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JAMA Report Page
The chemicals cited in
reports/studies below are used by the various carbonless copy paper
manufacturers: paratoluene sulfinate of Michler's hydrol (PTSMH)."
trimellitic anhydride (TMA) Phenol-Formaldehyde Resins, Crystal Violet
Lactone (CVA), Azo dyes, Diisopropylnaphthalenes (DIPN), Formaldehyde
isocyanates; solvents/hydrocarbons; polyaromatic hydrocarbons,
polyxypropylene diamine, epoxy 6010 resin, and
diamino-N-methyldproylamine, aliphatic isocyanate, Tamol L. from Rohm
and Haas Bisphenol A, diethylenetriamine 2291 A (now numberedN-3200)
and N-100 from Mobay.
Here is the abstract from
http://toxnet.nlm.nih.gov/ of an article that appeared in the JAMA in
1984 on Carbonless paper.
Acute Systemic Reactions to Carbonless
Copy Paper
Associated with Histamine Release Authors:
LaMarte FP Merchant JA Casale TB
Source: Journal of the American Medical Association, Vol. 260,
No. 2, pages 242-243, 8 references, 19881988 Abstract: Acute
systemic reactions to carbonless copy paper (CCP) were reported in two
office workers. In each case documented laryngeal edema was present and
one of the patients demonstrated an increase in plasma histamine levels.
The first case was a 39 year old women with a 2 year history of recurring
episodes of hoarseness, cough, flushing, pruritus, and rash appearing
within half an hour of exposure to CCP. She was a clerk/typist with
frequent exposures to CCP during her working hours. Blind challenge tests
with six chemical ingredients showed sensitivity to 1 percent
alkylphenol-novolac-resin contained in the developing material of the
coated front sheet of the CCP. Plasma histamine levels obtained at the
onset and at the peak of her symptoms were six times the level before
challenge. The true vocal chords were pale and more rounded and had a
generalized fullness 30 minutes after challenge. The second case, a
coworker of the first case, was a 45 year old woman with a 6 months
history of hoarseness, cough, flushing, and localized angioedema
subsequent to skin contact with CCP. She also demonstrated a positive
reaction to exposure to 1 percent alkylphenol-novolac-resin. Not only do
these cases demonstrate a connection to a specific component of CCP, but
they also indicate a potentially life threatening adverse reaction in the
laryngeal edema in susceptible patients. The authors suggest that
physicians carefully evaluate any possible connection between symptoms and
exposures to CCP. Keywords:
DCN-170487 Office workers Skin exposure Allergic reactions
Contact allergies Histamine liberation Pulmonary system disorders
Skin tests
Coden: JAMAAP
Entry Month: March, 1990
Year of Publication: 1988
Secondary Source ID: NIOSH/00181728
Marks Jr., JG, et al. 1984. Contact urticaria and Airway
Obstruction From
Carbonless Copy Paper. JAMA Aug. 24/31 1984; Vol. 252: 1038-1040.
"A 27 year-old woman experienced pruritus, eye, and throat irritation,
hoarseness, shortness of breath, and fatigue within half an hour of
exposure to carbonless copy paper. On two separate occasions, she was
purposely challenged in a controlled-blinded fashion with portions of the
carbonless copy paper. This resulted on both occasions in contact
urticaria of the hand that held the paper and changes in
pulmonary function flow-volume loops characteristic of upper airway
obstruction.
To determine if alterations in prostaglandin (PG) metabolism might explain
these
findings, plasma PGF and thromboxane B, (both capable of causing these
symptoms)
were measured before and during the second exposure period. Both PGF and
thromboxane B, increased substantially. We conclude that the cutaneous and
respiratory symptoms induced by carbonless copy paper were probably
related to PG
release."
Marks, Jr., JG. 1981. Allergic Contact Dermatitis From Carbonless Copy
Paper.
JAMA June 12, 1981-Vol. 245. 2331-2332.
"A unique coating was common to the positive white, pink and green papers
but
absent from the yellow paper. This coating material was composed of a
color-forming chemical, a binder solution, and an oily, liquid carrier.
Testing with these three
ingredients resulted in a positive reaction to the color former composed
of
paratoluene sulfinate of Michler's hydrol (PTSMH)."
Zhang-XD; Fedan-J; Millecchia-L; Lewis-D; Siegel-P. 2003. Dermal exposure
to trimellitic anhydride (TMA) powder induces airway sensitization in an
animal model. Toxicologist 2003 Mar; 72(S-1):60-61
TMA is a low-molecular-weight chemical used as a dry, fine powder by
industry. Specific IgE and subsequent occupational asthma have been
reported in exposed workers. The respiratory tract is considered to be a
major route of TMA exposure, but dermal exposure is also possible. The
role of exposure route in the development of TMA asthma is not known. The
present study investigated the potential role of dermal exposure to dry
TMA powder in both immunological sensitization and subsequent pulmonary
responses to TMA inhalation challenge using the Brown Norway rat. Various
doses of TMA were applied to the back (hair clipped carefully with
scissors) on day 0, 7, 14 and 21, occluded with surgical tape and washed
away after overnight, or after 5 hours of non-occluded exposure. Sera were
collected on day 0, 7, 14, 21, 28 and 35 for specific IgE test. Exposed
skin was also taken for morphologic study. TMA aerosol challenge was
performed on day 35 and respiratory parameters including enhanced pause
(Penh) recorded overnight. Bronchoalveolar lavage was performed and
pulmonary eosinophils assessed. The application area appeared normal,
without any sign of inflammation examined grossly or microscopically.
Immunohistochemical study (with one exposure only) found TMA-adduct
staining in the stratum corneum and hair follicle. Specific IgE was noted
by day 14 and levels were TMA dose-dependent. Eosinophilic inflammation
and both early (EAR) and late airway response (LAR), were observed after
airway challenge. EAR subsided within 30 min following challenge. LAR
typically began 2 or more hours following challenge and persisted longer
than 8 hours. TMA specific IgE and airway responses occurred in both
occluded and non-occluded dermally exposed rats. Dermal exposure to dry
TMA powder can induce specific-IgE and subsequent asthmatic-like EAR and
LAR following TMA aerosol challenge. This model may be useful for
mechanism study of dermal exposure and asthma from low-molecular-weight
chemicals.
The Toxicologist, Society of Toxicology 42nd Annual Meeting and ToxExpo,
2003, Cutting-Edge Science, Networking, New Perspectives, Salt Lake City,
Utah, March 9-13, 2003
NIOSHTIC 20022546
Bruze, M., Fregert, S. Zimerson, E.. Contact Allergy To
Phenol-Formaldehyde Resins.
Contact Dermatitis, Vol. 12, No. 2, pages 81-86, 22 references, 1985 1985
"Contact allergy to phenol formaldehyde resins was studied in Sweden. A p-tert-butylphenol/formaldehyde
(50000) resin (resin 3) and another phenol formaldehyde resin called resin
1 were used in patch tests on 1220 patients over the course of a year. The
last 440 patients were also tested with a second phenol formaldehyde
resin, designated resin 2. Patients reacting to at least one of the resins
were also patch tested with 2-methylphenol (95487), 4-methylol-phenol
(623052), 2,4,6-trimethylphenol (527606), formaldehyde, phenol (108952),
and p-tert-butylphenol. Positive reactions to at least one resin were
found in 26 patients. Ten reacted to resin 3 and 12 to resin 1. Of 440
patients, 13 reacted to resin 2. Of these, five subjects reacted to resin
1 also. All positive to resin 1 reacted to resin 2 as well. No patient
reacted to all three resins simultaneously, but simultaneous reactions to
resin 3 and either of the other resins were seen in two patients for each
resin. Only one patient had a positive reaction to formaldehyde. All
reactions to phenol and p-tert-butylphenol were negative. Five patients
reacted to 2-methylphenol. Three also reacted to 4-methylol-phenol and two
reacted to all three methylol phenols. All of these patients had positive
reactions to resin 3. Most patients positive to resin 1 were negative to
methylol phenols. The authors conclude that the sensitizing ability of
phenol formaldehyde resins is established. A battery of resins should be
used in patch testing since sensitivity to one alone will not identify
allergy to all. Those sensitive to phenol formaldehyde resins may be
sensitive to other ingredients of resins, such as methylol phenols." Material Safety Data Sheet (MSDS) for
"alkylphenol novolac resin".
. A. Shehade, et al. 1987.Allergic Contact Dermatitis To Crystal
Violet In Carbonless Copy Paper. Contact Dermatitis 1987. 1987 In this
article Dr. Shehade, et al., informs about an office clerk who develops a
vesicular rash that spreads over the entire hand. The clerk took a leave,
upon returning to work developed itchy patches on upper arm and legs.
