Note: Descriptions are shown in the official language in which they were submitted.
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PIIO TOrOL~rVn~,R~7,~110 N EUEA CIIO NS INnDUCED BY
CEnE~nLU~ nESCENC~E
Field of the Invention
This h.~ tioll relates to photopolyllleli~alion rç.~ction~ More specifically,
this invention relates to photopolyllwl~&Lion reactione that are initi~ted by
ele~ .. 7.~.. el;c rn~ ti~n emitted from a c~ .l... ..n~sc~ reaction.
Ba~ kDround
Applir~tiQns of rh~mil~ .nescP~-ce as a light source are known in the art.
F.Y~mrlPe include optical display devices (US 5,222,797), as a light source for
endQscQpic e~ n (US 5,179,938), as a lighting device for emergcne;es or in
the absence of ~lec,triçity (US 5,043,851), and in fishing lures (US 5,190,366).U.S. Patent No. 3,698,391 to Ulman desc~ es a mPtho~l for chPmi~ y
p. photochPmi~l re~ctiQne in the ~hse~ e of an P,~tern~l light source.
Chpm~ escp~l rç~ctione and electroçhPmil~ il-escç~.l reactions are descl;l ed
for carrying out various re~ctione in~ rli~ cyclo~ ition~ isomerizations, and
20 lc~lilnp~ Yields are des.;lil~ed in the single digits, and no disdosure is
provided related to tne p.~&~Lion of polymers.
-ry of the I~
The present invention relates to a method for carrying out a polyllleli~alion
25 reaction. In this method, a photopoly...~. .,- hle material is exposed to
ele~llu~ p~-1;c radiation emitted by a çh~.. l.. ;~-~sc~ reaction, thereby
phulopolymeri7;ng the photopolymeli~le material.
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Detailed D~r ;I,tion
For pul~oses ofthe present invention, ç~lPmil~ escP~-~e is the emission of
elecllo..~AgnPtic radiation of wa~cl~Lh between about 250-1400 nanometers by
means of a chemical reaction. Chsn~ ..;nesce--~e is defined as the emission of light,
from at ieast one mf lecut~; by means of a ~hPm;~.~i re~ction A cl~ .esce-.reaction results in the form~tion of an excited state molecule that is capable of
direct light çmi~ion or capable of energy L-~ sf~r to at least one other molecllle that
emits light or gene,aLes a plloLoiniLialol. Plerc..cd wa~clength ranges for light
emission are in the W range (250~00 nm), the visible range (400-800), the near
0 IR range (700-1400).
Che...il~ escent light sources have .ei~nific~nt advantages over traditional
electric light sources that are used for photl~in;~ ecl reaction.~. For example,~tl~ .ccf-.nt sources may have low cost, are portable, and are safe to use in
specific enviro.-...~ such as under water or in places where fl~mm~ble materials1~ make other light sources dangerous. ,A~ iti~?n~ly" hpmihlmine~cpnt light sources
may be provided in a flexible specified shape or configuration that provides light in
envholm~enLs that are difficult to access using traditional light sources. When
provided as a liquid, gel, or paste, the ~hemilllminesc~nt material will co"ro,-,. to
any ~.... .....n~jl . y.
The polyl"~ aLion reaction of the present invention is carried out by first
providing a photopolymerizable composition, so that upon exposure of the
colll~osiLioll to an z~,c,p,iale cle~ o...~ etic ladiaLiol- source, the Gl- ..i.,i~l
species ofthe compo~ition will undelgo a polymerization reaction to form a high
(e.g. greater than about 10,000 molecular weight) molecllt~r weight compound.
2s P~cr~l~bly, the resl-hin~ polymer is cro~linked or clo~ le.
Under the present invention, the electrom~n~tic r~ tion source is
provided by a chPmil-~.-;-.esc~ readion. Typical r~ sc~l-ce sy~Lt;llls
involve the readion of t~vo reactive species, such as the reaction of hydrogen
peroxide ~,vith oxalate compounds. These reactive species are generally provided30 as two separate I czcLioll co",polle,lls that are mixed together at the time of use.
The reaction co~ oll~"Ls; may optionally be added directly to the poly,i,e,i~al)le
-2-
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WO 97~33922 PCTnUS97tO150S
comrosition, but more ~IGrw~ly is provided as a distinct article or solution that is
physically separate from the poly...~ hle composition.
