CA1047822A - Method of producing a hardened gelatin layer - Google Patents
Method of producing a hardened gelatin layerInfo
- Publication number
- CA1047822A CA1047822A CA211,252A CA211252A CA1047822A CA 1047822 A CA1047822 A CA 1047822A CA 211252 A CA211252 A CA 211252A CA 1047822 A CA1047822 A CA 1047822A
- Authority
- CA
- Canada
- Prior art keywords
- halopyridinium
- compound
- aqueous
- gelatin
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/30—Hardeners
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Pyridine Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
A B S T R A C T
of the Disclosure METHOD OF PRODUCING A HARDENED GELATIN LAYER
This invention relates to the hardening of gelatin layers. The gelatin is heated with an aqueous solution of a 2-halogeno pyridinium compound.
of the Disclosure METHOD OF PRODUCING A HARDENED GELATIN LAYER
This invention relates to the hardening of gelatin layers. The gelatin is heated with an aqueous solution of a 2-halogeno pyridinium compound.
Description
10471~Z;~
According to the present invention there is provided a method of producing a hardened gelatin layer which com-prises treating an aqueous gelatin solution with an aqueous solution of a compound of the formula (I) j _ ~ Z
where X is a halogen atom, Y is a hydrogen or a halogen atom, Z is an anion and R is an alkyl, aralkyl, or aroylalkyl group, or a group of the formula X
(II) z ~ ~ (C~2)n where X, Y and Z have the meanings assigned to them above and n is an integer of 2 to 12.
When the compound of use in the present invention is a mono(2-halopyridinium) salt, Y is preferably a halogen atom in the 2 or 4 positions.
; 1-5 Further in regard to the mono(2-halopyridinium) salt particularly useful compounds are those wherein R is methyl, phenylethyl and benzoylmethyl.
According to the present invention there is provided a method of producing a hardened gelatin layer which com-prises treating an aqueous gelatin solution with an aqueous solution of a compound of the formula (I) j _ ~ Z
where X is a halogen atom, Y is a hydrogen or a halogen atom, Z is an anion and R is an alkyl, aralkyl, or aroylalkyl group, or a group of the formula X
(II) z ~ ~ (C~2)n where X, Y and Z have the meanings assigned to them above and n is an integer of 2 to 12.
When the compound of use in the present invention is a mono(2-halopyridinium) salt, Y is preferably a halogen atom in the 2 or 4 positions.
; 1-5 Further in regard to the mono(2-halopyridinium) salt particularly useful compounds are those wherein R is methyl, phenylethyl and benzoylmethyl.
- 2 -Particularly preferred compounds are those wherein X is c'nlorine or bromine.
When the compound Or use in the present invention is a bis(2-halopyridinium) salt preferred compounds have the S for~ula (III) ~ ~ -(C~2)n N ~ l 2 Z
where X and n have the meanings assigned to them above.
In compounds of the above formula (III) it is preferred that n is 3-8.
Particularly preferred compounds are compounds of ~~
the above formula (III) wherein X is a chlorine atom.
Examples of anions are chloride, perchlorate and fluoro-borate. The preferred anions since they render the compounds more stable are perchlorate and fluoroborate.
The method of the present invention finds particular use as a step in the preparation of photographic silver halide materials and according to a preferred embodi~ent of the present invention in a process for the production of a gelatino silver halide photographic material there is provided the steps of treating an aaueous ~elatino silver halide emulsion with an aqueous solution of a co~pound of fo~nula I or III and then coating the aqueous emulsion as a layer on a photobase.
Prele-~6bly rom 0.1 g -to 50 g o~ th~ com~ound of formuia I per 100 g of gelatin in tlle solution are used in the method of the present inventlon, The compowlds of formula(I)may be prcpared by quaternizing a halopyridine with the appropriate alkylating agent, Compounds of for~ula(III)may be prepared by quaternizing pyridine wi'ch an a ,~ dihaloallsane, oxidising with alkaline potassium ferricyanide and then treating the bis-pyridone so formed with phosphoryl chloride, ~ .
