CA2136315A1

CA2136315A1 - Metal oxide free fluoroelastomer compositions and fusing member containing same

Info

Publication number: CA2136315A1
Application number: CA 2136315
Authority: CA
Inventors: Chris F. Delrosario; James A. Lentz
Original assignee: Individual
Current assignee: Ames Rubber Corp
Priority date: 1992-05-22
Filing date: 1993-05-24
Publication date: 1993-12-09
Also published as: EP0641361B1; US5922416A; US5474850A; WO1993024538A1; JPH08502081A; EP0641361A1; ATE163295T1; DE69317048D1

Abstract

A fluoroelastomer composition free of metal or metal containing compounds, such as metal, metal alloys, metal salts or metal oxide suitable for the upper layer of a fuser roll which does not require the use of mercapto functional active release agents to prevent offset is provided. The fluoroelastomer compositions contain at least 23.4 mole percent hexafluoropropylene. They can be cured by electron beam treatment, fugitive base treatment or by the use of blocked/hindered bases.

Description

~ W093/245~8 ~ 1 3 6 3 1 5 PCT/US93/0U~
. 1 MBTAL 02ID~ F~E~ FLnORO~La~O~æR
CO~PO8~T~ON8 AND F~8I~ ~B R CONTAI~ING 8AME

BAC~GRO~ND OF ~ INVBN~ION
The invention relates generally to metal oxide free fluoroelastomer compositions and to a fusing member having an outer layer of the fluoroelastomer for applying heat and pressure to fix toner particles to recording paper.
A fuser roll is a roller designed to apply direct heat and pressure to a toner image. The fluoroelastomer s~rface permits toner to be fixed to the recording paper without adhering to the roller surface and can withstand continuous exposure to hi~h temperatures, silicone oils, toners, toner additives and paper product residue without unacceptable physical degradation.
In general, when forming images by xerographic processes, an image formed of a heat fusible toner powder is selectively disposed cn a web-like surface of a recording medium, such as paper, by electrostatic forces. Toner powders are commonly formed of a mixture of thermoplastic and/or thermosetting resin c~rriers and additives such as amorphous carbon and magnetic particles. They are conventionally fixed to the recording paper by direct contact with a fuser roll which applies pressure and heat at temperatures betwPen about 200 to 400-F.
The fusing process is conventionally accomplished by feeding a recording medium having the toner image thereon between the nip where two mated rollers meet. One or both of the rollers are heated, typically by an internal heat source within the roll~r, so that the surface temperature of the roller will be above the softening point of the resinous carrier of the toner.
The recording med um with the toner image thereon is fed between the two rollers which press towards each other to apply direct heat and pressure to the toner image. The amount of pressure and the length of time that the toner is heated determines the degree of fusing. The actual temperature range suitable for fixing toner images to recording paper is referred 2~363~
W093/24538 - PCT/US93/~K4 ,~

to as the "fusing window". The fusing window, TW can be defined by the formula: I
q'W = TOF F ~ T~
wherein TOFF is the Hot Offset temperature and T~IN is the minimum fusing temperature. Hot Offset temperature is the temperature at which the cohesive forces within the molten toner layer are less than the adhesive forces between the toner and roll surface so that toner adheres to the fuser roll. T~IN
is the minimum temperature at which toner~càn be acceptably fixed to the recording paper. This tem~erature range is dependent on the raw materials, type of toner, release agents and the pressure applied by the roller. It is important that the toner is fixed without "offset" occurring, in order to produce copies of acceptable quality. For commercial applications, a fusing window of at least 30-F is acceptable for some applications. However, it is preferable to have as large a fusing window as possible. Thus, a 60~F fusing window is desirable and a 100-F fusing window is particularly ideal.
Conventional fusing systems have drawbacks. Softened toner generally ~as an af f inity for the surface of the fuser roll it contacts. When toner adheres to the surface of a fuser roll, it can unintentionally be deposited on an unselected ~- portion of the recording medium during the next rotation of the roll~ This phenomenon is referred to as offset.
To prevent offset, a thin coating of a release agent such as polysiloxane fluid is commonly spread over the surface of the fuser roll which contacts the surface of the toner image. The polysiloxane fluid reduces the surface free energy of the roll surface and decreases the affinity of the toner for the roll. Surface tension values for several conventional fuser roll materials are set forth below in Table I.

~ W093~24538 2 1 3 ~ 3 1 5 PCT/US93/~4 !

