May 7, 1999 - Course Program, Orlando, ... Technical Support Package: Details of AtornicâOXygen ... Treatment of Polymer Surfaces, NASA Tech Briefs,.
US006146462A
United States Patent [19]
[11]
Patent Number:
Yializis et al.
[45]
Date of Patent:
[54]
STRUCTURES AND COMPONENTS
4279092
10/1992
THEREOF HAVING A DESIRED SURFACE CHARACTERISTIC TOGETHER WITH METHODS AND APPARATUSES FOR PRODUCING THE SAME
2081611
2/1982
WO9424358 9627044 9718692 9727356 9905358
10/1994 9/1996 5/1997 7/1997 2/1999
[75] Inventors: Angelo Yializis; Richard E. EllWanger; Michael G. Mikhael; Wolfgang Decker, all of Tucson, AriZ.; C. Barry Johnson, Mt. Pleasant, SC;
Gale Shipley, Mauldin, S.C.; Timothy
[73] Assignee: AstenJohnson, Inc., Charleston, SC. [21] Appl. No.: 09/307,078 [22] Filed: May 7, 1999
[51] [52]
Int. Cl.7 ................................................... .. C23C 16/00 US. Cl. .................................. .. 118/718; 118/723 HC;
[58]
Field of Search ............................... .. 118/718, 723 E,
118/723 Fl
. ......................... .. D06M 10/02 ............................ .. H05H 1/44
. ............................. .. D21F 1/00
OTHER PUBLICATIONS
Maike Rabe et al., “Hydrophobierung und Verbesserung der Farbechtheiten von Polyestergarn durch Plasmapolymerisa
Bahners T. et al., “AnWendung der Niedertemperaturplas ma—Technologie in der Textilvorbehandlung. Teil 1: Ver fahren der Niedtemperaturplasma—Technologie”, Textil Praxis International, vol. 49, No. 6, Jun. 1, 1994, pp. 118—1997, American Association of Textile Chemists & Colorists Technical Manual, 1997, pp. 191—193. Plasma Finishing: 5.1 Possibilities and Processes Today,
TechteXtil—Symposium ’97 (May 14, 1997). Plasma Treatment Basics, Sigma Labs (latest 1996).
118/723 HC, 723 I, 729, 733, 723 FE; 156/345
Plasma Surface Modi?cation and Plasma Deposition, NeoMecs Web site (1996). NeW: Atmospheric Plasma; March Instruments Inc. Web site
References Cited
Plasma and Surface Technology; Fraunhofer Institut
3/1967
(List continued on next page.)
0168131 0172057 0191680A1
1/1986 2/1986 8/1986
0192510A1 0492649B1 0727508
8/1986 7/1992 8/1996 10/1976 2/1986 9/1988
Primary Examiner—Shrive Beck Assistant Examiner—ParviZ HassanZadeh
Attorney, Agent, or Firm—Volpe and Koenig, PC.
FOREIGN PATENT DOCUMENTS 10/1982
(List continued on neXt page.)
Mantell ................................. .. 204/165
11/1969 Friedlander et al. .. 11/1969 Van Dyk .............................. .. 252/126
0062491
(1997). AngeWandte Materialforschung Web site (1997).
U.S. PATENT DOCUMENTS
122692 61-035235 63-223043
United Kingdom . WIPO WIPO WIPO WIPO WIPO
Oil Repellency: Hydrocarbon Resistance Test, Test Method
[60]
3,479,129 3,480,547
Japan ............................. .. H05K 3/38
422—424, (translation enclosed).
Related US. Application Data Provisional application No. 60/084,768, May 8, 1998.
3,309,299
Nov. 14, 2000
tion”, Jun. 1994, pp. 513—517 (translation enclosed).
D. O’Brien, Summerville, SC.
[56]
6,146,462
[57]
ABSTRACT
European Pat. Off. ......... .. C08J 5/06
European Pat. Off. European Pat. Off. European Pat. Off.
C08J 5/06 C08J 5/06 C08J 5/06
European Pat. Off. ...... .. B29C 59/14 European Pat. Off. ..... .. D06M 10/10 European Pat. Off. ...... .. C23C 16/44 Germany .................... .. D06C 1/02 Japan ........ .. B29D 23/22 Japan ............................... .. C08J 7/16
Methods and apparatus for plasma modifying a substrate are
disclosed along With associated techniques for applying coatings to the substrate. Particular utility has been found using a holloW cathode to generate the plasma along With magnetic focusing means to focus the plasma at the surface of a substrate.
