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09/01) 1,1:0 1 FAX *02 ** 5170 * BUSINEliS CONFIDENTIAL TT. RECORDS CTR. LAW FILES XT52T @002/043 PROJECT REPORT AEROSOL ADHESIVESCOMPATIBILITY TESTS FOR DENNISTON CHEMICAL CO. Author: R. J. Scott Supervisor: E. M. LaComte Date: December 9, 1969 Project No.: 123U10 File No.: 69-352 SUMMARY Denniston Chemical Co., requested assistance in pressure packag ing: a styrene/butadiena adhesive. It was found chat addition of fluorocarbon pro pellant to the concentrate as supplied caused flocculation and precipitation of the rain- Dilution with methyl chloroform, however, along with use of a fluoro carbon 12-vinyl chloride propellant blend produced only a small amount of precip itate snd retained an apparently stable supernatant dispersion. UNION CARBIDE CORPORATION - CHEMICALS AND PLASTICS RESEARCH AND DEVELOPMENT DEPARTMENT TARRYTOWN, NEW YORK BLAND/UCC 070 a::/Q0/0# U-.or FAX 802 88* 5770 VT, records ctr. LAW FILES I75I7 @008/048 TECHNICAL SERVICE REPORT by R. J. Scott AEROSOL ADHESIVES COMPATIBILITY TESTS FOR DENNISTON CHEMICAL CO. Union Carbide Corporation - Chemicals and Plastics Research and Development Department Tarrytown, New York 10591 BLAND/UCC 071 09/011 LI; or FAX 802 888 57T0 VT. RECORDS CTR. LAW FILES X7527 0004/043 INTO ODUCT ION The Chicago Mastic Ca , requested assistance from Denniston Chemical Co., in j&ckaging their pressure sensitive adhesive In aerosol form. Denniston Chemical, ic turn, requested that we determine the compatibility of the resin con centrate *dth propellant. Two samples cf adhesive concentrate were supplied for experimentation, one with the resin dispersed in methylene chloride and the other in methyl chloroform. The results of the propellant tolerance compatibility tests that were carried out on these samples are described below- DISCUSSION Both concentrates contained 12. 5% resin solids. Neither formed a true solution of resin in solvent, but rather an opaque, colloidal dispersion* When titrated with propellant 12 in glass compatibility tubes, both con cern rates produced a flocculant precipitate at the first additions of propellant. Such behavior is typical when nonsolvents ara added to resins that require high solvent systems. Denniston Chemical Co. reported that methylchlorofarm was a better solvent for the resin than methylene chloride and that fluorocarbon - vinyl chloride mixtures fad .oeer. used with the product. Accordingly, the second concentrate was packaged itl glass with 35% propellant 12/vinyl chloride 65/35. The flocculant precipitate' observed before did not form, but a dark gray material gradually fell out of solution to the bottom of the tube, leaving an opaque supernatant dispersion. Toluene is reported * to be a primary-solvent for styrene/butadlene resins and it was "bought that this, along with a hydrocarbon propellant, might have suffi cient solvency to keep the rosin dispersed. However, when the concentrates were diluted 50/!>0 with toluene and the resultant mixture packaged 50/50 with isobutane, the resin flocculated and separated. Lowor solids content was next explored as a possible route to keeping the resip. dispei: seel. The second concentrate with methylchloxofonn was diluted 1:1 with .s:ddr.ti onal methylchioroform, low ering the solids content from 12. 5% to 6.25%. The raeuita.it mixture was diluted 1:1 again, bringing the solids content down co 3.12?. When the two diluted mixtures were packaged with 35% of propellant 12/ vinyl chloride 65/35, a dark gray precipitate was observed in the bottom of the rubes, tmt in relatively small amounts. The supernatant liquid appeared to remain as a stable dispersion. Thus, it may be possible to package the adhesive by diluting the second concentrate 1: t with methyl chloroform and pressurizing with 35% propellant. This would make :he overall formulation as follows: "Adhesive'Solvents, " Union Carbide Corp. F-42616, September 1969. . BLAND/UCC i;:/09/00 ii;01 FAI 802 888 57i0 VT, RECORDS CTR. -3" Resin Methyl Chloroform UCOrf Propellant 12/Vinyl Chloride 65/35 LAW FILES I752T 0005/043 4ft 61 35 As a precaution, it might be advisable to put a statement on the label that the container should be inverted and actuated after use In oxdex to clear the vitlvc and diptube.. This is a common practice with aerosol paints* R, J.5;ott:mIw BLAND/UCC 073 /I19/00 li;Oi F4l 802 888 5T70 VT. RECORDS CTR. LAW FILES 17527 0006/045 NOTEBOOK REFERENCES &.H 6 ACKNOWLEDGEMENT Thanks to W. W. MarkowskL for carrying out the experimental work. DISTRIBUTION E. M. LaCombe 1NDE3C LIST Aerosol Adhesives Siyre ne/butadiene BLAND/UCC 074 ' (U:/09'00 14:0) FA I 802 888 8770 BUSINESS CONFIDENTIAL VT. RECORDS CTR. LAW FILES 17627 007/04 PROJECT REPORT AEROSOL PROPELLANTS TECHNICAL SERVICE SUMMARY JANUARY - JUNE 1973 Author: R. J. Scott iJuparvisox; D. A. McKenzie Project No. Date; File No; 123 U 10 July 23, 1973 P-73-113 SUMMARY: The main customer problem Involved the withdrawal of vinyl chloride hb an aerosol propellant because of increasingly adverse toxicity data coming from tosics new in progress. Substitutes are going to require compromises on cost, fl ammability, vapor pressure and solvency. A number of changes appeared in the antipersplrant area after a relatively quiescent second half last year. Gillette responded to Carter-Wallace's. "New Light Powder Extra Dry" with a similar "Right Guard" fbrmylatum, and changed their "Soft and Dri" from propellant 12/114 13/85 to 12/ll 50/50. Proctor and Gambit: Introduced "Sure" containing Zirconium chlorhydrol in addition to the standard aluminun cMorhydnol. Preliminary results from the Inter-Industry Program bn the toxicity of fluarc carbon propellent are encouraging, but growing optimism was tempered by tfc,a P. D. A. recall of "Pertussin" medicated Bpray after it was involved in the death of a young child. The cooperative program with Bound Brook to find a UCG resin for pl.*isiic aerosol containers was completed. The beat prospect appeared to be ICI's "HycranV which is under consideration for a licensing arrangement.. Fluorinnted HDPB is another possibility, but strength characteristics will have to be Improved. Gulf States Plastics finally ran an evaluation of our experimental blowing' agent. The U- ll/Methyl Formate Azeotrope was preferred, and showed some advantages over U-11 alone. Purthsr tests are scheduled. Union Carbide Corporation - Chemicals and Plastics Research and Development Department Tarrytown, New York BLAND/UCC 075 /08/00 U:0) FAX 002 888 5170 VT. RECORDS CTR. LAW FILES I752T @008/043 aerosol propellants TECHNICAL SERVICE SUMMARY JANUARY- TUNE 1973 I. OVERALL Total customer and sales contacts amounted to 480, a slight increase over the 460 tor the second half of 1972. Technology Requests and specific customer contacts are listed in the Appendix. The number one spot was retained by National Spray Can Filling Corp. with 16 contacts { although the majority of these wore by telephone) and second place wets to The Gillette Co. wiich cix contacts. The latter involved some detailed calculations for their International Division to devise blends to substitute fox straight fluorocarbon being usel in Gillette products overseas. The most important customer problem had to do with the with drawal of Vinyl chloride as an aerosol propellant. This caused acute difficulties with p lints where propellent 12/vinyl chloride 65/33 has been used in very large velum a. The mixture was economical and, because of its better solvency than propellant 12 alone, had better tolerance.for.paint resins. Reverting back to propellant 12, which was the original paint propellant, would increase costs and reduce the solvency of the system. Diluting propellant 12 with hydrocarbons such us profane and Isobutane would lower costs, hut the solubility problem would remain and thti problem of flammability would be introduced. Thus, paint fillers are on the horns of a dilemma,, and it Is difficult to predict In what direction they will go. The danger is that the economics might drive them to straight hydrocarbon, which many palms already use, and to solve the solubility problem by adding methylene chloric e to the concentrate. A number of customer calls were made to diacusa the situation, but most customers were non-committal as to their intentions. There are rumors that Dupont hae a substitute tor the vinyl chloride blend at the same cost and solvency; if so, it most likely would Involve ethyl chloride as a substitute for vinyl cjooride. This would sacrifice nonflammability and pressure ( vinyl chloride has rapot pressure of 35 psig at 70*F, whereas that of ethyl chloride is only about 5 pi3lg)jor solvency and low cost. Similar results could ha obtained without sacrificing nonflan inability by adding methylene chloride to the concentrate# In any event, we are following the situation and aspect to be able to respond with similar or better mixtures if the industry should go the ethyl chloride route. An unusual requestwas received from Petersou/Puritan tor an aerosol laundry detergeat. The concept was to dispense the detergent as a foam into the oveicap and then plop the foam into the washing machine; this saves the housewife from sc poping and spilling a laundry power or dripping and slopping a liquid In a buttle. A sample of our new ''Formula 41" was submitted to Peterson/Puritan for evaluation. 