Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~3L;;;~';'~3
B~CKGROUND OF TIIE: INVI~NTION
The initiatioll oE cures of polymeric systems either with peroxides or actinic
radiation has long been Imowll to the macromolecul~r art. Some macromolecules,
oteal~ly those contaillillg chlorine, can mclergo cure directly with actinic radiation.
Irradiation of this type molecule with ultraviolet or violet ligllt causes the chlorine-
cnrbon ~ond in the lholec~lle to lbreak resulting in loss of chlorine and induction of a
frce rndical on the molec-llar skelton. Because most of the prepolymers and monomers
~s~d ~vllen a radiation cure is desired are relatively poor absorbers of radiation in the
violet and neai~ ultraviolet regions of the radiation spectrum, it is common to use a
radiation cure accelerator. These radiation cure accelerators, which usually up to
the l)rcsent have been relatively low molecular weight compouncls, are efl`icienl
~sorl)ers of light in the violet and ultraviolet regions. When this radi~tion is
.11)9Orl)C(] CICClrOllS al`C l)J.OIllOtOd to higllcl ollcrLy lovol9 il) t]lC IllOIl.`C~llC. 'l'llis
encrLy is lllcn transrcr1~e(l to tllc monomer or prepolymcric oli~omers whicll it is
desired to cure~ This procedure greatly increases the efl~iciency of utili~ation o~
incidcnt radiatioll enerLy and renders the ,~rocess practical.
,
.~ ~
~7~73
The use of these radiation cure accelerators is attended
by certain inher6nt problems. Being relatively low
molecular weight compounds, they tend to bleed out of a system
in which they are incoxporated both before and after cure. This
results in lack of shelf stability for materials preformulated
for Iater cure and manifestly is undesirable in the finished
product. In addition, while aiding in and initiating cure these
compounds do not actually enter into the cure reaction. They
remain as low molecular weight inclusions in the cured polymer.
Their presence thus reduces the maximum physical properties ob-
tainable in the cured system. Such properties as hardness,
abrasion resistance, extensibility and even 1exibility are all
adversely affected. U.S. Patent 3,661,744 does suggest that
the photo cure rate accelerator may be chemically co~bined with
one of the reactive structures in the system to be cured but
the illustration given thereof is of a benzophenone combined
with a number of monomeric units.
The novel compositions of the present invention provide
oligomeric prepolymers which are themselves good absorbers o ;
actinic radiation and which therefore do not require the pre-
sence of a separate radiation cure accelerator in the system. `
These compounds are also relatively high molecular weight radia-
tion cure accelerators which enter into the curing reaction.
SUMMARY OF THE INVENTION
The invention provides as a composition aspect a chemical
compound which is an oligomeric prepolymer having appended
thereto at least one functional group capable of absorbing
actinic radiation thereby inducing electronic excitation in said ;
compound.
Thus, in accordance with the present teachings, a compound
is provided which has the general ~ormula
C - ~ R
. . ....
:
, :
~3~73
in which R is the residue of a prepolymer derived by the re-
moval of a hydrogen atom from one or more hydroxyl groups of a
hydroxy-terminated polyester or polyether, A is a group derived
from a diisocyanate, X is a group derived from a benzoin by re-
action of a hydroxyl group thereof with an isocyanate group of
the precursor of A or the precursor of R--~A]n, n is, on the
average, at least 0.5, provided that R is free from terminal or
pendant -CR"'=CH2 groups in which R"' is hydrogen or methyl,
which groups are unconjugated with other carbon to carbon un-
saturation.
Examination of the products produced by the herein des-
cribed processes reveals, upon infrared analysis, spectral data
supporting the molecular structure herein set forth.
The tangible embodiments of this composition aspect of the
invention posses the inherent applied use characteristics of in-
itiating cures of polymeric system containing them, while par-
ticipating in the polymerization reaction themselves.
