CA1126427A

CA1126427A - Coupling agents for thermoplastic composites

Info

Publication number: CA1126427A
Application number: CA334,229A
Authority: CA
Inventors: Edward J. Augustyn
Original assignee: NL Industries Inc
Current assignee: NL Industries Inc
Priority date: 1978-09-11
Filing date: 1979-08-22
Publication date: 1982-06-22
Also published as: NL7906769A; SE7907492L; DE2936510A1; GB2031910B; AU5042679A; JPS5538874A; GB2031910A; BE878559A; FR2435500A1; IT7925413A0; IT1122930B

Abstract

ABSTRACT OF THE DISCLOSURE
Filled thermoplastic resin composites are provided con-taining a novel coupling agent selected from the group con-sisting of mono-,di- and tri-long chain fatty acid esters of C1 to C36 mono and polyhydric alcohols.
The coupling agents are particularly effective bonding agents for calcium carbonate filled thermoplastic resins for which previously used coupling agents, such as organo-silanes, proved ineffective.

Description

~;26'~2~

This invention is concerned with coupling agents for filled plastics particularly calcium carbonate filled plastics.
In view of the recent shortages of petroleum feed stocks necessary to manufacture such polymers as polyethylene, PVC, polypropylene and other polyolefins and the ex~ectancy that these shortages will continue, there has arisen a need to incorporate larger volumes of inexpensive filler products into these polymers. These fillers function as extenders and reinforcing aids to improve the mechanical properties of the polymer in which they are incorporated such as tensile impact strength, ductility and Gardner impact strength. It is expected that the volume of thermoplastic polymers requiring fillers will continue to grow at increasing rates each year.
Coupling agents or adhesion promoters are often used in filled plastic composites to aid in the incorporation of filler into the polymer and to form an adhesive bond between filler and polymer. These coupling agents become more essential as higher loadings of filler are incorporated into the plastics. By virtue of such coupling agents, useful thermoplastic composites containing about 70%
~iller can be processed using conventional extrusion and injection molding equipment.
Heretofore~ organo-silanes have been the most widely used coupling agents for filled plastic composites. These organo-silane coupling agents have demonstrated a high degree of success in bonding numerous polymer resins filled with silica, metal silicates or metal oxides. They have not been as effective, however, in other systems, such as with ~L~Z~7 calci~m carbonate fillers which are used extensively in many resins. Organo-titanates function to some degree as bonding agents for calci~m carbonate filled polymers and are therefor useful as coupling agents.
The present invention, on the other hand, provides non-titanate, non-silane coupling agents which bond thermo-plastic polymers to a variety of inorganic mineral fillers.
Thermoplastic resin filler composites containing these agents exhibit improvements in physical properties, processability and thermal stability. The agents of this invention perform as well or better than the organo-titanates as coupling agents for calcium carbonate filled polymers but are distinctly superior to the titanates in terms of cost.
The coupling agents of this invention comprise mono-, di-,and tri-, long chain fatty acid esters of Cl to C36 mono and polyhydric alcohols and preferably Cl to C4 mono and polyhydric alcohols. Preferably, coupling agents from this class will be selected from the ~roup consisting of the mono-,d -, and tri-esters of hydroxy fatty acids or acetyl derivatives thereof.
The present coupling agents are prepared by esterify-ing the fatty acids with Cl to C36 alcohols and polyols such as methanol ! propanol, butanol r ethylene glycol, propylene glycol, pentaerythritol, glycerol, decanol, dodecanol, tetrade-canol, pentadecanol, hexadecanol, octadecanol, eicosanol, doco-sanol and tetratriacontanol as well known in the art to form mono-, di- and tri-esters of fatty acids.
Typical long chain hydroxy fatty acid esters or acetyl derivatives thereof of this invention are methyl ricinoleate, methyl acetyl ricinoleate, ethyl acetyl ricinoleate, ethyl ~2~;~Z~

ricinoleate, butyl ricinoleate, butyl acetyl ricinoleate, glyceryl tri (ricinoleate), glyceryl tri (acetyl ricinoleate) methyl hydroxy stearate, methyl acetyl stearate, ethyl hydroxy stearate, ethyl acetyl stearate, butyl hydroxy stearate, butyl acetyl stearate, glyceryl tri hydroxy ~stearate), and glyceryl tri (acetyl stearate).
The hydroxy fatty acids or acetyl derivatives thereof may have saturated or unsaturated fatty acid chains and contain ~8 to 22 carbon atoms, and preferably 18 carbon atoms. Exemplary compounds are hydroxy stearic acid and ricinoleic acid ti.e.
hydroxy oleic acid) and acetyl derivatives thereof.
The coupling agents of this invention may be repre-sented by the formula:

IRl Formula I CH3(CH2)5-CH-cH2 R2 (CH2)7 3 wherein Rl is a hvdroxyl group or acetyl group; R2is -CH=CH-, or -CH2-CH2-; R3 is a mono, di- or tri- ester group containing from 1 to 36 carbon atoms.

A preferred compound is an ester of acetyl ricinoleic acid, i.e. 12-acetyl-9-octadecenoic acid, represented by the formula wherein 23 represents the ester group:

4-C~-CH
Form~la II: CH3~CH2)5C`H-CH2-CH=cH(cH2)7cOoR3 Another preferred compound is an ester of acetyl stearic acid, i.e. 12-acetyl-9-octadecanoic acid, represented by the formula wherein R3 represents the ester group:

Formula III: CH3(CH2)5CH-CH2 CH2 CH2 (C 2)7 3 The preferred hydroxy fatty acid esters and acetyl derivatives thereof of this invention are lower alkyl mono ricinoleates and hydroxy stearates wherein the alkyl group contains from 1 to 36 carbon atoms. While all of the compounds of this invention act as excellent bonding agents between the resin and inorganic filler, the methyl acetyl ricinoleate imparts superior reinforcing properties, such as tensile impact strength and ductility to the filled resin composites in which it is incorporated.
The amount of hydroxy fatty acid ester or acetyl derivative thereof incorporated in the filled thermoplastic composite can vary over wide ranges. It should however be employed in amounts of about 0.5 to about 7.5~ by weight of the filler component, and preferably about 0.5 to about 5%
by weight of the filler component.
It has been found that by virtue of the present coupling agents, up to 80% by weight, preferably 5~ to 75%
and most preferably 10% to 70~ of inorganic filler can be incorporated into the resin to form a composite based on the weight of total composite.

~26~27 As previously mentioned, the coupling agents of this invention can be used with a variety of inorganic mineral fillers including silicas, metal silicates, metal oxides, hydrated aluminum oxides and antlmony trioxide, the latter of which are used as flame-retardant additives for polyolefins and combinations thereof. The thermoplastic resins in which the coupling agents of this invention may be used to bond fillers thereto include the polymeric amides, such as nylon and products of polymerization of organic monomers containing one or more unsaturated double bonds such as ethylene, propylene, styrene, acrylobutadiene styrene, methacrylic acid, vinyl acetate, vinyl chloride and mixtures thereof.
The coupling agents of this invention are particu-larly useful in calcium carbonate filled thermoplastic resin composites such as calcium carbonate filled high density poly-ethylene resins, homopolymer polyprop~lene resins and polyvinyl chloride resins. The calcium carbonate fillers can be either coated or uncoated and can vary in particle size distribution from 0.06 to 6.0 microns. Moreover, resin filler composites containing the inventive coupling agents can be processed at temperatures of about 335F. without change in color which indicates a heat stabilizing effect on the composite.
The long chain fatty acid esters and acetyl deriva-tives thereof of this invention can be incorporated with the resin and filler by a variety of conventional methods. For example, the resin may first be fluxed on a 2 roll calender at temperatures sufficient to fuse the resin. Next, the coupler may be blended by mixing with the resin followed by blending the filler in the resin-coupler mix. In another 26~27 ,, .

method, the filler and coupling agent may be blended in a high speed mixer to coat the coupling agent on the filler.
The coated filler is then milled with the resin on a 2 roll calender. In still another method, the coupling agent is first dissolved in toluene followed by slurrying the solu-tion with filler to again coat the filler. The slurry is then dried and fluxed with the resin on a 2 roll calender.
The so-formed composite may be compounded and processed by conventional techniques to fabricate a large variety of self-supporting or laminar plastic forms.

