### e)AtALppendix ]SI Foreign Literature Citation s

On January 28, 1988, Renee Rico, Petition Coordinator, Economics and Technology Division, USEPA Office of Pesticides and Toxic Substances, provided DCMA wit h a list of six foreign literature citations on phthalocyanine pigments . To date, DCMA has obtained and translated four of these six literature citations . DCMA's Phthalocyanine Pigment Committee does not believe any of these studies contribute significant new information on the toxicity of phthalocyanine pigments . Copies of the referenced articles and their translations are provides as follows : 1 . PLItylina, L . W . and Yevsiukov, W . Y ., "Toxic Properties of Dyestuffs for

renes and Polyolefins", Plast . Massy, 12, 47 (19 7
2 . Kurlandskii, Graude, E . B . et . xicity Studies of Copper Phthalocyanine", Gig . San 1, 92-
3 . Garcia-Segura the Attachment of Various Cations to the Extern ace of Neurons", Re um, Med . Neurol . Psychiatr ., 16 (2), 8 (1978) . 4 . Guricheva, Z . G ., Krynskaya, 1 . L ., et .al ., "Toxicological Evaluation of the Migration of Phthalocyanine Blue Dye from Polyethylene", Gig . Primenn . Polim . Mater . Izdelii Nikh, (1), 347-354 1969) . =MEOW DC timin fn emaining r nces, and will forward them to EPA when received . The s 

### 1 . Putylin W . and Yevsiukov, W . Y ., "Toxi rties of a Phthalocyanine Green Pigmen a Yellow 12 "Z" P* Okhrana Okruzh . Sredy pri Prve Plastmass i a Prim lastmass, L . 144-9 (1978) . 2 . Bjoerndal, H . erin En ironmental Effects of Supplementary %&l %mm- P T n -, t

### V**W"ILUttvaardsfork, (Publ .)N IVL B 739, 202 pp . (19

### p. 2

TO'XICOLOr!ICAL rVAIUATION Ov TFE MIGRATIOM CIT PHTHALOCYANINE ?LUF DYE 'mPOV PL)1Yr'_rTTYLE'NrF,
. 

### Gu,richeva,Z .G ., Yr,-
.rrsi :aya L ., Rudakova M . N ., Bukevich G . Y., Nauzhno-Issled . Proekt . Inst . Polim . Plastmass, Leningrad, PS!~R
. With a problem of dyeing synthe'i-- materials are preocupied not only technologists but -31so hypienistc, becaus3 a dye should not only gi,re a pleprant arDearan!~e to an article but also must be safe for a hur-i "he4na

. R . N . Faward (1961) pointed out that dyes , aaded to thf~ polyrer may migrate oiAt from the pol,, .-Per mass . According to his understanding mig-ration may be limited by adding to polyner organic or inorgamic dyfs, which are not soluble in the polymer masr, and,thus, in essence, are irro))ile

. G . W
. Iri ;-Io (1960) while investiratir97 rig-ation of a pirnert, ba .-5~i on cadmium sulrilwhich he intrcdii,~e~' into polystyren- Pt a 1 % concentration found that fror, 0 .01 to 0 .002 marts of a pigment may 're rigratin ;- from polymer into solutions irritating food prolucts

. Kochanov, V. 11" . (1966) . Yplinin, P . Y ., Raskunpn3rina, Z
. A . (1966) whiie studying toxic mrop~rties of dyes, withorl determining thp. intensity of their miggration from r1astics designated a -umber of dyes as toxic or slizhtly toxic . Such classification prevented irior-)oration of of these dyes into p1pstics wbich have contact wit-i the 14'~od anO cosmetic mroducts and .1roTr which toys and medicEl accesscries are made
. Our goal was to determini, the effect of cne of the dyer on the organism at quantities which could migrate Iron the pla-,tic#to the envirnnrent
. Polyethylpre cf hig'- r-pps,ir- was ~ye3 witl a soli~ '~lli- r1,tb ;,locv :1ni'.ne An .'i u-fd for our st"Oiss

. The blue T)hthalocyanine pigment - a conrlex sRlt of copper, tomposed of four plithelonitrile ends - is extremely stablp to light and temperature (Wheni heated to 500 - 6000C It bursts into flames but does not decompose)

. It is also characts-rized with richness and beauty of color . Some invfstigatore believe, thet nhthF- .Iocyanine blue is, practically, insnluble in organic solvents . It is ineifferent to the Fction of acids and bases . (3oguclavsk
' y4 , 'P . W., laptev, X .1%, 1960) . Fowever, we wc-re able to detprmine . that this Pigment is completely decomposed by heating in conc . nitric acid
.

