U.S. patent application number 11/805361 was filed with the patent office on 2007-10-04 for device having low outgassing photo or electron beam curable rubbery polymer material.
Invention is credited to Kelsee L. Coykendall, Paul G. Dewa, Robert Sabia, David C. Sauer, Paul J. Shustack, Kamal K. Soni.
Application Number | 20070232714 11/805361 |
Document ID | / |
Family ID | 32595067 |
Filed Date | 2007-10-04 |
United States Patent
Application |
20070232714 |
Kind Code |
A1 |
Coykendall; Kelsee L. ; et
al. |
October 4, 2007 |
Device having low outgassing photo or electron beam curable rubbery
polymer material
Abstract
Disclosed are photo or electron beam polymerizable compositions,
and preparation thereof and devices containing them. The
composition contains completely or substantially completely
hydrogenated hydrocarbon-based material completely free or
substantially free of carbon-carbon double and triple bonds
containing photo or electron beam curable terminal or pendant
groups, low-outgassing photoinitiators, an optional viscosity
adjustment component and an optional filler. The composition is
visible light, UV or electron beam curable. It cures into a
low-modulus, low outgassing polymer material. The composition can
be used as an adhesive, sealant or lens potting material. It is
ideal for use in lithographic tools involving deep or vacuum
ultraviolet radiations, in particular, as lens potting materials
for 157 nm lithographic tools.
Inventors: |
Coykendall; Kelsee L.;
(Henrietta, NY) ; Dewa; Paul G.; (Newark, NY)
; Sabia; Robert; (Corning, NY) ; Sauer; David
C.; (Horseheads, NY) ; Shustack; Paul J.;
(Elmira, NY) ; Soni; Kamal K.; (Painted Post,
NY) |
Correspondence
Address: |
CORNING INCORPORATED
SP-TI-3-1
CORNING
NY
14831
US
|
Family ID: |
32595067 |
Appl. No.: |
11/805361 |
Filed: |
May 24, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10703800 |
Nov 7, 2003 |
7256221 |
|
|
11805361 |
May 24, 2007 |
|
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60424958 |
Nov 7, 2002 |
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Current U.S.
Class: |
522/34 ; 522/1;
522/158; 522/159; 522/161; 522/33; 522/45; 522/63; 522/65; 522/68;
522/70 |
Current CPC
Class: |
C08C 19/02 20130101;
C08F 279/02 20130101; C08K 5/0025 20130101; C08K 3/013 20180101;
C08J 3/28 20130101; C08K 3/013 20180101; C08F 290/048 20130101;
C08K 5/0025 20130101; C08F 255/02 20130101; C08L 83/04 20130101;
C08L 15/00 20130101 |
Class at
Publication: |
522/034 ;
522/001; 522/158; 522/159; 522/161; 522/033; 522/045; 522/063;
522/065; 522/068; 522/070 |
International
Class: |
C08F 2/46 20060101
C08F002/46; C08J 3/28 20060101 C08J003/28 |
Claims
1-12. (canceled)
13. A device comprising a cured composition of matter as an
adhesive or sealant material, the composition of matter consisting
essentially of a reaction product of (i) a photo or electron beam
curable material component comprising a material having the
backbone of a completely or substantially completely hydrogenated
hydrocarbon based rubber material, which is completely or
substantially free of carbon-carbon double and triple bonds, and
bears at least one photo or electron beam polymerizable terminal or
pendant group; (ii) a photoinitiator/photosensitizer component
having essentially no volatility at room temperature and also
yielding photoproducts after exposure to actinic radiation that
have minimal or no volatility at room temperature; (iii) an
optional viscosity adjustment component that is either
homopolymerizable or is capable of copolymerizing with the photo or
electron beam curable material component of (i); and (iv) an
optional inert filler, wherein the composition of matter, when
cured, has a low outgassing rate such that it passes the
ASTM-E-595-93 (1999) test and has a low outgassing rate when
exposed to ultraviolet radiation having a wavelength less than or
equal to about 248 nm.
14. A device in accordance with claim 13 which is a lithographic
device involving using deep and/or vacuum ultraviolet
irradiation.
15. A device in accordance with claim 14 comprising the cured
composition of matter as lens potting material.
16. A device in accordance with claim 14 wherein the wavelength of
the lithographic radiation is approximately 157 nm or shorter.
17. A device in accordance with claim 14, wherein the lens material
is doped or undoped high purity fused silica or crystalline
CaF.sub.2, optionally coated with antireflective material selected
from the group consisting of: magnesium fluoride, aluminum
fluoride, calcium fluoride, gadolinium fluoride, thorium fluoride,
lanthanum fluoride, yttrium fluoride, neodymium fluoride,
dysprosium fluoride, sodium aluminum fluoride, alumina, silica,
fluorine-containing silica, hafnia, scandium oxide, thorium oxide,
zirconia, yttria, and compatible combinations thereof.
18. The device according to claim 13, wherein the photo or electron
beam curable material component of (i) is functionalized by at
least one polymerizable terminal or pendant group selected from the
group consisting of: acrylate, methacrylate, acrylamide, maleimide,
thioacrylate, thiomethacrylate, vinyl sulfide, itaconate,
crotonate, styrene and N-vinyl amide, hydroxyl, thiol, oxetane,
episulfide, vinyl ether, propenyl ether, allyl ether, and
compatible mixtures and/or combinations thereof.
19. The device according to claim 13, wherein the composition of
matter is essentially free of silicone.
20. The device according to claim 13, wherein the photo or electron
beam curable material component of (i) comprises a functionalized
material bearing at least one photo or electron beam polymerizable
terminal or pendant group selected from the group consisting of:
polybutadiene, polyisoprene, polyethylene propylene rubber and
combinations thereof, which material comprises a backbone that is
completely hydrogenated or substantially completely hydrogenated
and completely or substantially completely free of carbon-carbon
double and triple bonds.
21. The device according to claim 23, wherein the photo or electron
beam curable material component of (i) is functionalized by at
least one polymerizable terminal or pendant group selected from the
group consisting of: acrylate, methacrylate, acrylamide, maleimide,
thioacrylate, thiomethacrylate, vinyl sulfide, itaconate,
crotonate, styrene and N-vinyl amide, hydroxyl, thiol, epoxy,
oxetane, episulfide, vinyl ether, propenyl ether, allyl ether, and
compatible mixtures and/or combinations thereof.
22. The device according to claim 24, wherein the photo or electron
beam curable material component of (i) is functionalized by at
least one polymerizable terminal or pendant group selected from the
group consisting of: epoxy, acrylate and methacrylate.