The cu~ o~ ls used to provide ~hpm~ esc~ light may be com~ ed
ofthose ~h. -..icf~ known in the art to create light chell~.cally upon mixing.
s E~t;rellt;d sy~ lls are the two~ o~ çl~ ;es con.~ g an oxalate
component, a peroxide colll~olle~L tog~ r with a fluorescer and a catalyst.
F.Y n.ple~ of such SY~ ;.IIS include those ~ ose(l in US Patent No. 5,281,347 and
3,689,391, the disclosules of which are illcGl~Glaled by lt;r~rence. These sy~L~"~s
may include ~ tionftl fluol~scell~ species, catalysts, solvents, acc~l~,.alol~ and
0 additive systems.
Chemi~ ..;. .escç~ light can be "tuned" to provide light at distinct
wavelength regions via an excited state energy Llall~ral reaction to specific acceptor
mole~Jl~ A donor molecule is defined as an excited state molecule that is formedfrom a ch~mi~.l...;nescF~-~e reaction. This molecule may directly emit light or
15 Ll~alls~l energy to an acceptor molecule. Acceptor molecules may be molecules that
accept energy from a donor molc~lle and then emit light or genelate
phoLo;...~ o. ~. Fy~mr~s of acc~Lor mole~ules that emit light throughout the
visible region are described in, e.g. US 3,597,362 and US 3,749,677, and ~,~.a~ JIeS
of acceptor molec-llee that emit light throughout the near i~ rt;d region are
described in, e.g.US 3,630,941 and US 3,590,003, the ~ osllres of which are
illcol~ul,lLed herein by reference. Light e~ ;o.. from a ~~.h~mil-l...;.~çsce..l reaction
may provide adv~ ges in co.~ to solid state light sources, for
pholopoly"w,.,alion r~ction~ Light emission from a chemil~ .esc~ ~I reaction
can be controlled through use of an acceplor molecule or a nli~L~llt;of~cceptQr
25 molecules to provide light that overlaps with the absol~Lion region of a
~hotortiactive molecule that is capable of il~ photopolyllleli~;aLion l~lthoup~h
solid-state light sources such as lasers, laser diodes, and light-e~ g diodes
provide light in the W, visible, and near infrared energy regions, there are regions
within this wa~,~elel~Lh range ~250-1400 nm) that cannot readily or ~;ullelltly be
30 ~cce~sed using these solid-state light sources.
--3--
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Other light sources (e.g. ~ n mclculy vapor, xenon lamps, etc.~
provide a broad light emissiôn in the W, visible, and near hlr~ cd regions, but may
be inP,fficiPnt for photopoly..~ ;c~n reactiol-.e because only a small wavelength
region ofthe emitted light is utilized by the light abso.l,ll~ ph~ tnl. Withsuch light sources, filters may be used to select the desired ~ ~LI~ while
el;~ the il.f ~cl~e wavd_n~lh of light. Chemil~ escç..l light sources, on
the other hand, may be selected that have single, ml-ltiple, broad, or narrow light
emission spectra, so that more of the emitted light is utilized in the
photopoly...c. ;"~;on process. A narrow emission ~ecL-uln is a region of light that
0 is cGmlJ~u~le to the absorption spe-iL, .1lll region of the photc initi~tor molecule.
Typical pho(c.i~ c~r molecules have an abso,l,lion spectrum range of about 100
nm. Suitable acceptor molecll1es that emit light in a ch~mi~ .;..esce~l reaction have
an em;~ion specLlulll range of about 100 nm. Preferably, the chPmil~ esce..l
C,nllS;~;On spectrum is sl~bs~ lly, equal ~o or enco"~l ~cced by the photoi~ Qr
5 abso.l~allce spectrum. Thus, pl creldbly most of the M~ tic n emitted by the
çhc ~ e~ccçnt reaction is absoll,ed by the photoinitiator mc lecule
The use of at least two diLrt;lelll ms)lecllles in a ch~mil--min~oscent system
(that emits light in two distinct spectral regions3 provides the opportunity to utilize
20 at least two di~cle.~L phok~ ;hlor molecules that absorb light in the desiredspectral regions. This system may be adv~nt~f~eo-l~ to provide "staged" curing
during the photopolyn c~ ion process. Compositions of this nature can utilize
one or more curing mecl~ c.--c each of which could be initi~te(l via a distinct
pholoil~ r. Each material could be i..;~ ecl at distinct wavele.~LI, of light
25 a~ro~ teri~lc that could be polymel.~cd independently for ob~ g unique
material pr~cl lies. For example, adhesives that could be applied as liquid,
photopoly.~ ed to tacly stage, and further photopolyll,cliGcd with a second
wavcL,I~glll of light to a structured cross-linked state.
