[0001] This invention relates to an imaging element which contains an aromatic dialdehyde
as a dye-forming component of a radiation-responsive image-forming composition. More
specifically, an element is provided which includes a layer of a polymer that seals
the dialdehyde into the element as a means of increasing the maximum neutral densities
available from the imaging element.
[0002] Imaging elements have been devised which rely upon the photodestruction of o-phthalaldehyde
which, where not destroyed, forms a dye when suitably developed. Examples are disclosed
in U.S. Patent No. 3,102,811 wherein poly(vinylpyrrolidone) and poly(vinyl alcohol)
are listed as exemplary binders for an o-phthalaldehyde image-forming composition.
o-Phthalaldehyde is also used as a dye-forming material in imaging elements which
rely upon the reduction of cobalt (II) complexes, as described in Research Disclosure,
Vol. 158, June, 1977, Publication No. 15874, published by Industrial Opportunities
Ltd. Hampshire, United Kingdom.
[0003] Such imaging elements are susceptible to loss of phthalaldehyde during element formation,
due to the high volatility of the compound. Such losses can decrease drastically the
amount of dye density available during development. One solution to this problem is
to use a polysulfonamide as a binder for the image-forming composition. The polysulfonamide
binder is useful to retain phthalaldehyde in the element. Particularly useful polysulfonamide
binders which provide superior levels of retention are described in U.S. Patent No.
4,107,155 by Fletcher et al, granted August 15, 1978.
[0004] Although the binders described in the aforesaid patent greatly increase the available
dye density in elements using phthalaldehyde as the dye-forming material, some phthalaldehyde
is still lost by volatilization during image processing. Particularly, losses occur
when the exposed element is heated for image development. Therefore, it is desirable
to provide such an element which better retains phthalaldehyde.
[0005] Now, it has been discovered that phthalaldehyde is more effectively retained, as
a dye-forming material, in an imaging element when the element is overcoated with
a layer of certain polymeric materials, More specifically, the present invention is
an imaging element comprising a support bearing at least one layer of a radiation-sensitive
image-forming composition containing an aromatic ortho-dialdehyde as a dye-forming
component, characterized in that superimposed over said layer of image-forming composition
there is a layer of a compatible polymeric material selected from gelatin, gelatin
grafted with recurring units of acrylonitrile and bisacrylamidoacetic acid, or a polymer,
or copolymer having at least 50 percent by weight of recurring acrylamide units.
[0006] . By "compatible" is meant a polymeric material having other physical properties
appropriate to an imaging element, e.g., sufficient adhesion to the radiation-sensitive
underlayer, transparency to activating radiation, and freedom from cracking.
[0007] An overcoat layer of an imaging element according to the present invention is prepared
preferably by coating a solution at a pH of 3 and containing 20 milligrams per square
decimeter of a compatible polymer as described above. On exposure for 5 seconds to
a 400 watt medium-pressure mercury arc lamp and heat development for 5 seconds at
130°C, an imaging element of this invention produces an image having a maximum neutral
density at least 10% greater than that produced by an indentically processed, identical
element without the overcoat.
[0008] Although this invention is described in connection with phthalaldehyde as the preferred
aromatic dialdehyde, the invention is not limited thereto. Rather, it can be used
advantageously with any volatile aromatic dialdehyde capable of reacting to form a
dye. Other aromatic dialdehydes with are useful as dye-forming materials include,
for example, 4-hydroxy-l,2-phthalaldehyde, 4-benzoyloxy-1,2-phthalaldehyde, 4-methacryloyloxy-1,2-phthalaldehyde,
4-t-butyl-1,2-phthalaldehyde and 4-bromo-1,2-phthalaldehyde; 5,6,7,8-tetrahydro-5,5,8,8-tetramethylnaphthalene-2,3-
dialdehyde; and 2,3-naphthalenedialdehyde.
[0009] Preferably, phthalaldehyde is only one component of the radiation-responsive, image-forming
composition. It may also contain a material for imagewise-generating a product which
can react with phthalaldehyde to form a dye. Although the preferred embodiments hereinafter
disclosed employ materials for generating amines as the reaction product; the-invention
is not limited to such embodiments. Any composition capable of imagewise-converting
phthalaldehyde to a dye can be incorporated into the imaging element of this invention.