23. The device according to claim 13, wherein the
photoinitiator/photosensitizer is selected from the group
consisting of the following compounds and/or mixtures in purified
and/or diluted form: oligo
[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]; oligo
[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], diluted
in tripropylene glycol diacrylate (25% TPGDA);
1-[4-(4-benzoylphenylsulfonyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)-
propan-1-one; bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide;
2-benzyl-2-N,N-dimethylamino-1-(4-morpholino-phenyl)-1-butanone;
bis 5-(2,4-cyclopentadien-1-yl) bis(2,6-difluoro-3
-(1H-pyrrol-1-yl)phenyl)titanium; bis
(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide;
2-oxepanone, homopolymer,
2-[[4-[2-methyl-2-(4-morpholinyl)-1-oxopropyl]phenyl]thio]ethyl
ester; mixture of 2-isopropylthioxanthone and
4-isopropylthioxanthone;
1,3-dimethyl-2-hydroxy-9H-thioxanthen-9-one, 2-ethylhexyl ester;
4,4'-bis(methylethylamino)benzophenone;
4,4'-bis(isopropylphenoxy)benzophenone; 4-benzoyl-4'-methyldiphenyl
sulfide; 2-chloro-thioxanthone; 1-chloro-4-propoxythioxanthone;
2,4-diethylthioxanthone; poly[oxy(methyl-1,2-ethanediyl)],
.alpha.-[4-(dimethylamino)benzoyl-.omega.-butoxy-;
2,2'-bis-(2-chlorophenyl)-4,5,4',5'-tetraphenyl-2'H-<1,2'>biimidazo-
lyl; (tolylcumyl)iodonium tetrakis(pentafluorophenyl) borate;
[4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoro
antimonate; mixture of bis(4-dodecylphenyl)iodonium
hexafluoroantimonate, isopropylthioxanthone, and C12+C14
alkylglycidyl ethers; mixture of bis(4-dodecylphenyl)iodonium
hexafluoroantimonate and C12+C14 alkylglycidyl ethers;
phenyl-4-octyloxyphenyl iodonium hexafluoro antimonate; mixture of
triaryl sulfonium hexafluoroantimonate salts; mixture of triaryl
sulfonium hexafluorophosphate salts; perylene; anthracene;
1,2-benzanthracene; 9-n-butoxyanthracene; 9,10-di-n-butoxy
anthracene; 9,10-di-n-propoxy anthracene; 9,10-diethoxy anthracene;
anthrone; pyrene; 2-ethyl-9,10-dimethoxy anthracene;
2,5-diphenyl-1,3,4-oxadiazole; diphenyl anthracene;
9,10-dimethylanthracene; 1,3-diphenyl-2-pyrazoline;
1,3-diphenylisobenzofuran; N,N,N',N'-tetraphenyl benzidine; and
NN,N',N'-tetraphenyl phenylene diamine; and compatible mixtures
thereof and/or compatible combinations thereof.
24. The device according to claim 13, wherein the inert filler is
an inorganic filler selected from the group consisting of alumina,
crystobalite, aluminum trihydroxide, talc, feldspar, calcium
carbonate, mica, clay, wallastonite, nepeleline syenite, silica,
and compatible mixtures thereof and compatible combinations
thereof.
25. The device according to claim 13, wherein the cured composition
of matter is obtained by exposing the composition of claim 1 to
visible light, ultraviolet light ,or electron beam, and wherein the
cured composition of matter has a low modulus ranging from 25 to
10,000 psi (1.7.times.10.sup.5to 6.8.times.10.sup.7 Pa).
26. The device according to claim 28, wherein the cured composition
of matter has a Tg of equal to or lower than 25.degree. C.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority of U.S. provisional patent
application serial No. 60/424,958, filed on Nov. 7, 2002, entitled
"Low Outgassing Photo or Electron Beam Curable Rubbery Polymer
Material," by Paul J. Shustack, the disclosure of which is
incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to UV, visible light or
electron beam curable, rubbery material, preparation thereof and
device comprising the same. In particular, the present invention
relates to UV, visible light or electron beam curable rubbery
material that after being cured exhibits exceedingly low outgassing
of volatile organic materials, as well as preparation thereof and
device comprising the same. The present invention is useful, for
example, as an adhesive, sealant, or lens-potting material.
BACKGROUND OF THE INVENTION
[0003] There are a number of applications where it is necessary to
bond materials together using adhesives and it is undesirable for
the adhesive to give off any volatile organic materials after cure.
The process of evolving volatile organic materials after cure is
often called outgassing or offgassing. Examples of such
applications are in the area of food packaging where the outgassed
compounds can impart an off-taste to the packaged food material. In
the area of optics and photonics, outgassed compounds can condense
on optical surfaces and negatively affect the transmission of
light.
[0004] For many adhesive or lens potting applications, it is
necessary to bond together materials (substrates) of different
coefficients of thermal expansion. In these applications, the
adhesive or potting material must allow for the expansion and
contraction of the two different substrates as the temperature
changes yet still maintain the adhesion of the two substrates
together. This requires the use of a soft, low modulus, low T.sub.g
rubbery type material. The ability to formulate materials that cure
to soft, compliant, rubber-like solids and yet still have low
outgassing after cure is very difficult. This is especially true if
the cured material also has to have excellent thermal, oxidative
and hydrolytic stability.
[0005] Many room temperature vulcanized (RTV) silicone materials
cure to soft, compliant rubber-like solids that have good thermal,
oxidative and hydrolytic stability but they still evolve an
unacceptable amount of volatiles after cure. The outgassed products
of the RTV silicones are usually low molecular weight, sometimes
cyclic, siloxanes. These materials are particularly problematic
because if they condense on surfaces, they are difficult to remove
due to their very low surface tension.
[0006] Other materials often considered are polysulfides,
polyurethanes, and hydrocarbon rubbers like polybutadiene,
polyisoprene, etc. These products do not possess sufficient
thermal, oxidative and hydrolytic stability for applications where
the rubbery material must remain rubbery throughout its entire
lifetime which may be as long as 30 years. Such applications are in
the optics and photonics area where in order to simulate 30 year
lifetime, materials are subjected to various accelerated aging
tests like exposure to conditions of 85.degree. C. and 85% RH for a
minimum of 500 hours and up to as long as 2000 hours.
[0007] It is also advantageous for the material to be curable with
actinic radiation such as UV or visible light or an electron beam.
This enables the material to be applied as a liquid, then optical
alignments, or other positional adjustments can be made. When the
adherends are in their optimized position, the actinic radiation
can be turned on which cures the materials quickly (within seconds
or minutes) and with minimal amount of heat. This process retains
the delicate alignment of the adherends.
[0008] Engineering solutions have been proposed to eliminate or
mitigate the outgassed products from adhesives. These involve novel
joint designs that allow for elimination of the outgassed materials
from the adhesive into non-sensitive areas (JP 2001155855 and JP
2002106719). In another case, the surface of the adhesive material
is coated with an impervious inorganic layer that seals in possible
outgassed products (US2001028062). Other methods involve heat
and/or vacuum treatments of the cured adhesive to remove possible
outgassed products prior to final assembly of the device. All of
these methods require extra steps that are unnecessary if a true
low outgassing adhesive, sealant, or potting compound were
available.
[0009] JP 2002146230 by H. Kawakami et al. describes an adhesive
composition that is for semiconductor-mounted circuit boards and
devices therewith. This composition gives a B-stage adhesive film
containing less volatile components. However, the composition is
not UV curable, contains MEK solvent, and is based on bisphenol A
epoxy and phenolic resins which require heat to cure and cure to
hard, non-flexible, thermoset polymers.
[0010] E. A. Boulter et al. claims zero volatile release from their
high service temperature polyether amide thermoset resins. These
materials are not UV curable and require a cure schedule of 1 hour
at 177.degree. C. followed by a postcure at 225.degree. C. The
final cured properties resemble that of cured bisphenol A type
epoxies. See E. A. Boulter, M. Cohen, M. L. Deviney, Proceedings of
the Electrical/Electronics Insulation Conference (1997), 23.sup.rd,
249-53.
[0011] JP 2001164737 by I. Tanaka et al. describes using low
out-gas adhesives to make floor sheets useful for clean rooms. The
adhesives are of the two component epoxy resin-polyamideamine
class. Such materials require the mixing of the two parts (an extra
manufacturing step), are not photocurable, and cure to form
polymers that are not low T.sub.g rubbers.
[0012] JP 2001057065 by K. Fukuda et al. describes sealant
compositions for computer hard disc drives that claim no gas
volatilization, good sealability and adhesive strength. EP302620 by
G. M. Vanhaeren describes a crosslinkable hot-melt adhesive
containing a polyol and a blocked isocyanate that provides a
flexible heat-resistant bond without forming volatiles. However,
both of the above materials must be applied as hot melts and the
high temperatures involved would negatively effect the delicate
alignment required for many optical devices.
