CA1096082A - Uniformly pigmented, low shrinking polyester molding compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

There is disclosed thickened, low shrinkage polyester molding compositions having improved pigmen-tation. The improved pigmentation in thickenable polyester molding compositions containing a carboxylated vinyl ester polymer low profile additive is achieved either by incorporating a surfactant in the composition, by using as the low profile additive a vinyl acetate/
maleic acid copolymer, or by a combination of the two methods.

Description

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The invention relates to a means for improving the uniformity of pigmentation in thickenable, low shrink polyester molding compositions.
BACKGROUND OF THE INVENTION
A major advance in commercial polyester mold-ing technology was the introduction several years ago of chemically thickened systems. Chemical thickening is always employed in sheet molding compounds ("SMC"), and is increasingly being used in bulk molding compounds ("BM~"). In such systems, an alkaline material such as magnesium oxide or magnesium hydroxide is added to the uncured polyester along with ~illers, glass fiber, and other standard materials. The alkaline material inter-acts with residual acidity in the polyester to build viscosity. The thickened system is relatively tack-free and easy to handle, and the high viscosity carries the glass fiber reinforcement to the extremities of the mold during crosslinking of the system. Thus, the use ;
of thickened systems has made a major contribution to the commercial expansion of polyester molding.
Another technical improvement that has made a significant contribution to commercial polyester molding technology is the use of low profile additives to reduce shrinkage during the curing reaction, and to thereby improve dimensional stability and surface smoothness.
Low profile additives are thermoplastic polymers such as vinyl acetate polymers, polystyrene, acrylic polymers, and polycaprolactones. There are a number of theories that seek to explain the low profile or anti-shrinkage action of these polymers, but the one that seems to best explain the phenomenon is the following:
The low profile additive is at least partly soluble in the uncured polyester/styrene solution. As the polyester/styrene mixture crosslinks, the thermo-plastic polymer becomes incompatible or less soluble and at least partly comes out of solution. This action causes a volume expansion that compensates for the shrinkage that occurs when the polyester/styrene mixture crosslinks.
When a low profile additive is employed iIl a thickened composition, the increase o~ viscosity that occurs can cause the low profi:Le additive to separate, and thereby cause a tacky surface. This problem is usually most severe with the more reactive polyesters, l.e., those having lower molecular weight to double bond ratios. To combat this, carboxylic acid function-ality is incorporated in the low profile additive. The thermoplastic polymer itself can then enter the thicken-ing reaction, thereby ensuring that a tack-free surface ` will result.
However, while alleviating the tackiness problem the introduction of these carbo~yls into the ~, ~ ~ 6 ~ ~

thermoplastic can present other difficulties if not properly understood. For the thermoplastics to function optimally as shrinkage control agents they must become incompatible with the crosslinked polyester structure.
Therefore, if the polyester resin, carboxylated thermo-plastic, and thickening agent structure are not care-fully controlled and balanced, the chemical thickening agent can bond the thermoplastic into the thermoset system through the carboxyl groups. This will reduce the ~mount of thermoplastic-thermoset incompatibility, thus re~cing, and in extreme cases, actually elimi-nating the shrinkage control.
Another property of these composites which can be notably effected by this thickening process is internal pigmentability. Beca~lse of the thermoplastic-thermoset incompatibility, low shrink, low profile SMC
and BMC is more difficult to uniformly pigment than conventional SMC and BMC. By careful formulation, and with the use of certain pigments, it is possible to baLance adequate shrinkage control and dimensional stability with internal pigmentation in thickened poly-ester composites using commercially availabLe carboxyl-ated polycaprolactone low profile additive. However, truly zero shrink thickened polyester composites have ~-not yet been uniformly and reproducibly pigmented in commercial molds except when certain black pigments _~ _ ~ 11013 ~ 3~ ~8 ~

were used with carboxylated polycaprolactone low profile additive.
DESCRIPTION OF THE INVENTION
The invention provides a means for improving the uniformity of pigmentation in internally pigmented, thickened polyester molding compositions. In one aspect, the invention provides a curable composition comprising:
(a) a polyester resin comprising the reaction product of an ole~inically unsaturated dicarboxylic acid or anhydride and a polyol; ~:
(b) an olefinically unsaturated monomer that is copolymerizable with said polyester resin;
(c) a thickening agent comprising an oxide or hydroxide of a metal o Group I, II, or III of the Periodic Table;
(d) a pigment;
(e) a carboxylated vinyl acetate polymer low ~ :
profile additive; and ;~ ~`
() a surface active compound.
In ~nother aspect, the invention provides a curable composition comprising (a), (b), (c), and (d), as defined above, and (g) a low profile additive com- ~ ~
prising a vinyl acetate/maleic acid copolymer. - ~`
The invention also provides the cured comp- ~
osites produced by curing the above-described curable - :
compositions.

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~ 2 The polyesters that are employed in the inven-tion are reaction products of a dicarboxylic acid or anhydride, with a polyhydric alcohol. The dicarboxylic acids or anhydrides that are employed to produce the polyester, either singly or in combination, must include those that contain olefinic unsaturation, preferably wherein the olefinic unsaturation is alpha, beta- to at least one of the carboxylic acid groups. Such acids include maleic acid or anhydride, fumeric acid, tetra-hydrophthalic acid or anhydride, hexachloroendomethyl-ene tetrahydrophthalic anhydride ("chlorendic anhydride"), Diels-Alder adducts of maleic acid or anhydride with compounds having conjugated olefinic unsaturation, such adducts being exemplified by bi.cyclo[2.2.1~hept-5-en3-

2,3-dicarboxylic anhydride, methyl maleic acid, and itaconic acid. Maleic acid or anhydride and fumaric acid are the most widely used commercially.
; In addition to the olefinically unsaturated acid or anhydride, saturated and/or aromatic dicarb-oxylic acids or anhydrides can also be empLoyed in producing the polyester. Such acids include phthalic acid or anhydride, terephthalic acid, hexahydrophthalic acid or anhydride, adipic acid, isophthalic acid, and "dimer" acid (i.e., dimerized fatty acids).
A polyol is also employed to produce the poly-ester. Such polyols include ethylene glycol, diethylene : -6-:~ .
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glycol, dipropylene glycol, butylene glycols, neopentyl glycol, glycerol and l,l,l-trimethylolpropane. As a rule, not more than about 20 mole per cent of the polyol will be a triol, with the remainder being one or more diols.
As is known in the art, polyesters that are employed in thickened molding compositions must contain residual acidity in order to enter into the thickening reaction. The nature and production of the polyesters used in such applications are known in the art.
The polyester composition of the invention also contains a monomer that contains ethylenic unsat-uration, and which is copolymerizable with the polyester.
Styrene is the preferred monomer in commercial practice today, although others can be used. Such others include vinyl toluene, methyl methacrylate, chlorostyrene, and diallyl phthalate.
The said monomer is employed in the polyester composition for the purpose of dissolving the polyester (which is a solid at ambient tèmperatures, i.eO, about 20-25C.~ to ensure that the polyester composition is : a fluid. Enough monomer is employed so that the thick-ness or viscosity of the fluid is such that the fluid can be processed conveniently. Excessive amounts of the monomer are normally to be avoided, because such excess can have an adverse effect on properties. For instance, too much of the monomer may tend to cause embrittlement of the cured polyester. Within these guidelines, effective proportions of the monomer are normally found within the range of from about 35 to about 70, and preferably 40 to 55, weight per cent, based on weight of polyester plus monomer, plus low profile additive.
A thickening agent is also employed in the in~ention. Such materials are known in the art, and include the oxides and hydroxides of the metals of Groups I, II and III of the Periodic Table. Specific illustrative examples of thickening agents include magnesium oxide, calcium oxide, zinc oxide, barium oxide, potassium oxide, magnesium hydroxide, and others known to the art. Thickening agents are normally employed in proportions of ~rom about 0.1 to about 6 weight per cent, based upon weight of polyester resin, plus monomer, plus low profile additive.
Pigments are also employed in the invention.
Illustrative examples include black iron oxide, titan ium dioxide, carbon black, chrome yellow, phthalocyanine blue and green, ceramic black, chrome green, ultramarine blue~ chrome-cobalt-alumina turquoise, cobalt aluminate (blue), brown iron oxide, ceramic yellow (antimony, titanium-chrome oxide), titanium pigments ~yellow, buf~
molydate (orange), chrome orange, manganese ~violet), chrome-tin (pink), ca~mium mercury (maroon, red, orange), and the like.
Pigments are employed in the invention in conventional proportions, e.g., from about 0.5 to about 10 weight per cent, based upon weight of polyester resin plus monomer plus low profile additive.
The invention has shown improvement in pig-mentability with all pigments thus far tested.
In one aspect, the invention employs a car-bo~ylated vinyL acetate polymer low profile additive.
Such polymers include copolymers of vinyl acetate and ; e~hylenically unsaturated carboxylic acids such as acrylic acid, methacr~lic acid~ maleic acid, fumaric acid, itaconic acid~ and the li.ke; vinyl acetate/vinyl chloride/maleic acid terpolymer, and the like.
Reference is made to Comstock et al., U.S. Patent No.

3,718,714 and Comstock et al. British Patent No.
1,361,841, for descriptions of carboxylated vinyL
acetate polymer low profile additives.
The useul carboxyla~ed vinyl acetate polymer low profile additives ordinarily have molecular weights ; within the range of from about 10,000 to about 250,000, and preferably from about 25,000 to about 175,000. They are usualLy employed in proportions of from about 6 to 20, and preferably from about 9 to 16, weight per cent, basea on weight of polyester plus low profile additive, _9_ ~ ;

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plus monomer.
As a general rule, the solution polymerized carboxylated vinyl acetate polymers are preferred in commercial practice because of their better batch-to-batch uniformity.
The polyester molding composition may also contain one or more of the known types of conventional additives, which are employed for their known purposes in the usual amounts. The following are iLlustrative of such additives:
1. PoLymerization initiators such as t-butyl hydroperoxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, and others known to the art. The polymerization initiator is employed in a catalytically efective amount, such as from about 0.3 to about 2 to 3 weight per cent, based on the weight of polyester plus monomer 21us low profile additive;
2. Fillers such as clay, hydrated alumina, ~;
silica, calcium carbonate and others known to the art, 3. Reinforcing fillers such as glass fibers or fabrics, asbestos fibers or fabrics, various organic fibers or fabrics such as those made of polypropylene, acrylonitrile/vinyl chloride copolymer, and others known to the art; and

4. Mold release agents or lubricants, such as zinc stearate, c~lcium stearate, and others known to the art.
The polyester molding compositions of the invention can be cured under conditions similar to those used for known polyester compositions. Typical curing conditions are a temperature of from about 200 to 350F.
for 1 to 4 minutes at a pressure of 300 to 2000 psi.
In combination with the carboxylated vinyl acetate polymer low profile additives, the invention employs a surface active compound. A wide variety of surface active compounds can be employed. As a general rule, the ionic surface active compo~mds have given the ~ best results. Classes o~ surfactants that deserve ; particular mention include:
Alkali metal, alkaline earth metal, and ammon-ium sulfonates;
certain ethylene oxide adducts of long chain (e,g., Cg-C18) aliphatic alcohols;
certain polyoxyethylene-polyoxypropylene block ; copolymers;
polyglycerol oleate;
ethoxylated sorbitan monooleate;
sodium 2-caprylic-l(ethyl beta oxipropanoi~ -`
acid) imidazoline;

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ethoxylated alkylguanidine amine complex;
sodium ~nd methyl-N-long chain aliphatic taurate;
sodium isethionate coconut ester;
certain ethoxylated long chain alkylphenols;
N-long chain aliphatic quaternary ammonium halide;
Ethoxylated N-long chain aliphatic alcohol `
quaternary ammonium halide; and Polydimethylsiloxane oil and certain other silicones.
The surfactant is employed in the invention in effective amounts, usually in the range of from about 0.1 to about 8 weight per cent, based on weight and polyester plus low profile additive pLus monomer.
The Examples below discuss in more detail the nature and propor~ion of the surfactants that are used in the invention.
In an alternative aspect of the invention, the low profile additive employed is a vinyl acetate/
maleic acid copolymer. (The maleic acid can be replaced by the equivalent fumaric acid or maleic anhydride.) The maleic acid is used in the copolymer in conventional amounts, e.g., in amounts sufficient to provide about 0.1 to about 3 weight per cent carboxyl groups, based on weight of copolymer. The molecular weight of the : . . ..

