GB1579080A - Uniformly pigmented low shrinking polyester moulding compositions - Google Patents

Description

(54) UNIFORMLY PIGMENTED, LOW SHRINKING POLYESTER MOULDING COMPOSITIONS (71) We, UNION CARBIDE CORPORATION, a Corporation organised and existing under the laws of the State of New York, United States of America, of 270 Park Avenue, New York, State of New York 10017, United States of America, do hereby declare this invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to composition having improved uniformity of pigmentation and based on thickenable, low shrink, curable polyster compositions, which are particularly suitable for moulding articles.

A major advance in commercial polyester moulding technology was the introduction several years ago of chemically thickened systems. Chemical thickening is always employed in sheet moulding compounds ("SMC"), and is increasingly being used in bulk moulding compounds ("BMC"). In these systems, an alkaline material such as magnesium oxide or magnesium hydroxide is added to the uncured polyester along with fillers, glass fiber, and other standard materials. The alkaline material interacts 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 mould during crosslinking of the system. Thus, the use of thickened systems has made a major contribution to the commercial expansion of polyester moulding.

Another technical improvement that has made a significant contribution to commercial polyester moulding technology is the use of low profile additives to reduce shrinkage during the curing reaction, and thereby to 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 best to 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 thermoplastic 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 in a thickened composition, the increase of viscosity that occurs can cause the low profile additive to separate, and thereby cause a tacky surface. This problem is usually most severe with the more reactive polyesters, i.e., those having lower molecular weight to double bond ratios. To combat this, carboxylic acid functionality is incorporated in the low profile additive. The thermoplastic polymer itself can then enter the thickening reaction, thereby ensuring that a tack-free surface will result.

However, while alleviating the tackiness problem the introduction of these carboxyl groups into the thermoplastic polymers can present other difficulties, if not properly understood. For the thermoplastic polymers to function optimally as shrinkage control agents they must become incompatible with the crosslinked polyester structure. Therefore, if the polyester resin, carboxylated thermoplastic, and thickening agent structure are not carefully controlled and balanced, the chemical thickening agent can bond the thermoplastic polymer into the thermoset system through the carboxyl groups. This will reduce the amount of thermoplastic-thermoset incompatibility, thus reducing, and in extreme cases, actually eliminating the shrinkage control.

Another property of these composites which can be notably effected by this thickening process is internal pigmentability. Because of the thermoplastic-thermoset incompatibility, low shrink, low profile SMC and BMC is more difficult to pigment uniformly 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 polyester composites using commercially available carboxylated polycaprolactone low profile additive. However truly zero shrink thickened polyester composites have not yet been uniformly and reproducibly pigmented in commercial moulds except when certain black pigments were used with carboxylated polycaprolactone low profile additive.

The invention provides compositions having improved uniformity of pigmentation and based on internally pigmented, thickened, curable polyester compositions. In one aspect, the invention provides a curable composition comprising: (a) a polyester resin comprising th'e reaction product of an olefinically unsaturated dicarboxylic acid or anhydride and a polyol; (b) an olefinically unsaturated monomer that is copolymerizable with the 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; and (l) a surface active compound.

In another aspect, the invention provides a curable composition comprising (a), (b), (c), and (d), as defined above, and (g) a low profile additive comprising a copolymer either of vinyl ocetate with maleic or fumeric acid or of vinyl acetate with maleic anhydride.

The invention also provides the cured composites produced by curing the above-described curable compositions, as well as a method for forming a moulded article from these compositions.

The polyesters that are employed in the invention 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. These acids include maleic acid or anhydride, fumaric acid, tetrahydrophthalic acid or anhydride, hexachloroendomethylene tetrahydrophthalic anhydride ("chlorendic anhydride"), Diels-Alder adducts of maleic acid or anhydride with compounds having conjugated olefinic unsaturation, such adducts being exemplified by bicyclo[2.2.1] hept-5-ene-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 dicarboxylic acids or anhydrides may also be employed in producing the polyester. These 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 polyester. These polyols include ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycols, neopentyl glycol, glycerol and 1,1,1trimethylolpropane. As a rule, not more than 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 moulding compositions must contain residual acidity in order to enter into the thickening reaction. The nature and production of the polyesters used in these applications are known in the art.

The polyester composition of the invention also contains a monomer that contains ethylenic unsaturation, and which is copolymerizable with the polyester. Styrene is the preferred monomer in commercial practice today, although others can be used, including 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 temperatures, i.e., 20"-25"C.) to ensure that the polyester composition is a fluid. Enough monomer is employed so that the thickness 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 they 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 35 to 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 invention. These 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 examples of these 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 from 0.1 to 6 weight per cent, based upon weight of polyester resin, plus monomer, plus low profile additive.

Pigments are also employed in the invention. Examples of these include black iron oxide, titanium 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, buff), molydate (orange), chrome orange, manganese (violet), chrome-tin (pink), and cadmium mercury (maroon, red, orange).

Pigments are employed in the invention in conventional proportions, e.g., from 0.5 to 10 weight per cent, based upon weight of polyester resin plus monomer plus low profile additive.

The invention has shown improvement in pigmentability with all pigments thus far tested.

In one aspect, the invention employs a carboxylated vinyl acetate polymer low profile additive. These polymers include copolymers of vinyl acetate and ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and the vinyl acetate/vinyl chloride/maleic acid terpolymers.

Reference is made to Comstock et al., United States Patent No. 3,718,714 and Comstock et al. British Patent Specification No. 1,361,841, for descriptions of carboxylated vinyl acetate polymer low profile additives.

