close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2403533

код для вставки
July 9, 1946-
F. J. KASZUBA
2,403,533
NONSTATIC PHOTOGRAPHIC FILM
Filed Aug. 1s, 1945
@j
3
/ [Mms/olv
„9
/
GMAT/NE Juas/NG ¿A yff?
\ fìnv/ 5,455
INVENTOR
HP0/wf .I /1//15205/1
ATTO R N EY
Patented July 9, 1946
2,403,533
UNITED STATES PATENT oFFlcE
2,403,533
NONSTATIC PHOTOGRAPHIC FILM
Frank J. Kaszuba, Binghamton, N. Y., assigner to
General Aniline & Film Corporation, New York,
N. Y., a corporation of Delaware
Application August 18, 1943, Serial No. 499,037
’
10 Claims.
(Cl. 95-9)
l
2
The present invention relates to the manufac
ture of anti-static articles and is particularly
directed to the production of sheets or ñlms hav
hydride condensation products, casein sheets.
ing anti-static properties valuable for use as
gelatin and the like.
'
The non-static material which I employ is, as
stated, the intermolecular polycondensatlon
photographic films.
product of a dibasic acid or anhydride and a
One of the principal objects of this invention is
hydroxy amine. The dibasic acid may be either
to provide moulded articles which have proper
an aromatic acid such as phthalic acid or an
ties which prevent defects and avoid diiiiculties
hydride, a saturated aliphatic acid, succinic or
caused by the accumulation of static electricity
adipic acid or their anhydrides, or an unsatu
on such articles. Additional objects will be ap 10 rated aliphatic acid such as maleic or fumarie
parent from the detailed description which
acid or their anhydrides, The hydroxy amine
may be either a monohydric or polyhydric sub
follows:
In the accompanying drawing Figs. 1, 2, 3 and
stance; suitable monohydric amino alcohols are
4 are diagrammatic sections of three speciñc
Z-amino, y2 methyl, 1 propanol and 2 amino, 1
embodiments of the present invention as applied 15 butanol. Suitable polyhydroxy amines are 2
to photographic iilm. It is well known that
amino, 2 methyl, 1,3 propandîol and tris (hydroxy
sheets or ñlms and- other moulded articles manu
methyl) amino methane. It should be under
factured from electrifiable highly polymeric
stood that the foregoing polybasic acids and hy
droxy amines are speciiically mentioned merely
colloids such as cellulose derivatives, polyvinyl
compounds, albumen derivatives such as gelatin 20 as illustrative of suitable compounds and that
the broad class of polybasic organic acids and
and casein, easily become charged with static
hydroxy amines are operative for the present
electricity. This property is frequently quite
invention.
troublesome. For instance, in the case of photo
The non-static resin may be prepared by mix
graphic films, the photographic emulsion layer
is liable to so-called static markings which are 25 ing in suitable lproportions a dibasic organic acid
and a hydroxy amine and heating until esteri
capable of development and thus spoil the film.
ñcation, amidation and imidation reactions
It is also undesirable in very thin films of elec
take place. The proportions of the ingredients
trifiable highly polymeric colloids such as poly
may be Varied Within fairly Wide limits. Thus
vinyl chloride or acetyl cellulose which are used
in the manufacture of cigarette tips and numer 30 I have found that suitable non-static resins may
ous uses in the textile field.
When these articles
receive static charges they tenaciously adhere
to non-conductors and can be removed there
from without injury only with greatest difficulty.
I have discovered that moulded articles of
electri?iable highly polymeric colloids may be
made non-static by incorporating in such ma
be produced when the molar proportions are in
the range of 1 to 3 mols of the hydroxy amine
to 3 to 1 mols of the polybasic organic acid.
These resins per se do not form a part of the
present invention, their preparation is not there
fore described in complete detail here. Suitable
methods for their preparation are disclosed in
the literature, thus, Xthe preparation of several
terials a relatively minor amount of resin of the
resins falling Within the class which are em
type obtained as the intermolecular polycon
ployed in accordance with the present invention
densation product of a dibasic organic acid or 40
is disclosed in the Journal of American Chem
anhydride and a hydroxy amine. This anti
istry Society, vol. 6l, page 3381 (1939), and the
static resin may either be incorporated in direct
methods therein described are applicable gen
admixture with the electriflable highly polymeric
erally to producing resins of this class.
colloid or may be applied to one or both surfaces
thereof as a separate layer.