[0013] R. C. Benson et al. and C. T. Mooney et al. investigated the
measurement of volatile organic species that evolve during cure and
after post-cure processing of epoxy or polyimide based die attach
adhesives. Similar studies were performed by R. C. Benson et al. on
adhesives for microelectronics. These formulations are not
photocurable and also do not cure to the soft rubbery type polymers
required for the application. See R. C. Benson, T. E. Phillips, N.
DeHaas, Proc.-Electron. Compon, Conf. (1989), 39.sup.th, 301-8. See
also R. C. Benson, T. E. Phillips, N. DeHaas, M. Bonneau, Int.
SAMPE Electron, Conf. (1990), 4 (Electorn). Mater.-Our Future),
267-81. See also C. T. Mooney, J. C. Bolger, Natl. SAMPE Symp.
Exhib., [Proc.], (1984), 29.sup.th (Technol. Vectors), 639-50.
[0014] R. Leoni describes adhesives that have very low emissions of
volatile organic compounds. Such adhesives are high tack, contact
adhesives intended for floor coverings, tiles, carpets, vinyl
sheeting, etc. These materials are not photocurable and are not
suitable for this application due to their permanent tackiness. See
R. Leoni; FATlPEC Congress (2000), 25.sup.th (Vol. 1), 253-265.
[0015] J. Kuczynski studied the possibility of eliminating the
outgassing from UV curable adhesives. Such outgassed products were
shown to corrode thin film magnetic discs. The volatility of the
corrosive species was dependent on the adhesive's glass transition
temperature which varied linearly with flexibilizer concentration.
Thermogravimetric analysis revealed that outgassing was reduced an
order of magnitude in adhesives containing reduced concentrations
of polycaprolactone based flexibilizer. See J. Kuczynski, J. of
Adhesion (1996), 56 (1-4), 107-119. For the current application, it
is desirable to simultaneously have a low T.sub.g and low
outgassing. Also, polycaprolactone type materials are undesirable
due to their inherent hydrolytic instability.
[0016] Finally, JP 2001163931 by Y. Arai and T. Nemoto describes
photocurable sealing compositions generating a reduced amount of
volatile gas for electronic devices. Such compositions are based on
a high MW (.about.50,000) urethane (meth)acrylate synthesized from
a polypropylene glycol extended bisphenol A diol,
tetrahydrofurfuryl acrylate, and phenoxy ethyl acrylate. Such
compositions would not have the outstanding thermal and oxidative
stability or the higher, inherent hydrophobicity of the present
invention.
[0017] There remains a genuine need of an adhesive material that is
photo or electron beam curable, and that upon being cured forms a
material with low outgassing rate, low modulus and low T.sub.g that
is suitable for use in, inter alia, the optics area.
SUMMARY OF THE INVENTION
[0018] In a first aspect, the present invention provides a
composition of matter consisting essentially of a mixture, blend
and/or reaction product of: [0019] (i) a photo or electron beam
curable material component based on a completely or substantially
completely hydrogenated hydrocarbon based rubber material
completely or substantially free of carbon-carbon double and triple
bonds; [0020] (ii) a photoinitiator/photosensitizer component
having essentially no volatility at room temperature and also yield
photoproducts after exposure to actinic radiation that have minimal
or no volatility at room temperature; [0021] (iii) an optional
viscosity adjustment component that is either homopolymerizable or
is capable of copolymerizing with the photo or electron beam
curable material component of (i); and [0022] (iv) an optional
inert filler.
[0023] In a second aspect of the present invention, it is provided
a process for producing a composition of matter having low
outgassing rate and low mudulus, comprising the following steps
of:
[0024] (A) providing a completely or substantially completely
hydrogenated hydrocarbon-based rubber material (i) completely or
substantially completely free of carbon-carbon double bond and
triple bond having terminal and/or pendant groups that are photo
and/or electron beam polymerizable;
[0025] (B) mixing the material (i) with a
photoinitiator/photosensitizer (ii) having essentially no
volatility at room temperature and also yielding photoproducts
after exposure to actinic radiation that have minimal or no
volatility at room temperature; (iii) an optional viscosity
adjustment component that is either homopolymerizable or is capable
of copolymerizing with material (i); and (iv) an optional inert
filler;
[0026] (C) curing the mixture resulting from step (B) by visible
light, UV light or electron beam to form a composition of matter
having low outgassing rate and low modulus.
[0027] According to an embodiment of the process of the present
invention, the step (A) includes the following steps (A1) and
(A2):
[0028] (A1) providing a completely or substantially completely
hydrogenated hydrocarbon-based rubber material (i') completely or
substantially completely free of carbon-carbon double bond and
triple bond having reactive terminal and/or pendant groups;
[0029] (A2) modifying the rubberzmaterial (i') into material (i) by
introducing photo and/or electron beam polymerizable terminal
and/or pendant groups to the rubber material (i') by allowing the
reactive terminal and/or pendant groups of (i') to react with
agents having the photo and/or electron beam polymerizable
groups.
[0030] Preferably, in the composition of matter of the present
invention, the photo or electron beam curable material component of
(i) is a functionalized material selected from the group consisting
of: polybutadiene, polyisoprene, polyethylene propylene rubber and
combinations thereof, said material being completely hydrogenated
or substantially completely hydrogenated and free or substantially
free of carbon-carbon double and triple bonds. Preferably, the
photo or electron beam curable material component of (i) is
functionalized by at least one polymerizable terminal or pendant
group selected from: acrylate, methacrylate, acrylamide, maleimide,
thioacrylate, thiomethacrylate, vinyl sulfide, itaconate,
crotonate, styrene and N-vinyl amide, hydroxyl, thiol, epoxy,
oxetane, episulfide, vinyl ether, propenyl ether, allyl ether, and
compatible mixtures and/or combinations thereof. Most preferably,
the photo or electron beam curable material component of (i) is
functionalized by at least one polymerizable terminal or pendant
group selected from acrylate, methacrylate and epoxy.
[0031] The composition of matter of the present invention after
exposure to actinic radiation or electron beam cures to a soft,
rubbery polymer that exhibits an exceedingly low amount of
outgassing of volatile organic materials. Such material is useful
as an adhesive, sealant, or lens-potting compound. Such cured
material constitutes part of the subject matter of the present
invention. The cured material has preferably a low modulus and a
low T.sub.g of lower or equal to 25.degree. C.
[0032] The composition of matter of the present invention can be
used as an adhesive or sealant. Such use can be advantageously in
applications where low outgassing of the adhesive is required. For
example, the composition of matter of the present invention can be
used in clean rooms. Preferably, the composition of matter of the
present invention is used in devices containing elements susceptive
and sensitive to outgassed species from the materials, such as
lenses used in deep and vacuum ultraviolet photolithography
involving using UV radiation having wavelength of, for example, 248
nm or shorter. The composition of matter is particularly
advantageous for use in connection with 157 nm photolithography as
lens potting materials owing to its low outgassing even when
exposed to 157 nm irradiation.
[0033] Thus accordingly, a third aspect of the present invention is
concerned with a device comprising the cured composition of matter
of the present invention as an adhesive or sealant. The device is
advantageously a lithographic device involving using deep or vacuum
ultraviolet radiation. The lithographic radiation of the device can
have a wavelength as low as 157 nm, and even shorter. The cured
composition of matter of the present invention is advantageously
used as lens potting material in the lithographic device. The lens
may be made of, for example, doped or undoped high purity fused
silica, or crystalline CaF.sub.2 optionally coated with
antireflective coatings.
[0034] Additional features and advantages of the invention will be
set forth in the detailed description which follows, and in part
will be readily apparent to those skilled in the art from the
description or recognized by practicing the invention as described
in the written description and claims hereof, as well as the
appended drawings.
[0035] It is to be understood that the foregoing general
description and the following detailed description are merely
exemplary of the invention, and are intended to provide an overview
or framework to understanding the nature and character of the
invention as it is claimed.
