DE1597558A1 - Process for resensitizing a photographic material - Google Patents

Description

PATENT AGENCIES 78/25/77 ^ $ f ^ ^ 58

DR.-ING.WOLF ^ H.BARTELS,. ⁸ ScSsE ^ *

DR. BRANDES, DR.-ING. HELD phone = «» 11) 293297

Reg, No. 120 971

Eastman Kodak Company, 3 ^ 3 State Street, Rochester, New York State, United States of America

Method of resensitizing a photographic

Materials

The invention relates to a method of resensitizing a photographic material for recording latent images, consisting of a carrier and one on top of it applied, developable, unshifted SiI overhalide emulsion layer of the negative type, which by means of a chemical desensitizing agent consisting of a heavy metal salt, a sulfoalkylaminosulfonreet containing anthraquinone dye, a non-heterocyclic, aromatic containing at least one nitro radical Compound or a heterocyclic compound

00-9834 / 0346 bathroom original

»597558

with at least one sulfur and / or nitrogen atom opposite Light with a wavelength of 1 to 1200 nm is desensitized became.

It is known that desensitized silver halide photographic emulsions can be resensitized. Such desensitized silver halide photographic emulsions can be used for a wide variety of purposes »for example, if the emulsion before its exposure is processed or handled in an environment with strong radiation. So it is, for example from the U.S. Patent 3,250,618, known desensitized photographic Resensitize silver halide emulsions thermally. Although dealing with a thermal Resensitization would produce good results in many cases it would be desirable if the resensitization could be carried out at room temperature.

The object of the invention is to provide a process for resensitizing a photographic material for recording latent images which has been desensitized by adding desensitizing agents without the use of elevated temperatures being necessary for this purpose . ^iVj ■■ '■■ "- ■■'""· ■ · ■ ^: " ■■ - ■ - ■■: - ■ ■ ■ ■ - - ■■ - ■

009334/0349

5597558

It has been found that desensitized photographic Resensitizing materials by treating them with certain chemical resensitizers brings in contact.

The invention accordingly provides a process for the resensitization of a photographic material for the recording of latent images, consisting of a support and a developable, unfogged silver halide emulsion layer of the negative type applied thereto, which by means of a chemical desensitizing agent consisting of a heavy metal salt, an anthraquinone dye containing a sulfoalkylaminosulfone radical , a non-heterocyclic, aromatic compound containing at least one nitro radical or a heterocyclic compound with at least one sulfur and / or nitrogen atom, has been desensitized to light having a wavelength of 1 to 1200 nm, characterized in that the photographic material is mi- t brings into contact a resensitizing agent consisting of a tetrazole, triazaindene, tetrazaindene, pentazaindene, pyrldine or a cyclic disulfide.

The resensitizers are preferably kept in contact with the photographic material for so long.

00983Λ / 03A9

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until the sensitivity of the emulsion layer to wavelengths from 1 to 1200 nm is at least ten times greater is as i (4 the sensitivity of the emulsion in desensitized State.

The method of the invention thus achieves that desensitized photographic silver halide emulsion layers are spectrally restored without heat treatment sensitive layers can be transferred »

If a tetrazole or an azaindene is used as the resensitizing agent, this is preferably through a Substituted hydroxyl radical '.

Resensitizers suitable for practicing the method of the invention are for example:

Compound resensitizers

1 i | -Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene

2 5-thioctic acid

3 i | -Hydroxy-6-methyl-1 _J 3a _i 7-trlÄzainden ^ 5- (3, ⁱ * -Dimethoxyphenyl) tetrazole

5. 5- (iJ'-cyanophenyl) tetrazole, monohydrate

6 a-Picolinium-ß-phenylethiodide

7 l | -Hydroxy-6-methyl-1,2,3 »3a, 7-pentazaindene

chT s 009834/0349

cii, cii - cii ₉ - cii ₉ - ch ₉ - c - oh

^kQI Z · ®AD ORIGINAL

8 6-Hydroxy- ⁱ l-methyl- _{1,2 J1} 3,3a, 7-pentazaindene

9 α-picolinic acid

10-β-pieolinic acid

11 γ-picolinic acid

12 2 _i 4-dihydroxy-6-methyl-1,3a, 7'-triazaindene

13 2,5-Dimethyl-7-hyelroxy-1,4,7a-triazaindene

14 5-Amino-7-hydroxy-2-methyl-l, ¹ ', 7-triazaindene

15 5-carboxy-it-hydroxy-1,3.3a _t 7-tetrazaindene

16 1,2-bis (4-hydroxy-6-methyl-1,3,3a, 7-tetrazainden-5-yl) ethane

17 l, 2.3 ,. ¹ l-Tetrakis (4-hydroxy-6-raethyl-1,3,3a, 7-tetrazainden-2-yl) butane

18 2-Amino-5-carboxy-lt-hydroxy-1,3,3a, 7-tetrazaindene

19 i | -Hydroxy-2-ß-hydroxyethyl-6-methyl-1,3,3a, 7-tetrazaindene

20 S-carbethoxy-iJ-hydroxy-l. ^^ a ^ -tetrazainden

21 7-hydroxy-l, 2,3, ¹ t _t pentazaindene 6-

22 4-Hydroxy-2 [-1-hydroxypropyl-6-methyl-1,3,3a _f 7-tetraza-

in the

23 4-Hydroxy-2 ( ¹ »-pyridyl) -6-methyl-1,3,3a, 7-tetrazaindene

24 5-Amino-2 - (p-carboxyphenyl) -7 -hydroxy-1,3 » ¹ ^ » 6-pen taza · indene

25 pyridine.

Others suitable for carrying out the method of the invention Azaindenes are used, for example, in the USA patent

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00 9834/0349

Writings 2 735 769, 2 743 l8l, 2 835 58I, 2 756 147, 2 7 ^ 3 I8O, 2 716 O62, 2 772,164, 2 713 5 ¹ U, 2 852 375, 2 566 658, 2 566 659, 2 444 605, 2 444 606, 2 444 6O.7, 2 449 225 and 2 449 226 as well as in the Zeitschrift für Wissenschaftliche Photographie 4 £, pages 2-28 (1952).