076bland/ucc ti::/ofl/on U'.O) TAX 502 555 5770 VT. RECORDS CTR. LAW FILES 17527 @009/043 -2- OJ NDUSTRY TRENDS AND DEVELOPMENTS A. Atytiperapiiants in contrast to the last half of 1972. when activity in the . uiitiperspirant area was relatively quiescent, the first half of 1973 saw the market heat up again. Gillette responded to Garter-Wallace's "New Light Powder Arrid" ( which, deposit# a dry powder instead of the oil-powder paste left liy the original "Arrid Extra Dry'') With a Similar "Right Guard" formulation, and also made a major change in the propellant system of their "Soft and Dri". The latter had used P-12/114 15/85 since its inception several yeaxa ago, and now Gillette has switched to P - 12/11 50/50. This is a favorable development for Carbide, since we do not make P-114, and also for Gillette since they can cow use a much lower cost propellant while retaining the same retail price for their product, and can use the same formulation for both "Right Guard" and "Soft and Dri", Procter and Gamble finally introduced their antiperspirant "Sure" with i. thirty-millioii dollar promotion campaign. The product was due late last year, but wasn't released until Spring. The special feature of "Sure" is the use of 2lr:onium chlorhydrol along with aluminum chlorhydrol; this supposedly increases the ef 'eefclvenaae, The formulation is a slurry type, similar to Che original "Right Guard" and " Arrid Extra Dry", with 90% propellant 12/11 3S/65, and entirely differ ant from. P. and GIs "Secret" which was a wet system using P- 142b. This is another favorable development for Carbide because we do not make P~ 142b and most of the "Sure" filling is being done at our best propellant customer, Petersott/Puritan in iDarville, Illinois. "Sure" uses dibutyl phthalate as the carrier, but P. and G. is committed to its removal for toxicity reasons. Our Fluid AP is under evaluation as a tfubetitutc; P. and G. reportedly has stated that Fluid AP would have been used aheeady, if Jr were not for an odor problem in the initial sampling. A visit was made to Rebels Chemical Company, Division of .Armour Pharmaceutical, the supplier of aluminum chlorhydrol, which is the principal antiperspirant agent iu use today. The purpose of the visit was to. t-stabiieh laison with Reheis and to explore future developments. The next generation sintipexspirant, according to Reheis, will be Basic Aluminum Bromide complex - Oil} shr - bearing the acronym of ( what else 7) BAB. It reportedly is 50% more effective than aluminum chlorhydrol/ and produces less staining. Comment from tie irdustry indicates that reception of BAB has been somewhat restrained, mainly because tha FDA will probahly require New Drug Applications to use it, aud the.!* ax* very costly in time and money. A revised application for a patent on Fluid AP has been sub mitted. There has been no response from the Patent Office as yet. Our first application was rejected because the examiner thought that Fluid AP ( UCON Fluid LI l-250) was a pxopoxyiated fatty alcohol surfactant. BLAND/UCC 077 (UI/OS/OU Li:l) FAX 302 *33 3770 YT. RECORDS CTR. - 3- LAW FILES 17327 0010/013 B. Toxicity of Propellants Preliminary results axe starting to come in from the late:r-Industry program to determine the biological effects of abuse of fluorocarton propellants. Exposure of humans to 100, 250 and 1000 ppm of fluorocarlon 12 for varying time periods showed no adverse effects nor any indication of Ciixdiotoxicity on the part of the subjects'. This woe encouraging because the first inhalation deaths occurred with cocktail glass chillers, which are Straight uoj.'ocarbon 12. Metabolism studies on dogs with P-11 showed complete ertpi: ration, i. e., there was no metabolism of the propellant to toxic compounds* This was another encouraging development, for P-11 is the least stable of all the fluorocarbons, and the most likely to undergo metabolic change. These agreeable developments were offset somewhat by the . PDA recall of "Pertussin" cough sprays and breath fresheners late in the first hiilf. Similar products of Morton Pharmaceutical have also reportedly been recalled. All but one of the eighteen deaths associated with those products have bcten attributed to gross misuse; the one exception involved a child too young to know bow to abuse an a&rsol. Details of the PDA investigation have not been revealed, but the situation is being watched closely by the industry. Meanwhile, investigations of the medical and environmental aspects of aerosols are spreading. The New England Research Corporation is studying sources of indoor pollution, including aerosols, the Southwest Research Corperacion is determining the effects on lungs of basic constituents of hair sprays, diwdorante and other products, Penn State University and Rutgers University are mveoiiguing the photochemical reactivity of fluorocarbons and their fate in the atmosphere, and OSHA is developing a program in Salt Lake City to evaluate the atnosphere in beauty salons. If'aerosols survive all of this, they will end up being the safest and most thoroughly tested products of all time. `C. Plastic Aerosols Our cooperative program with Bound Brook to find a UCC candidate resin for & plastic aerosol container was concluded. Four candidates were submitted for evaluation; DYNEL, vinyl, DYNEL/Vinyl 50/50, and "Hycran" ( aery]onltxlte/styrene 78/22 modified with 8 to 12%butadiene graft).. The most unusual results were obtained with the DYNEL/Vinyl 50/50 resin. Containers made uith it would explode unpredictably during filling or Standing on the bench top. Ddaminatioa was evident, audit was concluded that the DYNELand vinyl resins were simply incompatible. DYNEL alone was a disappointment, the more so because preI. ioniumry sample sheets indicated it to be a very tough material. It proved to have tie lowest burst strength of all the candidates, however, and behaved poorly in hamperature-'pressure tests. BLAND/UCC 078 /09/00 U;ll FAl 92 * 5T70 YT, RECORDS CTR "4- - LAW FILES X7S17 0011/049 Straight vinyl also was a disappointment in that stress ' clicking and crazing1 occurred at room temperature. Fluorinating the surface with the UCR1 process ( see below ) did not help. The beet performer was "Hycrau", hul UCC's interest in this resin is tenuous at best; 1CI holds patents on it, and Carbide is considering a licensing arrangement for the beverage market, hut negotiations are inactive ar present. UCRI has developed a process for surface heating plastics with elemental fluorine. In the case of high density polyethylene, it was found the: the permeability toward propellant 12 could be reduced 40 to 50 fold by surface fluorination. Arrangements were made by Coneupak for fabrication of some fclDPB containers and preliminary tests on them indicate excellent resistance to permeation. Strength characteristics axe marginal, however, and UCRl and Corsupak are jointly trying to improve them. Meanwhile, industry interest in plastics continues. Consupak reports no negative feedback from their second "Barex" sampling program last Pal., an air freshener is being introduced in a "Celcon" container, and the CSMA Task Force to develop guidelines for plastic containers, on which we ;ire participating, has been given a broadened assignment to draw up standards . for ultrasonic welding of the valve and suggested geometries to minimise stress. It is apparent that a lot of work is being done In design and evaluation and that peojde are getting into the nitty gritty of plastic aerosols. D. New York City Fire Department In a late -breaking development, the NYCFD modified their regulations to give the CSMA moot of the concessions they were seeking in.court. If th-s csma accepts the amendments, the long dispute may finally come to an end. The NYCFD is retaining certain storage requirements based on their tests, Jiowever, which may delay a settlement. S. Trade Association Activities . 