In the fluid state, ch~mil~ ;-escence provides a unique light source for
30 many photopolyme~ization applications. While the use of ~h~mil~ escf ..~ light
sources for photopoly~-.c~ ;on is cont~ ed in all environm~.ntc the present
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invention finds particular advantage for uses in which electrically gelle~ d light is
undesirable or unsafe. Such as ~ql~eo~l~ env~n...~ the oral cavity, areas of
l,ole~ o~;on, and for applications that are physically restricti~ for the
r11aliv~1y bulky lamps. Rec~ e the ~hP ~ sc~nt mateAal may be provided as
s a liquid, the light source may be placed in loc~tion~ that electric light sources cannot
readily reach, such as in cracks, fissures, in enclosed areas, or undel ~. aLe. .
Some phoLopolymerization ~pplicption~ may require a ~.h~ F ~
,~ a ~ - ~ in a dirr~.e.~l l)l~;,;c&l form, such as described in U. S. Patent null~er
3,590,003. For ~ ple, the ch~mil----.;..escel~ source may be provided as a stick
0 or in tubular form; as described in US Patent Nos. 4,508,642; 5,043,851; and5,190,366; in pouches as described in US 3,539,794; in a parallel or helically
woven pattern as desclil,ed in US 5,222,797; in a thin sheet as describe in US
5,226,710, US 4,814,949; or in a spray as des-,lil ed in US 3,697,434. The
lieclQsllres ofthe above cited patents descl;l,i--g delivery systems are incorporated
herein by lt;rel~nce.
An alternative method of delivering ~hP.mil~ sce~l m~tP,ri~l~ to a desired
surface is by use of a ~ .e~ h.sL~ e"l co~ g one or all components of the
~.hP.milllmin~scent l~ io~ For eA~Il~)le, one or more components may be
delivered throughout a marker, pen, paint brush, spray or crayon. One component
may be sep~led from the other conlpollelll by microenc~rs 11~tir n. Crayons may
particularly be an appropliale delivery vehicle for micro~ c~l-s~ ted components,
because the microc~psl-le will rupture on ..,~-k;--~ ofthe ~ul~LI~Le with the crayon.
Such crayons may be ,~ ri.clllred generally as described in IJS Patent No.
5,039,243 (the ~ic~losllre of which is ;ncol~olaled herein by lertile -ce) by
2~ s ~ the fragrance des~ ed therein with components of the
~.h~milllminescent reaction. When using a dis~en:,illg appa~ s to deliver a
colllpoll~ll ofthe ~~hPmil~ sce..~ reaction, the second component may optionallybe pre-placed on the ~ub~LI~le, or may be delivered by a second dispensing
app~lus or sprayed onto the substrate in an alternative delivery mode as will be30 appal~lll to the artisan.
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Another ~llel~ali~re delivery system is by providing the c~ mponrnt~ in a dual
barrel cartridge with a mixing ~lem~qnt or ~It~rn~tive shapes that contain the
scpa.~Led çhrmi~try that can be ae~ivaled with a mixing elemPnt
The çhemil~...; )esce .1 effect may be optionally Pnh~nçed by use of one or
5 more ~rCh~ c~l appalalu~es~ such as a l~,ne~ e coating on l~ e for
direction~l light (e.g US 5,121,302, il.col~o.aled herein by refc,~"~ce), or by
focu~ing ofthe rh~-mil~lminescçnt light using lenses (.,lic osl-uctured plastic or
glass)
A particu}arly ~ ~--ed delivery system for rhPmill. ..;~iesc~ .I materials is to~o provide the components in the form of a liquid, ~el or paste This m~tP,ri~l is mixed
to~.o,th~r (for ;. . le, on site) to initiate the chemil.~ esce~l reaction, and the
system is placed adj~cent the photopoly...e.i~able material~ thereby exposing the
photopoly...~ hle system to poly,lle.i~Lion rn~i~tion It will be understood that"a~j~cent" for purposes of the present invention means in direct physical contact or
physically spaced from the photopoly---~ able material at a location close enough
for e~eclive l.~ ;on of ra~i~tion to the m~teri~l
For curing dental i-l-p-ession materials, a rh~milu ..;..~sc~ l reaction may be
carried out in a tray (leçi~ed for holding such maten~1~, as described in co-pending