In addition to pyridine itself, picolines, ß-LuÜidine, α-lutidines, Y-Colliäinejajß-collidines, α-propylpyridine, 2-ethyl-3,5-dimethylpyridine, vic- Tetramethylpyridine, ethyl collide, coridine (C ₁₀ H ₁₅ N), rubidine (C ₁₁ H ₁₇ N) and viridine (C ₁₂ H ₁₉ N). The pyridines suitable for carrying out the process of the invention can optionally also be substituted by hydroxyl or carboxyl radicals. For example, picolinic acids and 2- or 4-hydroxypyridines are also suitable reselling agents.

Under "desensitized" silver halide photographic emulsion layers are to be understood here as opposed to the formation of latent images through exposure to light a wavelength of 1 to 1200 nm were made practically insensitive or desensitized »As" resenibilized "

009834/0340

Emulsion layers are here and in the following layers ■ with at least a tenfold increase in sensitivity versus "desensitized" emulsion layers at wavelengths from 1 to 1200 nm.

Resensitization can be achieved by simply bringing them into contact the desensitized emulsion with the resensitizer.

Preferably, the resensitizing agent is used in the form of a solution such as an aqueous solution. Solutions in which the resensitizing agent is contained in amounts of 1 to 100 g / l of solution are particularly suitable. The solution can be sprayed over the desensitized silver halide emulsion layer or the desensitized emulsion layer can be immersed in the solution of the resensitizing agent. The effective contact time for a sufficient resensitization depends on the desensitizing agent used in the individual case and the ReSe ₁ , mizing agent used. Contact times of 15 seconds to 10 minutes are expediently used in order to resensitize the emulsion layer.

00 9 834/03 49

In a further advantageous embodiment of the method According to the invention, the desensitized silver halide emulsion with the resensitizers is brought through in contact, that the latter is incorporated into a hydrophilic colloid, the mixture obtained is applied to a support and the hydrophilic colloid layer containing the resensitizer with the desensitized photographic Bringing silver halide emulsion layer into contact

In this case, the resensitizing agent is advantageously used containing hydrophilic layer prior to contacting with the desensitized emulsion layer moistened with water.

To produce such hydrophilic colloid layers, hydrophilic colloids customary for photographic purposes, such as gelatin, polyvinyl alcohol, hydrolyzed cellulose esters, albumins, and other hydrophilic ones Colloids of the | at column 13 * lines 43-67 of the United States patent 3 039 873 described type can be used »

The hydrophilic colloid containing a chemical resensitizer can be applied to conventional photographic supports, for example on carriers made of cellulose acetates, poly-

009834/0349

'carbonates, polyesters, for example polyethylene terephthalate and the like, as well as on paper backing or with synthetic resins coated paper supports are applied. The concentration of resensitizing agent is preferably in the range

1.076 to 538 hydrophilic colloids at around QgQQ (SC3fö3! SCX3XiÖfS6c mg

Resensitizers per dm of support area.

The hydrophilic colloid layer containing a resensitizer can be mixed with the desengibilized photographic Silver halide emulsion layer can be brought into contact in a conventional manner. The contact time should be sufficient to ensure a vigorous resensitization. Normally the contact times are 10 seconds to 10 minutes.

The photographic emulsions that can be resensitized by the process of the invention are customary, developable, unfogged, photographic silver halide emulsions of the negative type, such as, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide or silver chlorobromoiodide emulsions. Emulsion layers produced from such emulsions generally show after 5 minutes of development at 20 ^° C. in a developer A of the following composition:

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. "5597558

N-methyl-p-aminophenol sulfate 2.2 g

Sodium sulfite, dried 72.0 g hydroquinone 8.8 g

Sodium carbonate, dried 130.0 g potassium bromide 4.0 g

Made up to 1.0 liter with water

a concealment of less than about 0.5. Furthermore, such emulsions usually have sensitivities of at least about 3 log E, corresponding to an exposure of at least 1000 meter candle seconds, preferably 0 to 1.5 log E, corresponding to exposures of 1 to 0.33 meter candles, before they are desensitized -Seconds. Favorable results can also be achieved with emulsions if their sensitivities have a value of up to about Ü> log E, corresponding to an exposure of 0.001 meter-candle-seconds. E is exactly the exposure in meter-candle-seconds, at the constant to a 5 minute development at 2O ⁰ C in a developer A is the stated composition to produce a density of 0.2 above fog is required.

The emulsion layers can be made using the usual photographic binders such as gelatin, hydrolyzed polyvinyl esters ^ hydrolyze cellulose esters, Albumins, agar-agar, gum arabic and the like. Be constructed. Gelatin is preferably used as the binder. The de-, sensitized emulsions can be coated on conventional photographic supports or films.

009834/0349 "bad ^ ₁ ■■

To carry out the method of the invention are suitable also "photographic materials with such emulsion

in ■
layers which are used in X-ray photography

will.

The photographic silver halide emulsion layers resensitizable according to the process of the invention can contain a wide variety of conventional chemical desensitizers which inhibit the ability of these emulsions to form latent images. The photographic silver halide emulsions can be desensitized by adding chemical desensitizers to light having a wavelength of 1 to 1200 nm and waves in the wavelength range of gamma radiation and infrared radiation (about 1 × 10 * "^ to 1 χ 10 * nm). Such desensitized emulsions can, for example, be exposed to X-rays of up to 100 X-rays, preferably up to 1000 X-rays, without a density of greater than 0 in a developer A of the specified composition ^{after 5 minutes of development at 20 ° C.} , 1 results.

