos.
in the photoconductive layer of the element of the 2,361,019 and 2,258,423. Suitable resins of the type
present invention is from 10 to bout 60 weight percent. contemplated for use in the photoconductive layers of
As noted hereinabove, inorganic photoconductive the invention are sold under such trademarks as VlTEL
materials may also be used in the element of the pre 20 PE-lOl, CYMAC, Piccopale 100, Saran F-220, and
sent invention. These materials are generally well LEXAN 105 and 145. Other types of binders which can
known in the art and include such inorganic photocon be used in the photoconductive layers of the elements
ductive materials as zinc oxide, cadmium sul?de, cad of the invention include such materials as paraffin,
mium selenide, lead oxide, selenium, selenium deriva mineral waxes, etc. -
tives, mixtures thereof, etc. These photoconductive 25 The photoconductive layer used in the element of the
inorganic materials may also be dispersed in a poly present invention can be applied to the underlying
meric binder to form a photoconductive composition support in the form of a homogeneous coatingcompo
sition including the photoconductor, sensitizer, and
which may be coated on a support. -
Typically a sensitizing dye or other material is also binder (if one is used) dissolved in a suitable solvent.
incorporated in the photoconductive composition. A Or, the photoconductive substance. such as an inor
wide variety of such sensitizing materials are known in ganic photoconductive material may be dispersed in
the art. These materials are generally selected depend the form of ?nely-divided particles in a resinous binder,
ing on the particular photoconductive substance uti such as a binder solution, and applied to the support in
lized. For example, sensitizing compounds useful with the form of a coating composition having dispersed
an organic photoconductive material would include a 35 therein the photoconductive‘ material and the sensitiz
wide variety of sensitizing materials. A partial list of ing dye, if a sensitizing dye is utilized. Alternatively, the
such materials includes pyryliums, including thiapyryl photoconductive composition including an organic
ium dye salts, disclosed in VanAllan et al. U.S. Pat. No. photoconductor, sensitizing dye and binder may be
3,250,615; fluorenes; aromatic nitro compounds of the applied to the support as a heterogeneous composition
type described in U.S. Pat. No. 2,610,120; anthrones 40 such as described in Light, U.S..Pat. No. 3,615,414,
like those disclosed in U.S. Pat. No. 2,670,284; qui issued Oct. 26, .1971, hereby incorporated by reference
nones, such as those described in U.S. Pat. No. thereto. If the photoconductive composition is applied
2,670,286; benzophenones described in.U.S. Pat. No. to the support in the form of a homogeneous dope,
2,670,287; thiazoles, such as those described in U.S. solvents which may be used and the vehicle for the
Pat. No. 2,732,301; mineral acids; carboxylic acids, 45 photoconductive dope composition include a number
such as maleic acid, dichloroacetic acid, salicylic acid; of solvents such as benzene, toluene, acetone, 2-buta
sulfonic and phosphoric acids; and various dyes, such none, chlorinated hydrocarbons, for example, methy
as cyanine (including carbocyanine), merocyanine, lene, chloride, ethylene chloride, etc., others, for exam
diarylmethane, thiazine, azine, oxazine, xanthene, ple tetrahydrofuran, or mixtures of these solvents, etc.
phthalein, acridine, azo, anthraquinone dyes and the 50 Coating thicknesses of the photoconductive compo
like and mixtures thereof. Preferred sensitizing dyes for sition ‘on the support can vary widely in accordance
use with organic photoconductive materials include with usual practice. Normally, a-coating in the range of
pyrylium and thiapyrylium salts, and cyanines including about 3 microns to about 300 microns is useful.
carbocyanine dyes. These sensitizing dyes may be pre If desired, an adhesive interlayer or subbing layer
sent in photoconductive compositions in widely varying 55 may be inserted between the photoconductive compo
amounts. Normally, the sensitizer is added in a concen sition and the repellent overcoat.
tration range from about 0.001 to about 30 percent by If the repellent-surfaced electrographic element used.
weight based on the weight of the photoconductive in the present invention does not have a photoconduc
composition. Preferably, the sensitizer is added to the tive layer incorporated therein, the electrographic ele
coating composition in an amount of about 0.1 to about 60 ment maybe used as a receiving element for an electro
10 percent by weight of the total photoconductive static charge image. In such case, as noted above, the
electrographic element comprises a support, generally
composition. .