U S patent applic~ti~n entitled "Dental In~rt;:jsion Tray with Chemil-lminescentLight Source" attorney docket number 52326USA2A filed on even date he.t;wilh
In one aspect ofthe present invention, the rh~mil-lminescrnt material is
selecte(l such that the photopolylll~ al)le m~teri~l is insoluble in the
cl....;1 .~ .esc~nt sol-ltioll/gel/paste, and the çhrmilllminesc~nt material is applied
directly to the photopoly..le.~able m~teri~l willloul s~1bst~nti~l mixing between the
2~ chemil~ esc~l m~teri~l andthephotopoly .,~ blematerial
In anolller aspect of the present invention, the .e~c~ for the
~,hemilllminescent reaction are mjxed togeth~r on site to initiate the
çh~mil~lminesc~nt reaction, and the system is applied ~incrnt to a radiation-
tr~n~mi~ive barrier layer system, thereby exposing the photopoly,ne,i~able material
30 to poly.l.c;l~aLion r~ tic n
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In yet another aspect ofthe present invention, the ~t~ esc-k~ll material
is dis~el~ed or dissolved directly in the photopoly...e~ hle material. The
~holopoly,l,~ lc material is cured by the light or energy emitted by the i
mixed ~hsmil.. :.. P.sc~ mAtPri~l The nature of the rçs~hing polymer is
5 delc;".,i-~ed by the conc~ - ~1. ation and degree of ~itAtion of the r~&cLull sollltiQn
Thus, me polymer may poly~ e to a solid form, with ch~mil~ esckr~l reaction
products el~llailled within the polymer. OptionA~ly, the cllf .~ e,3c~ reaction
co",l~o~le.,Ls may be provided with poly...~ ble fimction~lities so that the
~,hPmil.. ;i-esc~ reaction colllpo~ s, in ~A~d~iition to providing light, also
lo participate directly in the polym~ A~ Il reActiQn It is also co..~e.~ e~1 that the
poly~ alion reaction may be carried out in a dilute solution, so that particles of
poly...~ ed ...~ ;A1 are formed. With agitation of the solution and the use of
multiple phases of solutions (e.g. oil and water), sphelical particles, hollow particles
and particles having alternative geol"t;l.ies may be formed by following the
l5 plin~ le s of ~nc~l~s~ tion technology, such as described for PY~mple in U.S. Pat.
No. 3,516,941, the ~i~C~osllre of which is incorporated herein by l~t;,ellce.
An A1tern~tive format for delivery of chemil~ Psce~l light utilizes adhesive
tape. In this embodiment, one or more components ofthe ch~mil-lminP~scent
reaction is microP.nc~pYl1~te~l, and the c~rslllP,s are provided on the adhesive-side of
20 a tape. The cohesive ~Llt;llglh ofthe ÇArs~llP~s is s~lP,cted to be less than the adhesive
~lr~ l. of the adhesive, so that as the tape is unrolled, microcapsules are ruptured,
thereby l~leA.~ g the capsule fill and ..~;I;h~ the eh~milllminPscent reaction. This
tape is adhered to a surface and the c~ ..;..esce..l light cures a
photopoly,nc:, ~al: le material.
2s Microc~s~lle~ used in any delivery system of the present invention may be
made by processes known in the microPncArs~llAtion art. For example,
microcapsules may be prepared by in situ processes such as aminoplast
polymerization. The techniques ~ rlose~l generally referred to as an in situ
poly~k~ lion reaction, yield for eYAmrlP~, an aminoplast photopolyl.leli;G~ble
~ . ;A1 capsule wall material. In the process, a hydrophobic oil phase is dispersed
in an aqueous phase col.l~ g the aminoplast photopolyllle-i~able material
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precursors by applying high shear ~tatiQn ~d~lition of an acid catalyst initiAtes
the poly~ n~e~ on ofthe aminoplast pl'~uf~Ol:i,reSl~lting in the deposition ofthe
~-----oplast pholopolyme.i~ble mAtPt~Al about the di~.~ed droplets ofthe oil
phase, produrinf~ the micrwA~ 5
s The Ly~l~opllobic inner phase for the capsule may be any in situ aminoplast
~ncfil~s~ ble co~ o~ilion as di~ SG;I in U.S. Pat. No. 3,516,941, provided that
the inner phase meets the criteria for acting as a solvent to the binder.