When using particularly active chemical desensitizers amounts of a few mg / mol of silver halide are sufficient to increase the photographic sensitivity

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■ ■ ■ ■ - w ^

SAD ORIGINAL

the emulsion layer by a considerable factor. When using less effective DesensitSLisie-

from
. means such as photographic, spectral

sensitizing dyes, are usually amounts of several grams are required to achieve sufficient photographic sensitivity of the silver halide emulsion layer to reduce fogging of the silver halide emulsion layer to prevent exposure to room light. Usually used in the emulsion layer about 0.01 to 5 grams of desensitizer per mole of silver halide. The one for any desensitizer optimal amount can easily be determined.

Typical desensitizers are heavy metal salts such as mercury salts, rhodium salts and the like. furthermore heterocyclic compounds which contain at least one sulfur and / or nitrogen atom as a hetero atom. Particularly advantageous heterocyclic desensitizers are those which have at least one benzene ring and preferably contain at least one nitro radical on the benzene ring.

Typical suitable organic desensitizers are benzotriazole compounds with a nitro radical on the benzene ring of the benzotriazole nucleus, such as. B. 5-Nltrobenzo-

009834/0349

^G ' ^NAi

1,2,3-triazole and 4-nitrobenzo-l, 2,3-trlazole, as well as their halogen-substituted derivatives, such as, for example, the 5-chloro and 6-chloro derivatives.

Non-heterocyclic aromatic desensitizers are also suitable with at least one nitro radical, such as, for example, 3,5-Dinltrobenzhydrazid and the like.

Suitable desensitizers are also dyes, in particular styryl dyes with at least one nitro radical on the benzene ring · Other particularly suitable desenibilizers are anil and safranine dyes as well as anthraquinone dyes with a sulfoalkylaminosulfone residue.

Typical "chemiiche Desenslbilisierung & medium _f can be with what dl" Silberhalogenidemul.8ionen desensitized are:

Mercury (II) chloride

Triammoniuahexachlororhodite

0098 34/0349

NO

2 O

! NHNH,

3,5-dinitrobenzhydrazide

NO.

5-nitrobenzo-1,2,3-triazole

il-NItro-6-chlorobenzotriaBOl

2,3-Diraethyl-6-nitrobenzothiaEOliuap-tolueneBulfon * t

00983A / 0349

:. Br "

2-phenylbenz0-1,2,3-thiadiazolium bromide

ClQ,

ClO,

N, N ^r -decarethylene bis (quinoxaline perchlorate

(CH ₃ ) ₂ N

Methylene blauchiorid

Cl '

1-methyl-2 # (p-nitroa ^ rryl) -6-ethoxyquinolinium-p-t ^ pluene-sulfonate

009834/0349

BAD ORIGIN «.

- ΐβ -

Cl '

2- (p-Diethylarainophenyliminomethyl) -1,6-dimethylquinolinium chloride

N (CH ₃ J ₂

OSO ₃ C ₂ H ₅

2- (p ~ Dimethylaminophenyliminomethyl) -3-ethylbenzothiazoline> athosulfate

Phenosafranine cliloride

Pinakrypt ο] prün (chi orid)

UD d 8 3 A / 0 3 A 9

1,3-diamino-5-methylphenazine chloride

3-methyl-2-bis (phenylazo) methylenebenzothiazoline

NH-CH ₂ CH ₂ -SO ₃ H

Anthraquinone

-2-suljk

otaurld

For desensitizing photographic silver halide emulsions suitable Desenslbilisatoren are further described in United States Patents 1653 31 ¹ I; 1,760,756; 2,196,162;

2,541,472; 2,669,515 and 2,794,802, British Patents 465,343 and writing French patent / 1049

together with x-i ^

c e French additional patent very if tw * 64 756 and 1 092 537 described. .

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ORIGINAL

159755R

2-Phenylbenzo-1,2,3-thiadiazolium bromide suitable as a desensitizing agent can be found in the journal "Journal Chemical Society" (London), page 90 (1956) by A. Burowoy, A. Chaudhuri and C. E. Vellins. The desensitizer 2- (p-diethylaminophenyliminomethyl) -3-äthylbenzothiazoliumäthosul- fat is described by Mees in "The Theory of the Photographic Process", 1st Edition (MacMillan), page 1043, as well described in British Patent Specification 447,109. Of the Desensitizer 3-methyl-2-bis (phenylazo) methylenebenzothiazoline is described in French patent publication 1 049 896 (for the formula cf. French patent specification 1 092 537).

A particularly useful class of desensitizers can be represented by the following general formula:

Herein mean:

R is an optionally substituted alkyl radical, for example a methyl, ethyl, propyl, butyl,

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Ethoxycarbonylmethyl, ß-hydroxyethyl, carboxyalkyl or sulfoalkyl radical;

an optionally substituted aryl radical, for example a phenyl radical or one by hydroxyl, nitro, amino, alkylamino, dialkyl amino, methyl, Substituted ethyl, ethoxyl or methoxyl radical Phenyl radical, or a substituent of the following general formula:

; - f _V

(B) (.— L == L) ^ - GH «C (—CHeCH) - J-N-

in which the radicals Z, R ₂ and m have the same meaning as the radicals Z, R and m | defined in more detail below .

L is a methine radical, for example a radical of the formula -CJ '=, in which R' is a hydrogen atom or an alkyl radical, for example a methyl or ethyl radical ₈ ;

X is an acid residue, for example a chloride, bromide, Iodide, perchlorate, benzenesulfafconate, p-toluenesulfonate, Methyl sulfate or A "thy! Sulfate residue;

0 098 34/0 3A9 - ^ - -,

SAB = ORJGiWM.

η and d = 1 or 2 and

Z those non-metallic atoms that make up a 5- or 6-membered heterocyclic Ring with at least one sulfur and / or nitrogen atom are required.

The styryl dyes represented by the formula (A) preferably contain at least one benzene ring which has at least one nitro radical.

Typical rings that Z can stand for are, for example benzothiazole, optionally substituted by methyl, ethyl, methoxyl, ethoxyl, hydroxyl or amino radicals, Quinoline, benzoxazole, indolenine or ß-naphthothiazole rings.

Another class of particularly useful desensitizers are merocyanine dyes, which are characterized by give the following general formula lassefi:

(C) R, -N (-CH-CH) -T C ("L-L) - C-C" O

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- ■ 21 - '' ■

where PU, Ζ ~, L, and ρ are those given for R, Z, L and η, respectively Have meaning, ρ = 1, 2 or 3 and Q those Represents atoms necessary to complete a 5- or 6-membered heterocyclic ring with an oxygen, Nitrogen, sulfur or selenium atom are required as a hetero atom.

Q preferably stands for those atoms which are necessary to complete a 5-membered ring which contains 3 carbon atoms, 1 nitrogen atom and, as the fifth atom, a nitrogen, sulfur or oxygen atom.

Suitable heterocyclic desensitizers also include the customary photographic, spectral sensitizing dyes which, when used in high concentrations, desensitize photographic silver halide emulsions. Typical, spectrally sensitizing dyes, which are suitable in high concentrations as desensitizers for silver halide emulsions, contain an amidinium ion, a carboxyl ion or an amide ion as a chromophoric group. Such chromophoric systems are described, for example, in the book by Μ ·· β and James "The Theory of Photographic Process", 3rd edition, Verlag MacMlllan Co., 1966, page 201 .

The dyes with chromophoric systems also include the dyes represented by formulas (B) and (C).

Typical, spectral sensitizing dyes with chromophoric systems are, for example, cyanine, merocyanine, hemicyanine, p-dialkylaminostyryl, hemioxonol and holopolar and allopolar cyanine dyes. Specific dyes of this type, which have proven useful as desensitizers in high concentrations, are described by Mees and James in the cited book. One advantage of using a spectral sensitizing dye or a combination of such dyes as desensitizing agents is that a silver halide emulsion desensitized therewith, after being resensitized according to the invention, is spectrally sensitive in the region in which the dye in question absorbs. Thus, the compound used as a desensitizing agent gives the emulsion a spectral sensitivity again after its resensitization.

The spectrally emollient dyes indicated below can be used both as desensitizers as well as acting as spectrally sensitizing compounds after research.

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dye

A anhydro-3-ethyl-9-methyl-3 ^t - (3-5Ulfobutyl) -4 _s 5-; ; 'benzothiacarboncyanine hydroxide

B ■ 9- [Hp-dimethylarainophenyl) propen-2-yl3-3 »3'-dimethylthiacarbocyanine bromide

C 3 ^l -ethyl-3-niethyl-9, ll-neopentylen-oxathiadIcarbo-

cyaninjodld

D 1 / L ¹ -Diet hyl-2,2 · -carbocyanine odicl

E anhydro-1-ethyl-1 «- (il-sulfobutyl) -2 _? 2-carbocyaiiin-

hydroxide

F 2.2 ^l -Di-ß-hydroxyäthylthiadicarbocyaninbromId

G g-ethyl-l'.J-dlmethylthia-S'-carbocyanine iodide

H l-Ethyl-2- [ _c (3-ethyl-4-oxo-2-thioxo-5-thiazolidinylidene) ethylidene-4- L (1,3,3-triniethyl-2-indoiinylidene) -äthylidenl-S- phenyl-S-imidazolinone

I anhydro-3 ~ ethyl-9-methyl-3 '- (3-sulfobutyl) -thiacarbo-. cyano hydroxide

J anhydro-9-ethyl-3-methyl-3 ^l - (3-sulfopropyl) -itol, 5; 4 ^l _f 5'-

dibenzothias carbocyanine hydroxide

K 5- [di (l-ethyl-2 (lH) -ß-naphthothiazolylidene) -iso-

propyliden-1,3-dl (ß-methoxyethyl) barbituric acid

L-3,3'-dimethyl-4,5; * J ', 5'-dlbenzothiacarbocyanine chloride

M ^ aS'-diethyl-g-methylselenacarbocyanine bromide

0 5 _i 5 ^f -Dichloro-3 _i 3 ^t y9-triethylthiocarbocyanine bromide

It may be useful to use combinations of non-spectral sensitizing desensitizers and desensitizing concentrations photo'gra-

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phisher, spectral sensitizing dyes to be used * turn around. When such combinations are used, the emulsion layer retains spectral sensitivity and additionally has the lowest fogging for a given sensitivity or the highest relative sensitivity for a given fogging.

The silver halide emulsion layers may be conventional ones Emulsion additives, e.g. chemical sensitizers, Antifoggants, plasticizers, hardeners, coating aids, and the like.

Emulsion layers sensitized by gold and sulfur compounds are particularly advantageous. The emulsion layers can, for example, with sulfur, selenium or Tellurium compounds according to US patents 1,574,944, 1 623 499 and 2 410 689 must be sensitized. Emulsion layers sensitized with gold salts are z. Tie U.S. Patents 2,399,083 and 2,642,361. Suitable sensitizing gold compounds are, for example, potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, Gold (III) chloride and 2-aurosulfobenzothiazole methochloride.

009834/0349 O / & _{0 / s}

The following examples are intended to illustrate the method of the invention illustrate in more detail.

Example 1 .

In this example, the resensitization of a desensitized photographic emulsion layer by treatment with a solution of a tetrazaindene is described.

A silver chlorobromide gelatin photographic emulsion sensitized with sulfur and gold sensitizers was divided into two parts. Part of the dye anhydro-3-ethyl-9-methyl-3 '- (3-sulfobutyl) thiacarbocyanine hydroxide was used in a desensitizing concentration (1.5 g / mol silver) added "The dye used is, in low concentrations" if applied, a spectral one Sensitizers. No dye was added to the second part of the emulsion.

The two emulsions were then applied to poly (ethylene terephthalate) film support in such a way that 32.29 mg of silver and 74.27 mg of gelatin were used ^{per dm 2 of support surface.} The photographic films obtained were cut into several strips and, prior to exposure, treated for 1 minute with differently concentrated solutions of a resensitizing compound in distilled water. 4-Hydroxy-6-roethyl-> 1,3,3a, 7-tetrahydrofuran was used as a resensitizing compound. The obtained | rg »bnl» ee were compared with the results obtained with

BATH ORIGINAL

Films were obtained which were not resensitized, but merely immersed in distilled water.

All films were 10 "x ^ seconds in a sensitometer exposed to light modulated by a step wedge and developed in the specified developer A for 5 minutes.

Table 1

Resensitive

Comparative film investigation "material Relative " 7th- Relative verse

Resensibilisierungs- sensitivity squint squinting Emplind- process llchkelt γ erunq llchkeit γ 'tion

1. Comparison attempt

without treatment 69 3.9 0.07 <1 0.05

2. Comparison attempt

- treatment in.

distilled '

Water 105 5.5 0.08 <1. 0.05

3. 66.7 g / l resensitizing dye 209 3.8 0.20> 1000 3.8 0.1?

^. 33.3 g / l resensitization dye
etoff 214 H, 6 0.09> 1000 3.9 0.09

5. 6.7 g / L reaensibilization dye 138 5.0 0.07 603 3.9 0.06

From the values in the table it follows that according to the procedure of the invention resensitized one by more than had a 600-fold increase in sensitivity.

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Example 2

In the previous example, this causes desensitized films resensitized that she was using a resensitizer containing developer tape are brought into contact. >

The procedure described in Example 1 was repeated, however, with the exception that the desensitized films, instead of being dipped in a solution prior to exposure, by rolling for four minutes in contact with a poly (ethylene terephthalate) film base, which contains 0.193 mg of gelatin and 4.844 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per dm of support surface was coated, were resensitized. Before the developer tape in contact with the desensitized. When the emulsion layer was brought, it was immersed in water. The films were exposed as described in Example 1 and developed. The film in Example 1 used as a comparative film, film which did not contain a desensilizing agent. The results obtained are given in the following table 2:

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Table 2 Relative
sensitivity 4.75
3.75 Wear
eration 6i) 6
355 0.15
0.05 Comparison film
Resensitized
Investigation material

Similar results were obtained when the resensitizer was used instead of the resensitizer Azaindenes, tetrazoles, cyclic disulfides or pyridine were used. Similar results were also obtained when the emulsion layer with ^ -nitro-6-chlorobenzotriazole had been desensitized.

Example 5

The following example illustrates chemical resensitization a silver halide photographic film, w hich with a desensitizing agent substituted by a nitro group has been desensitized.

One was sensitized with sulfur and gold sensitizers gelatin-silver chlorobromide photographic emulsion was prepared. The emulsion was in different proportions

008834/0349 ^nu O /? _{/ Q}

. 29- '1b 9 7 5 58

divided, "With one of these shares vnirde nln carrier coated serving as Ver ^ ileichsprobe dtenle .Ut -ItOi other shares ver." F.iiulsion were verochifdene Πεπ - χη dea PoHenaibilisixii'uncsraJtteV.l ^ i-Iiitro->. j-ehl>rLen:; ot ,, rlt: _; (! , '. nrßi - \ nbnn, Velvet borne bnulsions were made on PolyCathylent ^ rephtlinlat) «- f hat rager in the k'eise on & etrri. Oji,> fro dii "carrier surface 1 * 1.75 mg silver and 7 ^ 27 mfi gelatine ^ nti'ielen. The three test films contained 1, 1.6 and 3 ^ dye sensitizing agent per wood over films were cut into strips. strips of film-were exposed for comparison purposes and treated. Other strips of the films were pre-exposure for one minute in a solution of 6 "67 g / liter ⁱ i-hydroxy-6-methyl-l, 3 , 3a, 7-tetrazainden immersed in defilled water The various test strips were then exposed and developed as described in Example 1. The results obtained are shown in Table 3 below.

Table 3

llight resensitized resensitized

Comparative film examination material

Concentration of Relative Ver Relative Ver

Desenslbillsator Sensitive squint- sensation-, veil-

. ^ »_« ______-_- ™ ______. Handles γ run % lichkelt γ tion

Without 20ή, Ο 3.20 0.07 I'll 1.52 0.13

1.0 g / mole. Ag 5.7. 1.80 0.06 83 1.71 0.08

1.6 g / mole Ag 5.5 3.50 0.05 l \ 2 2.22 0.05

3.0 g / Hol Ag 1,., 'II, 80 I), 0 ¹ J Vl -2.10 0.07

^8AD

_ 30 - 1 b 9 7 5 5

From the In the table v.dr; -lev-re ^ level fourth it follows that by ile invent> ^ iHaär> e Reaensibiliöieruiu ;; The desensitized emulsion-trained persons develop a strong increase in sensation.

The following example illustrates the resensitization of desensitized films with a variety of resensitizers useful in practicing the method of the invention.

It was prepared as described in Example 1, a test emulsion with 1 g Anhydro-3-ethyl-9-methyl-3 ^I - stabilizes (3-sulfobutyl) thiacarbocyaninhydroxyd per mole of silver desensi- \. The resulting emulsion was applied to a poly (ethylene terephthalate) film support in the same concentration as that rubbed in Example 3Jb. The individual films produced in the manner described were treated for different lengths of time with various solutions of various resensitizers suitable for carrying out the process of the invention. The resenibilizing agents used and the treatment tents used are given in Table ¹ below.

005) 03 4/0349

bath

Films that were not bathed before exposure and films that were single, • borrowed to bathe in water. The exposure and development took place as described in Example 1. In one case, a 1.5 neutral density filter was also used and a No. 16 Wratten filter (yellow filter) exposed to obtain the minus blue sensitivities. The two . Results obtained from investigations are also shown in Table 4.

Tabel

Concentration of - Treat Relative 331 Relative 13th γ Ver Resensitizing 10 g / 11 lung minus 7Ml Blue- 23 veil in 10 g / l 1 time in Blue emp 251 Sensation 7.1 water 10 g / l 2 Min. sensitive 251 opportunity 5.5 - 0.18 10 g / l 3 speed 209 i}, 8 o m ίο g / i n ■. 200 s 0 26 - 5.0 4 _S 8 t 10 g / l 5 """""""""Max 316 11.2 9 ₉ 2 0.13 10 g / l 6 5 Max 398 O ₈ O 12.6 6.7 0.08 £ 10 pyridine 1 759 30th 3, M 0.10 10 % pyridine 5 100 3t * H _§ 1 0.13 ίο g / i 7 5 417 10.2 H, 8 0.06 10 g / l 8 5 5.2 0.06 5 3.8 0.09 • 5 5.3 0.07 5 1 * 6 0.22 1 ** 3 0.07 5 0.07 . 5 5

0 09 834/034 9

BATH

From the results contained in the table it follows that with the most varied of resensitizers one effective resensitization of desensitized emulsion layers

can be achieved unexpectedly. This fact is because dye solvents, such as acetone and methanol, for example, do not cause the films to be resensitized.

Example 5

The following example illustrates the resensitization of silver halide emulsion layers made with a wide variety of photographic spectral sensitizing dyes have been desensitized at high concentrations. -

A silver chlorobromide photographic emulsion was prepared and divided into various proportions. Various spectral sensitizing dyes in the desensitizing concentrations indicated in Table 5 below were added to the individual emulsion components. The variously modified emulsions were then applied to poly (ethylene terephthalate) film support in such a way that 32.29 mg of silver and ^{7.27 mg of gelatin were used per dm 2 of support surface.} The films obtained were obtained by bathing for one minute in a 6.67 g / l * J-hydroxy-6-methyl-l, 3 »3a, 7-

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solution containing tetrazine resensitivity, 1/1000 sec, exposed in a SensItometer through a 1.5 neutral density filter and developed in the specified developer A for 5 minutes. The individual sensitizing dyes marked with letters correspond to those in the above compilation on perceived sensitizing dyes. The following results were obtained:

Table 5 Relatively sensitive
after the dye
(g / mole silver) Relative
sensitivity > 1000 A 1.5 g <1 129 B 1.5 g <1 174 c 1.5 g 3.2 2] Λ D 1.5 L <1 __, E 1.0 g 1.9 214 E 1.5 g < 1 93.3 F 1.5 g <1 G 1.0 g 1.7 363 G 1.5 g <1 ___ I 0.625 g and
0.625 g - J ³ ' ³ > 1000 I 0.62 5 g and
- 0.625 - J and
0.063 - ■ - K

H 1.5 K

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BATH ORIGINAL

_ ₃ i, -

The following two examples demonstrate the use of combinations of concentrations with a desensitizing effect photographic, spectrally sensitizing dyes with non-spectrally sensitizing unsensitizers described. The advantage of this combination is that for a given concealment, the highest possible relative sensitivity or, given sensitivity, the lowest obscuration.

Example 6

First, a photographic gelatin-silver chlorobromide emulsion sensitive to sulfur and gold sensitizers was prepared. 625 mg of anhydro-3-ethyl-9-ynethyl-3 '- (3-sulfobutyl) -thiacarbocyanine hydroxide, 625 mg of anhydro-9-ethyl-3-methyl-3' - (3-SuIfOPrOPyI) were added to this emulsion per mole of silver. - ^ jS; ¹ ! ^1, 5 '-dibenzothiacarbocyanlnhydroxyd and 63 mg of 5- [di- (l-ethyl-2 (lH) -ß-naphthothiazocylH: idene) -isopropyliden2-l, 3-di- (beta-methoxyethyl) barbituric acid was added. Different concentrations of the desensitive solvent oil 2-plienyl-1,2,3-benzothlazolium bromide were added to different proportions of the single ion obtained. Each of the variously modified emulsions was applied to a polyethylene terephthalate film base in the manner

Q0983W0349

11) 97558

that 14.75 milliliters of silver and 7 ³ { _s ? -7 mg of gelatin were omitted per dm ^{2 of support surface.} Several samples of the films prepared as described were exposed to 1000 X-rays using 100 kV X-rays. '

The individual films were then resensitive by you can use one made of a polyester carrier and a

2 on the coated gelatin layer, which per dm support surface 194 mg gelatin and "53.9 mg of 4-hydroxy-6-methyl-l, 3, -3a _a tetrazaindene _7-s contained existing developer tape in contact GAH brought" Individual strips of the developer tape were 5 seconds, immersed in water and then reacted with each film as H min at 21.1 ° C in contact. The individual films were then exposed in an intensity sskalensensitometer. Several samples of each film were different lengths (between 30 seconds and 3 minutes ) in a 3-pyrazole donor / ascorbic acid developer of the type described in US Pat. No. 2,688,5 * f9. The films were then fixed in the usual manner, washed and dried. The results obtained are shown in Tables 6 and | 7 below Table 6 shows the degree of fogging at various relative sensitivities. Table 7 shows the relative sensitivities obtained at various degrees of fogging.

00 9834/0349 ~ - ,

Table 6 Obfuscation at a relative
Sensitivity of 126 159 2-phenyl-1,2,3-
benzothiadiazo- 100 0.65 1.09 Movie
No. lium bromide
(mg / mole silver) 0.48 0.45 0.55 1 0 0.36 0.29 0.49 2 100 0.23 3 300

Movie
No.