The useful carboxylated vinyl acetate polymer low profile additives ordinarily have molecular weights within the range of from 10,000 to 250,000, and preferably from 25,000 to 175,000. They are usually employed in proportions of from 6 to 20, and preferably from 9 to 16, weight per cent, based on weight of polyester plus low profile additive, 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 moulding 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 examples of these 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 effective amount, such as from 0.3 to 2 to 3 weight per cent, based on the weight of polyester plus monomer plus 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. Mould release agents or lubricants, such as zinc stearate, calcium stearate, and others known to the art.

The polyester moulding 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 200C to 3500F. 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 compounds have given the best results. Classes of surfactants that deserve particular mention include:: alkali metal, alkaline earth metal, and ammonium sulfonates; certain ethylene oxide adducts of long chain (e.g., Cg-Cl8 aliphatic alcohols; certain polyoxyethylene-polyoxypropylene block copolymers; polyglycerol oleate; ethoxylated sorbitan monooleate; sodium 2-caprylic-1(ethyl beta oxipropanoic acid) imidazoline; ethoxylated alkylguanidine amine complex; sodium and 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 0.1 to 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 proportion 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 0.1 to 3 weight per cent carboxyl groups, based on weight of copolymer. The molecular weight of the 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 preferred in most cases.

Experimental In. the Examples below, the following materials were used: Polyesters Polyester A - made from isophthalic acid, maleic anhydride, propylene glycol, and dipropylene glycol in approximate molar proportions of 0.3:0.7:0.8:0.2, respectively; Polyester B - made from 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: Table I Weight % Molecular Acid Solids in Weight to Polyester Number Styrene Double Bond Ratio A 16.4 72.4 286.7 B - - 244.4 C 28.5 65.5 156.1 D 219.9 65.4 224.7 Miscellaneous Additives "Camel Wite" - Finely divided calcium carbonate used commercially as a filler in polyesters; Zinc Stearate - used as a mold release agent; t-Butyl perbenzoate - a peroxide initiator; p-Benzoquinone - a polymerization inhibitor; "RS-5988" - a 33 weight per cent dispersion of magnesium oxide in a polypropylene male ate polyester; "Marino H" - Magnesium hydroxide; "Modifier M" - a 33 weight per cent dispersion of magnesium oxide in a polypropylene maleate polyester; "JM-308A" glass fibers - 1/4-inch chopped glass fibers, of medium hardness; ; "PPG-303" glass fibers - 1/4-inch chopped glass fibers of medium hardness, but a bit softer than JM-308A; and Alumina trihydrate - a flame retardant filler.

Low Profile Additives LP-A - 40 weight per cent solids solution of a 99.2/0.8 (by weight) vinyl acetate/acrylic acid copolymer in styrene, having the following properties: Solution Viscosity 4000-6000 centipoises at 25"C.

Copolymer Inherent viscosity 0.48; 16-17 Ford cup MN 42,000 Mw 92,000 LP-B - 40 weight per cent solids solution of vinyl acetate/maleic acid copolymer in styrene.

Different versions contained from 0.7 to 2.1 weight per cent maleic acid in the copolymer, the remainder being vinyl acetate. The styrene solution viscosities varied from 3400 to 16,000 centipoise at 25"C. The Ford Cup viscosities of the copolymer varied from 12.4 to 17.8; LP-C - 35 weight per cent solution of polystyrene in styrene, having a solution viscosity of 5000 cps at 25"C; and LP-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.

Pigments PDI-1416 - A green pigment; PDI-1600 - An orange pigment; CM-3308 - A gray pigment; CM-2015 - a black pigment; and CM-3131 - A blue pigment.

(The pigments employed were all commercial materials marketed as dispersions in a low molecular weight polyester. The pigment weights indicated in the formulations 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 manifested in any of several ways, such as the presence of small spots on the sample, cloudiness, flow marks, waviness, 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 moulding composition containing thickener, pigment, LP-A low profile additive, and no surfactant.) The invention provides a means for improvement 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 moulding compositions.

Example I Bulk moulding compounds were made from the following formulations: Table I Component 1 2 3 4 Polyester D 60 60 60 60 LP-B (1) 35 35 - LP-A - - 35 35 Styrene 5 2 5 2 Surfactant A (2) - 6 - 6 Camel Wite 175 175 175 175 Zine Stearate 3 3 3 3 PD1-1416 10.5 10.5 10.5 10.5 Modifier M (3) 0.53 0.7 2.5 2.5 t-butyl perbenzoate 1.0 1.0 1.0 1.0 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 acetate and 1.5 per cent maleic acid, the solution having a viscosity of 15,720 centipoises at 250C.

(2) Sodium salt of isododecylbenzene sulfonic acid ("Siponate DS-10", Alcolac Chemical Company), 50 weight per cent solution in styrene.

(3) Less magnesium oxide is required with the formulation containing LP-B than with the one containing LP-A because the higher proportion of carboxyl groups in LP-B causes more viscosity build-up (i.e., thickening). Run 2 uses slightly more than Run 1 because of the effect of the particular surfactant used. Run 4 was not similarly adjusted for presence of surfactant because the overall proportion of magnesium oxide in Runs 3 and 4 was much higher than in Runs 1 and 2, and the effect of the surfactant was therefore not sufficient to require adjustment.

(4) Runs 1-4 were first made using PPG-303 glass fibers, and were then repeated using JM-308A glass fibers.

The general procedure for making bulk moulding compounds that was used in this Example 1 and in many of the other Examples was the following: General Procedure for Preparation of Bulk Moulding Compound (BMC) Formulations The liquid components (including the pigment dispersion) were weighed individually into a Hobart mixing pan placed on a Toledo balance. The t-Butyl perbenzoate was weighed into a vial and added to the contents of the pan and the pan was attached to a Model C-100 Hobart (Registered Trade Mark) mixer (in a hood). The agitator was started at slow speed, then increased to medium speed to completely mix the liquids and pigment over a period of 3 to 5 minutes. The agitator was then stopped, and the zinc stearate (internal mold release agent) was added to the liquid from an ice cream carton.The Hobart mixer was restarted and the zinc stearate mixed with the liquid until it was completely wet-out. The Camel Wite (calcium carbonate filler) * was next added to the pan contents (agitator off) then mixed, using medium to high speed, until a consistent paste was obtained. 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 reweighed and styrene loss made up, and 175 grams of the paste was removed from the pan (using a large spatula) and transferred to a wide-mouthed 4-ounce bottle. This paste sample was stored in the capped bottle at room temperature and the viscosity was measured periodically using a Model HBT Brookfield Viscometer on a Helipath Stand.