TAB~ I
Surface Tension of Fuser RoLl Materials Fuser Roll Surface Surface Tension nMn Polytetrafluoroethylene (PTFE) 18.0-18.5 Polyvinylidene fluoride (PVF2) 21-22 Polysiloxane Compounds 28-29 Polyfluorocarbon Elastomers 35-37 Polysiloxane Release Agents 19-21 When compounding or formulating fluorocarbon elastomers, metal oxides are typically included to act as an acid accepter, cure activator, reinforcing filler and/or as an additive to promote improved chemical resistance. It is believed that every commercially available fuser roll having a fluoroelastomer surface contains metal oxide particles in at least the fluoroelastomer surface layer. U.S. Patent Nos.
4,257,699, 4,264,181 and 4,272,179 describe fuser rolls in which additional metal oxide filler particles are added to the fluoroelastomer surface material to increase the metal oxide content of the surface of the fuser rolls beyond that needed to promote cure of the materlal. Fluoroelastomers described in U.S. Patent No. 5,035,950 contain only so much metal oxide as is necessary to effect cure of the high fluorine content -~ material.
These patents describe that use of a polymer release agent having mercapto functional groups applied to the surface of a fuser roll having metal oxide filler decreases problems associated with offset. When the metal-containing filler in the elastomer surface layer is present in sufficient amount, it interacts with the polymeric release agent to produce an active release film. This active release film prevents the thermoplastic resin toner from contacting the elastomeric material itself and accordingly, offset is avoided.
- Although this active release construction has proven to be commercially acceptable, it nevertheless has drawbacks.
Release agent fluids having mercapto functional groups are expensive. They can also present an unpleasant odor in the ` ; 2`1363iS `

office environment and interfere with the ability to write or type on the copy sheet.
A wide variety or fluoroelastomers have been suggested in the prior art. For e~ample, in U.S. Patent No. 3,674,763 a process for curing fluoroelastomers in the presence of two diamines is disclosed. The elastomers are copolymers of polyvinylidene fluoride and a fluoro-olefin. The ratio of polyvinylidene fluoride and fluoro-oLefin may be witnin the range of 10:90 to 95:5 by weight. Preferably, a vinyl compound is included in the polymer.
Japanese Application 73-38,467 purposes US2 of ~ylenediamine carbamates as crosslinking agents for hexaîluoropropylene-vinylidene fluoride copolymers which are useful as sealing agents. U.S. Patent 3,622,549 to Keller discloses a process for vulcanizing fluoroelastomers by heating ~he elastomer in the presence of a seconda~y monoamine and an aroma~.ic polyamine or aromatic polyol. The fluoroelastomers include coDolymers or vinylidene fluoride and at least one other ephenical'y unsaturated fluorinated monomer normally containing from 2 ~o 6 carbon atoms. The copolymers usually contain at least about 30 percept by weight vinylidine fluoride. Preferred copolymers are those derived from between 70 to 30% by weight vinylidene fluoride and between 30 to 70% by weight hexafluoropropene.
While amines are present in curing systems, Keller teaches incorporation of conventional compoundlng agents, such as a metal oxide and a reinforcing fuller, such as carbon black into the elastomer.
JP Application 74-42,756 teaches utilizing amine vulcanizing agents for hexafluoropropene-tetrafluoroethylene-vinylidene fluoride copolymers cured in the presence of carbon black.
Japanese Application 7a-34, 545 utilizes 2-mercaptoim-idazoline and dithyocarbamate as an acid acceptor for curing hexafluoropropene-tetrafluoroethylene-vinylidene fluoride copolymsrs with carbon blac~, MgO and Na diethyldithiocarbamate.
Additional elastomers including metal oxide are disclosed EP 1 960 762. European application 0 455 70 also discloses various poly (vinylidene- hexafluoropropylene-tetrafluoroethylene) AMEI~GcJ~ T

. .
4a elastomers, al' including metal oxide. These elas~omers are utilized in fusing me~bers. European application 0 441 645 discloses elastomers of vinylidene fluoride and high hexafluoropropylene content which have been cured u~ilizing a metal containing acid acceptors.
Accordingly, it is desirable .o provide an improved fusing system which overcomes the shortcomings of the conventional fuser systems described above.

SUMMARY OF T~E INVENTION
Gener~lly speaking, in accordance with the ~nvention, fluoroelas.omer compositions ,ree of metal or metal ^ontaining compounds, such as metals or metal oxides, which ar- pa-~icularly well suited for the topcoat oî a using member for apo ying heat and pressure .~ ix toner to a recording medium ar_ ?rovided.
?he fluoroelastomer composition _an be cured by ele~~ron beam treatment, rugitive base treatment or the use of blocked/hlndered amines. A fusing member having metal free fluoreelastomer surfaces have advan~ages over conventional ,~using memDers because they do not re~uire the use of expensive mercapte -unctional active release agents to prevent offset.
Accordingly, it is an object of the 'nvention to j provide an improved fluoroelastomer composition free o_ metal or metal containing compounds, such as metal oxides.
¦ Another object of the invention is to provide an improved fuser roll having a topcoat of fluoroelastomer free of i metal or metal containing compounds for fixing t~ner to a recording medium.
A fur~her object of the invention is to provide a fuser roll having a metal or metal containing compound free }fluoroelastomer topcoat for fusing without the need to use mercapto functional release agents.
Still other objects and ad~antages of the invention will in part be obvious and will in part be apparent from the specification and drawings.
The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others, and the composition possessing the features, AMENDED SHEET

