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R R I Paint Research Institute OP THK PCOBKAriON OP OOClCTia# POP PAINT TeCNNOLOOT
PROCEEDINGS/NUMBER 101
Acerbic Approach to Problem Of Old Lead-Base Paints -- Feasibility Study
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Al l e n II. Ra u iic h I and Ra y mo n d R. Mvt.aa*
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KfT WOWS: Inattiian: Acerbic tabalancaci Sactata acia acaiatt: Fiparini; LMO-feai* painrt.
in t r o d u c t io n
It is a matter of record that repeated ingestion of old lead-base paints bv children may result in lead poison ing. In many older residences currently uttUaed as multi-family units, surfaces carry heavy accumulations of such old paints. The condition at there Surfaces is such that loose Ibices or chips of paint are readily available to children. These old lead-base paints, iiHireuvc-r, seem to have a pleasant or sweet taste to children, which further increase* the chancre of lupimu ingestion.t|
While restriction of the lead content of new enntiut's can miflimiir tlsc hazard of future lead puisnniiii;. such measures do nothing to alleviate the dancer pri-si-ntcd by lead-base paints applied earlier. Neither can one expret prompt dimination of the liaaard hy
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removal of the old paint or by isolation of these curflew from children, since currently Available methods of removal or isolation are expensive and usually re quire vacating the residential area, at least temporar ily.
If it were possible, however, to tender the old paint unpalatable, the probability of ingestion by chil dren could be steady reduced. The trustee* of the Paint Research Institute, desiring to define more pre cisely the potential value of this approach to a re medial program, sponsored the study repotted here.
. OINMAl VKINCATIONI
As a point of departure, we determined that if successful large-scale treatment of detsrioraong painted surface* were to be possible the following properties were dreirahlo in the applied acerbic ma terial:
{1) Fragments or chips of the treated surfaces in troduced into the month should produce an intensely acerbic (unpalatable) sensation in a high percentage of the population.
(2) The acerbic potential of the treated surface* should be retained fur extended periods of normal use and cleaning.
(3) No substance* employed should present ap preciable rosiculogical nr flammability hqtard to ap plicators or rvsiditiis.
(4) The treatment shnuld not require the re moval of furniture or fixtures; reoecupancy should bo poasiWa within a short time after the treatment is completed.
A Journal of Paint Technology Rer
0007-SWP-037039
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(5) Application of the mawnal should be possible hy cither trained am or by unskilled residents.
ifl) Trccmieni should not interfere with or un duly complicate lubtrqnent relimshing or rcdccorat-
?' The ent of m.ittrwli ami application l.ihor should be mull.
su*vir o f acetate suasTANcn
Diitaitifn). or.il u-ns,iti>nii may In* classified fur present purpotes at. Intter; peppery (.hot, burningi, sour i.iculi. or .ittmigrnt I [tuckering).
Scmatiniis intuiting primarily olfactory rciponses have nut been inrluded here Iwcausc continued exposurc in resideutul areas tumid tend to render oc cupants injciisitite to the repelling agent.
flitter substance] generally prndticc the most in- tense acerbic reactions. Some chemieaJl produce a
Imter tattc at concentration* near otic part per million.1 Cnforttinatrly. however, the senlilivity lu hitter oral sensations produced by synthetic chemicals is weak or entirely absent in up to 301 of humans fnr some compounds.' Sensitivity to bitterness Is thought to be an inherited trait Bittcmeis alone, therefore, should not be depended upon as the repelling force for all persons.
Peppers' taste, if intense, may be acerbic, but con tinued exposure to heavily seasoned foods may increate tolerance or even produce a desire for the sen sation. Some eL 'iren of Spsnish-American or East Indian extract*.!... for example, enjoy eating hot peppers which arc repugnant to others.
Sour and astringent principles may not be prom ising as acerbic agents for this use Inasmuch as most sre highly water-soluble (eg, zinc cMorida and alum). Furthermore, many (eg, tannic and gallic acid derivatives) decompose rather rapid/ by chem ical or photochemial reaction.
We believe that based on the factor* detailed above, the primary materials to consider as acerbating agents in treating paint film* should be some com bination of bitter and peppery principles.
It appears, therefore, that we should utilize a bitter principle as the primary source of repugnance and add a peppery principle to repel those children who are immune to bitterness. Table 1 lists some of the candidate substances in these two categories, to gether with some of their pertinent properties.
Sucrose oco-aeetate pomesses an inturuclv birtrr taste at low concentrstions. It exhibit* relatively Inw toxieitv* and it commercially available at a reasonable price. For these reasons, sucrose octa-acatate was chosen as the bitter principle for cur initial experi mentation.
The choice of a peppery principle wet more diffi cult. Crude extracts from red pepper* are highly colored (rad to orange) and hence treatment may cause the aopeannee of treated surfaces and surfaces inadvertently contacted to change. Extracts from
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pepper or from white peppers, on the other hand, are lighter in color or colorless, fiperino, a constituent of black pepper available as a purified, crystalline chem ical. was chosen for Ac initial experiments Extrac tion of ground blade and white pepper indialled diet lea expensive peppery principles may be obtained from mn sources.
XmiMINTAL
Sample* of sucrose octa-acetate.* and pipeline) were dissolved in methylene chloride. Thin films of these solutions were applied and dried on the surface of varnish-coated paper board, prepared to simulate the surface of old paint Small (1 sq cm) wafers of treated board produced pronounced acerbic tarnations in the mouth of lest individuals at solution concentra tions of Ins than IS far piperine and about SS for sucrose octa-acetatc.
More estemive testing was performed with the following solution:
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Of th* over 73 adult! who were given 1 sq cm wafers of board treated with this solution to chew. all but one reported a rmmutinied aei rle reaction witb lVli teeonds. The olfrmivf taste generally increated in intensity during flip lint minute and pet. 'istird /or to-.w mini.tr- .liter inisfuhnn. .Smoking >>r atine hicHly-lljtnred fowls prior to lotting appi'-irril to partial!- nusL tb- n-|>rti il .nerliic rexponw. Inti m on case sv.iv it rlmiin.it-nl Tin- (Iri-V'IKI- in ||K- nnmlli nf rnotm-ndiinii gbiMiiMle during testing did not ap pear tn alft-ct the .ui rlnc n-n\..lions of tin* few prrsims
tested.
It lai been inputted tlmt children |*iSevs mmc gmtjtriry receptors on elui-ltt and tongue surfaces than adults.' It may In' [tossilde, tlierefiire, tn obtain
the desired repugnanes to children with timer tonu-iilranuin of acerbic prnieipli-s than iImj m.' used in tlu-se cspenmeiiti.
To test the durability of the acerbic films, treated, v.iimslied surfaces were waslied repeatedly with sealer, and )ii>u.w-huld detergent in water with ou ap parent diminutinn of the acerbic property. Moreover. Slim exposed to bright sunlight for 11 days did not
change in appearance or become more palatable. Re peated scouring with abrasive household cleansers did reduce acerbic reaction, but resistance to removal by scrubbing appeared to increase with aging of the treated surface.
The persistence of the acerbic treatment do serfbed above ean be explained by the fact that sucrose octa-acctate solutions, on drying, form dear, flexible films possessing surprisingly low water sen sitivity. It was felt that' the physical properties of the
acerbating films, such as abrasion resistanee, should be improved by the addition of a small amount of an Inexpensive, compatible resin. This was confirmed ex perimentally by adding 51( by weight) of a petroleum resin* to a test solution. Careful adjustment of the >T* md content resin would be necessary to opti mise physical properties without appreciably dimiuishins die acerbic property.
Sucrose octa-acetatc has been known and used as n plasticiser for many polymer svstemt. It should, therefore, interact strongly'with the binders of old paint films. The mrthyjeiie chloride solvent is also rradily absorbed by paint films, so it Is likelv that appreciable amounts of acerbic principles can he ahtnrhrd into the old paint surface* diving the drying -if the treating solution. The degree of absorption may
he increased by the use of some less volatile solvent, such as tridihiroi-thylmc. This would, however, in crease the potential' toxicological haiard during ap plication and diving (TLV) of methylene chloride s 500 ppm: trichloroethylene =s 1U0 ppm).*
The test snhitiun (without fortifying resin) was sprayed so that the fringe of the spray pattern f the
"ovenpriv"fell on typical, nunpamted household surfaces. So damage or appreciable change m id |iearancv wav evident on wa'lpapcr, fatiric. f at!i<-r. or buck surfaces exposed to the light "ovrrsprjs * A 'light increase in gloss vsas noted when unpingi-nn -it approached a full triaiincot him. Adhesnm of tt... acs-rlnc film to glass or pnrtrl.ini surfaces is [tour tnj ovmpray eimlsl In1 runnved from wuiduws and iu. i elam fixtures hv normal w.ixlmn; procedures.
Application of the acerbic materials as ,ui rim.lsum ui water may base i csmonnc and other ads anlagex over sini|de solvent ssstems. The geni -a! fe.i.silwlitv of ixiinlsioii preparation seas cheiikixt bs
applying an emulsion of the following furmula:
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volume of svatcr (hv volume). The resulting emulsion
applied by spraying or by brushing dried in a fesv minutes, leaving the mated surface strongly acerbic. Addition of the rmolsifii-r increased tha water sensi tivity of the dried treatment film slightly.
'The raw materials employed in the emulsified
treatment are estimated to cost less than $0.01 per square foot of treated surface.
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MITHOM Of APPLICATION
The acerbic solutions described above could prob ably b* applied moat efficiently and economically by spraying, from either portable spray equipment (for trained application crews) or from aerosol spray cans (for ItmitM. topical application by householders).
Spray testa were first run utilising portabit airatomising spray equipment Proper choice of spraying tip and air pressure reduced the `overspray" to s satisfactory level while surfaces to be treated were covered w'ith an adequate wetting film. Excessive ap plication. resulting in "runs* was avoided by applying the material slightly Ik s than that required for a fully cxintinuous coating. No problems of equipment op eration or maintenance were observed. Equipment cleanup was accomplished satisfactorily with a mix ture til chlorinated hydrocarlxm (c.g., trichloroethy lene) und mineral spirits.
Airlmroc purticlc* of acerbic material were mud-
irately offensive to lltc applicator and nearby ohservers, causing a very unpleasant taste in the month and some sneezing. i\r of a respirator designed to
trap particulate matter eliminated this qpisanre for the opctabir. Fur targe scale operations, appl icators will apparently haw to wear respirators which would
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Voc. 13. No. 581. June 1973
37
0007-SWP-037041
0007-SWP-000115609
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screen out both solvent vapor and particulates, and 'thor person) will have to bo kept from the area until the a>r free from acerbic material and solvent vapors.
Spra'ing of (lie cmulMlicd acerbic formulation produced li-vs effort upon the operator than did the ' 'Kent volution. Tin me of respirators for largtMCsilr work (till cermv advivublc.
A portHHi nf the accrinr solvent dilution was packag'd in " riivnl cam mini' 110^1.1nr isohntjiw av 1 hr prn| ll.int." Contents uf tlw .irrinul can was ISIS I lav weight) .icerlne wilveut (nliitiiin anil SB pm. prllaiit. Xn problems nf filling or im: wear evident cxcr| that, during (praying. mtialalion of airlurnr ilruplctv of the dilution prodiicid very intense acerbic reaction almost imtantainsmsly 111 tlw minilli ami nasal pauagci of tlw applicator and pmnns in ad. jaernt mums liven brief exposure caused toughing. Mweamg and gagging. Delectable amminti nf acerbic' material in tlw air persisted fur alunit SO minutes. It wax concluded, therefore. that aenmil application uf this type of solution without adequate respiratury protection would not be practical.
Application by airlea spraying equipment was not attempted, became the experience reported above showed that formation of very finely atomiud drop lets is undesirable.
Application by swabbing, brushing or rolling
would eliminate the problem of lingering airborne droplets, but applying the methylene chloride solvent solution by these methods proved to be difficult due to the very high rate of evaporation and the resulting inability of laying down a reasonably even coating.
Replacing part of the methylene chloride with a lest volatile solvent blend might reduce the evaporation rate suficiently to permit application with reasonable control bv swabbing or brushing. For ex ample. sucres* octa-acetato dissolved in s blend of 201 (by weight) mineral spirits, ISt dipentane, and Ml methylene chloride was easily applied by swabbing with a cellulose sponge.
TOXICOUMICAl AND UAIIUTV MA2AIOS
So effort was made during this study to evaluate the toxicological haaard of ingredients employed in the experimental formulations except so determine from standard sources that none nf them was cited as Iwing acutely tuxie. When a Until formulation is pro poned for large-scale testing, the toxicity of both the
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vulatilc solvent fraction and the deposited acrrbie film must be determined precively.
Similarly. legal i|ueitimis. such as patent puotnm and possible liabihty fur either personal ur pruperty damage, will have to Iw csmvidcred. It i< nur under standing that a Ilrttivh patent has heen issued dealing with Mime aspects uf tiuv work and that additiimal patent applications liave Into nude in tlw l'. S.
CONCLUSIONS
Tlie iiisvstig.itiunv rr[*irli-d here confirm llie generul feuviliility uf treating ultl lead-h-ive panned urilia's lu render them unpalatable t a high pcarnt.igi* nf children. Slab treatment should appretuhly reducc the pmltability nf ingestion nf such materials and tlw acixtmpativing danger uf brad poisoning. A strongly aeerhir mfirtiun can Iw applied economically in the pntmtially liaxardiiu* surfaces uf 3 residence without stripping the living area uf furniture or fix tures. Reuceupanes' will Iw possible within a iliurt time following the treatment. Hitter and peppery principlci in combination appear to be best suited fur this nsc. Specifically, a combination uf sucrose octaacetate and black pepper extractions are proposed. When dissolved in Organic solvents, these substances may he applied directly nr as an emulsion of a more coneenBated solvent solution and water.
Application by spraying is attractive Grom the economic standpoint, but formation of very fine, airborne particles of the acerbic solution must be minimimd by cartful selection of spraying equipment and operating conditions.
AppliesBon by swabbing, rolling or brushing may also be feasible when Bailment of small areas by nontniiwd personnel is desired.
ACKNOWIfiDOMBm
The authors deeply appreciate the counsel and suggestions contributed by: Sevmour Maim, of Aeeto Chemical Co., Flushing, N. Y.; Robert L. Collins, of Sherwin-Williams Co- Cleveland. Ohio: George Buckrlv. of Btnls Mfg. Co- Chicago, Dlt end William Kapkovitx, of S. B. Pennick ana Ce, New York, X.Y. *
leferente*
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