A preferred embodiment of this composition aspect of the
invention provides a chemical compound of formula
rA ~ R
I
~ -3a-
., , ~, I , , ,
~3~ 3
wherein R is the residue of an oligomer derived by removal of an
active hydrogen or a halo atom ~rom said oligomer which has been
terminated with hydroxyl, carboxyl, halo or amine functions, the
monomeric units of said oligomer being linked by ester, ether,
urethane, silane, amide, sulfide, covalent carbon to carbon bond
functions, or mixtures thereof; said monomeric units exclusive
of the atoms attributable to said linkage functions being derived
from alkanes, alkenes, phenylene, naphthylene or mixtures there-
A is -O-, -OCNH-Y-NHC-O-, -OC-Y-~-O-, or -O~- ;
wherein Y is cycloalkylene of 5 to 7 carbon atoms, or carbocyclic
arylene of 6 or 10 carbon atoms; X is selected from alpha-, or
beta-naphthoxy, 2-, 3-, or 4- phenyl carbonyl phenyleneoxy, 2-,
3-, or 4- lower alkyl carbonylphenyleneoxy, or .
-O-CH- -R"
R'
wherein R' and R" are independently selected from phenyl, alpha-,
or beta-naphthyl, 2-, ~-, or 4- pyridyl, alpha-, or beta-furyl;
said naphthoxy and naphthyl radicals being unsubstituted or sub-
stituted with radicals, identical or mixed, selected from up to
6 straight chain lower alkyl of from 1 to about 8 carbon atoms,
up to 5 non all adjacent branched chain lower alkyl radicals of
from 1 to about 8 carbon atoms, up to about 6 lower alkyloxy of
from 1 to about 8 carbon atoms, up to 6 halo, up to 3 non-adjacent
trifluoromethyl, up to 3 non-adjacent trichloromethyl, methyl-
enedioxy, dilower alkyl amino of from 1 to 8 carbon atoms, or
lower alkanoylamido of from 1 to 8 carbon atoms; said phenyl
and phenylene radicals being unsubstituted or substituted with
radicals, identical or mixed, selected from up to 4 straight
chain lower alkyl of from 1 to about 8 carbon atoms, up to 3
non-adjacent branched chain lo~er alkyl of ~rom 1 to about 8
i ...
: ` ' , , ' ' ' '
~L3~3
carbon atoms, up to 4 lower alkyloxy of from 1 to about 8 carbon
atoms, up to ~ halo, up to 2 non-adjacent trifluoromethyl, up
to 2 non-adjacent trichloromethyl, methylenedioxy, dilower alkyl
amino of ~rom 1 to about 8 carbon atoms, or lower alkanoylamido
of from 1 to about 8 carbon atoms; said pyridyl and furyl radi-
cals being unsubstituted or substituted with up to 2 lower alkyl
of from 1 to about 8 carbon atoms; and n is on the average at
at least 0.5.
Particularly preferred embodiments are:
1. Those compounds of Formula I which absorb actinic radia-
tion in the wave length region o~ from about 3000 Angstroms to
about 4000 Angstroms.
2. Compounds of Formula I wherein the residue R is de-
rived from a hydroxy terminated polyester, or a hydroxy terminated
polyether. Still more particularly preferred are those compounds
of Formula I wherein the hydroxy terminated polyester or poly-
ether is capped with a diisocyanate. Special mention is made of
compounds of th,is type wherein the diisocyanate capped hydroxy
terminated polyester is reacted with a benzoin.
3. Compounds of Formula I wherein the residue R is de-
rived from a polyester or polyether and additionally contains a
residue derived from a hydroxy acrylate ester or from an iso-
propylidine hydroxy derivative.
The invention also provides in another composition aspect
an actinic radiation curable composition of matter which com-
prises:
a. an oligomeric prepolymer having at least one functional
group capable of absorbing actinic radiation thereby inducing
electronic excitation in said compound; and,
b. a prepolymer having at least one car~on to carbon un-
saturated bond in a terminal position.
The tangible embodiments of this composition asp~ct of
_5-
73
the invention possess the inherent applied use characteristics
of being curable to a substantially solid polymer upon exposure
to actinic radiation.
Preferred embodiments of this composition aspect of the
invention are
1. a composition of matter which comprises:
a. a compound of Formula I; and,
b. a compound of the formula
~ A ~ R
m
II
wherein R and A are as defined for Formula I; m is on the average
at least l; and Z is a residue derived from a hydroxy containing
acrylate ester, or a hydroxy containing derivative of a vinyl
ether.