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copolymer, and the amounts in which it is used, are conventional for carboxylated vinyl acetate low profile additives. The copolymer is used either with or without surfactant; although its use with a surfactant is pre-ferred in most cases.
Experimental In the Examples below, the ollowing materials were used:
Polyesters Polyester A - made from isophthalic acid, maleic anhydride, propylene glycol, and dipropylene glycol in approximate molar proportions of 0.3:0.7:0.8:
0.~, respectively;
Polyester B - made rom isophthalic acid, maleic anhydride, and propylene gLycoL in approximate molar proportions of 0.3:0.7:1.0, respectively;
Polyester C - made from maleic anhydride and propylene glycol in molar proportions of 1:1.1; and Polyester D - made from isophthalic acid, maleic anhydride, and propylene glycol, in approximate molar proportions of 1.0:3.0:4.4, respectively.
The above polyesters are further characterized as follows:

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` 11013 Table I

Weight % Molecular :
Ac~d Solids in Weight to Polyester Number ~2~ _ Double Bond Ratio A 16.4 7Z.4 286.7 `:
- B - - 244.4 C 28.5 65.5 156.1 D 19.9 65~4 224.7 Miscel~aneous Additives X "Camel Wite" - Finely divided calcium carbonate used c~mmercially as a filler in polyesters;
Zinc Stearate - used as a mold release agent;
t-Butyl perbenzoate - 8 peroxide initiator;
p-Benzoquinone - a polymerization inhibitor;
X "RS~5988" - a 33 weight per cent: dispersion of magnesium oxide in a polypropylene maleate polyester;
X''Marino H" - Magnesium hydroxide;
X''Modifier M" - a ~3 weight per cent dispersion o magnesium oxide in a polypropylene maleate polyester;
Xl'JM-308A" glass fibers - 114-inch chopped glass fibers, _ of medium hardness;
X "PPG~303" glass fibers - 1/4-~nch chopped glass fibers of medium hardness, but a bit softer than XJM-308A; and Alumina trihydrate - a flame retardant filler.
x _ trademark Low Profile Additives LP-A - 40 we~ght per cent solids solution of a 99.2/0.8 ~by we~ght~ vinyl acetate/acrylic acid copolymer in styrene, having th~
following properties:
Solution Viscosity 4000-6000 centipoises at 25C.
Copolymer Inherent viscosity 0.48; 16-17 Ford cup ~ 42,000 MW ~2,~00 `~
0 XLP-B - 40 ~eight per cent solids solution of vinyl acetate/maleic acid copolymer in styrene.
Different versions contained from ~.7 to 2.1 weight per cenl: maleie acid ln the copolymer, the remainder being vinyl acetate. The styrene solution viscosities v~ried from about :3400 to about 16,000 centipoises at 25C. The Ford Cup ` `-viscosities of the copolymer varied from 12.4 to 17.8;
0 XLP-C - 35 weight per cent solution of polystyrene in styrene, having a solution viscosity of 5000 cps at 25C; and ~ :-XLP-D - 33 weight per cent solution of a copolymer of `
methyl methacrylate, ethyl acrylate, and acrylic acid (weight ratio 85:12.5: 2.5)~.
in styrene.
x _ trademark o 15 -t~P~2 YPDI-1416 - A green plgment;
XPDI-1600 - An orange pigment;
CM-3308 - A gray pigment;
; XCM-2015 - a bl~ck pigment; and XCM-3131 - A blue plgment.
tThe pigments employed were all commercial materials marketed as dispersions in a low molecular weight poly-ester. The pigment weights indicated in the formula-tions below are all dispersion weights, and thus include the dispersing medium.) Surfactants The surfactants employed are described in the Examples below.
Evaluation The evaluation of the pigmentation was done visually. Non-uniformity of pigmentation can be mani-fested in any of several ways, such as the presence of small spots on the sample, cloudiness, flo~ marks, wa~iness, lack of color depth, streaks, mottling, and other similar defects. In most cases~ the various samples _ were compared with a control. (The control employed was usually a polyester molding composition containing thickener, pigment,XLP-A low profile additive, and no surfactan~.) x _ trademark i: i , .

The invention provides a means for improve-ment over polyester compositions containing LP-A low profile additive. Even though perfectly uniform pigmentation is not always provided, in its preferred aspects, the invention provides the best combination of uniform pigmentation and shrinkage control that is presently available in thickened polyester molding c~mpositions~

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~1 Bulk mold~ng compounds were made from the foll~wing formula~ions:
Table I
~ 555~L _~ 2 3 4 Polyes~er D 60 60 60 60 xLp_g(l) 35 35 - ~

Styrene 5 2 5 2 xSurfactant A (2) - 6 _ 6 XCamel Wite 175 175 175 175 ~.
Zinc Stearate 3 3 3 3 X~Dl-1416 lO.S 10.5 10.5 10.5 XModifier Mt3) 0.53 0.7 2.5 2.5 t-butyl 1.0 1.0 1.0 1.0 perbenzoate 1/4-inch glass fibers ~4) 20 20 20 20 (1) 40 weight per cent styrene solution of copolymer of 98.5 per cent vinyl scetate ~md 1.5 per cent maleic acid, the solution having a viscosity of 15,720 centipoises. at 25C.
(2) Sodium salt of isododecylbenzene sulfonic acid X("Siponate ~S-10", Alcolac Chemical Company), 50 weight per cent solut~on in styrene.
(3) Less ~agnesium oxide is required with ~he formulation containingXLP-B than with the one containingXLP-A
because the higher proportion of carboxyl groups in XLP-B causes more viscosity build-up (i.e.~ thick-ening), Run 2 uses slightly morP than Run 1 because of ~he effect of the particular surfactant used.
Run 4 was not s~milarly adjusted for presence of _ surfactant because the overall proportion of mag-nesium oxide in Runs 3 and 4 was much fi~gher than in ~uns 1 and 2, and the effect of the surfactant was ~herefore not sufficient to require ~djustment.
(4) Runs 1-4 were first made usingXPPG-303 glass fibers~ `
and were then repea~ed usingX3M-308A glass fibers.

x _ trademark , , . ~ . -The general procedure for making bulk molding c~mpounds that was used in this Example 1 and in many of the other Example~ was the foll~wing:
General Procedure for Preparation of Bulk ~ldin~