2-Chloropyridine 6~ and 6,5 g dimethyl sulphate were mixed and warmed on a ~Jater bath until a vigorous reaction began, When the initial reaction 'nad subsided, the mlxture was heated on a 3team bath for 1 hour gi~ing a yellow viscous product. Any excess dimethyl ~ulphate was removed by washing with ether then the residue was dissolved in a minimum of cold waterD A solution of 10 g sodium perchlorate in 10 ml water was added slowiy with stirring and the white precipitate which formed was filtered, The product was suspended in 50 ml cold water, filtered and then dried over P205, ~,p, 199 - 202, Yields 4,2g, ... ..
~ Preparation of 1,l'trimethylene-bis-(2-chloropyridinium ; perchlorate).
1,3 Di-bromopropane 20,2 g and 17 g pyrldine were warmed carefully on a water-bath, (A cold-water bath was needed to control the reaction once it had begun).
After the reaction had subsided the mixture was heated 1047~Z
for 15 mins, orl a steam-bath then cooled, dry ether added and the solid filteredO The product was recrystallised from eth-Inol to give 24,~ g l,l'-trimethylene bis-pyridinium chloride m.p, 241-3, 18 g of the sa]t was dissolved in a srnall quantity of water and mi~ed with a saturated solution of 66 g K3 Fe(CN)6 in water. The solution was cooled in ice-water and 60 ml of 40% NaOH added dropwise keeping temperature at about 10C. The mixture was left overnight at room 10 - temperature then neutralised ~Jith acetic acid and extracted with chlorofor~, The dried chloroform solution ~as evaporated and -the residue recrystallised from benzene to give 4~8 g l,l'trimethylene bis(2-pyridone), m.p. 132, 4,6 g of the bis-pyridone and 30 g phosphoryl chloride was refluxed for 2 hours, then the excess POCl3 removed under vaccum, The solid was dissolved in 50 ml cold water and a solution of lO g NaC104 in lO ml water added with stirringO The solid ~las filtered, washed wi-th water and recrystallised from acetone/water, adding a little ether to induce crystallisation, Yield of l,l'trlmethylene bis(2-chloropyridinium~
perchlorate 4,9 g m.p, 282~3, The following compounds of formula I were prepared in a mar.rer similar to that used to prepare 2-chloro-1-methyl-pyridinium perchlorate which ~s hereir~after referred to as co~pound l, , , . . . ., . , . .. , .. , .. . . . . . . ... . .. . . . . , ., ~ ...
- , ~ .
, - -- Conpouncl 2 2-bror~o-1-me-thyl pyridinium perchlorate
When the compound Or use in the present invention is a bis(2-halopyridinium) salt preferred compounds have the S for~ula (III) ~ ~ -(C~2)n N ~ l 2 Z
where X and n have the meanings assigned to them above.
In compounds of the above formula (III) it is preferred that n is 3-8.
Particularly preferred compounds are compounds of ~~
the above formula (III) wherein X is a chlorine atom.
Examples of anions are chloride, perchlorate and fluoro-borate. The preferred anions since they render the compounds more stable are perchlorate and fluoroborate.
The method of the present invention finds particular use as a step in the preparation of photographic silver halide materials and according to a preferred embodi~ent of the present invention in a process for the production of a gelatino silver halide photographic material there is provided the steps of treating an aaueous ~elatino silver halide emulsion with an aqueous solution of a co~pound of fo~nula I or III and then coating the aqueous emulsion as a layer on a photobase.
Prele-~6bly rom 0.1 g -to 50 g o~ th~ com~ound of formuia I per 100 g of gelatin in tlle solution are used in the method of the present inventlon, The compowlds of formula(I)may be prcpared by quaternizing a halopyridine with the appropriate alkylating agent, Compounds of for~ula(III)may be prepared by quaternizing pyridine wi'ch an a ,~ dihaloallsane, oxidising with alkaline potassium ferricyanide and then treating the bis-pyridone so formed with phosphoryl chloride, ~ .
