DE1772026A1 - Photographic recording material - Google Patents

Description

EASTiAK KODAK COlIPAMY, 343 State Street, Rochester, State. ¹ IeW York, United States of America

Phot o, qr aphis chos Auf ze i quinine. ^ Si'S ate rial

The invention relates to a photographic recording material, Consists of a single carrier and a minimum of one light-sensitive silver halide-containing layer and optionally one or more intermediate and / or outer layers and one in the silver halide layer or in a layer arranged adjacent to this layer Halogen acceptor #

The so-called developable photographic recording materials are known to be used for /: rzcuru. vo: .. i'ililern exposed, chemically developed, fixed. t, <J ^ e ^r _vu; "H:. . Such recording materials have between c.ne! Ic "- · - '■ -; findlic' .- ·

BAD ORJG / NAL

^mm tmt ^mt

speed and provide stable visible images, but are used to generate little or not at all of so-called copying images suitable.

On the other hand, conventional, photographic, for copy-out processes certain recording materials usually do not chemically engineered to produce stable visible images. In recent times, so-called photographic marriages have therefore been used Direct copy materials developed, which are much more sensitive than the usual copy materials, but not need to be developed chemically. Such photographic materials can also be developed chemically, but they can only under special working conditions, as the components contained in them with common developer compounds create strong veils.

It has therefore hitherto always been necessary to use special photographic techniques To prepare silver halide emulsions for either photographic Materials are suitable for development processes or for copy-out processes. The consumer was therefore forced to to keep several of these different photographic materials in stock at all times, even when in use The new, chemically developable print-out materials made it necessary to purchase additional special developers.

The object of the invention is to start photographic materials. * ie svivohl as developable as well as copyable

BATH ORIGINAL

CÖ9343 / CS7S

Photographic recordable materials can be used can and can be developed with a wide variety of developers.

The subject of the invention is a photographic recording material, consisting of a support and at least one light-sensitive silver halide-containing layer and one or several intermediate and / or outer layers and one in the silver halide-containing layer or in one of it Layer adjacent layer arranged halogen acceptor, which is characterized in that it is a silver halide-containing Layer whose silver halide grains are at least partially were precipitated in the presence of tetravalent lie tall ions, contains. The invented recording materials and layers containing silver halide contain tetravalents Ions or atoms included, which during the precipitation and / or were present in the formation of the silver halide.

Typical for the production of the photographic recording material Tetravalent metal ions suitable for the invention or ions of compounds of tetravalent metals are e.g. Platinum, iridium and osmium ions and their genes. The tetravalent metal ions can be used in the emulsion in different 'be added wisely. In an advantageous manner they are e.g. : with the aqueous used to precipitate the silver halide Solutions of the silver salt, e.g. silver nitrate, or the

BATH ORIGINAL

009843/0879

Halides, e.g. sodium or potassium iodide, bromide or -Chloride, or with a hydrophilic binder used as a binder Colloid such as gelatin added. The tetravalent lethal ions can be in the form of water-soluble inorganic Salts, of organic metal compounds, of complexes or in any other torrn, which lead to the formation of tetravalent metal ions during the precipitation of the silver halide.

The tetravalent metals can be used in various concentrations. Preferably at least 1 χ 10 iol% and generally 1 χ 10 "'to 2 mol%, based on the amount present Silver, used.

The type of binding of the tetravalent metal ions to the silver halide in the silver halide grains can be determined by washing the precipitated silver halide grains successively with a silver halide solvent, e.g. an organic thioether or an alkali metal thiocyanate, and analyzing the washing solutions. If the tetravalent ions are only superficially attached to the silver halide grains, practically the entire amount of the tetravalent ions is already present in the first washing solutions. If, on the other hand, larger amounts of the tetravalent ions are only found in the washing solutions obtained shortly before the silver halide has completely dissolved, then they have been included in the silver halide grains .

009843/0879

The precipitation of the silver halide grains takes place particularly advantageously in an acidic medium, ζ · B · at a pH value as a rule below 6 and preferably below 5. A wide variety of acids can be used to adjust the pH used, e.g. phosphoric acid, trifluoroacetic acid, Hydrobromic acid, hydrochloric acid, sulfuric acid or nitric acid.

For the production of the photographic recording material Silver halide grains with an average diameter of about 0.01 to 10 are particularly suitable about 0.05 to 2 microns.