Table 7

Relative sensitivity with a concealment of 0125 0.5

105 l4l

100 204

166 229

Example 7

A series of films were made and treated as described in Example 6, with the exception that the emulsion layers only have a desensitizing dye, namely 1.5 S 1 -ethyl ^ -fO-ethyl-il-oxo-a 5-thiazolidinylidene) ethylidene] -4 - [(l> 3,3-trimethyl-2-indolinylidene) ethylidene} -3-phenyl-5-imidazolinone per mole Contained silver. The results obtained are given in Tables 8 and 9:

009834/0349

- '37 -

Table 8

2-phenyl-1,2,3-

benzothladiazo obfuscation at a relative

Sensitivity of

Film lium bromide
No. mg / mole silver '

300
5.00

0.38 0.30 0.25

126

0.52 0.44 0.42

159

0.68 0.56 0

Table 9

Movie
No.

Relative sensitivity at a concealment of , 0.25 '0.5'

112
132
145

174 204 195

Example 8

In this example, the resensitization is one with a Heavy metal salt desensitized silver halide demulsions described.

First, one with sulfur and gold sensitizers was used; classified photographic gelatin silver chlorobromide

0 9 8 3 A / Q 3 4 9

BATH ORIGINAL

emulsion made. The emulsion was divided into different proportions, mixed with different amounts of mercury (II) chloride and then applied to a polyethylene terephthalate film support in such a way that 1.75 mg of silver and 21.74 mg of gelatin were used ^{per dm 2 of support surface.} The emulsion layers of the various films contained 0.3, 1.0 and 3.0 g of mercury (II) chloride per mole of silver, respectively. Various samples of each film were treated using the following procedures:

Treatment A) 1/1000 »second exposure in

a sensitometer through a 1.5 neutral density filter;

Treatment B) Same as Treatment A) _{but 1} became the film

before exposure by bathing for one minute in a solution which is per liter 6.67 g of Jl-Hydroxy-ö-methyl-l ^^ a ^ -tetrazainden contained, resenaibilized;

Treatment C) as treatment B) | However, the film was

bathing for one minute before exposure in a solution which contained 66.67 g of the Tetrazaindena per liter, resensitized »

009134/0349

The treated films were then left in the developer for 5 minutes A developed, then fixed, washed and dried. The results obtained are given in the following table OK:

Table 10

Treatment a

concentration

0.3
1.0
3.0

ReI.

Receive

speed

Treatment B Treatment C Ver ReI, - \ fer- 'ReI. Verve- emp- veil-'em- · veil discovery

lent- lent- ',

_ — _—— speed χ speed γ ______

2.8 1.30. 0.06 9.7 3.20 0.06 D _max = 0.12 0.10 5.7 4.20 0.06 no image 0.25 D _ma = 0.26 0.15

m 3, ¹ JO o, o6 8.7 3.50 0.06 4.2 4.00 0.12

Example 9 .

The procedure described in Example 8 was repeated, with the exception that 2-phenyl-1,2,3-benzothladiazoliurabromide was used as the desensitizing agent instead of mercury (II) chlorine. The test material contained 0.6 g of the desensitizer per mole of silver

009 * 34/0349

BATH "ORlGINAL.

- 4ο -

, Treatment A) 1/1000 second exposure in one transmitter

sitometer through a 1.5 neutral density filter, a Wratten No. 35 filter and a Wratten No. 3 & J filter

Treatment B) like treatment A), but the film was

before exposure by immersion in a 5 # pyridine solution and then, 1 minute rolling in contact with the developer tape described in Example 6 resensitized.

The exposed films were in a p-methylaminophenol sulfate / hydroquinone decoder for 10 minutes with a ratio of 1 part of p-methylaminophenol sulfate to 4 parts Hydroquinone developed. The results obtained here are given in Table 11 below.

A. Y Table 11 treatment B. 2 Y Ver
tench
tion: treatment , 02 Relative
Sensation
opportunity 2 , 70 0.15 Relative
Sensation
opportunity , 16 Ver
tench
tion 166 , 90 0.12 100 3 0.10 110 A ™ = 0 0.12

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Example 10

This example illustrates the effective desensitization, the one when using desensitizing concentrations of photographic, spectral sensitizing Dyes can achieve. ·

As described in Example 1, a photographic emulsion was prepared. A portion of this emulsion served as a comparative sample. 1 g of the dye anhydro-3-ethyl-9-ynethyl-3 ^l - (3-sulfobutyl) thiacarbocyanine hydroxide per mole of silver was added to a second part of the emulsion obtained. 1.5 g / mole of silver of the same dye were added to a further portion of the emulsion. The emulsions were applied to polyethylene terephthalate film support and, as described in Example 1, exposed and developed. The results obtained are given in the table below.

Table 12 ^l h 50 sleeper g dye /
Mole of silver Relative O ₉ 48 0.06 in the era 66 O ₉ 07 1 1 0.07 1.5 <1

BAD ORIGIWAL

The degree of desensitization of these emulsions to X-rays is given in Table 13 below. The results compiled in this table were obtained by placing the emulsion layers on the Polyesta'trägern irradiated with 100 kV X-rays and ■ subsequently developed in the specified developer A. The density values obtained after development are in given in the following table.

without
Color
material Table 13 1.5 g dye /
Mole of silver Intensity of
roentgen
radiation 0.07 1 g color
substance / mole
silver 0.06 - 3.14 0.05 0.07 50 x-rays > 4, oo -0.09 0.07 100 x-rays "> 4.00 0.12 0.09 200 x-rays > 4.00 0.17 0.14 500 x-rays > 4, oo 0.31 0.20 1000 x-rays 0.49

As already stated, they have a desensitizing effect Concentrations of photographic, spectrally sensitive protective agents Dyes for silver halide emulsions alone or in combination

00 9 834/0340; _{; rr,. Γ}

bath

me ins am with chemical desensitizers, polygamy no "spectral sensitizers are added, so the emulsion is spectral after its resensitization sensitive. It should be noted, however, that even when it is added, it is more common Amounts of spectral sensitizing dyes to one by non-spectral sensitizing chemical desisibilizers desensitized silver halide emulsion "" - the Desensitization is noticeably reduced. This is evident from Example 11 below.