9 Claims, 9 Drawing Sheets
6,146,462 Page 2 US. PATENT DOCUMENTS
5,514,472
5/1996 Baris et al. ........................... .. 428/365
5,527,396 5,622,773
6/1996 Saitoh et al. ...................... .. 118/723 E 4/1997 Reiner et a1_ ____ __ 442/135
- 428/131 - 528/339
5,629,052 5,714,308
5/1997 Trokhan e161. 2/1998 Romach et al.
68/5 E
5,732,477
3/1998
Toyama
68/5 C 12/1984 Olson et al. .......................... .. 361/311 1/1985 Walton 2/1985 Cichanowski ......................... .. 361/311
5,733,405 577537886 5,767,469 577897145
3/1998 5/1998 6/1998 8/1998
Takietal. .............. .. 118/723 E Iwamura et a1_ _ Glocker 61 al. .................. .. 204/157.15 Glocker et a1__
3,817,701
6/1974 Torsen ................................... .. 8/116 R
4,206,258 4,218,509 4,457,145 4,466,258
6/1980 8/1980 7/1984 8/1984
4,490,774 4,496,423
4,499,520 4,507,539 4,513,349 4,515,931
Balm EdgaretalSando 9t 91 sando er a1
3/1985 Sando er 91--
5,853,493
4/1985 5/1985
578977713
Olson et al. .......................... .. 361/311 Olson et al. ....................... .. 526/3232
4,533,710
8/1985 Olson etal.
4,586,111
4/1986
476017911
7/1986 Ueno et a1_
........
. . . ..
34/275
12/1998 Skelton e161. ............................ .. 134/7 4/1999
. 526/3232
CichanoWski ..
427/508 430/523
Tomioka et a1_ ____________________ __ 118/723 1
OTHER PUBLICATIONS
361/323
_
427/34
Charles Tornasino, Jerome Cuorno, Plasma Treatrnent—
8/11552 428/522
Textiles, Annual Report Sep. 1, 1994—Sep. 30, 1995, NTC Web site (1997 at latest).
Harn ...................................... ..
Plasma Processing of Surfaces Using Pulsed Streamer Coro
4,744,181
5/1988 Moore et al. ........................... .. 51/436
Has, University of California, Lawrence Livemore National
4,748,077
5/1988 Skinner et al.
428/224
Laboratory, Web Site (1995)'
4,803,332
2/1989 Koyama et al.
219/121.52
4,842,893
6/1989
Yializis et al. .
.... .. 427/44
4,954,371
9/1990 Yializisetet al. .
427/44
Banks, Course Bruce Program, A- etOrlando, a1-,At9m1
or
570977800
3/1992 Shaw et a1‘
' 118/730
Bailey, Sheila G. Faterni, Navid S., and Landis, Geoffrey A.:
5,109,636
5/1992
Lloyd 6161.
51/320
5,125,138
6/1992
Shaw 6161.
29/25.42
. . . . Texturing of InP Surfaces for Device Applications, Techni. _ . . cal Support Package. More about TeXture Etching of Indiurn
5,200,260
4/1993 Hsu ....................................... .. 428/234
Phosphldm NASA Tech Bnefs> LEW—16212~ (1997 of ear‘
5,207,873
5/1993 Sanduja e161. .................... .. 162/358.2
her)
571697499 12/1992 Ea g1 es et a1‘
428/175
5,244,543
9/1993 Fry ............... ..
5,283,110 5,334,444
2/1994 Gardner et al. ....................... .. 428/227 8/1994 Bhoon 61 al. ......................... .. 428/280
1?; ,
,
5,376,413
.. 162/358.2
gislll‘alov et al' ~~~~~~~~~~~~~~~~~~~~ " 8/11552 9
y
-
2/1995 Tanisaki
5,407,736
4/1995
McKeon . . . . .
Guanidine—Based _
12/1994 Callebert e161. ..................... .. 427/489
573917855
Veitch, LC; and Phillip, W.H.; ANovel Method for Depos itmg Precious Metal Films on Dif?cult Surfaces, Technical Support package; Depositing pt on A1203 Fibers From a
219/12L43 . . . .. 428/225
5,455,108 10/1995 Quincy 61 al. ........................ .. 428/266 5,456,972 10/1995 Roth etal. ............................ .. 428/224
Solution,
NASA
Tech
Briefs,
-
LEW 163.07‘ (1997.“ Gamer)‘
_
. .