When the microç~rs~lle is ~_p~d by interfacial polycon~Pn~t~ the
capsule skin may be composed of any con~l~n~Ation polymer or ad-~ition polymer,
0 e.g., polyamide, polyu-~th&l~e, polys1llfon~rni~1~ polyurea, polyester, poly~,a.l,onale,
etc. Poly ~es ~,. ~ ,d by interfacial polycon~PnsAtion of an an~ine with an acidrhlor--le or polymers formed by reaction of isocyanate prepolymer v~lith poly~ lcs
are p-c;r~lled. Microcapsules forrned by coacervation processes are also useful in
1~....ing microcapsule shells that may be used in the present invention.
lS Coacervation is the well known process of folllling higher molecular weight gelatin
polymers as taught in U.S. Pat. Nos. 5,800,458 and 2,800,457.
The mAteriAl to be poly..,eliGed may be any suitable
phoLopoly..~ i~Lion material, such as free-radically }eactive mAt~riAI~ çAtionicpolymeri7~tion materials, charge L.~"r~,l poly~ alion reactive materials,
20 hydrosilation reactive materials or photocyloa~ldition reactive poly~ ion
materials. Typically, many ofthese mAteri~l~ incorporate a sepalale çh~mic~t
initiA~t-)r that is activated by the light emitted from the ~.h~mil~ esce..l light
source.
The poly-. . .~. ;,~hle n.~le.ial may be se1ected from one or more
~s photopoly.l.~;l~able materials, in~ h~ ng photopoly..~ materials that cure
through di~-e -l cure merllA~ Such m~ixtures of photopoly--~ ble materials
are S~ f,~i,..~s l~fe--cd to as hybrid curing phc,lopoly--~ able m~AteriAl~ The
photopoly...~ le material may addition~ly utilize multiple cure i.~ccll~ for
the comrlete curing of the photopoly...~ ble material system. For c~---ple, heat30 may be utilized to cure a free radical curable co--~oncl-L, while the
~.h~m;l-....;l~esc~ light source may be used for the ~Ationic curable component of a
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WO 97~3922 PCT~US97101S05
hybrid system. ~ t~lition~lly~ m~lL;~,le w~ of light may be utilized for
curing di~elw~l aspects of a multi-component photopoly~ ble material system.
The nature of the Illtim~te poly~ d material is of course ~epen~lf nt on
the plup_llies ofthe backbone polymer and grafted filnction~litiçs Thus, polymers
of all natures may be ~r~h~d using the present invention, from brittle polymers or
J hard polymers to e~ ic polymers. The present invention th~ ole
cc~ .,r19~es the ~lepa-~lion of a wide variety of m~tçri~l~ having very di
uses, all of which have in co~-....o~- that they may be pl~;d by a
phulupoly...- ~ ;,,.1;on process using a Cllf ~ nill~ sc~ reaction as the r~ t;"li~
lO source.
~ )rçsf~ ;ve ~ .s.n.i~,les offree radically polyl.-~.~ble materials are those
co--lpoullds that contain at least one ethylenically ul~s&lulaled double bond and can
be ~ or..ers, oli~ , or prepolymers.
A wide variety of free-radically poly. I-f~ le monomers can be
lS pllo~opoly..le.i~ed using cl-fL~ esc~ reaction as a light source. Sll;t~ble
nlonc,nlw~ contain at least one ethylenically-llnsalu-aLed double bond, can be
oti~u~fL~ and are capable of undel~o.ng ~d~tition poly,lwli~alion. ~ert:l-ed
~ OI~O~f ~ S include mono-, di- or poly- aclylates and m~th~r,rylates such as methyl
acrylate, methyl mçth~(.rylate, ethyl acrylate, isopropyl meth~rrylate, n-hexyl
20 acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate,
ethyleneglycol diacrylate, diethyleneglycol diacrylate, triethylene~;lycol
t;...~lh~.;. ylale, I,3-propal~ediol diacrylate, 1,3-propanediol dim~ ( ylale,
L~illlt;lllylolp~upanf triacrylate, 1,2,4-b .f l~iol Ll;..i~ rylate, 1,4-
cycloh..~ ç-t;ol diacrylate, penta~ylh,iLol triacrylate, pentae ylh-ilol tetraacrylate,
25 p~ e~yllllilol It;Ll~ h~rrylate~ sorbitol hexacrylate, bis[l-(2-aclyloxy)]-p-
elllo~y~he..yldim~;llly~ ; bis[l-(3-acryloxy-2-llydlu,~y)~-p-plop~ir.yphenyl-
dillleLllyl~ e, ~ hydl~xyeLllyl-isoiy~ulul~Le tl;.~el~ i-ylate; the bis-acrylates
and bis-mçth~rylates of polyethylene glycols of molecular weight 200-500,
copoly...~ le ll~ LLIres of acrylated lnonu--lers such as those of U.S Patent No.