[0010] ortho-Phthalaldehyde, herein abbreviated as phthalaldehyde,or PA, is a convenient
dye-forming material capable of selective reation with amines to form a black dye.
By "amines" we refer to ammonia and primary amines. The dye reaction sequence, in
the case of NH3, is believed to be as follows:
[0011]
The invention employs a layer of an image-forming composition which contains phthalaldehyde,
a binder and a material which generates an amine in response to activating radiation.
Said amine and phthalaldehyde combine to form the oligomeric dye B noted above. Through
the selection of certain polymers applied in a layer over the image-forming composition
layer, improved maximum neutral density values of dye B can be obtained. As used herein,
"maximum neutral density" of an element refers to the density of a point on the characteristic
curve plotting developed density against the logarithm of the exposure, at which an
increase in exposure produces no increase in density. With the present type of imaging
element, the selection of an exposure level through a 0.15 Log E step table with produces
at least three developed steps produces a density in the most exposed step comparable
with the maximum neutral density. Actual density comparisons between elements are
made at the same level of exposure, in all cases that level is selected to produce
at least the three 0.15 log E steps in each element.
[0012] The preferred embodiments feature such superimposed polymers as overcoats, due to
the manufactur- in
g convenience resulting therefrom. However, other methods of superposition can be used
to achieve the same improvement in maximum neutral densities.
[0013] Thus, overcoats of a wide variety of polymers permit an enhancement of the densities
achieved from phthalaldehyde-containing imaging elements. Specifically, using overcoats
of the compatible polymers of this invention, the maximum neutral density valuse of
the image-forming composition are significantly greater than when using no overcoat,
or when using poly(vinylpyrrolidone). As used herein, "significantly greater" means
by an amount which is statistically significant, that is, an amount which iis more
than experimental error, determined to be about 7%. A number of compatible polymers
have been found which give improvements of about 40% or more-We believe that the superior
images are obtained because of the superior retention of phthalaldehyde when developing
an exposed phthalaldehyde-containing imaging element.
[0014] Overcoat polymers having the above-noted property of producing increased maximum
neutral density values include gelatin, gelatin grafted with recurring units of acrylonitrile
and bisacrylamidoacetic acid, and polymers or copolymers having at least 50 percent
of recurring units of acrylamide. Preferred polymers having acrylamide recurring units
are represented by the formula:
wherein:
R2 represents an alkylene group containing from 1-3 carbon atoms, such as methylene,
propylene and the like;
R3 represents an alkyl group containing from 1-3 carbon atoms, for example, methyl,
ethyl, propyl, isopropyl and the like;
R1 and R4 each independently represents a hydrogen atom or a methyl group;
G represents hydrogen or an oxo group
m and n each independently represents 1 or 0;
D, D' and D" each independently represents -NH-or -0-;
Z represents the atoms necessary to complete one or more saturated or unsaturated
heterocyclic rings containing from 4-9 ring atoms, such as 1-imidazole, 2-pyridine,
4-pyridine, 2-pyrrole, 2-pyrazole and the like;
x represents from 50 to 90% by weight;
y represents from 10 to 50% by weight;
z represents from 0 to 10% by weight; and
zl represents from 0 to 10% by weight.
[0015] The aforenoted gelatin grafts can have recurring units with the structure:
[0016] GEL represents gelatin;
D and D' each independently represents -NH- or -0-;
x" represents from 50 to 90% by weight;
y" represents from 10 to 50% by weight; and
z" represents from 0 to 10% by weight.
[0017] Noninterfering recurring units other than those mentioned can be included in the
copolymers useful in the invention.
[0018] The gelatin overcoats, or those having recurring units of formula (I) with pendant
active methylene (
) or primary hydroxyl groups, can be further improved for handling by crosslinking.
In the case of gelatin, such crosslinking improved the toughness and water resistance
of the overcoat. Useful crosslinking agents include formaldehyde and a 5 weight percent
aqueous solution of hexamethoxymethyl melamine.
[0019] The polymers of formula (I) are prepared by conventional addition polymerization
techniques using redox initiator systems, such as persulfate-bisulfite or hydrogen
peroxide, or using organic soluble free- radical-generating initiating systems such
as 2,2'-azobis(2-methylpropionitrile). Similarly, the graft polymers of structure
(II) are prepared by conventional techniques.
[0020] The following preparation is included by way of illustration:
Preparation of poly(acrylamide-co-N-vinyl-2-pyrrolidone- co-2-acetoacetoxyethyl methacrylate)
(50:45:5)*
[0021] To a 5- liter round-bottom flask, fitted with a stirrer, reflux condenser and nitrogen
inlet, were added 3240 ml of distilled water, 360 g of denatured ethanol, 200 g (2.81
mole) of acrylamide, 180 g (1.62 mole) of vinyl-pyrrolidone and 20 g (0.81 mole) of
2-acetoacetoxyethyl methacrylate. The contents were purged with nitrogen for 20 minutes
and then the flask was immersed in a 60°C water bath. Nitrogen bubbling and stirring
were continued for an additional 10 minutes and then 4.0 g (0.024 mole) of 2,2'-azobis(2-methylpropionitrile)
dissolved in 60 ml acetone were added. The solution was stirred under nitrogen for
an additional 5 hours at 60°C.
[0022] The resultant viscous polymer solution, when diluted to 5.1% solids with distilled
water, had a bulk viscosity of 40 centipoise at room temperature. After dialysis,
the polymer had an inherein viscosity, as measured in 1 N NaCl at 0.25 g/dl, of 1.27
at 25°C.
[0023] Gelatin grafted with recurring units of acrylonitrile and bisacrylamidoacetic (Formula
II) can be prepared according to the method described in U.S. Patent 3,756,814 except
that acrylonitrile and
[0024] As used herein, unless otherwise stated, all percentages of recurring units are weight
ratios of monomers as starting materials.
bisacrylamidoacetic acid in the desired proportions are substituted for the vinyl
monomers having attached mordant groups according to the patent.
[0025] The molecular weight of the polymer selected for the overcoat does not appear to
be critical to the formation of improved maximum neutral density values. Furthermore,
the molecular weights are subject to wide variation even within a given class of polymers,
depending on the preparation conditions. For example, useful terpolymers of acrylamide
of the type described above can have molecular weights within and beyond the range
evidenced by inherent viscosities from about 0.1 to about 6.0, measured as a 0.25
weight percent solution in dimethylformamide. A preferred range of inherent viscosities
is from about 0.5 at about 2.0.
[0026] The image-forming composition preferably comprises, as noted, phthalaldehyde and
a binder. The binder selected for the image-forming composition is not believed to
be critical, inasmuch as even binders which are relatively pervious to phthalaldehyde
can be used in such an image-forming composition if the overcoat of the invention
is also used. However, the best results are achieved when using as the binder for
the image-forming composition one of those disclosed in U.S. Patent No. 4,107,155.
Particularly preferred examples of such polymers include polysulfonamides such as
poly(ethylene-co-l,4-cyclohexylenedimethylene- l-methyl-2,4-benzenedisulfonamide),
poly(ethylene-col,4-cyclohexylenedimethylene-l-chloro-2,4-benzene- disulfonamide),
poly(ethylene-co-1,4-cyclohexylenedimethylene-1,2-dichloro-3,5-benzenedisulfonamide),
poly(ethylene-co-l,4-cyclohexylenedimethylene-l-chloro-3,5-benzenedisulfonamide),
poly(ethylene-co-l, 3-xylylene-l-methyl-2,4-benzenedisulfonamide), poly(l; 4-cyclohexylenedimethylene-l-methyl-2,4-benzenedisul-
fonamide), and poly(l,3-xylyene-l-methyl-2,4-benzene- disulfonamide). Highly useful
polymers also include polyacrylonitriles, e.g., poly(methacrylcnitrile), poly [N-(4-methacryloyloxyphenyl)methanesulfonamide],
and poly(ethylene-co-hexamethylene-l-,ethyl-2,4-benzene- disulfonamide. Of these,
poly(ethylene-co-l,4-cyclo- hexylenediemthylene-l-methyl-2,4-benzenedisulfonamide)
(50:50) is highly preferred. Preparation of the poly-(acrylonitriles) proceeds via
conventional processes. The polysulfonamides can be condensation polymers containing
sulfonamide groups in the polymer backbone. Preferably they are prepared by solution
polycondensation using aromatic disulfonyl chlorides and diamines in the presence
of an acid scavenger. Alternatively, the polysulfonamides can be addition polymers
derived from vinyl monomers having pendant groups containing -NR'S0
2- groups, R' being hydrogen or methyl.
[0027] The image-forming composition also preferably includes an amine-generating material
responsive to activating radiation. The amine when formed reacts with the phthalaldehyde
to form a dye. Any amine-generating material can be used. Preferred materials for
generating the amine are the cobalt (III) complexes containing releasable amine ligands
with or without a destabilizer, as disclosed in U.S. Patent No. 3,862,842. Examples
of useful complexes include those in the following Table 1. The suffix (U) designates
those which are thermally unstable above about 100°C and which therefore do not require
a destabilizer.
[0028] A highly preferred form of the material capable of generating amines is a composition
comprising a cobalt(III) complex that is thermally stable at temperatures slightly
above 100°C containing releasable amine ligands and a destabilizer which serves to
initiate release of amines from the complex in response to activating radiation. Such
a destabilizer-compound can be a compound responsive to heat, of which the following
are examples; organometallics such as ferrocene, 1,1-dimethylferrocene and tricarbonyls
such as N,N-dimethylaniline chromium tricarbonyl; and organic materials such as 4-phenylcatechol,
sulfon- amidophenols and naphthols, pyrazolidones, ureas such as thiourea, aminimides
in polymeric or simple compound form, triazoles, barbiturates and the like.
[0029] Alternatively, the destabilizers can be photoactivators which respond to exposure
to light to form a reducing agent for the cobalt(III) complex, whereby cobalt(II)
and free amines are formed. Such photoactivators can be spectral sensitizers such
as are described in Research Disclosure, Vol. 130, Publication No. 13023, the details
of which are expressly incorporated herein by reference.
[0030] Preferred photoactivators are photoreductants such as metal carbonyls, e.g., benzene
chromium tricarbonyl; p-ketosulfide, e.g., 2-(4-tolylthio)-chromanone; disulfides;
diazoanthrones; diazophenan- thrones; aromatic azides; carbazides; diazosulfonates;
0-ketosulfides; diketones; carboxylic acid azides; organic benzilates; dipyridinium
salts; diazonaphth- ones; phenazines; and particularly quinone photoreductants.
[0031] The quinones which are particularly useful as photoreductants include ortho- and
para-benzoquin- ones and ortho- and para-naphthoquinones, phenanthrene- quinones and
anthraquinones. The quinones may be unsubstituted or incorporate any substituent or
combination of substituents which do not interfere with the conversion of the quinone
to the corresponding reducing agent. A variety of such substituents are known in the
art and include, but are not limited to, primary, secondary and tertiary alkyl, alkenyl
and alkynyl, aryl, alkoxy, aryloxy, alkoxyalkyl, acyloxyalkyl, aryloxyalkyl, aroyloxyalkyl,
aryloxyalkoxy, alkylcarbonyl, carboxy, primary and secondary amino, aminoalkyl, amidoalkyl,
anilino, piperidino, pyrroli- dino, morpholino, nitro, halide and other similar substituents.
Such aryl substituents are preferably phenyl substituents and such alkyl, alkenyl
and alkynyl substituents, whether present as sole substituents or present in combination
with other atoms, typically incorporate 20 or fewer (preferably 6 or fewer) carbon
atoms.
[0032] A highly preferred class of photoreductants is that of internal hydrogen source quinones,
that is, quinones incorporating labile hydrogen atoms. These quinones are more easily
photoreduced than quinones which do not incorporate labile hydrogen atoms.
[0033] Particularly preferred internal hydrogen source quinones are 5,8-dihydro-1,4-naphthoquinones
having at least one hydrogen atom in each of the 5-and 8-ring.positions, or those
which have a hydrogen atom bonded to a carbon atom to which is also bonded the oxygen
atom of an oxy substituent or a nitrogen atom of an amine substituent with the further
provision that the carbon-to-hydrogen bond is the third or fourth bond removed from
at least one quinone carbonyl double bond. As employed in the discussion of photoreductants
herein, the term "amine substituent" is inclusive of amide and imine substituents.
[0034] Further details and a list of useful quinone photoreductants of the type described
above are set forth in Research Disclosure, Vol. 126, Oct. 1974, Publication No. 12617,
the contents of which are hereby expressly incorporated by reference. Still others
which can be used include 2-isopropoxy-3-chloro-1,4-naphthoquinone and 2-isopropoxy-I,4-anthraquinone.
[0035] The quinone photoreductants rely upon a light exposure between about 300 nm and about
700 nm to form the reducing agent which reduces the cobalt(III) complex. It is noted
that heating is not needed after the light exposure to cause the redox reaction to
take place. However, an additional thermal exposure can be used as part of the exposure
to drive the reaction to a more timely completion. Furthermore, the heat is desirable
to form the dye B.
[0036] An imaging element prepared in accordance with the invention preferably comprises
the amine-generating material, phthalaldehyde and the binder all mixed together, in
a single layer on the support, overcoated with a polymer layer of the type described.
Alternatively, however, the material generating the amines in response to the radiation
exposure can be associated with a separate phthalaldehyde layer. In this case, such
a radiation-exposure layer comprising a cobalt(III) complex, and a destabilizer, without
phthalaldehyde, can be simply applied, as by coating over the phthalaldehyde-containing
layer to form an integral element. To avoid yet another overlayer, the binder for
the cobalt(III) complex layer can be the overcoat of the invention as described above.
However, for the best density values, it is preferred that the overcoat of the invention
be applied over the cobalt complex layer.
[0037] Still another preferred embodiment is an element prepared by superimposing a second
overcoat layer over the first overcoat layer. The polymer in the second overcoat layer
can be different from the above-described polymers used in the first overcoat. Such
a technique allows the use of more readily hardenable second overcoat which would
not adhere well to the image-forming composition if coated directly. For example,
a second overcoat layer of poly(acrylamide- co-N-vinyl-2-pyrrolidone-co-2-hydroxyethyl
acrylate) (45:45:10) can be applied over a first overcoat layer of gelatin. Alternatively,
water-soluble cellulose acetate, crosslinked using the above-described melamine, can
be coated over crosslinked gelatin. At least one of the overcoat layers should comprise
one of the polymers described above as producing an increased maximum neutral density.
[0038] As yet another alternative, an amplifier can be included, such as phthalaldehyde;
the intermediate product A of reaction (1) serving as a reducing agent for remaining
cobalt(III) complex. Or the amplifier can be a compound which will chelate with cobalt(II)
to form a reducing agent for remaining cobalt(III) complexes. Such chelating compounds
contain conjugated bonding systems. Typical amplifiers of this class, and necessary
restrictions concerning pKa values of the anions which can be used in the cobalt(III)
complex in such circumstances, are described in U.S. Patent No. 4,075,019 issued Feb.
21, 1978, and in Research Disclosure, Vol. 135, July 1975, Publication No. 13505,
the details of which are expressly incorporated herein by reference.
[0039] In some instance, even thermally stable cobalt(III) complexes can be used without
a destabilizer. Examples include compositions and elements containing the complex
and a tridentate-chelate-forming amplifier, exposed to a pattern of incident electron
radiation as described in Research Disclosure, Vol. 146, Publication No. 14614, June
1976. The details of that publication are expressly incorporated herein by reference.
[0040] Other layers not particularly effective in enhancing the maximum neutral density,
but added for other purposes, can be disposed between the one or more overcoats described
herein, and the one or more layers comprising the image-forming composition, without
interfering with the function of the overcoat of this invention.
[0041] To form an imaging element, the image-forming composition is preferably coated onto
a support, particularly if the coating is not self-supporting. Any conventional photographic
support can be used in the practice of this invention. Typical supports include transparent
supports such as film-supports and glass supports, as well as opaque supports such
as metal and photographic paper supports. The support can be either rigid or flexible.
The most common photographic supports for most applications are paper, including those
with matte finishes, and transparent film supports such as poly(ethylene terephthalate)
film. Suitable exemplary supports are disclosed in Product Licensing Index, Vol. 92,
Dec. 1971, Publication No. 9232, at p 108, and Research Disclosure, Vol. 134, June
1975, Publication No. 13455. The support can incorporate one or more subbing layers
for the purpose of altering its surface properties so as to enhance the adhesion of
the radiation-responsive composition to the support.
[0042] Supports such as poly(ethylene terephthalate) are particularly preferred because
they tend to be relatively impervious at most processing temperatures to the volatile
aromatic dialdehydes. As a result, phthalaldehyde is not lost through the support
during the developmental heating of the exposed element. However, even supports which
are not resistant to such a loss can be used, provided they are given a protective
coating of one of the polymers described above for the overcoat of the element. In
such a case, the result is an image-forming composition sandwiched between two protective
layers, each of which comprises a polymer which results in increased maximum neutral
densities.
[0043] The aforedescribed image-forming composition, and therafter the overcoat are successively
coated out of a suitable solvent onto the support. Preferably, the coating solvent
is a nonaqueous solvent, such as acetone, a mixture of acetone and 2-methoxyethanol,
or dimethylformamide, to permit the use of other components such as photoactivators
which are soluble in nonaqueous solvents.
[0044] The proportions of the nonbinder reactants comprising the image-forming composition
to be coated can vary widely, depending upon which materials are being used. Where
cobalt(III) complex is present, the molar amounts for such compositions can be expressed
per mole of complex. Thus, if destabilizer materials are incorporated in addition
to cobalt(III) complex, they can vary widely from about 0.004 mole per mole of complex,
such as ferrocene, to about 5 moles per mole for succinimide. For example, 5,5-diphenylhydantoin
can be present in an amount of between about 0.1 mole and about 2 moles per mole of
the complex. With respect to the phthalaldehyde, it can be:present in an amount from
about 1 to about 15 moles per mole of cobalt(III) complex.
[0045] A convenient range of coating converage of phthalaldehyde is between about 2.5 and
about 25 mg/dm
2. Conveniently, the overcoat is applied at a coverage of between about 3 and about
100 mg/dm
2. The total combined thicknesses of a dual overcoat, if used, can be within the range
noted above for a single overcoat. Preferably, such dual coverage, when using crosslinked
gelatin, is about 20 mg/dm
2 with the gelatin being about 5 mg/
dm2.
[0046] Typically, the solutions are coated by such means as whirler coating, brushing, doctor-blade
coating, hopper coating and the like. Thereafter, the solvent is evaporated. Other
exemplary coating procedures are set forth in Product Licensing Index, Vol. 92, Dec.
1971, Publication No. 9232, at p 109. Addenda such as coating aids and plasticizers
can be incorpor-. ated into the coating composition. A particularly useful addendum
to the overcoat is one of the conventional matting agents.
Examples
[0047] The following examples further illustrate the invention.
Examples 1-3:
[0048] To demonstrate the manner in which various overcoat polymers affect the maximum neutral
density available from a preferred imaging element, the following machine coating
was prepared for each of the examples on a subbed poly(ethylene terephthalate) support:
[0049] The overcoats, listed in Table 2 were prepared as aqueous solutions, adjusted to
pH 3.0 and applied to give a dry coverage of 21.6 mg/dm
2. Each coating was then dried in the following order: 48 seconds at about 38°C, 2
minutes at about 60°C, 2 minutes at about 70°C, 2 minutes at about 80°C and 2 minutes
at about 27°C.
[0050] After 10 days of lab keeping at approximately 24°C and 65% RH, samples of each coating
were exposed for 0.5 seconds in an IBM Micromaster Diazo Copier, Model IID, to a 0.15
log E step tablet and processed for 5 seconds, support side to heated surface, on
a 130°C hot block. The maximum neutral density was measured and recorded.
[0051] These examples demonstrated that poly(N-vinyl-2-pyrrolidone of an ave. mole wt. of
350,000 gave a result which was not statistically significant compared with the use
of no overcoat at all; that is, the difference was less than the 7% experimental error.
On the other hand, the overcoats of the invention gave more than 10% improvement.
Therefore, the remaining Examples 4-16 used as the comparative control PVP K-90, which
is assumed to be equivalent to no overcoat at all.
Examples 4-16:
[0052] The procedure of Examples 1-3 was repeated, using different overcoat polymers identified
in Table 3. For comparative purposes, two other controls, a lower molecular-weight
poly(N-vinyl-2-pyrrolidone) and poly(vinyl alcohol) were also tested. The results
of Table 3 were measured as described for Examples 1-3, and further included speed
results as the number of 0.15 log E steps which were fully developed to a density
of greater than 1.0.
[0053] The slightly higher values obtained in tests of these Examples compared with similar
overcoats tested in Examples 1-3 are explainable due to the different batches of chemicals
and different batches of polymers which were used.
Examples 17-18:
[0054] To demonstrate the further improvement of the invention over other conventional overcoat
materials, the procedure of Example 1 was repeated except the following overcoat materials
were applied:
Control 6 - no overcoat
Control 7 - poly(ethyl acrylate-co-acrylic acid (60:40 wt %), coated from a mixture
of H20, acetone and propanol.
Control 8 - poly(styrene-co-butadiene), available from Philips Petroleum under the
trademark "KRO-3", coated from toluene without a pH adjustment. See Example 61 of
U.S. Patent 4,075,019.
Control 9 - polystyrene coated from toluene without a pH adjustment. See U.S. Patent
4,075,019, Col. 41, line 44.
Control 10 - poly(4,4'-isopropylidenediphenylene 1,1,3'-trimethyl-3-phenyl·5,4'-dicarboxylate)coated
from toluene without a pH adjustment. See Research Disclosure, Vol. 158, Pub. No.
15874, June 1977, P. 75, bottom of second column.
Control 11 - poly(vinylidene chloride-co-acrylonitrile-co-acrylic acid) (79.9:14.1:
6.0 wt %).
Example 17 - poly(acrylamide-co-N-vinyl-2-pyrrolidione-co-2-acetoacetoxyethyl methacrylate)
(50:45:5 wt %).
Example 18 - poly(N-vinyl-2-pyrrolidone, 2.7 mg/dm2, available from GAF Corp. under the trade name "PVP K-90", overcoated with 99.7%
hydrolyzed poly(vinyl alcohol), 18.9 mg/dm2.
[0055] In this series of tests, the phthalaldehyde had an acid content of 0.004 meq per
gm, and the maximum neutral density values hereinafter set forth in Table 4 differed
from those of the same overcoat test of previous tables for that reason. Lesser valuse
of acid impurity would be expected to produce greater maximum neutral density values.
[0056] The test demonstrated that none of the controls provided a maximum neutral density
that was at least equal to that of Example 17.
[0057] Comparative Examples 1 and 2:
Comparative Example 1:
[0058] Example 12 was repeated, except that the overcoat was poly(acrylamide-co-N-vinyl-2-pyrrolidone)
(25:75). The maximum neutral density produced was 2.76 at three 0.15 log E steps,
a result that was not significantly better than Control 2 of Table 2.
Comparative Example 2:
[0059] Example 1 was repeated, except that the overcoat was sodium cellulose sulfate. The
maximum neutral density produced was 2.29 at three 0.15 log E steps.
Comparative Example 3:
[0060] Example 17 was repeated, except that the overcoat was 5.4 mg/dm
2 of gelatin subsequently crosslinked that in turn was overcoated with 16.2 mg/dm
2 of water-soluble cellulose acetate having 17.1% acetyl content and crosslinked with
hexamethoxymethyl melamine. The D
max was 2.64, considerably less than the 2.9 value for Example 17.