DE2360638A1 - DEVELOPER OF HIGHLY CONTRAST PHOTOGRAPHIC MATERIALS AND PROCESSES FOR THEIR TREATMENT - Google Patents

Description

PATENT LAWYERS

DR. E. WlEGAMD DIPL.4NG.W. NtMNH

DR. M, KOHiER DIPL-ING. C. GERNHAfeDT 2360638

MÖNCHEN HAMBURG

TELEPHONE: 55547 «8000 MÖ NC HEN 2, -

TELEGRAMS: KARPATENT 'MATHILDENSTRASSE 12

41 864/73 - Κο / ΠΕ December 5, 1973

Fuji Photo lilm Ca., Ltd. « Minami Ashigara-shi, Kanagawa / Japan

Developer for high contrast photographic materials and procedures for their treatment

The invention relates to a method of processing high contrast photographic materials, and more particularly a process for the ph ο tographi.se he development those beneficial and valuable in the graphic arts field is. ■

According to the invention, a developer for photographic High contrast materials which contain a p-dihydroxybenzene type developing agent and a compound of the following formula "..

40 9824/082

contains, wherein R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a nitro group, this compound in an organic solvent is resolved. The application of the present developers does not cause any seams in the after. development photographic images formed therewith.

It is favorable if photographic images are used have only a maximum density range and a minimum density range in the graphic arts art and have no intermediate density area, the so-called fringe. As a result, they went to training of such photographic images, high-contrast photographic materials and a developer for infectious Development of these materials so far applied in numerous cases. The formation of such photographic images is by YuIe -in J. Frank. Inst. 239, 221 (1945).

It is well known to concentrate photographic developers and concentrated developers for development high-contrast photographic materials have also been suggested. For the production of concentrated Developers were often used organic solvents because of the solubility of the developing agent in water is low. Illustrative examples of such organic solvents are, for example, monoethylene glycol, diethylene glycol, Triethylene glycol, triethanolamine, triisopropanolamine and the same. However, the application of these organic solvents in developers for the graphic arts The subject is unfavorable and causes seams to appear in the formed images.

One object of the invention is a method for the treatment of high-contrast photographic materials without forming any seam in the images obtained.

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Another object of the invention is a developer for high-contrast photographic materials, its use does not cause any seams to be formed in the obtained images.

Within the scope of the invention, after numerous attempts for the purpose of achieving the above objects found that the use of indazole or a derivative thereof of the following formula

wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a nitro group, together with a developer contained in an organic solvent achieves the above objects.

The organic solvents used in the context of the invention can be used include various kinds of organic solvents and are, for example Triethanolamine, triethylene glycol, diethylene glycol, monoethylene glycol, Triisopropanolamine and the like as disclosed in U.S. Patent 3,552,969. In particular Triethanolamine is the cheapest solvent because triethanolamine serves to act as the developer during a for a long period of time without separating any of the materials from desensitizing agent, the compound of the foregoing To keep formula and other components stable. The other solvents listed above can also be used of course an excellent stability for the Developers result, even if their stability is not as superior as with triethanolamine and they are therefore

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half within the scope of the present invention, since these compounds of the above formula according to the invention are also effective in preventing the formation of seams which occur when organic Adjust solvents.

Addition of the compound of the above formula to a developer can be carried out using any one of them customary procedure including a separate addition to a prepared developer are carried out, however, it is particularly preferred to previously use the compound in one of the organic listed above Solvent to dissolve and then the resulting organic solution to an aqueous solution of the developing agent to add. The solution of the compound of the above formula in the organic solvent can be separated from the Developing agent or a solution thereof can be stored until the developer to be used is prepared.

The amount of the organic solvent which can be used according to the invention is such an amount the sufficient solubility of the indazole compound of the above formula with the developer gives and is generally 5 to 150 ml per 1 1 developer and the The amount of the compound of the above formula is generally 1 mg to 1 g, preferably 5 to 100 mg per 1 liter of developer.

Illustrative examples of compounds of the above given formula are for example 5-iTitroindazole and 6-Fitroindazole and those in UB patents 2,656,271, 2,271,291, 3,000,736, 2,436,940 and 2,497,917 Compounds commonly known as antifoggants. Prevent according to the present invention However, these compounds the hem caused by the use of organic solvents, so that these Clearly distinguish compounds from common antifoggants. '

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The components to be used according to the invention of the developer contain a developing agent, a sulfite ion buffer, and a sulfite ion buffer in addition to those mentioned above an alkali, as in U.S. Patents. 3 294 540, 3 516 830, 3 573 914, 3 625 689, 3 615 524, 3 600 174 and the like indicated.

The developing agent can be selected from the group of dihydroxybenzene type developing agents as desired be chosen in the photographic field are well known. Examples of such agents are the following: hydroquinone, chlorohydroquinone, bromohydroquinone, Isopropyl hydroquinone, tolu hydroquinone, methyl hydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, and the like. Of these, hydroquinone is in the Practice particularly suitable. These developing agents can be used alone or as a mixture of two or more. The amount of developing agent that is used can be, is 5 to 50 g, preferably 10 to 30 g per 1 1 developer.

The sulfite ion buffer is used in an effective amount used to keep the sulfite concentration practically constant in the developer and illustrative examples thereof are for example the following: aldehyde-alkali bisulfite adducts, like the formaldehyde-sodium bisulfite adduct, Ketone alkali bisulfite adducts, such as acetone sodium bisulfite adduct, CarbonyIbisulfite amine condensation products such as Sodium bis (2-hydroxyethyl) aminomethanesulfonate and the like. The amount of sulfite ion buffer that can be used is 13 to 130 g, preferably 30 to 80 g per 1 liter of the developer.

The alkali is added to make the developer alkaline, more preferably to its pH range the range of 9 or more, especially in the range of 9.7 to. 11.5 to be set. Therefore, the amount and type of

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alkaline agent which can be used is not limited

The developer free sulfite ion concentration that can be used in the invention can be can be controlled in a favorable manner by adding an alkali sulfite, for example sodium sulfite, for this purpose will. The amount of the sulfite to be added is generally 5 g or less, but it may be more than 5 g.

If necessary, the developer according to the invention can contain other agents in addition to the components specified above, for example pH buffering agents, such as water-soluble acids, e.g. acetic acid, boric acid, alkalis, e.g. sodium hydroxide or salts, e.g. sodium carbonate, or development control agents such as alkali halides. Some types of alkaline agents act not only to make the developer alkaline but also to act as a pH buffering agents or development control agents.

Still other compounds that can be added to the above developers are, for example Preservatives such as ascorbic acid or kojic acid, and antifoggants such as benzotriazole, 1-phenyl-5-mercaptotriazole and the same.

The developer prepared in the above manner may be in any IOrm or condition, if it contains all the necessary components that are necessary in its use, so that the developer composition can be divided into two or more parts by their use. For example, if the part that has the developing agent contains dissolved, and the part containing the alkali are prepared separately, these can be directly after diluting both parts before using them.

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The high contrast photographic materials that be treated by the method according to the invention include photographic silver halide emulsions such as those disclosed in U.S. Patents 2,656,271, 2,271,291, 3 OO 736, 2,496,940 and 2,497,917 are given. Illustrative examples of silver halides are e.g. ' Silver chloride, silver bromochloride, silver bromoiodochloride and the same. In order to effectively achieve the objects of the invention, it is particularly important that the weight of silver halide is 50 mol $ or more, preferably Contains 75 moles or more of silver chloride ..

The silver halide emulsion contains one or more hydrophilic colloidal substances as a dispersant, for example gelatin, acylated gelatin such as phthalated Gelatine or malonated gelatine, cellulose derivatives such as hydroxyethyl cellulose or carboxymethyl cellulose, soluble starches such as dextrin or alkali starch, hydrophilic High molecular weight polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, or polystyrene sulf onic acid.

The silver halide emulsion may further comprise a water-insoluble polymer of high molecular weight, for example a polyalkyl acrylate, polymethacrylate, polyacrylic acid or interpolymers of alkyl acrylate and acrylic acid and gelatin plasticizers such as glycerine or trimethanol propane contain.

