EP0671655B1

EP0671655B1 - Improved hardening of hydrophylic colloids with imidazolium and triazine combinations

Info

Publication number: EP0671655B1
Application number: EP19950103145
Authority: EP
Inventors: Ludovic Fodor; Richard R.M. Jones; Reinhold Rueger; Rolf Thomas Weberg; Timothy Donald Weatherill
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1994-03-11
Filing date: 1995-03-06
Publication date: 2000-06-21
Anticipated expiration: 2015-03-06
Also published as: EP0671655A2; JPH07325363A; DE69517541D1; EP0671655A3; DE69517541T2

Description

FIELD OF INVENTION

This invention is related to improved hardeners for proteinaceous materials. More specifically this invention is related to a combination of imidazolium and triazine hardeners for crosslinking a proteinaceous material in a photographic film.

BACKGROUND OF THE INVENTION

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.

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.

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.

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, described, for example, in US-A-3 288 775 or US-A-3 325 287, 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, described, for example, in JP-A-63 135 935 or EP-A-519 329 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. Unfortunatly, the strength of the peptide-coupled binder is insufficient to transit a processor and total binder destruction is frequently observed.

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.

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 imidazoliurn couplers and amine-amine couplers can be used concurrently to provide a strong matrix with low water absorption.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a process for forming a photographic element involving a hardening combination which effectively increases the strength of the matrix.

It is another object of the present invention to provide a process involving a hardening combination which decreases the amount of fluid absorbed and restrained during processing.

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.

These and other advantages, as will be apparent from the description, are provided 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 I as defined below and at least one compound II as defined below;

mixing said liquid photographic emulsion with said compound I and said compound 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,

wherein the time between addition of the hardeners and coating is not so long that crosslinking and decomposition begin to occur;
compound I is a compound of Formula I:

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 form 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 compound II is a compound of Formula II:

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 40 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 ;

and a photographic element obtainable by this process. DETAILED DESCRIPTION OF THE INVENTION

Photographic elements of the present invention comprise at least one binder layer and at least one emulsion layer is crosslinked with at least one compound defined by Formula I and at least one 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 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; 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.

Preferably in a compound of Formula I:

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 from C, N, O and S necessary to form a substituted or unsubstituted 5- or 6-membered ring; and
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.

In other preferred compounds of formula I

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; and
R8: represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 3 carbons.

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.

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; 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; potassium; 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 substituted 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.

Preferably in a compound of Formula II at least two or R¹², R¹³ and R¹⁴ are halogen;
one of R¹², R^13, R¹⁴ is -OR²¹; NR²²R²³; -OM; a divalent linking group; sulfonamide;

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; and
x: is an integer from 1 to 24.

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.

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-phenyioxazole;

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.

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.

Well known to the art is the advantage of using a surfactant to assist in coating a solution. Typically the surfactant is a separate 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 alkylenes, and polyalkyleneoxides.

While not limited thereto, particularly preferred hardeners represented by Formula I are:

The structure of the imidazolium ring is known to exist with a delocalized charge. Comparable resonance structures can be drawn including:

While not limited thereto, particularly preferred hardeners represented by Formula II are:

The hardeners to be used in the present invention react rapidly with a hydrophilic colloid and therefore addition of the hardener to a solution containing hydrophilic colloid must be done with care. This is particularly important in the present invention since the compounds of Formula I and Formula II are incompatible as detailed previously. The hardeners to be used in the present invention are preferably added by injection into the solution supply line which transports coating solution from the holding tanks to the coater. The injection time is dependent on the coater configuration but the time between injection and coating must be sufficiently long to allow thorough mixing. It is also important that the time is not so long that crosslinking and decomposition begin to occur. An addition time of no more than approximately 5 minutes prior to coating is preferred and no more than 2 minutes is most preferred. Injection is accomplished by passing the coating solution past a "T" and adding a second hardener solution to the flow. After the "T" the two solutions are allowed to mix sufficiently.

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. Slide-bead coating is a preferred method.

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.

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.

The hardeners to be used in the present invention are most suitable for crosslinking a hydrophilic colloid layer. The hardeners to be used in the present invention are used for an emulsion layer containing hydrophilic colloid.

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.

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, e.g., abrasion and may comprise dyes, surfactants, or other adjuvants as known in the art.

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.

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 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.

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: %WA = Wet weight - Dry weight (mg)Dry Weight x 100

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)

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)

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.

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 thiocarbaomyl 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)

To 13.6 g (0.2 mole) of imidazole (Aldrich Chemical Co., Milwaukee, WI, 99%) and 20.2 g 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 g (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 g (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 g (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)

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

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.

Physical Properties of Gelatin Layer Crosslinked with Hardeners of formulae I and II
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°C. 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

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.

Physical Properties of Gelatin Layer Crosslinked with Hardeners of formulae I and II
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 (Control)

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.

Physical Properties of Gelatin Layer Crosslinked with Hardeners of formulae II
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.

The combined results of Examples 1-3 indicates that the additive effect of the hardeners can be appreciated without degradation of either.

Claims

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 I as defined below and at least one compound II as defined below;

mixing said liquid photographic emulsion with said compound I and said compound 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,

wherein the time between addition of the hardeners and coating is not so long that crosslinking and decomposition begin to occur;

compound I is a compound of Formula I:
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 form 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 compound II is a compound of Formula II:
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 40 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.
The process recited in Claim 1 wherein in the compound of Formula I:

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 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.
The process recited in Claim 2 wherein the compound of Formula I is chosen from:

and
The process recited in Claim 1 wherein in the compound of Formula I:

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.
The process recited in Claim 4 wherein the compound of Formula I is chosen from:

and
The process recited in Claim 1 wherein in the compound of Formula II at least two or R¹², R¹³ and R¹⁴ are halogen;
one of R¹², R¹³, R¹⁴ is -OR²¹; NR²²R²³; -OM; a divalent linking group; sulfonamide;

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.
The process recited in Claim 6 wherein the compound of Formula II is chosen from:
A photographic element obtainable by the process of claims 1 to 7.