LAMINATING RESINS HAVING LOW ORGANIC EMISSIONS

RESINES POUR STRATIFIES A EMISSIONS FAIBLES DE SUBSTANCES ORGANIQUES

English Abstract

A laminating resin is made from (1) an unsaturated polyester resin, (2) a diacrylate or dimethacrylate of alkoxylated bisphenol-A,
and (3) either (A) vinyl toluene, (B) ethylene glycol dimethacrylate, or (C) styrene, divinyl benzene or a combination thereof. The resin
achieves excellent laminating resin properties, and is significantly inhibited from emitting volatiles during use. A method of laminating a
solid formed body with the resin above is also described.

French Abstract

Une résine pour stratifiés est réalisée avec (1) une résine polyester insaturé, (2) un diacrylate ou un diméthacrylate d'un bisphénol A alcoxylé et (3) (A) du vinyltoluène, (B) ou de l'éthylène glycol diméthacrylate ou (C) du styrène, du divinylbenzène ou une combinaison de ceux-ci. La résine est excellente pour la réalisation de stratifiés et elle émet très peu de matières volatiles en cours d'utilisation. On décrit également un procédé pour réaliser un corps solide stratifié, avec la résine ci-dessus.

Claims

- 23 -
Claims
1. A laminating resin composition
characterized by low volatile emissions comprising
(A) a base unsaturated polyester resin comprising
glycols, unsaturated polycarboxylic acids or
derivatives thereof, and, optionally, saturated
dicarboxylic acids and (B) alkoxylated bisphenol-A
diacrylate or dimethacrylate having at least two
alkoxy groups, in a weight ratio of (A) to (B) of
2:1 to 0.5:1, and (C) about 20% to about 60% by
weight, based on the total of components (A) and (B)
of a compound of the formula
<IMG>
where one H on the ring is substituted by CH3.
2. A laminating resin composition
characterized by low volatile emissions comprising
(A) a base resin comprising glycols, unsaturated
polycarboxylic acids or derivatives thereof, and,
optionally, saturated dicarboxylic acids and
(B) alkoxylated bisphenol-A diacrylate or
dimethacrylate having at least two alkoxy groups, in
a weight ratio of (A) to (B) of 2:1 to 0.5:1, and
(C) about 20% to about 60% by weight, based on the
total of components (A) and (B) of ethylene glycol
dimethacrylate.

-24-
3. A laminating resin composition
characterized by low volatile emissions comprising
(A) a base unsaturated polyester resin comprising
glycols, unsaturated polycarboxylic acids or
derivatives thereof, and, optionally, saturated
dicarboxylic acids and (B) alkoxylated bisphenol-A
diacrylate or dimethacrylate having at least two
alkoxy groups, in a weight ratio of (A) to (B) of
2:1 to 0.5:1, and (C) about 10% to about 60% by
weight, based on the total of components (A) and (B)
of an ingredient comprising: (i) X% divinyl benzene;
and (ii) 100-X% styrene, wherein x is 0-100.
4. Laminating resin composition of
claims 1, 2, or 3 including from 1% to about 10%,
based on the overall composition, of N-vinyl
pyrrolidone.
5. Laminating resin composition of
claims 1, 2, or 3 including from 1% to about 20%,
based on the overall composition, of cyclohexyl
methacrylate.
6. A laminating resin of claims 1, 2, or
3 wherein the weight ratio of (A) to (B) is about
1 : 1 .
7. A laminating resin of claims 1, 2, or
3 characterized by volatile emissions measured by
the test of Section 1162 of the Regulations of the
South Coast (California) Air Quality District no
greater than 20 grams per square meter.

-25-
8. Method of laminating a solid formed
body without creating significant volatile emissions
in the workplace comprising (a) providing a forming
surface having a desired positive or negative shape,
(b) providing a liquid mixture comprising (1) about
two parts by weight unsaturated polyester resin,
(2) about one part to about four parts by weight
alkoxylated bisphenol-A diacrylate or
dimethacrylate, (3) about 20% to about 60%, based on
the total weight of (1) and (2), of a monomer of the
formula
<IMG>
where one H on the ring is substituted by CH3, and
(4) an effective amount of a polymerization
catalyst, (c) applying said mixture to said forming
surface at ambient temperatures in layers while
permitting said layers incrementally to polymerize,
thereby building said shaped article without
creating significant volatile emissions, and
(d) removing the finished solid formed body from
said forming surface.