Preferred binders for use in preparing the photocon an electrically conductive support, having the repellent
ductive layers of the photoconductive compositions composition layer coated thereover. If desired, various
used in the present invention generally are ?lm-forming 65 intermediate subbing layers may also be used to pro
polymeric binders having fairly high dielectric strength vide improved adhesion or to improve the electrical
and which serve as good electrically insulating ?lm properties of the electrographic element. One type of
forming vehicles. Materials of the type comprise sty element which may be usefully employed as a base on
3,975,352
15 16
which the abhesive layer may be coated is described in particular development conditions or developer com
Gramza and Robinson, U.S. Pat. No. 3,519,819. An positions. Various techniques such as melt-blending,
other useful type of abhesive surfaced receiving ele spray drying, etc. may be used to form marking parti
ment which may be employed in the invention com cles suitable for these conventional dry developers. If
prises a multi-layer element having a base containing at desired, colorants may also be incorporated in said
least two layers, namely, a ?rst layer comprising a con-v marking particles. Typically, such developers contain
ductive support, e.g. a conductive paper support, and a from about 1—l0% by weight of the electrostatically
second layer coated thereover comprising a dielectric attractable marking particles and from about 90 to
layer having a surface of the repellent composition about 99% by weight of the particulate carrier. Further
described hereinabove. This type of receiving element 10 detail on formation of marking particles for a conven
is used in accompanying Example 5, and represents a tional dry developer may be found in U.S. Pat. No.
preferred electrographic element for use in the inven-’ 3,533,133 dated Jan. 5, 1971.
tion. A detailed description of a preferred electropho Liquid developers are also useful in the process of the
tographic process which may be used in conjunction present invention. One suitable developer composition
with this element may be found in U.S. Pat. Nos. for use in the present invention comprises a liquid de
2,825,814; 2,833,648; 2,937,943; and 2,975,052. Ac veloper containing a carrier liquid having dispersed
cording to a preferred technique, the multi-layered therein finely-divided oleophilic resinous marking par
receiving element is used in combination with a rough ticles. The particular carrier liquid utilized is not criti
ened surface photoconductive element as described in cal to the present invention and may include a variety
U.S. patent application Ser. No. 197,488, filed Nov. 10, 20 of electrically insulating organic liquids. Generally
1971. these liquid carriers have a dielectric constant less than
As noted hereinabove, electroscopic marking parti about 3.0 and a resistivity greater than about 109 ohm
cle (i.e. toner‘particles) are used in combination with cms. Suitable carrier liquids, typically include hydro
the repellent-surfaced clectrographic elements of the carbon liquids such as isoparaf?nic hydrocarbons hav
invention. These particles are typically used in con 25 ing a boiling range of from about 145°C. to about
junction with an electrostatic developer. The electro 185°C, such as lSOPAR G (Humble Oil and Re?ning
scopic marking particles should be oleophilic, that is Co.), cyclo hydrocarbons such as cyclohexane, etc.
capable of accepting an oil-based lithographic printing Additional carrier liquids which may be useful in cer
ink. A variety of electrostatic developers may be used. tain situations include oderless mineral spirits, octane,
These developers generally comprise'a carrier vehicle etc.
and marking particles. The carrier vehicle may com Oleophilic resins which may be used to form the
prise various materials and, as the name implies, serves ?nely-divided marking particles utilized in both the
as a medium for carrying the electrostatically respon liquid and dry developer used in the invention may be
sive marking particles to the charge image. Both dry selected from a wide variety of substances. The follow
and liquid developers may be used. Among the more 35 ing are illustrative of suitable materials generally pre
common types of developers are liquid developers ferred for use in liquid developers: rosins, including
where the carrier generally comprises an electrically hydrogenated rosins and esters of hydrogenated rosins,
insulating organic liquid; aerosol or powder-cloud de alkyl methacrylate resins having from two to ?ve car
velopers where the carrier comprises a gaseous mate bon atoms in each alkyl moiety, such as isobutyl metha
rial such as air; cascade developers where the carrier 40 crylate and N-butyl methacrylate copolymers, etc.;
typically is a particulate material such as glass or plastic phenolic resins, including modi?ed phenolic resins
beads; magnetic brush developers where the carrier such as phenol formaldehyde resins; pentaerythritol
typically is a particulate ferromagnetic material; etc. phthalate; coumarone-indene resins; ester gum resins;
Magnetic brush developers and techniques are de vegetable oil polyamides; polycarbonates; alkyd resins,
scribed in the following U.S. Pat. Nos.: 2,786,439; 45 including modified alkyds such as soya oil-modi?ed
2,786,440; 2,786,441; 2,81 1,465; 2,874,063; and linseed oil-modi?ed alkyds, phthalic, maleic and
2,984,163; 3,040,704; 3,1 17,884; and Re. 25,779. styrenated alkyds, polystyrene and polystyrene-con
Other dry developers such as cascade developers have taining resins, etc.; and the like.