The bonding action of the hydroxy fatty acid esters or acetyl derivatives thereof permits the plastics manufacturer to incorporate increasingly higher levels of low cost inorganic mineral ~illers without sacrificing certain highly desirable properties such as impact strength, melt flow and thermal stability. The fatty acid esters of this invention permit bonding of fillers other than the silicas, metal silicates and metal oxides, particularly calcium carbonate. Calcium carbonate and other non-silicatej non-oxide minerals have until now, resisted being bonded to organic polymers by means of conventional coupling agents such as the organo-silanes.
The thermoplastic composite may be compounded and processed by conventional techniques such as injection molding, and extrusion. Injection molded calcium carbonate filled composites prepared using couplers of this invention give improved reinforcement and melt flow properties relative to commercial injection molded resin composites filled with a metal silicate such as talc.

6~

The following examples are given to illustrate the invention, but are not deemed to be limiting thereof. All percentages given are based upon weight unless otherwise indicated.
EXAMPLES 1 to 6 These examples illustrate the effect of the alkyl acetyl ricinoleate coupling agents of this invention in im-proving the reinforcing characteristics of high density poly-ethylene (HDPE) filled with 30% by weight of an uncoated cal-cium carbonate product having a mean particle size distribu-tion of 2.5 microns. The coupling agents used ~ere methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl tri-(acetyl ricinoleate) and glyceryl tri (acetoxystearate).
A 3% coating of each coupling agent, based on the filler weig~t was accomplished by premixing 1.8g. of coupler ~ith 60g. of calcium carbonate in a Ronson blender for 1 ~inute at 250E. ~he resulting coated calcium carbonate powdPrs were processed with 140g. of HDPE for 8 minutes using a 2-roll calender set at 275E. The so-formed stocks were relnoved and compression molded for 5 minutes at 325~. to form 40 mil. slabs which were then te ted for tensile impact strength using a Plastics Ilnpact ~ester (Inodel TM 52004, Testing Machines, Inc.). The results obtained comprised an average of six test specimens on each example; 3 cut in a direction parallel to milling and 3 cut at 90 to the direction of milling.
As controls, a HDPE sample containing no filler and coupler, and a sample containing calciuln carbonate fil-ler and no coupler were tested. A sample containing calcium ~ carbonate filler and an organo titanate coupler, isopropyl :

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_________________ 6~Z7 triisostearic titanate was also tested. The results are given in Table 1 below:
As Table 1 shows, a significant improvement in the reinforcing properties of calcium carbonate occurred when coated wit'n alkyl acetyl ricinoleates of this invention (co,npare 2x. 2 with Examples 3,4 and 5). The methyl acetyl ricinolea~e, glyceryl tri (acetyl ricinoleate) and glyceryl tri (acetoxystearate) coated calcium carbonate performed as good or better than thè organo titanate.
EXAMPLES 7 to 17 These examples illustrate that various conventional cornpounding techniques can be used to incorporate the alkyl acetyl ricinoleates of this invention in a thermoplastic poly-meric material to yield a composite having excellent reinforce-ment properties.
In each example a filled composite containing 30%
calcium carbonate and 70% HDPE was prepared. Exa~21e 8, con-taining only 30% calcium carbonate without coupler was used as a control.
Two alkyl acetyl ricinoleates of this invention, methylacetyl ricinoleate and butyl acetyl ricinoleate were in-corporated in the composite by different conventional methods and the resulting milled stocks were compression molded for 5 minutes at 325~. to form 0.040 inch plaques. Specimens were cut from each plaque and used for tensile impact stren~tn and ductility tests. An or~ano titanate coupler, isopropyl triisostearic titanate, was also incorporated into the com-position for each method employed and ~ested.