Particularly preferred aspects of this preferred embodi-
ment are those compositions wherein R has a polyether or poly-
ester backbone, is terminated with an isocyanate and is end
capped on another terminal position with a benzoin. Also par-
ticularly preferred are those compositions wherein the compoundof Formula II has a polyether or polyester backbone, is terminated
with an isocyanate and is endcapped with an acrylate function.
The invention also provides in a process aspect an im-
proved process for preparing an article coated with a cured film
derived from a radiation curable coating applied to said article
wherein the improvement comprises applying to said article a
coating comprising:
a. an oligomeric prepolymér containing at least one
functional group capable of absorbing actinic radiation thereby
inducing electronic excitation in said oligomer; and
b. a prepolymer containing at least one functional group
having carbon to car~on unsaturated bonds, which comprises
~3~9~3
coating an article with a thin film of said mixture and then
subjecting said coated axticle to actinic radiation.
A preferred embodiment of this process aspect of the inven-
tion is a process for providing said coated article where said
coating is derived from a mixture of compounds of Formula I and
of Formula II.
This invention provides in another composition aspect an
article of manufacture comprising:
a. a substrate; and
10 b. a cured coating derived from a mixture comprising an
oligomeric prepolymer containing at least one functional group
capable of absorbing actinic radiation thereby inducing elec-
tronic excitation in said oligomer, and a prepolymer containing
at least one functional group having a carbon to carbon unsatur-
ated bond.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The liquid oligomeric prepolymers having at least one
functional group capable of absorbing actinic radiation thexby
inducing electronic excitation in said oligomer are readily pre-
pared by processes well known to those in the art. Typicallythese compounds will have polymeric backbones bearing as a
substituent a product derived from a hydroxy substituted naph-
thalene, hydroxy substituted benzophenone, a hydroxy substituted
acetophenone, a benzoin or hydroxy ethoxy benzophenone or
hydroxy ethoxy acetophenone. Conveniently, reaction between the
hydroxy function and a reactive functional group on the polymeric
backbone will suffice to prepare the desired oligomer. Typically
such reactions as esterification, reaction with an isocyanate
group, esterification, or displacement of a halogen atom will be
employed. More specifically, one may take a polyester polyol
having a molecular weight of between 300 and 3000 and treat it
~ith a difunctional isocyanate such as toluenediisocyanate,
7-
3~
hexamethylene diisocyanate or isophorone diisocyanate and the
like, and then treat that product with an equivalent amount of
the hydroxy substituted compound which it is desired to couple.
One may similaxly treat a polyether polyol in the same fashion.
Alternatively, a carboxy terminated polyether or polyester may
be esterified directly using standard techniques with a hydroxy
containing proposed substituent which it is desired to incor-
porate into the molecule.
A hydroxy terminated prepolymer may also be esterified
with one carboxyl function of a di basic carboxylic acid using
known techniques and a hydroxy containing substituent which it
is proposed to couple may be esterified with the other carboxyl
function also using standard techniques. A hydroxy containing
substituent which it is desired to incorporate may also be
coupled directly to a prepolymer having an active displaceable
halogen by the usual methods employed in that type of reaction.
The hydroxyl bearing proposed substituent may also be reacted
with a epoxide function on the prepolymer to which its attach-
ment is desired. For example, if desired, a hydroxyl terminated
polyester of molecular weight about 800 is end capped with toluene
diisocyanate to a final NCO content of about 3.0% and thentreated with benzoin in the presence of a basic catalyst. The
product is a benzoin terminated urethane capped polyether.
A similar polyester may, i~ desired, be esterified wlth a
molar equivalent of a dibasic acid such as adipic acid and the
product then treated with benzoin in the presence of a catalyst
under normal esterification conditions to produce a benzoin ter-
minated adipic acid end capped polyester. Both these reactions
may be run in an inert solvent, the identity of which is not
critical as long as it will not interfere with
-7a-
.. , .:
, , , ' ;
'
the course of the reactionO The ex~ct time and temperature of
the reactions are similarly not critical. The endpoint for
esterifications conveniently can be determined by running the
reaction at a temperature where water will distill out and the
lack of formation of further water will indicate the completeness
of ester formation. The isocyanate reaction can be monitored by
the remaining isocyanate content of the reaction mixture.