The photographic material can contain silver halide grains made from the usual silver halides, for example silver chloride, silver bromide, silver bromoiodide, silver chloroiodide or silver chlorobromoiodide. Preferably it contains silver halide grains the halide of which is at least 50 % bromide, less than 10% iodide and less than 50% chloride, calculated on a molar basis. Both silver halides, which form the latent images primarily on the surface of the silver halide crystals, and those which form the latent images primarily in the interior of the silver halide crystals, e.g. those described in US Pat. No. 2,592,250 *, can be used here.

009843 / Q & 76 ' ^BAD

The photographic recording material preferably has according to the invention on a silver halide emulsion layer. The layer can act as a binder for the silver halide grains contain a wide variety of common and well-known hydrophilic colloids, e.g. gelatin, colloidal albumin, polysaccharides, Cellulose derivatives, polyvinyl compounds, e.g. polyvinyl alcohol derivatives, Acrylamide polymers and the like. The binders can optionally also hydrophobic colloids, e.g., dispersed polymerized vinyl compounds, especially those containing the Increase the dimensional stability of the photographic materials. Typical suitable such compounds are e.g. water-insoluble polymers made from alkyl acrylates or methacrylates, Acrylic acid, sulfoalkyl acrylates or methacrylates and the like

However, the photographic materials can also be used in a vacuum Silver halide layers vapor-deposited on a carrier, which are practically free of conventional carriers, binders or dispersants included. In this case the analog acceptor becomes in one of the vapor deposited silver halide layers adjacent intermediate or top layer used.

That for the production of the photographic material according to the invention The silver halide used is not fogged and contains no visible or developable latent image. The silver halide is resistant to electromagnetic radiation, e.g.

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to electrons, visible light or X-rays, sensitive.

For the production of the photographic material according to the invention can be the most diverse known and used to manufacture Photographic copier materials can be used with all common analogue acceptors. Preferably nitrogenous ones Dialogue acceptors, especially those of the following general formulas used:

and R ¹ -N- R

in which mean:

I 7

II, R and R hydrogen atoms, optionally substituted

Alkyl or optionally substituted aryl

residues, or acyl residues, e.g. -C-R - residues, where R is a hydrogen atom, an alkyl or represents an aryl radical;

R is a nitrogen-containing residue, e.g. a ge

optionally substituted amino or optionally substituted thiocarbamyl radical and

009843/0879 _BAn

BATH

D to complete a heterocyclic ring with preferably 5 or 6 ring atoms and at least 2 Nitrogen atoms and at least one divalent radical of the formula H, in which X is a sulfur, oxygen or Selenatoi'i or an imino radical = NII means required Atoms.

>
If D or R "are nitrogen-containing radicals whose nitrogen atoms are bonded directly to the nitrogen atom of the above general formulas, at least one of the nitrogen atoms bears a hydrogen atom.

^- 9
If R is an amino radical, this can be given by the general formula

-N ₍ are shown, in which R and R advantageously have the meaning given for R and R hydrogen atom, alkyl, aryl or acyl radical.

2
If R is a thiocarbamyl residue, this can be represented by the general formula jj - ^ k, in which R and R '

-C-NiT _R

advantageously have the same meaning as R and R. or mean amino radicals.

Compounds of the following general formulas are particularly suitable as ilalogen acceptors:

009843/0879 BATH ORIGINAL

Formula A: I It I

R- - Ii- C - N -

R ¹⁰ SR ¹¹

Formula B: ι - H ■ _ΛΛ

' R ^1J - N - C - N - R ¹

_R 16 Formula C: |

"- ^! R ¹⁵ - NH - N - R ¹⁷

Formula D:

R ¹³ - K - NH -C = E

in which mean:

RO, R ¹⁰ , U ¹ⁱ ,, R ¹² , R ¹³ , R ¹⁴ Zr ¹⁵ Zr ¹⁶ , R ¹⁷ UnJR ¹³

1 ⁷ I.

Hydrogen atoms or those given for R and R ″ Alkyl, aryl or acyl radicals,

E is a sulfur, oxygen or selenium atom or an imino radical,

Q and Z are the atoms required to complete a heterocyclic ring with, as a rule, 5 or 6 ring atoms.

009843/0879 bad original

Q and Z are preferably those to complete triazolthiol, Mercaptoimidazole, imidazolidinthione, triazinthiol, Thiobarbituric acid, thiouracil or urazole, e.g. thiourazole rings.