These emulsions are used in photographic materials can be used using various methods during the manufacture of the same or are sensitized during the mounting of the photographic materials. For example, these can be emulsions chemically by methods that are well known in the field are known using sodium thiosulfate, alkyl thiourea and the like or gold compounds, for example a complex of monovalent gold and thio-

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- O - ■

cyanic acid or using a mixture of these compounds. The emulsions can also be a compound of a heavy metal such as platinum, palladium, iridium, rhodium, cadmium and the like contain. In addition, the emulsions can be ortho- or panchromatic by adding an optical sensitizer, such as a cyanine dye or merocyanine dye, Be sensitized and can continue to use an improver for line and halftone images (dot images) such as polyalkylene oxides and amine compounds (corresponding to Japanese Patent Publication 14402/64, German 0IS 1 932 882, Japanese patent publication 23466/65) and sodium benzene thiosulfate, Benzotriazole or 1,3,3a, 7-tetrazaindene derivatives, as in Japanese Patent Publication 15715/64, 17903/66 is given. The emulsions can also be treated with a hardener such as formaldehyde, dimethylolurea, 2,4-dichloro-6-hydraxy-1,3,5-triazine according to the US patent 3,325,287, or mucochloric acid can be hardened and coating auxiliaries, for example contain surfactants such as saponin. In addition, the emulsion can be a development accelerating improver, for example a 3-pyrazolidone derivative or a pyrazolone derivative. Furthermore, the Emulsions, a development accelerator such as a quaternary ammonium salt or a cationic one have surfactant. The photographic high contrasts applicable within the scope of the invention t materials can include a common silver halide developing agent, such as hydroquinone or derivatives thereof, p-aminophenol or derivatives thereof or derivatives of p-phenylenediamine included. The support of the photographic materials used in the present invention is not particularly limited and, for example, glass, cellulose acetate, polystyrene, polycarbonate, Polyethylene terephthalate and the like therefor 4 09824/0827 are used

According to the invention, it is extremely easy to dissolve the indazole and derivatives thereof, and so on divorce if the developer is stored or kept in an automatic developing machine will not turn off any crystals. Therefore, stable photographic properties can be obtained according to the invention even if the developer is used for a long period of time »

The invention is illustrated below with the aid of the following examples, without departing from the scope of the invention is limited. Palis unless otherwise specified, all parts and percentages are based on weight,

example 1

A gelatin silver halide photographic material consisting of 80 mol- # silver halide, 0.2 mol-? S silver iodide, balance silver bromide, was exposed to light through a Sensitometric exposure wedge using a 150 line magenta contact screen and then with the following developers in a automatic developing machine treated ^{at 27 0 C »}

Developer A:

Sodium carbonate 35 g

Potassium bromide. 2g

Sodium hydroxide 2.5 g formaldehyde-sodium bisulfite adduct 55 g

Sodium sulfite 5 g

Boric acid 6 g

Hydroquinone 15 g

Water to 11

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Developer B:

40 mg of 5-nitroindazole were added to developer A and 2 g sodium hydroxide added to increase the pH.

Developer C:

80 ml of triethanolamine were added to developer A.

Developer D:

A solution of 40 mg of 5-H "itroindazole, dissolved in 80 ml of triethanolamine, and 2 g Sodium hydroxide added.

An amount of preparation of 16 liters sprinkled from each of the above Developer was made and the four preparations were processed in four identical automatic developing machines given, in which development, fixing, washing and drying were executed. The following photographic properties were obtained.

Table I.

developer

additive

easy to manufacture

fresh solution

Half-photographic ton- phishe image sensitivity

after 24 hours

Semi-photographic image sensitivity

developer
A.

developer
B.

developer
C.

developer
D.

without

5-nitroindazole (40mg / l)

Triethanolaiain (80ml / l)

5-nitroindazole (40mg / l) triethanolamine (oOml / 1)

simple

difficult easy

simple

10

100

100

100

100

10

10

100

250

100

100

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The values of the halftone image were visually estimated and the quality was assessed using gradations from 1 to ΙΟ, i.e. 10 means whole excellent and 1 means extremely bad.