L. Pranev1c1us,'Coat1ng Technology. Ion Beam Deposition, Saws & ASS°C1ateS>WarW1Ck> R-I- 1993
_
D- Markgraf 9t 41-, Surface Treatment Of Plastlcsi Technol ogy and Applications, Seminar in Boston, Nov. 1996.
U.S. Patent
Nov. 14,2000
Sheet 2 of9
6,146,462
FIG. 2 14
8
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Q
38 ?r“ 36/,” 36\_ _
214 i
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18
i
MM
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U.S. Patent
Nov. 14,2000
FIG. 3
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Sheet 3 of9
6,146,462
U.S. Patent
Nov. 14, 2000
Sheet 4 0f 9
6,146,462
FIG. 4
00 6
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47
3
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U.S. Patent
Nov. 14,2000
Sheet 5 of9
6,146,462
404
402
FIG. 6
U.S. Patent
Nov. 14,2000
Sheet 6 of9
6,146,462
FIG. 7 \
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(.0 00
I12)!\L
\ I
\ /
UV
U.S. Patent
Nov. 14, 2000
Sheet 7 0f 9
FIG. 8A
6,146,462
302 303 304
FIG. 88
FIG. 8C 306
303 302
302 306
303
FIG. 8D
FIG. SE
306
304
304
306
302
302 303
303
FIG. 8F
v
M304 3_2_
, /
_
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303 306
FIG. 86
" 304
fvm
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U.S. Patent
Nov. 14,2000
Sheet 8 of9
6,146,462
126
FIG. 9
f”
150 at
)6 152 98
97\\3%l 151 “(if :Q\\\97 50 15a
127
FIG. 10
/
129
99
U.S. Patent
Nov. 14, 2000
Sheet 9 0f 9
6,146,462
124
FIG. 11
”/
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151
H
FIG. 12
125
130
/ 190
131
99
6,146,462 1
2
STRUCTURES AND COMPONENTS THEREOF HAVING A DESIRED SURFACE CHARACTERISTIC TOGETHER WITH METHODS AND APPARATUSES FOR PRODUCING THE SAME
treated With a highly ef?cient and controllable plasma treat ment. If desired, the structure or component may be further enhanced or modi?ed by exposure to a deposition treatment.
This application claims bene?t of Provisional Applica tion Ser. No. 60/084,768 ?led May 8, 1998.
nents having at least one inherent surface characteristic
SUMMARY OF THE INVENTION
The present invention provides substrates and compo
BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
10
thereof modi?ed by equipment and techniques Which are particularly suitable for achieving that modi?cation. The inherent surface property may be modi?ed by a plasma treatment process Which comprises the steps of providing a
The present invention relates generally to structures and their components Which have been treated With equipment and techniques that produce modi?cations to surface char
plasma treatment chamber Which includes one or more
holloW cathodes for generating a plasma Within the chamber.
acteristics in either the structures or the components. More 15 The chamber includes means for focusing the generated plasma at the surface to be treated as it is introduced into the particularly, the present invention relates to equipment and
chamber and reacted With the plasma.
techniques for treating substrates and components having commercial and industrial uses, particularly in industrial fabrics. Most particularly, the invention relates to plasma
DESCRIPTION OF THE DRAWINGS
treated components and substrates together With equipment and techniques useful in treating the same in an ef?cient and
FIG. 1 is a side elevation shoWing a plasma treatment apparatus in accordance With the present invention in an
accurate manner.
opened condition.
The prior art has recogniZed the advantages to be obtained
by plasma treating and deposition techniques, at loW pres sure and at atmospheric pressure, to achieve desirable char
25
acteristics in a product. Most generally, the products treated
FIG. 2 is an elevation of the other side of the plasma treatment apparatus of FIG. 1 taken along the line 2—2 of FIG. 1. FIG. 3 is an elevation of one side of the plasma treatment
in the prior art are single purpose products Which Were not
apparatus of FIG. 1 taken along the line 3—3 of FIG. 1.
intended to be exposed to a Working condition or an active
environment Where the treated product is subjected to vary ing conditions over an extended time period. Furthermore, the prior art products Were not exposed to varied treatment
FIG. 4 is a side elevation of one arrangement for treating a substrate in accordance With the present invention.
over time in a Work environment. For example, industrial
drip system.