, 4b properties and the relation of constituents and the article possessing the features, properties, and the relation of elements, which are all exemplified in the following AMEI~OE~S~F~T

--~ W093/~4~38 2 1 3 6 3 1 5 PCT/US93/~UK4 f detailed disclosure, and the scope of the invention will be indicated in the claims.

B~F D~8CRIPTION OF r~F DR~WING8 For a fuller understanding of the invention, reference is had to the following description taken in connection with the accompanying drawings, in which:
FIG. 1 is a schematic cross-sectional view of a fuser roll test assembly;
FIG. 2 is a cross-sectional view of a single layer fuser roll constructed in accordance with an embodiment of the invention; and FIG. 3 is a cross-sectional view of a multi-layer fuser roll constructed in accordance with another embodiment of the invention.

DF~CRIPTION OF ~H~ PR~F~RRED ~MBODIM~NT~
A fusing member constructed in accordance with an embodiment of the invention includes a fluoroelastomer topcoat surface that is substantially free of metal and metal containing compounds, such as metal or metal oxide particles.
The fusing member can be a belt, a flat surface or another substrate having suitable shape for fixing toner images to a recording medium, such as paper, at elevated temperatures under pressure. A preferred fusing member is a fuser roll having a metal core that can be hollow, covered with the fluoroelastomer material. A heating element can be included within the metal core to heat the fluoroelastomer surface. The fuser roll can be used to fix toner powder to a recording medium, such as paper, without offset and without relying on the interaction between metal oxides and mercapto functional release agent fluids.
The outer layer of the fusing member is of a fluoroelastomer composition having a greater molar content of hexafluoropropylene (HFP) than conventional fluoroelastomers.
The fluoroelastomer compositions prepared in accordance with the invention include more than about 23.4 mole% HFP and more preferably more than about 30.0 mole% HFP. A preferred 213631~

composition is a copolvmer or vinylidene rluoride (VF2) and hexafluoroprooylene (HFP) that includes more ~han about 69% total luorine by weight, preferably 69 to 71% fluorine by weight. It is preferable to include as much HFP as is practical. The molar ratio of VF, to HFP is preferably less than 2 and more preferably about 1.7 or less. An acceptable preferred range is between 1.25 and 1.75.
The fluoroelastomer composition can also include cure additives, such as hexafluoropropylidine diphenol, triphenyl benzyl phosphonium chloride/bromide and acid acceptors (though not metal oxides). The effectiveness of lncluding higher amounts of HFP than is conventional relates to the associa~ed reduction ~ - in surface energy at the expense oI other properties j conventionallv considered to be more important.
Fuser rolls having a fluoroelastomer surface substantial~y free of metal containlng compounds such as metal oxides -an be ~ured by several methods. Crossllnking can be induced by using diamines, a combination o~ d amines and bisphenol or bv other organic base treatments such as ammonia vapor deposit on. Another method involves the use or radiation curing such zs electron beam treatment. Such techni~ues are known for the use of curing various polymer systems, but are uniformly- not employed in the production of ^ommercially available fuser rolls, where the mechanical properties of polymers having metal oxide particles therein has been the accepted material of choice. Base treatment includes the use of bloc~ed/hindered amines, ~fugitive~ bases which will leave the polymer system after attack on the polymer material to yield unsaturation sites and electron beam treatment. The fugitive base treatment can be conducted in the vapor or liquid phases.
Metal oxide free curing can be accomplished with treatment by blocked/hindered amines. These include DIAK 3 (N, N' - D - Cinnamylidene - 1, 6-hexanediamine and DIAK
(hexamethylene - diaminecarbamate) which are commercially available curing agents sold by DuPont of Wilmington, Delaware.
This type of curing is described in Example 1.

A~AENDED SHEE~

' ' ` . .. ,. " ' . . ., . ' . ' 1 . ' ` ' ' .