The photographic sensitivity was assessed on the Sensitivity (100) related to that after development for 1 minute and 45 seconds with the developer A had been obtained, 'and is indicated relatively.

The following results from the values in Table I: all developers A, B, C and D have the same photographic speed shortly after their preparation (fresh solution), while after 24 hours in the automatic developing machine the sensitivity of developer B increased markedly, while the halftone image quality the same was markedly deteriorated. When investigating the developer used was found that the 5-nitroindazole was in the developer B said goodbye over time. On the other hand, in developer D according to the invention, which triethanolamine separated contained the 5-mtroindazole itself long time, so that the halftone image quality obtained was extremely good. The sensitivity continued to decrease of developer D neither increases nor decreases with the lapse of time. When treating with an automatic developing machine become the conditions for development such as temperature, medium sports speed and the like always kept constant, so it goes without saying is that the activity of the developer used is preferably always constant and that the treated film preferably always has the same properties. From the values in Table I it can be seen that the inventive A method very excellent for obtaining stable photographic properties in processing with an automatic developing machine. After this

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23R0638

the developers B and D used here were left to stand in a glass bottle for 2 weeks, of which Air was completely sealed off, no 5-liitroindazole at all precipitated in Developer D while a considerable amount of it separated in Developer B within 24 hours * In addition, the Developer D can be easily manufactured, while a very long period of time required to manufacture the developer 13 was.

Example 2

A silver halide emulsion containing 75 moles -? *; Silver chloride, 0.2 mol # silver iodide, remainder SiI berbromid, underwent gold sensitization using KAuCl * and sulfur sensitization Application of sodium thiosulfate and then was subjected optically with 3-carboxymethyl-5 "(2- (3-ethylthiazolinylidene) ethylidene) rhodamine sensitized and then this was a polyoxyethylene nonylphenyl ether with a content of 50 ethylene oxide groups and a development accelerator according to the following formula

* —CH ₂ CH ₂ CH ₂ CH — NHCONH

C.
j
CH ₃

exposed. The mixture obtained was coated with a polybutyl methacrylate polymer mixed and then mounted on a film base to form a lithotype film, after the film produced is exposed to light through a Exposure wedge for sensitometry using a 150 lines — magenta contact grid was exposed,

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BATH ORIGINAL

the PiIm was treated with each of the following four developers in an automatic developing machine for one minute and 30 seconds at 29 ^C C.

Developer E:

Potassium carbonate 50 g Potassium bromide 2 g

Ethylenediamine sodium tetraacetate 1.0 g

Formaldehyde-sodium bisulfite adduct 50 g Sodium sulfite 3 g

Boric acid 7g

Hydroquinone 18 g water at 11- '

Developer ff;

BO mg 6-nitroindasol and 2 g sodium hydroxide were added to developer E to increase the pH.

Developer G-:

35 ml of triethylene glycol were added to developer E.

Developer H:

A solution of 80 mg of 6-nitro ~ was used as developer E indazole, dissolved in 35 ml of triethylene glycol, and 2 g of sodium hydroxide were added to increase the pH.

A preparation in an amount of 16 liters was prepared from each of the above developers E, ff, G- and H and the four specimens prepared in this way were into the same four automatic developing machines in which development, fixing, washing and drying were carried out. The. in the table below II listed photographic properties obtained.

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-H-

additive Tabel II photogra
phical
Sensation
opportunity after 24 hours without 100 Half
volume
image photogra
phical
Sensation
opportunity developer 6-nitroinda-
zol (80mg / l) simple
Manuf
lung fresh solution 100 10 100 developer
E. simple Half
volume
image 100 5 220 developer
P. difficult 10 ^ 100 9 100 developer
G Triethylene simple
glycol (35ml / l) 10 10 100 developer
H 6-nitroinda- simple
zol (80mg / l)
Triethylene
glycol (35ml / l) 9 10