After removal of the paste sample, the chopped glass fibers were added slowly (from an ice cream 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 from the mixer and separate portions of the BMC mix of 650 grams each were removed using spatulas and transferred to aluminum foil lying on a balance pan (balance in the hood). The mix was tightly wrapped in the aluminum foil (to prevent loss of styrene via evaporation) and stored at room temperature until the viscosity of the retained paste sample reached a desired value. The mixes in this study usually reached this viscosity within 24 hours of their preparation.

The general procedure for molding the samples of BMC was the following: General Procedure for Moulding Panels The equipment used for compression moulding of panels from the glass reinforced unsaturated polyester moulding mixes was a 75-ton, Queen's hydraulic press fitted with a 12 x 12 inch matched metal die mould (chrdmed surface). The dies were heated to 3000F., and the 650 gram portion of mix was removed from the foil and placed in the mould. The mould was quickly closed (without stops) to a pressure of 600 psi, and the panel was cured for 2 minutes at 600 psi/300 F. The mould was opened, the panel was quickly removed, and allowed to cool (in a hood) under weights (to avoid warpage).

(Where any significant departures were made from the indicated general procedures for preparation of the BMC and moulded panel, they are stated in the text).

Panels were moulded (at 500 psi) from the abovedescribed formulations, and were measured for shrinkage and were visually evaluated for uniformity of pigmentation. The results are shown below in Table II: Table II Izod Impact Low Profile Moulding Viscosity, shrinkage, Strength Glass Fiber Additive Surfactant X10-6, centiposes mils/inch Pigmentation ft-lbs/inch JM-308A LP-B A 8.5 0.25 Good 6.1 JM-308A LP-B none 23.2 0.60 Fair 5.0 JM-308A LP-A A 14.4 0.30 Fair 5.0 JM-308A LP-A none 42.4 0.35 Poor 4.5 PPG-303 LP-B A 7.5 and 0.3 Fair 3.9 34.8 PPG-303 LP-B none 68.8 0.6 Fair-Poor 4.0 PPG-303 LP-A A 19.2 0.2 Fair-Poor 3.0 PPG-303 LP-A none 19.8 and 0.25 Poor 3.1 44.8 Shrinkage is determined on these 12 x 12 inch panels by measuring the length of each of the four sides with a microcaliper, adding the four lengths together, substracting this sum from 48, and then dividing the difference by 48 to thereby obtain the total shrinkage in mils/inch.

Example 2 A series of bulk moulding compounds were made and moulded into panels by the general procedures described in Example 1. The formulations, shrinkage, and results of evaluation for pigmentation are displayed in Table III. The LP-B low profile additive employed was the one described above in Example 1.

Table III Run No.

Component 1 2 3 4 5 Polyester A 60 - 60 - Polyester B - 60 - 60 Polyester C - - - - 60 LP-B 30 30 30 30 30 Styrene 10 10 10 10 10 Camel Wite 200 200 200 200 200 Pigment (CM-2015) 12 12 12 12 12 Zinc Stearate 4 4 4 4 4 t-Butyl perbenzoate 1.1 1.1 1.1 1.1 1.1 MgO 0.6 0.6 - - Mg(OH)2 - - 2.0 2.0 2.0 Glass(PPG-303) 15 15 15 15 15 Shrinkage, mils/inch 3.5 1.9 2.7 0.9 0.7 Pigmentation Good Good Good Fair Fair-Poor (clouds) Control 1 A series of bulk moulded compounds were made and then moulded by the general procedures described in Example 1 from the formulations displayed in Table IV: Table IV Run No.

Component 1 2 3 4 Polyester D 750 750 - Polyester C - - 360 360 Styrene 125 73 30 LP-A 375 - 210 LP-C - 420 - 240 Camel Wite 2500 2500 900 900 t-Butyl perbenzoate 13 13 9 9 Zinc Stearate 40 40 24 24 Modifier M (MgO) 30 38 18 18 Glass (PPG-303) 671 671 250 250 CM-2015 Pigment 148 148 - CM-2020 Pigment - - 50 50 The panels were measured for shrinkage and were evaluated visually for pigmentation, which was judged on the depth of color, uniformity, and presence of mottling. The results are displayed in Table V: Table V Low Profile Shrinkage, Run Polyester Additive mils/inch Pigmentation 1 D A 0.27 Fair 2 D C 2.00 Good 3 C A 0.48 Poor 4 C C 2.3 Fair to Good Example 3 A series of bulk mould compositions were made using the general procedure described in Example 1.The basic formulation is shown below in Table VI: Table VI Component Parts, by weight Polyester D 210 low Profile Additive varied Surfactant A varied Styrene varied Camel Wite 525 Alumina Trihydrate 175 Zinc Stearate 14 Pigment varied t-Butyl perbenzoate 4.2 p-Benzoquinone 0.1 MgO ^l'?' ,'? vaiied Glass (JM-308A)-to 20% 2j4 - 238 The variable parts of the formulations Bare, displayed below in Table VII. The LP-B employed was the one described in Example 1.

Table VII RUN NO.