1, CSMA The mid-year CSMA meeting was attended in Chicago, ac which time the annual product survey -was released. The survey showed a 10.5% increase in ae rosol production in 1972 over 1971, to a total of 2.8 billion units. The industry should pass the 3,0 billion mark this year. Antiperspirants axe the No. 1 product^ followed closely by hairsprays, both of which require large propellant contents per unit. The figures indicate that adverse publicity such as the Nader report and inhalation deaths is having virtually no effect on consumer sales BLAND/UCC 079 u::/o9/oo 11:1L F4J *02 *** 5T70 VT. RECORDS CTR. -5- * LAW FILES 17527 @012/043 2. CTPA We are cooperating with the CTFA in setting up standards to:: aerosol propellants. To this end, eighteen infra-red spectra were obtained anl submitted to the CTFA for reference standards. F. Polystyrene Foam - Fluorocarbon Blowing Agents At long last. Gulf States Plastics ran a machine test of our experimental blowing agents. One, a simple mixture consisting of U-ll/l sopentanc 90/l0, behaved like U-ll and showed no differences or advantages. The other, an azeotrope of U-ll/Methyl Formate 82/18, showed a slight increase in efficiency over U-ll, better mixing characteristics and, perhapB most significant, less coll collapse at ambient temperatures. The latter feature is apparently duo to the lower boiling pint of the azeotrope ( 68F.) compared to U-ll ( 7!i "F. ) which prevents condensation of the blowing agent after extrusion and consequent cell collapse. In the end, a better quality foam should result. The naat step la to be a single line production run for a day. or two followed by a multi-line run with a truckload of blowing agent. A lot of this depends on. negotiations between Gulf States and our marketing and sales departments which tire now in progress. R. j. Scott fi BLAND/UCC 080 /0$/0U U-.li FAX 80Z 888 5T70 VT. RECORDS CTR. -4 LAW FILES XT527 @013/043 APPENDIX Technology Requests /.exosol Service, Inc. Birmingham, Michigan. Packaging of three paint concentrates, none of which were found to bo compatible with the propellant when titrated. Chemical Packaging Cc., Ft. Lauderdale. Florida Analysis of a mold release material. P.rew CTI Corporation, Hialeah, Florida Analysis of a competitive stainless steel polishH^'San Corp. Chicago, Illinois Analysis of two palatable silicone oils which were found to be similar to Dow's DC-7030. MitchumThayer, Inc,, Tuckahoe, New York A lower cost substitute blend for P-12/114 25/75 was devised, using flammability curves and calculations based on Raoult's Law. Pet Chemicals, Miami Springs, Florida Packaging of a water based spray for disinfecting cat sprays. Workman Electronics, Inc, Sarasota, Florida Analysis cf the oil in a foam pad for cleaning TV tuners. Waasco, Inc, Hialeah, Florida Analysis of a competitive penetrating oil. BLAND/UCC 081 ::/09/00 U'.li FAX 802 SSS 5770 vt. records ctr. 4 Uff FILES X7527 @014/043 Significant Customer and Sales Contacts l. Barr-Stalfioxt Co-, Niles Illinois M> ( Capitol'Packaging Div., Alberto-Culver Co., Melrose Pk, Illinois ;i. Caiter-Wallace, Inc. Cranbury, N, J. (2) Chemical Packaging, Ft. Lauderdale, Florida Chemscope Corporation, Dallas, Texas <1. Claire Manufacturing Co., Chicago, Illinois " > DAP, Inc. Medina, Ohio (l. Faultless Starch Co., Kansas City, Mo. s. General Liquids Corporation, Baltimore, Md. 10. The Gillette Co.. South Boston, Moss ( 6 ) u. cjuerlaia, Inc. Somers, New York ,12 Kxylon Div. Borden Co., Norristown, Pa. 13. McKesson Chemical Co- Schenectady, New York 14. National Spray Can Filling Cotp. Elizabeth, N; J: (16) 15. Noxeli Corporation, Baltimore, Md. 16. Pet Chemicals, Inc. Miami Springs, Florida 17. Profcem Industries, Norristown, Pa.. 18. Revlon, Inc,, Bronx, New York 19. Scott's Liquid Gold, Inc., Denver, Colorado 2D. Shield Chemical Co. Canton, Mass. 21. Sprayon Div. Shexwin Williams Co. Bedford Hts., Ohio ,22 U. S. Chemical Co., Milwaukee, Wisconsin BLAND/UCC 082 ur./09/On U:U FAX 802 888 5770 VT, RECORDS CTR. LAW FILES X752T @015/043 DISTRIBUTION; H. T. Clayton D. A. McKenzie T. H. Welch BLAND/UCC 083 /08/on L 411 m 02 94 3770 BUSINESS CONFIDENTIAL YT. RECORDS CtR. + LAV FILES IT327 @010/043 PROJECT REPORT AEROSOL PROPELLANT BLENDS ETHYL CHLORIDE AS A REPLACEMENT FOR VINYL CHLORIDE Author: R. J. Scott Supervisor: D. A. McKenzie Date: August 29, 1973 Project No.: 123 U 10 File No.: P-73-139 SUMMARY The withdrawal of vinyl chloride as an aerosol propellant has pronopted a segret, for substitutes- Du Pont is making a strong move with ethyl chloride, but it hss disadvantages, the main one being a low vapor pressure. Hydrocarbon*, mainly isobutans and propane, have the right vapor pressure but have poor solvency and nonflfunmat fifty in blende can only be maintained with low concentrations. A review was made of possible substitutes for each of the three most widely used vinyl chloride blends, taking into account vapor pressure, flammability, cost and solvency. It was found that ethyl chloride mixtures would be the most ex pensive hut 'would provide some solvency, whereas fluorocarbon-hydrocarbon, blends would have a better vapor pressure match and lower cost, but would have poor sol vency. Specific mixtures derived ter customer evaluation with the recognition th.ai piobitbly none would be a satisfactory substitute in all respects for the vinyl chloride countexp art. UNION CAR BID* CORPORATION - CHEMICALS AND PLASTICS RESEARCH AND DEVELOPMENT DEPARTMENT TARRYTOWN, NEW YORK BLANDiUCC 084 /00/00 li:l> F3X 802 888 8770 VT. RECORDS CTR, LAW FILES X7S2T 0017/043 AEROSOL PROPELLANT BLENDS ETHYL CHLORIDE AS A REPLACEMENT FOR VINYL CHLORIDE INTRODUCTION Vinyl chloride has baen used in aerosol propellant blends for many years, mainly in paints as F- 12/vinyl chloride 65/35 and in moderate pressure mixtures as P-12/vinyl chloride/P-11 39/22/39. Because of recent toxicology and availability problems, it has been decided that vinyl chloride should be with drawn a; an aerosol propellant. The question then arose as to what should be used as a substitute. In the case of the F-12/11 mixtures, the application areas encom pass prtducts such as insecticides, mold releases and hair sprays where com patibility is usually not a problem- For thee a mixtures Propellant A or other f]voroc a rbon-hyrixocaxbn blends can be recommended as a direct substitute- I*1 th,a of paints, however, where the tolerance of the resin for propellant may be critical, substitution of straight fluorocarbon or fluorocarbon-hydrocarbon blends may cause precipitation and valve clogging. There are two ways to get around the compatibility problem: cither UE;2 a substitute for vinyl chloride that haa the same solvency, or add an-active Bl" vent such as methylene chloride to the concentrate so as to increase the'tolerance fo r low h-B propellants. The latter method is in common use. with paints pressur ized with propane and has the added advantage of utilizing the high density of meth ylene: chidride to offset the low density of the hydrocarbon and so minimize changes in net weight on the product label. Ethyl chloride la about the only substitute that retains slvenr properties of vinyl chloride, and Du Font Is already offering P- 12/etif* chloride mixtures in ratios from. 85/l5 to 65/35. Ethyl chloride is not a par/cUlar^y good propellant, however, having a pressure of only about 8 psig at 70'P toniParti to 35 osig fc r vinyl chloride. This means that, theoretically at leastsmore propel lant would be required to maintain the same pressure in the contai^ ^ chloride were substituted fox vinyl chloride on a one for one basis* Also* Hie tox icology of ethyl chloride under the name protocols that were applied *> vinyl cblo* xidu is unknown. ; Nevertheless, Du Font has made their move with etbykh^We and, in, view of the persistent need for a high K-B propellant, it was dacidd p camin# the possibilities for using ethyl chloride in aerosol propellant blend- . BLAND/UCC 085 fl/00 11: It FAX 802 888 57TC VT, RECORDS CTR 2- - - LAW FILES 17527 @018/015 t >-f :ffiCU55tt)K One of the Erst questions that bad to be faced was that of flamma bility. Ethyl chloride has a lower explosive limit (L. E. L.