- ~136315`

Electron beam processing and methods for estimating the required specifications of the electron accelera~or are discussed in Becker, RC, "Accelerator Requirements For Electron Beam Processing", Radiat. Phys. Chem., Vol. 14, Pages 353-375 (1975), the contents of which are incorporated herein by reference.
Typically, the fuser roll is conveyed in~o a chamber where it is bombarded by a highly energetic beam of electrons.
Curing occurs during the brief interval during which the fuser roll is exposed to the electron beam, which is spread over the entire surface.
Additional details regarding electron beam processing can be obtained rrom Radiation Dynamics, Inc., 1~1 Hartland Blvd., Edgewood, NY 11717. See also Cleland, M.R., et al., "High Powered DC Electronic Accelerators For Industrial Applications", RDI Technical Information Series TIS 79-6, pres2nted a~ the 3rd All-Union Conference on a part accelerators, Leningrad, USSR, June 26-28, 197g, the contents of which are incorporated herein by reference. S.ill further details can be round in Bly, JH. "Radiation Curing or Elastomers" presented at the Education Symposium of a meeting of the Rubber ~ivision, American Chemical Society, Philadelphia, Pennsylvania, May 3-6, 1982.
The curing of elastomeric material by Electron Beam (EB) radiation generates carbon-carbon bonds between molecules without using cure agents such as metal oxide powders.
Compounding for the electron beam is similar to that for other curing processes. Commercial applications are well developed in the manufacture of wire and cable, rubber tires, heat shrink products and others. However, it is believed that this technique has never been applied to curing polymer materials for fuser rolls in the absence of conventional cure system including the use of metal oxides.
Electron Beam (EB) dosages of 1-40 megarads are acceptable for many applications; 3-40 MRads is preferred and 5-20 M~ads is more preferred. It is useful to include cross linking aids (co-agents) in the polymer composition at AM~Y~0 SHEET

213631~`
` i; ,. ` . .

! 3 concentrations of about -~-lO par~s by weight per l~0 parts polymer. r.B crosslinkable di or poly runctional oligimers include: l,6 - Hexanediol Diacryla~e, Trimethylol Propane ~3 Triacrylate, Bisphenol A Expoxy Diacrylate ( EBECRYL 3700 ), TAC
~. (2,4,6 - Tris (Allylox,v) - S - Tri -azine and TAIC
s ( Trial 1 ylisocyanurate).
A fuser roll test assembly lO0 is shown generally in FIG. l and applies heat and pressure to fuse a quantity of toner particles 12 on a sheet of paper 13 between a fuser roll 20 and a pressure roll 30. Fuser roll test assembly lO0 also includes a release agent application unit ll lncluding a wick l~ for ap~lying release agent to the sur ace of ruser roll 20. A
stripper ~inger 16 ~acilitates ~he separation of paper 13 from ' roll 20.
FIG. 2 is a cross-sectional view of a fuser roll 200 constructed in accordance wlth an embodiment of the invention.
I Fus~r roll 200 includes a hollow miadle core 201 covered with a ¦ f1uoroelas.omer surface laver 202. A second fuser roll 300 is shown in crass-sec~ional v 2w in ~IC-. 3. Fuser roll 300 inciudes an insert 302 covered with a base coat 303 having a tie coat 3a4 disposed thereon and a to~coat 302 disposed on tie coat 30~.
Base coat 303 is preferablv l.27 to 12.7 microns (0.~ to ~ mil) thick and the overall coating (either surface layer 202 or combined layers 303, 30a, and 302) should be about 7.52 - 20.32 microns (3-8 mlls) thick.
The following Examples describe metal and metal oxide free fluoroelastomer compositions and fuser rolls having a topcoat of the composition prepared in accordance with the invention. These e~amples are presented for purposes of illustration only, and are not intended to be construed in a limiting sense.
Egample 1 A series of conventional fluoroelastomer compositions and metal oxide free fluoroelastomer compositions in accordance with the invention were made. The fluoroelastomer topcoat composition of five conventional fuser rolls having metal oxide therein (A-E) and two metal oxide free fluoroelastomer topcoat fuser rolls in accordance with the invention (F and G) are A~lENCEC ~nE~T

W093/24~38 2 1 3 ~ 3 1 ~ PCT/US93/~#K4 shown below in Table II. Compositions A throu~h D contain metal oxide filler conventionally used to promote interaction with a mercapto functional release agent. Composition E
contains no more than sufficient residual metal oxide to act as an activator and acid accepter for conventional cross-linking of the composition, but insufficient amount to react effectively with a mercapto functional release agent.
The seven compositions A through G were prepared by mixing the components with a two roll mixing mill. The polymer was loaded between the two mill rolls to obtain a "bank".
Cross-blending was o~tained by cutting sheets off the mill roll until a uniform viscosity is achieved. The powdered ingredients were then added over the polymer bank and dispersed therein by cutting and cross-blending. The curatives are then added and the composition was cut and cross-blended to obtain thorough and uniform dispersion of all ingredients. The resulting material was cooled in the air, compound tested then used as the surface material for a fuser roll. T h e components can also be mixed with an internal mixer device ~nown in the trade as a Banbury. When the fuser roller material is formed using a liquid state composition, the components can be effectively prepared by "in-situ" mixing techniques. In-situ mixing involves dissolving the polymer in a solvent, then adding the powdered ingredients including the activator and curatives. In compositions having a tendency to gel rapidly, it is preferable to employ a two or three component system to iso}ate the calcium hydroxide and/or the acceptor.
In compounding or formulating fluorocarbon elastomers, metal oxides are conventionally added to act-as an acid acceptor, cure activator, reinforcent filler and/or at times as an additive to promote improved chemical resistance.
The use of lead oxide, for example, improves the steam and acid resistance of fluoroelastomer compounds and is well known in the art. Metal fillers are a~so added to provide actual release by interaction ~ith mercapto functional compounds.
However, it has been determined tha~ metal and metal oxide free - 2t31~315 . ~ . .
.. . .

^o~?o~ition~ provide advantages as a :op _~at su~~ace :~
Cuser roll despite -he di~lni5hed .~echanical proper-ies.

AM~Eg~

. 2136315 lOa ;~

~ ~t ;:: ~
"
AM~ S~tEET

lOb ;~

3~

AM~tJD~ S~ET

~ 213~315 ~

ING~ED I ENT DATA

¦ CHEMICAL COMPOSITION TRAD. NAME ¦ MANUFACTURER
erpolymer of VF2, HFP 1t2430 50, ;luorel, ~ DuPon~, 3M
i I fluor1ne - ---- t- __ __ ¦ Co w lymer of VF2 and Vi~on --45, Fluorel, DuPont, 3M
HF? ~ith 65.~Z .luorine ;C 2145 Co w lymer of VF2, HFP Viron _-60, ;luorel, DuPon~, 3H
I ~ith o6% fluorine :C 2230 I ._ ......... ._ ._ ._ . _ _ ..... ~, ¦ Tetrapolymer of FV2 and Viton GF, Fluorel,3uPont, ;M
I HFP TFE and cure s1te ;LS 2690 monomer wi~h 69%
'luorine ._ ._ .. . _ ...... I
Copoiymer Ot VFz and .C 2530 3 HFP containing hosphonium salt _ acce~rator and Di sDneno l c rosslinker with o9.6X fluorine . _ _ . _ .
33X dispersion of C~ra~i~e 20 DuPon~
organopnosphonium saL;
in Viton '-45 ,, . ,, ........ _ . .
- ~ i% dispersion of Cura~1ve 30 DuPon~
DisDnenol (dihyro~y .~ aromatic compound) in ~ V1~on --45 -~ ~ . .. . _ 11 ~roprie~ary accelera~or Curar,~e ;O OuPont and bispnenol curative system .. .. ¦¦
Copolymer of VF2 and HFF '-12176 3M
con~aining phosphonium .
salt accelera~or and bispnenol crosslin~er l .
with 70% fluorine _ . . . I .
.~ N, N' - Di-cinnamylidene- DIAK No. 3 DuPon~
1,~6, hexanediamine . . . - - . ... ___ ;~ . Fuser roll samples were formed by covering a 3.81 cm (1.5 ~nch3 standard aluminum insert with a 10.16 microns (4 mil) thic~ fluoroelastomer base coat covered with a 5.08 microns (2 mil) bhick topcoat of the materials shown below in Tablè III.

The sample fuser rolls were prepared by first mixing the base ,~, coat material and topcoat material in a two roll mixing mill.

The base coat compound was formulated by combining 100 parts V-ITON E-60 (DuPont) fluoroelastomer, 30 parts thermal carbon black filler, 12 parts magnesium oxide (as , ~
~ ~ AMENDE~ S~IEET

~ .?136315 an activator/acld accepter) and ~.5 parts bl-nd CURATIVE 20 ~DuPont) and CURATIVE 30 (DuPont).
The mixed starting materials were dissolved in a 50:50 blend of met~yl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) solvents to approximately a 15% solid concentration. The aluminum insert was precured with a primer layer of THIXON
300/301 adhesive and then sprayed with the base coat solution to a thic~ness of about 12.7 - 1~.24 microns (,-6 mils). The coated sample was malntained at room temperature to permit residual solvent to ~vaporate and then cured in a circul~-ing oven for up to 2 hours at a temperature of 6~.5 to 232.2C 'lS0 to ~,oo F`.
The sample was then ground to a base coat thlckness of 7.62 -10.16 microns (3-~ mils). After washing the sample with solvent, it was over sprayed with a 1~% solid topcoat sclution to yiela a coating having a thickness of (4 to S mils). ~esidual solvent was permit~ed to evaporate and the sample was subjected to final curing in a hot air circulating oven for up to 24 hours at 232.2C (~,Oo F). The topcoat was then ground to a thickness of ~.08 to 7.62 microns (2 to 3 mlls).
Fusing tests herein were carried out by passing an 21.59 x 29.21 cm ~8.5 x 11.5 inch) 75g/m2 sheet of paper having toner particles thereon between fuser roll 20 and pressure roll 30 to fuse toner 12 to paper 13. Fuser roll life is indicated by the number of sheets of paper that can be successfully fused before failure by either offset, mechanical failure or some other difficulty. Fuser rolls including metal free compositions F and G from Table II were found to be acceptable.
The above procedure was followed for each of the following Runs 1 ~, except that the topcoat composition was A~ilENGEO ShEET

2136~

changed as set for.h in Table III and the inser~ was a ,.08 cm (standard ~wo inch) insert. Fuser roll samples produced from Runs 1, 2, 3 and ~ were installed and tes.ed in a Xerox 106--copier. The results of each copy life test are shown in Table IV, which demonstrates the advantages of a high ~luorine content and metal oxide free fluoroelastomer composition for fusing application.

TABLE III
- FORMULATION OF TOPCOAT COMPOS ~ TION

INGREDIENTS ¦ ~UN NUM9E25 I ~ 1 2 1 3 1 4 r; 2145 (66% F) ¦ 100 ¦ X ¦ X ¦ ,00 I X
_ _ _ 12176 (70Z j _ _ X ¦ _ 0 ¦ 100 ¦ X ! lC0 MAGNESIUM OXIDE 2 ¦ 2 2 X ¦ X
. - , i CALCIUM HYDROX7DE _ _ 4 I L 4 X X
DIAK NO 3¦ X ¦ X ¦ X 6 I o ~ - r I
l ¦ CuRATIvE Z0 1 1 4 ! x I x l x l x ::
__ fC 2145 - Copolymer OT VF2 ana HFP con~aining S6;. ~o~a~ f~uorine by ~eignt 3nd a VF2/HF~ mo~ar ratio of 3 76 _ _ FC 2530 - CopoLymer of VF2 anà HFP con~atn1ng 69-X. ~otal fluorine by ~e1gnt and a VF2/HFP mo~ar ratio of 1 70;_contains pnosDhonium sa~t acce~erator and bisohenol crosslinker L12176 - Copolymer of VF2 and HFP containing 70X to~al fluorine by ~eight and a VF2/HFP molar ra~io of 1 2~, contains Phosphonium salt acce~erator and bispnenol crosslinker DIAK NO 3 - N, N1 _ Di-cinnamylidene - 1, 6 Hexanediamine CURATlVE 20 - 33X dispersion of organoDhophonium sa k in Viton r45 _ CU~ATI~E 30 - 50% disDersion of bisphenol (dihydroxy aromatic compound~ in ~iton E45 A comparison was made in Table IV below between fuser rolls having the compositions of Runs 1, 2, 3 and 5.