4,652,274 and aelyla~ed oii~om~rs such as those of U.S. Patent No. 4,642,126;
unsaturated amides such as methylene bis-acrylamide, methylene bis-
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meth~c~rylamide~ 1,6-h~-~.nell~ylene bis-acrylamide, diethylene l-;&n~ e tris-
acrylamide and beta~ c~yl&-,~inoethyl me~ c.ylale, and vinyl cG~ )ou-~ds such
as styrene, diallyl pl.ll.AI~le, divinyl D.lcc:n~l~, divinyl adipate and ~livi-lyll~hth~l~te
Mi~lules oftwo or more .~OllO~ can be used if desired.
Other sui~al~'e free radically polylll~ blc composition.~ include the
co~ aLion of ethylenically un~alul. ted compounds and polythiol cGn.poullds suchas those rlicclosecl inPuad~ation Curingof PolJrmericMaterials, ~hapter 13, pp.
160-175, A,l-eli~l Ch~miG~I Society, 1990, and .ert;lences therein. Further
examples are di.~closed in U.S. Patent No. 4,808,638 and ler~ lces therein.
o A further class of free radically polylllel;~ble materials include
donor/acceplor charge co.~ comprised of the CO~1J;~ ;on of at least one
unsalu.~led cGlllpoulld having an electron donor group and one compound having
an electron wl~ .ing group such as those described in EP~ 0 618 237 A1.
Compositic n~ disclosed therein can be photopolym~ ed in the ~bsPnce or p- ~sence
of collvenlional free radical ini~ialc:lls.
Numerous ~ p!es of free radical pholQ...il ;~tors for the pol~ on Of
unsaturated compound have been ~i~close~ Representative examples are described
in the Handboo* of Organic Pho~ochemistry, Vol. J~, pp. 330-335, CRC Press Inc.,1989, and r~fe.e;l~,s therein. Other eY~mpl~ are tli~cl<}sed in US Patent
Appli~tion Serial No. 08/365,494 filed December 28, 1994, the tlisclosllre of which
is hereby illcol~oraled by rerelellce.
R~prf,s.~...~ e cationically poly..~ ble materials include epoxies,
epoxy/polyols vinyl ethers and a variety of other compounds as disclosed in
WO95/14716 and lefelellces therein. Other cationically polyl..cli~able
2s compositions are disclosed in the Journal of Polymer Science, Vol. A, pp. 977-999,
and U.S. Patent No. 4,264,703.
F.Y~mpl~s of organic materials polylll~,i;G~le by cationic polyn~ alion and
suitable for the hardenable compositions acco, ~ g to the invention are of the
following types, it being possible for these to be used by Lllelllselves or as miY~tures
of at least two components:
-10~
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I. Ethylenically u~aLulalt;d compounds poly~ ble by a c~tionic n .t~n
These inr,l~7~1e~
1. Monoolefns and ~liolPfin~, for ryAmrle isobu~ylene, bl~t~-liP.nP"
s is~p~ c, styrene, a-m~ ylsly-~le, di~,i"~ -.f s, N-~ lyl~yllolidone, N-
.~ vinylca~ ole and acrolein.
2. Vinyl ethers, for eYAmrle methyl vinyl ether, isobLllyl vinyl ether,
ell-yl~plopalle trivinyl ether and ethylene glycol divinyl ether; and cyclic vinyl
ethers, for ~.Y~rnrle 3,4-dihydro-2-formyl-2H-pyran (acrolein dimer) and the 3,4-
o dihydro-2H-pyran-2-carboxylic acid ester of 2-hydro~ylll~thyl-3,4-dihydro-2H-
pyran.
3. ~myl esters, for ~,Aample vinyl acetate and vinyl stearate.
