FIELD OF INVENTION
[0001] This invention is related to improved hardeners for proteinaceous materials. More
specifically this invention is related to a combination of imidazolium triazine hardeners
for crosslinking a proteinaceous material in a photographic film.
BACKGROUND OF THE INVENTION
[0002] Proteinaceous materials are used for a wide variety of applications. One of the predominant
useful properties is their ability to swell in aqueous solutions and yet form a solid
matrix which is permeable to aqueous solutions upon drying. These properties have
been exploited for many generations in the field of photographic sciences and proteinaceous
materials are still widely used as a binder for harbouring silver halide grains in
the photosensitive layer of photographic films.
[0003] Formation of a solid matrix is typically considered to be a result of inter-and intra-molecular
hydrogen bonding within both the helical and random regions of proteinaceous materials.
If only the natural hydrogen bonding is employed the strength of the matrix is typically
insufficient for use in a photographic film. Therefore, it is common practice to add
a hardener, also known as crosslinking agent, to a proteinaceous material when used
for photographic layers.
[0004] Hardeners are chosen, in part, for their ability to link one group on a proteinaceous
molecule with another group on the same, or different, proteinaceous molecule. The
linking generates a three dimensional network of proteinaceous material. This three-dimensional
network has sufficient strength to safely harbour a silver halide grain. Another important
aspect of the three dimensional network is an ability to allow solution to permeate
freely during the photographic processing steps of development, fix (or bleach) and
wash. It is imperative that the solution which freely permeates the matrix is not
strongly absorbed. This is particularly important for photosensitive elements since
they must often be capable of transiting the photographic processing steps of development,
fix, wash and dry in 20-120 sec.
[0005] Crosslinking of a binder matrix most often involves the carboxyl groups, amine groups,
or combinations thereof. The number of carboxyl groups is substantially larger than
the number of amine groups in most commercially available gelatin. Traditional hardeners,
such as triazines, are widely accepted as capable of combining amine groups and are
thus termed amine-amine crosslinkers. Amine-amine crosslinkers provide a very strong
matrix yet the carboxyls are largely unaffected. The unreacted carboxyl groups are
deleterious since they strongly absorb processing solution and increase the time required
to remove the absorbed solution. The result is an increase in the time and/or energy
required for transiting the photographic processing steps identified above. Peptide
couplers, such as imidazoliums, are widely accepted as combining a carboxyl group
with an amine group to form an amide linkage between binder strands. This is advantageous
since the number of free carboxyls is decreased. Unfortunantly, the strength of the
peptide-coupled binder is insufficient to transit a processor and total binder destruction
is frequently observed.
[0006] There has been a long felt need in the art to provide a method of crosslinking a
binder which has the strength of an amine-amine crosslinked matrix and the permeability
and low solution retention of a binder crosslinked by amide linkages.
[0007] An important consideration in crosslinking a binder is the pH of activity. This is
particularly important when comparing amine-amine crosslinking reactions with reactions
that form amide linkages. Amine-amine crosslinkers, like triazines, are typically
stable around a neutral pH (∼7) and decomposition, or decreased reactivity, is observed
above or below neutrality. Peptide couplers, especially imidazoliums, are susceptible
to instablility at higher pH and decomposition is accelerated above a pH of approximately
6.2. Therefore, if a pH is employed for optimum amine-amine crosslinking, the decomposition
of imidazolium complexes is in competition with crosslinking reactivity. If a pH is
employed which is suitable for formation of amide linkages by an imidazolium the amine-amine
crosslinking reagents become unstable in solution. At intermediate ranges neither
crosslinking method is efficient. Partly due to the stability differences, skilled
artisans have considered imidazolium type coupling agents, and amine-amine coupling
agents to be incompatable since a suitable solution pH was unavailable. By methods
described herein the advantages of imidazolium couplers and amine-amine couplers can
be used concurrently to provide a strong matrix with low water absorption.
SUMMARY OF THE INVENTION
[0008] It is an object of the present invention to provide a novel hardening combination
which effectively increases the strength of the matrix.
[0009] It is another object of the present invention to provide a novel hardening combination
which decreases the amount of fluid absorbed and restrained during processing.
[0010] It is yet another object of the present invention to provide a combination of hardeners
which are suitable for use in a photographic element.
[0011] A particular feature of the present invention is the ability to provide a photographic
element which has a strong matrix, low fluid absorption and can undergo photographic
development without detrimental effects.
[0012] These and other advantages, as will be apparant from the description, are provided
in a photographic element comprising at least one hydrophilic colloid layer; at least
one said hydrophilic colloid layer is hardened with at least one compound chosen from:

wherein:
- Y¹ is
- an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of
6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen
from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered
ring; -L¹CR⁸CH₂, or a polymer thereof; -C(Y⁴)E; or

- E is
- an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of
6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; -OR⁹; -CN; the
atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5 -or 6-membered ring;
- L¹ is
- a linking group;
- R¹ is
- hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; -OR¹⁰; halogen;
nitro, carboxyl, mercapto; alkylamino or substituted alkylamino of 1 to 24 carbons;
the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
- R² and R³
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of
7 to 25 carbons; R² and R³ independently may represent, or be taken together to represent,
the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered ring;
- R⁴ and R⁵
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl or substituted aryl of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to
25 carbons; nitro; carboxyl; mercapto; -OR¹¹; halogen; alkylamino or substituted alkylamino
of 1 to 24 carbons; the atoms chosen from C, N, O, and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring;
- R⁴ and R⁵
- may be taken together to represent the atoms chosen from C, N, O, and S necessary
to form a substituted or unsubstituted 5- or 6-membered ring;
- X- is
- a counterion;
- Y², Y³ and Y⁴
- independently represent O or S;
- R⁶ and R⁷
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of
7 to 25 carbons; the atoms chosen from C, N, O and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring;
- R⁶ and R⁷
- may be taken together to represent the atoms chosen from C, N, O and S necessary to
form a substituted or unsubstituted 5- or 6-member ring;
- R⁸
- represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; -C(O)R²⁸;
-CN; aryl or substituted aryl of 6 to 24 carbons;
- R⁹
- represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; aryl or substituted
aryl of 6 to 24 carbons;
- R¹⁰ and R¹¹
- independently represent hydrogen, an alkyl, or substituted alkyl, of 1 to 5 carbons;
- R²⁸
- represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or substituted
alkoxy of 1 to 24 carbons; amine; alkylamine or substituted alkylamine of 1 to 24
carbons;
and at least one hydrophilic colloid layer is hardened by at least one
[0013] compound defined by:

wherein:
at least two of R¹², R¹³ and R¹⁴ are independently chosen from the groups represented
by halogen, preferably Cl or Br;
- one of R¹², R¹³ or R¹⁴
- may represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; halogen;
-OR²¹; -NR²²R²³; -OM; a divalent linking group to another triazine; sulfonamide; substituted
or unsubstituted alkylether of 1 to 20 carbons; polyethylene oxide of 2 to 40 carbons;
-(OR²⁴)xR²⁵; -L²CR²⁶CH₂ or a polymer thereof;
- R¹⁵ and R¹⁶
- independently represent sodium; potassium; ammonium; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; hydrogen; alkyl or substituted alkyl of 1 to 20
carbons;
- R¹⁷ and R¹⁸
- independently represent sodium; potassium; ammonium; hydrogen; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1 to 20 carbons;
- R¹⁹ and R²⁰
- independently represent sodium; potassium; hydrogen; ammonium; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1 to 20 carbons;
- R²¹
- represents hydrogen; alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalky or
substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 40 carbons;
aralkyl or substituted aralkyl of 7 to 41 carbons; alkylthioether or substituted alkylthioether
of 1 to 40 carbons;
- R²² and R²³
- independently represent hydrogen; alkyl or substituted alkyl of 1 to 20 carbons; aryl
or substituted aryl of 6 to 20 carbons; alkylether or substituted alkylether of 1
to 20 carbons; arylether or substituted arylether of 6 to 20 carbons; alkylthioether
or substituted alkylthioether of 1 to 20 carbons; arylthioether or substituted arylthioether
of 6 to 20 carbons; sulfonyl; alkylsulfonyl of 1 to 20 carbons;
- R²⁴
- represents an ethylene or substituted ethylene;
- R²⁵
- represents an alkyl or substituted alkyl of 1 to 20 carbons; an ether or substituted
ether of 1 to 20 carbons;
- R²⁶
- represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
- L² is
- a chemical linkage;
- M is
- a counterion preferably chosen from sodium, potassium, lithium, calcium, barium, strontium,
ammonium, or alkyl ammonium with 1 to 20 carbons;
- x is
- an integer from 1 to 24.
[0014] Other advantages are provided in a preferred embodiment of the present invention
as observed in a process for forming a photographic element comprising the steps of:
forming at least one liquid photographic emulsion in at least one storage vessel wherein
said liquid photographic emulsion comprises silver halide, hydrophilic colloid and
a solvent;
transporting said liquid photographic emulsion to an interface region; adding at least
one compound defined by

wherein:
- Y¹ is
- an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of
6 to 24, carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen
from C, N, O, and S necessary to form a substituted or unsubstituted 5 - or 6-membered
ring; -L¹CR⁸CH₂, or a polymer thereof; C(Y⁴)E; or