From the results of Table II, the following can be seen: the somewhat decreasing halftone image quality due to the addition of triethylene glycol was due the addition of 6-ITitroindazole increases and the difficulty In the preparation of the developer P was somewhat improved due to the use of triethylene glycol or relieved. The two developers P and H have the same photographic sensitivity and halftone image quality shortly after the preparation of the same (fresh solution), while after 24 hours in the automatic developing machine the sensitivity of the developer P markedly increased while the halftone image quality thereof was markedly deteriorated. Upon careful examination of the developer P used, it was found that therein the 6-nitroindazole separated over time. On the other hand, in developer H according to the invention, which contained triethylene glycol, the 6-ltitroindazole does not decrease even in the course of time and the

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sustained halftone image quality was extremely good. It can be seen from the values in Table II that the method of the present invention is quite excellent in obtaining stable photographic properties when processed by an automatic developing machine. If each developer F and H used here was left to stand for 2 weeks in a closed glass bottle, from which air was completely closed, the 6-nitroindazole did not separate at all in developer H - while this was within the other developer I ¹ Pretty goodbye 24 hours.

Example 3

A silver halide emulsion containing 84 mol% silver chloride, 0.2 mol% silver iodide, the remainder of silver bromide, was subjected to gold sensitization and rock sensitization and was then optically treated with 3-carboxymethyl-5- (2- (3-ethylthiazolinylidene) -äthyliden) -rhodamine, and then a polyoxyethylene nonylphenyl ether containing 50 ethylene oxide groups and a development accelerator according to Japanese Patent Publication 23465/65 were added. The obtained mixture was mixed with a polybutyl methacrylate polymer and then coated on a base film to form a lithotype film. After the film thus formed was exposed to light through an exposure wedge for sensitometry using a 150 line magenta contact screen, the film with each of the following four developer in an automatic developing machine for 1 minute and 45 seconds was treated at 27 ⁰ G.

4 0 9 8 2 4 / OJB 2 7

Developer J-I;

Formaldehyde-sodium bisulfite adduct 50 g

Sodium SuIfit 5 g

Hydroquinone 18 g

Boric acid 3 g

Water to 167 ml

Developer J-II:

Sodium carbonate 50 g

Potassium bromide 2 g

Sodium tetrapolyphosphate 1.0 g

167 ml of water

Developer K-I:

40 mg of 5-nitroindazole was added to Developer J-I.

Developer K-II:

2 g of sodium hydroxide was added to developer J-II to increase the pH.

Developer L-I:

40 ml of triethanolaroin were added to developer J-I.

Developer L-II:

Like developer J-II.

Developer M-I:

In developer J-I, 40 ml of triethanolamine and mg of 5-nitroindazole dissolved.

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Developer M-II:

2 g of NaOH were added to developer J-II to increase the pH.

Developers J-I and J-II were mixed together and water for this purpose to form 1 liter of the developer J added. Similarly, developer K-I and developer K-II are mixed together and water to form 1 l of developer K added. The developers L-I and L-II were also mixed together and water to form 1 liter of the developer L was added. The developer M-I and the developer M-II were also mixed and water to form one Liters added by developer M.

A preparation in the amount of 16 l was made from each of the above developers J, K, L and M and the four preparations thus prepared were prepared put into the same four automatic developing machines, in which developing, fixing, washing and tracking were executed. As a result, the photographic properties shown in Table III below were obtained obtain.

developer

additive

Table III

fresh solution after 24 hours

Half-photographic half-photographic simple ton- phic ton- phic manufacture

Developer J

Developer K

Developer L

Developer M

without

simple

5-nitroinda- difficult zol (40ml / l)

Triäthanol- simple aroin (40ial / l)

5-liitroinda- simply zol (40ml / l) Triethanolainine (40 ml / 1)