"Patch tests were done on 5 colour-formers supplied by the manufacturers
of the carbonless copy paper." " The results indicated an allergic
reaction to crystal violet lactone.....tests were repeated as the
suppliers suggested that a freshly available specimen was less likely to
have impurities. The repeated tests gave similar results." "It was stated
that Crystal Violet Lactone is a triaryl methane derivative." Also stated,
"We have shown that patch tests to carbonless copy paper alone are
insufficient to detect allergic contact dermatitis from colour formers,
and would therefore suggest that patients with hand eczema and regular
contact with such papers should be patch tested to a series of colour
formers including those present in the papers in use." To be noted
was the help in providing the ccp and colour formers. "They were provided
by Wiggins Teape LTD." This is, at that time, was the parent company of
Appleton Papers, Inc.
Smith, H. R., et al. 1999. AZO DYES AS ALLERGENS IN CARBONLESS COPY PAPER
MANUFACTURING Contact Dermatitis.
More carbonless copy paper dyes shown to cause allergic dermatitis. Here
is further research from the United Kingdom on ccp causing allergic skin
reactions. Dr. Smith, et al wrote, "a 49 year old man presented with a
2-year history of hand dermatitis. He had worked ......at a paper mill
producing carbonless copy paper. On examination, he had fissured
hyperkeratotoic eczema of the thumbs. On patch testing, he was positive to
p-phenylenediamine in the standard series." "On the testing to a dye
series, he reacted to the azo dye Disperse Orange 3. Enquiry revealed that
several azo dyes were used to colour paper manufactured at the mill. A
site visit showed that his job en- tailed the collection of used dye
containers." As you can see, more documented evidence on the toxicity of
carbonless copy paper is
being presented to us.
MAFF of the UNITED KINGDOM
January 1999 Food Surveillance Information Sheet
Diisopropylnaphthalenes in Food Packaging Made From Recycled
Paper and Board. "Recycled paper used in making board may
include carbonless copy paper(also known as self-duplicating paper).
DIPNs are used as the solvant for the colour former in carbonless
copy paper. Not all DIPNs may be removed by the treatment of the
recycled fibres. Some may be present in the finished board and thus
could migrate into food." MAFF U.K. did a survey to test the board
and recycled paper packaging used for food containers. They cited the
previous studies don in other countries that showed DIPNs in food
containers and food products. This study went further by using not
only retail food products but several well known FAST FOOD VENDORS
PRODUCTS!!! They did research on which companies
and vendors that used recycled paper products for food containers.
Gockel, DL, Horstman, SW, Scott, CM 1981 Formaldehyde Emissions From
Carbonless Copy Paper Forms. Am Ind Hyg Assoc J 42(6)474-476. The authors
were at the Department of Environmental Health, School of Public Health
and Community Medicine, University of Washington. "Formaldehyde released
to the air from carbonless copy paper forms is suspected of causing eye,
skin and respiratory irritation among office workers. significant levels
of HCHO (Formaldehyde) emanating from the multi-page forms have been
measured. There is evidence that the residual formaldehyde dissipates to
the air as a result of handling and storage." Introduction: The study was
done after many reported complaints from the office workers in different
areas of the University. "Similar problems have been reported in usage of
carbonless copy forms by the Washington State Liquor Control Board,
several offices in Portland, OR. and at hospital clinics in London and
Stockholm. For this study, epidemiologic data compiled from a
questionnaire and a medical assessment of health complaints have been
added to industrial hygiene evaluations of the work site in order to focus
on the extent, the nature and the chemical cause of the problems. " "Since
there has been no indication of an allergic type reaction and many
complaints involve eye and respiratory symptoms, an airborne irritant
emanating from the forms has been sought." "This report details the
preliminary results showing appreciable quantities of airborne
formaldehyde are release from the carbonless copy paper forms." Great care
was taken to develop the procedures to measure the formaldehyde emissions
of the carbonless copy paper. One of the tests performed by ....... "spectrophotometrically
for formaldehyde by the chromotropic acid method as in NIOSH P&CM No. 125,
0.18 to 1.89 milligrams of formaldehyde were found per 21.6 x 27.9 cm
(81/2 x 11") top sheet of carbonless copy paper." Other findings from
"Table III, using Employment Notice forms. An unopened new package emitted
.72 ppm's, a printing office Employment Notice, emitted .44, other
Employment forms .41, .34, .33. In table II; formaldehyde released using a
standard amount of paper (ccp) was measured. This test showed ug sampling
area of 4 sheets at levels of 16.6, 2.73, .73, 10.4, and .45. " It goes on
to say, " The evolution of formaldehyde from carbonless copy papers is
supported by additional monitoring done by the Department of Environmental
Health. Air concentrations as high as .51ppm HCHO (formaldehyde) have been
measured in filing cabinet drawers, where the forms have been separated
and stored for over six months." This study concluded," Formaldehyde
released to the air from multi-page forms is suspected of causing the
irritation." Their" method has been developed which shows significant
quantities of HCHO released from the copy paper." They also suggested
further studies be done testing on "the encapsulated solvents, resins, and
dyes in the carbonless copy paper forms to discover the part played in
creating/ adding to the adverse health problems."