A~E~loE~ SHEET

W093/~538 PCT/US93/D~

.~363~5 14 TABL~_IV
MatPrial DescriPtion Roll Life TY~e Re~ se ~aent ~on-Functio~l ~un # Poly~im~thysilo~a~
1 - 66% F with metal oxide 6,000 2 - 69% F with metal oxide 12,000 3 - 70% F with metal oxide 21,000 5 - 70% F no metal oxide 115,000 -By comparing Examples 1 and 2, it can be seen that including a high HFP percentage is associated with 100%
increase in roll life. Example 3 having 70% F shows a 75%
~ increase in roll life compared to Example 2 and a 250% increase i ~ver Example 1 with 66% F. However, the most dramatic results I can be seen by comparing Examples 3 and 5. The elimination of I metal oxide within the fuser roll surface material led to a j 450% increase in roll life of 94,000 copies. Accordingly, it is preferred to provide a fuser roll without any metal oxide in the material.
During conventional cross-linking, metal oxides are used to generate unsaturation in the polymer material.
However, the reaction is generally not easy to control and accordingly, it is has been common to employ excess metal oxides to achieve acceptable resu'ts. However, this typically ~ generates excess unsaturation. The unsaturation in the cured ¦ polymer material increases the surface energy and may decrease fuser roll life before offsèt occurs. The metal particles at the roll!s,urface also increase the surface energy.
' .: ' ~.' 213631S ~-`
-`~ W093/24538 P~T/US93/~#U~ 1 ~1`
It has been discovered that by carefully controlling the curing of metal-oxide free polymer material, sufficient cross-linking is achieved to cure the polymer and also provide acceptable mechanical properties, without creating excessive unsaturation and without any residual ma~erial to increase the ~urface energy of the fuser roll. Metal free compositions in accordance with the invention include sufficient sites for cross-linking, but not excessive sites which would oxidize, thereby increasing surface energy and impede toner release.
Furthermore, without residual metal oxide particles, the composition will inherently yield a polymer surface having lower surface energy particularly well suited for fusing applications.
Example 2 A fuser roll is prepared in accordance with Example 1, employing L-12176 as the surface material, which is sprayed onto a procured base layer having a 4 mil thickness. The surface material is air dried and then positioned in an electron beam apparatus curing device and exposed to an energy dose of 15 MRad. The resultant fuser roll will perform acceptably with polydimethylsiloxane release fluid having a viscosity of about 500 CSTKS and will exhibit excellent roll life and release properties, including adequate release at a temperature of about 185C.
Example 3 A fuser roll is prepared as in Example 2, except that the top coat material is formed of 100 parts L-12176 together with five parts EBECRYL 3700. EBECRYL 3700 (available from W093/2453~ PC~/US93/n#K~
c~363 16 RADCURE of Louisville Xentucky) is a conven~ional metal-oxide free cross-linking aid (co-agent) that has been found to improve the efficiency of electrons beam cures. The roll is cured with an electron beam dosage of about 5 MRad's and will perform similarly to the roll of Example 2.
Exam~le 4 Curing without metal oxides can also be effected by treatment with a base in either the vapor or liquid phase. For example, ammonia, methylamine, ethylamine and dimethylamine gas can be passed over a fuser roll coated with metal oxide free fluoroelastomer material. The base will attack the polymer chain and create unsaturated sites for cross-linking.
Subsequent heat treatment will cure the material and provide a fuser roll surface having exceptional release properties that does not require interaction with a mercapto functional release agent.
Base treatment as described herein can also be accomplished in the liquid phase. The above~noted gaseous materials can be solved in a suitable solvent, such as ether or alcohols and the uncured fuser roll can be completely immersed therein. Propyl and butyl amines can also be employed, as well as combinations of the above bases.
Exam~le 5 A fuser roll is prepared as in Example 1, except that the surface layer is formed of L-12176 which is sprayed onto the precured base layer. The surface material is air dried and placed in a cylindrical stainless steel chamber equipped with a gas inlet and exhaust apparatus. A gaseous mixture of 5%

W093/24~38 ~ 1 3 6 3 1 5 PCT/US93/~#~

anhydrous ammonia and 95% N2 (by ~olume) is allowed to flow over the roll surface until sufficient unsaturation is developed as can be evidenced by a change in surface color or through ir.strumental analysis. The roll is then removed and placed in a forced air oven at a temperature of about 200 C
for a~out 24 hours. It will perform well with a polydimethylsiloxane release fluid having a viscosity of 500 CSTK at surface temperatures of about 185-C.
Examnle 6 - A fuser roll is prepared as in Example 1, except that the surface layer is formed of Fluorel 2530 which is sprayed onto a precured base layer. The Fluorel layer is air dried and then placed in a cylindrical steel chamber equipped with gas inlets and outlets. A gaseous mixture of 5% anhydrous ammonia and 95% N2 ~by volu~e) is allowed to flow over the roll surface. The roll is then removed and placed in a forced air oven at 200- C for 24 hours. The roll will exhibit adequate release with a 500 CSTX linear reactive polydimethylsilicone fluid copolymer containing 0.1 wt% mercaptopropylmethylsiloxane modification at temperatures of about 185-C.
ExamDle 7 A fuser roll is prepared as in Example 1, except that the surface layer is formed of L-12176. The material is cured by immersing the fuser roll in a lowt% solution of butylamine E
in diethylether at 25~ C until surface discoloration is apparent. The roll is then removed from the amine-ether '~
solution and washed with ethyl alcohol and _istilled water. It is then heat treated at 200- C for 24 hours. The roll will W093/24538 PCT/US93/~K~~

.~363~ 18 exhibit adequate release properties at temperatures of about 185 C with a 500 CSTK liner polysiloxane release fluid.
It will t~us be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained and, since certain changes may be made in carrying out the above method, and in the composition and article set forth without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description and shown in the - accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
It is also to be understood that the following claims - are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.
: Particularly it is to be understood that in sa~d , claims, ingredients or compounds recited in the singular are intended to include compatible mixtures of such ingredients wherever the sense permits.

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, ` :~

Claims

19 WHAT IS CLAIMED IS:

1. A cured fluoroelastomer, comprising:
vinylidene fluoride (VF2) and hexafluoropropylene (HFP) formulated so that the fluorine content of the elastomer is at least 65% by weight and free or metal oxide.