- ~he liquid component~ cluding the pigment dispers~on) were weighed individually into a Hobart mixing pan placed on aXToledo balance. The t-Butyl perbenzoate ~as weighed into a vial and added to ~he contents of the pan and the pan was attached to aXModel C-100 Hobart mixer (in a hood). The agitator was started at slow speed, then increased to medium speed to com-pletely mix the liquids and pigm~ent over a period of 3 to 5 minutes. The agitator was then stopped, and ~he zinc stearate (internal mold rellease agent) was added to the liquid f;rom an ice cream carton. The ~obart mixer was restarted and the zinc stearate mixed with the liquid until ~t was c~mpletely wet~out. TheXCamel Wite (calcium carbonate filler)* was next added t~ the pan ~ ~.
~0 oontents (agitator off) then mixed, using medium to high speed, until a consistent paste was ob~ained. The mixer was again stopped and the weighed amount of~Modifier M
was poured into the pan from a tared beaker, The ~Modifier M was mixed into the paste over a period of 2-3 minutes, the mixer was again stopped **, and 175 grams of the paste was removed fr~m the pan ., ,. , _ :
* or other fillers **reweighed and styrene loss made up x _ trademark ! ......... . . .

(using a large spatula) and transferred to a wide-mouthed 4-~unce bo~tle, This paste ~ample was stored in the c~pped bo~tle at room temperature and the viscosity was meRsured periodically using a ~odel ~BT Brookfield ~ Viscometer on a~Helipath Stand.
After removal of the paste sample, the chopped glass fibers were added slowly (fr~m an ice cre~m carton) to the pan with the mixer running on low speed. The mixer was run for 30 seconds after all the glass was in the paste. This short time gave glass wet-out without glass degradation. The pan was then removed fr~m the mixer and separate portions of the BMC mix of 650 ~rams each were removed using spatulas and transferred to aluminum foil lying on a balance pan (balance in the hood). The mix was tightly wlapped ~n the aluminum foil (to prevent loss of styrene vla evaporatlon) and stored at room temperature until the viscosity of ~he retained paste sample reached a desired value. The mixes in this study usually rPached this viscosity within 24 hours of their preparation.
The gener~l procedure for molding the samples of BMC was the following:
General Procedure for Moldin~ Panels The equipment used for c~mpression molding of panels from the glass reinforced unsaturated polyester x _ ~rademark J ^2~-~. .

molding mixes was a 75-ton~XQueen~s hydraulic press fitted with a 12 x 12 in~h matched metal die mold (chr~med Rurface). The dies were heated to 300F., and the 650 gram portion of mix was remo~ed from the foi and placed in the mold. The mold ~as quickly closed (without stops) to 8 pressure of 600 psi, and the panel was cured for 2 minutes at 600 psi/300F. The mold was opened, the panel was quickly removed, and allowed to cool (in a hood) under weights (to avoid warpagP).
(Where any significant departures were made from the indicated general procedures for preparation of the BMC and molded panel, they arle ~tated ~n the text.
Panels were molded (at S00 psi) from the above-described formulations, and were measured for shrinkage and were visually evaluated for u~niformity of pigmen-tation. The results are shown below in Table II:

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Shrinkage ls determined on these 12 x 12 inch panels by measuring the length of each of the four sides with a mlcrocaliper, adding the four lengths together, substracting this sum fr~m 48, and then div~ding the difference by 48 to ~hereby obtsin the total ~hrinkage in mils/inch.
Example 2 A series of ~uLk molding compounds were made and molded into panels by the general proce~ures ~ :
described in Example 1. The formulations, shrinkage, ~nd results of evaluation for pigmentation are displayed in Table III. The ~ -B low profile additive employed was the one described above in Example 1.

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Control 1 A ~eries of buLk molding cGmpounds were made and then ~olded by the general procedures de~cribed in Example 1 fr3m the formula~ions displayed in Table IV:
Table IV
Run No.
Comnonent 1 2 3 4 Polyes~er D 750 750 - -Polyester C - - 360 360 Styrene 125 73 ~0 -Camel Wite 2500 2500 900 gO0 t-Butyl perbenzoate 13 13 9 9 ; ;
Zinc Stearate 40 40 24 24 ~odi~ier M (MgQ) 30 38 18 18 Glass (PPG-303) 671 671 250 250 CM~2015 Pigment 148 148 - -CM-2020 Pigment - - 5~ 50 ~ `
- The panels were measured for shrinkage and were evaluated visually for pigmentation, which was -~ :
~udged on the depth of color, uniformity, ~nd presence of mottling. The results are displayed in Table V: .

x _ trademark T~ble V
Low Profile Shrinkage, Run Polyester Additive m~ls~inch Pigmentation 1 D A 0.27 Falr 2 D C 2.00 Good - 3 C A 0.48 Poor 4 C C 2.3Fair to Good ~ ,:
A ser~es of bulk mold eompositions were made using the general procedure described i~ Example 1. The bas~c formNlation is shown beLow in Table VI: .
Table VI
Component Parts,bY wei~ht Polyester D 210 Low Profile Additive varied Surfactant A varied Styrene ~aried XCamel Wite 525 Alumina Trihydrate 175 Zinc Stearate 14 : .
Pigment varied t-Butyl perbenzoate 4.2 ~-Benzoquinone O.l MgO varied Glass (JM-308A~-to 20% 234-238 The variable par~s of the formulations are displayed below in Table VII. The LP-B employed was the one described in Ex~mple 1.

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The BMC formulations described above were molded in a transfer mold using a 100-ton hydraulîc press. 180-Gram charges were added to the ram, and a piston injected the BMC into the several mold cavities using a force of 800 pounds. There were five mold cavities in the transfer mold that were each con-nected to the ram by 126-millimeter (diameter) feed lines. The circular gates leading into the mold cavi-ties had diameters of 64 millimeters. There were two rectangular cavities, each having dimensions of

5 x 1/2 x 1/2 inches, a 4-inch diameter by 1/8-inch circular cavity, a 2-inch by 1/8-inch circular cavity, and a 7 x 1/2 ~ 1/8-inch "dog bone" (tensile testing bar) cavity. The BMC was cured in the mold for 2 minutes at 300F., and then discharged.
The molded specimens were evaluated as follows:
Shrinkage The length of one of the nominally 5-inch bars from the same mold cavity were measured in all cases) was measured with micro-calipers. The shrinkage in mils (one mil = 0.001 inch) is reported for each run.
Pigmentation The large circular disk was examined for deep-ness of color, uniformity, and mottling. The best sample was rated 114~ and the worst ~ . The others were rated visually using these as standards. The results are d~splayed in Table VIII:
Table VIII

Low Profile ~elght % Shrinkage, Run No. Additive Surfactant A mils ~$E~3 XLP-B 1.5 10 2

6 LP-B - 17 2

7 XLP-~ 3 12 1 : ~

8 LP-B+C 3 20 4 :

9 ~LP-A+C 3 19 3 XLP-B~C 3 20 4 11 XLP-A~C 3 19 2 Exæmple 4 ~-A series of bulk molding compositions were made, and were ~hen molded using the transfer ~ -mold described in Example 3. The several ~uns 20 di~fered ~n the presen e or absence of Surfactant A, the proportions (weigh~ per cent) of maleic acid in the copolymer of~LP-B, and in the molecular weight (as ev -denced by styrene solution viscosity) of the copolymer ~ :
ofXLP-B. TwoXLP-A control runs were also ~ncluded. The basic formula~ion used is shown below in Table IX:

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XLP-A control runs were also included. The bas~c formulat~on used is ~hown below in Table TX:

- 5l~ _ __ __ Run 1 ~uns 2-9 _ Polyester D 630 210 Low Profile Addi~ve 408 122.5 ~Surfactant A 66 varied Styrene 18 varied XCEmel Wite 1575 525 Aluminum trihydrate 525 175 Zinc ~tearate 42. 14 XPDI-1416 Pigment 117 39 t-Butyl Perbenzoate 12.6 4.2 p-Benzoquinone 0.1 0.1 x Modifier M 16.5 varied Glass (JM 308A) 808 235 The variable parts of l:he formulation are shown below in Table X, along with the shrinkage, in mils. The best pigmentation was formed in Run No. 1, the worst i~ R~n No. 9, with Runs 2-8 being ~ntermediste between them in descending order. The fac~ that Run No. 5 was rated better than Run No. 7 appears at this time to be anomolousO ~:

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~1013 ~a~Y~s2 A serieC of 12 x 12 inch panels were compres-~ion molded from BMC using the general procedures described above in Example 1. The several.runs differed in the proportion of maleic acid ~n the copolymer of :~
XLP-B, and in the molecular weight of the copolymer of `~
XLP-B, as evidenced by styrene solut~on viscosity. No surfac~ant was used in this series. A con~rol conta~ning :~
XLP-A is included. The general formulation is shown below in Table XI:
Table XI
Com~onent Parts. by weight Polyester D 360 Low Profile Additive 210 Styrene 30 ~Camel Wite 1050 XPDI 1416 Pigment 63 Zinc Stearate . 18 XModifier M varied t-Butyl Perbenzoate 6 XGlass (JM 308A~ 391 :~
The variable parts of the formulation are displayed below in Table XII, along wi~h the shrinkage, in mils/inch, measured as described above in Example 1.
As was the case in Example 4, the ~uns are arranged in the table in d~scending order of pigmentation rating.
x _ trademark ~` :

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mples wo~ 11 with t xtures to obt~in d in these ing experis; entS is Bho~TL , .; T~ ~ .

`; 20- ~ 30 - pobestcfrile AddieLve 67.5 f:

: ~amel ~ite 1. 5 Xc~oate varLed surf actant ~ ~ - trademark 34_ :

;

11~13 ~ 6~ ~ ~

After curing and remo~ing fr~m the aluminum dish, ~he ca~t par~s wer~ rated ~isually for depth of color, uniformity of pigmentation, presence or absence of ~mall white ~pecks, and mottling. The six foDmulations shown below in Table XIV were used as .tandards sgainst wh~ch all the others were compared. The wors~ was given a xa~ing of 1, the best 6, with the others being inter-mediate between them. The six standard foxmulations `
were the following (the LP-B employed in this Example was the one described in Exam~.le 1):

Table XIV
Ratin~
Component 1 2 3 4 5 6 LP-A 17.5 - - _ _ _ LP-B - 17.5 17.5 17.5 - 17.5 LP-C ~ 17.5 Modifier M 1.25 1.25 0.75 0.750,5 0.75 Surfactant A 3 - 3 6 Surfactant B(l) ~ 3.6 . . 0 (1) 42 weight per cent styrene solution of sodium salt of alpha-olefin sulfonate In the surfactant screening séri~s, the low profile additive employed was LP-B. Each surfactant was used in two proportions, 3 and 6 weight per cent of active surfactant, based on weight of polyes~er, ~LP-B, plus 6tyrene. Modifier M was used in amounts of 0.75 parts9 by weight~ Table XV, ~elow, displays the chemical name of the surfactant, its Trade Name, its classifica~ion in McCutcheon's 1975 Edition of x _ trademark ~ 3 "Detergents & Emulsifiers", and the pigmenta~ility ratings for the two proportions of surfact~nt used. In the table, "EO" represents ethylene oxide, "PO" repre-~ents propylene oxide, "~C~' represents "did not cure", - ~nd the ~urfactants marked wi~h an asteri~k* were employed as a solution in styrene.
Table XV
Surfactant Class 3% 6%

10 Xl'TERGITOL Min Foam 2x" AT-28 2 EO/PO adduct of linear alcohol ~"TERGITOL Min Foam Lx" ~T-28 EO/PO adduct of linear alcohol X "TERGITOL 15-S-3" AT-28 1 2 EO adduct of linear alcohol X"TERGITOL 15-S-5" AT-28 3 EO adduct of linear alcohol X"TERGITOL 15-S-9" AT-28 1 3 EO adduct of linear alcohol X''TERGITOL 15-S-15"* ~T-28 2 2 EO adduct of linear alcohol X''TERGITOL 15-S-30"* AT-28 2 EO adduct of linear alcohol X"TERGITOL 15-S-50" AT-28 1 2 EO adduct of linear alcohol ~ X"TERGITOL TMN-6" AR-12 4 3 Trlmethy~nonyl poly(EO) ~ `~
ether "TERGITOL TMN~10" AR 12 4 3 Trimethylnonyl polytEO) ether x _ trademark Table XY (cont'd.) Surfactant Cl~ss Pi~=entability "TERGITOL-~8" AP-10 4- NC
Na~2-ethyl-1-he~anol) Sulfate "TERGITOL-4" AP-12 3 Na(7-ethyl-~-methyl-4-undecanol) Sulfate ''TERGITOL 15-S-7" EO AT-28 1 ~C
adduct of linear alcohol ''Pluronic F-98"* EO/PO AW-80 2 3 ~ :
adduct of propylene glycol ''Pluronic F-88"* EO/PO AW-80 2 adduct of propylene glycol "Pluronic F-68"* EO/PO AW-8Q 2 2 adduct of propylene glycol ''Pluronic F-68LF"* EO/PO ~W-80 2 2 adduct of propylene glycol '~TERGITOL XH"* EO adduct AT-28 2 2 of linear alcoXol "TERGITOL XJ" EO adduct AT-28 2 2 of linear alcohol "TERGITOL 15-S-40"* EO AT-28 2 2 adduct of linear alcohol ~.
''TERGITOL 15-S-12" EO AT-28 2 adduct of linear aleohol ~.
"Pluronic 3IR4" EO/PO AW-82 2 1 ~dduct of ethylene glycol "Pluronic 3IRl" EO/PO A~82 2 adduct of ethylene glycol "~luronic 17R4" EO/PO AW-82 3 2 :
adduct of ethylene glycol ''Nbodol 25-3" EO adduct AT-28 of ethylene glycol ~.

x _ trademark .

110~3 T~

Surfactant Class Pirmentabillty Neodol 25-7" E0 adduct of AT~28 1- 1 linear alcohol "Neodol 25-12" E0 adduct AT~28 2 ?
of linear alcohol "Neodol 25-3A" NH4 salt of AQ-18 4 E0 adduct of linear aLcohol sulfate "Neodol 25-3S" Na salt of AQ-18 4 NC -E0 adduct of linear alcohol ~ulfate t'Plurafac RA-43" E0/P0 AW-82 1 2 adduct of ethylene glycol "Pluraac RA-40" E0 adduct AT-28 of linear alcohol "Plurafac D-25" E0 adduct AT-28 2 2 of linear alcohol (Modified) ~'Ucane 111' Na alkylbenzene AK-8 6 sulfonate "Calsoft T~60" B-13 6 6 triethanolamine dodecyl-benzene sulfona~te Glyeeryl monooleate AE-14 2 2 Glyceryl dîoleate AE-14 2 &lyceryl trioleate AE-23 -- Polyglycerol oleate AE-14 3- 2 X''Tween 80" Sorbitan W-9 1 2 monooleate X"Tween 21" E0 adduct of W-5 3 3 sorbitan monooleate - trademark ~3 , Surfactant Class "Abrosol 0" Diethanolamine- A-28 2 2 oleic acid condensa~e "Bri~ 30" E0 adduct of BB-4 2 2 lauryl alcohol, 4 EO's Na propyl oleate sulfonate A0-2 4 4 :
''M~ranol MSA" Na 2-Caprylic- BA-6 4 1- (Ethyl beta oxipropanoic acid~ Imidazoline "Petronate K" AI-6 2 Na petroleum sulfonate ~a Xylene sulfonate AJ-18 4 3 "Tide" - mixture of Na B0 4 3 tallow alcohol sulfat2 and linear alkyl benzene sulfonate Na alpha-olei~ sulfonate* AG-l 6 5 Na alpha-olefin sulfonate AG-l 2 (powder form) 'Centrolene-S'' Lecithin M-l 2 ''Aerosol C-61" BM 3 l Ethoxylated alkylguanidine amine complex "Igepon T-33" Na and H-4 3 3 ;~
Methyl-N-oleyl taurate IIIgepon TN-74" Na and H-6 3 Methyl-N-palmi~oyl ~aurate l'Igepon ACo78' I-12 4 3 Coconut ester, ~a i~ethionate 'IAerosol OT-75" Dioctyl I~12 4 3 Na isethionate _ trademark T~ble XV l~co~t'd ~

Surfactant Class Pi~mentabili~y 3% 6%
''Triton X-100" EO adduc~ of AR-8 2- 2 octylphenol "Triton X-45" EO adduct of AR-12 3 2 tr~methylnonylphenol ''Emulphor ON-877'1 E0 adduct AT-26 5 5 of fatty alcohol "Emulphor VN-430" EO adduct AU-22 of fatty acid .
''Emulphor EL-719" EO adduct AU-24 2 2 of vegetable oil Polyethylene glycol 600 AW-6 2 2 monooleate Polyethylene glycol 600 AW-8 2 2 dioleate Polyethylene glycol 200 AW-42 1 2 monostearate Polyethylene glycol 200 AW-48 2 distearate ''Arquad C-50" D-17 3 5 Trimethyl cocoammonium -chloride .
Arquad S-50" Trimethyl D-17 3 6 soyammonium chloride "Arquad T-50" Trimethyl D-17 5 5 tallow-~mmonium chloride "Ethoquad O/12" Poly- C-33 4 ethoxylated quaternary ammonium chloride-etho~y-lated alkylol ~mide/amine-oleic x ~ .
- trademark - ... . ., .. ~, ~ . . ., ., -Table XV (contld.3 Surfactant Class~J2~ LLLE2~
3% ~%
"Eth~meen T-12" C-37 2. 2 3is(2-hydroxyethyl)tall~w amine "Ethodumeen T-20" C-37 2 2 N,~'-polyoxyethylene(10)-N-tallsw-1,3-diaminopropane "Nek~l ~A-77" Na alkyl S-15 2 naphthalene sulfonate "Daxad 21" Monocalcium AB-2 4 2 polymeriæed aIkyl aryl sulfonic acid ''Byk-MalliDkrodt ST-80" P~2 2 3 S~licone ''Byk-Mallinkrodt ST-60" P-2 3 1 -~
silicone ''Byk-Mallinkrodt FL-O" P-2 3 3 Silicone ''BykqMallinkrod~ FL-l" P-2 3 3 Silicone "Norlig 11 DA" Lignosulfonic ~-lO 2 acid derivative ''Marasperse N-22" Na ligno- L-8 4 4 sulfonate "Ultrawet DS" Na alkyl AK-8 4 4 aryl sulfona~e ''Sellogen HR-gO" Na alkyl S-15 4 naphthalene sulfonate x"CDnoco SA-597" dodecyl ~K-12 5 5 benzene sulfon~c acid .. . . . . . . .
X''Dowfax 2Al" AL-8 4 4 ~~ra dodecy~ diphenyl ether disulfonate x _ trademark -41- :

. . . .

;,, . , ~ t Table XV ~con~ 2 Surfactsn~ Class 3% 6%
X''Tflmol SN" Na ~alt of con- S-15 3 3 dens~d naphthalene sulfonate X~silicone L-76"(1) P 4 2 X"Silicone y~590o~ ) P 2 2 X''Silicone L-45"(1) P-2 5 1 Polydimethyl~iloxane X"Silicone Y-6446"(1) P 4 X"Silicone W-900 2 ~'Silicone S-10"(1) P 2 X''Silicone S-50"(1) P

"Silicone L-5420"~1) P--6 2 2 Siloxane-polyoxyalkylene Block copolymer X''Silicone L-5303"(1) P-6 2 2 Siloxane-polyoxyalkylene Block Copolymer X"Siponate DS-10"* ~ 8 3 4 Na dodecylbenzene sulfonate Dioctyl Na Sulfosuccinate V-8 3 3 Those surfactants that are solids in the 100 per cent active form should be dissolved in a solvent, preferably styrene, before being added to ~he mixture _ in order to ensure complete and uniform distribution throughout the mixture.
The following surfactants yielded a pigmenta-bility rating of 3 or more, in at least one of the ~wo concentrations employed, which means that they improved (l)All silicones used in proportions of 0.3 and 0.6 per cent. ~ :

_~ x _ trademark , ! -42-.' .

the pigmentability when compared with the same formula-tion containing no sur~actant:

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' .

:.' . :' ~ 11~13 Example 7 The procedure described in Example 6 was repeated, with the exception that the formulation employ-ed LP~A as the l~w prof~le additi~e. X~odif~er M was employed ln a prcportion of 1.25 parts, by weight.
Table XVII dlsplays he Trade Name of the surfactant (all are identified above in Table XV), the surfactant class, t~e weight per cent in which the surfactant was used, (based on weight of polyester plus low profile additive plus styrene)~ and the pigmentability rating, using as the pigmentability standards the six formula-tions described in Table XIV.
Table XVII

Pigment-Surfactant Class % ability , X''Arquad S-50" ; D-17 4.2 5 X"Emulphor ON-877" AT-264.3 Na alpha olefin sulfonate AG-l 4.1 ~"Tween 80" W-9 4.4 X''Silicone L~45" P-2 0.3 2 X''Tergitol 08" AP-104.1 1 ~-~ X"Tergitol TM-10" AR-124.4 2 ~ :
~ ~'Daxad 21" AB-24.4 5 Na Xylene Sulfonate AJ-18 4.2 1 ;:
x~lcOnoco SA-597 AK-12 4.4 4 X''E~hoquad 0/12" C-33 4.3 4 x _ trademark ~46- :

Table XVII (con~'d.
"
Pigment-Surfactant Class % ~bility Xl'Marasperse N-22" L-8 4.4 ; 2 X"Siponate DS-10" AK-8 4.2 3 - ~Styrene solution) Control (no surfactant) - O
The following surfactant~ gave pigmentability ratings of 2 or more, which means that they improved the pigmentability compared with the formulation con~aining no surfactant:
Table XVIII, Surf.
Structure Type Trade Name Class No. Manufacturer 1. Ethoxylated XEthoquad C-33 Armak Co.
Propoxylated 0/12 Amides/Amlnes 2. Amines and XArquad S-50 D-17 Armak Co.
Quaternary Derivatives 3. Lignin XMarasperse L-8 American Derivatives XN-22 Can Co.
4. Silicone XL-45 P Union Derivatives Carbide ~. Polym rs XDaxad 21 AB-2 Dewey and - Almy Chem.
Co .
6. Alkyl Aryl XSiponate DS-10 AK-8 Alcolac, Inc.
Sulfonates XConoco SA-597 AX-12 Conoco Chem.
7. Ethoxylated X~ERGITOL TMN-10 AR-12 Union Alkyl (Aryl) Carbide Phenol Sulfates x _ trademark . ~ -Control Example 2 The surfact~nt screening experimen~s of Examples 6 and 7 were repeated, except that the low prof~le addi~ive employed was the acryl~c based~LP-D.
Modifier M was employed i~ a proportion of 1.25 par~s, by weight. Table XIX displays the Trade Name of the surfactants, the surfactant class, the we~ght per cent in which the surfactant was used, and the pigmentability rating.
Table XIX

Pigment-Sufactant_ _ _ Class ~ ability lEthoquad 0/12" C-33 4.3 2 "Daxad 21" AB-2 4.4 3 "Marasperse N-22" L-8 4.4 2 ''Arquad S-50" . D-17 4.2 4+
''Emulphor ON-877" AT-264.3 3 "Siponate DS-10" AK-8 4.2 2 : :
(Styrene solution~ ~ -Control (no surfactant) 0 0 4+
None of the surfactants improved the controL, and all but one gave a lower rating than the control.

The general procedure of Example 1 was employed to prepare 12 x 12 inch molded p~nels from the ::
following formulations:
'.`
x _ trademark :

' ~

' Tilble Xl~

Run No.
~ (3) ~4)`

Polyester D 300 300 300 300 Styrene 50 28 50 20 ~amel Wite 875 875 875 87 Zinc Stearate 20 20 ~0 20 t-Butyl per~en7-oate 5 S 5 5 CM-20~5 42 42 42 42 Modifier M ~5 :L5 10 10 Paste Sample 175 175 175 175 PPG~303 Glass (~0/O) 128 12~ 128 128 Visual panel evaluations for pigmentability consisted of comparing the finished panels for color dep~h (pigment), dispersion of pigment, glossiness, etc. ~:
The pigmentability ratings of these four systems con-taining different low profile additives were as follows:

Fo~ulation No. Pi~mentability #2 (Containing2~P-C~ Best #3 (ContainingXLP-B) Less ~4 (Containing~LP-D) Less #l (ContainingXLP-A) Worst - trademark ~9-~, ~, ;. , .