Example 11

One sensitized with sulfur and gold sensitizers Gelatin silver chlorobromide photographic emulsions were desensitized with 1.6 g * 1-nitro-6-chlorobenzotriazole per mole of silver. The emulsion would be divided into different parts. Some of these proportions were made by adding the various sensitizing dyes spectrally sensitized. The sensitizing dyes were used in usual low concentrations, which result in spectral sensing ensure with a minimum of desensitization, admitted. These concentrations were approximately 10 to 20 mg of dye per liter of emulsion. The single ones

00983A / 0349

, - BAD ORIGINAL

Dyes and the results obtained are given in Table I ¹ J. These results were obtained by applying the individual emulsions to poly (ethylene-

terephthalate) film carrier were applied that per dm 14.75 mg of silver and 21.74 mg of gelatin were used for the support surface. The films produced in the manner described were exposed to 1000 X-rays using 100 kV X-rays. Develop after 5 minutes in the developer A, the films were fixed, washed and dried. The comparative film was arbitrary assigned a relative sensitivity of 100.

Comparative film
Film with dye L Film with dye M Film with dye D Film with dye N Film with dye Q

Table 14 Density according to
Irradiation
with 1000 x-rays Relative
Sensation
opportunity 0.13 100 • 2.14 1230 2.35 1380 1.79 680 2.43 2040 2.05 780

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>. 45 -.

The Wratten filters mentioned in the preceding examples are described in the brochure Scientific and Technical Data Book B-3, "Kodak Wratten Filters for Scientific and Technical Use ¹ ", published in 1965, published by Eastman Kodak.

009834/0349

Claims (10)

PATENT CLAIMS 1. A method of resensitizing a photographic material for the recording of latent images, consisting of a carrier and a developable, applied to it, unveiled silver halide emulsion layer from Negative type, which by means of a chemical desensitizer, Consists of a heavy metal salt, an Änthraquinone dye containing a sulfoalkylaminosulfone residue, a non-heterocyclic, aromatic compound containing at least one nitro radical or a heterocyclic compound with at least one sulfur and / or nitrogen atom against light of one wavelength was desensitized from 1 to 1200 nm, characterized in that the photographic material with a Resensitizers consisting of a tetrazole, triazaindene, tetrazaindene, pentazaindene, or pyridine brings a cyclic disulfide into contact. 2. The method according to claim 1, characterized in that. the resensitizer used is 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene; 5-thioctic acid; M-Hydroxy-6-methyl-1 _t 3a »7-trlazaindenj 5- (3,4-Dlmethoxyphenyl) tetrazoli 5 - (^ '- 0 0 9 8 3 4/0349 ^8AD Cyanophenyl) tetrazole monohydrate; α-Plcolinium-ß-phenyläthjodidj 4-hydroxy-6-methyl-1,2,3,3a, 7-pentazaindene, 6- ] hydroxy-4-methyl-1,2,3,3a _s 7-pentazaindene or pyridine are used . 3, method according to claims 1 and 2, characterized in that that the photographic emulsion layer is treated with 1 to 100 g / l of a resensitizer for 15 seconds to 10 minutes Bringing containing solution into contact. 4. Process according to Claims 1 and 2, characterized in that the resensitizing agent is incorporated into a hydrophilic colloid, that the mixture obtained is applied to a support in such a way that about 1.076 mg to 538 mg of is dispersed in the colloid ^{per dm 2 of support surface} Resensitizers are omitted and the desensitized photographic emulsion layer is brought into contact with the hydrophilic colloid layer containing the resensitizer until the photographic emulsion layer is resensitized. 5 «Method according to claims 1 to 4, characterized in that that one resensitizes a photographic material, '-' · ■ '■■ ■ ■■ "■■ · ■ ■' ■ ■. '; ■" * its emulsion layer as a heterocyclic desensilbili- 00983 4/0349 bad sator contains a photographic, spectral sensitizing dye in such a concentration that the emulsion layer is roughly insensitive to light having a wavelength of 1 to 1200. 6. Process according to Claims 1 to 5, characterized in that a photographic material is resensitized, its emulsion layer by a photographic, spectral sensitizing dye with a chromophoric system, consisting of an amidinium ion-j carboxyl ion or Amide ion system is desensitized. 7. The method according to claims 1 bisjb, characterized in that a photographic material is resensitized, its emulsion layer by a spectral sensitizing Dye, consisting of a cyanine, merocyanine, hemicyanine, p-dialkylaminostyryl, hemioxonol, holopolar or desensitized allopolar cyanine dye is. 8. The method according to claims 1 to 7, characterized in that a photographic material is resensitized, the Emulsion layer with anhydro-3-ethyl-9-methyl-3 '- (3-sulfobutyl) -thiacarbocyanine hydroxide has been desensitized as a spectral sensitizing dye. 009834/0349 9. Process according to Claims 1 to 3 and 5 to 8, characterized in that a photographic material is resensitized, its emulsion layer by about 1.5 g of anhydro-3-ethyl-9-methyl-3 '- (3-sulfobutyl) thiacarbocyanine hydroxide per mole of sitdlber is desensitized, and that one the desensitized photographic material for 5 minutes Bathing in an aqueous solution containing about 33 g / l 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene contains resensitized. 10. The method according to claims 1 and 2 and 4 to 9, characterized characterized in that a photographic material is resensitized, its emulsion layer by about 1.5 g of anhydro-3-ethyl-9-methyl-3 '- (3-sulfobutyl) thiocarbocyanine hydroxide is desensitized per mole of silver and that the desensitized photographic material is left for about 4 minutes long with a coated on a carrier, moistened with water and about 4.8 mg of 'l-hydroxy-ö-methyl-' per dm ^{2 of support area} _Λ Ii3 ₈ 3a, 7-tetrasainden / containing, hydrophilic colloid layer brings into contact. 11 ο Process according to claim 1, characterized in that a triaaindene, tetrazaindene or pentazaindene substituted by a hydroxyl radical is used as the resonsibilizing agent «