DE888045C - Process for the production of photosensitive layers, the latent image of which can be developed by the action of heat - Google Patents
Process for the production of photosensitive layers, the latent image of which can be developed by the action of heatInfo
- Publication number
- DE888045C DE888045C DEF3075D DEF0003075D DE888045C DE 888045 C DE888045 C DE 888045C DE F3075 D DEF3075 D DE F3075D DE F0003075 D DEF0003075 D DE F0003075D DE 888045 C DE888045 C DE 888045C
- Authority
- DE
- Germany
- Prior art keywords
- silver
- heat
- developed
- layers
- latent image
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- ZYDVNTYVDVZMKF-UHFFFAOYSA-N [Cl].[Ag] Chemical compound [Cl].[Ag] ZYDVNTYVDVZMKF-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- UOBCZXSWQQWTGC-UHFFFAOYSA-N amino(phenyl)carbamic acid Chemical compound OC(=O)N(N)C1=CC=CC=C1 UOBCZXSWQQWTGC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- -1 hydrazine compound Chemical class 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- BXDUJMLIUYJHNH-UHFFFAOYSA-L mercury(2+);oxalate Chemical compound [Hg+2].[O-]C(=O)C([O-])=O BXDUJMLIUYJHNH-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 239000004297 potassium metabisulphite Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 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
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
-
- 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
- G03C1/42—Developers or their precursors
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
Verfahren zur Herstellung lichtempfindlicher Schichten, deren latentes Bild durch Einwirkung von Wärme entwickelbar ist Es ist bereits vorgeschlagen worden, den latenten Lichteindruck auf gewissen Schwermetallschichten, wie z. B. auf solchen, die Silber- oder Quecksilberoxalat enthalten, durch nachträgliche Erwärmung sichtbar zu machen. Hierbei tritt die Zersetzung von z. B. Silberoxalat zu Silber an den vom Licht getroffenen Stellen schneller ein als an den unbelichteten Stellen.Process for the production of photosensitive layers, their latent Image is developable by the action of heat It has already been suggested the latent light impression on certain heavy metal layers, such as B. on those which contain silver or mercury oxalate, visible through subsequent heating close. Here, the decomposition of z. B. silver oxalate to silver on the areas hit by the light faster than in the unexposed areas.
Diese Schichten haben aber den Nachteil einer verhältnismäßig geringen Empfindlichkeit, so daß sie in vielen Fällen praktisch nicht anwendbar sind. Es wurde nun gefunden, daß man durch Wärme entwickelbare, photographische Schichten von wesentlich höherer Empfindlichkeit erhält, wenn man Silbersalze in Gegenwart solcher reduzierend wirkender Stoffe verwendet, die, in Lösung angewandt, an sich oder in Gegenwart von Alkalien belichtete Silbersalze zu metallischem Silber entwickeln können.However, these layers have the disadvantage of being relatively small Sensitivity so that they are not practical in many cases. It it has now been found that heat developable photographic layers can be produced of much higher sensitivity obtained when silver salts are present such reducing substances used, which, applied in solution, per se or develop silver salts exposed to light in the presence of alkalis to form metallic silver can.
Die nachstehenden Ausführungen sollen die Grundlage dieses Verfahrens näher erläutern.The following explanations are intended to form the basis of this procedure explain in more detail.
r. Versetzt man eine verdünnte Silbernitratlösung mit z. B. P'henyfhydrazinkarbonsäure, so tritt, sofern man Licht ausschließt, auch nach längerer Zeit 'keine Abscheidung von metallischem Silber ein. Belichtet man jedoch diese Lösung nur ganz kurz, so verursachen die hierbei entstandenen Silberkeime auch beim weiteren Verbleiben der Lösung im Dunkeln eine restlose Umwandlung des Silbernitrates in Silber, wobei eine Erwärmung zur Beschleunigung der Reaktion beiträgt. Es gelingt so, unter Einhaltung gewisser Vorsichtsmaßregeln, die nachstehend im ersten Ausführungsbeispiel angegeben sind, Schichten herzustellen, die nach der auf eine kurze Belichtung folgenden Wärmebehandlung das an sich unsichtbare latente Bild erscheinen lassen. Die im Licht gebildeten Silberkeime haben in diesem Falle also zu einer wesentlichen Beschleunigung der Reduktion des Silbernitrates zu metallischem Silber durch die Hydrazinverbindung beigetragen. Derartige Schichten lassen sich übrigens auch durch kurzes Wässern entwickeln, da die Reaktion von Silbernitrat mit Phenylhydrazinkarbonsäurc in der feuchten Schicht sehr viel schneller verläuft, allerdings nur an den Stellen, an denen durch Belichtung Silberkeime entstanden sind.r. If you add a dilute silver nitrate solution with z. B. phenyfhydrazine carboxylic acid, so, if light is excluded, no separation occurs even after a long period of time of metallic silver. However, if this solution is only exposed for a very short time, so cause the resulting silver nuclei even if the remains of the Solution in the dark a complete conversion of the silver nitrate into silver, whereby a Heating contributes to the acceleration of the reaction. It succeeds in compliance certain precautionary measures, the following in the first embodiment are indicated to produce layers after the one following a brief exposure Heat treatment to make the inherently invisible latent image appear. The ones in the light In this case, the silver nuclei formed have a substantial acceleration the reduction of the silver nitrate to metallic silver by the hydrazine compound contributed. Incidentally, such layers can also be removed by briefly soaking develop because the reaction of silver nitrate with phenylhydrazine carboxylic acid in the damp layer runs much faster, but only at the places which silver nuclei have formed through exposure.