It should be noted that the resins obtained by
reacting a monohydroxy amine with a dibasic
acid or by reacting a polyhydroxy amine with
phthalic acid are thermoplastic rather than
Many materials used for the production of
ñlms and sheets are electriñable highly poly
merio colloids and are rendered non-static in
thermosetting. These thermoplastic resins are
accordance with the present invention. Typical 50 frequently desirable since they do not require the
examples of such electrifiable highly polymeric
rigid control in preparation which is necessary
colloids are: cellulose derivatives, as cellulose
in -the case of the thermosetting types of resins.
acetate and cellulose nitrate, regenerated cellu
They are also frequently preferable from the
lose and the like, polyvinyl compounds such as
use standpoint since the thermoplastic resins are
esters (polyvinyl chloride) polyvinyl alcohol, an
55 not affected adversely in numerous process steps
2,403,538
4
to which the moulded article in which they are
densation product of 2 amino, 2 methyl. 1,3-pro
incorporated are subjected, such as drying steps
pandiol and phthalic anhydride. This gelatin
and the like.
subbing solution was employed for coating photo
The accompanying drawing shows the inven
graphic ñlms in the usual manner on both sides
tion applied to a photographic film. In Figure
of the film and producing X-ray films as illus
I the support I is made from an electrifiable high
trated in Fig. II and on only one side of the film
polymeric colloid. for instance, cellulose acetate
as illustrated in Fig. I. The films were subse
with the addition of a minor amount of the
quently coated with a photographic emulsion in
intermolecular polymeric product of a dibasic
the usual manner and all the films were found
acid and a hydroxy amine. It should be noted 10 to have excellent anti-static properties. Similar
that the non-static resins of the type employed
films were produced using the intermolecular
in accordance with the present invention are
polycondensation product of 2 amino, 1 butanol
among the few resins which are compatible with
and maleic anhydride and the films obtained were
cellulose acetate. The support I bears a con
found to have excellent anti-static properties.
ventional gelatin subbing layer 2 and a light 15
sensitive layer I such as a gelatino-silver halide
emulsion.
,
.
Example 3.--The intermolecular polycondensa
tion product of 2 amino, 2 methyl, 1,3 propandiol
and maleic anhydride was incorporated in a cel
In another embodiment of the present inven
tion illustrated in Figure II the support I is made
from an electrifiable high polymeric ccllcid, for
the same manner.
instance, cellulose acetate which may or may not
vsolution and photographic emulsion in the known
be impregnated with a minor amount of a non
static resin oi the type employed in the present
invention. This support I is coated on both sides
lulose acetate iilm dope and the mixture cast in
The thus obtained film base
was coated' with conventional gelatin subbing
manner and the photographic iilm which was
similar to the film illustrated in Fig. I thus ob
tained was found to have excellent anti-static
with a gelatin subbing layer 2 in which is in 25 properties.
corporated a minor amount, generally about 12%
It should be understood that the foregoing ex
of the solids content of a non-static resin, a con
amples are illustrative only of the present inven
ventional gelatino-silver halide emulsion light
tion and this invention is not limited to such ex
sensitive layer 3 is supported on the subbing layer
amples. Other resins which I have employed and
2. It should be noted that the resins employed 30 which impart excellent anti-static properties to
in the present invention are among the few that
photographic films are the intermolecular poly
are compatible with gelatin subbing layers comv
monly used in photographic films and thus the
present invention is particularly valuable for the
production of X-ray films in which, in accordance 35
with conventional practice, both sides of the film
are coated with a light sensitive layer and a gelatin
subbing layer.
condensation product of tris (hydroxy methyl)
amino methane and phthalic anhydride, also the
intermolecular polyccndensation product of 2
amino, 2 methyl, 1 propanol and adipic acid.
As indicated above, various modifications may
be made `in the present invention. Specifically,
the anti-static resin may be incorporated in the
In the form a film illustrated in Fig. III the film
finished photographic film in several manners. It
base I which may be cellulose acetate is coated on 40 may be admixed directly with the film base, it may
one side with a gelatin subbing layer 2 to which in
be applied in admixture with a conventional
turn has been applied a conventional gelatine
gelatin subbing layer, or in admixture with a layer
silver halide emulsion light sensitive layer 3, on
applied for some special purpose, for instance, an
the other side of the iilm base has been applied
anti-halation layer or it may be applied as a sep
an anti-static layer 4 of the intermolecular poly 45 arate layer or it may be applied in any combina
condensation product of a polybasic organic acid
tion of these manners. Generally, I prefer to in
and a hydroxy amine.
corporate the anti-static resin in either the film
Another possible form of film embodied in the
base dope, or in the conventional gelatin subbing
present invention is illustrated in Fig. IV. As
layer, since by so doing the iinished photographic
shown there the film base I is coated on one side 50 film will be anti-static, but a separate processing
with a conventional gelatin subbing layer 2, which
step to impart such non-static properties thereto
in turn is coated with an anti-static layer 4 of the
is unnecessary. Various other modifications will
intermolecular polycondensation product of a pol
be apparent to those skilled in the art.
ybasic organic acid and a hydroxy amine. A con
As heretofore stated the anti-static resins em
ventiona1 gelatino-silver halide emulsion light 55 ployed
in accordance with the present invention
sensitive layer 3 is applied to the anti-static
are not claimed as novel per se and it should be
layer 4.