[0036] The accompanying drawings are included to provide a further
understanding of the invention, and are incorporated in and
constitute a part of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] In the accompanying drawings,
[0038] FIG. 1 is a schematic illustration of the cross-section of a
lens element potted with the polymer lens-potting material of the
present invention.
[0039] FIG. 2 is a schematic illustration of the cross-section of a
lens element potted with the polymer material of the present
invention with a layer of the polymer lens-potting material of the
present invention applied on one surface of the lens.
[0040] FIG. 3 is a schematic illustration of the cross-section of
three stacked lens elements potted with the polymer lens-potting
material of the present invention.
[0041] FIG. 4 is a schematic illustration of the slant view of the
three stacked lens elements potted with the polymer lens-potting
material of the present invention as illustrated in FIG. 3.
[0042] FIG. 5 is a schematic illustration of the apparatus set-up
for testing the outgassing of the polymer lens-potting material of
the present invention using the stacked lens elements illustrated
in FIGS. 3 and 4.
[0043] FIG. 6 is schematic illustration of the cross-section of the
stacked lens elements in FIG. 5 potted with the polymer
lens-potting material of the present invention during the test for
outgassing.
[0044] FIG. 7 is a typical energy decay curve of a 157 nm laser
source used in the apparatus set-up for testing the outgassing of
the lens-potting material of the present invention as illustrated
in FIG. 5.
DETAILED DESCRIPTION OF THE INVENTION
[0045] The composition of matter of the present invention contains
as a first component a photo or electron beam (EB) curable material
based on a completely or substantially hydrogenated hydrocarbon
based rubber. The rubber can be based on, for example,
polybutadiene, polyisoprene, polyethylene propylene rubber (EPR),
and combinations thereof, and the like. The hydrocarbon chain of
such rubber must be completely or substantially free of
carbon-carbon double or triple bonds. Normally, this is achieved by
hydrogenation of the rubber backbone. The hydrogenated rubber
materials are functionalized with a group that renders the rubber
molecules polymerizable. Such polymerization must occur in the
presence of actinic radiation or electron beam. A
photoinitiator/photosensitizer may be necessary to initiate said
polymerization. As used herein, the term
"photoiniator/photosensitizer" means a photoiniating system for
photo or electron beam polymerization comprised of one or more
photoiniators and optionally one or more photosensitizers. The
polymerizable group on the hydrogenated rubber may be terminal or
pendant. The group may be free radically or cationically
polymerizable. Examples of free radically polymerizable groups are,
but not limited to, acrylate, methacrylate, acrylamide, maleimide,
thioacrylate, thiomethacraylate, vinyl sulfide, itaconate,
crotonate, styrene, and N-vinyl amides, and the like. Examples of
cationically polymerizable groups include, but are not limited to:
epoxy, oxetane, episulfide, vinyl ether, propenyl ether, allyl
ether, and the like. The thiol functional group is also useful
especially if stoichiometrically balanced with an ene functional
material in the composition as in the well known thiolene
photopolymerization. The preferred functional groups are epoxy,
acrylate, and methacrylate.
[0046] The hydrogenated rubber, if initially functionalized with
hydroxyl, amino, or thiol groups, can be first reacted with an
excess of a di- or triisocyanate functional compound to form the
corresponding urethane, urea, or thiourethane compound. Then the
material can be end-capped by reacting it with a hydroxyl
functional molecule that also has a free radically or cationically
polymerizable group (e.g. hydroxyethyl acrylate, hydroxybutyl vinyl
ether, etc). This type of functionalization of the hydrogenated
rubber results in a urethane, urea, or thiourethane material with a
hydrogenated rubber backbone and end-capped with free radical or
cationically polymerizable functional groups.
[0047] The functionalized hydrogenated rubber material, if a liquid
of an acceptable viscosity for the desired application, can be
mixed directly with the proper non-volatile
photoinitiator/photosensitizer and photocured. If viscosity
adjustment is necessary, any copolymerizable or simultaneously
polymerizable component may be used. This component must be
compatible with the hydrogenated rubber material. This component
must not generate detrimental amount of volatile organic compounds
when exposed to UV irradiation when the composition is being cured
or used.
[0048] If an electron beam is used to induce the polymerization, a
photoinitator is only necessary if cationic polymerization is
desired. For UV or visible light photocure, a
photoinitiator/photosensitizer is necessary. The
photoinitiator/photosensitizer component must be non-volatile and
also not yield photoproducts that are volatile. Examples of
commercially available free radical photoinitiators are but not
limited to: Cyracure 6974, Cyracure 6976, Cyracure 6990 and
Cyracure 6992 available from Dow Chemical; Esacure KIP 150, Esacure
KIP 75 LT and Esacure 1001 available from Lamberti S.p.A; Irgacure
819, 369, 784; CGI 113, 124, 403, and 754 from Ciba Geigy Chemicals
Corp.; Chivacure 3482 from Chitec Chemical Co.; ITX, LTX, MEAB and
IPPBP from Albermarle Corp.; and BMDS, CTX, CPTX, DETX, and PDA
from Aceto Corp. Suitable cationic photoinitiators are but not
limited to Rhodorsil 2074 from Rhodia Inc., Sarcat CD-1012, from
Sartomer Co., and UV9380C, UV9385C, UV9390C, and UV9392C from
General Electric Co. The following compounds, mixtures and
compatible combinations thereof, in purified or diluted versions,
may be advantageously used as the photoinitiators in the present
invention: [0049] oligo
[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]; [0050]
oligo [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone],
diluted in tripropylene glycol diacrylate (25% TPGDA); [0051]
1-[4-(4-benzoylphenylsulfonyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)-
propan-1-one; [0052] bis(2,4,6-trimethylbenzoyl)-phenyl phosphine
oxide; [0053]
2-benzyl-2-N,N-dimethylamino-1-(4-morpholino-phenyl)-1-butanone;
[0054] bis n.sup.5-(2,4-cyclopentadien-1-yl)
bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium; [0055] bis
(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide;
[0056] 2-oxepanone, homopolymer,
2-[[4-[2-methyl-2-(4-morpholinyl)-1-oxopropyl]phenyl]thio]ethyl
ester; [0057] mixture of 2-isopropylthioxanthone and
4-isopropylthioxanthone; [0058]
1,3-dimethyl-2-hydroxy-9H-thioxanthen-9-one, 2-ethylhexyl ester;
[0059] 4,4'-bis(methylethylamino)benzophenone; [0060]
4,4'-bis(isopropylphenoxy)benzophenone; [0061]
4-benzoyl-4'-methyldiphenyl sulfide; [0062] 2-chloro-thioxanthone;
[0063] 1 -chloro-4-propoxythioxanthone; [0064]
2,4-diethylthioxanthone; [0065] poly[oxy(methyl-1,2-ethanediyl)],
.alpha.-[4-(dimethylamino)benzoyl-.omega.-butoxy-; [0066]
2,2'-bis-(2-chlorophenyl)-4,5,4',5'-tetraphenyl-2'H-<1,2'>biimidazo-
lyl; [0067] (tolylcumyl)iodonium tetrakis(pentafluorophenyl)
borate; [0068] [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium
hexafluoro antimonate; [0069] mixture of
bis(4-dodecylphenyl)iodonium hexafluoroantimonate,
isopropylthioxanthone, and C.sub.12+C.sub.14 alkylglycidyl ethers;
[0070] mixture of bis(4-dodecylphenyl)iodonium hexafluoroantimonate
and C.sub.12+C.sub.14 alkylglycidyl ethers; [0071]
phenyl-4-octyloxyphenyl iodonium hexafluoro antimonite; [0072]
mixture of triaryl sulfonium hexafluoroantimonate salts; and [0073]
mixture of triaryl sulfonium hexafluorophosphate salts.
