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 container

1 1 .31 0.30 0 .48

2 0.0-1 0.54 0.35

3 0.36 0,41 1 .93

4

5 - 0

- 0.21 0.07

6 - - at

.71 0,07

o6map not fcund

7 1,10 me 06HO P

6 0.15 me o6omp

9 0.80 Ut o6wip.

10 0.83 0 .15 we 06map .

11 - 0.9~

12 0,62

2

bL

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 2 - Fil- Ftt 20 * C ; 3 Containers at 60c"' ;

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 If,.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 found

0,19 not found

Toxicolorical investigations were corducted in chronic exDeriments with

white rats and white mice . Water extrFets fror a nonstabilized polyethylene

film, 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 film 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 A T TTR F

'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 ; PuAylina, 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) .
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