2. The fluoroelastomer of claim 1, wherein the VF2/HFP molar ratio is less than 2Ø

3. The fluoroelastomer of claim 1, wherein the VF2/HFP molar ration is less than 1.75.

4. The fluoroelastomer of claim 1, wherein the VF2/HFP molar ration is between 1.25 and 1.75.

5. The fluoroelastomer of claim 1, wherein the fluoroelastomer has been cured by exposure to diamines.

6. The fluoroelastomer of claim 1, wherein the fluoroelastomer has been cured by treatment with ammonia.

7. The fluoroelastomer of claim 1, wherein the fluoroelastomer has been cured by treatment with at least one organic base.

8. The fluoroelastomer of claim 6, wherein the organic base is a blocked/hindered amine.

9. The fluoroelastomer of claim 1, wherein the fluoroelastomer has been cured by electron beam treatment.

10. The fluoroelastomer of claim 9, wherein the fluoroelastomer composition includes at least one crosslinking aid.

11. A cured fluoroelastomer, formed from a fluoroelastomer composition, consisting essentially of:
vinylidene fluoride (VF2) and hexafluoropropylene (HFP) formulated so that the fluorine content of the elastomer is at least 65% by weight which has been cross-linked by treatment with blocked/hindered amines and is free of metal containing material.

12. A fusing member for fixing toner particles to a recording medium, having a substrate and an outer layer of fluoroelastomer material on the substrate, characterized in that:
the outer layer of fluoroelastomer material is a polymer including vinylidene fluoride and hexafluoropropylene formulated so that the fluorine content is at Least 65% by weight and the elastomer is free of metal containing material.

13. The fusing member of claim 12, wherein the member is a fuser roll.

14. The fusing member of claim 13, wherein the fluoroelastomer includes at least 30 mole percent hexafluoropropylene.

15. The fusing member of claim 13, wherein the fluoroelastomer is a coplymer of hexafluoropropylene (HFP) and vinylidene fluoride (VF2).

16. The fusing member or claim 15, wherein the molar ratio of VF2 to HFP is less than 2.

17. The fusing member or claim 12, wherein the substrate is in he form of a metal core having a layer of silicone material including metal oxide material therein, disposed on the metal core.

18. The fusing member of claim 17, including a tie coat or fluoroelastomer material between the surface layer and the silicone material.

19. A fusing system for fusing toner to a recording medium, including a fuser roll having an outer surface formed of fluoroelastomer material being a polymer including vinylidene fluoride and hexafluoropropylene and a release agent fluid disposed on the surface of the fuser roll, characterized in that:
the fluoroelastomer material is formulated so that the fluorine content is at least 65% by weight and the elastomer is free of metal containing material and the release agent is a fluid.

20. The fusing system of claim 19, wherein the release agent fluid is a polysiloxane free of mercapto functional compounds.

21. The fusing system of claim 19, wherein the fluoroelastomer includes at least 23.4 mole percent hexafluoropropylene.

22. The fusing system of claim 19, wherein the fluoroelastomer includes at least 70% by weight fluorine.

23. A method of forming a fuser roll, comprising:
providing a substrate;
disposing uncured fluoroelastomer material on the substrate, the fluoroelastomer material being a polymer including vinylidene fluoride and hexafluoropropylene formulated so that the fluorine content is at least 65% by weight and is free of metal containing material; and curing the fluoroelastomer material.

24. The method of claim 23, wherein curing of the fluoroelastomer material includes exposure to electron beam radiation.

25. The method or claim 24, wherein the dose of electron beam radiation is from about 3 to 40 MRads.

26. The method of claim 24, wherein the dose of electron beam radiation is from about 5 to 20 MRads.

27. The method of claim 24, wherein crosslinking aids are added to the fluoroelastomer material.

28. The method of claim 27, wherein the crosslinking aids are selected from the group consisting of 1,6 Hexanediol Diacrylate, Trimethylol Propane, Triacrylate, Bisphenol A Expoxy Diacrylate, TAC (2, 4, 6 - Tris (Allyloxy) - S - Triazine, TAIC
(Triallylisocyanurate).

29. The method of claim 23, wherein curing of the fluoroelastomer material includes treatment with a base to provide unsaturated sites in the fluoroelastomer material.

30. The method of claim 29, wherein the base treatment includes exposure to a base selected from the group consisting of methylamines, ethylamines, diethylamines, propylamines and butyl amines.

31. The method of claim 29, wherein the base exposed to the fluoroelastomer is in the gaseous phase.

32. The method of claim 29, wherein the base is ammonia.

33. The method of claim 29, wherein the base treatment of the fluoroelastomer is in the liquid phase, dissolved in a solvent.

34. The method of claim 33, wherein the base is ammonia.

35. The method of claim 29, wherein curing of the fluoroelastomer includes treatment with a blocked/hindered amine.

36. The method of claim 35, wherein the amine is N, N1 - Di-cinnamylidene - 1,6 - Hexanediamine.

37. The method of claim 35, wherein the amine is Hexamethylene-diaminecarbamate.