2-Chloropyridine 6~ and 6,5 g dimethyl sulphate were mixed and warmed on a ~Jater bath until a vigorous reaction began, When the initial reaction 'nad subsided, the mlxture was heated on a 3team bath for 1 hour gi~ing a yellow viscous product. Any excess dimethyl ~ulphate was removed by washing with ether then the residue was dissolved in a minimum of cold waterD A solution of 10 g sodium perchlorate in 10 ml water was added slowiy with stirring and the white precipitate which formed was filtered, The product was suspended in 50 ml cold water, filtered and then dried over P205, ~,p, 199 - 202, Yields 4,2g, ... ..
~ Preparation of 1,l'trimethylene-bis-(2-chloropyridinium ; perchlorate).
1,3 Di-bromopropane 20,2 g and 17 g pyrldine were warmed carefully on a water-bath, (A cold-water bath was needed to control the reaction once it had begun).
After the reaction had subsided the mixture was heated 1047~Z
for 15 mins, orl a steam-bath then cooled, dry ether added and the solid filteredO The product was recrystallised from eth-Inol to give 24,~ g l,l'-trimethylene bis-pyridinium chloride m.p, 241-3, 18 g of the sa]t was dissolved in a srnall quantity of water and mi~ed with a saturated solution of 66 g K3 Fe(CN)6 in water. The solution was cooled in ice-water and 60 ml of 40% NaOH added dropwise keeping temperature at about 10C. The mixture was left overnight at room 10 - temperature then neutralised ~Jith acetic acid and extracted with chlorofor~, The dried chloroform solution ~as evaporated and -the residue recrystallised from benzene to give 4~8 g l,l'trimethylene bis(2-pyridone), m.p. 132, 4,6 g of the bis-pyridone and 30 g phosphoryl chloride was refluxed for 2 hours, then the excess POCl3 removed under vaccum, The solid was dissolved in 50 ml cold water and a solution of lO g NaC104 in lO ml water added with stirringO The solid ~las filtered, washed wi-th water and recrystallised from acetone/water, adding a little ether to induce crystallisation, Yield of l,l'trlmethylene bis(2-chloropyridinium~
perchlorate 4,9 g m.p, 282~3, The following compounds of formula I were prepared in a mar.rer similar to that used to prepare 2-chloro-1-methyl-pyridinium perchlorate which ~s hereir~after referred to as co~pound l, , , . . . ., . , . .. , .. , .. . . . . . . ... . .. . . . . , ., ~ ...
- , ~ .
, - -- Conpouncl 2 2-bror~o-1-me-thyl pyridinium perchlorate
3 2-icdo-1-methyl uyridinium iodide " 4 2,6~dlchloro-1-methyl pyridinium perchlorate 2,6-clibromo-1 methyl pyridinium perchlorate " 6 2,4-dichioro-1-met~yl pyridinium perchlorate " 7 2-chloro-1-(2 phenylethyl) p~Jridinium bromide " 8 2-bromo-I-benzoylmethyl pyridinium bromide 9 1,1'-trimethylene-bis-(2-chloropyridinium perchlorate) " 10 1,1'-octamethylene-b.is-(2-chloropyridinium perchlorate), prepared in a manner similar to that used to prepare compound 9.
`
10 EX~MPLE
The compounds were tested by the scratch resistance method This involves drawing a loaded stylus across a swollen gelatin layer, and determining the minimum weight required to scratch the surface.
~5 The aqueous~gelatin coating solutions were made up . .
as follows:-Gelatin 17.5 g in water 150 ml soaked for 20minutes and melted out at 60 for 10 minutes. The pH
of this gelatin solution was ad~usted to 6.5. Each test compound, 0~00125 moles, was dissolved in ethanol 25 ml~
water 35 ml, and added to separate portions of the .