One skilled in the art will recognize that in addition to
the specific prepolymers isocyanates, dicarboxylic acids~ and
benzoin illustrated herein above and in the following examples
the other prepolymers, isocyanate, dicarboxylates, benzoins,
acetoins, benzophenones, and hydroxy ethyl benzophenones contem-
plated as equivalents in this invention may be substituted in
analogous reactions to produce the other compounds of Formula I.
It will also be obvious to one skilled in the art that
hydroxy substituted acrylate esters, or hydroxy containing vinyl
ether may be substituted for the benzoin illustrated to obtain
the compounds of Formula II through analogous reactions.
It will also be obvious to one skilled in the art that
where a prepolymer is functionaliæed at more than one terminal
portion that the reaction can be performed at each of those ter-
minals by proper control of the relative proportions of the re-
actants so as to end-cap the number o~ terminal positions desired.
Through control of the relative proportions of the reac-
tants it will also be obvious that molecules of Formula I con-
taining mixtures of the various ultraviolet sensitive end capping
moieties may be prepared, and that similarly molecules of Formula
II containing mixtures of acrylate esters and/or vinyl ether re-
sidues may be prepared.
Similarly, if desired, one may prepare molecules end capped
with mixtures of the ultraviolet sensitive end groups and acrylate
esters and/or vinyl ether functions. Such molecules will, of
'
", .: ".;, ~ ~ ..",,.
~L3~
course, be self curing upon exposure to radiation of the ap- :
propriate wave length.
Typical illustrati~e prepolymers which may be used for the
R function in compounds of Formula I and II are: liquid poly-
esters derived from such polyhydric alcohols as ethylene glycol,
1,3-propanediol, 1,2-propanediol, 1,3-hutanediol, 1,4-butanediol,
2,3-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol,
2,3-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol,
1,4-hexanediol, 1,3-hexanediol, 2,3-hexanediol, 2,4-hexanediol,
2,5-hexanediol, 1,7-heptanediol, 1,5-heptanediol, 3,5-heptanediol,
l,10-decanediol, para-xylene glycol, the bis-(B-hydroxyethyl-
ether) of hydroquinone, neopentylglycol, ylycerine, pentaery-
thritol, trimethylol propane, triethylolethane and the like and
polycarboxylic acids such as, for example, adipic acid, oxalic
acid, succinic acid, methyl adipic acid, sebacic acid, glutaric
acid, pimelic acid, azelaic acid, suberic acid, phthalic acid,
terephthalic acid, isophthalic acid, 1,2,4-benzene tricarboxylic
acid, thiodiglycolic acid, thiodipropionic acid, maleic acid,
fumaric acid, itaconic acid, citraconic acid and the like, liquid
polyamides derived from the reaction between polycarboxylic acids
as illustrated hereinabove and polyamines such as, for example,
ethylene diamine, propylene diamine, butylene diamines, penta-
methylene diamine, hexanethylene diamine, phenylene diamine,
tolylene diamine, xylylene diamine, 4,4'-diamino-diphenylmethane,
cyclohexylene diamine, naphthylene diamine, and the like, or
liquid polyester polyamides from polycarboxylic acids and amino
alcohols such as amino ethanol, amino propanol, amino butanol,
and the like, also polyesters prepared from lactones such as
caprolactone and the like, polyhydric polyalkylene ethers such
as, for example, the condensation products of an alkylene oxide
such as ethylene oxide, propylene oxide, butylene oxide, amylene
oxide, and the like with a suitable:initiator such as ~ater or
_g_
,
any of the polyalcohols, polyamines, or amino alcohols set ~orth
herein, also prepolymers containing urethane linkages may be pre-
pared by treating any of the active hydrogen containing compounds
listed hereinabove with polyisocyanates s~ch as, for example, 1-
methoxyphenyl-2,4-diisocyanate, 1-methyl-4~methoxyphenyl-2,5-