} in. air of 3.83% and ..n upper explosive limit (U- E. L.) of 15.4%. We did not have a flammability diagram of ethyl chloride-fluorocarbon. mixture on hand, and since our eudionc':(?r xube had long since been, dismantled, and since Mr. F. H. Small's appa ratus at South Charleston had been destroyed in an explosion, it was not likely that we were going to grit one experimentally. Thus, without much hope of suc cess. a sesrch was made of the literature. The Bureau of. Mines1 had only on reference to work done with odiyi ctiortde-fluorocarbon 12 mixtures. This was a relatively old paper in a Netherlands publication3 which, by a stroke of luclc, was on hand in the Bound B took L'Jbrary in English. The paper was concerned mainly with determining rite length of flame propagation, with mixtures in the neighborhood of explosive limits. Fcux ternary systems wers studied including miracle of miracles, thy.I ctlorj.de/air/P-12. By taking points from composition curves given in the papur where no flame propagation occurred, !x was possible to construct the attached flammability diagram. The interpretation of the diagram has been explained previously.3 The imjKJitant point is the intersect of the dotted line with the diagonal; this sets the maximum amount ci ethyl chloride vapor that con be mixed with P-12 vapor v;it!lout forming explosive limits at any dilution with air. Ab can be seen from the diagram, this amounts to approximately 33% ethyl chloride, even allowing for a gcocl safety margin in drawing the tangent line. To convert this figure to a liquid phase composition, an equation der ived previously3 for a two component system was applied; ICOAMWjP0^ a = -A(MWjPi - MWjpVj v/hare: a = Percent by weight of component 1 (ethyl chloride} in the liquid phase A = The limit for component 1 in the vapor phase = 0.35 for ethyl cliloride pi - Vapor pressure of component 1 = 22.7 psia for ethyl chloride at 70'F MV/j = Molecular weight of component l = 64.5 Tor ethyl chloride p2 = Vapor pressure of component 2 (propellant 12) = 84.7 at 7D*F MWj = Molecular weight of component 2 = 120. 9 for propellant 12. BLAND/UCC 086 '09/00 11 11 F.1I S02 89S 5770 VT. RECORDS CTR. -3- * L1W FILES I752T Si019/04-5 Substitu'dag numerical values gives: 100(0 35)(64 5)(84.7) a = (l2G.9)(22. 7) - 0. 35[(120. 9}(22,7) - (64- $)(U.7)) a = 30?. This ia an astonishingly large amount, and indicates that a mixture si; ca as i',l/ethyl chloride 65/33 would probably be nonflammable even under frac tion a dot; conditions. This was confirmed with a flash point determination, which is a crude fractionation teat. No flash was observed even with a boiling mixture. Having thus establish2d the fiammability parameters, attention was turned to devising substitute mixtures fer the three vinyl chloride blends now in iue; I. Propellant 12/vinyl Chloride 65/35 The problem with this mixture Is pressure: it has a vapor pressure o:i 5.S p0:,g at ?0*F compared to 42 peig for the ethyl chloride substitute. The presa-.ire cqlId he raised by the addition of P-22 (120 paig at 70^}, but this would also x 'dnE; th^ coat. Mr. W. W. Foster was asked to determine, with the aid of the computer, what combinations would have pressures of approximately SO and 53psig ec: tius lowest cost- Using input consisting of Raoult's Law, vapor pressure, mol ecular v'eight and cost information, Mr, Foster developed the data shown in the at:cched table. The cost figures in. the footnote were supplied by Mr. W. H, Schneider a-; a meeting at Institute on July 31. The data in the table show that: (l) The cost of any mixture will be ecus idea'fitly more than the ?-12/viayl chloride 65/35 blend (12.75//lb.) or the ethyl chloride substitute (13.1/ /lb.) but less than P-12 alone (15. 84//Ib,); (2) The cost of J'-22 can be offset simply by adding an equivalent amount of ethyl chloride, 1 s., ths cost does not change appreciably as the amount of U-22 is increased as long efl he ethyl chloride content is also increased; and (3) That a 50 paig mixture would bt! approximately 0.5//lb. less expensive than a 33 psig mixture. Since the calculations were based on. Raoult's Law and measured pressures are usually higher than cal:ulated, It was decided to use the data for 50 psig mixtures to choose a can didate in expectation that the pressure would be sufficiently close to the desired 5;-. psig :o be acceptable. Finally, the selection had to consider the industry custom of expres sing propellant mixtures in multiples of 3% and also the need to have sufficient P-22 present so that small deviations would not effect the overall pressure. If only 5% P-2'J we;:e specified, for example, the normal industry tolerance of 1% could lead to unacceptable variations it pressure from one batch to another. BLAND/UCC 087 Od.'tili IMS BI S02 888 3770 VT. RECORDS CTR. LAW FILES 17527 @020/043 Taking all of these considerations in.f.0 account, ttie following was ::hi;:.i:n for an. experimental substitute for UCON' Propellant 12/Vinyl Chloride UCON Propellant 22 = 13 UCON Propellant 12 = 55 Ethyl Chloride = 30 Vapor Pressure = 57 psig at 70'F bough this mixture at 15.16//lb. will cost more than the P-12/ethyl chloride c5/35 1dug ottered by Du Pont (13, l/Ab-) the latter should require more proneuutit per container to maintain Epray characteristics whereas our blend should ;:e usaiZe on a one for one basis. A sample cf the above mixture has been sent to Sprayon Products Company, .Bedford Heights, Ohio, for evaluation, in acxcsol paints. Depending on eiotr feedback, the composition ra&y be changed tor the computer showed that tie re in cotsicierable flexibility in adjusting the ratios with little change in cost. II. Propellant 12/Vinyl Chloride 80/20 Tide blend in used in much smaller volume than the 65/35 mixture but ;is significant enough to be Looked at. It has a pressure ot 67 psig at 70*F which l; very close to that of propellant iz alone (70 psig). The ethyl chloride inslogue has a pressure of only S2 psig, reflecting the depressant effect of ethyl cblond * and its unsuitability as a propellant, at least for these high pressure ap plications. To determine how much P-22 to add to raise the pressure to 67 psig. u c rival* uj:e of a simple Raoult1 s Daw calculation: Present composition: 60% (0. 662 moles) P-12 20% (0.310 moles) ethyl chloride Tctal Moles = 0.972 Tc lOQ parts of the mixture are added y parts of. P-22 to obtain the desired pressure P1, so that the total moles of the new mixture become* whence: where; P1 = 67 psig or 81. 7 psia at 70*F p = Partial pressure of a given component x - Mole Fraction bland/ucc 088 t)J/fJU Lt:l> FAX 502 558 5770 VT. RECORDS CTR. LAW FILES 17527 021/043 p = Vapor pressure of tho pure component in psia at "0* F {subscripts refer to P- 12, ethyl chloride nad p-22, respectively- Substituting numerical values: (0,662)(84.7) + (0.310)(22.7) 134.7 j - 26 Thus, 26 parts of F-22 would nave to be added to the mixture to P".mg ebe pressure up to 67 pstg. Kormaltaiog to a percentage basis gives: P-12 = 64% Ethyl Chloride = 16 P-22 = 20 Using the cost figures la the table, the above mixture would have s. cost of 16- 8//lb. va. 14. 27//lb. for P-12/ethyl chloride 80/20. On this basis, cue might better use ?~2i alone or P- 12/propatie 9l/9 blond at 14. 8//lb. when solvtstc;r is not a problem. If solvency Is required, then P-12/ethyl chloride Ti'ighr au well be used as is and mak.& up for the lower pressure by using more prop ell* at. Another altarnative that might be considered is the substitution of isofc'Utare (vapor pressure = 31 psig at 70'F) for vinyl chloride (vapor pressure = 3b pidg) to give a P~12/isobutane S0/20 blend. Although at first sight this much ispbutar e was assumed to produce a flammable vapor, a calculation based on our i: liriiar ble-od work showed that it would not: Taking a flamm able Umlt of 24/o by volume isobutane4 and using the squttian above for a rvvo component system, we have: 1Q0(0.24)(58.1)(84.7) a = (l20.9)(45.7) - 0. 24 ((120. 9j(45. l) - (58.1/(84. 7)1 v-toere; 58.1 = Molecular weight of isobutane 84. 7 = vapor pressure of F-12 la psla at 70 *F 120. 9 - Molecular weight of P-12 45.7 Vapor pressure of isobutane in psia at 70"F C axrying out the calculation gives: a =21. 9% BLAND/UCC 089 09/00 Li l> FAX 502 585 5770 YT, RECORDS CTR. 6- - - LAW FILES 17527 @022/043 Thi3,, again., is a relatively large amount and Indicates that a P-12/ uobutanu 80/20 mixture would be nonflammable and could be suggested as a subsututrj fcr P- 12/vinyl chloride 80/20. It would have approximately the same vapor px jcsurc ar.d possibly even lower cost, hut it would not have the solvency of either ti:>; vinyl chloride ox ethyl chloride counterpart. It. could become fhiuumibU- under fiac::JoTU,ciot. conditions, but so could the vinyl chloride analog. The reason that such, large amounts of ethyl chloride and isobutane esa he incorporated with straight propellant 12 but lesser amounts with, propellant 11/11 mixtures i3 due to the higher specific heat of P-12 (0. 125 cal/g/'C vs. 0 145 cel/g/'C fox P- ll), end also to the vapor pressure and molecular weight roianoQi.hips which give rise to a much more complicated equation when P-11 ia present5 HI. Propellant 12/vinyl Cbloride/Propellapt 11 39/22/39 This mixture is second only to P-12/vinyl chloride 6&/3S in volume usage, tt has a pressure of 38 psig at 70F compared to 26 paig (calculated) for an ethyl chloride analog. In this case the pressure could probably best be inorspsed by adjusting the P-12/11 ratios rather than adding a fourth component such as P-22. Accordingly: P - 52.7 psia TsI^Hscjb2-7 +fehl13 120 22 120. 9 T 64.5 T 137.4 whore a and b are weight percentages of P-12 and P-11, respectively. Sneer a + b 4 22 * 100 then: a a 100 - 22 - b * 78 - b Substituting: !SI84-7^l23-7+{T3b) 13 5i:.7 78-b . 22 . b 120.9 64.5 137.4 b * 18.67/ BLAND/UCC 090 .13-Tlti it'l? Fill S02 888 577ft YT. RECORDS CTR. -7- UW FILES 17527 0O2J/O4J Pounding off gives; U- 12/Ethyl Chloride/U-11 60/20/20 This mixture would have a cost of 13.27/ /lb. compaxed to 12.16* /lb. lor ,:hc vinyl chlcride blend and 12. 40^/lb. for Propellant A. On this basis, Propellane a "Quid be the batter substitute when solvency is not a factor. CONCLUSION Vinyl chloride was originally introduced as an aerosol propellant only an me basis or low cost. It turned out to be unique, however, in that the lower part of :ts Earmnability curve had a sr.eep slope (allowing a high concentration to be used ''itbout forming a flammable vapor)5; it had a high K-B value (good solvency); it had i h_i;>h expansion ratio of 350 vs. 250 for fluorocarbons (giving good breakup to che sprny); and it had an ideal pressure of 35 peig at 70F, right in the moderate pres sure range of moat aerosols. There is m satisfactory replacement for vinyl chloride and any sub stitute is going to increase propellant costs with the exception of hydrocarboa-fluoro carbon mixtures when they can be used. Ethyl chloride requires gerrymandering The mixtures to get around the preasux-e problem and is more expansive itself than vinyl cMoride. In addition to the 8/ /lb. cost listed in the table, we have leexned that aocthe" 1, 5 to 3. 7s//ib. has to be added fox freight- Thus, even a one for one Mb=t:tirioc of ethyl chloride for vinyl chloride will raise the cost, and adjustments of the f.uoxocarbons present or required will further increase the cost. The danger 5; that -fxetssive increases in cost will drive customers to straight hydrocarbon pvop allants with any solvency requirements being met by addition of methylene chloride t:1 the concentrate. Thus, wherever possible, it would be to our advantage to switch rauoniKre to fluorocarbon-hydrocarbon blends. In summary, the following are options that can be suggested to customers: L For U-12/Vinyl Chloride 65/35: U-22/U-12/Ethyl Chloride 15/55/30 U-12/Propane 91/9 U-12/Ethyl Chloride 65/35 11- For U-12/Vinyl Chloride 80/20: U-12/leobutane 80/20 U-12/Propane 9l/9 u 12/Ethyl Chloride 80/20 BLAND/UCC 091 U9/0 11:1/ FM. 602 38 577U IT, RECORDS CTK. -* UR FILES I732T 024/043 m. For V- 12/Vinvl Chloridc/U-11 39/22/39 Propellent A U- 12/Ethyl Cblortde/u-11 60/'20/20 Li- 13/'Ethyl Chloricie/u-11 39/22/39 PATEN I'ABLE FEATURES Since ethyl chloride has been suggested as a propellant tn the post, no riaieit action is contemplated at present. The writer wishes to thank W. W. Foster for the computer study. 1/7. A'- M&rkowski Tor trie experimental werk involved la this report, and the 'lantytown library for locating the flammability paper at Bound Brook. iitS-LlOOR APHY 1. H. F. Coward and G. W. Jones, "Limits c Flammability of Ca.v;s and Vapors, " Bulletin 503, Bureau ot Mines (1952), 2. A. M. Van Deventor, "Flame Ranges and Explosive Regions, i?ec-eii Tr.avaux Chetnie Pays Bas, 57:95 (1S38). 3. R. J. Scott and R. R. Terrill, "Aerosol Propellant Blends, tfoap and Chemical. Specialties, January, 1962. 4. R. J. Scott and R. E. Feathers, "Aerosol Propellant Blends," haop and Chemical Specialties, June. 1962. 5. R. J. Scott and R. R. Terrill, "Vinyl Chic ride-Fluorocarbon Mirfcursa an Aerosol Propellants, " Aerosol Age, January, 1562. : OTEBQOK REFERENCES Book No. 1235 Pages - d, 20, 29 Date Written: 3/24/73 DSte Typed: 8/28/73 BLAND/UCC 092 U:lF FAX 402 S770 TT, RECORDS CTR. LAW FILES X7527 02S/043 PROPELLANT 22/12/ETHYL CHLOKIPE MBCTURSS composition vs. COST p q c SO psig pressure at 70 JP tj-22 U-12 Ethyl Chloride 0% 79.7% 2 76-1 4 72.4 6 68.8 5 65.1 10 61.4 12 57. S 14 54.1 16 50.4 20.3 21-9 23.6 25.2 26.9 28.6 30.2 31.9 33.6 'l. Fo.t 55 psig Pressure gx 7Q*F 0 85.5 2 31.9 4 73.3 6 74. 8 8 71.2 10 67. 7 12 64.1 14 61). 6 16 57.0 14.5 16.1 17-7 19.2 20. 8 22.3 23. 9 25.4 27.0 Cost, '/ /ID. * 14.22 14.31 14.41 14.50 14.60 14. 69 14.79 14. 88 14.97 14.67 14.77 14. 67 14.97 13.08 15.18 15.28 15.39 15.49 J-22 = 27, GO*'/lb. a-12 = 15,84^/lb- Ethyl. Chloride = &f Ah. r^uwnl J. = 10.33^/lb. Vinyl Chloride - 6^/lb. 093bland/ucc U-U F.4X 60 $88 $770 VT- RECORDS CTR. LAW FILES 17527 0028/043 '.IV./US/Ot! I i ' 1 5 FA I 902 8 & 8 5??Q VT. BECGSDS CTR. - Law FILES IT52T O27-'043 aagSTraiowflTio aar F. J. Costello P. A- Hiznay R P. Lavac-h S. M- Livaagood D. A. McKenzie A. A. Meeo D. J. Napoli D. W. Urban 095bland/ucc 09/00 LLl) FAI 802 88$ 5T70 ;JUIi!NE >5 CONFIDENTIAL. VT. RECORDS CTR. - Uff FILES 17527 @028/045 PROJECT REPORT AEROSOL PROPELLANTS TECHNICAL SERVICE SUMMARY OCTOBER - DECEMBER, 1973 Author: R. J. Scott fc'ljpfrvisot; D. A. MefCeosie Date: Jacuaxy 21, 1974 Project No. : 123 U 10 File No. : P-74-5 summary Customers are still searching for a substitute for vinyl chloride c.s n aurosol propellant. Ethyl chloride, a. possible but cot satisfactory enbastute, Is now questionable on availability. It appears that UCON 12/lsobuhui<s S0/2C* Is what we will be able to supply, with the customer meeting solvent r3cvj.ire1neD.t3 by reformulating the concentrate, Gillette's withdraws! of "Extra Strength Right Guard" ia being E:ttiibut=d tq lung inflammation from zirconium chloihydrol which was present in the product. This has ominous implications for Procter & Gamble's "Sure" which CDntains the same salt. As various sections of the Inter Industry propellant toxicity pro gram a::a completed, fluorocarbon# look better and better. Precautionary la beling nay be required co warn against gross abuse, but fluorocarbons appear to be Bite for normal, and considerable abnormal, use. The CSMA suit against the New York City Fixe Department was sailed !or household and specialty products under Federal preemption. How ever, the ;nYCFD is insisting that their regulations be applied to cosmetics aid if upheld, they could have a damaging effect on the industry. The CTFA I;; bundling the appeal here. An evaluation of our fluorocarbon ll/methyl formate 82/18 a:jeotro;;e as a.blowing agent for thermoplastic foams was made at Gloucester Engineering Company. A parent disclosure has been filed based on the data obtained. UMiCK CARBIDE CORPORATIOH - CHEMICALS AND PLASTICS RESEARCH AND DEVELOPMENT DEPARTMENT TARRYTCWN, NEW YORK 096bland/ucc ii:IJ Fhl 50Z '158 5773 IT. RECORDS CTR, ' LAV FILES 175Z7 @ O20/(J4S AEROSOL PROPELLANTS TEQHMICAL SERVICE SUMMARY OCTOBER - DECEMBER, 1973 OVE RALL Total customer and sales contacts amounted to ISO -which, -with 210 n the t lird quarter, amouuted to 360 for the second half of 1973. This is a sharp ilmp from the 480 contacts in the first half, and reflects a decreasing emphasis on oxetomar service. Technology Requests and significant customer contacts are Kitted i a the appendix. Substitutes for vinyl chloride-fluorocarbon blends continued to be a major problem. Ethyl chloride-based mixtures, into which we had put consider able efiort. now appear to be questionable because of availability and reaction with .srocfucis containing ethanol. It now seems likely that UCON 12/Isohntane 80/20 vlli be our standard replacement, with solvency requirements being met with ad; aocnaeuts in die concentrate. It. INDUSTRY TRENDS AND DEVELOPMENTS A. Antiperapuraacs A little more information on Gillette's withdrawal of "Extra Strength iiUght Guard," discussed in the previous report, was revealed. Original indications vers that a skin reaction was involved, but it now appears that a lung Inflammation 'itas found in monkeys exposed to dosages 100 times normal. The inflammation is 1'eitg sttri-xitfid to zirconyl chiorhydrol which Was being used ia addition to alumi.