- E is
- an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of
6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen
from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered
ring;
- L¹ is
- a linking group;
- R¹ is
- hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; -OR¹⁰; halogen;
nitro, carboxyl, mercapto, alkylamino or substituted alkylamino of 1 to 24 carbons;
the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
- R² and R³
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of
7 to 25 carbons; R² and R³ independently may represent, or be taken together to represent,
the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered ring;
- R⁴ and R⁵
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl or substituted aryl of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to
25 carbons; nitro; carboxyl; mercapto; -OR¹¹; halogen; alkylamino or substituted alkylamino
of 1 to 24 carbons; the atoms chosen from C, N, O, and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring;
- R⁴ and R⁵
- may be taken together to represent the atoms chosen from C, N, O, and S necessary
to form a substituted or unsubstituted 5- or 6-membered ring;
- X- is
- a counterion;
- Y², Y³ and Y⁴
- are independently represent O or S;
- R⁶ and R⁷
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of
7 to 25 carbons; or the atoms chosen from C, N, O and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring;
- R⁶ and R⁷
- may be taken together to represent the atoms chosen from C, N, O and S necessary to
form a substituted or unsubstituted 5- or 6-member ring;
- R⁸
- represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; -C(O)R²⁸;
-CN; phenyl or substituted phenyl of 6 to 24 carbons;
- R⁹
- represents hydrogen; alkyl or substituted alkyl or 1 to 24 carbons; aryl of substituted
aryl of 6 to 24 carbons;
- R¹⁰ and R¹¹
- represents hydrogen; an alkyl, or substituted alkyl, of 1 to 5 carbons;
- R²⁸
- represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or substituted
alkoxy of 1 to 24 carbons; amine; alkyl amine or substituted alkyl amine of 1 to 24
carbons;
and at least one compound defined by

wherein:
at least two of R¹², R¹³ and R¹⁴ are independently chosen from the groups represented
by halogen, preferably Cl or Br;
- one of R¹², R¹³ or R¹⁴
- may represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; halogen;
-OR²¹; -NR²²R²³; -OM; a divalent linking group to another triazine; sulfonamide; substituted
or unsubstituted alkyl ether of 1 to 20 carbons; polyethylene oxide of 2 to 40 carbons;
-(OR²⁴)xR²⁵; -L²CR²⁶CH₂ or a polymer thereof;
- R¹⁵ and R¹⁶
- independently represent sodium; potassium; ammonium; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; hydrogen; alkyl or substituted alkyl of 1 to 20
carbons;
- R¹⁷ and R¹⁸
- independently represent sodium; potassium; ammonium; hydrogen; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1 to 20 carbons;
- R¹⁹ and R²⁰
- independently represent sodium; potassium; hydrogen; ammonium; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1 to 20 carbons;
- R²¹
- represents hydrogen, alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl or
substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 40 carbons;
aralkyl or substituted aralkyl of 7 to 41 carbons; alkylthioether or substituted alkylthioether
of 1 to 40 carbons;
- R²² and R²³
- independently represent hydrogen; alkyl or substituted alkyl or 1 to 20 carbons; aryl
or substituted aryl of 6 to 20 carbons; alkylether or substituted alkylether of 1
to 20 carbons; arylether or substituted arylether of 6 to 20 carbons; alkylthioether
or substituted alkylthioether of 1 to 20 carbons; arylthioether or substituted arylthioether
of 6 to 20 carbons; sulfonyl; alkylsulfonyl of 1 to 20 carbons;
- R²⁴
- represents an ethylene or substituted ethylene;
- R²⁵
- represents an alkyl or substituted alkyl of 1 to 20 carbons; an ether or substituted
ether 1 to 20 carbons;
- R²⁶
- represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
- L² is
- a chemical linkage;
- M is
- a counterion preferably chosen from sodium, potassium, lithium, calcium, barium, strontium,
ammonium, or alkyl ammonium with 1 to 20 carbons;
- x is
- an integer from 1 to 24;
mixing said liquid photographic emulsion with said compound defined by Formula
I and said compound defined by Formula II thereby forming a coating solution;
transporting said coating solution to a coater;
coating said coating solution on a substrate thereby forming a liquid layer; removing
said solvent from said liquid layer to form a dry coated layer.
[0015] A most preferred embodiment is provided in a combination of ingredients for crosslinking
a hydrophilic colloid comprising at least one compound chosen from:

wherein:
- Y¹ is
- an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of
6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen
from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered
ring; -L¹CR⁸CH₂, or a polymer thereof; -C(Y⁴)E; or

- E is
- an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of
6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; -OR⁹; -CN; the
atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
- L¹ is
- a linking group;
- R¹ is
- hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; -OR¹⁰; halogen;
nitro; carboxyl; mercapto; alkylamino or substituted alkylamino of 1 to 24 carbons;
the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered ring;
- R² and R³
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of
7 to 25 carbons; R² and R³ independently may represent, or be taken together to represent,
the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered ring;
- R⁴ and R⁵
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl or substituted aryl of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to
25 carbons; nitro; carboxyl; mercapto; -OR¹¹; halogen; alkylamino or substituted alkylamino
of 1 to 24 carbons;the atoms chosen from C, N, O, and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring;
- R⁴ and R⁵
- may be taken together to represent the atoms chosen from C, N, O, and S necessary
to form a substituted or unsubstituted 5- or 6-membered ring;
- X- is
- a counterion;
- Y², Y³ and Y⁴
- independently represent O or S;
- R⁶ and R⁷
- independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons;
aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of
7 to 25 carbons; or the atoms chosen from C, N, O and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring;
- R⁶ and R⁷
- may be taken together to represent the atoms chosen from C, N, O and S necessary to
form a substituted or unsubstituted 5- or 6-member ring;
- R⁸
- represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; -C(O)R²⁸;
-CN; phenyl or substituted phenyl of 6 to 24 carbons;
- R⁹
- represents hydrogen; alkyl of substituted alkyl of 1 to 24 carbons; aryl of substituted
aryl of 6 to 24 carbons;
- R¹⁰ and R¹¹
- independently represent hydrogen; an alkyl, or substituted alkyl, of 1 to 5 carbons;
- R²⁸
- represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or substituted
alkoxy of 1 to 24 carbons; amine; alkyl amine or substituted alkyl amine of 1 to 24
carbons;
and at least one compound defined by:

wherein:
at least two of R¹², R¹³ and R¹⁴ are independently chosen from the groups represented
by halogen, preferably Cl or Br;
- one of R¹², R¹³ or R¹⁴
- may represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; halogen;
hydrogen; -OR²¹; -NR²²R²³; - OM; a divalent linking group; sulfonamide; substituted
or unsubstituted alkyl ether of 1 to 20 carbons; polyethylene oxide of 2 to 40 carbons;
-(OR²⁴)xR²⁵; -L²CR²⁶CH₂ or a polymer thereof;
- R¹⁵ and R¹⁶
- independently represent sodium; potassium; ammonium; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; hydrogen; alkyl or substituted alkyl of 1 to 20
carbons;
- R¹⁷ and R¹⁸
- independently represent sodium; potassium; ammonium; hydrogen; alkyl ammonium or substituted
alkyl ammonium of 1 to 10 carbons; alkyl or substituted alkyl or 1 to 20 carbons;
- R¹⁹ and R²⁰
- independently represent sodium; potassium; hydrogen; ammonium; alkyl ammonium or substituted
alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1 to 20 carbons;
- R²¹
- represents hydrogen; alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl or
substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 40 carbons;
aralkyl or substituted aralkyl of 7 to 41 carbons; alkylthioether or substituted alkylthioether
of 1 to 40 carbons;
- R²² and R²³
- independently represent hydrogen; alkyl or substituted alkyl or 1 to 20 carbons; aryl
or substituted aryl of 6 to 20 carbons; alkylether or substituted alkylether of 1
to 20 carbons; arylether or substituted arylether of 6 to 20 carbons; alkylthioether
or substituted alkylthioether of 1 to 20 carbons; arylthioether or substituted arylthioether
of 6 to 20 carbons; sulfonyl; alkylsulfonyl of 1 to 20 carbons;
- R²⁴
- represents an ethylene or substituted ethylene;
- R²⁵
- represents an alkyl or substituted alkyl of 1 to 20 carbons; an ether or substituted
ether of 1 to 20 carbons;
- R²⁶
- represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
- L² is
- a chemical linkage;
- M is
- a counterion preferably chosen from sodium, potassium, lithium, calcium, barium, strontium,
ammonium, or alkyl ammonium with 1 to 20 carbons,
- x is
- an integer from 1 to 24.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Photographic elements of the present invention comprise at least one binder layer
and at least one binder layer is crosslinked with at least one compound defined by
Formula I and at least one binder layer is crosslinked with a compound defined by
Formula II.

Referring specifically to Formula I, Y¹ is an alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl or substituted
aralkyl of 7 to 25 carbons; the atoms chosen from C, N, O, and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring; -L¹CR⁸CH₂, or a polymer thereof;
-C(Y⁴)E; or

E is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; -OR⁹; -CN;
the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring. L¹ is a linking group preferably chosen from a covalent chemical
bond; alkyl, or substituted alkyl, of 1 to 20 carbons; aryl, or substituted aryl,
of 6-24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; carboxyl. Most
preferably L¹ represents a chemical linkage; an alkyl, or substituted alkyl, of 1
to 3 carbons. R¹ is hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl,
or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to
25 carbons; halogen; -OR¹⁰; halogen; nitro; carboxyl; mercapto; alklyamino or substituted
alkylamino of 1 to 24 carbons; the atoms chosen from C, N, O and S necessary to from
a 5- or 6-membered ring. Preferably R¹ represents hydrogen; alkyl, or substituted
alkyl, of 1 to 3 carbons; aryl, or substituted aryl, of 6 to 10 carbons; aralkyl,
or substituted aralkyl, of 7 to 11 carbons. Most preferably R¹ represents hydrogen;
alkyl, or substituted alkyl, of 1 to 3 carbons. R² and R³ independently represent
hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons. R² and R³
independently may represent, or be taken together to represent, the atoms C, N, O
and S necessary to form a 5- or 6-membered ring. Preferably R² and R³ independently
represent alkyl, or substituted alkyl, of 1 to 6 carbons; aryl, or substituted aryl,
of 6 to 10 carbons; aralkyl, or substituted aralkyl, of 7 to 11 carbons; or taken
together R² and R³ represent the atoms C, N and O necessary to form a 5- or 6-membered
ring. Most preferably R² and R³ represent alkyl, or substituted alkyl, of 1 to 3 carbons
or R² and R³ are taken together to represent the atoms C, N and O necessary to form
a substituted or unsubstituted 5- or 6-membered ring. R⁴ and R⁵ independently represent
hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl or substituted aryl
o f6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; nitro; carboxyl;
mercapto; -OR¹¹; halogen; alkylamino or substituted alkylamino of 1 to 24 carbons;
R⁴ and R⁵ independently may represent the atoms chosen from C, N, O, and S necessary
to form a substituted or unsubstituted 5-or 6-member ring or R⁴ and R⁵ may be taken
together to represent the atoms chosen from C, N, O, and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring. Preferably R⁴ and R⁵ independently represent
hydrogen; alkyl, or unsubstituted alkyl, of 1 to 4 carbon atoms. X- is a counterion
preferably chosen from the set consisting of halide, CF₃SO₃-, ClO₄-, BF4- and p-CH₃C₆H₄SO₃-.
Y², Y³ and Y⁴ independently represent O or S. R⁶ and R⁷ independently represent hydrogen;
alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of 6 to
24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons. R⁶ and R⁷ independently
may represent, or be taken together to represent the atoms C, N, O and S necessary
to form a substituted or unsubstituted 5- or 6-member ring. Preferably R⁶ and R⁷ independently
represent alkyl, or substituted alkyl, of 1 to 6 carbons; aryl, or substituted aryl,
of 6 to 10 carbons; aralkyl, or substituted aralkyl, of 7 to 11 carbons; taken together
R⁶ and R⁷ may represent the atoms C, N and O necessary to form a substituted or unsubstituted
5- or 6-membered ring. Most preferably R⁶ and R⁷ represent alkyl, or substituted alkyl,
of 1 to 3 carbons; or R⁶ and R⁷ are taken together to represent the atoms C, N and
O necessary to form a substituted or unsubstituted 5- or 6-membered ring. R⁸ represents
a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; -C(O)R²⁸; -CN; aryl
or substituted aryl of 6 to 24 carbons. R⁹ represents hydrogen; alkyl of substituted
alkyl of 1 to 24 carbons; aryl of substituted aryl of 6 to 24 carbons. R¹⁰ and R¹¹
independently represent hydrogen; an alkyl, or substituted alkyl, of 1 to 5 carbons.
R²⁸ represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or
substituted alkoxy of 1 to 24 carbons; amine; alkyl amine or substituted alkyl amine
of 1 to 24 carbons.
[0017] Consistent with terminology used in the art, the compound represented by:

represents a vinyl imidazolium. The vinyl group of the vinyl imidazolium can be polymerized
as known in the art to form a polymer. Preferably the vinyl group of the vinyl imidazolium
can be polymerized with other substituted vinyl compounds to form a copolymer. Preferably
the vinyl imidazole is a copolymer defined by:

where R¹, R², R³, R⁴, R⁵, R⁸, L¹ and Y² correspond to the definition above for similiarly
referenced groups. The subscript "p" represents the mole fraction of vinyl imidazolium
monomer in the polymer and is preferably no more than 95% and more preferably no more
than 50%. A and B independently represent copolymerized monomers. Preferably the monomers
A and B are independently chosen from the set consisting of acrylic acid ester, methacrylic
acid ester, acrylamide, styrene, styrene sulfonate, maleic anhydride, butadiene and
vinyl chloride.
[0018] Referring specifically to Formula II. At least two of R¹², R¹³ and R¹⁴ are independently
chosen from the groups represented by halogen, preferably Cl or Br;

The most preferred group represented by R¹², R¹³ or R¹⁴ is chlorine or bromine. One
of R¹², R¹³ or R¹⁴ may represent hydrogen; alkyl, or substituted alkyl, of 1 to 24
carbons, preferably 1 to 4 carbons; halogen; -OR²¹; -NR²²R²³; -OM; a linking group
to another triazine; sulfonamide; substituted or unsubstituted alkyl ether of 1 to
20 carbons; polyethylene oxide of 2 to 40 carbons; -(OR²⁴)
xR²⁵ where x is an integer from 1 to 24; -L²CR²⁶CH₂ or a polymer thereof. Preferably
one substituent chosen from R¹², R¹³ or R¹⁴ is alkyl, of substituted alkyl, of 1 to
4 carbons; a halogen chosen from Cl and Br; -OR²¹; -NR²²R²³; -OM; a divalent linking
group; sulfonamide; amino or substituted amino; substituted or unsubstituted alkyl
ether of 1 to 20 carbons; polyethylene oxide of 2 to 40 carbons; -(OR²⁴)
xR²⁵ where x is an integer from 1 to 24; - L²CR²⁶CH₂ or a polymer thereof. Most preferrably
one substituent chosen from R¹², R¹³ or R¹⁴ is -OM. R¹⁵ and R¹⁶ independently represent
sodium; potassium; ammonium; alkyl ammonium or substituted alkyl ammonium of 1 to
20 carbons; hydrogen; alkyl or substituted alkyl of 1 to 20 carbons. Preferably R¹⁵
and R¹⁶ independently represent sodium; potasium; ammonium; alkylammonium or substituted
alkylammonium of 1 to 4 carbons. R¹⁷ and R¹⁸ independently represent sodium; potassium;
ammonium; hydrogen; alkyl ammonium or substituted alkyl ammonium of 1 to 20 carbons;
alkyl or substituted alkyl or 1 to 20 carbons. Preferably R¹⁷ and R¹⁸ independently
represent sodium; potassium; ammonium; or alkyl ammonium of 1 to 4 carbons. R¹⁹ and
R²⁰ independently represent sodium; potassium; hydrogen; ammonium; alkyl ammonium
or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1
to 20 carbons. Preferably R¹⁹ and R²⁰ independently represent sodium, potassium, ammonium,
or alkyl ammonium of 1 to 4 carbons. R²¹ represents hydrogen, alkyl or substituted
alkyl of 1 to 20 carbons; alkoxyalkyl or substituted alkoxyalkyl of 1 to 40 carbons;
aryl or substituted aryl of 6 to 40 carbons; aralkyl or substituted aralkyl of 7 to
41 carbons; alkyl thioether or substituted alkyl thioether of 1 to 40 carbons. Preferably
R²¹ represents hydrogen. R²² and R²³ independently represent hydrogen; alkyl or substituted
alkyl of 1 to 20 carbons; aryl or' substituted aryl of 6 to 20 carbons; alkylether
or substituted alkylether of 1 to 20 carbons; arylether or substituted arylether of
6 to 20 carbons; alkylthioether or substituted alkylthioether of 1 to 20 carbons;
arylthioether or substituted arylthioether of 6 to 20 carbons; sulfonyl; alkylsulfonyl
of 1 to 20 carbons. Preferably R²² and R²³ independently represent hydrogen, sulfonyl,
alkylsulfonyl of 1 to 4 carbons. R²⁴ represents an ethylene or substituted ethylene.
Preferably R²⁴ represents ethylene or isopropylene. R²⁵ represents an alkyl or substututed
alkyl of 1 to 20 carbons; an ether or substituted ether of 1 to 40 carbons. R²⁶ represents
a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons. Preferably R²⁶ represents
a hydrogen or methyl. L² is a divalent chemical linkage preferably chosen from a chemical
bond; alkylene or substituted alkylene of 1 to 20 carbons; arylene or substituted
arylene of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; or
carbonyl. Preferably L² represents a chemical bond, alkylene or substituted alkylene
of 1 to 10 carbons; arylene or substituted arylene of 6 to 10 carbons; aralkyl or
substituted aralkyl of 7 to 12 carbons. M is a counterion. M is preferably chosen
from sodium, potassium, lithium, calcium, barium, strontium, ammonium, or alkyl ammonium
with 1 to 20 carbons. Most preferably M is chosen from sodium, potassium, ammonium;
or alkyl ammonium of 1 to 20 carbons.
[0019] Throughout this disclosure the group CH₂ = CR⁸- or CH₂ = CR²⁶-refers to the unpolymerized
monomer. A polymer or copolymer formed by the polymerization or copolymerization of
the vinyl group is also considered to be within the teachings of the present invention.
The process of polymerization, or copolymerization, is well known in the art and includes
specifically radical initiated polymerization.
[0020] The recitation "atoms chosen from C, N, O, and S necessary to from a 5- or 6-membered
ring" or the equivalent thereof, refers to substituted or unsubstituted rings including
but not limited to: the thiazole series; e.g. thiazole, 4-methylthiazole, 4-phenylthiazole,
5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole;
the benzothiazole series; e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole,
6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole,
6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole,
5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,
5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole,
tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole,
5-hydroxybenzothiazole, 6-hydroxybenzothiazole;
the naphthothiazole series; e.g., naphtho[1,2]-thiazole, naphtho[2,1]thiazole,
5-methoxynaphtho[2,1]-thiazole, 5-ethoxynaphtho[2,1]thiazole, 8-methoxynaphtho[1,2]thiazole,
7-methoxynaphtho[1,2]thiazole;
the thianaphtheno-7',6',4,5-thiazole series; e.g. 4'-methoxythianaphtheno-7',6',4,5,thiazole;
the oxazole series; e.g., 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole,
4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole;
the benzoxazole series; e.g., benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole,
5-phenylbenzoazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,5-dimethylbenzoxazole,
5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole,
5-hydroxybenzoxazole, 6-hydroxybenzoxazole;
the naphthoxazole series, e.g., naphtho[1,2]oxazole, naphtho[2,1]oxazole;
the thiazoline series; e.g., thiazoline, 4-methylthiazoline;
the 2-quinoline series; e.g., quinoline, 3-methylquinoline, 5-methylquinoline,
7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline,
6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline;
the 4-quinoline series; e.g., quinoline, 6-methoxyquinoline, 7-methoxyquinoline,
7-methylquinoline, 8-methylquinoline;
the 1-isoquinoline series; e.g., isoquinoline, 3,4-dihydroisoquinoline;
the 3-isoquinoline series; e.g., isoquinoline;
the benzimidazole series; e.g., 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole;
the 3,3-dialkylindolenine series; e.g., 3,3-dimethylindoline, 3,3,5-trimethylindolenine,
3,3,7-trimethylindolenine;
the 2-pyridine series; e.g., pyridine, 5-methylpyridine; and the 4-pyridine series;
e.g., pyridine;
the 3,3-dialkylbenz[e]indole series; e.g., 3,3-dimethylbenz[e]indole;
the tetrazole series: e.g., 1-phenyltetrazole, 1-methyltetrazole;
the triazole series: e.g., 1-phenyl-triazole, 1-methyltriazole;
the pyrimidine series: e.g., pyrimidine;
the thiadiazole series: e.g., 1,3,4-thiadiazole.
[0021] The terms "alkyl", "aryl", "aralkyl", "5- or 6-membered ring", and other groups refer
to both unsubstituted and substituted groups unless specified to the contrary. Preferred
substituents include halogen, nitro, carboxyl, hydroxyl, alkoxy, amine, thiol, amide,
vinyl, sulfate, cyano, thioether, carboxylic acid, sulfonic acid, sulfato, and combination
thereof.
[0022] Well known to the art is the advantage of using a surfactant to assist in coating
a solution. Typically the surfactant is a seperate entity which is useful during coating
and may be detrimental after coating is complete. By incorporating the surfactant
into the chemical structure of the hardener the detrimental properties can be circumvented.
A preferred embodiment of the present invention is realized when at least one of R¹,
R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³ or one of the
set consisting of R¹², R¹³ and R¹⁴ comprises a surfactant moiety incorporated into
the chemical structure of the hardener. This allows a single compound to accomplish
multiple task, namely, act as a coating aid during the coating process after which
they act to crosslink the matrix as detailed above. Surfactant moieties which are
known in the art include alkyls chains over 6 carbons, preferably 6 to 24 carbons;
polyalkyleneoxide chains such as -(R²⁷O)
m-, wherein R²⁷ is ethylene, propylene or combinations thereof and m is an integer
of 1 to 30; or combinations of alkyenes, and polyalkyleneoxides.
[0024] The photographic element of the present invention can be coated onto a substrate
with any method common to the art including but not limited to curtain coating, extrusion
coating, slide-bead coating and the like. Slide-bead coating is a preferred method.
[0025] Slide-bead coating is well known in the art to provide a means for supplying a flowing
liquid layer or plurality of liquid layers down a slide surface to an efflux end,
or lip, at which a liquid bridge, or bead, is formed in the gap between the lip and
the moving substrate. The moving substrate carries away liquid from the liquid inventory
in the bead in the same layered structure established on the slide. Exemplary examples
include, for example, Russell, et.al., U. S. Patents 2,761,791 and 2,761,419.
[0026] The amount of hardener solution added depends on the degree of crosslinking desired.
For use in a photographic emulsion the hardener solution is typically added in an
amount sufficient to equal approximately 0.01 to 1.0 mmoles of Formula I per gram
of hydrophilic colloid and approximately 0.01 to 1.0 mmoles of Formula II per gram
of hydrophilic colloid. More preferred is approximately 0.02 to 0.30 mmoles of the
hardener represented by Formula I per gram of hydrophilic colloid and approximately
0.02 to 0.30 mmoles of the hardener represented by Formula II per gram of hydrophilic
colloid. The amount added may be different for different hydrophilic colloids.
[0027] The hardeners of the present invention are most suitable for crosslinking a hydrophilic
colloid layer. It is most preferred to use the hardeners of the present invention
for a coated layer of hydrophilic colloid. The commercial application includes, but
is not limited to, the use of a hardened hydrophilic colloid layer in a photographic
element as either a photosensitive layer, an underlayer, an overcoat layer or a dyed
layer.
[0028] A photosensitive layer typically comprises silver halide dispersed in a hydrophilic
colloid binder. The silver halide is optionally chemically and optionally spectrally
sensitized as known in the art and the layer may contain other adjuvants such as dyes,
stabilizers, development agents, color coupling agents, toners, surfactants, and the
like.
[0029] An underlayer typically comprises a hydrophilic colloid layer with an optional dye
dispersed therein. The overcoat is typically coated supra to the photosensitive layer
as protection from abrasion and the like and may comprise dyes, surfactants, or other
adjuvants as known in the art.
[0030] The term "hydrophilic colloid" or its homologues "gelatin" and "proteinaceous material"
are used herein to refer to the protein substances which are derived from collagen.
In the context of the present invention "hydrophilic colloid" also refers to substantially
equivalent substances such as synthetic analogues of gelatin. Generally gelatin is
classified as alkaline gelatin, acidic gelatin or enzymatic gelatin. Alkaline gelatin
is obtained from the treatment of collagen with a base such as calcium hydroxide,
for example. Acidic gelatin is that which is obtained from the treatment of collagen
in acid such as, for example, hydrochloric acid and enzymatic gelatin is generated
with a hydrolase treatment of collagen. The teachings of the present invention are
not restricted to gelatin type or the molecular weight of the gelatin.
[0031] The film support for the emulsion layers used in the novel process may be any suitable
transparent plastic. For example, the cellulosic supports, e.g. cellulose acetate,
cellulose triacetate, cellulose mixed esters, etc. may be used. Polymerized vinyl
compounds, e.g., copolymerized vinyl acetate and vinyl chloride, polystyrene, and
polymerized acrylates may also be mentioned. Preferred films include those formed
from the polyesterification product of a dicarboxylic acid and a dihydric alcohol
made according to the teachings of Alles, U.S. Patent 2,779,684 and the patents referred
to in the specification thereof. Other suitable supports are the polyethylene terephthalate/isophthalates
of British Patent 766,290 and Canadian Patent 562,672 and those obtainable by condensing
terephthalic acid and dimethyl terephthalate with propylene glycol, diethylene glycol,
tetramethylene glycol or cyclohexane 1,4-dimethanol (hexahydro-p-xylene alcohol).
The films of Bauer et al., U.S. Patent 3,052,543 may also be used. The above polyester
films are particularly suitable because of their dimensional stability.
[0032] Meltpoint was measured by observing the melting temperature in 0.1 M NaOH for a hardened
gelatin coating. Melt time was measured by observing the time, in minutes, required
for the hardened layer to dissolve in a 1.5% NaOH solution at 50
oC. Water absorption was determined by weighing a dry 10cmx10cm film sample, submerging
the sample for 30 minutes in an aqueous solution buffered to a pH of approximately
10.0 by a borate buffer, allowing the excess water on the surface to drain off of
the film, and weighing the swollen film. Water absorption (WA) is defined as the weight
gain per surface unit or as a percentage according the the equation:

Wet gouge is a measure of the strength of the binder under processing conditions
and is measured by dragging a stylus which increases force with distance over a film
submerged in a mock developer solution comprising all ingredients except hydroquinone
and phenidone. The wet gouge is then determined as the distance traversed by the stylus
prior to destruction of the film surface. A larger distance indicates a stronger matrix.
SYNTHESIS OF HARDENERS OF FORMULA I
1,3-bis-(dimethylcarbamoyl)-imidazolium chloride (I-14)
[0033] 10.75 g (0.1 mole) dimethylcarbamoyl chloride are added dropwise with stirring to
a solution of 6.8 g. (0.1 mole) imidazole and 11 g. triethylamine in 70 ml dry acetone.
On warming, triethyl- ammonium chloride precipitates. After 5 hours standing at room
temperature, the reaction mixture is filtered and 10.75 g. dimethyl- carbamoyl chloride
is added again to the filtrate. After 2 days at room temperature, the crystalline
product is filtered off, washed with acetone, and vacuum dried.
1,3-bis-(morpholinocarbonyl)-imidazolium chloride (I-20)
[0034] 7.5 g. (0.05 mole) morpholino-4-carbonyl chloride are added to a solution of 3.4
g. (0.05 mole) imidazole and 5.5 g. triethylamine in 60 ml dry tetrahydrofuran. The
mixture is stirred 30 minutes at 50
oC. The precipitated triethyl-ammonium chloride is filtered off. An additional 7.5
g morpholino-4-carbonyl chloride are added to the filtrate. After standing 2 days
at room temperature, crystals of 1,3-bis-(morpholinocarbonyl)-imidazolium chloride
separate, are filtered off, washed with ether and vacuum dried.
[0035] Standard organic reaction synthetic procedures can be employed as known in the art.
While other synthetic procedures may be employed, the hardeners of Formula I were
prepared in a consistent manner according to the following procedure. The appropriate
N-substituted imidazol (0.2 mol) and the appropriate carbonyl chloride, or thiocarbomyl
chloride (0.2 mol) were dissolved in 100 ml. of acetone and refuxed for approximately
2 hrs. The reaction mixture was cooled to precipate the product which was then recovered
by filtration. The filtrate was rinsed with acetone and dried in a dessicator at ambient
conditions.
1-decyl-3-dimethylcarbamoylimidazolium bromide (I-1)
[0036] To 13.6 gm (0.2 mole) of imidazole (Aldrich Chemical Co., Milwaukee, WI, 99%) and
20.2 gm of triethylamine (Aldrich, 99%) in 100 ml dry acetone (Fisher Scientific Co.,
Pittsburgh, PA) in a magnetically stirred 250 ml round bottom flask under dry nitrogen
was added 21.5 gm (0.2 mole) dimethylcarbamyl chloride (Aldrich, 99%) dropwise over
a 20 min. period from a side-arm pressure equalizing addition funnel. A white precipitate
formed during the addition under conditions of mild exothermicity. The addition funnel
was replaced with a reflux condensor and the reaction refluxed for a further one hour.
After cooling to room temperature, the precipitate was isolated by Buchner filtration
onto Wattman #1 paper, rinsed on the filter with acetone, and discarded. The combined
filtrate and rinse acetone solution was divided into two equal parts, each containing
0.1 mole of 1-dimethylcarbamoylimidazole. To one of these parts was added 22.1 gm
(0.1 mole) of 1-bromodecane (Aldrich 98%) and the solution refluxed for seven hours
under dry nitrogen. The acetone was evaporated at water aspirator vacuum in a rotoevaporator
to the point where two layers formed. The upper layer contained largely unreacted
bromodecane and the lower yielded 12 gm (0.043 mole for a 21.4% theorical yield) of
the imidazolium salt as a waxy solid upon cooling to 5
oC. The purity and identity of this product was confirmed by proton and carbon NMR
in deuterium oxide solution.
SYNTHETIC PROCEDURE FOR HARDENERS OF FORMULA II
2,4-dichloro-6-hydroxy-1,3,5-triazine, sodium salt (II-1)
[0037] 1215 g of sodium phosphate tribasic was added to 70000 g. of water. The mixure was
cooled to 24
oC and stirred until the sodium phosphate dissolved. 5000 g. of cyanuric chloride was
added slowly. The pH was maintained between 8.0 and 9.5 with 1 N NaOH. After reaction
is complete the pH is adjusted to approximately 7.8. The pH should not be allowed
to drop below 7.7 at any time during the preparation or storage since rapid decomposition
will commence.
EXAMPLE 1
[0038] A photographic emulsion was prepared as known in the art. The emulsion comprised
tabular silver halide grains and 70 grams of gelatin per mole of silver halide. The
emulsion was coated on a subbed polyethylene terephthalate support to a silver coating
weight of approximately 4.8 g/M². The combinations of hardeners listed in Table 1
were added either as a 2% solution (hardener I) or as a 10% solution (hardener II).
The samples were held for approximately 1 week and analyzed yielding the results provided
in Table 1.
Table 1
Physical Properties of Gelatin Layer Crosslinked with Inventive Hardeners |
Hardener I |
Hardener II |
|
|
Hardener |
Amount |
Hardener |
Amount |
MT |
|
HCHO |
20.0 |
- |
- |
3 |
Control |
HCHO |
30.0 |
- |
- |
15 |
Control |
HCHO |
40.0 |
- |
- |
24 |
Control |
I-14 |
5.0 |
- |
- |
3 |
Control |
I-14 |
10.0 |
- |
- |
6 |
Control |
I-14 |
15.0 |
- |
- |
12 |
Control |
I-14 |
20.0 |
- |
- |
18 |
Control |
- |
- |
II-1 |
5.0 |
3 |
Control |
I-14 |
5.0 |
II-1 |
5.0 |
6 |
Inventive |
I-14 |
10.0 |
II-1 |
5.0 |
12 |
Inventive |
I-14 |
15.0 |
II-1 |
5.0 |
15 |
Inventive |
I-14 |
20.0 |
II-1 |
5.0 |
18 |
Inventive |
- |
- |
II-1 |
15.0 |
6 |
Control |
I-14 |
5.0 |
II-1 |
15.0 |
9 |
Inventive |
I-14 |
10.0 |
II-1 |
15.0 |
12 |
Inventive |
I-14 |
15.0 |
II-1 |
15.0 |
15 |
Inventive |
I-14 |
20.0 |
II-1 |
15.0 |
21 |
Inventive |
- |
- |
II-1 |
20.0 |
6 |
Control |
I-14 |
5.0 |
II-1 |
20.0 |
9 |
Inventive |
I-14 |
10.0 |
II-1 |
20.0 |
12 |
Inventive |
I-14 |
15.0 |
II-1 |
20.0 |
18 |
Inventive |
I-14 |
20.0 |
II-1 |
20.0 |
33 |
Inventive |
Amount of hardener is listed as mmoles of hardener per 200 grams of gelatin. MT represents
the melt time in minutes in 1.5 wt % NaOH at 50
oC. The data demonstrates an increase in the crosslinking of the hydrophilic colloid
binder as indicated by the increased MT observed with combinations of hardeners.
EXAMPLE 2
[0039] An emulsion substantially similar to that used in Example 1 was prepared. Various
hardener levels were added to individual aliquots as recorded in Table 2. The melt
time (MT) and water absorption (WA mg/cm²) were measured after approximately 1 month
and recorded in Table 2.
Table 2
Physical Properties of Gelatin Layer Crosslinked with Inventive Hardeners |
Hardener I |
Hardener II |
|
|
|
Hardener |
Amount |
Hardener |
Amount |
MT |
WA |
|
I-14 |
10.0 |
- |
- |
3 |
.60 |
Control |
I-14 |
20.0 |
- |
- |
9 |
.44 |
Control |
I-14 |
30.0 |
- |
- |
15 |
.39 |
Control |
I-14 |
40.0 |
- |
- |
22 |
.35 |
Control |
- |
- |
II-1 |
10.0 |
3 |
.56 |
Control |
I-14 |
10.0 |
II-1 |
10.0 |
9 |
.42 |
Inventive |
I-14 |
20.0 |
II-1 |
10.0 |
18 |
.38 |
Inventive |
I-14 |
30.0 |
II-1 |
10.0 |
24 |
.35 |
Inventive |
I-14 |
40.0 |
II-1 |
10.0 |
33 |
.31 |
Inventive |
- |
- |
II-1 |
20.0 |
15 |
.41 |
Control |
I-14 |
10.0 |
II-1 |
20.0 |
18 |
.38 |
Inventive |
I-14 |
20.0 |
II-1 |
20.0 |
22 |
.37 |
Inventive |
I-14 |
30.0 |
II-1 |
20.0 |
28 |
.33 |
Inventive |
I-14 |
40.0 |
II-1 |
20.0 |
37 |
.31 |
Inventive |
- |
- |
II-1 |
30.0 |
24 |
.39 |
Control |
I-14 |
10.0 |
II-1 |
30.0 |
25 |
.37 |
Inventive |
I-14 |
20.0 |
II-1 |
30.0 |
34 |
.32 |
Inventive |
I-14 |
30.0 |
II-1 |
30.0 |
34 |
.32 |
Inventive |
I-14 |
40.0 |
II-1 |
30.0 |
42 |
.30 |
Inventive |
- |
- |
II-1 |
40.0 |
37 |
.39 |
Control |
I-14 |
10.0 |
II-1 |
40.0 |
33 |
.35 |
Inventive |
I-14 |
20.0 |
II-1 |
40.0 |
43 |
.35 |
Inventive |
I-14 |
30.0 |
II-1 |
40.0 |
46 |
.34 |
Inventive |
I-14 |
40.0 |
II-1 |
40.0 |
49 |
.31 |
Inventive |
The data of Table 3 indicates that the amount of water absorbed is lower when the
combination of hardeners are used and the crosslinking is higher as indicated by the
melt time.
EXAMPLE 3
[0040] An emulsion substantially similar to that described in Example 1 was prepared. The
hardener levels recorded in Table 3. In Table 3 %WP represents the amount of water
absorbed as a percentage of the total weight of the film; MT is the melt time in minutes;
WG is wet gouge in grams.
Table 3
Physical Properties of Gelatin Layer Crosslinked with Inventive Hardeners |
Hardener I |
Hardener II |
|
|
|
Hardener |
Amount |
Hardener |
Amount |
%WA |
MT |
WG |
II-14 |
10.0 |
II-1 |
4.1 |
14 |
7 |
4 |
II-14 |
10.0 |
- |
- |
16 |
4 |
0 |
- |
- |
II-1 |
4.1 |
17 |
3 |
0 |
II-14 |
20.0 |
II-1 |
8.2 |
13 |
19 |
3.5 |
II-14 |
20.0 |
- |
- |
15 |
13 |
1.5 |
- |
- |
II-1 |
8.2 |
15 |
3 |
0 |
In every case the film crosslinking is higher, as indicated by the MT or WG, and the
water absorption is lower, as indicated by %WA when the combination of hardeners is
employed.
[0041] The combined results of Examples 1-3 indicates that the additive effect of the hardeners
can be appreciated without degradation of either.
1. A photographic element comprising at least one hydrophilic colloid layer; at least
one said hydrophilic colloid layer is hardened with at least one compound chosen from:

wherein:
Y¹ is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen
from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered
ring; -L¹CR⁸CH₂, or a polymer thereof; -C(Y⁴)E; or

E is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; -OR⁹; -CN;
the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
L¹ is a linking group;
R¹ is hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted
aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; -OR¹⁰;
halogen; nitro, carboxyl, mercapto; alkylamino or substituted alkylamino of 1 to 24
carbons; the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
R² and R³ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; R² and R³ independently may represent, or be taken together
to represent, the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered
ring;
R⁴ and R⁵ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl or substituted aryl of 6 to 24 carbons; aralkyl or substituted aralkyl
of 7 to 25 carbons; nitro; carboxyl; mercapto; -OR¹¹; halogen; alkylamino or substituted
alkylamino of 1 to 24 carbons;the atoms chosen from C, N, O, and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring;
R⁴ and R⁵ may be taken together to represent the atoms chosen from C, N, O, and
S necessary to form a substituted or unsubstituted 5- or 6-membered ring;
X- is a counterion;
Y², Y³ and Y⁴ independently represent O or S;
R⁶ and R⁷ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; the atoms chosen from C, N, O and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring;
R⁶ and R⁷ may be taken together to represent the atoms chosen from C, N, O and S
necessary to form a substituted or unsubstituted 5- or 6-member ring;
R⁸ represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; C(O)R²⁸;
-CN; aryl or substituted aryl of 6 to 24 carbons;
R⁹ represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; aryl of substituted
aryl of 6 to 24 carbons;
R¹⁰ and R¹¹ independently represent hydrogen, an alkyl, or substituted alkyl, of
1 to 5 carbons;
R²⁸ represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or
substituted alkoxy of 1 to 24 carbons; amine; alkylamine or substituted alkylamine
of 1 to 24 carbons;
and at least one hydrophilic colloid layer is hardened by at least one compound defined
by:

wherein:
at least two of R¹², R¹³ and R¹⁴ are independently chosen from the groups represented
by halogen, preferably Cl or Br;
one of R¹², R¹³ or R¹⁴ may represent hydrogen; alkyl, or substituted alkyl, of 1
to 24 carbons; halogen; -OR²¹; -NR²²R²³; -OM; a divalent linking group to another
triazine; sulfonamide; substituted or unsubstituted alkylether of 1 to 20 carbons;
polyethylene oxide of 2 to 40 carbons; -(OR²⁴)xR²⁵; -L²CR²⁶CH₂ or a polymer thereof;
R¹⁵ and R¹⁶ independently represent sodium; potassium; ammonium; alkyl ammonium
or substituted alkyl ammonium of 1 to 20 carbons; hydrogen; alkyl or substituted alkyl
of 1 to 20 carbons;
R¹⁷ and R¹⁸ independently represent sodium; potassium; ammonium; hydrogen; alkyl
ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl
or 1 to 20 carbons;
R¹⁹ and R²⁰ independently represent sodium; potassium; hydrogen; ammonium; alkyl
ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl
or 1 to 20 carbons;
R²¹ represents hydrogen; alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl
or substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 40
carbons; aralkyl or substituted aralkyl of 7 to 41 carbons; alkylthioether or substituted
alkylthioether of 1 to 40 carbons;
R²² and R²³ independently represent hydrogen; alkyl or substituted alkyl of 1 to
20 carbons; aryl or substituted aryl of 6 to 20 carbons; alkylether or substituted
alkylether of 1 to 20 carbons; arylether or substituted arylether of 6 to 20 carbons;
alkylthioether or substituted alkylthioether of 1 to 20 carbons; arylthioether or
substituted arylthioether of 6 to 20 carbons; sulfonyl; alkylsulfonyl of 1 to 20 carbons;
R²⁴ represents an ethylene or substituted ethylene;
R²⁵ represents an alkyl or substituted alkyl of 1 to 20 carbons; an ether or substituted
ether of 1 to 20 carbons;
R²⁶ represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
L² is a chemical linkage;
M is a counterion;
x is an integer from 1 to 24.
2. The photographic element recited in Claim 1 wherein in at least one compound:
Y² represents O;
R¹ is hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted
aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; halogen;
R² and R³ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; R² and R³ independently may represent, or be taken together
to represent, the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered
ring;
R² and R³ may be taken together to represent the atoms chosen from C, N, O, and
S necessary to form a substituted or unsubstituted 5- or 6-membered ring;
Y¹ is

wherein Y³ is O;
R⁶ and R⁷ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; or the atoms chosen front C, N, O and S necessary to
form a substituted or unsubstituted 5- or 6-membered ring;
R⁶ and R⁷ may be taken together to represent the atoms chosen from C, N, O and S
necessary to form a substituted or unsubstituted 5- or 6-member ring.
3. The photographic element recited in Claim 2 wherein at least one compound is chosen
from the set consisting of:
4. The photographic element recited in Claim 1 wherein in at least one compound:
Y¹ is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; the atoms chosen from C, N, O, and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring; -L¹CR⁸CH₂, or a polymer thereof;
L¹ is a linking group;
R⁸ represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 3 carbons.
5. The photographic element recited in Claim 4 wherein at least one compound is chosen
from the set consisting of:
6. The photographic element recited in Claim 1 wherein at least two of R¹², R¹³ and R¹⁴
are halogen;
one of R¹², R¹³ or R¹⁴ is -OR²¹; -NR²²R²³; -OM; a divalent linking group; sulfonamide;
amino or substituted amino;
R²¹ represents hydrogen, alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl
or substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 10
carbons; aralkyl or substituted aralkyl of 7 to 41 carbons; alkyl thioether or substituted
alkyl thioether of 1 to 40 carbons;
R²² and R²³ independently represent hydrogen; alkyl or substituted alkyl or 1 to
20 carbons; aryl or substituted aryl of 6 to 20 carbons; alkylether or substituted
alkyl ether of 1 to 20 carbons; aryl ether or substituted aryl ether of 6 to 20 carbons;
alkyl thioether or substituted alkyl thioether of 1 to 20 carbons; aryl thioether
or substituted aryl thioether of 6 to 20 carbons; sulfonyl; alkyl sulfonyl of 1 to
20 carbons;
R²⁴ represents an ethyl or substituted ethyl;
R²⁵ represents an alkyl of 1 to 20 carbons or an ether or 1 to 20 carbons;
R²⁶ represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
L² is a chemical linkage;
M is a counterion chosen from sodium, potassium, lithium, calcium, barium, strontium,
ammonium, or alkyl ammonium with 1 to 20 carbons;
x is an integer from 1 to 24.
7. The photographic element recited in Claim 6 wherein at least one compound is chosen
from the set consisting of:
8. A process for forming a photographic element comprising the steps of:
forming at least one liquid photographic emulsion in at least one storage vessel
wherein said liquid photographic emulsion comprises silver halide, hydrophilic colloid
and a solvent;
transporting said liquid photographic emulsion to an interface region; adding at least
one compound defined by

wherein:
Y¹ is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen
from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered
ring; -L¹CR⁸CH₂, or a polymer thereof; -C(Y⁴)E; or

E is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; -OR⁹; -CN;
the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
L¹ is a linking group;
R¹ is hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted
aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; -OR¹⁰;
halogen; nitro, carboxyl, mercapto; alkylamino or substituted alkylamino of 1 to 24
carbons; the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
R² and R³ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; R² and R³ independently may represent, or be taken together
to represent, the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered
ring;
R⁴ and R⁵ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl or substituted aryl of 6 to 24 carbons; aralkyl or substituted aralkyl
of 7 to 25 carbons; nitro; carboxyl; mercapto; -OR¹¹; halogen; alkylamino or substituted
alkylamino of 1 to 24 carbons;the atoms chosen from C, N, O, and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring;
R⁴ and R⁵ may be taken together to represent the atoms chosen from C, N, O, and
S necessary to form a substituted or unsubstituted 5- or 6-membered ring;
X- is a counterion;
Y², Y³ and Y⁴ independently represent O or S;
R⁶ and R⁷ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; the atoms chosen from C, N, O and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring;
R⁶ and R⁷ may be taken together to represent the atoms chosen from C, N, O and S
necessary to form a substituted or unsubstituted 5- or 6-member ring;
R⁸ represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; -C(O)R²⁸;
-CN; aryl or substituted aryl of 6 to 24 carbons;
R⁹ represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; aryl of substituted
aryl of 6 to 24 carbons;
R¹⁰ and R¹¹ independently represent hydrogen, an alkyl, or substituted alkyl, of
1 to 5 carbons;
R²⁸ represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or
substituted alkoxy of 1 to 24 carbons; amine; alkylamine or substituted alkylamine
of 1 to 24 carbons; and at least one compound defined by