100

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10

100

100 6th 200 100 8th 100 100 10 100

The following results from the values in Table III: that due to the addition of triethanolamine The halftone image quality (developer L) decreased somewhat due to the addition of 5-nitroindazole (Developer M) improved, and the difficulty in preparing the Developer K became due to the inclusion improved or facilitated by triethanolamine (developer M). The two developers K and M have the same photographic speed and halftone image quality shortly after making the same (fresh solution) while after 24 hours in the automatic Development machine the sensitivity of the developer K increased markedly, while its halftone image quality was markedly deteriorated. Upon careful examination of the developer E used, it was found that that here the 5-nitroindazole in the course of Time separated. On the other hand, in the developer M according to the invention, which contained triethanolamine, separated the 5-nitroindazole itself does not decrease over time, so that the halftone image quality obtained was extremely good and stable. Plus, it's very easy to become a developer how to make the developer J, while it is very difficult to make a concentrated solution like the developer J-I manufacture. In particular, it is extremely troublesome to completely dissolve the hydroquinone and even if the hydroquinone is initially dissolved, it separates easily in the resulting solution with decreasing temperature the same from. With the developers L-I and M-I, the Triäthanolarain contained, however, the hydroquinone can be easily dissolved and furthermore no deposition was dea Hydroquinones were observed at lower temperature over time.

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In the foregoing, the invention has become more preferred by way of example Embodiments described without referring to it is limited.

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Claims (22)

Claims (j \ J) A developer for high contrast photographic materials containing a p-dihydroxybenzene type developing agent and a compound represented by the following formula NH ^N N wherein R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a nitro group, taking this compound in an organic solvent is resolved. 2. Developer according to claim 1, characterized in that that the organic solvent consists of triethanolamine. 3. developer "according to claim 1, characterized in that that the organic solvent from triisopropanolamine consists. 4. Developer according to claim 1, characterized in that that the organic solvent from triethylene glycol, Diethyleiiglykol or monoethylene glycol. 5. Developer, according to claim 1 to 4, characterized in that the amount of the organic solvent is 5 to 150 ml .j ^e ^ 1 developer. 6. Developer according to claim 1 to 5, characterized in that the compound consists of 5-nitroindazole or G- nitroindazole » 7. Developer according to claim 1 to 6, characterized in that that the amount of the compound i mg to 1 g each Liters of developer. 409824/0827 8. Developer according to claim 7> characterized in that the amount of the compound 5 to 100 rag per liter Developer amounts. 9. Developer according to claim 1 to 8, characterized in that the developing agent of hydroquinone, Chlorhydroquinone, Brorahydroquinone, Isopropy! Hydroquinone, Ioluhydroquinone, Kethy! Hydroquinone, 2,3-dichlorohydroquinone and 2,5-dimethylhydroquinone. 10. Developer according to claim 1 to 9, characterized in that that the amount of developing agent. -5 to £ 50 j per liter of developer. 11. Developer according to claim 10, characterized in that that the amount of the developing agent 10 to 30 g per idter Developer amounts. 12. A method for developing high-contrast photographic materials, characterized in that the Materials with a developer who is a development ~ p-dihydroxybenzene type agent and a compound represented by the following formula contains, wherein R is a hydrogen atom, a lower alkyl group with 1 to 4 carbon atoms or a nitro group means where the compound is in an organic solvent is resolved, is treated. • 13. The method according to claim 12, characterized in that that used as an organic solvent triethanolamine will. ■ 14. The method according to claim 12, characterized in that that used as an organic solvent triiaopropanolamine will. 409824 / 08.27 15. The method according to claim 12, characterized in that that as a solvent triethylene glycol, diethylene glycol or monoethylene glycol is used. 16. The method according to claim 12 to 15, characterized in that that an amount of the organic solvent of 5 to 1.50 ml per 1 liter of developer is used. " 17. The method according to claim 12 to 16, characterized in that the compound 5-l-titroindazole or 6-titroindazole is used. 18. The method according to claim 12 to 17, characterized in that an amount of the compound from 1 rag to 1 g per liter of developer is used. 19. The method according to claim 18, characterized in that an amount of the compound of 5 to 100 rag per liter Developer is used. 20. The method according to claim 12 bi · 19 »characterized in that that as development hookers 1 hydroquinone, chlorohydroquinone, Bromohydroquinone, isopropylhydroquinone, toluohydroquinone, Me thy! Hydroquinone, 2,3-dichlorohydroquinone and / or 2,5-dimethylhydroquinone can be used. 21. The method according to claim 12 to 20, characterized in that an amount of the development element of 5 up to 50 g per liter of developer is used. 22. The method according to claim 21, characterized in that an amount of the developing agent from 10 to 30 g per liter of developer is used. 409824/0827