*me. uhtorlydrol- The number of units of Gillette's product that was recalled was jmue'XI, but the implications are horrendous for P 4* G'c "Sore" which has capCured ii huge parr, of the antiperspiraut market. "Sure" has the same combination of i;alts a s the Gillette product, and the FDA reportedly has received 250 complaints frota u ?ers of "Sure. " if? & G should have to reformulate or, worse, withdraw their p roduct. all antiperspirants could get a consumer backlash. So far, however, A C has not pulled in their horns on their TV advertising. Adttperspiraute axe now the No. 1 aerosol product and, at S>0 percent ooncea ration of propellant, the No. I outlet for fluorocarbon prop ellants. Changes ,1a this ares are watched closely. BLAND/UCC 097 [t:voa/au K !j TaI 802 m 3770 vt. RECORDS CTR. LAW FILES I7S27 2. @030/013 B. Toxicology of Prcpfellaats The CSMA-CTFA Inter Industry program to determine the biologinal effects of abuse of fluorocarbon propellants is coming to a conclusion. At toe OSMA meeting ia D&cember a brief summary was released rather than detaiitsd medical reports. The gist of it all is that tha test results were highly favorable and fluorocarbons appear more and more to be safe fox normal, and cfin.>s:ide::able abnormal, use. Gross abuse, such as the inhalation problem of recon. i ears, can lead tc- csrdiotoxic effects which tnay have been involved in soa-.e of the fatalities. It ia planned so publish speedily papers based on the Inter Indus try program in medical journals during the first quarter of 1974. At the same rime, the Aerosol -Education Bureau IS planning a large-scale publicity campaign tc let tha public know what trie industry has done and to offset efforts of such groups is the "Center for Science in the Public Interest" which requested the CP5G te ban aerosols in the home. The toxicology program ie being continued with both new and old p rotocots, and the FDA also has funded an extensive 500 million dollar' program tutbe Lovelace Foundation, At the moment, however, it looks as though fluoro carbon .propellants will he cleared, with the gross abuse problem being handled by precautionary labeling. 0. New York City Fire Department The C3MA court suit against the NYCFD has been settled with the N.YCFD acknowledging Federal preemption of household and specialty products, however, their regulations will be applied to cosmetics, and the effect of this may ha re been underestimated by the industry. As explained previously, the NYCFD goes by flash point wkereaa Federal labeling is based on flame extennlo i and drum tr.a. la addition, tha NYCFD places restrictions on storage of low finish materials, so that products such as hair sprays that contain ethanol, ibx example, may become less available in the city and the overall market re duced. Also, it is known that other major cities ore watching the outcome of cue NYCF.D situation and may impose similar restrictions. The CTFA is han dling tb-i appeal fox cosmetics through city and state courts, but the outcome fit tires 9at is highly uncertain. D. Plastic Aerosols Our work with plastic aerosol containers was concluded* A nifcanmj; was held with UCRI to review the work that had been done with HEPE and, to lay plans for the. future. UCRI has designed a new container and has contracted to have a mold made for fabricating it. An injection blow molding process; will be used to provide an accurate finish at the cup opening; straight Mow nuldicg at Coosupak produced a container that required machining to obMitt a tight valve crimp. BLAND/UCC 098 _u::/09/oti 14 2 > fax su2 sas s?7o VT. RECORDS CTR. - LAW FILES X7S27 @031/043 3. UCJu will continue do its own with the development and marketing ; f so irradiated and .fluorinated HOPE container. The CSMA committee to draft guidelines fox plastic containers, in which m are participating, presented a final drait at the meeting ia December. The guidelines are expected to become official at the next meeting in May. Overall, iuduetxy interest in plastics continues but has been over;-'h<Adov ed I'omcwhat by shortages of materials which have required the attention of people just to keep production lines in operation. Celaucse is still putting a major effort iuto their "Celcon" container; Vistroa reports, via Consupak, re newed interest in their 11 Barex'' resin; and General Electric claims to have a tav.ior development ready for 1974 yvirh their ''Valox11 polyester resin. E- Thcxmoplaatic Foamo An evaluation of our fluorocarbon ll/methyl formate azeotrope was m ide at Gloucester Engineering Company, Gloucester, Massachusetts. This company is a supplier of equipment for thermoplastic foams and a booster of liq uefied gas blowing agents as opposed to charaical agents. They had agreed some lime e,jo to make an evaluation for ue and the call finally came in October. We wei-c able m be present fox the test to collect data; on the basis of the information u toilet fd a patent disclosure has been filed, in general, the azeotrope allowed opor itior; at lower die pressures (an increase in efficiency of power input); a slower rxpaneion (a projected advantage with polyethylene); higher heat retention; and a larger cel*, size than fluorocarbon 11 alone. The latter should allow less blowing ig.s&t to b> usad to obtain tb stuns cell size. Here, too. our program is being concluded and the project turned over a: the cellular products area. Further progress will hinge on their efforts. F. Miscellaneous I. CSMA The annual CSMA meeting was attended in Washington, D. C. in addition, to the toxicology program discussed above, the CSMA Is making a num ber of aggressive moves to anticipate future adverse developments for aerosols. These include: a.. Formation of a Safety Committee to deal with pressure release devices and flammability regulations. In the case of the latter, i;tatist:cai data have been accumulated on the incidents of complaints involving ilammiibility injuries from aerosols (1 in 60.000, 000), and a method of catego rizing and defining flammability hazards was developed to have ready in case of i4et*d ir. th*: future. BLAND/UCC 099 l ! - 2 t FAX 502 5770 YT. RECORDS CTR -* LAW FILES 17527 032/043 4. b. Labeling committees are preparing suggested wc-rdm j to caution agajnet inhalation abuse, and against hazards peculiar to bar ;:l&r (j. e., two component) systema. c. A committee to respond to the ''Center for !Je ,enc<i in the Public Interesstt*"' ''ss petition to the CPSC discussed above. A public Jicmnj: is scheduled for February, 1974. We are participating in all of these committees. It addition, CSMA attorneys plan to build a fire under the CPSC jy :rtq-jesting release of all information regarding the ban on aerosol adhesives mvier .he Freedom of information Act. The intent here is to see if the CPSC . -w-ith undue haste and, if so, retard them from doing likewise in the future. For the first time m several years a good technical program was jivea on the subject of particle size measurement. Detailed evaluation of the pspecs will have to await their publication, but one by Dr. Ken Vos of S. C. John using light scattering and another on laser techniques were standouts. 2. FDS In the face of adverse publicity AlbextorCulver is intro- during a reformulated version of theix FOS feminine spray. This is another high propeLant product (about 95%) ana the propellant suppliers all wish them well. BLAND/UCC 100 iilvua/nn L 4: 21 FAI 02 SS5 377C VT. RECORDS CTR. LAW FILES 17527 0033/043 Technology Requests 3-P Rt'gaarch Labtf, Inc,, Tucker, Georgia -- Packaging of a lubricant with two .prostitutes' fox propellant 12/vittyi chloride 65/S5. Drew (ITT. Coiporation, Hialeah, Florida -- Follow up on propellant blend for an alarm system. Significaat Customer S Sales Contacts ;h Aerosol Systems, Inc., Macedonia, Ohio Barr-Stslfoxt Company, Nilea, Illinois , Chuse Products Company, Broadview, Illinois i. Helene Curtis, Inc., Chicago, Illinois Hynan Corporation, Chicago, Illinois 6. Revlon, Inc., Bronx, New York 7. Spr&yoti Products, Bedford Heights, Ohio BLAND/UCC 101 ii i >. TAX 602 til. .3 T TO VT. RECORDS CTR. BUSINESS CONFIDENTIAL TBCKHICAL SERVICE SUMMARY AEROSOL PROPELLANTS JUNE - DECEMBER, 1974 LAW FILES ITS IT @03S-043 PROJECT REPORT Author: R. J. Scott '.Supers lsor: D. A. McKenzie Date: December 31, 1974 project No.: 123 U 10 File No. : P-74-211 SUMMARY The oscoe problem was the milieu oi aerosols in. the second half. Although some ccusumerisf, environmental and political groups