II. Heterocyclic co."poul,ds poly...~ Ahle by cationic poly.n~ ;on, for P~Y-Amrle
5 ethylene oxide, propylene oxide, epichlorohydrin, glycidyl emers of monohydricAlcohols or phenols, for ~A~IUple; n-butyl glycidyl ether, n-octyl glycidyl ether,
phenyl glycidyl ether and cresyl glycidyl emer; glycidyl acrylate, glycidyl
.A~ylate, styrene oxide and cyr,1ohP~ ne oxide; ~ el~nes such as 3,3-
dilneLl,yk.~ ne and3,3-di(chlorom~ l)oYP,tAnç; tetrahydrofilran; d;
20 trioxane and 1,3,~-trioxacyclooctane; l~vk.nP,s such as ,13-propic~ o--P; ~-
valerol~ ~c --- and ~-caprol~ctone; IL~ es such as ethylene sulfide and propylene
sulfide; A7ietidines such as N-acylA7eti-1inP~ for example N-benzoyl~7eti-linç, as well
as the A~d~lct~ of A7et~ ne with diisocya~ es, for example toluylene-2,4-
diisocyanate and toluylene-2,6-diisocyanate and 4,4'-diAmint~ hellyl~ AIlP,
2s diisocyanate; epoxy resins; and linear and bl~ched polymers with glycidyl groups
in the side-chains, for PY~Ample homopolymers and copolymers of polyacrylate andpoly.n~ nrrylate glycidyl esters.
Of particular importance among these above-mentionP~l polyl"e, . ~able
compounds are the epoxy resins and especially the diepoxides and polyepoxides and
30 epoxy resin prepolymers of the type used to prepare crosslinked epoYy resins. The
diepoxides and polyepoxides can be aliphatic, cycloAlirh~tic or aromatic
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W O 97/33922 PCT~US97/01505
co~ ounds. F~ es of such compounds are the glycidyl ethers and ~-
methylglycidyl ethers of ~iph~tic or cycloaliphatic diols or polyols, for ~
those oft;lhyl~,nc glycol, propane-1,2-diol, p,.-pal~e-1,3-diol, butane-1,4-diol,
diethylene glycol, polyethylene glycol, poly~-u~ylene glycol, glycerol,
Llil.~lLylop,op&~e or 1,4-di-methylolcycloh~Y~ne or of 2,2-bis(4-
Lyd~ y~;y~lohe~Y~yl)l)lo~ e and N,N-bis(2-~1ydlu~yt;Lllyl)~nilin~; and the glycidyl s
ethers of d;l-hF ~ and poly~)h~ for C~ ple~eSOlCnlOI, 4,4'-
dihydloAydiph~ P; 4,4'-diLyd-oAydiphenyl-2,2-1)1op&l~e, novolaks and
1,1,2,2-tetrakis(4-l,y.l.~ ~y~henyl)ethane. Further ~ ..ples are N-glycidyl
0 compounds, for eY~mple the diglycidyl compounds of ethylelleult;a, 1,3-
propyleneult;a, 5-dllll~LllylllydallLoill or 4,4'-Il-e~ e-5~5'-t~;LIanlclllyldillyd~ oi.-,
or those like triglycidyl iso.;yanu-~le.
Other glycidyl compounds of induslllal importance are the glycidyl esters of
ca~ sAylic acids, especially dic~Lx>~yl;c and polycarboxylic acids. ~Y~mrles of
these are the glycidyl esters of sllccinic acid, adipic acid, azelaic acid, sebacic acid,
phthalic acid, terephthalic acid, tetrahyd-o~ alic and hexahydrophthalic acids,
isophll.alic acid or trim~llitic acid, or of fatty acid dimers.
nples of pol~epoAides other than glycidyl compounds are the diepoxides
of vinylcyc~oh~Y~n~ and dicyclop~nt~ n~, 3-(3', 4'-epoAy-;y-,loheYyl)-8,9-epoAy-2,4-r~ y;~ o[5,5]llndec~ne, the 3',4'-epoAycyclolh,~yhllethyl ester of 3,4-
epoxycycloh~ F~ --l,oAylic acid, butadiene diepoxide or isoprene diepoxide,
epo~i~i7ed linoleic acid derivatives or epo~i-ii7ed polybutadiene.
p~ er~., ed epoxy resins are diglycidyl ethers (which may or may not have
been lel.~,l t~ d b-;;role;halld) of dihydric phenols or dihydric ~lirh~tic alcohols
2s having 2 to 4 carbon atoms. Particular plerelence is given to the diglycidyl ethers
(which may or may not have been le~ ed be~orel~ld) of 2,2-bis(4-
hyd~o~y~ e~yl)-propane and bis(4-Lyd-o~Ly~ enyl)..~ s~-e.