Component 1 2 3 4 5 6 7 8 9 10 11 LP-A 122.5 - - - - - 122.5 - 70 - 70 LP-B - 122.5 122.5 122.5 122.5 122.5 - 70 - 70 LP-C - - - - - - - 80 80 80 80 Styrene 6 6 17.5 6 12 17.5 6 - - - Surfactant A 22 22 - 22 11 - 22 22 22 22 22 CM 3308 39 39 39 - - - - 39 39 - CM 3015 - - - 44 44 44 44 - - - PDI 1600 - - - - - - - - - 39 39 Modifier M 2.6 - 1.8 2.6 2.6 1.8 7 - - - MgO powder (100%) - 7 - - - - - 4.2 4.9 4.9 7.5 The BMC formulations described above were moulded in a transfer mould using a 100-ton hydraulic press. 180-Gram charges were added to the ram, and a piston injected the BMC into the several mould cavities using a force of 800 pounds. There were five mould cavities in the transfer mould that were each connected to the ram by 126-millimeter (diameter) feed lines. The circular gates leading into the mould cavities 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 x 1/8-inch "dog bone" (tensile testing bar) cavity. The BMC was cured in the mold for 2 minutes at 3000F., and then discharged.

The moulded specimens were evaluated as follows: Shrinkage The length of one of the nominally 5-inch bars from the same mould 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 deepness of color, uniformity, and mottling. The best sample was rated "4",, and the worst "1". The others were rated visually using these as standards. The results are displayed in Table VIII: Table VIII Low Profile Weight So Shrinkage, Run No. Additive Surfactant A mils Pigmentation LP-B 3 12 4 2 LP-A 3 10 3 3 LP-B - 10 3 4 LP-B 3 13 3 5 LP-B 1.5 10 2 6 LP-B - 17 2 7 LP-A 3 12 1 8 LP-B+C 3 20 4 9 LP-A+C 3 19 3 10 LP-B+C 3 20 4 11 LP-A+C 3 19 2 Example 4 A series of bulk moulding compositions were made, and were then moulded using the transfer mould described in Example 3.The several runs differed in the presence or absence of Surfactant A, the proportions (weight per cent) of maleic acid in the copolymer of LP-B, and in the molecular weight (as evidenced by styrene solution viscosity) of the copolymer of LP-B. Two LP-A control runs were also included. The basic formulation used is shown below in Table IX: LP-A control runs were also included. The basic formulation used is shown below in Table IX: Table IX Component Parts, by weight Run I Runs 2-9 Polyester D 630 210 Low Profile Additive 408 122.5 Surfactant A 66 varied Styrene 18 varied Camel Wite 1575 525 Aluminum trihydrate 525 175 Zinc Stearate 42 14 PDI-1416 Pigment 117 39 t-Butyl Perbenzoate 12.6 4.2 p-Benzoquinone 0.1 0.1 Modifier M 16.5 varied Glass (JM 308A) 808 235 The variable parts of the formulation are shown below in Table X, along with the shrinkage, in mils. The best pigmentation was formed in Run No. 1, the worst in Run No. 9, with Runs 2-8 being intermediate between them in descending order. The fact that Run No. 5 was rated better than Run No. 7 appears at this time to be anomolous.

TABLE X % Acid in Low Profile LP Viscosity LP Additive Parts of Styrene, Modifier Shrinkage, Run No. Additive at 25 C., CPS. Copolymer Surfactant A parts M, parts Mils 1 LP-B 3920 0.71 66 18 16.5 16 2 LP-B 3920 0.71 - 17.5 3.5 24 3 LP-B 6060 1.2 22 6 4.2 15 4 LP-B 8060 1.6 22 6 3.1 18 5 LP-B 14,840 1.4 - 17.5 1.8 16 6 LP-B 3400 1.1 22 6 4.2 14 7 LP-B 14,840 1.4 22 6 2.8 20 8 LP-A 5000 0.8 22 6 12 15 9 LP-A 5000 0.8 - 17.5 8 16 Example 5 A series of 12 x 12 inch panels were compression moulded from BMC using the general procedures described above in Example 1. The several runs differed in the proportion of maleic acid in the copolymer of LP-B, and in the molecular weight of the copolymer of LP-B, as evidenced by styrene solution viscosity. No surfactant was used in this series. A control containing LP-A is included.The general formulation is shown below in Table XI: Table XI Component Parts, by weight Polyester D 360 Low Profile Additive 210 Styrene 30 Camel Wite 1050 PDI 1416 Pigment 63 Zinc Stearate 18 Modifier M varied t-Butyl Perbenzoate 6 Glass (JM 308A) 391 The variable parts of the formulation are displayed below in Table XII, along with the shrinkage, in mils/inch, measured as described above in Example 1. As was the case in Example 4, the Runs are arranged in the table in descending order of pigmentation rating.

Table XII Low Profile LP Viscosity % acid in LP Modifier M, Shrinkage, Run No. Additive at 250 C, cps. Copolymer parts milslinch 1 LP-B 3400 1.1 7.0 0.42 2 LP-B 6060 1.2 3.4 0.52 3 LP-B 3480 1.7 4.0 0.00 4 LP-B 3970 1.4 3.8 0.42 5 LP-B 3920 0.71 6.0 0.33 6 LP-B 7540 1.5 3.0 0.65 7 LP-B 11,860 1.2 2.8 0.52 8 LP-A 5000 0.8 12 0.19 Example 6 Surfactant Screening Studies In this series of experiments, the following standard formulation was mixed in a 1/2-pint can, stirred with a Cowles dissolver (spinning propeller type), poured into a 3-inch (diameter) aluminum dish, and immediately cured for 15 minutes at 1500C. While the samples were all cast, not moulded under pressure, the pigmentability evaluation correlates well with the results obtained for similar formulations in moulded parts.While the thickener (MgO in this case) must be present in the samples, the mixture must be cured before the mixture has thickened or increased in viscosity. The probable reason for this is that, in the absence of pressure, there is insufficient flow in thickened mixtures to obtain homogeneous castings.