have called for immec.iat*: action, it appears that the industry will get the time needed to carry ,,"jt research eitaer to prove or disprove the Rowland and Molina theory. There ;s more at stake than just fluorocarbons, however, aud more than, just aerosols. When he implications are recognised, it is likely that any acdon that Is taken will be! carefully weighed. The propellent toxicology program IS nearing completion, and the emphasis now will he oa formulated products. All indications point to the safety of fluorocarbons in normal, and considerably abnormal, use. An advisory panel to di FDA has recommended that zirconium aalte lie removed from aerosol emtiperspiraats. The FDA has taken no action 3.5 yet but if it does, Procter Si Gamble's "Sure" could be hurt. It is the only major product using zirconyl hydroxychioride, although others were reported retdy to enter the market until the panel's recommendation, was made public. The Consumer Products Safety Commission has not acted on any of the petitions and hearings concerning aerosols, except to ban vinyl chloride aa a. p ropeUant. The Commission apparently le wisely gathering information, and it is known that an internal CPSG report recommended no action bo taken cc. pressure relief devices, one of the major topics at the hearing last February. V/e are continuing: to participate in a newly structured CSMA. A major change was made in the Scientific Committee to a smaller number of Stand ing subcommittees covering broad areas of aerosol technology. American Can Company introduced a new plastic container made from General Electric's "Yakut" polyester resin. Interest in plastic containers centimes and we axe participating with UCRJPs fluorinated HDPE unit. UNION CARBIDE CORPORATION - CHEMICALS AND PLASTICS RESEARCH AND DEVELOPMENT DEPARTMENT TAWRYTOVH, MEW YORK BLAND/UCC 102 n;:/ 06/oo U;2! FAl 8U2 S8& 57*0 VT. RECORDS CTR. uw FILES 17527 3034/043 - jonsrsiseTMSN B. T. Clayton 5. U. Llvengood D. A, McKenzie T. H. Welch BLAND/UCC 103 !;:/03/ui> l i: 2 ! IAI 80? S68 3T70 VT. RECORDS CTR. * LAW FILES ITS27 .121036/043 TECHNICAL SERVICE SUMMARY . ABKOSOL PROPELLANTS JUNE - DECEMBER, 1974 I.. OVERALL I?it isn't cue thing, it's another- After having virtually surmounted the toxicology problem (at least <is fa:: as propellants are concerned), the aerosol industry is now facing a barrage o? Adverse publicity from. the ozone problem. For some reason this has been c-verly diamsbeed by the press end blown up to such proportions that legislators at both, the state and Federal level hava proposed baas on all aerosols and on flu orocarbon manufacture without any factual information at all. The CPSC hearing bust February, the vinyl chloride- ethyl chloride crisis, exploding aerosol cans {nee lxslow), the inhalation fatalities are all passe' now, as is the ban on aerosol adhesives (chromosomal damage) which was lifted with nowhere near tbe fanfare vtith which it was imposed. Such is the pace of change in today's environment. There has bocn great concern over the effect of all of this on con. a .ma:: attitudes about aerosol packaging. To date, tbe effect seems to have been very umatl as far as purchases are concerned: all of the people the writer has talked to Indicate that it was hot until December that a significant drop in demand for aerosol production showed up, and this is being attributed to economics rather ttosb adverse publicity. Nevertheless, the CSMA has commissioned a study to ex plore conmmier attitudes and concerns about aerosols to see if there is & need for a corn utmar information program- Such a program was proposed last spring in the fo rm of a two million dollar TV campaign but was quietly set aside when it cans dew to cough up two million, dollars. Tbe consumer survey is a more modest scbsttcuce. H. CUSTOMER AND SALES CONTACTS The cuswmer service effort continued at a low level In the second half, reflecting the need for materials rather, than technical assistance on the part of our customers. This situation may be changing, however, and there could be a snore competitive situation developing fox 1973. A list of significant customer contacts is given in the attached table. Thare wan no particular pattern to tbe contacts except chat, even after all these yorrs, we regularly receive requests for information ox calculations on the flainmafoOI.y of propellant blends. BLAND/UCC 104 09/0j< U : Z 1 3DJ 535 5770 VT. RECORDS CTS. LAV FILES I75Z7 2. @037/043 lU. INDUSTRY TRENDS AND DEVELOPMENTS A, The Qzoae Problem As indicated previously, this is the present industry crisis, De vils on the ozor-e depletion theory have been described in a report of a Briefing Conference held in Washington in Novenrber and will not be repeated here. SufUvf; It co ,ay that much more is at stake than just aerosols; there axe many more (and more likely) sources for chlorinated materials la the stratosphere than flu orocarbons. If the latter are hanaed, the effect on our air conditioning and refxiger itioii way of life would be horrendous, and should give any over zealous ie jisJiitor pause before acting rashly. In addition, all organic chlorinated mairerialr would be subject to similar bans, la fact, the EPA recently notified Congr essman Rogers that it will take jurisdiction over the ozone question and that it will be contacting fluorocarbon manufacturers and others oa the economic itqpac- of eliminating T'certain chemicals. " It appears now that the industry will get the time.it needs (approx imately three years) to collect data either to prove or disprove the ozone depletion Theory. In actuality, the probability that the theory is valid is extremely small. Riere may be as many as 0 possible reactions occurring tn the stratosphere, vbere.ts tiie theory focuses on. only one. The writer ventures the prediction that stratOispheric chemistry will prove to be far more complex than now envisioned, md. thitt a clear cut understanding of ozone processes In. the stratosphere will re quire ,i lot more than three years. B. Toxicology of Propellants A full-scale review meeting of the Inter Industry Toxicology Pro gram 'vas held in. September, Representatives of the contractors, the FDA, the National Institute of Health Sciences and the Department of Health and Welfare of Oenadji were in attendance. Again, details of the meeting were described in a iiepame report and will not be repeated here. However, Dr. Ben Lanham, chair man oi the later industry Aerosol Safety Group and Medical Director of Bristol Myers, summarized it all when he said that there was no question that those who itrosslv and deliberately abuse fluorocarbon, propelled aerosols can gat in trouble, hu;: that Chair ''safety range in normal use is tremendous. " Most of the propellant studies have been completed and the thrust now is toward formulated products. An epidemiology study is underway at the University of Washington Medical School involving people exposed to hair sprays in beai.cy shops, and the FDA has contracted with the Lovelace Foundation for a three tn four year program on the bioeffects from inhalation of anriperspirant and fiair spray components. Likewise, the Notional Institute, of Health is studying the offset >f materials commonly used in aerosols on the lungs of hamsters and rats. These are all long-term programs and although semiannual briefing conferences are planned for the future, a definitive toxicology picture on formulated BLAND/UCC 105 /00/00 11-2t FAX 802 888 5770 VT. RECORDS CTR. LAW FILES 17327 0058/013 3. products is probably a long- way off. C. Antiperepirsatfl Zirconium is the bad word now with antiperspirants. Procter & Gamble Ins been using a mixture of zirconium, and aluminum hydrcxychloridcs fMs{0H)$Ci] as the active agent in their `'Sure. " About a year ago Gillette inooduc ed. and then withdrew, a similar autiperspirant, ostensibly because of lung irritation in monkeys subjected to massive doses of their product- Procter fir Gamble claimed that "Sure" did not exhibit such irritation and vigorously forget! ahead with their promotions to such an extent that "Sure1' became the market leader. Now, an FDA advisory committee has recommended that zir conium compounds not be used in1-aerosol annperspirants until they are proved side, claiming that increased perspiration control is only marginal. So far the PDA las not acted on the recommendation, and hearings have been scheduled to allow industry to present its views a the matter. This means that Procter S Chimb; e will probably have to carry the ball aloue, since Gillette can hardly sup port the use o' zirconium salts after having withdrawn their product which con tained them. D. Consumer Products Safety Commission The CPSC has not acted on any of the petitions and hearings con:emicg aerosols, except to ban vinyl chloride as a propellant. Since vinyl chloride was withdrawn over a year ago, the industry has no objections to the CPSC scoring points With the public by a big fanfare over a dead issue. One of the points that w&e hammered hard during die hearing last .Februsiry was the need for mandated pressure release devices Oh all aerosols, ft has recently been learned, however, that an internal CPSC report recommended 'but nc action be taken in this direction at present since the incidents of exploding caas s seined to be so small. In addition, because NBES* data are so inaccurate, the CP;>C started a project to investigate la depth 100 incidents of exploding con tainers to .run from July through December of thla year, but a late report has it Jhat: rhay were not able to find 100 incidents. Taking a cue from the FDA, the CPSC has proposed regulations for record keeping of consumer product safety complaints. The proposal would re quire that records be maintained for five years, be subject to inspection upon oral ;>r writ ten request by a CPSC aguut, and that immediate replies ha given to queelious f:;om the CPSC, 'National ISlectronic Injury Surveillance System. -- A method of collecting injury data from hospitals. Only the fact that an injury occurred and its relatedness is recorded, hov/ever, so that an aerosol Can thrown by one person at another would be.recorded jie an aerosol related injury. BLAND/UCC 106 /OB'00 II n Til 82 358 5770 VT. RECORDS CTR. LAW FILES 17527 @039/043 4. E. FDA Last May the FDA unexpectedly published a proposal in the Federal .Register to prohibit the use of neoprene in cosmetic and aerosol products because i'ra Z-rnercaptoimidazolme accelerator can, under certain conditions, convert to ethylene thiourea, a Kuowo carcinogen. The industry requested an 18-mootb phase out period, cf which eight months have already been consumed, to use up old stocks o:? val 7ss, It appears that this will be granted, although the FDA has not formally said so aii yet. As an indication of how rigorous regulatory action has become, a fioweibir, gaskat end. a stem gasket have a total weight of about 0. 2 mg- In an asro:sqI c an with 100 to 400 grams of product, '.he amount of accelerator picked up would be less than 0- 1 to 0- 3 ppm, which Du Pont claims is not detectable with present-day equipment. F. New York Ciry Fire Department The CTFA has filed 81 appeals on behalf of itself and both member and nimmsrnbez companies from regulations tor pressurized personal care prod uces promulgated by the NYCFD. This is the first step in a seemingly never-ending process to get out of the New York City quagmire. As explained previously, the CSMA won its court suit for specialty products on the basis of Federal preemption, but such preemption is weak on flammability for personal cars products, and the C TFA will have so take a laborioua rows through the city Board of Appeals, thence to the srare courts and ultlmarely, perhaps, co Federal courts. The industry aeems to be overlooking this one, for if the NYCFD Is upheld, every major city will jump ou the bandwagon and create havoc with product labeling and limitations on storage. Judging from the past, however, a resolution of the situation is not imminent. G. CSMA There is now a new CSMA, which has little resemblance to the old. His oTice has been moved cc Washington and the entire staff replaced with what ap pear t-j be professionals in association management. The new director, Mr. Ralph En&el, is trying to take a more aggressive and anticipatory stance, and ha* gotten the CSMA into a leadership position on the ozone problem even though the MCA ie doing the contract work. We axe continuing to participate actively on technical committees. One involved a reorganization scheme for the Aerosol Scientific Committee; this whj? presented at the annual meeting in. December and accepted by the Executive Soazd. There will now be only four major standing subcommittees covering broad areas (compared to nioe previously) end the writer accepted chairmanship of the Testa and Standard Methods Subcommittee. We are also participating oq several TtuiK Forces within the subcommittee structure, such as those involving an Aerosol Gotle cf Practice and guidelines for plastic containers. BLAND/UCC 107 I 1 - Z ' f'.^X snz 43S 57 70 IT. RECORDS CTK. - LAW FILES I73ZT 1040/043 S. H. Plastic Containers "We have bad several meetings with. UCRI to assist In. the intro duction ot their HDFE units. Avon and Faberge' were selected as targets tor aeros-'>1 perfumes, and Carter.Wallace and Gillette for antiperspirants. We am waiting for a large number of samples to do some of our own testing; so far, v!6 ciive only worked with a small number (ten or so at a titae) and do not have s.caristically significant data as yet. American Can Company introduced a cologne packaged in their new " palor" (G. E.) polyester container at the CSMA meeting in December. It was a\ elegantly designed unit, but no technical information on burst strength, dfiibnnarion temperatures and so on was given out. We have requested samples to work with but have not received them as yet. Interest in plastic containers continues and may become more intense as materials shortages ease in. the coming year and laboratories can get bazk to new developments. Cost ia probably going to be more of a factor in ie future than it has in the pact, and this should give UCRI a real advantage with their unit. iv. miscellaneous 1. We sis participating on an internal fluorocarbon committee tc lie* a management posted on developments in this area and to help draft posi tion statements. 2. The Kartridge Pak adder-the-cap filler finally arrived and has been i istalled ia the aerosol laboratory. A 200-ucit andperspirant run and a 500iilit prewash spotter ran were made without a birch, and what would hava taken seven or eight days by hand filling was accomplished in a few hours. V. STRAWS IN THE WIND1 2 3 1. Cosmo Expo, the exposition for the cosmetic industry, has ar ranged for a 80 percent increase in epace at the New York Coliseum next June for Ae.toso l exhibits. 2. Dr. Frank Bower of Du Pont, after attending the National ocean ographic and Atmospheric Administration, meeting in November, reported that most of the investigators present were leaning toward the view that the ozone situation is a potential chlorine problem rather than a potential fluorocarbon problem. 3. Late word has been received that Procter & Gamble has contracted vritii P<Cer*?oa/Puriten for a large production run. of "Sure" antipersplrant tor a new promolion early in 1973. It is not known IX zirconium salts will be used in the new nm, BLAND/UCC 108 il9/0i 14'2? F.X 902 SflS 577i> VT. RECORDS CTR U<? FILES 17527 @041/043 4. pan sprays are apparently selling so well, in spite of adretse publicity by the "Pam Club. " that three new competitive entries axe > 3ing introduced: "Clorox1 "Cooking Ease," Masola's "No Stick, " and Blue Cross .Laboratories' "Pan Pal." These products contain approximately two percent release agent [usually lecithin) and 9S percent propellant. R.J.Scott/jlt Attachment Jh--4 / BLAND/UCC 109 /09/rill LI: 2 5 FAX 802 835 57 70 YT. RECORDS CTR. LAW FILES 17527 @042/043 SIGNIFICANT CUSTOMER AND SALES CONTACTS Peun-Cbs-mp Division, Bissel Company, Sutler, Fccmsyivania -- Jdaxitnutn amount ^fpsopaae/Sbiiutane 4j/55 that could Be incorporated with UCON propellant 12 'vUiT.iuc lorming a Samenable mixture. National Spray Can Filling Corporation. Elizabeth. New Jersey -- Formulation for "in Uiirosoi make up ''set.,T Pet Chemicals Company, Miami, Florida -- EPA registered insect repellent. X, 2hn & Fink Products, Monr/ale. New jersey -- Documentation on the flammability ciTJ(:0M~Propell'aac 12/lsobutane ttS'/lD for insurance purposes. Apollo, Inc. , Atlanta, Georgia Ten formulations for aerosol products. PFG Jndujstxiee. corpus Christ!, Texas - Polymer JR in aerosol form for a timedrelease tippiiiatioa. " Gertr.aine MoareU Cosmetique. Inc.. Dear Park, New York -- KPvOMFAX thiodvjjlyooTas a reductaat for thermal aerosolo BLAND/UCC 110 00. 01! it. 2* Fax 802 888 5770 VT, RECORDS CTR. LAW FILES X7S27 @04Jv04S lBBSTaSMaTOOKl E- T. Clayton J. "W. Goetz . P. A. Kiznay S. M. Livengood P. G- Motfnuason 8. G. McQueen D. A. McKenzie D. J- Napoli J. E. Flkula A. J. Sabia T- H. Welch BLAND/UCC 111