Numerous ,~holoi~ for cationic polylne-iz~Lion have been disclosed.
Re~ s~,.lL~ e examples include onium salts and mixed ligaIld arene
cyclop~nt~ ne metal salts with CGI~ e~ metal halide ions, U.S. Patent No. L
5,375,115. A variety of cationic pho~Q~ ;A~Qrs are disclosed in the Handbook of
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W O 97133922 PCTrUS97/0150S
Organic Photo~-h~n.~ y,, Vol. II, pp. 335-337, CRC Press Inc., 1989 and
~~f~lellces cited within. ~ tion~l cationic pholQi~ ol~ suitable for use with
visible light are disclosed in U.S. Patent Application Serial No. 08/550,635, filed
~, October 31, 1995 (the ~lic~los~lre of which is i,~co,lJu.~led herein by ,crercnce~ and
s PCT WO 95/14716.
Rcpres~ ;vc I.,~.L _ PI~S of a hydrosilation reaction involving the reaction of
a co---~ und co..~ ~ aliphatic un;,alul~lion with a compoulld co~ g silhon
bonded hydrogen are flicclosed in ~.S. Patent No. 5,145,886 and ~tre.ci.ces therein.
Methods of in~ cin~ photohydrosil~tiQn ntili7.inp~ photoac.:Li~,a~ed pl~
catalysts are ~licc~ose~ in U.S. Patent Nos. 5,145,886, 4,530,879; 4,510,094; and
4,916,169 and rcrcle~ ces therein.
Co,..h;... ~ions ofthe above poly.~ ~le compositions and iniliàLul~ may
be utilized to provide new co~ ,osilions of matter.
The present method for polylllcl~ii~g a poly...c.~le material by using a
lS rh~m~ esc~ light source finds specific advantage in appliç~tionc such as
custom gasket m~t~ lc, auto-body filler, ceramic repair material, dental restorative,
adhesive and hl.~ress;on materials, casting materials, and other m.q~ and dentalapplications wl~cle;ll polylllcli~alion reaction is carried out in-situ. Additional uses
ofthe inventive system include ...~ .L~.E,ose adhesives, structural adhesives,
20 p-~tecli~e co~ , se~l~ntC, ~nich~s, caullc, grout, custom molded shapes, repair
kits for cable sheath, wire sealing in wet en~ n...~.ls, marine products
(undel ~aler repair e.g. putty and adhesives) and the like. It is cont~mpl~ted that
the present system may provide significant advantage in custom
photopolyll.eli~Lion applications le~luilillg irregular shapes and sizes.
2s
The following non-limiting ~ lc illustrates the ability to rapidly
photopolyllle;li e a liquid monom~r composition utili~ng a ~~h.smii-lminescent light
,. source.
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A photopolyllleli~able composition was prepared as descl,bed below.
r Parts b~Wei~ht
L~ cl~y~ u~ e ll;d~ilyl~ (l~MPTA) 3.00
pe,l~,y~l.;L~I tetrakis(3~ cl~pt~r~,~ ) (PETMA) 1.00
(r~6-xylyl)(~S ~ q). .~ l)iron 1~ n~,v~ - (CpXylFeSbF6) 0.04
~JULyl~ fi O. lO
.
0 The CpXyll~eSbF6 compound was L,~lsrt;lled to a lOcc glass vial and
dissolved with the ~ hion of butyrolactone. TMPTA and PETMA were then
added to the vial and mixed thoroughly until homogeneous. The sample was
capped and w~ped in foil to exclude extraneous light. Approx;...~lP.ly I gm ofthe
solution was ~ r~ d to each oftwo 1.~ dram clear glass vials. This ~ylesel~ed
15 an applo~ ly a lcm thick sample. Both vials were covered with foil to excludelight. A co....ne~,ially available light stick ~"~n~l ligl~ ) 12 hour lightsti~.k from
Coghlan's LTD) was wrapped in foil with the exception of a cylindrical se~i..~.,l
fitted to the base ofthe 1.5 dram glass vial. The foil was removed from one ofthe
glass vials with photopolymer, the lightst~ activated and the vial immerli~tPIy
20 placed into the light e~ f~;selvoil-. The photopolymer sample was probed with
a stick as a fim~.tion of time. After approximately 30 seconds, the sample had
polymel"5ed to a hard, tack-free solid whereas the sample protected from light
.ed fluid for an eYt-on-led period of time.
-14-