diisocyanate, l-ethoxyphenyl-2,4-diisocyanate, 1,3-dimethoxy-
phenyl-4,6-diisocyanate, 1,4-dime~hoxyphenyl-2,5-diisocyanate,
l-propoxyphenyl-2,4-diisocyanate, l-isobutoxy 2,4-diisocyanate,
1,4-diethoxyphenyl-2,5-diisocyanate, toluene-2,4-diisocyanate,
toluene-2,6-diisocyanate, diphenylether-2,4-diisocyanate, naph-
thalene-1,4-diisocyanate, 1,1'-dinaphthalene-2,2'-diisocyanate,
biphenyl-2,4-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate,
3,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4~-
diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-
2,2'-diisocyanate, 3,3'-dimethoxy diphenylmethane-4,4'-diiso-
cyanate, benzophenone-3,3'-diisocyanate, ethylene diiocyanate,
propylene diisocyanate, butylene diisocyanate, pentylene diiso-
cyanate, methylbutylene diisocyanate, tetramethylene diisocyanate,
pentamethylene diisocyanate, hexanethylene diisocyanate, dipropyl
diisocyanate ether, heptanethylene diisocyanate,2,2-dimethyl-
pentylene diisocyanate, 3-methoxy-hexamethylene diisocyanate,
octamethylene diisocyanate, 2,2,4-trimethylpentylene diiso-
cyanate, 3-butoxyhexamethylene diisocyanate, 1,3-dimethylbenzene
diisocyanate, 1,4-dimethyl benzene diisocyanate, 1,2-dimethyl-
cyclohexane diisocyanate, 1,4-dimethylcyclohexane diisocyanate,
1,4-diethylbenzene diisocyanate, 1,4-dimethylnaphthalene diiso- :
cyanate, 1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-
diisocyanate, cyclohexane-1,4 diisocyanate, 1-methylcyclohexane-
2,4-diisocyanate, 1-methycyclohexane,~2,2-diisocyanate, 1-
ethylcyclohexane-2,4-diisocyanate, dicyclohexylmethane-4,4'-
diisocyanate, dicyclohexylmethylmethane-4,4'-diisocyanate,
j`````~ --10-
`
~ .. ..
:
~- . . ,-: .,, ~.
` ~3'^J~3
dicyclohexyldimethylmethane-4,4'-diisocyanate,2,2-dimethyldi-
cyclohexylmethane-4,4'-diisocyanate r 3,3',5,5'-tetramethyldi-
cyclohexylmethane-4,4'-diisocyanate, 4,4'-methylenebis (cyclo-
hexylisocyanate), ethylidene diisocyanate, 4,4'-diphenyl diiso-
cyanate, dianisidine diisocyanate, 1,5-naphthalene diisocyanate,
m-phenylene diisocyanate, isopropylidene bis(phenyl or cyclo-
hexyl isocyanate), 1,3-cyclopentylene diisocyanate, 1,2-cyclo-
hexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4',4"-
triphenylmethane triisocyanate, 1,3,5-triisocyanate benzene,
phenylethylene diisocyanate, and the like, also poly silanols
derived in the usual fashion from lower alkyl or vinyl silanol
and silanes, also polyphospholanes derived in the usual fashion
from phosphoxychlorides and polyols and the like also hydroxy
terminated polybutenes and polybutadienes and the like.
While the processes for the practice of the invention
have been described for the preparation of specific embodiments
o~ the invention having a group capable of absorbing actinic
radiation derived from benzoin, it willlbe obvious to one skilled
in the art that in place of benzoin one may substitute other
substituted benzoins such as those described in Organic Reactions,
Vol. IV, Chapter 5, John Wiley, New York, N.Y., or those pre~
pared by the general methods described therein; acetoins as de~
scribed or prepared by the methods set forth in the same volume
of Organic Reactions, referenced above; hydroxyalkoxy substituted
benzophenones, or hydroxy alkoxy substituted acetophenones, as
described in Vol. I of Organic Reactions, John Wiley, New York,
N.Y.; hydroxy alkoxy acetonaphthanes or hydroxy alkoxy anthra-
quinones.
Similarly one skilled in the art would recognize that in
place of benzoin at one or more terminal positi~ns one could
substitute an hydroxy substituted acrylic ester or an isopropyli-
dene hydroxy derivative to prepare *he compounds of Formula II.
-lOa-
. .
, ,. :,
- - .
3~ 3
In using the compositions of the in~ention one may employ
the standard procedures norimally employed when using radiation
curable polymers.