FIG. 5 is a partial cutaWay perspective vieW of a capillary
fabrics are frequently required to Work under conditions of high mechanical stress and hostile environments. Special
applications, like papermaking, require industrial fabrics
FIG. 6 is a side elevation of a solution bath. FIG. 7 is an elevation, similar to FIG. 2, shoWing a 35
that generally Work in hot, moist and chemically hostile environments. As such, the fabric may be exposed to high
plurality of discrete substrates being treating simultaneously. FIG. 8 shoWs a plurality of substrates A—F in cross-section
Water content in a formation step, heat, pressure and rela
With or Without plasma treating and secondary coating.
tively high Water content in a pressing step, and then, exposed to high temperatures in a drying step. Thus, the
treatment chamber.
FIG. 9 shoWs an alternative arrangement of the plasma FIG. 10 shoWs a treatment chamber for metal deposition. FIG. 11 shoWs a treatment chamber for vapor deposition
fabrics may see a variety of conditions in the process.
Industrial fabrics may also be exposed to varying conditions in industries such as food processing, Waste treatment,
of a monomer.
assembly line processes or surface painting and treating
techniques.
FIG. 12 shoWs a curing unit. 45
The art has recogniZed that it Would be desirable to have substrates and components With certain mechanical properties, such as strength, dimensional stability, and Hex ibility over extended periods. While these characteristics are desired as properties, it is sometimes desired to have surface properties Which are contrary to these properties. For instance, it may be desirable to have a component Which exhibits good internal resistance to moisture at its core While having an external af?nity for moisture at its surface. It is not uncommon to have a con?ict develop betWeen the desired
GLOSSARY A component is a structural or modular element that is capable of producing a structure When a plurality thereof are
assembled together. A fabric structure is formed by arranging individual strands in a pattern, such as by Weaving, braiding, or
knitting. A ?ber is a basic element of a textile and is characteriZed 55
mechanical properties and the preferred surface properties. The prior art has recogniZed and there have been attempts at
A holloW cathode is an energy ef?cient chamber for
producing a mechanically robust core Which supports a
generating a plasma.
surface layer that has speci?c characteristics for the desired application. It has been recogniZed that important surface
An industrial fabric is one designed for a Working func tion such as transport devices in the form of a moving or
layer properties such as hydrophilicity, hydrophobicity, oleophilicity, oleophobicity, conductivity, chemical resis tance and abrasion resistance may not necessarily be opti miZed in a single component Which optimiZes core proper ties such as strength, ?exibility, and the like. The present invention addresses the shortcomings of the prior art by providing structures and components Which are
by having a length at least 100 times its diameter. A ?lament is a continuous ?ber of extremely long length.
conveying belt. An inherent property or characteristic is one that exists 65
prior to any treatment by plasma or other means. A mono?lament is a single ?lament With or Without tWist. Amulti?lament yarn is a yarn composed of more than one ?lament assembled With or Without tWist.
6,146,462 3
4
A nonWoven structure is a substrate formed by mechanical, thermal, or chemical means or a combination
along the line 3—3 of FIG. 1. The plasma focusing side 6 includes a plurality of focusing arrays 50 Which are located
thereof Without Weaving, braiding, or knitting. A plasma is a partially ioniZed gas; commonly ioniZed
in space relative to each other so as to achieve a reinforce
gases are argon, xenon, helium, neon, oxygen, carbon
ment of the magnetic focusing ?eld. Surrounding the mag nets 50 (shoWn in crosshatch for clarity) are the cooling
dioxide, nitrogen, and mixtures thereof.
ducts 52 Which serve to control the temperature in the
Astrand is a ?lament, mono?lament, multi?lament, yarn, string, rope, Wire, or cable of suitable length, strength, or
chamber, thereby protecting the magnets from overheating.
construction for a particular purpose. Astructure is an assemblage of a plurality of components.
