US2263002A - Desensitization of photographic emulsions - Google Patents
Desensitization of photographic emulsions Download PDFInfo
- Publication number
- US2263002A US2263002A US335339A US33533940A US2263002A US 2263002 A US2263002 A US 2263002A US 335339 A US335339 A US 335339A US 33533940 A US33533940 A US 33533940A US 2263002 A US2263002 A US 2263002A
- Authority
- US
- United States
- Prior art keywords
- desensitizing
- desensitization
- diaminotetrazine
- photographic emulsions
- neutral
- 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 - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title description 11
- 238000000586 desensitisation Methods 0.000 title description 3
- 238000000034 method Methods 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- RTKMFQOHBDVEBC-UHFFFAOYSA-N 3-bromo-3-buten-1-ol Chemical compound OCCC(Br)=C RTKMFQOHBDVEBC-UHFFFAOYSA-N 0.000 description 3
- ROPQCOBYNJQQRZ-UHFFFAOYSA-N 5-phenylphenazin-5-ium-1,3-diamine;chloride Chemical compound [Cl-].C12=CC(N)=CC(N)=C2N=C2C=CC=CC2=[N+]1C1=CC=CC=C1 ROPQCOBYNJQQRZ-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 229940075610 mercuric cyanide Drugs 0.000 description 3
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 2
- 229940090898 Desensitizer Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000004905 tetrazines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/32—Latensification; Densensitisation
Definitions
- sions can be desensitized with. for example, mercuric cyanide, plnakryptol yellow and pinakryptol green. It has now been found that 3:6-diamino 1.2.4.5.tetrazines are powerful desensitizersfor Such compounds have the general formula: I
- aralkyl such as phenylethyl, or acyl such as acetyl, propionyl or benzoyl, or other monovalent organic radicals.
- R1, Ra, Re, and R4 are all hydrogen atoms.
- simple 3:6-diaminotetrazine lowers the speed of a fast negative emulsion to less than half its original speed.
- a photographic emulsion particularly a gelatinosilver halide emulsion
- a gelatinosilver halide emulsion is desensitized by treatment' withna substituted. or unsubstituted 3:6- diaminotetrazine.
- the treatment may take place by bathing the emulsion before development may be kept in the form of a stock solution of a one part in one thousand parts of water and such solutlonis also quite stable to light and air. It is a reducing agent and will develop a latent image but the salts are water-soluble solids 5 generally yellow in colour and are not reducing llents. at the concsn
- the red solution of the free base evention indicated does not stain the so vel per.
- The'following table shows the desensitizing effect of the free base in three different concentrafingers or gelatine orfilm and not poisontions compared with t ee known desensitizers.
- stepwedge 1' metre from a 25 watt lamp
- the total desensitization is represented by the figure for the desensitization alone multiplied by six.
- Ra, R: and R4 are selected from the group consis1 ting of hydrogen, alkyl, aryl, aralkyL. and acy High fog density.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
neutral emulsions.
Patented Nov. 18, 1941 UNITED STATES PATENT OFFICE 2,263.00: i A nnsnusmza'ggg gf iggomanarmc Edward a... mu, weaumne, Mamland. assignor to Eastman Kodak Rochester, N. Y., a corporation of New Jersey.
No Drawing. Application May 15, 1040, Serial Compa y.
No. 335,339. In Great Britain August 15, 1989 BOlaims.
sions can be desensitized with. for example, mercuric cyanide, plnakryptol yellow and pinakryptol green. It has now been found that 3:6-diamino 1.2.4.5.tetrazines are powerful desensitizersfor Such compounds have the general formula: I
n. /N=N\ 'R.
ya. N-N- m' where R1, Ra, Ra, Rt-file hydrogen, alhyl, such as methyl. or ethyl, aryl, such as phenyl or tolyl,
aralkyl such as phenylethyl, or acyl such as acetyl, propionyl or benzoyl, or other monovalent organic radicals. The most powerful desensitizing elect appears to be exerted by the simple diamine where R1, Ra, Re, and R4 are all hydrogen atoms. At a concentration as low as .0002 gram per litre. simple 3:6-diaminotetrazine lowers the speed of a fast negative emulsion to less than half its original speed.
According to the present invention, therefore.
- a photographic emulsion, particularly a gelatinosilver halide emulsion, is desensitized by treatment' withna substituted. or unsubstituted 3:6- diaminotetrazine. The treatment may take place by bathing the emulsion before development may be kept in the form of a stock solution of a one part in one thousand parts of water and such solutlonis also quite stable to light and air. It is a reducing agent and will develop a latent image but the salts are water-soluble solids 5 generally yellow in colour and are not reducing llents. at the concsn The red solution of the free base evention indicated does not stain the so vel per. Since thedeveloper-desensitizes roughly ous. Although it is a developer, it has no harmful eiiect on latent images as is-shown by the fact that an exposed photographic :plate bathed for two minutes in a one-inflve thousand aqueous solution shows no trace of latent image destruction. Its desensitiaing power is, like that of pinakryptol yellow, effected by sulphite in the developer but its desensitizing power is comparable with that of mercuric cyanide or pinakryptol green, disregarding the effect of the developer.