2. Für eine Entwicklung des latenten Bildes durch Wärme eignen sich ferner Schichten, die z. B. neben Halogensilber Substanzen, wie Hydrochinon, enthalten, die in alkalischer Lösung als photographische Entwickler verwendet werden. Bei stärkerer Wärme entwickeln derartige Stoffe das latente Silberbild auch dann; wenn diel Schichten neutral bzw. schwach sauer sind. Diese Schichten haben jedoch den Nachteil, daß die Temperatur, die zu ihrer Entwicklung notwendig ist, ve@rhältnismäßig hoch liegt, jedenfalls nahe am Zersetzungspunkt der als Bindemittel verwendeten Gelatine. Es hat sich nun gezeigt; daß man die zur Entwicklung notwendige Temperatur weitgehend herabsetzen kann, wenn man den Schichten Stoffe zusetzt, die bei der Erwärmung Wasser abgeben oder sich unter Bildung von alkalisch reagierenden Stoffen zersetzen. Geeignet sind z. B. Harnstoff, Salze der Triglykolamidsäure u. a. Je nach der Art der verwendeten Halogensilberemulsion kann man auf diese Weise Schichten von sehr verschiedener Lichtempfindlichkeit herstellen. Gegenüber den bisher bekannten Schichten, die nur eine verhältnismäßig geringe Lichtempfindlichkeit besitzen, bereitet die Herstellung von Schichten auf Halogensilberbasis, die eine sehr hohe Lichtempfindlichkeit aufweisen, nach dem vorliegenden Verfahren keine Schwierigkeiten und wesentliche Vorteile.2. Suitable for latent image development by heat also layers that z. B. contain substances such as hydroquinone in addition to halogen silver, which are used in alkaline solution as photographic developers. With stronger Such substances develop heat, the latent silver image; if the layers are neutral or slightly acidic. However, these layers have the disadvantage that the temperature necessary for their development is relatively high, in any case close to the decomposition point of the gelatin used as a binder. It has now shown itself; that the temperature necessary for development is largely can be reduced if one adds substances to the layers which, when heated, water release or decompose with the formation of alkaline substances. Suitable are z. B. urea, salts of triglycolamic acid and others. Depending on the type of used Halogen silver emulsion can be made of very different layers in this way Establish photosensitivity. Compared to the previously known layers that only have a relatively low photosensitivity, prepares the production of layers based on halogen silver, which have a very high sensitivity to light, according to the present method no difficulties and substantial advantages.
Für die Wärmeentwicklung eignen sich praktisch alle - Silbersalze, gleichgültig, ob sie leicht oder schwer löslich sind. Als reduzierend wirkende Stoffe kommen in Frage Hydrazen sowie seine organischen Derivate, wie Phenylhydrazin, Säurehydrazide, Semikarbazide, sowie alle organischen Stoffe, die, wie Methyl-p-amidophenolsulfat, Hydrochinon oder Brenzkatechin, als photographische Substanzen geeignet sind.Practically all are suitable for heat generation - silver salts, regardless of whether they are easily or difficultly soluble. As reducing substances Possible hydrazines and its organic derivatives such as phenylhydrazine, acid hydrazides, Semicarbazides, as well as all organic substances that, such as methyl p-amidophenol sulfate, Hydroquinone or catechol, are suitable as photographic substances.