Plasma treatment to remove loW molecular Weight mate 10
available, inexpensive, environmentally benign gases. In
A substrate is any structure, component, fabric, ?ber,
some applications, plasma treatment alone may be sufficient, hoWever, it can be folloWed by coating With metals,
?lament, multi?lament, mono?lament, yarn, strand, extrudate, modular element, or other item presented for plasma treatment or coating. A Web is an array of loosely entangled strands. A yarn is a continuous strand of textile ?bers, ?laments, or material in a form suitable for intertWining to form a textile structure. A 100% solids solution is a ?uid such as a monomer, combination of monomers or other coating material Which
15
20
25
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiments Will be described With refer ence to the draWing Figures Wherein like numerals indicate
like elements throughout.
ceramics, or polymeriZable compounds. Preferred polymer iZable compounds are radiation curable organic monomers containing at least one double bond, preferably at least tWo
includes no carriers or solvent.
A 100% solids bath is a tank ?lled With a ?uid such as a monomer, Which includes no carriers or solvent.
rial or surface impurities Will preferably use readily
double bonds, especially alkene bonds. Acrylates are par ticularly Well-suited monomers. Metals suitable for deposi tion include, but are not limited to Al, Cu, Mg, and Ti. Ceramics suitable for deposition include, but are not limited
to, silicate-containing compounds, metal oxides particularly aluminum oxide, magnesium oxide, Zirconium oxide, beryl lium oxide, thorium oxides, graphite, ferrites, titanates, carbides, borides, silicides, nitrides, and materials made therefrom. Multiple coatings comprising metal, ceramic or radiation curable compound coatings are possible.
30
Plasma treatment leads to one or more of the folloWing
bene?ts: cleaning, roughening, drying, or surface activation.
With reference to FIG. 1, there is shoWn plasma treatment chamber 2 Which is useful in accordance With the present
Plasma treatment can also lead to chemical alteration of a
invention. Plasma treatment chamber 2 is divided into a
substrate, functional groups, ions, electrons, or molecular
plasma generating side 4 and a plasma focusing side 6. In use, the plasma generating side 4 and the plasma focusing side 6 are joined together in a sealed relationship except for openings 8 and 10 at the respective upper and loWer ends. Entry and exit openings are created by the recesses 12, 14, 16 and 18. Since the pressure in the plasma treatment
substrate by adding to a substrate or removing from a 35
All materials are of interest for plasma treatment or
application of a secondary coating. Those of primary interest are polymers, such as aramids, polyesters, polyamides, 40
chamber 2 is preferably beloW atmospheric pressure, the recesses 12, 14, 16 and 18 Will be provided With air locks of under the trade name Velcro®. Presently, a closed cell 45
sphere so as to maintain the desired vacuum level Within the 50
plasma treatment chamber 2. The vacuum in chamber 2 is draWn through the outlet ducts 30 and 32 by a suitable vacuum generating device as Will be knoWn to those skilled
in the art. Currently, the plasma is being generated betWeen 900 milli torr (0.900 torr) and 3 torr. In earlier trials, plasma
polyimides, ?uorocarbons, polyaryletherketones, polyphe nylene sul?des, polyole?ns, acrylics, copolymers and physi cal blends or alloys thereof. Preferred secondary layer coating thickness for polymers is in the range of 0.1 to 100 microns, more preferably 20 to 100 microns, most prefer
foam material or loop pile material, such as is available
polyole?n, such as polyethylene or polypropylene, foam is preferred. When chamber 2 is closed, the Walls 20 and 22 Will form a channel 24 through the apparatus 2. A substrate passing betWeen the air locks at openings 8 and 10 Will pass into channel 24 and be suf?ciently sealed against the atmo
fragments, possibly accompanied by cross-linking.
ably 20 to 40 microns. Preferred metal or ceramic secondary layer coating thickness is in the range of 50 angstroms to 5 microns, more preferably 100 to 1000 angstroms. A pre ferred polymer is an acrylate of acrylic acid or its esters. The preferred acrylates have tWo or more double bonds.
Monoacrylates have the general formula (I)
55
Was generated at up to 34 torr.
With reference to FIG. 2, taken along line 2—2 of FIG. 1, there is illustrated a substrate 3 as it passes through the plasma treatment chamber 2 and the holloW cathode assem
blies 36. As shoWn in FIGS. 1 and 2, the holloW cathode assemblies 36 de?ne multiple holloW cathodes 38. The
plasma generated in the holloW cathodes 38 Will be initially focused in the vicinity of the substrate 3. Additional focusing of the plasma on the substrate is accomplished by the focusing means included in plasma focusing side 6. Turning noW to FIG. 3, there is a vieW of the plasma
focusing side 6 of plasma treatment apparatus 2 that is taken
60
65
Wherein R1, R2, R3, and R4 are H or an organic group. Diacrylates are acrylates of formula I Wherein either R1, R2, R3, or R4 is itself an acrylate group. Organic groups are usually aliphatic, ole?nic, alicyclic, or aryl groups or mix
tures thereof (eg aliphatic alicyclic). Preferred monoacry lates are those Where R1, R2 and R3 are H or methyl and R4 is a substituted alkyl or aryl group.