been described in a number of U.S. and foreign patents, Advantageously, the size of the ?nely-divided resin
such as U.S. Pat. Nos. 2,297,691; 2,551,582; 50 ous marking particles utilized in the liquid developer
2,618,551; 2,618,552 and in “RCA Review" Vol. 15 may 'vary within the range of about 0.05 micron to
(1954) pages 469-484. \ about 20 microns, preferably within the range of from
Typical dry developers comprise a particulate car about 0.1 micron to about ‘2.0 microns.
rier, for example, non-magnetic particles such as glass The liquid developer utilized in the present invention
beads, crystals of inorganic salts such as sodium or 55 ordinarily has a composition as follows: the ?nely
potassium chloride, hard resin particles, metal parti divided, oleophilic resinous marking particles are pre
cles, etc. In addition magnetic carrier particles may be sent in concentrations within the range of from about
used such as iron, cobalt, nickel and alloys thereof. The 0.01 to about 10 percent by weight of the liquid devel
size of such carrier particles may vary from about 30 oper composition and the liquid carrier is present in an
microns to about 1200 microns although particles hav amount of from about 80 to about 99.99 percent by
ing a size outside this range may also be used for partic weight of the liquid developer.
ular development conditions or developer composi As described above, the repellent compositions of
tions. If a dry developer comprising a particulate car the inventions are also particularly well suited for use
rier is used, the ?nely-divided electrostatically attract as a dielectric repellent coating in a liquid-developed
able resinous marking particles conventionally have a 65 electrographic image transfer process. In this embodi
diameter between about l/2;t and about 8011., with parti ment of the invention it is advantageous to utilize a
cles between about 2p. and l5,u. being preferred, al repellent composition of the invention containing a
though larger particles can be used where desired for ?uorinated oil rather than a silicone oil due to the
3,975,352
‘i' 17
solubility of silicone oils in conventional liquid devel could'be used to establish an electric ?eld of suitable
polarity and suf?cient'stren‘gth to cause transfer of the
oper compositions. ‘ " ' ' ' ' ~
In such processes, an electrostatic charge image is wet toner imageto the .receiving element.
formed on the surface of a suitable electrographic eleé The receiving element itself may be any of a variety
ment bearing a surface coating of the repellent compo of materials. Typically 1a paper receiving element is
sition of the present invention in a manner identical to ?used such as plain bond ‘paper, However, a variety of
that described above in connection with the el'ectro- other organic and inorganic materials may valso be used
static imaging of waterless printing plates; The electro- depending primarily on the particular type of substrate
static image bearing element is then contacted with a to which one desires to transfer the wet toner image.