In the general formulas given, the aryl radicals preferably consist of optionally substituted naphthyl or Phenyl residues. The substituents of these radicals can consist, for example, of halogen atoms, alkyl or acyl radicals. The alkyl radicals in the formulas given and, if appropriate, in the naphthyl or phenyl radicals, 1 to 20 and particularly advantageous Way have 1 to 8 carbon atoms, which are optionally substituted by halogen atoms, aryl or acyl radicals could be.

Typical suitable halogen acceptors of the thiourea type, as represented by the general formulas A and B are described, for example, in U.S. Patents 3,241,971 and 3,326,689. Typical suitable halogen acceptors of the hydrazine type as represented by the general formula C. are described, for example, in U.S. Patent 2,588,982. Typical suitable halogen acceptors of the urazole and thiourazole types represented by the general formula D are used, for example, in the French U.S. Patent 1,450,984.

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Type is ca e and advantageous ilalopenic acceptors are, for example:

1,3-iJi: iethyl-2-iriidazolidinthione _> 2-inidazolid.inthiGn, T-phenyl-S-mercaptotetrazole, thiosenicarbnzid,

Yctranethylthiourea, p-üinethylasiinobenzaldehyd-thiosenicarbazon, i-isopentyl-2-thiourea, T- (2-diethylaninoethyl) -T, 2,5,6-tetrahydro-1,3,5'-triazine-4-tliiol,

T, 2-bis (1,2,5,6-tetrahydro-1,3,5-triazine-4-thiol) itthane ₍ (

1-phenyl-2-thiiourea, 1,3-l) iphenyl-2-thiourea, 4-thiobarbitic acid, 2-ihioufacil,

1-Acetyl-2-thiourea £, 1,3-dibenzyl-2-thiourea _t 1,1-diphenyl-2-thioharnsto £ f, T-ethyl-l- (a-naphthyl> -2-thiourea, 2-. lercaptoimidazole, 5-selenourazole,

Hydrazine,, ■

Phenylhydrazine hydrochloride,

2,5-dichlorophenyl hydrazine,

i-phenyl-2-iinidazolidinthione, 4,5-diphenyl-4-imidazolidine-2-thione, 1-, iethyl-2-niercaptoiinidazole, 1-n-butyl-1,2,5 _# 6-tetrahydro-1,3 , 5-triazine-4-thiol, p-iOliiolsulfonyl-Iiydrazine,

0098/43/0879

BAD OHiGINAt

Hexylhydrazine, thiourea, 1-methyl-2-iniidazolidinthione, D-lannose-thiosemicarbazon, morpholino-2-propane-thiosemicarbazon, D-galactose thiosemicarbazone, urazole,

3-thiourazole, 3,5-dithiourazole, 3,5-dithiourazole hydrazine salt, 4-aminourazole hydrazine salt, 3,5-dithiourazole hydrazine salt, urazol, sodium salt, 4- (1-naphthyl) urazole, 4-Athylurazol, 1-Phenylurazol, 4-phenylurazole, 1-butylurazole, 1-octylurazole, 4-butyl-3,5-dithiourazole, 1,4-diphenylurazole, 1,4-dibutylurazole, 1,4-dibutyl-3,5-dithiourazole, 1 ^ -diphenyl-S, 5-dithiourazole, 1-ethyl-4 * -phenylurazole, 1-ethyl-4-phenyl-3,5-dithiourazole, 3-thio-5-luinourazole, p-tolylhydrazine, llydrochloride,

α-Naphthylhydrazine, 009843/0879

O-lignzvl-a-phenvlhydraztn.

BATH ORIGINAL

Suitable halogen acceptors are also aromatic iercaptans, e.g. Thiosalicylic acid; also hydroquinones, for example hydroquinone, chlorohydroquinone, gentisic acid and t-butylliydroquinone; Catechols such as phenyl catechol and t-butyl catechol; p-aminophenols, for example Ti-. ethyl p-aminophenol sulfate; 3-pyrazolidones, for example i-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone and 1-phenyl-4,4-di-methyl-3-pyrazolidone; Phenylenediamines; Nitriles; Phenols; Glycine; Sodium sulfite and alkaline substances, e.g. borax, alkali metal hydroxide and the like »

The Ilalogenakzeptoren can -in the most varied of usual Concentrations are used. Appropriately, about 0.01 to 100 ..... IqI-I, preferably about 0.1 to 25 MoI-S, based on existing silver halide is used.

The halogen acceptors can, for example, be the same layer that also contains the silver halide, e.g. the silver halide emulsion layer, or a layer adjacent to the silver halide layer.

The photographic material according to the invention can have one of the customary known supports, for example a support made of paper, paper coated with polyethylene or polypropylene, made of films made of cellulose acetate, polyvinyl acetals, polystyrenes, polyesters, for example polyethylene terephthalate, polycarbonate, polyimide , and supports made of Glass, jetall and the like.

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The photographic material according to the invention can be particularly favorable for the production of photographic "frosted prints" use. Becomes a silver halide emulsion layer prepared according to the invention applied to a carrier with a halogen acceptor and if the material is exposed, this is the case according to the Exposure copy-out image obtained compared to further cesant exposure unstable. However, after image-wise print-out exposure, the halogen acceptor is washed out or with the aid

removed from oxidizing agents such as bromine water, acidic permanganate, sodium hypochlorite or N-brortosuccinimide, an extremely stable recording is obtained. V, ^r ird the silver halide emulsion without an Ilalogenakzeptor applied to a support, may be in the resulting photographic "iaterial after exposure also obtain a stable recording! Herds, if one uses methods in which imagewise a halogen acceptor is formed and the ilaterial then a Gesaratbelichtung subjects. In both cases, will not fade t the picture with continued exposure.

The extremely low sensitivity of photographic materials in the absence of an Ilalogenakzeptors and the high copying capacity in the presence of an Ilalogenakzeptors are complete surprised. In view of the fact that most of the known print-out materials only used special developers can be developed into satisfactory images, it can be anticipated that the photographic material after the Invention in various types of developers chemically

0 0 9 8 A 3/08 7 9 BAD original

can be developed and that in doing so images with a high maximum Density and good contrast can be obtained.

The inventive photographic materials can optionally after exposure to high temperatures up to almost Charring temperature of the carrier are heated to the generated To stabilize the image or to suppress the copying of unexposed or high-image areas. Should be heated for imaging are, in a particularly advantageous iv'eise carrier with high Heat deformation temperature, e.g. carrier made of polyesters, polyimides, Polycarbonates and the like., Used.

The following examples are intended to explain the invention in more detail.

example 1

A radiation-sensitive gelatine silver chlorobromide emulsion, the silver halide of which consisted of 5 mol% and chloride and 95% bromide, was prepared by simultaneously haliding an aqueous solution of silver nitrate and an aqueous solution of alkali metal was added slowly and with stirring to an aqueous gelatin solution of 35 ⁰ C, the 'pH .war been adjusted with nitric acid to about 2.0. The emulsion obtained was used as a comparative sample. A second emulsion was prepared in a corresponding manner, the aqueous gelatin solution of which contained 25 mg of 1-1, PtCl ^ per ha of silver. Each emulsion was divided into two parts * One

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Part was applied to a paper carrier without any further additives. The second part was each rated with 5.0; iol- ^? 5 dithiourazole hydrazine salt, based on the silver present, were added, whereupon the coating compositions obtained were applied to paper backing. The test specimens obtained were exposed to cold, white, fluorescent light for about 134,300 lux minutes (12,500 foot candlesticks). The following reflective densities as determined by a No. 15 Wratten filter were obtained

.Film sample Ilalogen acceptor density

Comparative sample
Comparative sample

Sample with H ₉ PtCl, 2 6

Sample with H ₀ PtCl.

L D

Example 2

Following the procedure described in Example 1, several photographic emulsions were prepared in which various amounts of H ^ PtCl .. were incorporated. Each emulsion was again divided into two parts and the same amount and the same Hßlogenacceptor as described in Example 1 were added. The test specimens were exposed as described in Example 1. The following results were obtained!

no 0.04 Yes 0.96 no 0.02 Yes 1.27

0 0984 3/08 79 bad original

Test item (ng / .Ιοί Ag)

Comparison sample comparison sample sample with 5 mg 1I ₂ Pt sample with 5 mg sample with 25 mg sample with 25 mg H sample with 75 mg H sample with 75 m <? H

Halogen acceptor

density

no 0.04 Yes 0.96 no 0.02 Yes 1.03 no 0.02 Yes 1.27 no 0.03 Yes 1.24

Example 3

As described in Example 1, photographic emulsions were prepared, but this time instead of the platinum compound K ₉ IrCl, - was used. The following results were obtained:

Test item (mg / mol Ag).