Die Entwicklung derartiger Schichten durch Wärme kann auf verschiedenartigen Wegen erfolgen. Im allgemeinen gilt die Regel, daß bei verhältnismäßig hohen Temperaturen für die Hervorrufung des Bildes nur wenige Sekunden notwendig sind, während bei niedrigen Temperaturen die Entwicklung längere Zeit beansprucht. Auch ist es möglich, die Schicht wäh - .e,- Rh+, durch den Schichtträger hin urch von -rückwärts zu erhitzen, so d.aß man das Entstehen des sichtbaren Bildes direkt während der Belichtung beobachten kann. Derartige, durch Wärme entwickelbare Schichten eignen sich vor allem für Registrierpapiere, bei denen die schnelle Erscheinung des Bildes von Bedeutung ist. Je nach der Art des verwendeten Silbersalzes laufen die durch Wärme entwickelten Bilder bei einer weiteren Belichtung mehr oder minder stark an, was jedoch für viele Zwecke belanglos ist, sofern nur ein sichtbarer Kontrast zwischen; entwickelten und unentwickelten Stellen erhalten bleibt. Bei Verwendung von Silbernitrat erhält man z. B. Papiere, die im diffusen Tages-oder Lampenlicht praktisch'keine weitere Verfärbung ergeben. Verwendet man aber z. B. Chlorsilber, das sich im Tageslicht bekanntlich stärker verfärbt; so kann man das Papier bei der Herstellung mit einer Schutzschicht versehen, welche Substanzen enthält, die sich bei der Einwirkung von Wärme unter Bildung gelb gefärbter Stoffe zersetzen. Diese wirken nunmehr als Lichtfilter und absorbieren d le für die Verfärbung der Chlorsilberschicht in Frage kommenden blauen Lichtstrahlen. Beispiele 30 g Phenylhydrazinkarbonsäure, gelöst in 300 ccm Wasser und 30,0 ccm Aceton, werden mit t100 ccm einer i 5 "/obigen Gelatinelösung versetzt. Hierzu setzt man im Dunkeln bei etwa -25,"#C 135 g Silbernitrat, gelöst in 2o ccm Wasser, sowie io ccm einer ioa/aigen Salpetersäure und 2o ccm einer 25 o/oigen Schwefelsäure zu. Man gießt das Gemisch in üblicher Weise auf einen Schichtträger und sorgt für eine rasche Trocknung. Bei zu langsamer Trocknung tritt unter Umständen eine Abscheidung des Silbers bereits im Dunkeln ein. Zur Entwicklung dieser belichteten Sc'hic'hten ist eine Erhitzung auf etwa ioo° erforderlich.Such layers can be developed by heat in a variety of ways. In general, the rule applies that at relatively high temperatures only a few seconds are necessary to produce the image, while at low temperatures the development takes longer. Also, it is possible currency layer - .e -, d urch urch to heat the substrate out of -rückwärts, we can d.aß the formation of the visible image directly observed during the exposure Rh +. Such heat-developable layers are particularly suitable for recording papers where the quick appearance of the image is important. Depending on the type of silver salt used, the images developed by heat tarnish to a greater or lesser extent in a further exposure, but this is irrelevant for many purposes, provided there is only a visible contrast between; developed and undeveloped areas is retained. When using silver nitrate you get z. B. Papers that produce practically no further discoloration in diffuse daylight or lamp light. But if you use z. B. Chlorine silver, which is known to be more discolored in daylight; For example, the paper can be provided with a protective layer during manufacture, which contains substances that decompose when exposed to heat to form yellow-colored substances. These now act as light filters and absorb the blue light rays that may cause the discoloration of the chlorine silver layer. EXAMPLES 30 g of phenylhydrazine carboxylic acid, dissolved in 300 cc of water and 30.0 cc of acetone, are mixed with 100 cc of an i 5 "/ above gelatin solution. For this purpose, 135 g of silver nitrate, dissolved in 2o cc of water, as well as 10 cc of 10% nitric acid and 20 cc of 25% sulfuric acid. The mixture is poured onto a support in the usual way and allowed to dry quickly. If the drying time is too slow, the silver may deposit in the dark. To develop these exposed layers, heating to about 100 ° is necessary.
Beispie12 Man verwendet eine übliche Chlorsilberemulsion und setzt dieser pro Liter folgernde Lösung zu: i50 ccm Wasser, 2o g Hydrochinon, io g Kaliummetabisulfit, loo g Harnstoff. Die Mischung wird in der iiblichen Weise auf einen Schichtträger vergossen; die Entwicklung erfolgt am besten durch Auflegen auf eine auf etwa i30° erwärmte Heizplatte.Example 12 One uses a common chlorosilver emulsion and sets add the following solution per liter: 150 ccm water, 20 g hydroquinone, 10 g potassium metabisulphite, loo g urea. The mixture is applied to a support in the usual way potted; the development is best done by placing it at about i30 ° heated heating plate.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF3075D DE888045C (en) | 1943-06-29 | 1943-06-29 | Process for the production of photosensitive layers, the latent image of which can be developed by the action of heat |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0003075 | 1943-06-29 | ||
| DEF3075D DE888045C (en) | 1943-06-29 | 1943-06-29 | Process for the production of photosensitive layers, the latent image of which can be developed by the action of heat |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE888045C true DE888045C (en) | 1953-08-27 |
Family
ID=25973689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF3075D Expired DE888045C (en) | 1943-06-29 | 1943-06-29 | Process for the production of photosensitive layers, the latent image of which can be developed by the action of heat |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE888045C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1003578B (en) * | 1952-09-04 | 1957-02-28 | Zindler Lumoprint Kg | Process for producing photographic images and means for carrying out the same |
-
1943
- 1943-06-29 DE DEF3075D patent/DE888045C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1003578B (en) * | 1952-09-04 | 1957-02-28 | Zindler Lumoprint Kg | Process for producing photographic images and means for carrying out the same |
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