The'following table shows the desensitizing effect of the free base in three different concentrafingers or gelatine orfilm and not poisontions compared with t ee known desensitizers.
A panchromatic film- W treated for two minutes in the desensitizing'solution and exposed for two minutes through a tricolour and neutralbalanced stepwedge, 1' metre from a 25 watt lamp and then developed in the dark. In the table is shown the light intensity required to give the density of .1 above the fog.
Desensitisatlon Fog Neutral Blue In the above on the des'en'sitizing agent was neglected.
six minutes in the dark. Under these conditions the desensitizing action of the 'tetrazine was Green table the effect of the developer In thegfollowing table we show similar com- 5 greatly reduced at concentrations of l in 10,000
and 1 in 5,000. Concentrations of l in 2.000 or In the table the ratio of light intensities togive a density of 0.1 above fog is shown. Since the controlis treated without first desensitizing it shows only'the desensitizing' effect due to the del in 1,000 still had good desensitizing properties.
. curic cyanide.
to one-sixth oi the initial speed, the total desensitization is represented by the figure for the desensitization alone multiplied by six.;
where R1. Ra, R: and R4 are selected from the group consis1 ting of hydrogen, alkyl, aryl, aralkyL. and acy High fog density.
As can ,be seen the eifect oi the developer on the desensitizer for at least 4-6 minutes after bathing at 1:2,000 is negligible.
Although the desensitizing power of -3:6-diaminotetrazine is less than that of pinakryptol green, or pinakryptol yellow, it is sufliciently powerful for practical purposes and for the same fog density is practically equal to that or mer- On the other hand, mercuric cyanide brings about a latent image destruction equivalent'to reduction in speed of 50% at 112,000 and about 30% at 1:10,000', whereas 3:6-diaminotetrazine, as stated above, has no action.
The manufacture of 3:6-diaminotetrazine is given in Gazzetta ChimicaItaliana, 43 (2) (1913) at page 162 and 45 (I) at page 182.
I claim:
1. The method of desensitizing a gelatino-silver halide emulsion prepared by the neutral process. which comprises treating it in a bath containing a compound having the following formula: I
2. The method of desensitizlng a gelatino-silver halide emulsion prepared by the neutral 20 process, which comprises treating it in a bath containing a 3:6-diaminotetrazine.
3. The method of desensitizing a gelatino-silver halide emulsion prepared by the neutral process, which comprises treating it after exposure in 25 a bath containing a 3:6-diaminotetrazine.
4. The method of desensitizing a gelatino-silver halide emulsion prepared by the neutral process, which comprises treating it after exposure in a bath containing a 3:6-diaminotetrazine in an amount of at least 0.0002 gram per liter.
5. The method of desensitiaing a gelatino-silver halide emulsion prepared by the neutral process, which comprises exposing it and developing it in a, bath containing a 3:6-diaminotetrazine in 35 an amount oi at least 0.00.02 gram per liter.
EDWARD B. KNo'rr.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB23472/39A GB532895A (en) | 1939-08-15 | 1939-08-15 | Improvements in desensitisation of photographic emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2263002A true US2263002A (en) | 1941-11-18 |
Family
ID=10196169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US335339A Expired - Lifetime US2263002A (en) | 1939-08-15 | 1940-05-15 | Desensitization of photographic emulsions |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US2263002A (en) |
| FR (1) | FR866741A (en) |
| GB (1) | GB532895A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461679A (en) * | 1944-09-04 | 1949-02-15 | Wingfoot Corp | Method of reacting a piperylene with a halo substituted maleic anhydride |
| US4011081A (en) * | 1973-09-19 | 1977-03-08 | Eastman Kodak Company | Direct-positive double exposure process utilizing a primitive, unfogged silver halide emulsion containing an electron acceptor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2857273A (en) * | 1953-07-31 | 1958-10-21 | Gen Aniline & Film Corp | Photographic film having enhanced herschel effect susceptibility and the process using the same |
| GB1052876A (en) * | 1962-12-03 |
-
1939
- 1939-08-15 GB GB23472/39A patent/GB532895A/en not_active Expired
-
1940
- 1940-05-15 US US335339A patent/US2263002A/en not_active Expired - Lifetime
- 1940-08-14 FR FR866741D patent/FR866741A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461679A (en) * | 1944-09-04 | 1949-02-15 | Wingfoot Corp | Method of reacting a piperylene with a halo substituted maleic anhydride |
| US4011081A (en) * | 1973-09-19 | 1977-03-08 | Eastman Kodak Company | Direct-positive double exposure process utilizing a primitive, unfogged silver halide emulsion containing an electron acceptor |
Also Published As
| Publication number | Publication date |
|---|---|
| GB532895A (en) | 1941-02-03 |
| FR866741A (en) | 1941-08-30 |
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