[0074] The following photosensitizers may be used as well in the
composition of matter of the present invention if desired: [0075]
perylene; [0076] anthracene; [0077] 1,2-benzanthracene; [0078]
9-n-butoxyanthracene; [0079] 9,10-di-n-butoxy anthracene; [0080]
9,10-di-n-propoxy anthracene; [0081] 9,10-diethoxy anthracene;
[0082] anthrone; [0083] pyrene; [0084] 2-ethyl-9,10-dimethoxy
anthracene; [0085] 2,5-diphenyl-1,3 ,4-oxadiazole; [0086] diphenyl
anthracene; [0087] 9,10-dimethylanthracene; [0088]
1,3-diphenyl-2-pyrazoline; [0089] 1,3-diphenylisobenzofuran; [0090]
N,N,N',N'-tetraphenyl benzidine; and [0091] N,N,N',N'-tetraphenyl
phenylene diamine.
[0092] It is also possible to blend the free radical polymerizable
materials with the cationically curable materials and then on
exposure to actinic radiation, both materials simultaneously
cure.
[0093] Similar to other sealants and adhesives, various inert
fillers, particularly inorganic fillers can be used in the
composition of matter of the present invention. These fillers may
be added to the composition to improve the physical properties of
the cured product, and also to modify the rheology of the uncured
materials. They can be reinforcing or non-reinforcing. Reinforcing
filler may contain surface moieties capable of strong interactions
with the cured polymer matrix. They may function to increase the
strength and modulus of the cured adhesive. Understandably they may
also alter the viscosity of the uncured composition. The extent of
such effects is dependent on factors such as filler loading,
particle size, shape, and surface chemistry. As non-limiting
examples of such fillers, mention can be made of alumina,
crystobalite, aluminum trihydroxide, talc, feldspar, calcium
carbonate, mica, clay, wallastonite, nepeleline syenite, silica,
and the like. Preferably, silica is used as the inert inorganic
filler. Preferably, these fillers are those as transparent to the
curing UV light as possible so as not to significantly inhibit the
UV curing of the composition where UV curing is used. In the case
of cationically cured formulations, the filler should be
non-alkaline so as not to inhibit the acid cure. For free radically
cured systems, the pH of the filler is not as important. The amount
of the filler used can range from 0-90%, preferably 0-75%, more
preferably 0-50%, by weight of the total composition. Particle size
of the fillers should be less than 125 .mu.m, preferably less than
50 .mu.m and more preferably less than 10 .mu.m.
[0094] The composition of matter of the present invention can be
cured by visible light, UV radiation or by electron beam. One
skilled in the art can choose the proper equipment and curing time
to fully cure the formulation having the specific composition to a
bulk material. For example, when using UV curing at 365 nm, the
composition may be advantageously fully cured within 2 hours,
preferably within 1 hour, more preferably within 30 minutes, most
preferably within 15 minutes. The curing process can be effected at
room temperature. It generally does not generate substantial heat,
and can be carried out after the uncured composition has been
applied. These advantages render the adhesive composition of the
present invention particularly suitable for attaching elements of
precision devices sensitive to high temperature.
[0095] The cured product of the composition of the present
invention advantageously has a low modulus ranging from 25 to
10,000 psi (1.7.times.10.sup.5 to 6.8.times.10.sup.7 Pa),
preferably from 50 to 5,000 psi (3.4.times.10.sup.5 to
3.4.times.10.sup.7 Pa), more preferably from 100 to 2,500 psi
(6.8.times.10.sup.5 to 1.7.times.10.sup.7 Pa).
[0096] The adhesive composition of the present invention, upon
being properly cured, is a low outgassing material at room
temperature when exposed to solar radiation or typical lighting
conditions. Therefore, a natural application of it is in clean room
and similar environment where low outgassing is preferred or
required.
[0097] Surprisingly, the present inventors have discovered adhesive
composition after cure of the present invention even does not
outgas substantially when directly exposed to high energy UV light
at wavelength as short as 157 nm for a prolonged period of time and
that the outgassed material, in their relatively small amounts, do
not tend to contaminate lithographic lens surfaces. This is
contrary to typical wisdom that chemical bonds in polyhydrocarbons
tend to break subject to the high energy of the UV photons.
[0098] As indicated supra, it is well known that the lenses used in
deep and vacuum UV photolithography, such as 193 nm and 157 um,
particularly at 157 um, contamination of the lens surface
(CaF.sub.2 lenses in 157 um lithography, for example) can reduce
the transmission of the lithographic illumination radiation and
thus is highly undesirable. Room temperature curable silicone
sealants are notorious for outgassing and strong tendency to
contaminate lens surfaces and thus cannot be directly used in these
settings.
[0099] Since the properly cured adhesive composition of the present
invention has low outgassing, even when directly exposed to the
lithographical UV radiation at wavelength as short as 157 nm, and
the outgassed species do not tend to contaminate lens surfaces, it
is ideal for use in lithographical devices at short wavelengths
such as deep and vacuum ultraviolet radiation of 248 nm or shorter.
It may be used to attach and join various components of these
devices. Particularly, it is highly advantageous to be used as lens
potting materials to securely fix the lens elements in their
housings. Those lenses may be made of high purity fused silica,
doped or undoped, or CaF.sub.2 or other materials. The lens
surfaces may be coated with antireflective coatings, such as
magnesium fluoride, aluminum fluoride, calcium fluoride, gadolinium
fluoride, thorium fluoride, lanthanum fluoride, yttrium fluoride,
neodymium fluoride, dysprosium fluoride, sodium aluminum fluoride,
alumina, silica, fluorine-containing silica, hafnia, scandium
oxide, thorium oxide, zirconia, yttria, and the like. When used as
lens potting material, the adhesive composition of the present
invention can, for example, be applied to the desired locations of
the lens element or lens housing before cure before or after the
lens element is carefully aligned. The adhesive composition is
subsequently exposed to visible or UV curing light or electron beam
for a short period of time, thereby attaching and fixing the lens
element to the housing. Such devices, especially the lithographic
devices, comprising the cured composition of matter of the present
invention, also constitute an aspect of the present invention.
[0100] The present invention is further illustrated by the
following examples, which is for illustration purpose only and
shall not be interpreted to limit the present invention as claimed
in any way.
EXAMPLES
Example 1 (the Present Invention)
[0101] An UV curable composition was prepared by mixing the
following components in the following weight percentages:
TABLE-US-00001 88.00% Kraton Liquid Polymer L-207 10.00%
1,12-dodecanediol dimethacrylate 0.75% Rhodorsil Photoinitiator
2074 1.00% Esacure KIP 150 from Lamberti SpA 0.25%
Isopropylthioxanthone
[0102] Kraton Liquid Polymer L-207 is a hetero-telechelic polymer
from Kraton Polymers consisting of a hydrogenated polybutadiene
polymer that has a primary hydroxyl finctionality on one end and an
epoxidized isoprene functionality on the other end. The
1,12-dodecanediol dimethacrylate is Mhromomer BM-721 from Rohm
America. Rhodorsil Photoinitiator 2074 is (tolylcumyl) iodonium
tetrakis (pentafluorophenyl) borate available from Rhodia Inc.
Esacure KIP 150 is oligo [2-hydroxy-2-methyl-1-[4-(1-methyl vinyl)
phenyl]propane] available from Lamberti SpA. The
isopropylthioxanthone is available from Albermarle Corp.
[0103] The viscous liquid mixture was drawn down on a glass plate
using a 6 mil (1.52.times.10.sup.-2 mm) Bird applicator. The glass
plate was placed into an aluminum purge box equipped with a UV
transparent lid and a nitrogen inlet. The box was purged with
nitrogen for one minute. Then a UV light (Xenon Model RC-500B)
situated at 10 inches (25 cm) directly above the purge box was
turned on. The sample was exposed for 10 minutes to the UV
(.about.3000 mJ/cm.sup.2) with continuous nitrogen purging. After 4
days at room temperature the 6 mil (1.52.times.10.sup.-2 mm) film
was removed from the glass and tested for outgassing using a UV
Gerstel Thermal Desorption/GCMS. For this technique, a 25 mg to 30
mg film sample was placed in an empty 7.0 inch ( 18 cm)
long.times.6.0 mm O. D. glass cartridge and outgassed at 25.degree.