- ' - .. .. ... ,. . , , , , , . ...
'', 1~47822 gelatin solution, The p~l of the gelatin solu-tions was readJusted to 6.5 and made up -to 250 mls wi-th water, 200 thick coa-tings were made with a doctor bar on film base and dried in a fan assisted drying cabinet withou-t heat, The coatings ~ere kep-t at 22C, 50% ~I and 43C~
6~o RH~ Scratch measurements were r.~ade after ~O minu-tes soaXing in water a-t 20C, The results obtained are sho~m ln the acoomp~nying Table, --~047822 _ __ . .
. .
o U~ ~ o o o o o ~ o U~
~ o O ~J (\J ~ 0 ~ .--1 N 15`\
~
In . ... ~
Q~
~ ISO~ ~
O O O U~ O O O
~ ~ ~ ~ ~ ~ O r-~ o 0~ rt ~ ~ ~ U~ ~U ~ ~ ;t 1 ~`J
_ _ _ ~P
~, OOO'OOC~OOOOO
1~ tl ) O r ~ O O O U~ C~
C~
;l- . , .
~ ~ . . .
~`~
~ ~ b~ .
C~ O O O U~ O O 1~ O O U~
E-~ ~) 1~ C~ O ~ ~ ~ ~
(U ~ ~ ~ 1 ~ . ~ .
_ .
~ , 5 b.O ~
:' . ~.~ O ~ O U~ O O ~ C) O
h P. ~ a~ tD J ~D
~ o~
~¢ ~ . ~ :
.
El O
C~ C~ : .
, .. , , . .. . .. ... .. . . . ... . ~ . . . . .. ~ . , . , .. .. . . ~ . . .
`
10 EX~MPLE
The compounds were tested by the scratch resistance method This involves drawing a loaded stylus across a swollen gelatin layer, and determining the minimum weight required to scratch the surface.
~5 The aqueous~gelatin coating solutions were made up . .
as follows:-Gelatin 17.5 g in water 150 ml soaked for 20minutes and melted out at 60 for 10 minutes. The pH
of this gelatin solution was ad~usted to 6.5. Each test compound, 0~00125 moles, was dissolved in ethanol 25 ml~
water 35 ml, and added to separate portions of the .
- ' - .. .. ... ,. . , , , , , . ...
'', 1~47822 gelatin solution, The p~l of the gelatin solu-tions was readJusted to 6.5 and made up -to 250 mls wi-th water, 200 thick coa-tings were made with a doctor bar on film base and dried in a fan assisted drying cabinet withou-t heat, The coatings ~ere kep-t at 22C, 50% ~I and 43C~
6~o RH~ Scratch measurements were r.~ade after ~O minu-tes soaXing in water a-t 20C, The results obtained are sho~m ln the acoomp~nying Table, --~047822 _ __ . .
. .
o U~ ~ o o o o o ~ o U~
~ o O ~J (\J ~ 0 ~ .--1 N 15`\
~
In . ... ~
Q~
~ ISO~ ~
O O O U~ O O O
~ ~ ~ ~ ~ ~ O r-~ o 0~ rt ~ ~ ~ U~ ~U ~ ~ ;t 1 ~`J
_ _ _ ~P
~, OOO'OOC~OOOOO
1~ tl ) O r ~ O O O U~ C~
C~
;l- . , .
~ ~ . . .
~`~
~ ~ b~ .
C~ O O O U~ O O 1~ O O U~
E-~ ~) 1~ C~ O ~ ~ ~ ~
(U ~ ~ ~ 1 ~ . ~ .
_ .
~ , 5 b.O ~
:' . ~.~ O ~ O U~ O O ~ C) O
h P. ~ a~ tD J ~D
~ o~
~¢ ~ . ~ :
.
El O
C~ C~ : .
, .. , , . .. . .. ... .. . . . ... . ~ . . . . .. ~ . , . , .. .. . . ~ . . .