### p. 3

40 ?00

### p. 4

2 To elucidate the derree of nigration of this pigm'-~nt from the rolymer, a method for quantitative deterrinstion of the pigment ine'model compoun d wae worked out . T)ithizone methei for determination of copper ion (Lure, Y . T ., and Eybniknva, A .T . 1966) arDpared to be the most nonvinient and sufficiently sensitive one . This method makes possible copper determination 'in ouantity as;low as ly in a model COMDOund

. -ror our investigation samrles of films and snall containers were prenared frn high pressure iDolyethvlene : pigmented and nonpigmented, stabilized and nonstabilized
. A film thickness was 34 to 15 microns . The wall thicknesE of containers ranged fror

. 1 .3 tc 1-5 rr. The water extracts were Drspared by placing a filn in the distilled wpter at a surface rntio of film to a volume of water eoual 20 : 2 cmVContainers were filled with water for 100 to 120 dayE . Fvery ten days water was changed

. Tqh rater extracts the total quantity of organic compounds, which migrated fror. polyethylene were determined (oxydation) and phthalocyan,-ne blue pigment ( CoDper ion)were also determined

. 

### Nonstabilized dyed polyethylene during soaking in water for 100- 120 days, released into water 0 .57 rg/L of-kpigment in experiments conducted at 200 C and 1 .18 - 0 .05 mg/L at 60*r-'
. A maximum concentration of a yiRrent was observed in the first few extracts then followed by a gradual decrease at is -shown in Piz
. 1 . Oxydation at 200C fluctuated within 1 .41 and 0 .05 mg C, /L . At 6016C it increased from 5 .54 to 24 .84 rg 0.4 /L, Pnd in the film from 6 .21 to 90 mg 02./L . Table I and rig . 2
. 

## Oxydation data indicate, that pigmented, nonstabilized polyethylene fairly qi;ckly deteriorates at 600' when immersed in water (Oxydatior. is increasintr from one imrtrpion to th,~ olhor) .The n-)n :)ig-,-nte' -olypthyl-ne ur~e- the, ;e

-~:ondltions is I-ss susceptib2e to destruction/Orydation decreases/

.In water extractions from the film of a pigmented and stabilized (stabilizer - mc,rosulfide) higin-pressure polyethylene only the first extraction at 60'C contained 0 .09 mg/L of a pigment . In the subseque-nt extractions no pigment was foud . Oxydation of water extracte from pignented,stabilized polyethy'A'e.ne was gradually decreasing with subsequent extractions

. A maximum oxydation was observed at the beginning of the experiment (pig

. 3) . After 120 days of extraction no visible changes were observed on the inner surlaces of the containers made from stabilized and nonstabilized DiEnented Polyethylene . The nonstabilized pigmented film after 100 days in wFter at 600 C 3

### p. 5

Table 1 . Oxydation of water extracts (rg 0 /L) nonstabilized high-pressure polyet1hylene (10 daye soakinir at 20100 . N~mlner Pielmentei PiRrented NTOVIDigment,~!d immersions filn container containe r 1 1 .31 0.30 0.48 2 0.0-1 0.54 0.35 3 0 .36 0,41 1 .93 4 - 0.21 0.07 5 - 0 .71 0,07 6 - - at o6map not fcund 7 1,10 me 06HOP 6 0 .15 me o6omp 9 0 .80 Ut o6wip. 10 0

.83 0.15 we 06map. 11 - 0 .9~ 12 0,62

2 b L rE 

## 3 44,
0 V

CLI

10 ID 30 4D SU 60 70 19 90 10: IID no Tmmersion Time, Day s 'Fig
. I 113'ynaric Yigration of A blue Phthaloc .-, anine Pigment From

Nonstabilized High-pressure Polyethylele into Distilled Water
. 1 - Containers at 20 C' M Containers at 60c"' ; 2 - Fil- Ftt 20 * 

## C ; 3 4 - Film at 60 C

### p. 6

lost its elasticity and started crumbling . The behaviour of nonstabil17ed in a model environment (2 % acetic acid, 40 % ethanol sol,itions) were studied
. It has been found,that the pigment does not mirrate faster intc model Eolutions than into distilled water Table 11)
.
Table 11 . Contents of a piment in the model environments after 10 days irmersior

. of a nonstabilized dyed film (mg/L)

. Nimber of 2 % acet . 4 0 %' ethanol imMersions I f, .nid I 1 0,15 tio 2 k2b 0,10 3 0 .26 0 .05 4 0.31 0.06 5 0 .36 0 .05 6 0 .41 not foun d



### 0,19 not found Toxicolorical investigations were corducted in chronic exDeriments with white rats and white mice . Water extrFets fror a nonstabilized polyethylenefilm, containing a blup phthaloe,,yanire pigrent or the extracts frim containers made fro-, the same materiEl %s the film were red to the animals for 12 montne . Extracts were vreDar~-d in the same ranner as for sanita-y-che'rical irvestigations . During experiment general conditions and a dyna-rics of weights of +he treated animals were obser-ed . A . clinical analveis of the blood and urine was made . The influ~nce nf water extract on some blood ferments and on a central nerve Eysten was investigated . Stibility ti 7bysinal load of the animpls was investigal~ed . Pathohistological ex&rinRtions of internal or,-Pn s of killed aninals were made after the ex-Periments were COrDleted

. (1 ) The physiological, I)iocAmical Pnd mcrphological indicators die not change in animals durirL, a test period . Any sign of change would indicate thpt water extracts have a detrimental effezt on health of the animals

. 