C. The 25.degree. C. thermally desorbed VOC's were cryogenically
collected for 60.0 minute time period using a constant 15.0
ml/minute helium purge. The outgassed volatiles were identified
using GCMS with the following instrument conditions.
[0104] GCMS Instrument Conditions:
[0105] Instrument: Hewlett Packard 5989B Gas Chromatograph Mass
Spectrometer
[0106] Carrier Gas: Helium Flow Rate 2.00 ml/minute
[0107] Tank pressure: 50 psi (3.4.times.10.sup.5 Pa)
[0108] TDS pressure gauge: 9.5 psi (6.6.times.10.sup.4 Pa)
[0109] Column: 30 M.times.0.32 mm ID, 0.5 .mu.m film DB-XLB Temp.
Max. 350.degree. C. Fused Silica Capillary
[0110] Temp. Program: 50.degree. C. hold for 5 minutes, ramp up @
10.degree. C./minute, to 300.degree. C. and hold for 5 minutes
[0111] Injection via: Gerstl TDS Thermal Desorption unit
[0112] Detector: Mass Spectrometer Detector--Electron Impact
Ionization mode
[0113] Detector: Temp.: 250.degree. C.
[0114] Injector Temp.: 275.degree. C.
[0115] Source: 200.degree. C.
[0116] Quadrupoles: 100.degree. C.
[0117] Scan Range: mass 45 to mass 450
[0118] MS ON 0.0 minute
[0119] Run time: 35.0 minutes
[0120] Sampling rate: 1.0 A/D Samples 2
[0121] Scans/second: 0.7
[0122] Noise Threshold: 100
Example 2 (Comparative Example)
[0123] A series of commercially available adhesives were cured as
recommended by their suppliers and tested for their outgassing
rates in accordance with the same procedure described in EXAMPLE 1.
The outgassing results were then compared with the outgassing rate
of the cured composition of EXAMPLE 1. Comparison results are
listed in TABLE I below. TABLE-US-00002 TABLE I Sampling time/
Total Adhesive Sample Size outgassed VOC's (.mu.g) Sylgard After 5
Days - 27.8 mg 24.98 OG 133-5 After 10 Days - 26 mg 3.51 EMCAST 714
After 9 Days - 29.5 mg 12.03 Cyberbond 4696 After 10 Days - 25.6 mg
5.00 DP-190 B/A After 7 Days - 27.9 mg 4.76 Translucent OP-4-20641
(Dymax) After 28 Days - 19.8 mg 12.52 OP-4-20647 (Dymax) After 28
days - 10.6 mg 8.80 OP-4-20655 (Dymax) Could not be analyzed
(Rubber cement consistency) EXAMPLE 1 After 4 Days - 27.5 mg
0.33
[0124] Surprisingly, the total amount of outgassed VOC's are
markedly lower for the EXAMPLE 1 composition than for all of the
commercially available adhesives.
Example 3 (Comparative Example)
[0125] In another test, a commercial room temperature vulcanizing
(RTV) silicone rubber was evaluated. RTV silicone materials, in
general, are known as low outgassing, rubbery materials (see ASTM
method D6411). This material, hereinafter referred to as SiRTV, is
listed in the NASA Reference Publication 1061 "Outgassing Data for
Selecting Spacecraft Materials" as a molding compound having a
total mass loss (TML) of 1% or less and a collected volatile
condensable materials (CVCM) of 0.10% or less. It was cured as
recommended by the supplier. The cured material was stored at room
temperature for different periods of time and then tested or
outgassing as above. The test results for SiRTV are listed in TABLE
II below: TABLE-US-00003 TABLE II Sampling Time Sample Size (mg)
Total Outgassed VOC's (.mu.g) Day #7 - 145.0 hours 25.0 3.28 Day #8
- 169.0 hours 24.5 2.53 Day #9 - 193.0 hours 27.2 1.85 Day #16 -
356.0 hours 24.7 0.87 Day #17 - 380.0 hours 24.8 0.75 Day #24 -
549.0 hours 25.1 0.09
[0126] It should be noted that SiRTV has approximately an order of
magnitude higher amount of total outgassed VOC's after 7 days than
the EXAMPLE 1 composition has after 4 days. Also, the level of
outgassed VOC's for SiRTV does not drop to below those of EXAMPLE 1
until 24 days after cure. It is also important to note that SiRTV
is not photocurable and takes 7 days at room temperature to fully
cure whereas the composition in EXAMPLE 1 fully cures in 10 minutes
at room temperature under the UV light.
Example 4 (the Present Invention)
[0127] The composition in this example demonstrates that pigments
can be added to the composition in EXAMPLE 1 to render the liquid
material more visible and allow for easier monitoring of the flow
of the potting compound before cure. Composition below is in weight
percent. TABLE-US-00004 87.92% Kraton Liquid Polymer L-207 10.00%
1,12-dodecanediol dimethacrylate 0.75% Rhodorsil 2074 1.00% Esacure
KIP 150 0.25% Isopropylthioxanthone 0.08% 9R445 (24% organic red
pigment in TMPTA paste from Penn Color Inc.) (TMTPA =
Trimethylolpropane triacrylate)
[0128] This composition was used to pot three CaF.sub.2 lens
elements into a stainless steel housing to test for outgassing on
exposure to 157 nm light. The cross-section of one potted lens
element is illustrated in FIG. 1. In FIG. 1, 101 is the stainless
steel lens housing, 103 is the CaF.sub.2 lens element, and 105 is
the lens potting material. Three lens elements potted in the same
manner were stacked to form a lens assembly. The last element in
the stack has a layer of the potting material 107 (5 mil or
1.25.times.10.sup.-2 mm thick) applied to the surface, as shown in
FIG. 2.
[0129] The potting material layer 107 on the last element was
applied to the element prior to potting. The adhesive layer was
cured in an inert environment (N.sub.2 purge) for 15 minutes. The
distance the element was from the bottom of the reflector housing
was approximately 9-10 inches (23 to 25 cm). The adhesive layer was
cured using an 80 mW/cm.sup.2 UV curing flood source. The peak
curing wavelength was 365 nm.
[0130] When potting, the elements were placed in the housing and
the adhesive (potting material) was applied. The potting material
was cured in an inert environment (N.sub.2 purge) for two 15-minute
cycles. The distance the cells were from the bottom of the
reflector housing was approximately 9-10 inches (23 to 25 cm). The
adhesive was cured using an 80 mW/cm.sup.2 UV curing flood source.
The peak curing wavelength was 365 nm. This data was obtained from
the manufacture of the UV source (Adac Model Name: Curezone 2). The
intensity was measured approximately two inches (5 cm) from the
bottom of the reflector housing. The potted elements were placed in
a nitrogen purge for 6 hours. After the purge, the cells were
placed in a vacuum for a minimum of 8 hours. Twenty-four hours
after the initial cure was completed, a secondary cure was
performed. The cure was performed in an inert environment (N.sub.2
purge) using a Xenon pulsed UV source. The Xenon unit was
configured to irradiate at 10 pulses per second. The intensity of
the pulses ensures the adhesive was irradiated through the entire
thickness. The cure time was 10 minutes at a distance of
approximately 51/2 inches (14 cm) from the bottom of the reflector
housing. The intensity of this source, as measured by the
manufacture, was 1811 W/cm.sup.2 (peak power) measured
approximately 1.25 inches (3.18 cm) from the bottom of the
reflector housing. The cells were placed in a vacuum for a minimum
of 8 hours; followed by a purge cycle of six to eight hours. The
potted elements were placed in a final purge cycle of 8 hours prior
to 157 nm exposure.
[0131] The three potted lens elements were then assembled in a
stack as depicted in FIG. 3. Note the direction of the 157 nm laser
light source and that the potting compound layer on the third lens
element was directly in the 157 nm light path. In FIG. 3, chambers
301 and 303 between the lens elements are called "Before Window"
and "After Window," respectively.
[0132] FIG. 4 shows an exterior view of the assembled cells with
the purge gas input ports 401, 403 and gas exhaust ports 405, 407.
401 and 405 are the gas input port and exhaust port to the Before
Window 301, respectively, and 403 and 407 are the gas input port
and exhaust port to the After Window 303, respectively. Thus each
chamber 301 and 303 has an independent input and exhaust port for
N.sub.2 purge.
[0133] A schematic illustration of the testing system setup is
provided in FIG. 5. In this figure, 501 is the purge box in which
the stacked lens elements 505 is placed. 503 is a fluorescing field
stop, used to control the spot size and to ensure the 157 nm laser
was operating properly. 507 and 509 are exhaust tubes connecting
with Before Window exhaust port 405 and After Window exhaust port
407, respectively. Traps 511 and 513 are installed on the exhaust
tubes 507 and 509, respectively, in order to sample the purge
exhaust gases. FIG. 6 is a schematic view of the cross-section of
the stacked lens elements for further illustration of the purging
and testing process. Upon exposure to 157 nm radiation, the
surfaces 601 and 603 of the first and second lens elements will be
analyzed for surface contamination caused by the outgassing of the
lens potting material by using ToF-SIMS (Time-of-Flight--Secondary
Ion Mass Spectroscopy).
[0134] The assembled cells were then purged with nitrogen at 15 psi
(1.0.times.10.sup.5 Pa). Purge gas from each chamber was sampled
for 48 hours at approximately 0.5 liters per minute. The laser was
configured to have a repetition rate of 100 Hz. The fluence at the
cell was 0.06 mJ/cm.sup.2, when the laser gas was fresh. A typical
gas fill would last for approximately 750 minutes or 4500000 pulses
before the pulse energy would decay. Integrated energy over one gas
fill was about 180 J/cm.sup.2. A typical energy decay curve is
displayed in FIG. 7. Each sample ran for 48 hours with four fills
during that time period at approximately the same intervals for
each sample.
[0135] Carbotrap 300 multi-bed adsorbent resin traps 511 and 513
were used to sample the atmosphere from the Before Window and After
Window of the experimental setup (see FIG. 5). The adsorbent resin
trap was assembled on the outlet port of each chamber and the
volatile organic compounds (VOC's) from the cell atmosphere were
collected on the trap as the gas passed over the adsorbent. The
adsorbent resin trap was connected directly to the cell exit port
via 1/4 inch (0.63 cm) Swagelok fitting. An external vacuum pump
was needed to achieve the correct flow because the resin bed
offered too much restriction to the box exhaust flow. The
experimental atmosphere was sampled at a flow rate of 0.5
liters/minute for 48 hours.
[0136] The adsorbent resin trap samples were run using a Gerstel
Thermal Desorption/GCMS. The VOC's were thermally desorbed from the
adsorbent resin at 325.degree. C. for 15.0 minutes in a constant
15.0 ml/minute helium purge. The outgassed VOC's were cryogenically
trapped and identified using GCMS (Gas Chromatography-Mass
Spectrometry). The detection limit of the technique is .apprxeq.500
ppt (parts per trillion) based on a 720 liter sample volume (400 ng
on column).
[0137] The total VOC concentration of outgassed products after 48
hours of 157 mn light exposure is shown in TABLE III below.
TABLE-US-00005 TABLE III Total VOC Concentration (ppb) Composition
of Before Window After Window EXAMPLE 4 (Present Invention) 2.60
3.27 EXAMPLE 5 (SiRTV) 12.10 21.87
[0138] In addition to the need for having a minimal amount of
outgassed products, the type of outgassed products is also
important. The outgassed products and their concentration for the
EXAMPLE 4 formulation is shown in TABLE IV below. TABLE-US-00006
TABLE IV VOC Concentration (ppb) VOC Name (Retention time, min)
Before Window After Window Benzene (1.86) 0.38 0.02 Toluene (3.33)
0.25 Not Detectable Isopropyl Benzene (7.88) 0.32 0.23 Iodobenzene
(13.27) 0.7 1.21 4-Iodoisopropyl benzene (15.95) 0.95 1.81
[0139] For the lens potting material of this example of the present
invention, ToF-SIMS analysis of lens surfaces 601 and 603 of all
samples showed abundant Ca.sup.+2 ion signals suggesting only
partial surface of contamination. Contamination species of the
surfaces include: silicone from handling, packaging, unclean
environment; hydrocarbons both aliphatic and aromatic; phthalates;
sodium; sulfur compounds; iodine; and chlorine. Iodine is likely
the result of the cationic photoinitiator Rhodorsil 2074 used in
the adhesive formulation. In addition, the various aromatic
hydrocarbon signals could also come from this compound and other
minor additives. No significant presence of methacrylate or epoxy
rubber was detected, which are the main constituents of the
adhesive. It appears that the iodine-containing photoinitiator was
the most dominantly outgassed species that adsorbs onto the lens
surfaces. Boron was present at ultra-trace level and it is
difficult to determine if it was outgassed from the B-containing
initiator. Silicone was detected at small levels on these samples
also even though the adhesive itself did not contain any silicone.
This observation points to the tendency of various contaminants to
adsorb onto the CaF.sub.2 surfaces. It is highly recommended
silicone contamination be avoided because of its tenacious bonding
to the surface and associated difficulty in removal.
Example 5 (Comparative Example)
[0140] In this example, SiRTV, a room temperature vulcanizing
silicone rubber described in EXAMPLE 3, supra, was used to pot
CaF.sub.2 lenses and tested for outgassing on exposure to 157 nm
radiation using the same method, equipment and procedure in
accordance with EXAMPLE 4, supra, with the exception that for
SiRTV, after the lenses were potted, SiRTV was allowed to cure for
ten days at ambient temperature (70.degree. F.) prior to any
further work. The 157 nm exposure commenced on the eleventh day.
Data of off-gassed VOC's were obtained. Total VOC concentration
data are reported in TABLE III. It was found that the VOC's from
SiRTV were cyclosiloxane hexamethyl-cyclotrisiloxane (D-3) to
hexadecamethylcyclooctasiloxane (D-8). The three cyclosiloxanes
with the highest concentration were decamethylcyclopentasiloxane
(D-5, approximately 13%) dodecamethylcyclohexasiloxane (D-6,
approximately 40%) and tetradecamethylcyclohepasiloxane (D-7,
approximately 25%). The relative siloxane concentration profile was
similar for each sample with the only difference in overall
concentration. The peak identification and associated retention
time is listed in Table V below. TABLE-US-00007 TABLE V SiRTV
Silicone adhesive VOC Concentration % 8.75 min D-4 2% 11.84 min D-5
12% 12.31 min Linear D-5 13% 14.66 min D-6 40% 17.06 min D-7 25%
19.13 min D-9 6%
[0141] These siloxane materials are particularly problematic for
lens potting. In addition, it has been found that on long term
exposure to 157 nm light, the siloxanes can decompose into
compounds that can react with the lens surface forming a permanent
layer that negatively affects lens function.
[0142] In addition to measuring outgassing, ToF-SIMS surface
analysis of the CaF.sub.2 lens surfaces 601 and 603 was conducted.
The results were as follows.