The photoinitiator prepolymer and the photocurable polymer
are blended by conventional methods, if necessary. If the photo-
initïator function, and the photocurable function are both con-
tained in the same prepolymer, of course, such blending would not
be necessary, but additional photocurable prepolymer may be added
if desired.
Various optional additives such as plasticizers, solvents
and flow control agents may also be incorporated in the final
formulation. The photoinitiator prepolymer may be incorporated
a~ about 5 to about 25 parts per hundred commonly from 10 to
about 20 parts per hundred most preferably about 15 parts per
hundred of the final formulation weight. The photocurable pre
polymer may be incorporated at about 30 to 95 parts per hundred
commonly about ~0 to 70 parts per hundred, preferably about 50
parts per hundred of the final formulation when a separate photo-
initiator of photocurable prepolymer is employed. When a com-
bination photocurable, photoinitiator prepolymer is employed itmay be employed at from about 30 to about 80 parts per hundred,
commonly about 4n to 70 parts per hundred, preferably about 50
to 60 parts per hundred of the final formulation and up to about
25~ additional photocurable prepolymer containing no photoini~
tiator function on the same molecule may be incorporated.
The blended material may then be cast as a film over the
surface it is desired to coat and then the coated surface exposed
to actinic radiation in the range from 2000 to 4000 ~ preferably
from about 3000 to 4000 ~. The exact time of exposure is not
critical, and will depend somewhat, of coursel on the intensity
of the radiation incident on the surface, and will be suf~icient
to allow the formation of a cured film which ph0nomenon will be
.
- . ~ .: ,. , : : :
~37~'73
observable.
The following Examples ~urther illustrate the best mode
contemplated by the inventor for the practice of his invention.
-lla-
~3~3
EXAMP~E 1
This Example illustrates the preparation of a benzoin end-
capped urethane terminated polyester.
To a mixture of a hydroxyl terminated polyethylene adipate
having an average molecular weight of about 800 end capped with
tolue~e diisocyanate to a final -NCO content of about 3.0(623.8g),
benzoin (100.3 g) and methyl ethyl ketone (482.7 g) was added
triethylamine (1.4 g). The mixture was heated with stirring to
60C. after 3 hours the NCO content had dropped from 3.1 to 0.1%.
".
~ -12- `
~L~37~73
EXAMPLE 2
This Example illustrates the use of the product of
Example I as an initator in a photocure reaction.
A ten mil film was cast from a mixture of 15 parts of the
product of Example I and 50 parts of an acrylate terminated oli-
gomer obtained by capping an isocyanate terminated polyethylene
adipate prepolymer containing 1.65~ NCO with 2-hydroxyethyl-
acrylate. The film was then subjected to ultraviolet radiation
using a QC 1202 AN Processor (P.P.G. Industries Inc. Radiation
Polymer Co.) at a conveyor speed of 20 feet per minute under two
12 inch lamps having a linear power density of 200 watts per
inch~ A flexible cured film having an ultimate tensile strength
of 1720 psi and an elongation of 270% was obtained.
-13-
' ~
i
.
1~3~
EXAMPLE 3
This Example further illustrates the use of a benzoin end-
capped, toluene diisocyanate terminated poly(ethylene)adipate as
a photoinitiator.
A. A hydroxy terminated poly(ethylene)adipate of average
molecular weight about 1600 was end-capped with ~oluene diiso-
cyanate (Hylene~ TM) at an NCO/OH ratio of 1.67 and then with
benzoin at an OH/NCO ratio of 1.05 in methyl ethyl ketone (60%
solids) in a fashion similar to that described in Example I.
B. 15.1 parts of the product of part A are mixed with
83.9 parts of an acrylate terminated oligomer prepared by end-
capping 2-hydroxy ethyl acrylate at an OH/NCO ratio of 1.05, an
ethylene/propylene adipate copolymer of average about 2500 mole-
cular weight end-capped with Hylene~ TM to an approximate NCO
content of 1.65~, and 1 part of an organo modified silicone UCC
L-7602 as a flow control agent. A 17 mil film was cast from this
mixture allowed to air dry overnight then samples were ultra- `~
violet cured as in Example 2 at 20(A), 40(B), and 60(C) feet per
minute. -
The following physical properties were obtained.