K ₂ IrCl ₆ (50) K ₇ IrCl ₆ (50)

Ilalogenaccept or

density

no

less than 0.02 1.42

Example 4

There were wio described in Example 1, photographic emulsions, which jadoch the platinum compound by various.! Close K-OsCl ₆ was replaced * Di © samples in% UQii- _t as described ■ in Example Ϊ, vorarbeitet and tested "Ks were

die £ alß @ na & n Ergflmlf.g © Gvkaltcnt

. 0Q && 43/087

BATH ORIGINAL

Test item (mg / Ιοί Ag) Ilalogen acceptor density

no <0.02

yes 1.06

no <0.02

yes 1.13

K ₀ OsCl.
2 6 (10) K ₉ OsCl.
2 6 (10) K ₂ OsCl ₆ (50) K ₂ OsCl ₆ (50) example 5

This example shows that the photographic material of the invention can be chemically developed in a wide variety of conventional developer solutions. Gelatin-silver chlorobromide emulsions , the silver halide of which consisted of 5% chloride and 95% bromide, were prepared by simultaneously adding an aqueous solution of silver nitrate and an aqueous solution of alkali metal halides to one aqueous gelatin solution containing various densities of the tetravalent metal salts listed in the table below was added. The emulsions were washed, mixed with 5 g of dithiourazole hydrazine salt per hol of silver present and placed on paper carriers in this way.

2
brought about 1.07 g of silver (100 ing / sq.ft,) and 2.37 g of gelatin (220 mg / sq.ft.) per m of support area. The test specimens were exposed under the same conditions and for 90 seconds in a p-: lethy laminophenolsulfat-Ilydrochin-Lintwickler (developer A) diluted with water in a ratio of 1: 1 or for 4 minutes in a paraforinaldehyde-hydroquinone developer (developer B) developed.

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The developers had the following composition:

Developer A:

Water, about SO ⁰ C .................................... 500 ml

p-'iethylaminoplienol sulfate "............................ 3.0 g

Dehydrated sodium sulfite ............................ 45.0 g

Sodium carbonate, ionohydrate 80.0 g

Potassium bromide 2.0 g

filled up to the liter with! / water,

diluted 1: 1.

Developer E::

Water, about 30 ⁰ C 500 ml

iiatriun sulfite »dehydrated 30.0 g

Boric acid, crystalline 7.5 g

Water filled to the liter,

■ ·

The following results were obtained!

0098A3 / G879 bao whether _{I & nal}

Tetravalent Iletall connection

Ag)

H ₂ PtCl ₆ (5)

H ₀ PtCl. (25)

Lj O

II ₉ PtCl _r (75)

K ₂ OsCl ₆ (10) K ₂ OsCl ₆ (50)

Developer Λ

D D.

iriax mn

1.62
1.59
1.42
1.52
1.14

0.03 0.03 0.02 0.02 0.02

Developer B
max min

1.52
1.43
1.42
1.42
1.10

0.05 0.0 ^ 0.03 0.02 0.02

Similar results were obtained when, for developing, a dietol-IIhydroquinone developer or a paraphenylenediamine-glycine developer and Paraariinoplienol hydrochloride developer is used became.

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Claims (5)

Claims 1) A photographic recording material, consisting in a support and at least one photosensitive silver halo "genidhaltigen layer and optionally one or more -Zwischen- and / or cover layers and a disposed in the silver halide layer or in a layer adjacent to this layer layer Ilalogenakzeptor _t in that it contains a layer containing silver halide, the silver halide grains of which have at least partially been precipitated in opposition to tetravalent metal ions. 2) Photographic material according to claim 1, characterized in that it contains a layer containing silver halide, the silver halide grains of which were precipitated in the presence of tetravalent ι lethal ions in acidic iledium 3) Photographic material according to claims 1 and 2, thereby characterized in that it contains a layer containing silver halide, the silver halide grains of which in the presence of osmium, Precipitated platinum or iridium ions or mixtures thereof became. BAD ORfGfNAL - 22 - 4) Photographic .'laterial according to claims 1 to 3, thereby characterized in that it is a halo ^ enacceptor contains nitrogenous halopene acceptor. 5) Photographic isaterial according to claims 1 to 4, characterized marked that. it as Ilaionenakceptor Jrazol, Tiiiourazol or contains thiourea. BATH