U.S. patent number 3,879,205 [Application Number 05/390,767] was granted by the patent office on 1975-04-22 for method of preparing photosensitive silver halide emulsions.
This patent grant is currently assigned to Polaroid Corporation. Invention is credited to Maurice J. Fitzgerald, Lloyd D. Taylor.
United States Patent |
3,879,205 |
Fitzgerald , et al. |
April 22, 1975 |
METHOD OF PREPARING PHOTOSENSITIVE SILVER HALIDE EMULSIONS
Abstract
A photosensitive silver halide emulsion wherein the emulsion
binder comprises an amine-acrylamide polymer or copolymer.
Inventors: |
Fitzgerald; Maurice J. (Canton,
MA), Taylor; Lloyd D. (Lexington, MA) |
Assignee: |
Polaroid Corporation
(Cambridge, MA)
|
Family
ID: |
26883466 |
Appl.
No.: |
05/390,767 |
Filed: |
August 23, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
187852 |
Oct 8, 1971 |
|
|
|
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Current U.S.
Class: |
430/627; 430/641;
430/630; 526/307 |
Current CPC
Class: |
G03C
1/053 (20130101) |
Current International
Class: |
G03C
1/053 (20060101); G03c 001/04 () |
Field of
Search: |
;96/114 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Smith; Ronald H.
Attorney, Agent or Firm: Kiely; Philip G. Matthews; Mart
C.
Parent Case Text
CROSS-REFERENCE TO OTHER APPLICATIONS
This application is a continuation-in-part of U.S. application Ser.
No. 187,852, filed Oct. 8, 1971, now abandoned.
Claims
What is claimed is:
1. A method of preparing a photosensitive silver halide emulsion
which comprises reacting in the absence of gelatin a water-soluble
silver salt with a water-soluble halide salt in an aqueous solution
containing a polymer having in its structure repeating units of the
formula: ##SPC73##
wherein R.sub.1 is selected from the group consisting of hydrogen,
lower alkyl, and halogen; R.sub.2 is selected from the group
consisting of hydrogen, lower alkyl, halogen and cyano; R.sub.3,
R.sub.4 and R.sub.5 each is selected from the group consisting of
hydrogen, lower alkyl, cycloalkyl; R.sub.4 and R.sub.5 together may
be chemically joined to form a cycloalkyl group; Y is selected from
the group consisting of alkylene or cycloalkylene; and n is a
positive integer greater than 1.
2. The method as defined in claim 1 wherein said polymer comprises
a copolymer of a first monomer of the formula: ##SPC74##
and a second ethylenically unsaturated monomer.
3. The method as defined in claim 2 wherein said first monomer is
N-[.beta.-(dimethylamino)ethyl]acrylamide.
4. The method as defined in claim 2 wherein said first monomer is
N-(diethylaminomethyl)acrylamide.
5. The method as defined in claim 2 wherein said comonomer is
acrylamide.
6. The method as defined in claim 2 wherein said comonomer is
N-isopropylacrylamide.
7. The method as defined in claim 2 wherein said comonomer is
acrylamidoacetamide.
8. The method as defined in claim 1 wherein said aqueous solution
further comprises polyvinyl alcohol as a bodying polymer.
9. The method as defined in claim 1 wherein said aqueous solution
further comprises hydroxyethyl cellulose as a bodying polymer.
Description
BACKGROUND OF THE INVENTION
This invention relates to photography and more particularly, to
novel photosensitive photographic elements, particularly novel
photosensitive emulsions.
As a result of the known disadvantages of gelatin, in particular,
its variable photographic properties and its fixed physical
properties, for example, its diffusion characteristics; much effort
has been expended in the past in order to replace gelatin with a
suitable synthetic colloid binder for photographic silver halide
emulsions. Many synthetic polymeric materials have heretofore been
suggested as peptizers for silver halide emulsions, however, these
have generally not functioned satisfactorily and frequently have
not fulfilled all of the basic requirements for a photosensitive
silver halide emulsion binder listed following:
1. absent (or constant) photographic activity;
2. ability to form an adsorption layer on microcrystals of silver
halide permitting stable suspensions to be obtained;
3. ability to form adsorption layers as described in (2) above
which do not prevent growth of silver halide microcrystals during
physical ripening; and
4. solubility in water solution.
In addition, hithertofore, much emphasis has been placed on the
ability of the synthetic polymeric material to mix with gelatin, as
this property has been critical for employment in partial
substitution reactions with gelatin.
Consequently, many synthetic polymers of the prior art have been
materials which allow for the growth of silver halide crystals only
in the presence of gelatin.
A class of synthetic polymers has now been found which is not
susceptible to the deficiencies of the prior art and which may
replace gelatin entirely in photosensitive silver halide
emulsions.
SUMMARY OF THE INVENTION
The present invention is directed to a photosensitive silver halide
emulsion wherein the silver halide crystals are disposed in a
synthetic polymeric binder comprising a polymer having in its
structure repeating units represented by the formula: ##SPC1##
Wherein R.sub.1 is hydrogen, lower alkyl group, e.g., 1-4 carbon
alkyl group, preferably methyl or ethyl, or halogen, e.g., chloro,
bromo, or iodo; R.sub.2 is hydrogen, lower alkyl, e.g., 1-4 carbon
alkyl, halogen or cyano; R.sub.3, R.sub.4 and R.sub.5 each is
hydrogen, lower alkyl or cycloalkyl;
Y is lower alkylene or cycloalkylene, e.g., 1-4 carbon atoms; and n
is a positive integer greater than 1. In an alternative embodiment,
the above-described polymer comprises only a portion of the binder,
the remainder constituting gelatin or a second synthetic
polymer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to photosensitive silver halide
emulsions wherein photosensitive silver halide crystals are
disposed in a synthetic polymer binder comprising a polymer having
in its structure repeating units represented by the formula:
##SPC2##
Wherein R.sub.1 is hydrogen, lower alkyl group, e.g., 1-4 carbon
alkyl group, preferably methyl or ethyl, or halogen, e.g., chloro,
bromo or iodo; R.sub.2 is hydrogen, lower alkyl, e.g., 1-4 carbon
alkyl, halogen or cyano; r.sub.3, R.sub.4 and R.sub.5 each is
hydrogen, lower alkyl, or cycloalkyl; Y is lower alkylene or
cycloalkylene, e.g., 1-6 carbon atoms; and n is a positive integer
greater than 1.
Such polymers have been found to substantially provide all of the
basic requirements for a gelatin substitute, as delineated above.
The emulsions of the present invention are readily sensitized by
conventional sensitizing agents and are characterized by excellent
latent image stability and excellent film speed. In addition, the
emulsions of the present invention are more stable against
degradation, particularly hydrolysis and the growth of
microorganisms than gelatin.
As examples of monomers represented by the formula: ##SPC3##
suitable for providing the amine-acrylamide polymers, mention may
be made of the following: ##SPC4##
N-[3'-(dimethylaminomethyl)cyclobutyl]acrylamide ##SPC5##
N-[.beta.-(dimethylamino)ethyl]acrylamide
Ch.sub.2 =ch--co--nh--ch.sub.2 --n--ch.sub.2 ch.sub.3).sub.2
n-(diethylaminomethyl)acrylamide ##SPC6##
N-[1'-(methylamino)ethyl] -2-chlorocrotonamide ##SPC7##
N-methyl-N-[.beta.-(ethylamino)ethyl]-2-bromo-2-pentenamide
##SPC8##
N-ethyl-N-[3'-(n-propylamino)prop-1'-xl]-2-cyano-3-chloroacrylamide
##SPC9##
N-(n-propyl)-N-(ethylmethylaminomethyl)-.beta.-bromomethacrylamide
##SPC10##
N-isopropyl-N-[2'-(butylamino)prop-1'-yl]ethacrylamide
##SPC11##
N-cyclopropyl-N-[2'-(isopropylamino)prop-2'-yl]acrylamide
##SPC12##
N-(n-butyl)-N-(cyclopropylaminomethyl)acrylamide ##SPC13##
N-cyclobutyl-N-[.beta.-(cyclobutylmethylamino)ethyl]methacrylamide
##SPC14##
N-[3'-(diethylamino)propyl]methacrylamide ##SPC15##
N-[2'-(dimethylamino)cyclopropyl]acrylamide
The instant polymers may be homopolymers or interpolymers having,
in addition to the repeating units defined above, any compatible
repeating unit or various repeating units which are not detrimental
to photographic silver halide emulsions and which allow the
resultant polymer to be soluble in water. Examples of typical
comonomers which may be employed in forming the polymers suitable
for use in the present invention include the following
ethylenically-unsaturated monomers:
Ch.sub.2 =ch--cooh
acrylic acid ##SPC16##
methacrylic acid ##SPC17##
.alpha.-chloroacrylic acid ##SPC18##
.alpha.-bromoacrylic acid
Ch.sub.3 ch=ch--cooh
crotonic acid
Ch.sub.3 ch=ch--cooh
isocrotonic acid
Cl--CH=CH--COOH
.beta.-chloroacrylic acid
Br--CH=CH--COOH
.beta.-bromoacrylic acid ##SPC19##
.beta.-chloromethacrylic acid
Ch.sub.2 =ch--coo--ch.sub.3
methyl acrylate ##SPC20##
ethyl methacrylate ##SPC21##
n-propyl-.alpha.-chloroacrylate
Br--ch=ch--coo--ch--ch.sub.3).sub.2
isopropyl-.beta.-bromoacrylate ##SPC22##
isobutyl methacrylate
Ch.sub.2 =ch--coo--ch.sub.2 ch.sub.2 oh
.beta.-hydroxyethyl acrylate
Ch.sub.2 =ch--coo--ch.sub.2 ch.sub.2 ch.sub.2 oh
.gamma.-hydroxypropyl acrylate ##SPC23##
2-hydroxy-n-propyl methacrylate
Ch.sub.2 =ch--co--nh.sub.2
acrylamide ##SPC24##
.alpha.-chloroacrylamide ##SPC25##
.alpha.-bromoacrylamide ##SPC26##
methacrylamide ##SPC27##
.alpha.-ethylacrylamide ##SPC28##
.beta.-chloromethacrylamide ##SPC29##
2,3-dibromoacrylamide
Ch.sub.3 ch=ch--co--nh.sub.2
crotonamide ##SPC30##
N-methylmethacrylamide
Ch.sub.2 =ch--co--n--ch.sub.3).sub.2
n,n-dimethylacrylamide ##SPC31##
N-ethyl-.alpha.-chloroacrylamide
Ch.sub.2 =ch--co--nh--c--ch.sub.3).sub.3
n-tertiary butylacrylamide ##SPC32##
N-cyclohexylacrylamide ##SPC33##
N-tertiary octyl acrylamide
Ch.sub.2 =ch--co--nh--ch.sub.2 oh
n-methylolacrylamide
Ch.sub.2 =ch--co--nh--ch.sub.2 ch.sub.2 oh
n-(.beta.-hydroxyethyl) acrylamide ##SPC34##
diacetone acrylamide
Ch.sub.2 =ch--co--nh--ch--ch.sub.3).sub.2
n-isopropylacrylamide ##SPC35##
N-benzylacrylamide
Ch.sub.2 =ch--o--ch.sub.3
methylvinyl ether ##SPC36##
ethyl .alpha.-chlorovinyl ether
Ch.sub.2 =ch--o--ch.sub.2 ch.sub.2 cl
.beta.-chloroethyl vinyl ether
Ch.sub.2 =ch--o--ch.sub.2 ch.sub.2 --och.sub.3
.beta.-methoxyethyl vinyl ether ##SPC37##
isobutyl isopropenyl ether
Ch.sub.2 =ch--o--ch.sub.2 ch.sub.2 ch.sub.2 ch.sub.2 ch.sub.2
--ch--ch.sub.3).sub.2
isooctyl vinyl ether ##SPC38##
methylvinyl ketone ##SPC39##
ethyl isopropenyl ketone ##SPC40##
n-propyl-.alpha.-chlorovinyl ketone ##SPC41##
.beta.-methoxyethyl-.alpha.-bromovinyl ketone ##SPC42##
.beta.-hydroxyethyl-1-butene-2-yl ketone
Ch.sub.2 =ch--cho
acrolein
Ch.sub.2 --ch=ch--cho
crotonaldehyde ##SPC43##
.alpha.-chloroacrolein ##SPC44##
.alpha.-bromoacrolein
Ch.sub.2 =ch--c.vertline.n
acrylonitrile
Ch.sub.3 ch=ch--c.tbd.n
crotononitrile ##SPC45##
.alpha.-chloroacrylonitrile ##SPC46##
.alpha.-bromoacrylonitrile ##SPC47##
.beta.-bromomethacrylonitrile ##SPC48##
.beta.-chloroethacrylonitrile ##SPC49##
methyl .alpha.-cyanoacrylate
Ch.sub.2 =ch--co--nh--ch.sub.2 --co--nh.sub.2
acrylamidoacetamide ##SPC50##
methacrylamidoacetamide ##SPC51##
2-crotonamido-N-methylpropionamide ##SPC52##
2-acrylamidopropionamide ##SPC53##
2-methacrylamidopropionamide ##SPC54##
2-(.alpha.-chloroacrylamido)-3-methylbutyramide
Ch.sub.2 =ch--co--nh--ch.sub.2 --nh--co--ch.sub.3
n-(acetamidomethyl)acrylamide ##SPC55##
N-(propionamidomethyl)methacrylamide ##SPC56##
N-(n-butyramidomethyl).alpha. -chloroacrylamide ##SPC57##
maleic anhydride
Hooc--ch=ch--cooh
maleic acid
Hooc--ch=ch--co--nh.sub.2
maleic acid amide
Hooc--ch=ch--co--nh--ch.sub.2 ch.sub.3
n-ethylmaleic acid amide
Ch.sub.3 --ooc--ch=ch--co--nh--ch.sub.3
n-methyl methylmaleate amide
Ch.sub.2 =ch--ooch
vinylformate
Ch.sub.2 =ch--ooc--ch.sub.3
vinyl acetate
Ch.sub.2 =ch--oh (obtained by hydrolyzing copolymerized vinyl
acetate)
vinyl alcohol ##SPC58##
isopropenyl bromoacetate
Ch.sub.2 =ch--ooc--c--ch.sub.3).sub.3
vinyl pivalate
Ch.sub.2 =ch--nh--coo--c--ch.sub.3).sub. 3
n-vinyl-tertiary butylcarbamate ##SPC59##
ethyl-3-carboxy-3-butenate ##SPC60##
.alpha.-vinylfuran ##SPC61##
.alpha.(-acryloyloxymethyl)-tetrahydrofuran ##SPC62##
p-hydroxystyrene ##SPC63##
m-hydroxystyrene ##SPC64##
o-hydroxystyrene ##SPC65##
p-carboxystyrene ##SPC66##
m-carboxystyrene ##SPC67##
o-carboxystyrene ##SPC68##
N-vinyl-2-pyrrolidone
Ch.sub.2 =ch--co--nh--ch.sub.2 ch.sub.3
n-ethylacrylamide ##SPC69##
N-acryloylvaline ##SPC70##
N-acryloylmethionine ##SPC71##
N-acryloylmethionamide ##SPC72##
N-methacryloylmethionine
Polymerization of the indicated monomers is achieved by
conventional free radical polymerization techniques.
The following non-limiting example illustrates the preparation of
polymers within the scope of the present invention.
EXAMPLE
2:1 copolymer of acrylamide/N-[.beta.-(dimethylamino)
ethyl]acrylamide
7.1 g. of acrylamide and 7.1 g. of N-[.beta.-(dimethylamino)
ethyl]acrylamide were added to 200 ml. of distilled water under
nitrogen. The pH was adjusted to 6.3 with nitric acid and then 0.03
g. of potassium persulfate and 0.03 g. of sodium bisulfite were
added. The polymerization was carried out at 25.degree. C. for 4
hours. The thus-formed polymer was precipitated into acetone,
washed, dried and redissolved for use in making an emulsion.
Other polymers within the scope of the present invention were
prepared by similar procedures. As illustrative examples of such
polymers, mention may be made of:
1:1 N-ethylacrylamide/N-[.beta.-(dimethylamino)ethyl]acrylamide
9:1 acrylamide/N-[.beta.-(dimethylamino)ethyl]acrylamide
5:1 acrylamide/N-[.beta.-(dimethylamino)ethyl]acrylamide
10:9:1
acrylamide/N-.beta.-(dimethylamino)ethyl]acrylamide/N-acryloylvaline
3:1 N-isopropylacrylamide/N-[.beta.-(dimethylamino)
ethyl]acrylamide
4:1 acrylamide/N-[.beta.-(dimethylamino)ethyl]acrylamide
1.65:1 acrylamide/N-[.beta.-(diethylamino)methyl]acrylamide
The following general procedure may be used for preparing
photographic emulsions using the polymers of the instant invention
as the colloid binders.
A water-soluble silver salt, such as silver nitrate, may be reacted
with at least one water-soluble halide, such as potassium, sodium,
or ammonium bromide, preferably together with potassium, sodium or
ammonium iodide, in an aqueous solution of the above-described
polymer. The emulsion of silver halide thus-formed contains
water-soluble salts, as a by-product of the double decomposition
reaction in addition to any unreacted excess of the initial salts.
To remove these soluble materials, the emulsion may be centrifuged
and washed with distilled water to a low conductance. The emulsion
may then be redispersed in distilled water. To an aliquot of this
emulsion may be added a known quantity of a solution of bodying or
thickening polymer, such as polyvinyl alcohol having an average
molecular weight of about 100,000 (commercially available from E.
I. duPont deNemours & Company, Wilmington, Del., designated
Type 72-60). A surfactant, such as dioctyl ester of sodium
sulfosuccinic acid, designated Aerosol OT, (commercially available
from American Cyanamid Company, New York, N.Y.), may be added and
the emulsion slot coated onto a base of cellulose triacetate sheet
5 mls. thick having a coating of 30 mg./sq. ft. of hardened
gelatin.
Alternatively, the soluble salts may be removed by adding to the
emulsion a solution of polyacid such as 1:1 ethylene:maleic acid
copolymer and lowering the pH to below 5, thereby bringing about
precipitation of the polyacid carrying the silver halide grains
along with the precipitate, and then to wash and resuspend the
resulting precipitate by redissolving the polyacid at pH 6-7.
The emulsions may be chemically sensitized with sulfur compounds
such as sodium thiosulfate or thiourea, with reducing substances
such as stannous chloride; with salts of noble metals such as gold,
rhodium and platinum; with amines and polyamines; with quaternary
ammonium compounds such as alkyl .alpha.-picolinium bromide; and
with polyethylene glycols and derivatives thereof. The emulsions of
the present invention require only 5 percent as much gold for
chemical sensitization as do gelatin emulsions.
The polymers employed as the binders in the emulsions of the
present invention may be cross-linked according to conventional
procedures. As an example, polymers containing amine groups may be
cross-linked with zirconium salts under alkaline conditions wherein
amine-containing polymer is coated with a zirconium salt, for
example, zirconium sulfate, and the pH is raised cross-linking the
polymer.
The emulsions of the present invention may also be optically
sensitized with cyanine and merocyanine dyes more easily than are
gelatin emulsions. Cyanine dyes tend to aggregate less on the
polymers of the instant invention than with gelatin providing less
light filtering and speed loss. Where desired, suitable
antifoggants, toners, restrainers, developers, accelerators,
preservatives, coating aids, plasticizers, hardeners and/or
stabilizers may be included in the composition of the emulsion.
The emulsions of this invention may be coated and processed
according to conventional procedures of the art. They may be
coated, for example, onto various types of rigid or flexible
supports, such as glass, paper, metal, and polymeric films of both
the synthetic type and those derived from naturally occurring
products. As examples of specific materials which may serve as
supports, mention may be made of paper, aluminum, polymethacrylic
acid, methyl and ethyl esters, vinylchloride polymers, polyvinyl
acetal, polyamides such as nylon, polyesters such as polymeric film
derived from ethylene glycol-terephthalic acid, and cellulose
derivatives such as cellulose acetate, triacetate, nitrate,
propionate, butyrate, acetate propionate, and acetate butyrate.
These novel emulsions of the instant invention have been found to
adhere to supports in a most satisfactory manner.
The polymers employed in the practice of the instant invention may
contain from 5-100 mole percent of the above-indicated repeating
units. The specific amount employed may be selected by the operator
depending upon the grain particle size and habit desired.
By selecting appropriate comonomers, the instant copolymers may be
made to be compatible with all water-soluble bodying polymers.
Emulsions made from these novel polymers, may be bodied with any
water-soluble polymers, overcoming the disadvantage encountered
with gelatin which is only compatible with a very few polymers in a
most limited pH range. As examples of specific materials which may
serve as bodying polymers are gelatin, polyvinyl alcohol,
polyacrylamide, polyalkylacrylamides, polyvinyl pyrrolidone,
polymethacrylamidoacetamide, vinyl alcohol/N-vinylpyrrolidone
copolymers, poly-N-ethylaziridine, poly-N-(2-hydroxyethyl)
aziridine, poly-N-(2-cyanoethyl)aziridine, poly(.beta.-hydroxyethyl
acrylate), polyethylene imine and cellulose derivatives such as
hydroxyethyl cellulose, hydroxypropyl cellulose and methyl
cellulose. It has been found that using only a small amount of one
or more of the instant polymers, large amounts of photosensitive
silver halide grains may be obtained.
An emulsion made from one of these polymers of the instant
invention may therefore be bodied with a water-soluble polymer such
that the polymeric constitution of the resulting emulsion comprises
a relatively large percentage of the bodying polymer.
By selecting appropriate comonomers, copolymers with selected
diffusion characteristics may be prepared.
The instant polymers containing acidic comonomers may be pH
flocculated in order to remove the soluble salts formed as a
byproduct of the double decomposition reaction between the
water-soluble silver salt and the water-soluble halide, in addition
to any unreacted excess of the initial salts. As an example, an
acid copolymer may be precipitated by lowering the pH below 5 and
then washed and resuspended by raising the pH to above 7.
The instant invention will be further illustrated by reference to
the following nonlimiting examples in which the preparation of the
emulsion was carried out in the following general manner.
Procedure A
A solution of 4.15 g. of the dry polymer in 266 ml. of distilled
water was adjusted to pH 6.30 with dilute nitric acid and
maintained at a temperature of 55.degree. C. To this solution, 44.0
g. of dry potassium bromide and 0.50 g. of dry potassium idoide
were added.
A solution of 55 g. of silver nitrate in 500 ml. of distilled water
was prepared. From this silver nitrate solution, 100 ml. was
rapidly added with continuous agitation to the polymer-halide
solution and an additional 396 ml. was added over a period of 22
minutes. Thereafter, the emulsion was ripened for 30 minutes at
55.degree. C., and then rapidly cooled to below 20.degree. C.
Procedure B
In an alternative procedure for preparing the emulsion, the pH of
the polymer solution was adjusted to 3.0; the amount of dry
potassium bromide used was 88.0 g. and the amount of dry potassium
iodide used was 1.0 g. In addition, the emulsion was ripened for 60
minutes instead of for 30 minutes.
The emulsion mixture in both procedures was centrifuged and washed
with water to a low conductance. The emulsion was then redispersed
in distilled water. To an aliquot of this emulsion was added a
known quantity of a solution of bodying or thickening polymer of
polyvinyl alcohol having an average molecular weight of about
100,000 (commercially available from E. I. duPont de Nemours &
Company, Wilmington, Del., designated Type 72-60). A surfactant,
such as Aerosol OT, was added and the emulsion was slot coated onto
a base of cellulose triacetate sheet 5 mils thick having a coating
of 30 mg./sq. ft. of hardened gelatin, (Celfa, commercially
available from Instar Supply Company, New York N.Y.). This film so
prepared was air dried, exposed on a sensitometer, and processed
with a processing solution and an image-receiving sheet from a Type
107 film assembly (Polaroid Corporation, Cambridge, Mass). The
negative and image-receiving element were maintained in superposed
position for 15 seconds, after which they were stripped apart. The
photographic characteristics of the resulting positive print were
measured on an automatic recording densitometer.
The following table summarizes silver halide grain sizes obtained
in emulsions prepared with polymers of the present invention.
TABLE 1 ______________________________________ Grain Size (microns)
Polymer Range Average ______________________________________ 1.25:1
acrylamide/N-[.beta.-(diethyl- amino)methyl]acrylamide 0.4-3.7 1.5
Poly-N-[.beta.-(dimethylamino)ethyl] acrylamide 0.3-2 0.6 2:1
acrylamide/N-[.beta.-(dimethyl- amino)ethyl]acrylamide 0.1-1 0.5
1:1 acrylamide/N-[.beta.-(dimethyl- amino)ethyl]acrylamide 0.4-5 2
4:1 acrylamide/N-[.beta.-(dimethyl- amino)ethyl]acrylamide 0.2-2
0.8 9:1 acrylamide/N-[.beta.-(dimethyl- amino)ethyl]acrylamide
0.3-2.5 0.8 3:2 N-isopropylacrylamide/N-
[.beta.-(dimethylamino)ethyl]acrylamide 0.8-1.2 1 9:1
N-isopropylacrylamide/N- [.beta.-(dimethylamino)ethyl]acrylamide
0.2-0.6 0.4 19:1 N-isopropylacrylamide/N-
[.beta.-(dimethylamino)ethyl]acrylamide 0.8 1:1
N-methylacrylamide/N-[.beta.- (dimethylamino)ethyl]acrylamide
0.1-2.5 1 1:1 diacetoneacrylamide/N-[.beta.-
(dimethylamino)ethyl]acrylamide 0.6-1.2 1 4:1
methacrylamidoacetamide/N-[.beta. (dimethylamino)ethyl]acrylamide
0.3-2.3 1.2 1:1 ethylacrylamide/N-[.beta.-(dimethyl-
amino)ethyl]acrylamide 0.1-3 1 8:1:1 acrylamide/acryloylvaline/N-
[.beta.-(dimethylamino)ethyl]acrylamide 0.3-7.0 3.0 9:2:9
acrylamide/methacryloyl- methionine/N-[.beta.-(dimethylamino)
ethyl]acrylamide 0.2-1 0.6 16:1:16 acrylamide/methacryloyl-
methionine/N-[.beta.-(dimethylamino) ethyl]acrylamide 0.2-1.5 0.7
1:1 acrylamidoacetamide/N-[.beta.- (dimethylamino)ethyl]acrylamide
0.2-2.2 0.9 99:1:99 acrylamide/N-acryloyl-
methionineamide/N-[.beta.- (dimethylamino)ethyl]acrylamide 0.3-2.1
1 10:1:9 acrylamide/N-acryloyl- valine/N-[.beta.-(dimethylamino)
ethyl]acrylamide 0.2-3.8 2 17:3 N-isopropylacrylamide/N-
[.beta.-(dimethylamino)ethyl] acrylamide 0.2-1.4 0.4
Poly-N-[.beta.-(dimethylamino)ethyl] acrylamide 0.3-2 0.6 1:1
ethylacrylamide/N-[.beta.- (dimethylamino)ethyl]acrylamide 0.1-3 1
1:2 N,N-dimethylacrylamide/N-[.beta.-
(dimethylamino)ethyl]acrylamide 0.4-2.4 0.9 1:2
N-t-butylacrylamide/N-[.beta.- (dimethylamino)ethyl]acrylamide
0.4-3 1.3 1:3 N,N-diethylacrylamide/N-[.beta.-
(dimethylamino)ethyl]acrylamide 0.3-3.2 1.5 1:1
acrylamidoacetamide/N-[.beta.- (dimethylamino)ethyl]acrylamide
0.4-2 1.2 ______________________________________
The following table shows densitometer readings obtained on
positives prepared from emulsions within the scope of the present
invention.
TABLE 2
__________________________________________________________________________
Grain Growing Bodying Silver/Polymer Silver Polymer Polymer Ratio
mg/ft..sup.2 .sup.D max .sup.D min .DELTA..sup.D
__________________________________________________________________________
2:1 acrylamide/N-[.beta.- none .infin. 69.4 1.58 0.25 1.33
(dimethylamino)ethyl] acrylamide 2:1 acrylamide/N-[.beta.- 7:3
vinyl 1.24 72.4 1.32 0.90 0.42 (dimethylamino)ethyl] alcohol/N-
acrylamide vinylpyrrolidine copolymer 2:1 acrylamide/N-[.beta.- 2:1
acrylamide/N- 0.77 138.0 1.09 0.07 1.02 (dimethylamino)ethyl]
[.beta.-(dimethylamino) acrylamide ethyl]acrylate 2:1
acrylamide/N-[.beta.- polyvinyl alcohol 0.77 69.2 1.40 0.65 0.75
(dimethylamino)ethyl] acrylamide 2:1 acrylamide/N-[.beta.-
poly-N-(2-cyano- 0.77 74.2 0.20 0.07 0.13 (dimethylamino)ethyl]
ethyl)aziridine acrylamide 2:1 acrylamide/N-[.beta.- poly-N-vinyl
0.77 39.7 1.45 1.15 0.30 (dimethylamino)ethyl] pyrrolidine
acrylamide 2:1 acrylamide/N-[.beta.- gelatin 0.79 79.4 1.88 0.56
1.32 (dimethylamino)ethyl] acrylamide 1:1 N-ethylacrylamide/ 7:3
vinyl alcohol/ 1.24 149.3 0.92 0.16 0.76 N-[.beta.-(dimethylamino)
N-vinylpyrrolidine ethyl]acrylamide 9:1 acrylamide/N-[.beta.-
polyvinyl alcohol 1.36 121.8 1.25 0.50 0.75 (dimethylamino)ethyl]
acrylamide 5:1 acrylamide/N-[.beta.- none .infin. 144.1 1.52 0.05
1.47 (dimethylamino)ethyl] acrylamide 5:1 acrylamide/N-[.beta.-
polyvinyl alcohol 0.68 134.0 1.75 0.05 1.70 (dimethylamino)ethyl]
acrylamide 5:1 acrylamide/N-[ .beta.- gelatin 0.92 184.1 1.77 0.26
1.51 (dimethylamino)ethyl] acrylamide 5:1 acrylamide/N-[.beta.- 1:1
acrylamide/ 4.1 81.3 1.19 0.19 1.00 (dimethylamino)ethyl]
N-acryloylvaline acrylamide copolymer 5:1 acrylamide/N-[.beta.- 1:1
acrylamide/ 1.36 64.3 1.48 0.00 1.48
(dimethylamino)ethyl]N-acryloylvaline acrylamide copolymer and
polyvinyl alcohol 5:1 acrylamide/N-[.beta.- 1:1 acrylamide/ 0.92
43.6 1.38 0.17 1.21 (dimethylamino)ethyl] N-acryloylvaline
acrylamide copolymer and gelatin 10:9:1 acrylamide/N- polyvinyl
alcohol 0.68 127.6 0.92 0.18 0.74 [.beta.-(dimethylamino)ethyl]
acrylamide/N-acryloylvaline 3:1 N-isopropylacrylamide/ polyvinyl
alcohol 1.36 85.3 0.96 0.31 0.65 N-[.beta.-(dimethylamino)ethyl]
acrylamide 4:1 acrylamide/N-[.beta.- polyvinyl alcohol 0.91 57.2
0.92 0.20 0.72 (dimethylamino)ethyl] acrylamide 1:65:1
acrylamide/N- polyvinyl alcohol 1.36 98.1 1.84 0.20 1.64
[.beta.-dimethylamino) ethyl]acrylamide
__________________________________________________________________________
The emulsions of the present invention also show a significant
shortening of processing time as compared with conventional silver
halide emulsions. For example, an emulsion prepared with a 5:1
acrylamide/N-[.beta.-(dimethylamino) ethyl]acrylamide copolymer as
the grain growing polymer and polyvinyl alcohol as the bodying
polymer (silver polymer ratio 1.36 and silver coverage 6.43
mgs./ft..sup.2) when exposed and processed with Type 107C
processing composition and receiving sheet (Polaroid Corporation,
Cambridge, Mass.) showed a D.sub.max of 1.31 and a D.sub.min of
0.02 after 10 seconds of processing while a conventional Type 107C
film unit showed a D.sub.max of 0.36 and D.sub.min of 0.01 after 10
seconds.
In certain photographic applications, it may be desirable to
replace part, but not all, of the gelatin in the photosensitive
emulsion. In view of the characteristics of these polymers
described above, and further, in view of their compatability with
gelatin in substantially all proportions, it will be obvious that
these polymers are ideally suited for such work.
The term "photosensitive" and other terms of similar import are
herein employed in the generic sense to describe materials
possessing physical and chemical properties which enable them to
form usable images when photoexposed by radiation.
Since certain changes may be made in the above products and
processes without departing from the scope of the invention herein
involved, it is intended that all matter contained in the above
description shall be interpreted as illustrative only and not in a
limiting sense.
* * * * *