The standard formulation used in these screening experiments is shown in Table XIII: Table XIII Component Parts, by weight Polyester D 30 Low Profile Additive 17.5 Styrene 2.5 Camel Wite 87.5 Zinc Stearate 1.5 CM-2015 Pigment 5.3 t-Butyl Perbenzoate 0.5 Modifier M varied Surfactant varied After curing and removing from the aluminum dish, the cast parts were rated visually for depth of color, uniformity of pigmentation, presence or absence of small white specks, and mottling. The six formulations shown below in Table XIV were used as standards against which all the others were compared. The worst was given a rating of 1, the best 6, with the others being intermediate between them.The six standard formulations were the following (the LP-B employed in this Example was the one described in Example 1): Table XIV Rating 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 0.75 0.5 0.75 Surfactant A 3 - 3 6 - Surfactant B(l) - - - - - 3.6 (l) 42 weight per cent styrene solution of sodium salt of alpha-olefin sulfonate In the surfactant screening series, 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 polyester, LP-B, plus styrene. Modifier M was used in amounts of 0.75 parts, by weight.Table XV, below, displays the chemical name of the surfactant, its Trade Name, its classification in McCutcheon's 1975 Edition of "Detergents & Emulsifiers", and the pigmentability ratings for the two proportions of surfactant used. In the table, "EO" represents ethylene oxide, "PO" represents propylene oxide, "NC" represents "did not cure", and the surfactants marked with an asterisk * were employed as a solution in styrene.

Table XV Surfactant Class Pigmentability 3% 6% "TERGITOL+ Min Foam 2x" AT-28 2 1 EO/PO adduct of linear alcohol "TERGITOL+ Min Foam lx" AT-28 1 1 EO/PO adduct of linear alcohol "TERGITOL+ 15-S-3" AT-28 1 2 EO adduct of linear alcohol "TERGITOL+ 15-S-5" AT-28 3 1 EO adduct of linear alcohol "TERGITOL+ 15-S-9" AT-28 1 3 EO adduct of linear alcohol "TERGITOL+ 15-S-15* AT-28 2 2 EO adduct of linear alcohol "TERGITOL+ 15-S-30"* AT-28 2 1 EO adduct of linear alcohol "TERGITOL+ 15-S-50" AT-28 1 2 EO adduct of linear alcohol "TERGITOL+ TMN-6" AR-12 4 3 Trimethylnonyl poly (EO) ether "TERGITOL+ TMN-10" AR-12 4 3 Trimethylnonyl poly (EO) ether "TERGITOL±08" AP-lO 4 NC Na(2-ethyl-1-hexanol) Sulfate "TERGITOL±4" AP-12 3 1 Na(7-ethyl-2-methyl-4undecanol) Sulfate "TERGITOL+ 15-S-7" EO AT-28 1 NC 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 1 adduct of propylene glycol "Pluronic+ F-68"* EOIPO AW-80 2 2 adduct of propylene glycol "Pluronic+ F-68LF"* EO/PO AW-80 2 2 adduct of propylene glycol "TERGITOL+ XH"* EO adduct AT-28 2 2 of linear alcohol Table XV (cont'd.) Surfactant Class Pigmentability 3% 6% "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 1 adduct of linear alcohol "Pluronic+ 31R4" EO/PO AW-82 2 1 adduct of ethylene glycol "Pluronic+ 31R1" EO/PO AW-82 2 1 adduct of ethylene glycol "Pluronic+ 17R4" EO/PO AW-82 3 2 adduct of ethylene glycol "Neodol 25-3" EO adduct AT-28 1 1 of ethylene glycol Neodol 25-7" EO adduct of AT-28 1 1 linear alcohol "Neodol 25-12" EO adduct AT-28 2 2 of linear alcohol "Neodol 25-3A" NH4 salt of AQ-18 4 1 EO adduct of linear alcohol sulfate "Neodol 25-3S" Na salt of AQ-18 4 NC EO adduct of linear alcohol sulfate "Plurafac+ RA-43" EO/PO AW-82 1 2 adduct of ethylene glycol "Plurafac+ RA-40" EO adduct AT-28 1 1 of linear alcohol "Plurafac+ D-25" EO adduct AT-28 2 2 of linear alcohol (Modified) "Ucane+ 11" Na alkylbenzene AK-8 6 sulfonate "Calsoft T-60" B-13 6 6 triethanolamine dodecyl benzene sulfonate Glyceryl monooleate AE-14 2 2 Glyceryl dioleate AE-14 2 1 Glyceryl trioleate AE-23 1 1 Polyglycerol oleate AE-14 3 2 Table XV(cont'd.) Surfactant Class Pigmentability 3% 6% "Tween+ 80" Sorbitan W-9 1 2 monooleate "Tween+ 21" EO adduct of W-5 3 3 sorbitan monooleate "Abrosol O" Diethanolamine- A-28 2 2 oleic acid condensate "Brij+ 30" EO adduct of BB-4 2 2 lauryl alcohol, 4 EO's Na propyl oleate sulfonate AO-2 4 4 "Miranol+ MSA" Na 2-Caprylic- BA-6 4 1 1- (Ethyl beta oxipropanoic acid) Imidazoline "Petronate K" AI-6 2 1 Na petroleum sulfonate Na Xylene sulfonate AJ-18 4 3 "Tide+" - mixture of Na BO 4 3 tallow alcohol sulfate and linear alkyl benzene sulfonate Na alpha-olefin sulfonate* AG-l 6 5 Na alpha-olefin sulfonate AG-1 2 1 (powder form) "Centrolene-S" Lecithin M-1 2 1 "Aerosol C-61" BM 3 1 Ethoxylated alkylguanidine amine complex "Igepon T-33" Na and H-4 3 3 Methyl-N-oleyl taurate "Igepon TN-74" Na and H-6 3 Methyl-N-palmitoyl taurate "Igepon AC-78" 1-12 4 3 Coconut ester, Na isethionate "Aerosol OT-75" Dioctyl 1-12 4 3 Na isethionate "Triton+ X-100" EO adduct of AR-8 2 2 octylphenol "Triton+ X-45" EO adduct of AR-12 3 2 trimethylnonylphenol Table XV(cont'd.) Surfactant Class Pigmentability 3% 6% "Emulphor+ ON-877" EO adduct AT-26 5 5 of fatty alcohol "Emulphor+ VN-430" EO adduct AU-22 1 1 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 1 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-ammonium chloride "Ethoquad+ 0/12" Poly- C-33 4 2 ethoxylated quaternary ammonium chloride-ethoxylated alkylol amide/amineoleic "Ethomeen+ T-12" C-37 2 2 Bis(2 -hydroxyethyl)tallow amine "Ethoduomeen+ T-20" C-37 2 2 N,N' -polyoxyethylene(10)-N tallow-1 ,3-diaminopropane "Nekal+ BA-77" Na alkyl S-15 2 2 naphthalene sulfonate "Daxad+ 21" Monocalcium AB-2 4 2 polymerized alkyl aryl sulfonic acid "Byk-Mallinkrodt ST-80" P-2 2 3 Silicone "Byk-Mallinkrodt ST-60" P-2 3 1 silicone Table XV (cont'd.) Surfactant Class Pigmentability 3% 6% "Byk-Mallinkrodt FL-O" P-2 3 3 Silicone "Byk-Mallinkrodt F1" P-2 3 3 Silicone "Norlig 11 DA" Lignosulfonic L-10 2 1 acid derivative "Marasperse N-22" Na lignosulfonate Lr8 4 4 "Ultrawet DS" Na alkyl AK8 4 4 aryl sulfonate "Sellogen HR-90" Na alkyl 5-15 4 1 naphthalene sulfonate "Conoco SA-597" dodecyl AK-12 5 5 benzene sulfonic acid "Dowfax 2A1" Al8 4 4 Na dodecyl diphenyl ether disulfonate "Tamol SN" Na salt of condensed S-15 3 3 naphthalene sulfonate "Silicone L76"(') P 4 2 "Silicone Y-5900"(1) P 2 2 "Silicone L-45"(1) P-2 5 1 Polydimethylsiloxane "Silicone Y-6446"(1) P 4 1 "Silicone W-900"(1) P 4 2 "Silicone S-10"(1) P 2 1 "Silicone S-50"(1) P 1 1 "Silicone L-5420"(1) P-6 2 2 Siloxane-polyoxyalkylene Block Copolymer "Silicone L-5303"(1) P-6 2 2 Siloxane-polyoxyalkylene Block Copolymer "Siponate DS-10"* AK-8 3 4 Na dodecylbenzene sulfonate Dioctyl Na Sulfosuccinate V-8 3 3 (1) All silicones used in proportions of 0.3 and 0.6 percent.

+ Registered Trade Marks Those surfactants that are solids in the 100 per cent active form should be dissolved in a solvent, preferably styrene, before being added to the mixture in order to ensure complete and uniform distribution throughout the mixture.

The following surfactants yielded a pigmentability rating of 3 or more, in at least one of the two concentrations employed, which means that they improved the pigmentability when compared with the same formulation containing no surfactant: Table XVI The following structure types with LP-B gave better color ratings than the polyester plus LP-B and no surfactant Surfactant Structure Type Trade Name Class Manufacturer No.

1. Ethoxylated/Propoxylated Amides/Amines Ethoquad 0/12 C-33 Armak Co.

2. Amines and Quaternary Arquad C-50; D-17 Amrak Co.

Dervatives S-50; T-SO 3. Fatty Taurates Igepon T-33 H-4 GAF Igepon TN-74 H-6 GAF 4. Isethionates Igepon AC-78 I-12 GAF 5. Lignin Derivatives Marasperse N-22 L-8 American Can Co.

6. Silicon Derivatives Byk-Mallinckrodt P-2 Byk-Mallinckrodt FL-O; FL-1 UCC L-45; L-76; P-2 Union Carbide Corp.

W-900; Y-6446 7. Succinate, Sulfo Derivatives Aerosol OT-75 V-8 American Cyanamid 8. Sorbitan Derivatives Tween 21 W-5 ICI America 9. Naphthalene Sulfonates Sellogen HR-90 S-15 Nopco Chemical Div.

Tamol SN S-15 Rohm and Haas 10. Polymers Daxad 21 AB-2 Dewey and Almy Chem. Co.

11. Glycerol Fatty Esters Polyglycerol AE-14 ester of oleic acid 12. Olefin Sulfonates (alpha) alpha olefin AG-1 sulfonate Table XVI (cont'd.) Surfactant Structure Type Trade Name Class Manufacturer No.

13. Aryl Sulfonates Sodium Xylene AJ-18 Sulfonate 14. Diphenyl Sulfonates Dowfax 2Al AL-8 Dow Chemical Co.

15. Fatty Acid (Oil) Sulfates Sulfated propyl AO-2 and Sulfonates oleate, sodium salt 16. Alcohol Sulfates Tergitol 08 AP-10 Union Carbide Tergitol 4 AP-12 Union Carbide 17. Ethoxylated Alcohol Neodol 25-3A AQ-18 Shell Sulfates and Sulfonates Neodol 25-3S AQ-18 Shell 18. Ethoxylated Alkyl (Aryl) Tergitol TNM-6; Phenol Sulfates TMN-10 AR-12 Union Carbide Triton X-45 AR-12 Rohm and Haas 19. Ethoxylated Alcohols Emulphor ON-877 AT-26 GAF (Propoxylated) Tergitol 15-S-9; AT-28 Union Carbide 15-S-5 20. Fatty Glycols and Pro- Pluronic F-98 AW-80 BASF Wyandotte poxylated Glycols Pluronic 17R4 AW-82 BASF Wyandotte 21. Alkyl Aryl Sulfonates UCANE 11 AK-8 Union Carbide Ultrawet DS AK-8 ARCO Chemical Siponate DS-10 AK-8 Alcolac, Inc.

Conoco SA-597 AK-12 Conoco Chemical Co.

Calsoft T-60 AK-16 Pilot Chemical Co.

22. Amphoterics Miranol MSA BA-6 Miranol Chemical Co.

23. Cationic Surfactants Aerosol C-61 BM American Cyanamid (General) 24. Formulated/Blended TIDE (mixture of BO Proctor and Gamble Compounds and Mixtures tallow alcohol sulfonate and linear alkyl bonzene sulfonate) Example 7 The procedure described in Example 6 was repeated, with the exception that the formulation employed LP-A as the low profile additive. Modifier M was employed in a proportion of 1.25 parts, by weight. Table XVII displays the Trade Name of the surfactant (all are identified above in Table XV), the surfactant class, the 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 formulations described in Table XIV.

Table XVII Surfactant Class % Pigmentability "Arquad S-50" D-17 4.2 5 "Emulphor ON-877" AT-26 4.3 1 Na alpha olefin sulfonate AG-1 4.1 1 "Tween 80" W-9 4.4 1 "Silicone L45" P-2 0.3 2 "Tergitol 08" AP-10 4.1 1 "Tergitol TM-10" AR-12 4.4 2 "Daxad 21" AB-2 4.4 5 Na Xylene Sulfonate AJ-18 4.2 1 "Conoco SA-597" AK-12 4.4 4 "Ethoquad 0/12" C-33 4.3 4 "Marasperse N-22" L-8 4.4 2 "Siponate DS-l0" AK-8 4.2 3 (Styrene solution) Control (no surfactant) - 0 1 The following surfactants gave pigmentability ratings of 2 or more, which means that they improved the pigmentability compared with the formulation containing no surfactant: Table XVIII Surf.

Structure Type Trade Name Class No. Manufacturer 1. Ethoxylated Ethoquad 0/12 C-33 Armak Co.

Propoxylated Amides/Amines 2. Amines and Arquad S-50 D-17 Armak Co.

Quaternary Derivatives 3. lignin Marasperse L-8 American Derivatives N-22 Can Co.

4. Silicone L-45 P Union Carbide Derivatives 5. Polymers Daxad 21 AB-2 Dewey and Almy Chem. Co.

Table XVIII (cont'd.) Surf.

Structure Type Trade Name Class No. Manufacturer 6. Alkyl Aryl Siponate DS-10 Ak-8 Alcolac, Inc.

Sulfonates Conoco SA-597 AK-12 Conoco Chem.

7. Ethoxylated TERGITOL TMN-10 AR-12 Union Carbide Alkyl (Aryl) Phenol Sulfates Control Example 2 The surfactant screening experiments of Examples 6 and 7 were repeated, except that the low profile additive employed was the acrylic based LP-D. Modifier M was employed in a proportion of 1.25 parts, by weight.Table XIX displays the Trade Name of the surfactants, the surfactant class, the weight per cent in which the surfactant was used, and the pigmentability rating Table XIX Surfactant Class So Pigmentability "Ethoquad 0/12" C-33 4.3 2 "Daxad 21" AB-2 4.4 3 "Marasperse N-22" k8 4.4 2 "Arquad 5-50" D-17 4.2 4+ "Emulphor ON-877" AT-26 4.3 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.

Example 8 The general procedure of Example 1 was employed to prepare 12x 12 inch moulded panels from the following formulations: Table XX Run No.

Component ( (2) (3) (4) Polyester D 300 300 300 300 LP-A 150 - LP-C - 172 - LP-B - - 150 LP-D - - - 180 Styrene 58 28 50 20 Camel Wite 875 875 875 875 Zinc Stearate 20 20 20 20 Table XX(cont'd.) Run No.

Component (1) (2) (3) (4) t-Butyl perbenzoate 5 5 5 5 CM-2015 42 42 42 42 Modifier M 15 15 10 10 Paste Sample 175 175 175 175 PPG-303 Glass (10%) 128 128 128 128 Visual panel evaluations for pigmentability consisted of comparing the finished panels for color depth (pigment), dispersion of pigment, glossiness, etc. The pigmentability ratings of these four systems containing different low profile additives were as follows: Formulation NO.Pigmentability #2 (Containing LP-C) Best #3 (Containing LP-B) Less #4 (Containing LP-D) Less 41 (Containing LP-A) Worst Example 9 The general procedure of Example l was employed to produce 12 x 12 inch moulded panels from the following formulations:: Table XXI (1) (2J (3) (4) (5) (6) Polyester D 300 300 300 300 300 300 LP-A 150 150 150 150 150 150 Styrene 50 50 50 50 50 50 Camel Wite 875 875 875 875 875 875 Zinc Stearate 20 20 20 20 20 20 t-Butyl perbenzoate 5 5 5 5 5 5 CM-2015 42 42 42 42 42 42 Modifier M 15 15 15 15 15 15 TERGITOL TMN-10 23 - - - - - Conoco SA-597 - 23 - - - - Daxad-2 1 - - 23 - - Siponate DS-10 (50% solution in styrene) - - - 46 - Tween 80 - - - - 23 Silicone LAS - - - - - 2.3 Paste Sample 175 175 175 175 175 175 PPG-303 Glass (10%) 130 130 130 130 130 128 (The surfactants are all described above in Table XV.) The pigmentability ratings of these panels were as follows: Formulation No.Pigmentability #2 (Containing SA-597) Best #4 (Containing DS-10) Best #6 (Containing LA5) Less (No surfactant control) Less #3 (Containing Daxad-21) Less #1 (Containing TMN-10) Less #5 (Containing Tween 80) Worst As a series. these panels are generally worse than those from the experiments containing LP-B. which follow in Example 10.

Example 10 Using the general procedure of Example 1, 12 x 12 inch panels were prepared from the following formulations: Table XXII (1) (2) (3) (4) (5) (6) Polyester D 300 300 300 300 300 300 LP-B 150 150 150 150 150 150 Styrene 50 50 50 27 50 50 Camel Wite 875 875 875 875 875 875 Zinc Stearate 20 20 20 20 20 20 t-Butyl perbenzoate 5 5 5 5 5 5 CM-2015 42 42 42 42 42 42 Modifier M 10 10 10 10 10 10 TERGITOL TMN-10 23 - - - - - Conoco SA-597 - 23 - - - - Daxad-2 1 - - 23 - - Siponate DS-10 - - - 46 - Tween 80 - - - - 23 Silicone Lr45 - - - - - 2.3 Paste Sample 175 175 175 175 175 175 PPG-303 Glass (10%) 130 130 130 130 130 128 The comparative pigmentability rating of the panels prepared from these formulations are as shown: Color Formulation No. Depth Comments #4 (Containing DS-10) Best (Darker than Example 9 #4) #2 (Containing SA-597) (Darker than Example 9, #2) (No surfactant, Control) Control #3 (Containing Daxad-21) (Surface quite nice, darker than Example 9 #6) #6 (Containing Lr45) #1 (Containing TMN-10) (Ditto - Example 9, #1) #5 (Containing Tween 80) Worst (Ditto - Example 9, #5) Example 11 Using the same procedure described in Example 9 and 10, 12 x 12 inch moulded panels were made using the carboxylated acrylic low profile additive LP-D, and evaluating the same surfactants as in Examples 9 and 10. In this series, the control, which contained no surfactant, appeared better than all the panels containing surfactants. There was very little difference, if any, between the several panels which contained surfactants.

Claims (22)

WHAT WE CLAIM IS:

1. A curable composition comprising: (a) a polyester resin comprising the reaction product of an olefinically unsaturated dicarboxylic acid or anhydride and a polyol; (b) an olefinically unsaturated nonomer that is copolymerizable with the 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; and (f) a surface active compound.

2. A composition as claimed in claim 1 wherein the carboxylated vinyl acetate polymer low profile additive is of the vinyl acetate/maleic acid copolymer type.

3. A curable composition comprising: (a) a polyester resin comprising the reaction product of an olefinically unsaturated dicarboxylic acid or anhydride and a polyol; (b) an olefinically unsaturated monomer that is copolymerizable with the 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; and (e) a low profile additive consisting essentially of a copolymer either of vinyl acetate with maleic or fumaric acid or of vinyl acetate with maleic anhydride.

4. A composition as claimed in claim 1 or claim 2 wherein the surface active compound is: (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) a polyglycerol oleate; (e) an ethoxylated sorbitan monooleate; (f) a sodium 2-caprylic(ethyl beta oxipropanoic acid) imidazoline; (g) an ethoxylated alkylguanidine amine complex; (h) a sodium and methyl-N-long chain aliphatic taurate; (i) a sodium isethionate coconut ester; (j) an ethoxylated long chain alkylphenol; or (k) an N-long chain aliphatic quaternary ammonium halide.

5. A composition as claimed in claim 4 wherein the surface active compound is sodium dodecylbenzene sulfonate.

6. A composition as claimed in claim 4 or claim 5 wherein the surface active compound is present in an amount of from 0.1 to 8 weight percent, based on the weight of polyester plus low profile additive plus monomer.

7. A composition as claimed in any one of the preceding claims wherein the olefinically unsaturated monomer is styrene.

8. A composition as claimed in any one of the preceding claims wherein the monomer is present in an amount of from 35 to 70 percent by weight based on the weight of polyester plus low profile additive plus monomer.

9. A composition as claimed in any one of the preceding claims wherein the thickening agent is magnesium oxide or magnesium hydroxide.

10. A composition as claimed in any one of the preceding claims wherein the thickening agent is present in an amount of from 0.1 to 6 percent by weight, based on the weight of polyester plus low profile additive plus monomer.

11. A composition as claimed in any one of the preceding claims wherein the low profile additive has a molecular weight of from 10,000 to 250,000.

12. A composition as claimed in any one of the preceding claims wherein the low profile additive is present in an amount of from 6 to 20 percent by weight, based on the weight of polyester plus low profile additive plus monomer.

13. A composition as claimed in any one of the preceding claims wherein the pigment is present in an amount of from 0.5 to 10 percent by weight. based on the weight of polyester plus low profile additive plus monomer.

14. A composition as claimed in any one of the preceding claims including a polymerisation initiator, a filler. a reinforcing filler, a mould release agent or a lubricant.

15. A composition as clained in any one of the preceding claims wherein the polyester resin is derived from maleic acid, maleic anhydride or fumaric acid.

16. A composition as claimed in claim 1 substantially as hereinbefore described.

17. A composition as claimed in claim 1 or claim 3 substantially as hereinbefore described in any one of'the specific Examples.

18. A composition as claimed in any one of the preceding claims when cured.

19. A method of forming a moulded article which comprises supplying a composition as claimed in any one of claims 1 to 17 to a mould, compressing the composition within the mould, and curing the compressed composition.

20. A method as claimed in claim 19 substantially as hereinbefore described.

21. A method as claimed in claim 19 substantially as hereinbefore described in any one of Examples 1 to 5, or Examples 8 to 11.

22. A moulded article when formed by a method as claimed in any one of claims 19 to 21.