[0143] For SiRTV, all samples mounted using this silicone based
potting compound were covered with silicone to the extent that the
Ca signal from the CaF.sub.2 lens itself sample was almost
completely blanked. The spectra shows dominant ion signals from
silicone or polydimethylsiloxane (PDMS). Ion signals of Ca and F
were detected at trace levels only. Since ToF-SIMS spectra
essentially originate from the outermost monolayer, this
observation means that silicone completely covers the surface.
Silicone is a well known and useful material, however, it is also a
very common contaminant notorious for rapid spreading and difficult
removal. Silicone can polymerize and form a siloxane network. In
addition, it can bond with the CaF.sub.2 surface in a covalent
manner such as Ca--O--Si. Given its dominant migration to the
CaF.sub.2 surface, this compound is highly undesirable for use as a
CaF.sub.2 lens potting compound.
[0144] Phthalate, a common plasticizer and a ubiquitous
contaminant, was also detected on all samples. Phthalate may come
from polymeric packaging materials and from exposure to the
environment.
[0145] Sodium from handling and contamination was also detected at
trace levels.
[0146] In summary and in comparison to EXAMPLE 4, the
silicone-based adhesive SiRTV leads to significant outgassing and
completely envelopes the lens surface. In contrast, the
hydrocarbon-based lens potting material of EXAMPLE 4 causes little
outgassing. The dominant species for the latter were iodine-based
aromatic photoinitiator photoproducts. Silicone contamination
occurs even in the latter case highlighting the need for clean
conditions for preparing lens assemblies. Other contaminants
include Na, various hydrocarbons, and phthalates at minor levels
likely from the environment.
Example 6 (the Present Invention)
[0147] A lens potting material was prepared by mixing the following
materials in the following weight percentages: TABLE-US-00008
98.92% FM003-53 Hydrogenated rubber diacrylate from Designer
Molecules Inc., San Diego, CA 0.50% Irgacure 369 from Ciba Geigy
Corp., Tarrytown, NY 0.25% Isopropylthioxanthone 0.25% Speedure PDA
from Aceto Corp, Lake Success, NY 0.08% 9R445 (24% organic red
pigment in TMPTA paste from PennColor, Inc.) Speedure PDA =
poly[oxy(methyl-1,2-ethylenediyl),
.alpha.-(4-dimethylamino)benzoyl-.omega.-butoxy-] Irgacure 369 =
2-Benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone
[0148] This composition and the composition of EXAMPLE 4 were
poured into a 1 cm.times.2 cm.times.2 mm deep glass mold. The mold
was placed in a box with a UV transparent (High Purity Fused
Silica) lid and purged with nitrogen. The samples were cured with a
Xenon Model RC740 UV lamp source at 10 pulse/sec and 51/2 inches
(14 cm) height. A separate sample was cured for each of the
exposure times listed in TABLE VI below. Outgassing was evaluated
using Thermal Desorption/GCMS. TABLE-US-00009 TABLE VI Total %
Weight Loss (Calculated Wgt/Wgt) for these Exposure Times 2.0 min
4.0 min 8.0 min 16.0 min 32.0 min 64.0 min EXAM- 0.00154 0.00024
0.00038 0.00031 0.00035 0.00033 PLE 4 Com- position EXAM- 0.00192
0.00115 0.00103 0.00100 0.00046 0.00027 PLE 6 Com- position
[0149] The samples were run neat using Gerstel Thermal
Desorption/GCMS. A 80 mg to 100 mg film sample was placed in an
empty 7.0 inch (18 cm) long.times.6.0 mm O.D. Glass cartridge and
outgassed at 25.degree. C. The 25.degree. C. thermally desorbed
VOC's were cryogenically collected at 60.0 minute time period using
a constant 15.0 ml/minute helium purge. The outgassed volatiles
were identified using GCMS. Data of total weight loss were obtained
and reported in TABLE VI. Amount of outgassing is indicated by
these total weight loss data.
[0150] Note that the total outgassed products after 64.0 minutes of
UV exposure is approximately the same for both the EXAMPLE 4 and 6
compositions. From the total weight loss percentage data, it
appears that, for the composition of EXAMPLE 4, curing time longer
than 16 minutes does not alter outgassing amount significantly,
indicating that the composition was fully cured after 16 minutes of
UV exposure. However, for the composition of EXAMPLE 6, there is a
general trend that below 64 minutes curing time, the longer the
curing time, the lower the total outgassing amount.
Example 7 (the Present Invention)
[0151] TABLE-US-00010 50.00% Kraton L-207 16.00% DD-36 Dimer diol
(Jarchem Industries, Newark, NJ) 30.00% TJFS20 silica powder (4F
International Co., Gainesville, FL) 4.00% Dispersion of 5% Cyracure
6974 (Dow Chemical) in Kraton L-207 (Cyracure 6974 is a 50%
solution of mixed triarylsulfonium hexafluoroantimonate salts in
propylene carbonate from Dow Chemical.)
[0152] This composition (shown above in weight percent) was drawn
down onto a 4 inch (10 cm) diameter silicon wafer using a 6 mil
(1.52.times.10.sup.-2 mm) Bird applicator on top of 10 mil
(2.54.times.10.sup.-2 mm) thick shims to give a layer about 16 mil
(4.06.times.10.sup.-2 mm) thick. The coated silicon wafer was
placed in a box with a UV transparent (High Purity Fused Silica)
lid and purged with nitrogen. The sample was cured with a Xenon
Model RC-740 UV lamp source at 10 pulse/sec, 51/2 inches (14 cm)
height for 30 minutes. After storage in a desiccator for 48 hours,
the sample was exposed to 157 nm radiation for .about.7.5
J/cm.sup.2 at a fluence of .about.51 .mu.J/cm.sup.2 pulse at 200 Hz
for .about.12 minutes. The headspace vapors were collected and the
outgassed products were: TABLE-US-00011 82% Simple saturated
alkanes 16% Functionalized alkanes (alkenes mostly, some alcohols)
2% Aromatic compounds (benzene only)
[0153] There was no detected silicon, iodine, or sulfur compounds,
just hydrocarbons. The top few chemicals found, along with their
signal (not concentration) as a percentage of the total is listed
below. TABLE-US-00012 Pentane 24.711 Butane 23.246 Hexane 7.893
Pentanal, 3-methyl- 5.475 Heptane 4.265 Butane, 2-methyl- 4.251
Octane 3.016 1-Heptene 2.915 Benzene 2.288 Hexane, 3-methyl- 1.815
Pentane, 3-methyl- 1.744 Tridecane 1.419
Cis-1-Butyl-2-methylcyclopropane 1.374 Nonane 1.322 Hexane,
2,4-dimethyl- 1.298 Undecane, 6-methyl- 1.11
[0154] This example indicates that inert inorganic fillers can be
added into the adhesive composition of the present invention while
still attaining low outgassing.
Example 8 (the Present Invention)
[0155] TABLE-US-00013 58.00% Kraton L-207 8.00% DD-36 Dimer diol
30.00% TJFS05 silica powder 4.00% Dispersion of 5% Cyracure 6974 in
Kraton L-207
[0156] The above composition (in weight percent) was UV cured as in
EXAMPLE 4. The sample was then subjected to ASTM-E-595-93 (1999)
Standard Test Method for Total Mass Loss and Collected Volatile
Condensable Materials from Outgassing in a Vacuum Environment. The
results show the above UV cured composition passes all three of the
specifications of this test. TABLE-US-00014 TABLE VII EXAMPLE 8
Specification % Total Mass Loss 0.652% <1.00% % Collected
Volatile 0.096% <0.10% Condensable Materials % Water Vapor
Regain 0.080% <0.20%
[0157] It will be apparent to those skilled in the art that various
modifications and alterations can be made to the present invention
without departing from the scope and spirit of the invention. Thus,
it is intended that the present invention cover the modifications
and variations of this invention provided they come within the
scope of the appended claims and their equivalents.
* * * * *