suitable liquid developer composition: as ' described 10 ' Various optional modi?cations may be incorporated
above to form a wet liquid-developed toner particle ‘ . in the basic transfer process outlined above to further
image corresponding to the electrostatic image pattern. improve transfer ef?ciency and image quality, and to
The wet toner image thus formed'on the ele'ctro- reduce the amount of excess liquiddeveloper used
graphic element may be transferred to a‘s'uitable image‘ I vduring’development and transfer. For example, a hy
receiving or copy sheet, for example, plain paper, by l5 drocarbonrinse liquid may be applied to the surface of
contacting together the surfaces of the receiving ele- the wet toner image-bearing electrographic ‘element
ment and the electrographic elem‘ent'while applying a immediately prior to image transfer to enhance re
potential difference (hereafter referred to astransfer moval of excess amounts of liquid developer from
potential) between these two surfaces of a magnitude background areas of the image bearing element. Such
and polarity suf?cient to cause transfér'of't'lie wet liq- 20 rinse liquids are known in the art and are described, for
uid-developed toner image. -. example, in Moe et al. US. Pat. No. 3,356,498 issued
Although the precise transfer mechanism is’not fully Dec. 5, 1967. Typical of such rinse liquids are isoparaf
understood, it is apparent that electrophoretic migra- ?nic hydrocarbons such as lSOPAR liquids sold by
tion of the wet toner image from the surfacelof the ‘Humble Oil and Re?ning Co}; which have a boiling
original electrographic image-bearing element‘tothe 25 point in the range of, 145°C to 185°C. ‘ ' "
receiving sheet is occurring during transfer. In addition, the image receiving surface of the receiv
The polarity of the transfer potential; isideterm'i'ned ing‘element may have applied thereto an abhesive or
by the polarity of the particular toner image which is simply an oil repellent composition to reduce the
developed. For example, when a negative charge image amount of liquid developer carrier vehicle which would
is formed, one would conventionally/“develop such an 30 otherwise be soaked up or absorbed by the receiving
image with a so-called positive-working liquid devel- ‘element; For example, one may apply an oil repellent
oper, that is, a developer containingipositively charged coating or sizing to a paper copy sheet. This reduces
toner particles, to form a positive polarity liquid'devel- the amount of excess liquid carrier vehicle carried out
oped toner image. To transfer‘ this positive polarity by the‘copy sheet during transfer and also reduces the
toner image one would employ a negative transfer po- 35 drying. time needed to provide a ?nal dry imaged copy.
tential. That is, a transfer potential wherein the surface Any of various oil repellent ‘compositions may be used.
of the receiving sheet is negative withfrespe’ctto'the _ noneespecially useful sizing composition is a ?uori
positive liquid-developed ‘toner image to cause electro- nated polymer applied to the surface of the copy sheet
phoretic migration of the positive toner image to the ' '1 ir'ian aqueous-alcoholic media. Particularly useful ?uo}
negative receiving sheet. Of course, if the toner image .40 rinated polymers suitable for sizing paper- receiving
to be transferred is a negative image, i.e., an image sheets include polymers such as those described earlier
composed of liquid devloper toner particles bearing a herein in formula 1. Especially useful as a sizing is ZO
negative charge, then a positive transfer potential is NYL-RP, an anionic per?uoroalkyl phosphate ester
used. sold by E. l. duPont Ne'r'nours and Co.
The magnitude of the transfer potential may vary 45 The following examples serve to illustrate the inven
considerably. Typically, a transfer potential of at least tion.
l31:)(:)di-/olts and preferably greater than about 400 volts 1s EXAMPLE 1
The transfer potential which is applied may be cre- The compositions labelled l—20 in Table I, below, are
ated by a variety of techniquesfor example, electro; 50 coated at _0.00lqinch wet thickness upon a subbed poly
conductive rubber pressure'roller-(s) contacting the (ethylene terephthalate) support and cured. approxi
back of the receiying element maybe‘ vused ._'to provide ,matelyvoneminute at _l20?-12_5°C..The solutions are ,all,
contact betweenfthe receiving element and the‘ wet at. 2% solids in FreonnTF, a trademark .of E. l. duPont
toner image-bearingelectrographic1 element, during Co. for. l,l,2-trichloro_trifluoroethane. Each ‘film is
transfer and may also 'beuse'dto apply adirect current 55 scratched (?ngernail) and hand inkedv with‘ a litho
transfer, potential ‘through the baekwof,v the receiving graphic, ink ‘l‘D?ri Ink”, purchased from General
element to the image receiving ‘surfaee of the receiving ‘Printing lnk ,Co. (hereinafter referred to as G.P.l.)’,. to
_ element. Other means for applyinga'transferpotential ' test whether or not the layer accepts ink in these defect
may also be used, for example, La‘. coronachzir'ger areas. ~ » '
mounted adjacent to the back of the receiving element » i
‘ ' ""Tablell
Weight
% Zepel
' ' 'Weight g 2979“
. ' % Kel i .. . .(Solid ‘ e
t . . ' _ F-8002 Fluorocarbon Weight ,% Low Surface lnking ofa
--Sample No. ,. (Binder) Polymer‘) Energy Oil‘ Scratched Surface
.l _ v . . .l00 — — Heavy lnkingl