Sample Tensile (psi) Elongation
A 1720 200
B 760 210
C 610 205
*As used herein and in the following Examples all parts by weight.
-14-
:
. ~
- : , , .
,,
3~ 73
E,~ll'LI~
1~ radiatioll curable ol;~,omcr as describc(l in T~xamplc 3 (53. 7 parts), a1l
oligomeric initiator as described in ~,xample 3 (15 1 parts~, UCCL-7G02 (1 part) and
1,G-he~alle(liol cliacrylate (30.2 parts) are blended. A 15 mil thickncss film is cast
~ d allowed to air dry overnigllt. Samples are treated witll ultraviolet radiation as
described in E~ample 2 at speed of 20(A), ~LO(B) and GO(C) feet per minute. The
follo~ving physical properties ~,vere obtained: -
S~mple Tensile (psi) E:longation (%)
A 1300 30
B 1010 25
C 740 25
- '.
,
`
:
:
`
'
.
-15-
.
~3~
I~Y~I~l 1 Ll, 5
A radi;ltioll c~lra~)le oli~o~ner as dc.scribcd i~ ,xn~llplc .~ (5n p~ ts), ~Ul
oligomeric initiator as clescribed in l~cample 3 (15 parts), mctllyl etl~yl kc!,onc
(33 parts) an(l UCCI.-7(;0~ (o. (; parts) are blendc(l. A 17 mil lilm was casl oL this
blend, air clriecl overnigllt and samples ultraviolet cured at 20 feet per minute.
Tlle following physical properties were obtained:
Tensile 995 psi
Elongation: 175%
100,'o I~lodulus: 245
`~0
~ 375~3
~`,YAI\1PLE: (;
A ra(li~Lion cura1)1c oligomcr prep~red by en(l_capping with 2-hydro:cy cll~yl
acrylate, a hydroxyl terminatcd polyoxy propylcne glycol of !)87 avera~e n-olec~llar
~) .
~vciE~llt cappecl with l-Iylene TM at an NCO/OII ratio of 2. 0 (44~ 8 parts), an oligomeric
initiator prepared by encl-capping with benzoin at an OII/NCO ratio of 1~ 05, a polyoxy
propylene glycol of 18G5 avcrage molecular weigllt capped witll llylene 1 i~I at all
NCO/O~I ratio of 2. 0 G0% solids in methyl ethyl ketone (10. 3 parts), n~ethyl ethyl
ketone (23. 9 parts) and UCCL-7G02 (0. G parts) were blended. A 17 mil film was
cast and air driecl overIlight~ A s~nple was ultraviolet cured ns in I:x~mple 2.
l`he follo~ving physical properties were obtained:
Tensile:15 0 psi
Elongation: 20%
~0
_ I q_
~13~ 3
EXAMPLE 7
A photocurable oligomer prepared by end-capping with 2-
hydroxy ethyl acrylate, a hydroxy terminated poly(ethylene adi-
pate) of about 1600 average molecular weight end-capped with
Hylene~ TM at an NCO/OH ratio of 1.67 (17.8 parts), a photo-
initiator prepared by end-capping an ethylene/propylene adipate
copolymer of about 2500 average molecular weight with Hylene~ TM
to an approximate NCO content of 1.65% then treating with ben-
zoin (0.4 OH/NCO ratio) followed by treating with 2-hydroxy
ethyl acrylate (0.65 OH/NCO ratio) (55.3 parts), methyl ethyl
ketone (ll.9 parts), and UCCL-7602 (0.5 parts) were blended. A
17 mil film was cast and air dried overnight. After ultraviolet ~`
cure at 20 feet per minute as in Example 2 the following physical
properties were obtained:
Tensile: 360 psi
Elongation: 230%
Modulus: 100~ 80 ;
200% 1 120
~ -18-
1137~
EXAMPLE_8`
A photocurable oligomer as in Example 6 t4018 parts), an
oligomer initiator prepared by end-capping a polyoxy propylene
glycol of 1025 average molecular weight with Hylene~ TM at an
NCO/OH ratio of 2.0 followed by end-capping with 0.9 equivalent
of benzoin and 0.1 equivalent of diethyleneglycol monobutyl
ether as 72.8% solids in methyl ethyl ketone (12.7 parts), methyl
ethyl ketone (18 parts), UCCL-7602 (0.5 parts) were blended. A
14 mil film was cast and allowed to air dry overnight~ After
ultraviolet curing as in Example 2 at 20 feet per minute the
following physical properties were found:
Tensile:460 psi
Elongation:50%
~0
--1 9--
t73
ExAMæLE 9
A photocurable oligomer analogous to that of Example 3
23.9 parts), a photoinitiator prepared by end-capping a poly-
(ethylene adipate) of 1290 average molecular weight with Hylene~
TM an NCO/OH ratio of 1.82 followed by treating with benzoin
(0.4 equivalents) and 2-hydroxy ethyl acrylate (0.6 equivalents)
as 50% solids in methyl ethyl ketone (52.3 parts), methyl ethyl
ketone (7 parts), and UCCL-7602 (0.5 parts) were blended. A 17
mil film was cast and air dried overnight. After ultraviolet
cure as in Example 2 at 20 feet per minute the following physical
properties are found:
Tensile: 285 psi
Elongation: ~0%
;
-20~ ,~
- . ; . , . , , ~ . .. .