### These investigations als- showed that a colored polyethylene when kept in water at 60 OC is susceptible to destruction . Oxydation of water extracts progressively it increasing from extraction to extraction and eventually th e 

## (1) Robachevskyi, E . G . conducted pathohistological examinations
. 1-15---

### p. 7 5

film is completely degraled . There are no indications that a ncnDig-~ented polyethylene under the same con6itions can und-rgo similar degr dation . obviously , a pigment is stirulating degrqdation of ronstabilized polyethylene . 'The pigment was extracted with distilId r4ter fror a nonstabilized high-pressure rolyethylene not only at 6011.' but also at 20oC in the whole series of investigations . From astabilizO polyethylene the -Di~rnent was extracted once at 60 * C and only in min-Lite ouRntities . Therefore, it is pi-ssible -

.o conclude , that a stabilizer (Tronosulfide) not only inhibits degradation of the film but also prevents extraction of a pigment from the Dolyethylene material
. Vror, data obtained in the sanitary-chemical investigations of both film and containers it was DoEsible to calculate that during 100 - 120 days of extraction circa 0 .01 parts of the pig-ment migrated from polymer into distilled orater (total amount of the pigment introduced to polymer was eoual to 0-3 weight percent ) . These results are in accord with the Ingle!s findings
. (1966) . The average quantity of blue pkthalocyanine pigment, which was ingested by animals together with wate- extract-~ 'ror plgnertpr~ ro2yrer ei)ri .-67 12 ront,~ of r-'~rr~nlc experimentr c-isisted of 0 .01 to 0 .02 gr/kg weiakt .

2 0 20

A

IV U 32 440 so 60 70 go So 100 Ito t2D

Time of immersion, day s Fig . 2 . Cxydation changes of the water extracts from a nonstabilized

high-pressure polyethylene at 60cC . pigmented film, 2 - pigmented ccntainer, 3 - nonpigmented container

### _p. 8



## 6

X

C 4P

E 

### 3 

## 4 C>

30 AID So 60 

### 70 so 90 IN

Immersion Time, Day s
Fig . 3 . Changes in oxydation of water extracts from a stabilized

high - pr--?ssure polyethylene, dyed with a blue phthalocyanine pigrent . 1 - a f i lm at 210 * C nontainers at 20 a 3 - a f ilm at 60 C' C 4 - containers at 600 C .

### P. 9



### 7

Total dosage of a pigment which caused toxic changes when introduce d into animal stomachs by mouth ras determined by Kochanov, M .N. to be 1 .9-g/kg . Such ouantities cannot be, practically, extracted from a polymrr .The-,Z!J'othe abspnce of toxin siL-,ns in oi)r exps-~,imerts can be explained by the fact, that the amount of a pigment extrtcted by water from R polymer is so snall t~at it hrs no influence on the experirental animals . Literature dat a (Y6rin, v .v .,i96r-) agree, that a nonpigmented high-presaLre polyethylene an d also r3del environments, which are in contact with the film or the proCucts from this poly-er are harmless to the living organism
.
CONCLUS10r- . 1 . Insigni?icant quantity of a pigment migrate- from a nonstabilized highpressure polyethylene . 2 . Practically, there is no migration of a pigment from a stabilized dyed high-pressure polyethylene . 3- Water extracts frcm a high-presFure polyethylene are, practically, nontoxic
. A . A nonstabilized high-pressure polyethylene containing a blue phthalocyanine pt ;rent can be recommended for producing articles which may have temrorary contact with fool products, provided they dc not contain more than 0-3 % of the pigment . A high-pressure stabilized polyethylene dyed with this pigrent may be used for the Bame purpose for a much longer period

. LI TER AT TTRF 

### 'Roguslavskyi, M .Y ., Lartrv, W ." ., Chemistry of Dyestuffs, M . 1960 ; Kalinin, B . Y ., Raskumand-r .yna, Z .A . CCIL . Toxicology of High Molecular Products and Faw Chemical Vaterials for their Synthesis V . L . 292 (19W Kapper, P . Principle- of ()rgaric Chemistry, V . 1960 ; Kacharov, X .Y ., Coll . Tox . eto 264, (1966) ; Lure, Y .Y . F .nd 'Rybnikova, A . I ., Cherical Analysis of Industrial Sewages, 11 . 1965 ; Pu Aylina, L .T ., Robachevskaya, E .T! .ib . 279 ; Yorin, V .V ., Eygiene and Sanitary(Journal) A6, N 5 (1965), Haward, PAZ . , Chemistry and Industry 31,15, 1442 (1960) ; Ingle, G .W . S .F . E . J ., 16 N 2,203 (1960) .mc Ic 0 -4 E E -4 a Z opw 32 0 w In,

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= L
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. 0

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Cle

tm
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w r T- 0 ci

t Z b

### .12

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### 7 ;4 aj aj - u 0 %a a C j

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o
0 on 0 u 0 w co . 

### o Z . ck rr x 0 .j

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st 0 A :r Lug R

. ~; . ; ; ~ ; --- = t :! 'M 0

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0 cc w w ca

CL m 91 . 0 T" c6 rj .6 to A CL rl A A' '-i 'm '7p. 13

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### et, W 0 ic w -0 2f

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### rm 0 L, to

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