Rosenstock, Linda, et al. 1998. Occupational diseases--Reporting,
Asthma--Risk factors, Isocyanates-- Health aspects. A case of 71 patients
referred to a hospital-based occupational and environmental medicine
clinic for occupational asthma. The Former DIRECTOR OF NIOSH (National
Institute for Occupational Safety and Health), Dr. Linda Rosenstock
Published the following article in the Western Journal of Medicine; dated
FEBRUARY 1998. A case series of 71 patients referred to a hospital-based
occupational and environmental medicine clinic for occupational asthma.
The subjects listed were," occupational diseases--Reporting; Asthma--Risk
factors; Isocyanates--Health aspects." The database at the University of
Washington was used for the study. Information in the database included,"
occupation and industry, employer name, exposures, and work-related
diagnoses. When applicable, each diagnosis is associated with a specific
exposure and contains a physician-derived determination of how likely it
was that the diagnosis was work related." "The 71 had asthma determined to
be"definitely" or "probably" work related." Listed were, "--Agents
Associated With Patients With Occupational Asthma." Of these, "isocyanates;
solvents/hydrocarbons; formaldehyde; polyaromatic hydrocarbons." "Six
patients (9%) underwent a specific agent challenge test; 5(7%) tests were
positive, meaning that they displayed a 10% or greater decline in [FEV
.1]. The agents used in this challenge tests were polyurethane foam(n=2),
red cedar
CARBONLESS COPY PAPER MANUFACTURERS: MOORE BUSINESS FORMS, INC. AKA MOORE
CORPORATION, LTD> Information obtained from a public
record."TSMBF006----Phase III-D2000 capsule wall material is produced at
Moore's Honesdale, Pa. and Visalia, Ca. plants. In the Moore manufacturing
process polyxypropylene diamine, epoxy 6010 resin, and
diamino-N-methyldproylamine are reacted to form a highly cross linked
polymer. The resultant polymer suspended in
water is coated onto paper at Moore's Honesdale, Pa., Visalia, Ca., and
Monroe, Wisc. plants." "Rolls of coated paper are shipped to various Moore
plants for conversion into finished goods such as carbonless copy paper
business forms .Finished goods are shipped directly to customers of
warehouses for storage." "This is a polyurea epoxy composite polymer. The
composition (3) 59.3%(2) Bisphenol A diglycidy ehter 27.0% (3)
diethylenetriamine 13.7%h"Raw Materials "the super performance of the
polyurea is due to aliphatic isocyanate and Tamol L. Mobay makes the two
aliphatic polyisocyanates that Moore uses,~2291 A (now numberedN-3200) and
N-100. Both are viscous liquids." "Tamol L is a low molecular weight
polymer of naphthalene sulfonic acid and FORMALDEHYDE made by Rohm and
Haas." ".....a melamine FORMALDEHYDE second wall can be formed on top of
the polyurea. This can improve the shell wall and raise a low accelerated
self-contained result." "Animal testing results on the above: Rabbits were
tested for primary eye irritation. Three had either redness or chemosis.
Another test performed showed that one out of six animals exhibited very
slight erytheme. Five of the animals had abraded that exhibited very
slight to moderate edema." "products--carbonless "Bold Image" stock,
multiple part computer paper with a volume of $3 million per month with
customers of all major businesses and Government Agencies. Also "self
contained (002)"monthly sales volume of $1 million per month with
customers such as banks, Visa, Mastercar associations, processing centers,
all major oil companies, some hospitals, and Sears."
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