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In the first series of examples (8-11) the HDPE was fluxed on a 2 roll calendar at 275F. and after fusion took place (2 min.), the coupling agents were added and mixed for 3 minutes. The calcium carbonate filler was slowly added to the HDPE-coupling agent mixture and the resulting composite mixed for a total of 10 minutes. A composite containing no coupler was prepared as a control (Ex. 8).
In Examples 12-14 the calcium carbonate was first com-bined with the coupling agents in a high speed blender. The so-formed coated fillers were incorporated into the HDPE on a 2 roll calender and milled for 10 minutes.
In Examples 15-17 the coupling agents were first dis-solved in toluene and this solution was slurried ~ith calcium carbonate to form a 3% coating over the calciu~ carbonate. The slurry was dried at 120C. for 45 minutes and t'ne coated calcium carbonate fluxed with the HDPE for 10 minutes at 275F. on a 2 roll calender.
Table 2 below summarizes the results:
As Table 2 shows, irrespective of the method of coating the filler and incorporating t'ne coated filler in the resin, excellent reinforciny properties o the HDPE-filler composite result. Moreover, methyl acetyl ricinoleate coated fillers inparted more improved rein~orcing properties to the composite than the organo titanate coated fillers, except for the method used in Examples 8-11 in which the ricinoleate was comparable to the titanate.
EXAMPLES 18 to 30 ~ hese examples illustrate the effect on the reinforce-ment properties o a high density polyethylene resin containing calcium carbonate filler coated with various amounts of methyl acetyl ricinoleate.

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using a 2 roll calender to form a 30% calcium carbonate com-posite. The composites were fluxed for 10 minutes at 275F., sheeted off and compression molded to form 0.040 inch plaques ~hicl) were tested for tensile impact strength and ductility.

~ PE sample containing no filler (Ex. 18) and a HDPE sample containing 30% uncoated calcium carbonate (Ex. 19) ~ere also tested as controls.
The results are given in ~able 3 below:
As the table shows, improvement in tensile impact strengtll and ductility over the uncoated filler occurred at about 1.0% methyl acetyl ricinoleate. Optimum reinforcement occurred in composites formulated with calcium carbonate which had a 3.5-4.0% coating of methyl acetyl ricinoleate.
After about 4.0% coating levels, reinforcing properties of the composite were gradually reduced but still better than ~ith uncoated filler.
EXAMPLES 31 to 4 0 These examples illustrate the improvement of rein-forcing properties of an HDPE composite containing coated or uncoated calcium carbonate, by treating the calcium carbonate with an alkyl acetyl ricinoleate of this invention, methyl acetyl ricinoleate.
A variety of commercial coated and uncoated calcium carbonate products having a mean particle size distribution ranging from 0.06 microns to 6.0 microns were treated with 6~?.17 ____________________ _ ~;, .
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methyl acetyl ricinoleate using a high speed blender. The treated products were fluxed with HDPE for 10 minutes at 275F. on a 2 roll calender to form a composite containing 70~ HDPE and 30% filler. For comparison, a series of coated and uncoated calcium carbonate fillers were fluxed with HDPE
without prior treatment with a coupler. All stocks were compression molded 5 minutes at 325F. into .040 inch plaques and tested for tensile impact properties.
A HDPE sample containing no filler and coupler were tested as a control.
The results are given in Table 4 below;
As Table 4 shows, in each case, whether the calcium carbonate filler was coated or uncoated, significant improve-ment in the reinforcing properties of the HDPE composite was achieved using treatments of methyl acetyl ricinoleate.
EXAMPLES 41 to 54 These examples show that an alkyl acetyl ricino-leate of this invention methyl acetyl ricinoleate, can be used to improve the reinforcement properties of polypropy-lene homopolymer (PP)/calcium carbonate composite.
Methyl acetyl ricinoleate was used to provide a 3%
coating OVeE a series of uncoated calcium carbonate products or an additional 3% coating over coated calcium carbonate products using a high speed blender. For comparisons , the uncoated and coated calcium carbonate products alone were also employed for incorporation with PP.
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mixed an additional 8 minutes. The resulting stocks were com-pression molded for 5 minutes at 350F. to form 0.040 in.
plaques which were then used to determine tensile impact strength, ductility and Gardner impact strength at 75F.
The results are given in Table 5 below:
As Table 5 shows, at each level of calcium carbonate in the composite, ~hether or not such carbonate filler was coated or uncoated, improved tensile impact strength, ductility, and Gardner impact strength resulted when the fillers were treated with methyl acetyl ricinoleate according to this invention.
EXAMPLES 55 to 58 These examples illustrate that methyl acetyl ricinoleate also acts as a stabilizer additive for thermoplastic resins to pre-vent discoloration of the filled resin during thermal processing.
In these examples, PP resin composites were prepared with 30~ calcium carbonate alone, 30% methyl acetyl ricinoleate-coated calcium carbonate and 30~ isopropyl triisostearic titanate-coated calcium carbonate. As a control, a PP resin containing 0 no filler or coupling agent was also tested. All samples were heated to 335F. for 10 minutes and the color observed.
Table 6 below summarizes the results _ ~ _____ CaC03 ¦EXAMPLEI (2.8 microns)l COUPLER TYPE ICOMPOSITE COLOR
I l___ l10 mlns @335F. I
1 55 I none I None I Clear 'I I I I I
1 56 ! 30 I None I Off-White I
I 57 1 30 I Methyl Acetyl I Off-White - I I I Rincinoleate 1 58 1 30 1 Isopropyl Triiso-l Tan-Orange 3 1 1 I stearyl Titanate 1 ~6~27 As Table 6 shows the resin composite containing methyl acetyl ricinoleate coated calcium carbonate did not undergo any color change relative to the resin composite containing no coupling agent.
EXAMPLES 59 to 71 ~ . .. .
These examples illustrate that calcium carbonate treated with 3~ methyl acetyl ricinoleate (MAR) can be compounded at up to 50~ loading with homopolymer (PP) resin, and the resulting composite injection molded using conventional molding techniques.
A series of PP resin composite containing 30%
and 50~ uncoated and coated calcium carbonate were prepared.
Similarly another series of PP resin composites were pre-pared containing the above amounts of coated and uncoated calcium carbonate treated with 3% of MAR. PP resin con-taining no filler or coupler was selected as a control.
For each example, the tensile impact at 75 F.
and Gardner impact (75F. and 0F.) were determined;
melt flow characteristics were determined using procedures outlined in ASTM D~1238, "Measuring Flow Rate of Thermo-plastics by Extrusion Plastome~er" with a pressure mass of 2160 grams at 246C.
Comparisons were also made against commercial injection molded PP resins containing talc as mineral filler and also against a high impact un~illed copolymer PP resin.
Table 7 summarizes the results:

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As the Table shows, the treatment of CaC03 with methyl acetyl ricinoleate produces injection molded PP/CaC03 composites with improved reinforcement and melt flow proper-ties over untreated PP/CaC03 composites and over commercial injection molded PP composite.
EXAMPLES 72 to 74 These examples illustrate the improvement of rein-forcing properties of polypropylene resins filled with anti-mony trioxide wherein the antimony trioxide is treated with methyl acetyl ricinoleate as a coupling agent.
Antimony trioxide functions as both a flame retar-dant and a filler because of the relatively large amounts often required to flame retard polypropylene compositions.
Such antimony oxide often results in a loss in physical pro-perties of polyolefin composites.
In these examples, antimony oxide having a mean particle size distribution of about 1.5 microns was coated with 3% of methyl acetyl ricinoleate based on the antimony trioxide weight. The MAR treated antimony tiroxide was compounded with PP to provide a 16.7% loading on a 2 roll calender, compression molded and tested for tensile impact strength.
As controls, a PP resin containing no antimony trioxide and coupler and a PP resin/Sb203 composite containing 16.7~ Sb203 alone was also tested. The re-sults are given in Table 8 below:

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Sb203wt? I(ft-lbs/in ) I (millisecs)_l 1 72 1 0 1 0 1 133 1 1.2 - I 73 1 16.7 1 o I go l 0.9 1 74 1 16.7 1 3 1 121 1 1.5 ~L ............. _ . I .. _ I _ ................. I
As Table 8 shows, MAR treated antimony trioxide/PP
composite gave significant improvements on tensile impact strength and ductility over untreated antimony trioxide com-posite.
EXAMPL S 75 to 77 These examples illustrate the improvement in re-inforcing properties of polypropylene resin filled with aluminum trihydrate (ATH) wherein the ATH is treated with methyl acetyl ricinoleate as a coupling agent.
Aluminum trihydrate is useful as both a flame/smoke retardant and filler in many thermoplas~ic applications.
In these examples, ATH having a mean particle size of about 1 micron was coated with 3% of methyl acetyl ricino-leate based on the ATH weight. The MAR treated ATH was com~
pounded with PP to form a 25% loading using a 2-roll calender, compression molded and examined for tensile impact strength.
As controls, a PP resin without ATH and coupler and a PP resin/ATH composites containing 25~ ATH alone was also tested. The results are given in Table ~.