6,146,462 6
5 Preferred diacrylates have the formula
curing of a continuous substrate Which may most easily be thought of as a strand 3. In FIG. 4, a plasma treatment
apparatus 2, a coating applicator 60, and a curing unit 70,
(II)
provide an integrated system for treatment of the strand 3. The direction of movement of the strand 3 is indicated by the in and out arroWs. The strand 3 moves over a guide roller 88
and enters the plasma treatment apparatus 2 at the opening
Where R1, R2, R3, R5, R6, R7 are preferably H or methyl,
10
most preferably H.
R4 is preferably C2—C2O alkyl, aryl, multialkyl, multiaryl,
8. To achieve uniform coverage, the strand 3 Will not touch either Wall 20 or Wall 22. HoWever, the strand 3 Will pass closer to Wall 22 than to Wall 20. If it is desired to treat only one surface of a strand, the surface to remain untreated may be shielded, such as by contact With Wall 22. After the strand
3 passes through channel 24, it exits the plasma apparatus 2
or multiglycolyl, most preferably triethylene glycolyl or
through opening 10.
tripropylene glycolyl. The notation, C2—C2O alkyl, indicates
15 In the preferred embodiment, the coating applicator 60, is an alkyl group With 2 to 20 carbon atoms. a capillary drip system 400 including a reservoir 402, a R4 in a mono- or multiacrylate is chosen to yield the desired surface properties after the monomer has been pump 404, a dispensing manifold 406, a plurality of capil
radiation cured to form a surface on a substrate. Table 1
lary tips 408, and a separating roller 410 having a plurality
contains a list of examples.
of grooves 412 dimensioned to receive a substrate as shoWn 20
TABLE 1
the plurality of capillary tips 408. Each tip 408 is associated
R4
Surface Properties
—CH2CH2CH2OCH2CH2CH2OCH2CH2CH2— —CH2CH2OCH2CH2OCH2CH2—
Abrasion Resistance Abrasion Resistance
—CH2CH2COOH —CH2CH2OH
Hydrophilicity Hydrophilicity
Formula I and II can also include triacrylate and other polyacrylate molecules. Mixtures of diacrylates can be copolymeriZed, for example a 50:50 mix of tWo structurally different diacrylates. Diacrylates can also be copolymeriZed With other polymeriZable components, such as unsaturated alcohols and esters, unsaturated acids, unsaturated loWer
polyhydric alcohols, esters of unsaturated acids, vinyl cyclic compounds, unsaturated ethers, unsaturated ketones, unsat urated aliphatic hydrocarbons, unsaturated alkyl halides,
25
30
travels around the roller 410 and continues vertically upWard into the curing unit 70. The variation in the initial angle 0 determines hoW the strand 3 is coated. Depending on the angle 0, the strand contacts 25—50% of the roller 410 circumference. Use of this capillary tip system is accurate a more uniform coating than other methods. This approach is believed to be bene?cial because it alloWs for remote
35
location of the reservoir 402 aWay from potential curing radiation Which may impact a dip bath. Returning to FIG. 4, the strand 3 then enters into the curing apparatus 70 through channel 72 and passes out of the
40
by the extensions 75 and 76. The central channel 77 is de?ned by the Walls 78 and 79 of the curing apparatus 70. After passing the last guide roller 88, the strand 3 is handled
Diacrylates of interest also include 1,2-alkanediol diacry late monomers of formula
With a groove 412 in the separating roller 410. In this arrangement, the roller 410 may rotate or be held stationary. The strand 3 is directed to engage the roller 410 horiZontally or at an angle up to 45° above horiZontal. The strand 3
and efficient, requires less coating solution 61, and provides
unsaturated acid halides and unsaturated nitrites.