- 26 -
9. Method of laminating a solid formed
body without creating significant volatile emissions
in the workplace comprising (a) providing a forming
surface having a desired positive or negative shape,
(b) providing a liquid mixture comprising (1) about
two parts by weight unsaturated polyester resin,
(2) about one part to about four parts by weight
alkoxylated bisphenol-A diacrylate or
dimethacrylate, (3) about 20% to about 60%, based on
the total weight of (1) and (2), of ethylene glycol
dimethacrylate, and (4) an effective amount of a
polymerization catalyst, (c) applying said mixture
to said forming surface at ambient temperatures in
layers while permitting said layers incrementally to
polymerize, thereby building said shaped article
without creating significant volatile emissions, and
(d) removing the finished solid formed body from
said forming surface.
10. Method of laminating a solid formed
body without creating significant volatile emissions
in the workplace comprising (a) providing a forming
surface having a desired positive or negative shape,
(b) providing a liquid mixture comprising (1) about
two parts by weight unsaturated polyester resin,
(2) about one part to about four parts by weight
alkoxylated bisphenol-A diacrylate or
dimethacrylate, (3) about 20% to about 60%, based on
the total weight of (1) and (2), of an ingredient
comprising: (i) 100-X% styrene; and (ii) x% divinyl
benzene, wherein X is 0-100, and (4) an effective
amount of a polymerization catalyst, (c) applying

-27-
said mixture to said forming surface at ambient
temperatures in layers while permitting said layers
incrementally to polymerize, thereby building said
shaped article without creating significant volatile
emissions, and (d) removing the finished solid
formed body from said forming surface.
11. Method of claims 8, 9, or 10 wherein
the alkoxylated BPA is a dimethacrylate and has
about 2 to about 20 alkoxy groups.
12. Method of claims 8, 9, or 10 wherein
said mixture is applied by spraying.
13. Method of claim 8, 9, or 10 wherein
said mixture includes glass fibers.
14. Method of claims 8, 9, or 10 wherein
said alkoxy groups are ethoxy groups.
15. Method of claim 8 wherein said
alkoxylated BPA dimethacrylate has from 2 to 8
alkoxy groups.
16. Method of claim 10 wherein X is 0.
17. Method of claim 10 wherein X is 100.
18. Method of claim 10 wherein said
alkoxylated BPA dimethacrylate has from 2 to 10
alkoxy groups.

- 28 -
19. Method of making a shaped article
comprising repeatedly applying to a form a liquid
laminating resin of claims 1, 2, or 3 under
polymerizing conditions, and permitting said resin
to polymerize, thereby building said shaped article
without emitting significant amounts of volatile
monomers.

Description

W095/23828 pcT~ss5lo2lol
- 216088~
--1--
LAMINATING RESINS HAVING LOW ORGANIC EMISSIONS
Technical Field
This invention relates to resin
compositions which cure as they are shaped,
laminated, brushed, sprayed or otherwise more or
less incrementally placed into the space where they
are to form a product; such resins are broadly known
as laminating resins, commonly have an unsaturated
polyester resin base, are mixed with glass fiber
reinforcement, and nearly always are employed in a
solution of an organic monomer such as styrene. The
organic monomer is inten~e~ to copolymerize with the
resin but typically and notoriously may also tend to
volatilize in significant amounts into the workplace
environment. The present invention is drawn to
compositions and methods which can be used in
existing equipment, procedures, and workplaces, but
which will emit far less monomer than the typical
laminating resins and methods heretofore.
Background of the Invention
Many attempts have been made to devise
laminating resins having low volatile emissions and
still meet the physical specifications and other
desirable properties of the end products, while
remaining relatively easy to use. In Lee U.S. Patent
4,465,806, for example, a more or less conventional
unsaturated polyester resin is combined with,
instead of the usual styrene, a reaction product of

r
WO 95/23828 2 1 6 0 8 8 ~ PCT/US95/02101
a polyepoxy compound and acrylic or methacrylic acid
which may be the diacrylate of a polyglycidyl ether
of bisphenol-A. These compounds are made from epoxy
compounds, and the author of U.S. Patent 4,465,806
requires that a significant portion of the epoxy
groups be unreacted for use in their resin.
Moreover, unlike the present invention, they form
pendant OH groups.
Ethoxylated, difunctional, bisphenol-A has
been used in the past as an ingredient in various
types of resins, generally resins which include a
significant diisocyanate component, as in Ford, Jr.
et al U.S. Patent 3,876,726.
European Patent Application 0 234 692
discloses a composition said to be useful as a
molding resin, having the virtue of a low residual
monomer concentration in the final product. The
gist of the disclosure appears to be that
dimethacrylates such as ethoxylated bisphenol-A
dimethacrylate can be used as components of
otherwise more or less conventional unsaturated
polyester resins to reduce the amount of residual
styrene monomer in contained molding processes such
as cell molding, compression molding, and sheet
molding. See also Reid and Rex U.S. Patent
5,202,366, which includes a low-profile additive in
a similar composition.
The daunting problem of volatile emissions
during spray-up or other laminating procedures has
until now been unsolved. Applicants' dramatic
results detailed herein show that lamination can be
used with significantly reduced emissions in the
workplace.