Claims (10)
1. A method of producing a hardened gelatin layer which comprises treating an aqueous gelatin solution with an aqueous solution of a 2-halopyridinium compound of the formula (I) where X is a halogen atom, Y is a hydrogen or a halogen atom, Z is an anion and R is an alkyl, aralkyl, or aroylalkyl group, or a group of the formula (II) where X, Y and Z have the meanings assigned to them above and n is an integer of 2 to 12.
2. A method according to claim 1 wherein the 2-halopyridinium compound is a mono(2-halopyridinium) salt and Y is a halogen atom in the 2 or 4 positions,
3. A method according to claim 1 wherein the 2-halopyridinium compound is a mono(2-halopyridinium) salt and R is a methyl, phenylethyl or benzoylmethyl group.
4. A method according to claim 1 wherein the 2-halopyridinium compound is a mono(2-halopyridinium) salt and X is a chlorine or bromine atom.
5. A method according to claim 1 wherein the 2-halopyridinium compound is a bis(2-halopyridinium) salt of the formula (III) where X is a halogen atom, Z is an anion and n is an integer of 2 to 12.
6. A method according to claim 5 wherein X is a chlorine atom.
7. A method according to claim 1 wherein Z is a perchlorate or fluoroborate ion.
8. A method according to claim 1 wherein from 0.1 to 50 g of the 2-halopyridinium compound are used per 100 g of gelatin.
9. A method according to claim 1 wherein the aqueous gelatin solution is an aqueous gelatino silver halide emulsion.
10. In a process for the production a gelatino silver halide photographic material the steps of treating an aqueous gelatino silver halide emulsion with an aqueous solution of a 2-halopyridinium compound as defined in claim 1 and then coating the aqueous emulsion as a layer on a photo base.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4766973A GB1462789A (en) | 1973-10-12 | 1973-10-12 | Gelatin hardening agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1047822A true CA1047822A (en) | 1979-02-06 |
Family
ID=10445852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA211,252A Expired CA1047822A (en) | 1973-10-12 | 1974-10-11 | Method of producing a hardened gelatin layer |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5746538B2 (en) |
| BE (1) | BE820958A (en) |
| CA (1) | CA1047822A (en) |
| CH (1) | CH591550A5 (en) |
| DE (1) | DE2448432C2 (en) |
| FR (1) | FR2257929B1 (en) |
| GB (1) | GB1462789A (en) |
| IT (1) | IT1029615B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH537974A (en) * | 1970-07-07 | 1973-06-15 | Ciba Geigy Ag | Use of unsaturated onium compounds to crosslink gelatin |
-
1973
- 1973-10-12 GB GB4766973A patent/GB1462789A/en not_active Expired
-
1974
- 1974-10-10 FR FR7434066A patent/FR2257929B1/fr not_active Expired
- 1974-10-10 DE DE19742448432 patent/DE2448432C2/en not_active Expired
- 1974-10-10 IT IT5345074A patent/IT1029615B/en active
- 1974-10-11 CH CH1370174A patent/CH591550A5/xx not_active IP Right Cessation
- 1974-10-11 JP JP11623774A patent/JPS5746538B2/ja not_active Expired
- 1974-10-11 BE BE149430A patent/BE820958A/en not_active IP Right Cessation
- 1974-10-11 CA CA211,252A patent/CA1047822A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1462789A (en) | 1977-01-26 |
| DE2448432A1 (en) | 1975-04-24 |
| JPS5746538B2 (en) | 1982-10-04 |
| BE820958A (en) | 1975-04-11 |
| JPS5078655A (en) | 1975-06-26 |
| CH591550A5 (en) | 1977-09-30 |
| FR2257929B1 (en) | 1979-06-08 |
| FR2257929A1 (en) | 1975-08-08 |
| DE2448432C2 (en) | 1985-07-11 |
| IT1029615B (en) | 1979-03-20 |
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