apparatus at channel 74. The channels 72 and 74 are de?ned
(III) 0
in FIG. 5. The coating solution 61 is pumped from the reservoir 402 into the dispensing manifold 406 and through
R2
in the usual manner associated With normal production of an
unmodi?ed product. 45
In one embodiment, curing apparatus 70 has one section
80 With a plurality of UV lamps (one lamp is noted as 82) and an opposed section 84 With a plurality of opposing mirrors (one mirror is noted as 86). In a preferred arrange ment for curing certain monomer coatings, there are up to
Where R1 is in an acrylate radical having about 8 to 28
50
carbon atoms and R2 is hydrogen or methyl (See for example US. Pat. No. 4,537,710). The agent for promoting polymeriZation may be radiation,
adjustable for controlling their combined output. The sec tions 80 and 84 are hinged relative to each other to alloW
such as UV radiation or electron beam radiation. In some
instances, it may be preferred to use a photoinitiator, such as an appropriate ketone.
four lamps, in opposed pairs. Each lamp is preferably
55
access for startup and repair. The UV light used for curing preferably emits radiation betWeen 150 and 400 nanometers. The series of guide rollers 88 change the direction of the strand 3 so it passes continuously through plasma treatment
apparatus 2, coating applicator 60, and curing apparatus 70.
Acrylate-based formulations of interest also include het erogeneous mixtures. These formulations contain a very ?ne
The system components, plasma treatment apparatus 2,
dispersion of metal, ceramic, or graphite particles. These
coating applicator 60, curing apparatus 70, and rollers 88,
coatings are designed to enhance the abrasion resistance
60
(UV/Visible) of these pigmented dark acrylate-based
FIG. 7 illustrates the case for multiple strands 3, such as
mono?laments, passing through the plasma treatment appa
formulations, a long Wave length (>250 nm) radiation source in combination With a compatible photoinitiator may be
preferred. Turning noW to FIGS. 4 and 5, there are illustrated
apparatuses for sequential plasma treatment, coating, and
are secured in a stable manner to preserve the spacial
relationship betWeen them.
and/or the conductivity of the surface. For the photo-curing
65
ratus 2. The strands are spaced across the Width, preferably in individual paths, so that the entirety of the strand is exposed to treatment. The individual strands are preferably guided by grooves cut in the rollers 88. Using a series of
6,146,462 7
8
grooved rollers 88 keeps the strands in the desired relation
Woven into a ?lling ?oat fabric using conventional process
ship as they move through the treatment process. The treated substrate is tested according to Test Method
ing methods. The yarn survives the rigors of Warping and Weaving Without abrasion, or ?aking indicating the coating
118 developed by the American Association of Textile Chemists and Colorists (AATCC). Drops of standard test liquids, consisting of a selected series of hydrocarbons With varying surface tensions, are placed on the surface and observed for Wetting, Wicking, and contact angle. The oil
is securely af?xed. Resulting fabrics also have an oil, Water rating of 4, 6 on one surface designated as the face. The untreated PET control has an oil, Water rating of 0, 2—3.
In this particular example, a series of acrylate-based ?uorinated monomer/oligomer formulations have been
repellency grade is the highest numbered liquid Which does
tested for this application. These materials cover a broad
not Wet the surface. The method Was modi?ed to test for 10
range of surface energies (hydrophobic/hydrophilic and
If surface Wetting does not occur Within 10 seconds, the next
resistance and adhesion to the substrate. The formulation Sigma-MM-2116 is a solvent-free, acry
Water repellency, using test liquids of isopropanol and Water in ratios of 2:98, 5:95, 10:90, 20:80, 30:70, and 40:60 (in percent by volume) numbered one through six respectively.
test liquid is applied. LoWer ratings indicate oleo-or hydro
philicity While higher ratings indicate oleo-or hydrophobic
oleophobic/oleophilic), crosslinking densities, abrasion late based monomer/oligomer mix Which contains 50—95% 15
per?uorinated monoacrylate With ?uorine content ranging from 30—64%. The formulation also contains 3—50% multi
ity.
functional, compatible crosslinking agents, eg di- and
EXAMPLE 1
tri-acrylate monomers. Also 1—20% of an adhesion promoter
Using a continuous treatment system shoWn in FIGS. 1—5, a plurality of strands are treated. An extruder is adjusted to produce 10 ends of a polyethylene terephthalate mono?la
Was added to enhance diacrylate monomers functionaliZed 20
groups. The high ?uorine content loWers the surface energy of the cured coating and turns the coated yarn into hydro
ment With a nominal siZe of 0.26 mm>