6~Z7 MAR `~ I TENSILE
I EX. I ATH ~ I (based on I IMPACT STE~. I
ATH wt.) _ I(ft-lbs/in I _ _ !
Table 9 shows that tlAR treated PP/ATH composites develop significant improvements in tensile impact strength over the untreated ATH composites.
EXAMPLES 78 to 81 These examples illustrate the improvement in reinforcing pro-perties of polypropylene filled with the amounts of calcium carbonat (uncoated or coated) having a mean particle size distritubion of

- 2.5 microns according to the procedure of Examples l to 6. The coupling agents used were docosylhydroxystearate whérein the alcohol is a by~product mixture containing C20 - C28 linear primary alcohols containing about 60% C22; and tetratriacontyl ricinoleate wherein the alcohol is a by-product mixture containing .~ 20 ~5% C34 saturated primary alcohol and remainder being non-reactlve material being 500 molecular weight normal paraffin.
As Table lO shows, a significant improvement in reinforcing properties of calcium carbonate occurred when coated with the compositions of this invention.
The invention being thus described, it will be obvious that the same may be varied in many ways, such variations are not to be regarded as a departure from che spirit and scope of the invention, and all such modifications are intended to be included within the scope o the following claims.

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Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A composition comprising a thermoplastic resin containing a particulate inorganic mineral filler and a coupling agent, said coupling agent selected from the group consisting of mono-, di- and tri-long chain fatty acid esters of C1 to C36 mono and polyhydric alcohols, wherein said long chain fatty acid comprises hydroxy fatty acids or acetyl derivatives thereof, and wherein said coupling agent comprises from about 0.5 to 7.5% by weight of said filler.

2. The composition of claim 1 wherein said long chain fatty acid comprises acetyl ricinoleic acid.

3. The composition of claim 1 wherein said long chain fatty acid comprises acetyl stearic acid.

4. The composition of claim 1 wherein said long chain fatty acid comprises ricinoleic acid.

5. The composition of claim 1 wherein said long chain fatty acid comprises hydroxystearic acid.

6. The composition of claim 1 wherein said thermoplastic resin is the product of the polymerization of organic monomers containing one or more unsaturated double bonds.

7. The composition of claim 6 wherein said thermoplastic resin is selected from the group consisting of polymerized monomers of ethylene, propylene, styrene, acrylobutadiene styrene, methacrylic acid, vinyl acetate, vinyl chloride and mixtures thereof.

8. The composition of claim 1 wherein said inorganic mineral filler is selected from the group consisting of silicas, metal silicates, metal oxides, hydrated aluminum oxides, antimony trioxide, calcium carbonate and combinations thereof.

9. The composition of claim 8 wherein said metal oxide is antimony trioxide.

10. The composition of claim 1 wherein the particulate mineral filler is coated with the coupling agent.

11. A composition comprising a thermoplastic resin con-taining calcium carbonate filler and a coupling agent, said coupling agent represented by the formula wherein R1 is a hydroxyl group or acetyl group; R2 is CH=CH-, or -CH2-CH2-; R3 is a mono-, di- or tri- ester group containing 1 to 36 carbon atoms, and wherein said coupling agent comprises from about 0.5 to 5.0% by weight of said filler and said filler is coated with the coupling agent.

12. The composition of claim 11 wherein said thermoplastic resin is selected from the group consisting of polymerized monomers of ethylene, propylene, styrene, acrylobutadiene styrene, vinyl chloride, methacrylic acid, vinyl acetate and mixtures thereof.

13. The composition of claim 11 wherein said thermoplastic resin is a high density polyethylene resin.

14. The composition of claim 11 wherein said thermoplastic resin is a polypropylene resin.

15. The composition of claim 11 wherein said coupling agent is selected from the group consisting of methyl ricinoleate, methyl acetyl ricinoleate, ethyl ricinoleate, ethyl acetyl ricinoleate, butyl ricinoleate, butyl acetyl ricinoleate, glyceryl ricinoleate, glyceryl tri(acetyl ricinoleate).

16. The composition of claim 11 wherein said coupling agent is selected from the group consisting of methyl hydroxy stearate, methyl acetyl stearate, ethyl hydroxy stearate, ethyl acetyl stearate, butyl hydroxy stearate, butyl acetyl stearate, glyceryl tri(stearate) and glyceryl tri(acetyl stearate).