wherein:
at least two of R¹², R¹³ and R¹⁴ are independently chosen from the groups represented
by halogen, preferably Cl or Br;
one of R¹², R¹³ or R¹⁴ may represent hydrogen; alkyl, or substituted alkyl, of 1
to 24 carbons; halogen; -OR²¹; -NR²²R²³; -OM; a divalent linking group to another
triazine; sulfonamide; substituted or unsubstituted alkylether of 1 to 20 carbons;
polyethylene oxide of 2 to 40 carbons; -(OR²⁴)xR²⁵; -L²CR²⁶CH₂ or a polymer thereof;
R¹⁵ and R¹⁶ independently represent sodium; potassium; ammonium; alkyl ammonium
or substituted alkyl ammonium of 1 to 20 carbons; hydrogen; alkyl or substituted alkyl
of 1 to 20 carbons;
R¹⁷ and R¹⁸ independently represent sodium; potassium; ammonium; hydrogen; alkyl
ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl
or 1 to 20 carbons;
R¹⁹ and R²⁰ independently represent sodium; potassium; hydrogen; ammonium; alkyl
ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl
or 1 to 20 carbons;
R²¹ represents hydrogen; alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl
or substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 40
carbons; aralkyl or substituted aralkyl of 7 to 41 carbons; alkylthioether or substituted
alkylthioether of 1 to 40 carbons;
R²² and R²³ independently represent hydrogen; alkyl or substituted alkyl of 1 to
20 carbons; aryl or substituted aryl of 6 to 20 carbons; alkylether or substituted
alkylether of 1 to 20 carbons; arylether or substituted arylether of 6 to 20 carbons;
alkylthioether or substituted alkylthioether of 1 to 20 carbons; arylthioether or
substituted arylthioether of 6 to 20 carbons; sulfonyl; alkylsulfonyl of 1 to 20 carbons;
R²⁴ represents an ethylene or substituted ethylene;
R²⁵ represents an alkyl or substituted alkyl of 1 to 20 carbons; an ether or substituted
ether of 1 to 20 carbons;
R²⁶ represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
L² i s a chemical linkage;
M is a counterion;
x is an integer from 1 to 24;
mixing said liquid photographic emulsion with said compound defined by Formula
I and said compound defined by Formula II thereby forming a coating solution;
transporting said coating solution to a coater;
coating said coating solution on a substrate thereby forming a liquid layer; removing
said solvent from said liquid layer to form a dry coated layer.
9. The process for forming a photographic element recited in Claim 8 wherein in at least
one compound:
Y² represents O;
R¹ is hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted
aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; halogen;
R² and R³ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; or R² and R³ independently may represent, or be taken
together to represent, the atoms chosen from C, N, O and S necessary to form a 5-
or 6-membered ring;
R² and R³ may be taken together to represent the atoms chosen from C, N, O, and
S necessary to form a substituted or unsubstituted 5- or 6-membered ring;
Y¹ is

wherein Y3 is O;
R⁶ and R⁷ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; the atoms chosen from C, N, O and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring;
R⁶ and R⁷ may be taken together to represent the atoms chosen from C, N, O and S
necessary to form a substituted or unsubstituted 5- or 6-member ring.
10. The process for forming a photographic element recited in Claim 9 wherein at least
one compound is chosen from the set consisting of:
11. The process for forming a photographic element recited in Claim 8 wherein in at least
one compound:
Y¹ is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; the atoms chosen from C, N, O, and S necessary to form a substituted
or unsubstituted 5- or 6-membered ring; -L¹ CR⁸CH₂, or a polymer thereof;
L¹ is a linking group;
R⁸ represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 3 carbons.
12. The process for forming a photographic element recited in Claim 11 wherein at least
one compound is chosen from the set consisting of:
13. The process for forming a photographic element recited in Claim 8 wherein in at least
one compound:
at least two of R¹², R¹³ and R¹⁴ are halogen;
one of R¹², R¹³ or R¹⁴ is -OR²¹; -NR²²R²³; -OM; a divalent linking group; sulfonamide;
amino or substituted amino;
R²¹ represents hydrogen, alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl
or substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 10
carbons; aralkyl or substituted aralkyl of 7 to 41 carbons; alkyl thioether or substituted
alkyl thioether of 1 to 40 carbons;
R²² and R²³ independently represent hydrogen; alkyl or substituted alkyl or 1 to
20 carbons; aryl or substituted aryl of 6 to 20 carbons; alkylether or substituted
alkyl ether of 1 to 20 carbons; aryl ether or substituted aryl ether of 6 to 20 carbons;
alkyl thioether or substituted alkyl thioether of 1 to 20 carbons; aryl thioether
or substituted aryl thioether of 6 to 20 carbons; sulfonyl; alkyl sulfonyl of 1 to
20 carbons;
R²⁴ represents an ethyl or substituted ethyl;
R²⁵ represents an alkyl of 1 to 20 carbons or an ether or 1 to 20 carbons;
R²⁶ represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
L² is a chemical linkage;
M is a counterion chosen from sodium, potassium, lithium, calcium, barium, strontium,
ammonium, or alkyl ammonium with 1 to 20 carbons;
x is an integer from 1 to 24.
15. A combination of ingredients for crosslinking a hydrophilic colloid comprising at
least one compound chosen from:

wherein:
Y¹ is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen
from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered
ring; -L¹CR⁸CH₂, or a polymer thereof; -C(Y⁴)E; or

E is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl,
of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; -OR⁹; -CN;
the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
L¹ is a linking group;
R¹ is hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted
aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; -OR¹⁰;
halogen; nitro, carboxyl, mercapto; alkylamino or substituted alkylamino of 1 to 24
carbons; the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted
5- or 6-membered ring;
R² and R³ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; R² and R³ independently may represent, or be taken together
to represent, the atoms chosen from C, N, O and S necessary to form a 5- or 6-membered
ring;
R⁴ and R⁵ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl or substituted aryl of 6 to 24 carbons; aralkyl or substituted aralkyl
of 7 to 25 carbons; nitro; carboxyl; mercapto; -OR¹¹; halogen; alkylamino or substituted
alkylamino of 1 to 24 carbons;the atoms chosen from C, N, O, and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring;
R⁴ and R⁵ may be taken together to represent the atoms chosen from C, N, O, and
S necessary to form a substituted or unsubstituted 5- or 6-membered ring;
X- is a counterion;
Y², Y³ and Y⁴ independently represent O or S;
R⁶ and R⁷ independently represent hydrogen; alkyl, or substituted alkyl, of 1 to
24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted
aralkyl, of 7 to 25 carbons; the atoms chosen from C, N, O and S necessary to form
a substituted or unsubstituted 5- or 6-membered ring;
R⁶ and R⁷ may be taken together to represent the atoms chosen from C, N, O and S
necessary to form a substituted or unsubstituted 5- or 6-member ring;
R⁸ represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; -C(O)R²⁸;
-CN; aryl or substituted aryl of 6 to 24 carbons;
R⁹ represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; aryl of substituted
aryl of 6 to 24 carbons;
R¹⁰ and R¹¹ independently represent hydrogen, an alkyl, or substituted alkyl, of
1 to 5 carbons;
R²⁸ represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or
substituted alkoxy of 1 to 24 carbons; amine; alkylamino or substituted alkylamine
of 1 to 24 carbons;
and at least one hydrophilic colloid layer is hardened by at least one compound defined
by:

wherein:
at least two of R¹², R¹³ and R¹⁴ are independently chosen from the groups represented
by halogen, preferably Cl or Br;
one of R¹², R¹³ or R¹⁴ may represent hydrogen; alkyl, or substituted alkyl, of 1
to 24 carbons; halogen; -OR²¹; -NR²²R²³; -OM; a divalent linking group to another
triazine; sulfonamide; substituted or unsubstituted alkylether of 1 to 20 carbons;
polyethylene oxide of 2 to 40 carbons; -(OR²⁴)xR²⁵; -L²CR²⁶CH₂ or a polymer thereof;
R¹⁵ and R¹⁶ independently represent sodium; potassium; ammonium; alkyl ammonium
or substituted alkyl ammonium of 1 to 20 carbons; hydrogen; alkyl or substituted alkyl
of 1 to 20 carbons;
R¹⁷ and R¹⁸ independently represent sodium; potassium; ammonium; hydrogen; alkyl
ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl
or 1 to 20 carbons;
R¹⁹ and R²⁰ independently represent sodium; potassium; hydrogen; ammonium; alkyl
ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl
or 1 to 20 carbons;
R²¹ represents hydrogen; alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl
or substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 40
carbons; aralkyl or substituted aralkyl of 7 to 41 carbons; alkylthioether or substituted
alkylthioether of 1 to 40 carbons;
R²² and R²³ independently represent hydrogen; alkyl or substituted alkyl of 1 to
20 carbons; aryl or substituted aryl of 6 to 20 carbons; alkylether or substituted
alkylether of 1 to 20 carbons; arylether or substituted arylether of 6 to 20 carbons;
alkylthioether or substituted alkylthioether of 1 to 20 carbons; arylthioether or
substituted arylthioether of 6 to 20 carbons; sulfonyl; alkylsulfonyl of 1 to 20 carbons:
R²⁴ represents an ethylene or substituted ethylene;
R²⁵ represents an alkyl or substituted alkyl of 1 to 20 carbons; an ether or substituted
ether of 1 to 20 carbons;
R²⁶ represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons;
L² is a chemical linkage;
M is a counterion;
x is an integer from 1 to 24.