2160884
WO 95/23828 PCT/US95/02101
-
--3--
Summary of the Invention
Our new laminating resins comprises three
components. The first is a more or less
conventional base resin comprising glycols and
unsaturated dicarboxylic acids; optionally the base
resin may also contain a saturated dicarboxylic
acid. In polymeric form, they are typically maleic
and phthalic acid residues, with optional
isophthalic residues, interspersed with glycol
residues. These glycols are commonly ethylene
glycol, diethylene glycol, propylene glycol and
dipropylene glycol, usually as mixtures, but many
other glycols can be utilized; dicyclopentadiene may
be included as well, as is known in the art. The
second component is a diacrylate or dimethacrylate
of alkoxylated bisphenol-A of the formula
R3 Rl CH3 R2 R3
CH ~C C(OCHCH2)m O ~ I ~ O(CH2CHO)n " 2
O CH3 o
where m and n are inderen~ently numbers from 1 to
about 10, and Rl and R2 are in~erenA~tly, in each
alkoxy group, hydrogen or CH3, and each R3 is also
independently hydrogen or CH3. Hydroxyethyl or
hydroxypropyl groups can comprise about 19-71%
of the weight of this ingredient. These two
ingredients may be present in weight ratios of about
2.0:1 to about 0.5:1. The composition also includes
a third ingredient which may be (1) about 20-60%
based on the total of the two above ingredients of a
compound of the formula

~1~ 0 8 8 ~. ~ PCT/US95/02101
~ct~-C~
where one H on the ring is substituted by CH3, or
(2) about 20-60%, based on the total of the two
above ingredients of ethylene glycol dimethacrylate,
or (3) about 10-60% based on the total of the two
above ingredients, of styrene, divinyl benzene or
mixtures thereof.
The above-described composition may also
include from 1% to about 10% of N-vinyl pyrrolidone
or 1% to about 20% cyclohexyl methacrylate or both,
and/or 1% to about 30% of any combination of the
following, provided the ingredient is not included
above: ethylene glycol dimethacrylate, vinyl
toluene, and divinyl benzene, all based on the
overall composition. Since our objective is to
design a composition which works very well as a
laminating resin without significant emissions, the
addition of styrene to the recipe is not required,
but the composition will continue to be operable as
an excellent laminating resin even though styrene is
included either as the third ingredient, or as an
additional component. The composition will also
tolerate many other minor ingredients known to be
useful in the unsaturated polyester and laminating
art.

W095/23828 21608&q PCT/US95/02101
Detailed Description of the Invention
While the problem at hand is to create a
formulation which drastically differs from
commercial st~ rd laminating resins in terms of
volatile emissions during application, the market
dictates that it must be accomplished without
significantly altering the widely used equipment and
techniques of application. Accordingly, the
following criteria are to be kept in mind at all
times:
1. Reduced emission of volatile organic
compounds -- regulations will become
more stringent with time.
2. Less potential hazard to human health
and the environment -- regulations
will also become more stringent with
time.
3. Minimal increase in cost when
commercialized, and reason to believe
cost will be reduced in the long run.
4. Compatibility between components of
the resin system.
5. Reactivity that is similar to that of
styrenated polyester resins.
6. Viscosity that is similar to that of
styrenated polyester resins - 100 to
400 cps.
7. Physical properties similar to or
better than those of styrenated
polyester resin.
8. Ability to wet glass and bond to other
components of an assembly.

WO 95/23828 PCT/US95/02101
216088g . ~
Persons skilled in the art will realize
that number 7, relating to physical properties of
the final product, can by itself include several
important specifications. Thus, the problem is not
simply one of finding a monomer system which is not
as volatile or objectionable as styrene alone.
Rather, many criteria have to be balanced, and, with
thousands of chemicals to consider, analysis of the
combinations and their effects is extremely
difficult. One must decide on the important
functions and properties, settle on a systematic but
simple screening process, and try to develop a short
list of prospective formulations which have a good
chance of meeting all the criteria within a
practical time period.
The proliferation of input variables to
attain these objectives may be further appreciated
by considering the more or less conventional
unsaturated polyester compositions which may be used
as a base. They are prepared by polycondensation of
polycarboxylic acid derivatives, one of which must
be an alpha, beta-ethylenically unsaturated
polycarboxylic acid, and polyols. By polycarboxylic
acid derivatives we mean to include polycarboxylic
acids, their esters of lower alcohols, their acid
chlorides and their anhydrides.
The ratio of polycarboxylic acid to polyol
is usually a 1:1 molar ratio. However, in most
esterification processes, a slight excess of polyol
is utilized to compensate for polyol losses during
esterification. Also, although dicarboxylic acids
and diols are most frequently utilized and the 1:1

w095/23828 - PCT~S9S/02101
216~884
molar ratio is prevalent, the utilization of triols
and the like requires the ratio of acid to polyol to
be stated more precisely as one equivalent of acid
per equivalent of polyol.
The unsaturated polyesters useful in this
invention may be prepared from an acid mixture
wherein the unsaturated polycarboxylic acid
comprises as little as 20 mole percent of the total
acids present, although it is generally preferred
that the unsaturated polycarboxylic acid comprises
about 30% or more of the total acid content.
Some of the unsaturated polycarboxylic
acids useful in preparing unsaturated polyesters
used in this invention include:
Maleic acid Citraconic acid
Fumaric acid Glutaconic acid
Itaconic acid Chloromaleic acid
Mesaconic acid
and the like, wherein the term "acid" is used to
include the corresponding anhydrides where such
anhydrides exist.
Some of the saturated and aromatically
unsaturated polycarboxylic acids optionally useful
in preparing unsaturated polyesters used in this
invention include:
Phthalic acid Isophthalic acid
Tetrahydrophthalic acid Hexahydrophthalic acid
Endomethylene tetrahydrophthalic acid
Tetrachlorophthalic acid Glutaric acid
Hexachloroendomethylene tetrahydrophthalic acid
Succinic acid Suberic acid
Adipic acid Sebacic acid

W0 95t23828 21 6 0 8 8 4 . 1 PCT/US95/02101
.
and the like, wherein the term "acid" includes the
corresponding anhydrides where such anhydrides
exist.
Polyols useful in preparing polyesters for
use in this invention are polyfunctional alcohols of
the type conventionally utilized in polyester
preparation. Such polyols include:
Ethylene glycol 1,5 propanediol
Propylene glycol Triethylene glycol
Butylene glycol Glycerol
Diethylene glycol 1,4,6-hexanetriol
Trimethylolpropane Trimethylolethane
Dipropylene glycol Pentaerythritol
Neopentyl glycol
Alkoxylated 2,2-bis(4-hydroxyphenyl) propane
and the like. Although diols are generally
preferred in the preparation of unsaturated
polyesters, the more functional polyols, i.e.
polyols having a functionality of three to five, are
sometimes used.
In addition, dicyclopentadiene may be
included and may be considered a normal part of the
"base resin" as used herein.
During the development of the formulation,
various monomers and monomer substitutes were
screened, using two different "base" resins -- one
having dicyclopentadiene as a major ingredient and
one without dicyclopentadiene. Following are
results for the base resin without
dicyclopentadiene:

WO 95/23828 2 16 0 8 8 4 PCT/US95/02101
A base resin composition (hereafter
designated "Resin A") was prepared having the
following ingredients:
Base Resin ..................... 60 parts by weight
12% Cobalt (Promoter)........... 00.30
Potassium (Co-promoter)......... 00.20
N,N-Dimethylacetoacetamide
(Accelerator).................. 00.30
DDM-9 (Initiator)............... 01.50
Monomer (as indicated below).... 4o
Parts by
Base Resin (Polymer) weight lbs/100 lbs lbs/60 lbs
Propylene Glycol - 22.788 31.97 19.18
Diethylene Glycol - 04.937 6.93 4.16
Phthalic Anhydride - 32.734 45.92 27.55
Maleic Anhydride - 10.820 15.18 9.11
71.279 100.00 60.00
The following "monomers" were utilized with Resin A:

WO 95/23828 2 1 6 0 8 8 4 - -` PCT/US95/02101
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WO 95/23828 2 16 0 8 8 4 PCT/US95/02101
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WO95/23828 2 1 6 0 8 8 4 PCT~S95/02101
-12-
Liquid resin properties measured in the
experiments reported below were gel time, (reported in
the tables herein in minutes and seconds, as 13:17, for
example), room temperature interval time, which is the
time between gelation and the exothermic peak, room
temperature exothermic peak which is the highest
temperature reached in a 100 g mass of resin during
the curing process, Brookfield viscosity, and Barcol
hardness by ASTM D2583. For volatile emissions, we
followed the Rule 1162 StA~Ard Method for Static
Volatile Emissions of the South Coast Air Quality
Management District (California) which is incorporated
herein by reference. This test is accepted as a
predictor of volatile emissions in the workplace during
spray-up lamination procedures. Its results are
reported in two ways -- grams per square meter of
weight loss, and the time of emissions, in minutes and
seconds. The latter measurement entails noting the
point in time in which weight loss is no longer
recorded, thus requiring that weight be monitored
beyond the time noted.
A brief outline of the test is as follows:
An environment at 77C and 50% relative humidity is
maintained. If a controlled environment is not
available, conditions should be reported for which
measurements are made. A 200 gm pre-promoted resin is
weighed out into a suitable dry and clean container.
The container is covered and placed in a 25C
temperature bath. A balance is placed in a draft free
enclosure. A gallon lid is cleaned with solvent and
wiped dry. The diameter is measured to the nearest 0.1
cm. The gallon lid is placed on an inverted paper or
plastic cup mounted on the balance pan. A bent paper

WO 95/23828 2 1 6 0 8 8 4 PCTtUS95tO2101
clip is positioned in the center of the gallon lid.
This weight (TARE WEIGHT) is recorded. The container
is taken from the temperature bath and an appropriate
volumetric or weight measure of catalyst is added. A
timer is started at this point. The catalyst is mixed
with the resin for one minute. The INITIAL WEIGHT is
determined by pouring 100.0 + 0.5 gm of catalyzed resin
into the can lid and recording the weight. Next, the
paper clip is used to determine when the resin has
hardened sufficiently to allow the resin or lid to be
lifted. The time (gel time) is recorded at
this point. The resin is then allowed to harden in the
can lid and every 15 minutes it is reweighed until
concurrent weights agree to within 0.05 gm. This is
recorded as the FINAL WEIGHT. The entire procedure
should be repeated until duplicate samples agree to the
nearest 5 gm/m2.
The volatile emissions per square meter are
calculated as follows:
Volatile Losses per _ INITIAL WEIGHT - FINAL WEIGHT
Square Meter ~ Area of Sample in Square Meters
The clear castings tests adopted were as
follows:
1. Tensile strength - ASTM D638.
2. Tensile modulus - ASTM D638.
3. Elongation - ASTM D638.
4. Flexural strength - ASTM D790.
5. Flexural modulus - ASTM D790.
6. Heat deflection temperature -
ASTM D648.
7. Water absorption at 150F -
ASTM D570 (modified).

W O 95/23828 PC~rnUS95102101
2l~n~s~
-14-
The water absorption test was modified as
follows: the temperature was set at 150F and long
term immersion was set at one week. In the data
reported in Tables I and IV, Resin A is as described
above in terms of weight; it is, in molar
equivalents, a polyester resin composed of 1.0 mole
maleic anhydride, 2.0 moles phthalic anhydride, 0.42
mole diethylene glycol and 2.71 moles propylene
glycol. Resin B is similar to Resin A with a lower
viscosity by an adjustment of the cook, as is known
in the art. Sartomer CD480 is ethoxylated
bisphenol-A dimethacrylate where m and n
in the above formula total 10. Sartomer 348 is
ethoxylated bisphenol-A dimethacrylate where m and n
in the above formula are both 1. Mod L is 25%
hydroquinone and 75% propylene glycol.
From the data in Table I, it can be seen
that formulations Z, S, and O have better than
acceptable resin properties and clear casting
properties, and have volatile emissions far less
than the rate of the more or less classical
commercial resin A2. Formulation Z is about
one-fifth the rate of A2.
In Tables II and III, nine additional
formulations are shown. From these it will be seen
that cyclohexyl methacrylate causes undesirable
properties when used as the only material in
addition to the base resin and the ethoxylated BPA
dimethacrylate. But there are extraordinarily low
emissions from all nine of the formulations. The
use of vinyl toluene to reduce the viscosity is
certainly not detrimental to emissions results.

WO 95/23828 2 1 6 0 8 8 4 PCT/US95/02101
In Tables IV and V, formulations
containing both Sartomer and either styrene or
divinyl benzene are seen to compare very well in
terms of emissions with those not including styrene
as a monomer. From these it will be seen that the
use of alkoxylated BPA dimethacrylates have the
effect of significantly reducing monomer emissions
in styrene-containing laminating resins.

W 0 95/23828 ~ l 6 a 8 8`4 `; PCTrUS9S/02101
-16-
TABLE I
~FCT~ - A7 C2 S Z Al O
Resin A - 60.00 60.00 40.00 35.00 35.00 -----
Resin B - ---_- _____ _____ _____ _____ 45 00
Sartomer CD480 - ----- ----- lS.00 15.00 15.00 10.00
Sartomer 348 - ----- ----- 20.00 20.00 20.00 15.00
EG Dimethacrylate - ----- ----- 25.00 10.00 20.00 30.00
Vinyl Toluene - ----- 40.00 ----- 10.00 ----- -----
Cyclohexyl Methacrylate ----- ----- ----- 10.00 ----- -----
Divinyl Benzene - ----- ----- ----- ----- 10.00 -----
S~y~ane - 40.00 ----- ----- ----- ----- -----
Nod L - 0.20 0.22 0.06 0.12 0.12 0.06
~IN ~kOPEKll~S
Gel time, min:~ec - 12:59 13:17 21:18 18:29 11:30 5:20
Interval, min:sec - 5:58 6:54 4:32 4:11 3:26 3:19
Exotherm peak, F - 345 324 249 276 294 245
Viscosity, cps, 75F - 315 340 1,390 426 624 396
1162 Emissions, G/M2 - 31.5 20.6E 3.6 6.1 9.7 3.6
Barcol hardness
45 minutes - 45 42 47 44 52 34
One hour - 45 43 50 48 53 36
24 hours - 49 49 52 51 54 36
CLEAR CASTING PROP~ C
Tensile D~-~r,yLh, psi- 9,308 7,555 8,069 9,635 8,176 10,179
Ten. modulus, 10-5psi- 0.549 0.534 0.466 0.565 0.575 0.567
Elongation, % - 1.9 1.6 .3.2 2.7 1.9 2.3
Flexural ~L.er,~Lh,psi- 16,008 15,317 10,475 16,889 15,780 16,013
Flex modulus, 10-5psi- 0.586 0.573 0.322 0.444 0.482 0.498
Heat deflect. temp,F- 144 138 169 142 147 141
Water absorDtion % at 150CE
One day - 0.89 0.91 1.01 1.19 1.26 1.43
7 days - 1.89 1.89 2.12 1.65 ~.76 2.14A
E - This value was estimated based on,the difference in results
caused by using different end points for the 1162 test.
A - The surfaces of the test specimens were alligatored. This
indicates a more severe problem than the weight gain
indicates.
SIJBSTITUTE SHEET (RULE 26)

W O 95/23828 2 1 C~ 8 ~ PC~rrUS95/02101
TASLE II
r~w VOC Laminatin~ Resins B~scd on Gcneral PUrDOSe Polvester Polvmer
E5~in ~ F-3 G-3 H-3 I-3
ComDosition
Resin A 35.00 35.00 35.00 35.00 35.00
Sartomer 480 15.00 15.00 15.00 15.00 15.00
Sartomer 348 20.00 20.00 20.00 20.00 20.00
EG Dimethacrylate ----- 15.00 ----- 15.00 20.00
Cyclohexyl Methacrylate 30.00 15.00 15.00 ----- 05.00
Yinyl Toluene ----- ----- 15.00 15.00 05.00
Mod L 00.00 00.00 00.17 00.17 00.06
12% Cobalt 00.30 00.30 00.30 00.30 00.30
16% Potassium 00.20 00.20 00.20 00.20 00.20
Dimethyl Acetoacetamide 00.30 00.30 00.30 00.30 00.30
Resin ProDerties
Gel Time, min:sec 48:00 27:55 33:52 25:10 30:40
Interval, min:sec 10:49 05:01 07:07 03:51 05:23
Exotherm, F 229 239 244 291 258
Viscosity, cps e 75-F 1,280 1,085 560 650 930
Oarcol-45 minutes 00.0 31.7 00.0 00.0 26.6
-one hour 00.0 47.3 29.7 47.0 48.7
-two hours 00.0 48.6 45.6 50.8 51.0
-three hours 00.0 48.2 45.9 49.8 51.1
-four hours 00.0 48.6 46.0 50.3 51.2
-24 hours 38.2 48.4 47.2 50.7 51.5
1162 Emissions, G/M2 2.4 6.1 3.6 4.2 3.0
Emissions, min:sec 60:55 36:42 53:46 29:15 36:18
ProDerties of a Clear Castino
HDT, F 129 138 138 159 163
Tensile Strength, psi 9,290 8,980 9,580 9,140 6,050
Ten Modulus, 10-5 psi 0.451 0.481 0.485 0.544 0.587
Elongation, % 3.10 2.40 2.50 2.00 1.20
Flexural Strength, psi 14,400 >16,130 18,400 19,660 17,150
Flex Modulus, 10-5 psi 0.488 0.520 0.662 0.664 0.633
Water Absorption e 150-F
24 hours ~.06 1.08 1.07 0.95 1.07
seven days 2.43 2.19 1.78 1.84 2.06
SUBSTITUTE SHEET (RULE 26)

WO 95/23828 21 6 0 8 8 ~ PCT/US95/02101
--18--
TABLE III
Low VOC Laminatinq Resins Based on General PurDose Polvester Pol~mer
Bç~in U-3 ZA V-3 Z Q-4
comDosition
Resin A 35.00 35.00 35-00 35-00 30.00
Sartomer 480 15.00 15.00 15.00 15.00 20.00
Sartomer 348 20.00 20.00 20.00 20.00 20.00
EG Dimethacrylate 15.00 10.00 ----- 10.00 30.00
Cyclobexyl Methacrylate 05.00 10.00 ----- 10.00
Vinyl Toluene 10.00 10.00 30.00 10.00 ----
Mod L 00.13 00.06 00.20 00.12 00.10
12% Cobalt 00.30 00.30 00.30 00.30
16% Potassium 00.20 00.20 00.20 00.20
Dimethyl Acetoacetamide 00.30 00.30 00.30 00.30
Resin ProDerties
Gel Time, min:sec 38:05 38:15 37:36 18:29 14:10
Interval, min:sec 06:07 07:37 09:49 04:11 4:38
Exotherm, F 277 277 2~3 276 233
Viscosity, cps ~ 75F 790 710 382 426 400
Barcol-45 minutes 00.0 00.0 00.0 44.0 50.1
-one hour 37.0 32.2 39.9 48.0 51.9
-two hours 48.6 47.2 46.0 ---- 52.1
-three hours 48.5 47.6 46.2 ---- 52.1
-four hours 48.5 47.8 46.9 ---- 52.1
-24 hours 48.5 48.7 46.9 51.0 52.1
1162 Emissions, G/M2 7.3 2.4 1.8 6.1 0.6
Emissions, min:sec 44:22 48:20 51:35 ----- 16:00
ProDerties of a Clear Castina
HDT, F 136 138 138 142 210
Tensile Strength, psi 10,120 10,370 9,500 9,635 5,660
Ten Modulus, 10-5 psi 0.489 0.540 0.501 0.565 0.516
Elongation, % 2.70 2.60 2.30 2.70 1.30
Flexural Strength, psi 18,750 19,410 >19,150 16,889 14,550
Flex Modulus, 10-5 psi ----- ----- ----- 0.444 0.508
Water Absorption ~ l50-F
24 hours 1.06 1.04 0.81 1.19
seven days 1.78 1.87 1.43 1.65
SUBSTITUTE SHEET (R~LE 26)

W O 95/23828 21 6 0 8 8 IPCTrUS95/02101
--19--
TABLE IV
PF~IN - A2 C2 S Z Al
Resin A - 60.00 60.00 40.00 35.00 35.00
Sartomer CD480 - ----- - 15.00 15.00 15.00
Sartomer 348 - -- - - -- 20.0020.00 20.00
EG Dimethacrylate - ----- ----- 25.00 10.00 20.00
Vinyl Toluene - -- - 40.00 - - 10.00 -----
Cyclohexyl Methacrylate ----- -- - 10.00 -----
Divinyl Ben~ene - ----- - - - ----- 10.00
SLy.. ne - 40.00 - -- - - - ----- ---_-
Mod L - 0.20 0.22 0.06 0.12 0.12
IN PRO~h.l~
Gel time, ~in:sec - 12:59 13:17 21:18 18:29 11:30
Interval, ~in:sec - 5:58 6:54 4:32 4:11 3:26
Exotherm peaX, F - 345 324249 276 294
Viscosity, cps, 75-F - 315 340 1,390 426 624
1162 Emissions, G/M2 - 31.5 20.6E 3.6 6.1 9.7
Barcsl hardness
45 ~inutes - 45 42 47 44 52
one hour - 45 43 50 48 53
24 hours - 49 49 52 51 54
CBE M CASTING PROPERTIES
Tensile sL.er,~Lh, psi- 9,308 7,555 8,069 9,635 8,176
Ten. ~ c, 10-Spsi- 0.549 0.534 0.466 0.565 0.575
Elongation, ~ - 1.9 1.6 .3.2 2.7- 1.9
Flex~ral strength,psi- 16,008 15,317 10,475 16,889 15,780
Flex -' lu~, 10-spsi- 0.586 0.573 0.322 0.444 0.482
Heat deflect. temp,-F- 144 138 169 142 147
Water absorstion ~ at 150-F
One day - 0.89 0.91 1.01 1.19 1.26
7 days - 1.89 1.89 2.12 1.65 1.76
E - This value vas estimated based on the difference in results
caused by using different end points for the 1162 test.
A - The surfaces of the test speci~ens were alligatored. This
indicates a more severe problen than the weight gain
indicates.

WO 95/23828 ~ ` . PCT/US95/02101
216ff'g8~
--2~--
TABLE V
Lov VOC LAmi~tina Resi"~ Based on General PUrDOSe Polvester Polvmer
E~s~ E-4 _ V-3 F-4 G-3 D-4 2
ÇQm~osition
Resin A 3S.00 35.00 35.00 3S.00 3S.00 3S.00
Sartomer 480 15.00 15.00 lS.00 lS.00 15.00 15.00
Sartomer 348 20.00 20.00 20.00 20.00 20.00 20.00
EG Dimethacrylatc ----- ----- -- - ----- 10.00 10.00
Cyclohexyl Methac n late ----- ----- 15.00 15.00 10.00 10.00
StyrenQ 30.00 ----- 15.00 ----- 10.00 -----
Vinyl Toluene ----- 30.00 -- - lS.00 ----- 10.00
nod ~ 00.10 00.20 00.05 00.17 00.00 00.06
lZ% Cobalt 00.30 00.30 00.30 00.30 00.30 00.30
16% Potassium 00.20 00.20 00.20 - 00.20 00.20 00.20
Dimethyl Acetoacetamide 00.30 00.30 00.30 00.30 00.30 00.30
Res in proDert ies
Gel T~e, min:--c 29:20 37:36 31:47 33:52 19:45 38:15
Interval, min:sec 10:35 09:49 11:35 07:07 10:15 07:37
Exotherm, F 301 273 220 244 231 277
Viscosity, cps e 75-F 360 382 1570 560 990 710
Barcol-45 minutes 00.0 00.0 00.0 00.0 36.0 00.0
-one hour 39.6 39.9 00.0 29.7 47.2 32.2
-two hours 43.9 46.0 41.6 45.6 47.8 47.2
-three hours 46.4 46.2 43.9 45.9 48.2 47.6
-four hours 46.7 46.9 44.3 46.0 48.6 47.8
-24 hours 46.9 ~6.9 43.9 47.2 48.5 48.7
1162 Emissions, G/~2 9.7 1.8 4.8 3.6 3.0 2.4
E~issions, min:sec 46:12 51:35 50:00 53:46 36:10 48:20
ProDerties of a Clear Castina
HDT, F 147 138 127 138 133 138
Tensile Strength, psi 7,610 9,500 8,930 9,580 7,950 10,370
Ten nodulus, 10-5 psi 0.442 0.501 0.452 0.485 0.454 0.540
Elongation, % 2.00 2.30 2.70 2.50 2.00 2.60
Flexural StLer.~Lh, psi >19,220 ~19,150 >17,060 18,400 14,980 19 410
Flex Hodulus, 10-5 psi 0.536 ----- 0.509 0.662 O.S45 -- --
water Absorption ~ 150-F
24 hours 1.07 0.81 1.30 1.07 1.22 1.04
seven days 1.81 1.43 2.16 1.78 2.09 1.87

WO 95/23828 21 ~ 0 8 ~ 4 PCT/US9S/02101
TABLE V (cont'd?
Low VOC T~inatina Re~ins 8a-ed on General P~ ose Polvester Polv~er
EÇ~i~ H-4 _ U-3 G-4 H-3 Controls
~Qr~ition
nesin A 35.00 35.00 3S.00 35.00 60.00 60.00
Sartomer 480 lS.00 lS.00 lS.00 lS.00
Sartomcr 348 20.00 20.00 20.00 20.00 ----- -----
EG Dimethacrylate lS.00 lS.00 lS.00 lS.00 ----- -----
Cyclohexyl Methacrylate OS.00 OS.00 ----- ----- ----- -----
styrene 10.00 --- lS.00 --- 40.00 40.00
V$nyl Toluene ----- 10.00 ----- 15.00 ----- -----
Mod L 00.00 00.13 OO.OS 00.17 00.10 00.30
12% Cobalt 00.30 00.30 00.30 00.30 00.30 00.30
16S Potass'um 00.20 00.20 00.20 00.20 00.20 00.20
Dimethyl ~cet~o~b~smide 00.30 00.30 00.30 00.30 00.30 00.30
Resin Pro~ties
Gel Tlme, min:sec 09:22 38:05 15:26 25:10 OS:00 23:22
lnterval, min:sec 04:27 06:07 03:19 03:51 06:02 -----
Exother~, F 239 277 268 291 296 ---
Viscosity, cps e 75-F 910 790 1100 650 440 440
8arcol-45 minutes 46.1 00.0 44.5 00.0 41.9 ----
-one hour 48.7 37.0 48.1 ~7.0 44.8 ----
-two hours 49.2 48.6 50.0 50.8 45.4 ----
-three hours 49.7 48.5 50.5 49.8 45.5 ----
-four hours 49.6 48.5 S0.6 50.3 4S.9 ----
-24 hours 50.4 48.5 50.3 50.7 46.2 ----
1162 Emissions, CIM2 1.2 7.3 2.4 4.2 12.7 24.2
E~issions, min:sec 13:43 44:22 21:43 29:15 20:1: 23:22
Pro~erties of a Clear Castina
HD~, F 143 136 147 159 144 ---
Tensile Strength, psi 7,410 10,120 6,160 9,140 8,0~0 ------
Ten Modulus, 10-5 psi 0.473 0.489 0.521 0.544 0.478 -----
Elongation, % 1.80 2.70 1.50 2.00 1.80 ----
Flexural S~,e..~-h, psi S6,030 18,750 15,950 19,660 15,0~0 ------
Flex Hodulus, 10-5 psi 0.569 ----- 0.599 0.664 0.598 -----
Water Absorption e 150-F
24 hours 1.23 1.06 1.17 0.95 1.01 1.01
seven days 2.14 1.78 2.14 1.84 2.11 2.11

WO 95/23828 2 1 6 0 8 8 4 PCT/US95102101
Accordingly, our invention comprises
compositions comprising (a) the base polyester
polymer (resin) as described above and the
alkoxylated bisphenol-A diacrylate or dimethacrylate
in a ratio of 2:1 to O.S:l and (b) either (1) about
20-60%, based on the total of (a) and (b) of vinyl
toluene or divinyl benzene or a combination thereof,
(2) about 10~ to about 60%, based on the total of
(a) and (b), of either styrene or divinyl benzene or
a combination thereof, or (3) about 20% to about
60%, based on the total of (a) and (b), of ethylene
glycol dimethacrylate. In Tables I through V, the
various "Sartomer" compositions, i.e. the
ethoxylated bisphenol-A dimethacrylates, have 1 and
5 ethoxy groups on each side of the bisphenol-A;
however, we may employ a single compound or
compounds having any variation of combinations of
ethoxy or propoxy groups from two to about 20
groups, preferably a total of 2 to 8 alkoxy groups.