Z

Example 9 The ~eneral procedure of Exsmple 1 was e~ployedto produce 12 x 12 inch molded panels frcm the oll~wing ~ormulations:
Table XX}
~ ~ (3) t4! (5? (6~ : :
Polyester D 300 300 300 300 300 300 ~P-A 150 150 150 150 150 150 5tyrene 50 50 50 50 50 50 ~Camel Wite 875 875 875 875 875 875 Zinc Stear~te 20 20 20 20 20 20 t-Butyl perbenzoate 5 5 5 5 5 5 CM-2015 4~ 42 42 42 42 42 odifier M 15 15 15 15 15 15 Conoco SA-597 ' - 23 - - -Daxad-21 - - 23 Siponate DS-10 -:
(50% sol'n~ in styrene) - - - ~6 - -Tween 80 ~ 23 Silicone L-45 ~ 2.3 Paste Sample 175 175 175 175 175 175 Ppr-3o3 Glass (10%)130 130 130 130 130 128 --~The sufactants are alL described a~ove in Table XV.) _ trademark .
~50~

~3'~ 6~ ~ ~

The pigmentability ratings of these panels were ~s follows: .
Formulation No.
#2 (ContainingX5A^597) Best #4 (Containing~DS-10~ Best = ~t6 ~Contain1ng ~-45) Less (No surfactRnt control) Less ff3 (Containing~Daxad-21~ Less #1 (ContainingXTMN-10) Less #5 (Containing~ween 80) Wor~t As a series, these panels are generally worse than those from the experiments cont~ningXLP-B, which $ollow in Example 10.
Example 10 Us~ng the general procledure of Example 1, 12 x 12 inch panéls were prepared from the following formulations:
Table XXII

(1) (2) (3)_ (4? (5) . (62 ~
Polyester D 300 300 300 300 300 300 Styrene 50 50 50 27 50 50 Camel Wite 875 875 875 875 875 875 Zinc S~eara~e 20 20 20 20 20 ~0 t-Butyl perbenzoate 5 5 5 5 5 5 x _ trademark ~:

, ~6(~2 0~5 42 42 42 42 42 42 Modifier M 10 lO 10 ~0 10 10 .~
'TERGI~OL 1~- lO 23 Con~co SA~-597 - 23 Da~cad-21 - - 23 - - -Siponate DS-10 - - - 46 Tween B0 ~ 23 Silicone L-45 _ _ _ _ 2. 3 Paste Samplei 175 175 175 175 175 175 PPG-303 Glass (10%)130 130 130 130 130 128 The comparative pigmient~bility rating of the panels psepared from these formiulations ase as shown:
Color Formulation No. Depth ~=
~4 ~Con~ain~ng~DS-10) Best ~Darker tha~ Example 9 #4) ~2 (ContainingXSA-S97) ~Darker than Example 9, #2) :
(No æurfactant, Control) Control #3 (Containing~Daxad-21) ~Surface quite nice, darker than Example 9 ~6 ~Cont~ining~L-45) #6) ~:
~1 (ContainingXTMN-lO) (D~tto - E~ample 9, ~13 ~5 (Containing~Tween 80) Worst (Di~to ~ Example 9, #5) , x _ trademark ~52-, it-.il"~

: :., . , ~ ... ' ' , ' ' ',- .
- ~' . `' . ~ . . .. .i , :, ~.. ~., ;' ~a Uslng the same procedure described in Example 9 and 10, 12 x 12 inch molded panels were made using the earboxylated acrylic low profile additive3LP-D, and evaluating the 8ame ~urfactants as in Examples 9 and 10.
In this series, the con~rol, which contained no surfact-ant, appeared better than all the panels cv~taining surfactants. There was very little difference, if any, between the several panels which contained surfactants.

x _ trademark :. . o53_ ~ ~ . . .

,

Claims (11)

WHAT IS CLAIMED IS:

1. A curable molding composition contain-ing:
(a) a polyester resin that is suitable for use in molding and which comprises the reaction product of an olefinically unsaturated dicarboxylic acid or anhydride and a polyol;
(b) an olefinically unsaturated monomer that is copolymerizable with said polyester resin;
(c) a thickening agent comprising an oxide or hydroxide of a metal of Group I, II, or III of the Periodic Table;
(d) a pigment;
(e) a carboxylated vinyl acetate polymer low profile additive having a molecular weight within the range of from about 10,000 to about 250,000; and (f) a surface active compound that is employed in an amount sufficient to enhance the uni-formity of the pigmentation of the cured composite produced from said curable molding composition.

2. The curable molding composition of claim 1 wherein the olefinically unsaturated monomer is styrene.

3. The curable molding composition of claim 2 wherein the thickening agent is magnesium oxide or magnesium hydroxide.

4. The curable molding composition of claim 1 wherein the surface active compound is a member selected from the group consisting of:
(a) a sulfonic acid or an alkali metal, alkaline earth metal, or ammonium salt thereof;
(b) an ethylene oxide adduct of a long chain aliphatic alcohol;
(c) a polyoxyethylene-polyoxypropylene block copolymer;
(d) polyglycerol oleate;
(e) ethoxylated sorbitan monooleate;
(f) sodium 2-caprylic(ethyl beta oxiprop-anoic acid) imidazoline;
(g) ethoxylated alkylguanidine amine com-plex;
(h) sodium and methyl-N-long chain aliphatic taurate;
(i) sodium isethionate coconut ester, (j) ethoxylated long chain alkylphenol;
(k) N-long chain aliphatic quaternary ammonium halide; and (l) polydimethylsiloxane oil.

5. The curable molding composition of claim 1 wherein the surface active compound is sodium dodecylbenzene sulfonate.

6. The curable molding composition of claim 1 wherein the surface active compound is a sulfonic acid or an alkali metal, alkaline earth metal, or ammonium salt thereof.

7. The curable molding composition of claim 5 wherein the carboxylated vinyl acetate polymer low profile additive is a vinyl acetate/maleic acid copolymer.

8. The curable molding composition of claim 6 wherein the carboxylated vinyl acetate polymer low profile additive is a vinyl acetate/maleic acid copol-ymer.

9. The curable molding composition of claim 7 wherein the olefinically unsaturated monomer is styrene and wherein the thickening agent is magnesium oxide or magnesium hydroxide.

10. The curable molding composition of claim 8 wherein the olefinically unsaturated monomer is styrene and wherein the thickening agent is magnesium oxide or magnesium hydroxide.

11. The cured composite produced by curing the composition of claim 1.