~379~3
ExAMæLE 10
A radiation curable oligomer as in Example 6 (40.8 parts),
a photoinitiator prepared by end-capping a polyoxy propylene
glycol of 1025 average molecular weight with Hylene~ TM at an
NCO/OH ratio of 2.0 followed by capping with benzoin (0.9 equi-
valent) and isopropylidene glycerol (0.1 equivalent) as 72% solids
in methyl ethyl ketone (12.8 parts), methyl ethyl ketone (18
parts) and UCCL-7602 (0.5 parts) were blended. A 14 mil film
was cast and air dr'~ed overnight. Ultraviolet cure as in Example
2 at 20 feet per minute gave the following physical properties:
Tensile:410 psi
Elongation:40%
Modulus: 100% 220
~21-
.,
~L~3~
EXAMPLE 11
A photocurable oligomer as in Example 6 (40.2 parts), a
photoinitator prepared by end-capping a polyoxy propylene glycol
of 1025 average molecular weight with Hylene~ TM at an NCO/OH
ratio of 2.0 followed by capping with benzoin (0.4 equivalents),
and 2-hydroxy ethyl acrylate (0.6 equivalen~s) as 50% solids in
methyl ethyl ketone (19.5 parts), methyl ethyl ketone (12
parts) and UCCL-7602 (0.5 parts) were blended. A 14 mil film
was cast and let dry overnight. Ultraviolet cure as in Example
2 at 20 feet per minute gave the following physical properties:
Tensile:545 psi
Elongation:40%
Modulus: 100% 340
~0 :
'
-22-
~3~973
EXAMPLE 12
A radiation curable oligomer analogous to that of Example
3 (50 parts), a photoinitiator as in Example 3 (15 parts), methyl
ethyl ketone (33 parts), and UCCL-7602 (0.6 parts) were blended.
A 17 mil film was cast and air dried overnight. Ultraviolet
curing as in Example 2 at 20 feet per minute gave the following
physical properties:
Tensile: 2350psi
Elongation: 295%
Modulus: 100~ 200
200% 910
-23-
. . . . .
~l3~9~3
EXAMPLE 13
A photocurable oligomer Epocryl DRH 303.1 tan acrylated
bisphenol A epoxy resin unsaturation 0.356 equivalents/100 g,
Shell Chemical Co.) (52.3 parts), a photoinitiator as in Example
3 (12.9 parts), methyl ethyl ketone (35 parts), and UCCL-7602
(0.6 parts) were blended. A 17 mil film was cast and air dried
overnight. The film was ultraviolet cured as in Example 2 at 20
feet per minute.
; :;'.
24
~` .
~379~3
EXAMPLE 14
A radiation curable oligomer analogous to that of Example
3 (50 parts), a photoinitator as in Example 3 (15 parts), methyl
ethyl ketone (33 parts), and UCCL-7602 were blended. A 17 mil
film was cast and air dried overnight. Ultraviolet cure as in
Example 2 at 20 feet per minute gave the following physical pro-
perties:
Tensile: 2170 psi
Elongation: 315
Modulus: 100% 180
200% 85
250%950
. ~
.. .. . . ..