understood that these resins may be modified in
The following examples illustrate the present
various ways by suitable treatment. Thus their
invention:
molecular Weight may be increased and con
Example 1.-The intermolecular polycondensa 60 sequently their melting point raised by distillation
tion product obtained by reacting molar propor
in a high vacuum or by distillation of a solution
tions of 2 amino, 2 methyl, 1,3 propandiol and
cf the resins in a high boiling, water imiscible
phthalic anhydride was dissolved in a suitable
solvent (an acetone-methanol mixture) so as to
solvent (e. g. isophorone). The chemical groups
may be modified, for instance, by acylation of any
form a 0.2% solution of the resin. This solution 65 free ---OH, _NH2 or ---NH groups or by ester
iflcation of free carboxyl groups. If the amino
film of cellulose acetate. and the film was subse
groups are removed the product becomes more
quently coated on its other side with a conven
soluble in alkali while if the hydroxyl groups are
tional gelatin subbing layer and with a photo
removed the amino group is more active. Like
graphic emulsion. 'I'he film which is similar to 70 wise, mixtures of several polybasic acids and/or
that illustrated in Fig.'IV was found to have ex
amino alcohols or diols may be employed. The
was applied in known manner to one side of a
cellent anti-static properties.
Example 2.-A gelatin subbing solution con
taining about .7 gm. of gelatin- per 100 cc. was
mixed with 0.1 gm. of the intermolecular polycon
degree of polymerization may be controlled by in
corporating minor amounts of mono functional
acids, alcohols or amines. Also by employing an
unsaturated dibasic acid the double bond may be
2,403,533
5
combined with l,various agents to >impart speciai
6
of the intermoleoular polycondensation product
properties to the product. Thus the sulfonic acid -
of an organic polybasic acid and a hydroxy pri
groups may bej introduced by treatment with
mary mono amine and a layer of a photosensitlve
sodium sulñte orj bisulñte oran amino derivative
emulsion thereon.
may be obtained` by~treatment with liquid am
6. An anti-static laminated photographic ñlnr
monia. -By such treatment the water solubility 6 which comprises a base of an electriflable highly7
and 'conductibility ofthe non-static resin maybe
polymeric colloid, a. layer of a photosensitive
increased or modified..
,
`
emulsion thereon, and a layer of the intermolec‘n
ular polycondensation product of phthalic acid
1. An anti-static laminated photographic ñlm
which comprises a base of an electriñable highly
and a primary mono amino diol.
polymeric ` colloid, a layer of a. photosensitive
which comprises a base of a cellulose ester con
taining as an anti-static agent a minor amount of
emulsion thereon, and a layer of the intermolec
ular polycondensation product of an organic poly
basic acid and a hydroxy primary mono amine.
2. An anti-static laminated photographic ñlm
which comprises a base of an electriñable highly
7. An anti-static laminated photographic illm
the intermolecular polycondensation product of
phthalic acid and a primary mono amino diol and
a layer of a photosensitive emulsion thereon.
8. An anti-static photographic iilm which com
polymeric colloid, a snubbing layer of l gelatin
prises a base of an electriñable highly polymeric
emulsion containing as an anti-static agent a
colloid, a photosensitive emulsion, and an anti
minor amount ofthe intermolecular polyconden 20 static agent comprising a minor amount of an
sation product of an organic polybasic acid and a
intermolecular polycondensation product of an
hydroxy primary mono amine and a layer of a
organic polybasic acid and a. hydroxy mono
photosensitive emulsion thereon. l
3. An anti-static laminated photographic iilm
amine.
9. An anti-static photographic ñlm which com
which comprises a base of a cellulose ester, a layer
25 prises a base of an electrifiable highly polymeric
of a photosensitive'emulsion thereon, and a layer
colloid, a photosensitive emulsion, and an anti
of the intermolecular polycondensation product
static agent comprising a minor amount of the
of an organic polybasic acid and a hydroxy pri
intermolecular polycondensation product of an
mary mono almine.
organic polybasic acid and a hydroxy primary
4. An anti-static laminated photographic film 30 mono-amine.
which comprises a base of a cellulose acetate oon
10. An anti-static laminated photographic film
taining as an anti-static agent a minor amount
of the intermolecular polycondensation product
which comprises a 'base of an electriñable highly
polymeric colloid containing as an anti-static
agent a minor amount of an intermolecular poly
of an organic polybasic acid and a hydroxy pri
mary mono amine and a layer of a photosensitive
35 condensation product of an organic polybasic acid
emulsion thereon.
and a hydroxy primary mono-amine and a layer
5. An anti-static laminated photographic ñhn
which comprises a base of a cellulose ester con
taining as an anti-static agent a minor amount
of a photosensitive emulsion thereon.
FRANK J . KASZUBA.
Документ
Категория
Без категории
Просмотров
0
Размер файла
453 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа