DE2734335C2 - Lith type light-sensitive photographic spectrally sensitized silver halide recording material - Google Patents

Description

V = CH-CH = CH-CH

C ₂ H ₅

20th

contains.

4. SilberhalogenidaufnahmaungsmateriaJ according to claim 1, characterized in that it is used when a diffusible tetrazolium compound adjacent to this and the sensitizing dye Layers, if a diffusion-stable tetrazolium compound is used, these and the sensitizing dye contains in the same layer.

25th 30th

The present invention relates to a photosensitive, photographic, spectrally sensitized Lith-type silver halide recording material comprising a support and at least one coated thereon Silver halide emulsion layers, wherein the silver halide has an average grain size of 0.1 to 0.8 µm, at least 80% of the silver halide grains in the range 0.7 to 1.3 times the average Grain size lie and the silver halide from silver chloride bromide or silver chloride iodobromide with at least 50 mol% silver chloride content.

With photographic recording materials of the lith type, high-contrast point and line images are obtained, if they are exposed to very low sulfite ion concentrations after exposure to an alkaline hydroquinone developer bath developed. Lith materials contain silver halide emulsion layers with a high silver chloride content of at least 50 mol% and a low silver iodide content of at most 5 mole percent. The silver halide grains of such an emulsion are relatively small (average grain size 0.3 fxm) and uniform in size and shape, which results in a narrow grain size distribution.

When producing images for phototechnical purposes, it is first necessary to include an original image to convert continuous blackening (halftone image) into a point image (raster image). To this end, will exposed the halftone image to a lith-type recording material via a contact screen, and that initially still latent raster image converted into a visible one by development.

Selba when using a lith material with very small silver halide grains of uniform size and shape When developing with a standard black / white developer, there is a clear limitation of the Screen points rarely achieved. This is undesirable as a result of poor quality in the manufacture of printing plates l'point quality. In general, one then strives to achieve a gradation between 7 and 9, a task which cannot be solved with the use of a standard black and white developer, because in this way I hole values between 5 and 6 can be obtained. However, if you use a so-called infectious developer, leave it on Such high gradation values can be achieved, provided the sulfite ion concentration in the developer solution is low. However, low sulfite ion concentrations impair the shelf life of such Developer solutions. The use of tetrazolium compounds in a wide variety of photographic ! emulsions, e.g. unsensitized, orthochromatic, panchromatographic and X-ray emulsions, Paper and paint emulsions are already known from DE-AS11 77 002. However, they serve there to reduce the formation of eye eggs and if, in addition, there is talk of a good ability to contrast, then one of them is no more to be understood than that an already existing good contrast should be stabilized.

The invention is therefore based on the object of providing a light-sensitive, photographic, spectrally sensitized To provide lith-type silver halide recording material that can also be developed with a Ilydroquinone developer delivers high quality raster images.

This object is achieved in that the recording material is a tetrazolium compound of the general Formulas (I) to (III)

R ^l —Ν — Ν — R ³

Il I
NNX ^s (I)

Θ «

R ·· —Ν — Ν — D — Ν — Ν — R ⁵

NN NN 2Χ ^θ (Π)

γ γ

R ⁶ R ⁷

"R · —Ν — Ν — R * R ⁱ⁰ - Ν — Ν - R"

I I I Ii

NN NN 2X ⁰ (ΠΙ)

C C

I _ν I

contains, where mean:

R ¹ , R ³ to R ⁵ and R ⁸ to R "each represent an aryl group or a heterocyclic group,

R ² , R ⁶ and R ⁷ each represent a hydrogen atom, an aryl, alkyl or hydroxyl group, a heterocyclic group, a carboxyl group or a salt thereof, or an amino, mercapto or nitro group, D an arylene group,

E is an alkylene, arylene or aralkylene group, and
X® an anion that is omitted in the betaine structure.

According to the invention, diffusion-stable and diffusible tetrazolium compounds can be used. The term "diffusion-stable tetrazolium compound" denotes a compound which is not or only insignificantly dissolved from the photosensitive recording material by the developer bath during development. Is such a compound must not dissolve preferentially than 2% when a GeIatineschicht containing the compound for 10 minutes ir an aqueous solution at 30 ⁰ C. Immersed having the same ionic strength and the same pH value as the Shows developer bath.

Representative examples of tetrazolium compounds which can be used according to the invention are those of the general formulas (I) to (III) given, in which specifically mean:
R ¹ , R ³ to R ⁵ and R * to R "each have a phenyl group (e.g. a phenyl, tolyl, hydroxyphenyl, carboxyphenyl, aminophenyl or fctercaptophenyl, carboxyethylphenyl, nitrophenyl, ethoxyphenyl, iodophenyl, Methoxyphenyl, cyanophenyl and acetoamidophenyl group), a naphthyl group (e.g. an δ - naphthyl, jß-naphthyl, hydroxynaphthyl, carboxynaphthyl or aminonaphthyl group) or a thiadiazolyl, benzothiadiazolyl, pyrazolyl, It is advantageous if this Gt? <Ppe contains a lone pair of electrons that they can use to form metal chelates or one

so capable of complex, such as a primary, secondary, tertiary amino group, an oxime, thioether, keto, ThiokekK hydroxyl, mercapto, carboxyl, sulfo, phosphorus (e.g. with the O ₂ P group) and the Alkoxylgruppc and

R ² , R ⁶ and R ⁷ each represent a phenyl or naphthyl group, a methyl, ethyl, propyl, butyl, mercaptomethyl or mercaptoethyl group, a methoxycarbonyl or ethoxycarbonyl group or an amino, ethyiamino or anilino group.

In the general formula (III), E is preferably a phenylene, alkoxy-substituted phenylene group such as a methoxy-substituted phenylene group, a naphthylene, diphenylene or naphthylene diphenylene group.
Typical examples of cationic proportions of the tetrazolium compounds are given below.

1) 2- (Benzothiazol-2-yl) -3-phenyl-5-dodecyl-2H-tetrazoiium

2) 2,3-Diphenyl-5- (4-t-octyloxyphenyl) -2 H-tetrazolium

3) 2,3,5-triphenyl-2 H-tetrazolium

4) 2,3,5-tri- (p-carboxyethylphenyl) -2 H-tetrazolium

5) 2- (Benzothiazol-2-yl) -3-phenyl-5- (o-chlorophen. ^Ii l) -2 H-tetrazolium

6) 2,3-diphenyl-? H-tetrazolium

7) 2,3-Diphenyl-5-methyl-2 H-tetrazolium

8) 3- (p-Hydroxyphenyl) -5-methyl-2-phenyl-2H-tetrazolium

9) 2,3-diphenyl-5-; ithyl-2H-tetrazolium

10) 2,3-Diphenyl-5-n-hexyl-2H-tetrazolium

11) S-cyano ^^ -diphcnyl ^ H-telrazolium

12) 2- (Benzothiazol-2-yD-5-phenyl-3- (4-tolyl) -2H-tetr; i / olium

13) 2- (Bcnzothi; izci-2-yi) -5- (4-chlorophenyl) -V (4-nitrophenyl) -2 H-tetrazolium 5

14) 5-ethoxycarbonyl-2,3-di- (3-nitrophenyI) -2 H-tetrazolium

15) 5-acetyl-2,3-di- (p-iithoxyphenyl) -2 H-tetrazolium

16) 2,5-Diphenyl-3- (p-tolyl) -2H-tetrazolium

17) 2,5-Diphenyl-3- (p -iodophenyl) -2H-tetrazolium

18) 2,3-Diphenyl-5- (p-diphenyl) -2 H-tetrazolium io

19) 5- (p-Bromophenyl) -2-phenyl-3- (2,4,6-trichlorophenyl) -2 H-tetrazolium

20) 3- (p-Hydroxyphenyl) -5- (p-nitrophenyl) -2-phenyl-2H-tetrazolium

21) 5- (3,4-Dimoxyphenyl) -3- (2-ethoxyphenyl) -2- (4-methoxyphenyl) -2H-tetrazolium

22) 5- (4-Cyanophenyl) -2,3-diphenyl-2 H-tetrazolium

23) 3- (p-Acetamidophenyl) -2,5-diphenyl-2 H-tetrazolium 15

24) 5-acetyl-2,3-diphenyl-2 H-tetrazolium

25) 5- (Fur-2-yl) -2,3-diphenyl-2 H-tetrazolium

26) 5- (Thien-2-yl) -2,3-diphenyl-2H-tetrazolium

27) 2,3-L / ipricriv! -5-ipyriu-4-yi) -2 it-icifdZüiiürn

28) 2,3-Diphenyl-5- (quinol-2-yl) -2 H-tetrazolium 20

29) 2 _t 3-diphenyl-5- (benzoxazol-2-yl) -2 H-tetrazolium

30) 2,3-Diphenyl-5-nitro-2 H-tetrazolium

31) 2,2 ', 3,3'-Tetraphenyl-5,5'-1,4-butylene-di- (2H-tetrazolium)

32) 2,2 ', 3,3'-tetraphenyl-5,5'-p-phenyl-di- (2 H tetrazolium)

33) 2- (4,5-Dimethy! Thiazo! -2-y!) -3,5-diphenyl-2 H-tetrazolium 25

34) 3,5-Diphenyl-2- (triazin-2-yl) -2H-tetrazolium

35) 2- (Benzotniazol-2-yl) -3-14-methoxyphenyl) -5-phenyl-2H-tetrazolium

36) 2,5-diphenyl-3-ir-naphth .. 1-2 H-tetrazolium

37) 3,3 '- (3,3'-Dimethoxy-4,4'-diphenylene) -2,2', 5,5'-tetraphenyl-di- (2H-tetrazolium).

Examples of suitable anionic components are: halides, thiosulfate, sulfate, thiocyanate, alkyl sulfate, nitrate,
Acetate, lower alkylbenzenesulfonates for diffusible tetrazolium compounds and higher alkylbenzenesulfonates such as p-dodecylbenzenesulfonate, higher alkyl sulfates such as lauryl sulfate, dialkyl sulfosuccinates such as di-2-iithylhexylsulfosuccinate, polyether alcohol sulfates, polyether alcohol sulfates,
such as stearic acid, and polymers with acid groups, such as polyacrylates, fertilize for diffusion-stable tetrazolium compounds.

Typical examples of tetrazoum compounds which can be prepared according to the invention are:

[I) Diffusible Tetrazolium Compounds

1) 2,3,5-triphenyl-2 H-tetrazolium chloride

2) 2,3,5-tri (p-carboxyethylphenyI) -2H-tetrazoIium iodide

3) 2- (Benzothiazo! -2-yl) -3-phenyl-5- (o -chloropheny!) -2H-tetrazolium bromide

4) 2,3-Diphenyl-2H-tetrazolium thiosulfate

5) 2,3-Diphenyl-5-methyl-2 H-tetrazolium chloride 45

6) 3- <p-hydroxyphenyl) -5-methyl-2-phenyl-2H-tetrazolium sulfate

7) 2,3-Diphenyl-5-ethyl-2H-tetrazolium chloride

8) 2,3-Diphenyl-5-n-hexyl-2 H-tetrazolium chloride

9) 5-cyano-2,3-diphenyl-2 H-tetrazolium thiocyanate

10) 2-i-benzothiazol-2-yl) -5-phenyl-3- (4-tolyl) -2H-tetra2olium chloride 50

11) 2- (Benzothirjzol-2-yl) -5- (4-chlorophenyl) -3- (4-nitrophenyl) -2 H-tetrazolium chloride

12) 5-Athoxycarbonyl-2,3-di (3-nitrophenyl) -2 H-tetrazolium bromide

13) 5-Acetyl-2,3-diip-athoxyphenyl) -2 H-tetrazolium chloride

14) 2p-Diphenyl-3- (p-tolyI) -2H-tetrazolium methyl sulfate

! S) 2,5-D: phcny! -3- {p-jO {Jp} ieriyi) -2 K-icirazoiium chloride 55

16) 2 _T 3-Diphenyi-5- (p-diphenyi) -2 H-tetrazolium chloride

17) 5-ip-Bromophenyl) -2-phenyl-3- {2,4,6-trichlorophenyl) -2H-tetrazolium chloride

18) 3-ip-hydroxyphenyl) -5-methyl-2-phenyl-2 H-tetrazolium chloride

19) 5-13,4-dimethoxyphenyl) -3- <2-ethoxyphenyl) -2- {4-methoxyphenyl) -2 H-tetrazolium chloride

20) 5- (4-Cyanophenyl) -23- <aiphenyl-2 H-tetrazolium chloride 60

21) 3- (p-Acetamidophenyl) -2 _r 5-diphenyl-2 H-tetrazolium chloride

22) 5-acetyl-2,3-diphenyl-2 H-tetrazolium chloride

23) 5-iFur-2-ylh23-diphenyl-2H-tetrazolium chloride

24) 5-thien-2-yl) -2,3-diphenyi-2 H-tetrazolium chloride

25) 2 ^ -DiphenyI-5- (pyrid-4-yl) -2H-tetrazolium nitrate 65

26) 2,3-Diphenyl-5- (quinol-2-yl) -2H-tetrazoum chloride

27) 2,3-Diphenyl-5- (benzoxazol-2-y!) -2H-tetrazolium chloride

28) 2 ^ -Dipheny! -5-nitro-2H-tetrazolium methyl sulfate

29) 2,2 ', 3,3'-Tetraphenyl-5,5'-1,4-butylene-di- (2H-tetrazolium-chloride)

30) 2,2 ', 3,3'-tetraphenyl-5,5'-p-phenylene-di- (2 H-tetrazolium chloride)

31) 2- (4,5-Dimethylthiazol-2-yl) -3,5-diphenyl-2H-tetrazolium chloride

32) 3,5-Dipheny-2- (triazin-2-yl) -2H-tetrazolium suIfate

33) 2- (Benzothiazol-2-yl) -3- (4-methoxyphenyl) -5-pheny! -2 H-tetrazolium chloride

34) 2,5-Diphenyl-3-ar-naphthyl-2H-tetrazolium chloride

35) 3,3 '- (3,3'-Dimethoxy-4,4'-diphenylene) -2,2', 5,5'-tetraphenyl-di- (2H-tetrazolium-chloridejid j SP-MethoxyphenyO-SQ -trifiuormethylphenyO ^ -phenyl ^ H-tetrazolium acetate

[2] Diffusion-stable tetrazolium compounds

37) 2- (Benzothiazol-2-yl) -3-phenyl-5-dodecyl-2H-tetrazolium bromide

38) 2,3-Diphenyl-5- (4-t-octyloxyphenyI) -2 H-tetrazolium chloride

39) 2,3,5-triphenyl-2H-tetrazoIium diethylhexylsulfosuccinate

40) 2,3,5-tri (p-carboxyethylphenyl) -2H-tetrazolium-p-dodecylbenzenesulfonate

41) 2- (Benzothiazol-2-yl) -3-phenyl-5- (o-chlorophenyl) -2H-tetrazolium diethylhexyl sulfosuccinate

42) 2,3-Diphenyl-2H-tetrazoiium-p-octylbenzenesulfonate

43) 2,3-Diphenyl-5-methyl-2H-tetrazolium lauryl sulfate

44) 3- (p-Hydroxyphenyl) -5-methyl-2-phenyl-2H-tetrazolium isopropylnaphthalene sulfonate 45) 2,3-Diphenyl-5-ethyl-2H-tetrazolium-diethylhexylsulfosuccinate

46) 2,3-Diphenyl-5-n-hexyl-2H-tetrazolium-cetylpolyetheneoxy sulfate

47) 5-cyano-2,3-diphenyl-2 H-tetrazolium polyacrylate

48) 2- (Benzothiazol-2-yl) -5-phenyl-3- (4-tolyl) -2H-tetrazolium diethylhexyl sulfosuccinate

49) 2- (Benzothiazol-2-yl) -5- (4-chlorophenyl) -3- (4-nitrophenyl) -2H-tetrazolium diethylhexylsulfosuccinate 50) 5-EthoxycarbonyI-2,3-di (3-nitrophenyl) -2H-tetrazoIium diethylhexylsulfosuccinate

51) 5-Acetyl-2,3-di (p-ethoxyphenyl) -2H-tetrazoiium diethylhexylsulfosuccinate

52) 2,5-Diphenyl-3- (p-tolyl) -2H-tetrazolium-p-octylbenzenesulfonate

53) 2,5-Diphenyl-3- (p -iodophenyl) -2H-tetrazolium-p-octylbenzenesulfonate

54) 2,3-Diphenyl-5- (p-diphenyl) -2H-tetrazolium-p-octylbenzenesulfonate

55) 5- (p-Bromophenyl) -2-phenyl-3- (2,4,6-trichlorophenyl) -2H-tetrazolium isopropylnaphthalene sulfonate

50) 3- (p-Hydroxyphenyl) -5- (p-nitrophenyl) -2-phenyl-2H-tetrazoIium diethylhexylsulfosuccinate

57) S-O ^ -DimethoxyphenyO-S ^ -ethoxyphenyO ^^ - methoxyphenyO ^ H-tetrazolium-diethylhexylsulfosuccinate

58) 5- (4-Cyanophenyl) -2,3-diphenyl-2H-tetrazolium diethylhexyl sulfosuccinate 59) 3- (p-Acetamidophenyl) -2,5-diphenyl-2H-tetrazolium lauryl sulfate

60) S-acetyl ^ J-diphenyl ^ H-tetrazolium diethylhexyl sulfosuccinate

62) S-fThien ^ -yO ^ -diphenyl ^ H-tetrazolium diethylhexylsulfosuccinate

63) 2,3-Diphenyl-5- (pyrid-4-yl) -2H-tetrazolium diethylhexyl isulfosuccinate 64) 2,3-Diphenyl-5- (quinol-2-yl) -2H-tetrazolium diethylhexylsulfosuccinate

65) 2,3-Diphenyl-5- (benzoxazol-2-yl) -2H-tetrazolium diethylhexylsulfosuccinate

66) 2,4 Diphenyl-5-nitro-2H-tetrazolium polyacrylate

67) 2,2 ', 3,3'-Tetraphenyl-5,5'-1,4-butylene-di- (2H-tetrazolium) -laurylsu] fat

68) 2,2 ', 3,3'-Tetraphenyl-5,5'-p-phenylene-di- (2H-tetrazolium) -cetyl polyethene oxysulfate 69) 2- (4,5-dimethylthiazol-2-yi) -3,5-diphenyl-2H-tetrazolium polyacrylate

70) 3,5-Diphenyl-2- (triazin-2-yl) -2H-tetrazolium stearate

71) 2- (Benzothiazol-2-yl) -3- (4-methoxyphenyl) -5-phenyl-2H-tetrazolium-di-ethylhexylsulfosuccinate

72) 2,5-Diphenyl-3-cr -naphthyl-2H-tetrazolium dodecyl sulfate

73) 3,3 '- (3,3'-Dimethoxy-4,4'-diphenylene) -2,2', 5,5'-tetraphenyl-di- (2'-tetrazolium-polyacrylate)

74) 5- (3-Methyloxyphenyl) -3- (3-trifluoromethylphenyl) -2-phenyl-tetrazolium isopropylnaphthalene sulfonate 75) 2,3,5-triphenyl-2H-tetrazolium-isopropylnaphthalene sulfonate

These diffusion-stable or diffusible tetrazolium compounds are made by a suitable choice of anionic and cationic part synthesized. The diffusion stable tetrazolium compounds, e.g. 2,3,5-triphenyl-2 H-tetrazolium-dioctyl-suIfosuccinate, can be dispersed in a gelatin solution by that one first mixes in the difrusible, therefore also more easily soluble tetrazolium compound and then a water-soluble salt with such an anion, which with the tetrazolium cation a diffusion-stable, consequently less soluble tetrazolium compound results.

Alternatively, crystals of the diffusion-stable tetrazolium compound, which are synthesized in pure form dissolved in a suitable solvent such as dimethyl sulfoxide and then in the gelatin solution be dispersed.

If the dispersion is not sufficiently homogeneous, good results can be obtained by by subjecting the emulsified dispersion to the action of ultrasonic waves or a suitable one Homogenizing apparatus is used.

It is advantageous to use the diffusion-stable tetrazolium compound when a particularly good one Point quality is to be achieved.

If one assumes a very high-contrast recording material from the start, but this is for reproduction of raster images is not sufficient, it is advisable to use diffusible tetrazolium compounds

to add.

in preferred embodiments, a silver halide recording material according to the invention contains Use of a diffusible tetrazolium compound these and the sensitizing dye solids described later in adjacent layers when using a dilution-stable tetrazolium compound these and the sensitizing dye in the same layer.

The telrazole compounds may suitably be used in an amount of from 0.0001 to 10 moles and more preferably can be used in an amount of from 0.001 to 1 mole per mole of silver halide present.

Usable sensitizing dyes are, for example, carbocyanines, merocyanines, hemicyanines, oxonols, ilemioxonols or mixed merocyanines. Such dyes are described, for example, in "The Cyanine Dye and Related Compounds" by FM Hamer and in "The Theory of Photographic Process", 3rd edition by CE Kenneth Mees ίο and T. II. James.

Preferred sensitizing dyes are those of the following general formulas (IV) to (X):

71 .... 72

R ¹ - "N = N = CH- CH = H = C- L '= # L ² -L ³ H = C- (CH = CH) --- N - R ² (IV)

χ ^θ ... -ζ ¹

R'— N— (CH = CH) - "c = # L ^! - L ² H = C '^ Q ¹ (V)

-z ¹ ρ

R ¹ - N - (CH = CH) - C = 4L '- L ² H = C

χ ^θ

Q ¹ C = L ¹ - (L ² =

Q 'C = L ¹ - (L ^J = L ³

Ri_N- (CH = CH) - C = IL ¹ - L ² H = CN = L ¹ - (L ² = L ³ ) - C = 4CH - CHHfN® - R ²

C N ^ e

< I Λ

(VI) 30th (VI) 35
I. 40 (VID) 45

In these formulas:

R ', R ² and R ³ each represent an alkyl group (e.g. a methyl, ethyl, propyl, butyl and substituted alkyl group, such as a chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl, carboxymethyl, carboxyethyl) , Ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, jS-hydroxy-y-sulfopropyl, sulfatopropyl, allyl and benzyl group) or an aryl group (e.g. a phenyl, carboxyphenyl and sulfophenyl group),

L ¹ , L ² and L each represent a methynyl group including a substituted methynyl group (e.g.

-CH = -C (CH ₃ ) = -C (C ₂ H ₅ ) = -C (CH ₂ COOH) = -C (CH ₂ -C ₆ H ₅ ) = -C (C ₄ H ₅ ) = -C (C ₆ H ₄ COOH) =

Ζ ¹ , Z ² and Z ^{3 are} each the atoms that are required to complete a 5- or o-membered heterocyclic ring (e.g. the thiazoline, oxazoline, selenazoline, thiazole, selenazole, oxazole, benzothiazole, benzoxazole, benzoquinazole -, benzimidazole, 3,3-dialkylindolenine, naphthothiazole, naphthoxazole, naphthoselenazole, thienothiazole, 2-pyridine, 4-pyridine, 2-quinoline and the 4-quinoline ring), P and Q each for the cyano group, -CQQR. ⁴ , - CQR ⁴ or -SO ₂ R ⁴ , where R ^{4 represents} an AJkyigrnppe, furthermore

Q ¹ and Q ² each have the atoms necessary to complete a thioxazolone, pyrazolone, oxindole, barbituric acid, 2-thiobarbituric acid, 2,4-oxazolidinedione, 2,4-thiazolidinedione, 2,4- Imidazolidinedione, 2-thio-2,4-oxazolidinedione, 2-thio-2,4-thiazolidinedione, 2-thio-2,4-selenazolidinedione, 2-thio-2,5-thiazolidinedione, 2-thiohydantoin -, 4-oxazolinone, 4-thiazolinone or 4-imidazoline ring, where the rings can also be substituted,

Y is a hydrogen atom, the amino group, an alkylamino group with preferably 1 to 4 carbon atoms (e.g. an ethylamino group), a dialkylamino group with preferably 2 to 8 carbon atoms (e.g. the dimethylamino group), halogen atoms (e.g. a chlorine or bromine atom) or an alkyl group with preferably 1 to 4 carbon atoms (e.g. the methyl group),
m ^] and / η ² each O or 1,

n 'and n ² respectively 0 to 2 and
X ^{e is} an acid anion, e.g.

Cl ^e Bf J® ClOfm CH ₃ -Ct- SOf CH ₃ SOf and C ₂ H ₅ SOf

which is not applicable to the betaine structure.
Typical examples of sensitizing dyes which can be used according to the invention are:

(CHj) ₃ SOf (CHj) ₃ SO ₃ Na

(CH ₂ ^ SO?

CH ₃ CH = C-CH

CH ₂ CH ₂ CHSOl

CH ₃ S

1 C ₂ H ₅

C ₂ K ₅ CH = C-CH

C ₁ H ₅

(CHz) ₁ COOH

N (CHz) ₃ SOf

= C - CH = - /

N (CH ₂ ) J SOjH

CI

Se

CH ₃

Se

V \ I /

if> —CH = C-CH = <

As / \

N (CHj) ₃ SOf Se

N (CHiLSO?

CH ₃

(CHz) ^ O ₃ Na Se

= C - CH = /

C ₂ H ₅

(CHj) ₄ SO ₃ Na S.

V-CH = C-CH = <

(CHj) ₃ SOf

χ / \ <b

CH = CH-CH

1 1

(C Hz) ₁ SO ₃ HN (C ₂ H ₅ ), C ₂ H ₅

Cl

Cl

CjH _{: i}

I,> - ^cH = ^c - ^cH = < J

N N

(CHj) ₃ SO ₃ HN

C ₂ H ₅

CH = C-CH = / TjL _cl

N
(CH ₂ ) JSOjH

Cl

• Ο

C ₂ H ₅

Cl

Cl Cl

CH = CH-

(CHj) ₃ CHSO ₃ ⁹ CH ₃ C ₂ H ₅

ι Cl

(CHjJjCHSOjNa CH,

CH ₃ CH ₃

CH

AI)

C ₂ H ₅

CH-CH = CH- ^ N
C ₂ H ₅

¹⁶ (X _n - "

N y

CjH ₅

"■

C ₂ H ₅ S

C ₂ H ₅

C ₂ H ₅

· = Χ S

18. CH ₃ -I

CHjCHjOH

CjH ₅

CHjCOOH

//
0 CH ₂ CH ₂ OH O
\ = c N
= / \ _s ι
I. ' N
ι (CH ₂ ), Λ SO ₃ Na C)

\ ^s

V = CH-CH = CH-CH = / \ _, / I jT— -

== CH-CH = CH-CH O

24. C ₂ H ₅ -N

CH-CH

N H

C2H5 CH3-

CH ₃

CH ₂ -CH = CH ₂

C ₂ H ₅

N = CH-C =

CH

C ₂ H ₅

CH-CH = CH- ^

C ₂ H ₅

k-CH-CH,

These compounds according to the invention can, for example, according to the methods described in US Pat. 25 03 776, 35 76 641, 29 45 763 and 36 25 698 described processes.

These sensitizing dyes can be incorporated into a hydrophilic colloid containing the silver halide and a tetrazolium compound by placing them in water or in an organic solvent, such as methanol and ethanol, which is mischbur with water in any ratio. You can can be used singly or in combination of two or more.

The incorporation of the sensitizing dyes into the hydrophilic colloid can be carried out at any time during the preparation of the silver halide emulsion, but it is generally preferred to carry out this action after the end of the second ripening.

The sensitizing dye can be used in an amount of from 10 mg to 1 g, preferably from 30 to 300 mg, per mole Silver halide are used.

The silver halide photographic light-sensitive recording sheet according to the invention, the the sensitizing dye has been incorporated shows not only excellent stability during the Developed, but can also be sensitized in any preferred spectral range. Additionally can supersensitization through the use of a combination of two or more sensitizing agents are generally expected.

The silver halide contained in the silver halide photographic light-sensitive material employed in accordance with the invention includes any silver halide used in conventional photographic Silver halide recording materials are used, e.g. silver bromici, silver chloride bromide, Silver iodobromide, silver chloride iodobromide or silver chloride, in particular silver chloride bromide or Silver chloride iodobromide with at least 50 mol% silver chloride. The silver halides which can be used according to the invention with the mentioned average grain size and its distribution can according to any known processes are produced, such as those described, for. B. in US-PS 25 92 250.32 76 877.33 17 322.22 22 264, 33 20 069 and 32 06 313 and in Journal of Photographic Science 12 (5), 242-251 (1964). Silver halides produced by other methods can also be used in admixture will.

The silver halide emulsion of the invention can be mixed with various known chemical sensitizers sensitized and the various known stabilizers (see. US-PS 24 44 607.27 16 062, 35 12 982, 33 42 596, 37 26 686 and 37 17 465 and GB-PS 13 63 921).

In the case of the recording materials according to the invention, a rhodium or cadmium salt can be added to increase the contrast according to GB-PS 7 75 197 or Uo-PS 34 88 709 waive.

Recording materials according to the invention can contain customary hydrophilic colloids as binders, preferably gelatin. These hydrophilic colloids can be obtained in silver halide-containing and also in silver halide-free Layers, e.g. in an antihalation layer, a protective layer or an intermediate layer, be included.

A photosensitive recording material according to the invention suitably contains one Protective layer, in particular a gelatin protective layer with a thickness of 0.1 to 10 μm, in particular 0.8 to 2.0 μΓΤ).

The presence of the protective layer can effectively affect the stability, image quality and development impact. Presumably the protective layer should have the function of the infiltration speed Hydroquinone / N-methylaminophenol or l-phenyl-3-pyrazolidinone from the treatment solution to the photosensitive recording material or the diffusion rate of the tetrazolium compound within the photosensitive recording material or from this into the processing solution accordingly to brake or regulate.

Various kinds of photographic additives may optionally be added to the aforesaid hydrophilic Colloid can be added as long as they do not impair the effectiveness of the invention. As additives are suitable e.g. B. Gi; latine plasticizers, hardeners, surfactants, image stabilizers, ultraviolet Light absorbing agents, anti-staining agents, pH adjusting agents. Antioxidants, antistatic agents, viscosity increasing agents, granularity improving agents, dyes, optical brighteners, development control agents, matting agents and mordants.

Among the additives mentioned above, the following can preferably be used: as Means for increasing the viscosity and the plasticizers, which in US-PS 29 60 404,37 67 410,36 59 956 and 36 92 753, e.g. B. a Styrqj / sodium maleate copolymer and dextran sulfate, as a hardening agent an aldehyde, an epoxy compound, ethylene amine, active halogen, vinyl sulfone, isocyanate, a sulfone acid esters, carbodiimide, mucochloric acid or Acryloyle, as image stabilizers z. B. 6,6'-butylidene-bis- (2-t.-butyl-4-methylphenol) and 4,4'-methylene-bis- (2,6-di-t-butylphenol), as ultraviolet light absorbing agents the z. B. in US-PS 32 53 921, GB-PS 13 09 349, US-PS 35 33 794 and 37 07 375 and GB-PS 12 87 770 are described, in particular 2- (2-hydroxy-5-t.-butylphenyl) -benzotriazole, 2- (2-hydroxy-3,5-di-t.-butylphenyl) -bcnzotriazole, 2- (2-Hydroxy-3-t-butyl-5-butylphenyl) -5-chlorobenzotriazole and 2- (2-hydroxy-is 3,5-di-t.-butylpheny!) - 5-chlorobenzotriazole, surface-active agents as coating aids, emulsifiers, infiltration enhancing agents for the treatment solution, antifoam agents, or agents for regulating tower various physical properties of the photosensitive recording material, e.g. Am U.S. Patent Nos. 3,026,202 and 3,514,293; British Patent Nos. 5,48,532 and 12 16,389; and U.S. Patent 3,726,683 , including anionic, cationic, nonionic and amphoteric compounds, mordants that for example, in U.S. Patents 2,113,381 and 2,548,564. Agents to prevent staining, for example described in U.S. Patents 2,360,210, 2,728,659, 2,732,300 and 3,700,453, in particular 2-methyl-5-hexadecylhydroquinone, 2-methyl-5-sok.-octadecylhydroquinone and 2,5-di-t.-octylhydroquinone, antistatic agents that z. B. in U.S. Patents 2,882,157,29 72,535 and 3,573,093 and GB-PS 1,378,584 and U.S. Patents 3,549,369, 3,7 04,128 and 3,663,230. Matting agents, e.g. in the US-PS 29 92 10! and 29 56 884 and GB-PS 12 21 980 and 13 07 373, in particular SiIikagel a grain size of 0.5 Hs 20 μπι and polymethyl methacrylate a grain size of 0.5 to 20 μΐη, the development accelerating agents, e.g. B. Benzyl alcohol, and one of the series of polyoxyethylenes to be assigned Compound that can be added to the treatment bath.

With a recording material according to the invention, high contrast silver images are obtained.

The high-contrast silver images are presumably obtained by the fact that the oxidation of the hydroquinone takes place semiquinone produced in the developing solution by the tetrazolium compound in an abnormal state high concentration near the developed silver is accumulated. It is generally said that that so-called "infection phenomenon" does not occur, which is due to the immediate removal of the semiquinon or the Quinones declines through sulfonation when the sulfite ions are in a high concentration in the developer solution are present. On the other hand, in the present method, it is believed that the infectious development takes place at the location of the exposed silver halide in the Geiatineschicm, which is due to the prevailing Feed di: s semiquinons is decreasing.

A recording material according to the invention can thus be developed with a developer bath which contains a hydroquinone developer. An infectious developer bath therefore does not need to be used.

A lith-type recording material according to the invention requires a bath for development which only Hydroquinone, alkali, alkali bromide, sulfite ions in low concentration and as preservatives Contains condensation product of formaldehyde / sodium bisulfite or carbonyl bisulfite.

Hydroquinone developers that can be used are e.g. hydroquinone itself, chlorohydroquinone, bromohydroquinone, Isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydrothinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone and 2,5-dibenzoylaminohydroquinone.

In addition to the hydroquinone compound, N-methylaminophenol- and l-phenyl-3-pyrolidinone.

Preferred developers are, for example, in "The Theory of Photographic Process", 3rd ed., Pp. 374-378 (196 ^ \ described. The regulation of the pH value and the introduction of a buffer function by means of an alkali hydroxide, Alkali carbonates or amines or the addition of inorganic development retardants such as potassium bromide, or an organic development retarder such as benzotriazole can optionally be used as in a standard black and white developer bath.

The temperature at which the development is carried out is preferably below 50 ^° C., in particular close to 30 ² C. The time required for development is generally at most 30 minutes, preferably not more than 5 minutes.

After developing, the following measures, such as soaking, stopping, stabilizing and fixing, carried out. If necessary, procedural measures such as pre-hardening and neutralization, be performed. But they can also be left out if necessary. The procedural measures are either by means of the so-called manual treatment, such as a bath or shell development, or mechanical treatment such as roll or hanger treatment. at A preferred embodiment of the invention was the treatment solution in the bath treatment via a more than 20 times more stable than a conventional lith-type developer bath for a long time. Another one The life of the developing bath of one month was practically no difference in the development Determine the quality of the raster image.

Furthermore, the addition of a contrast-enhancing agent had no undesirable effect on the photographic quality.

example 1

A fine-grain silver chlorobromide gelatin emulsion, the silver halide of which consisted of 90 mol% of silver chloride, 9 mol% of superbromide and 1 mol% of silver iodide, was chemically sensitized with a sulfur and gold sensitizer. The silver halide had an average grain size of 0.25 μm, 80% of the grains being within the range from 0.19 to 0.31 μm grain size. 8 g of 2,3,5-triphenyltetrazolium chloride per mole of silver halide and the equimolar amount of diethylhexyl sulfosuccinate were added to this emulsion. This emulsion was applied to a polyethylene terephthalate support in such a way that an amount of silver halide corresponding to 53 mg of silver and 50 mg of gelatin were ^{required per 100 cm 2 of support area.}

Thereafter, the Aufzeichnuns ^ material exposed through a stepped gray wedge by means of a Wollramlampc and correspondingly treated the represented below procedure at 30 ⁰ C:

development 1.5 minutes Water 1 minute Fix 2 minutes Water 5 minutes dry until dry.

The developer had the following composition:

Developer bath:

N-methylaminophenol anhydrous sodium sulfite Hydroquinone sodium carbonate potassium bromide 5-nitrobenzimidazole l-phenyl-5-mercaptotetrazole topped up with water

Fixing bath:

Ammonium Thiosulfate Decahydrate Anhydrous sodium sulfite Sodium acetate trihydrate glacial acetic acid made up with water

3.5 g
60 g

9.0 g
54 g

2.5 g

0.5 g
10 mg

1 1 (pH = 10.25)

150 mg

10 g

15 g

15 ml

1 1 (pH = 6.80)

For the assessment of the raster image quality, 4 means excellent and 1 means extremely bad. Less than 3 can generally not be allowed.

The exemplified sensitizing dye 14, which was dissolved in methanol, was added to this emulsion. incorporated in an amount of 200 mg per mole of silver halide (Sample 2).

The results obtained are shown in Table I.

Table I. Sample sensitizing dye

Development time relative emp Schli (sec) delicacy 60 60 0.01 80 100 0.02 100 120 0.03 120 130 0.04 60 70 0.01 80 95 0.02 100 100 0.02 120 110 0.02

Raster image quality

no addition of the dye (outside the scope of the invention)

Dye 14 (invention)

3.0 3.7 3.3 3.0

3.3 3.7 3.7

3 ,:

Table I shows that the photosensitive recording material according to the invention in comparison better properties in terms of relative sensitivity and formation with other materials of a veil. Furthermore, the change in the raster image quality is also small.

Example 2

A silver chlorobromide emulsion was prepared, the silver halide of which was 60 mol% of silver chloride and 40 mol% consisted of suber bromide and the silver halide thereof had an average grain size of 0.3 μπι had, with 80% of the grains being within the range from 0.24 to 0.37 μπι.

14th

To this emulsion, hexammine cobalt (III) trichloride was added in an amount of 4.0 g per mol of silver halide given. The sensitizing dye 10 was never added in an amount of 200 mg per mole of silver halide had been, the emulsion was applied to a polyethylene terephthalate support so that per 100 cnv The carrier bottle contained an amount of silver halide corresponding to 55 mg of silver and 30 mg of gelatin. then was dried (sample 3).

Another sample was made except that 3.0 g of 2,5-diphenyl-3-a-naphthyltetrazolium chloride (35) were added instead of the hexammine cobalt (III) trichloride (sample 4).

These samples were treated in the same manner as in Example 1 along with Sample 5 which was not Contained oxidizing agent.

The results are shown in Table II.

Table Il

Sample development time relative sensitivity fog raster image quality

(outside of the invention)

(Invention)

(outside of the invention)

Development time relative sens Schle (sec) opportunity 60 30th - 80 50 0.0i 100 80 0.01 120 150 0.02 60 80 0.01 80 100 0.01 100 110 0.01 120 130 0.01 60 130 0.03 80 180 0.07 100 220 0.10 120 280 0.20

2.0

Z ₁ J

2.5 2.0

2.7
3.5
3.3
3.0

extremely bad
extremely bad
extremely bad
extremely bad

Table II shows that Sample 4 of the present invention has excellent halftone image quality when it is compared to samples 3 and 5.

Example 3

A silver bromide emulsion of which the silver halide had an average grain size of 0.25 μm and 80% of the grains were within a range of 0.19-0.31 μm was chemically sensitized by means of a gold sensitizer. 500 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per month were added to the emulsion. Silver halide added. This emulsion was applied to a polyethylene terephthalate support in an amount of silver halide corresponding to ^{50 mg of silver per 100 cm 2 of support area and dried.} In this case, the following compounds were added after chemical ripening.

Sample 6:

5.0 grams of hexammine cobalt (III) isopropyl naphthalene sulfonate per mole of silver halide.

Sample 7:

220 mg of sensitizing dye 12 per mole of silver halide for sample 6.

Sample 8:

Same as Sample 7 except that 2,3,5-triphenyl -2H-tetrazolium isopropylnaphthalene sulfonate [tetrazolium compound (75)] in the same molar amount in place of the hexammine cobalt (III) isopropylnaphthalene sulfonate was added.

Sample 9:

100 mg trisodium salt of tartrazine ^ S-di-hydro-S-oxo-H ^ sulfonyO ^ - ^ sulfonyO-azoJ-lH-pyrazoW-carboxylic acid} per mole of silver halide for sample 8.

These samples were treated as in Example 1, except that they 80, 100,120 and 140 seconds as long treated in the following developer solution 30 ⁰ C 60.

Composition of the developer bath: 1-phenyl-3-pyrazolidone anhydrous sodium sulfite potassium hydroxide

0.8 g

45 g 10 g

15th

10

! .5

20th

30th

35

40

45

Hydroquinone

anhydrous sodium carbonate

6-nitroindazole

topped up with water

20 g
20 g

0.1g

1 1

The results are shown in Table III below.
Table III

10 sample Development time relative sens veil Raster image quality (sec) opportunity 6th 60 20th 0.01 2.0 15th (except for ' 80 80 0.01 3.0 Invention) 100 100 0.02 3.2 120 140 0.03 3.0 140 170 0.04 2.5 20th 7th 60 35 0.01 2.5 (except for 80 80 0.01 3.0 Invention) 100 95 0.01 3.5 25th 120 107 0.02 3.7 140 120 0.03 3.0 8th 60 60 0.00 3.0 (Invention) 80 85 0.01 3.5 :O 1ST FLOOR 100 0.01 3.8 120 100 0.01 3.8 140 103 0.01 3.5 35 9 60 55 0.00 3.0 (Invention) 80 80 0.01 3.5 iöö y / 0.01 4.0 120 102 0.01 4.0 40 140 107 0.01 3.5 Example 4

In this example the same emulsion as in example 3 was used. The inferred links were added after the emulsion was chemically sensitized.

Sample 10:

3.0 g of 3- (p-hydroxyphenyl) -5-methyl-2-phenyl-2H-tetrazolium chloride (tetrazolium compound [18]) per Moles of silver halide.

Sample 11:

For sample 10, 150 mg of sensitizing dye 23 per mole of silver halide.

These samples were treated using the same development procedure as in Example 1 with the exception that they were developed for 80, 100, 120 and 140 seconds. The results obtained are shown in Table IV.

Table IV Development time
(sec) relative sens
opportunity veil Y Raster image
quality 60 sample 80
100
120
140 55
87
110
135 0.00
0.01
0.03
0.05 4.0
8.0
10.0
9.3 2.0
2.7
3.0
2.7 10
⁶⁵ (outside the
Invention)

continuation Development time relative sens veil Y v, o Raster image 5 1"; sample (sec) opportunity 10.0 quality 80 80 0.01 10.0 2.5 Il 100 100 0.01 9.5 3.0 (discovery) 120 107 0.02 3.0 10 ti 140 112 0.03 3.0 i I.

Sensitizing dye Development time relative sens veil Raster image (sec) opportunity quality no encore 60 45 0.01 80 100 0.02 2.0 100 130 0.03 2.5 120 150 0.04 1.5 200 ng of the dye 23 60 55 0 _t 01 1.5 per mole of silver halide 80 110 0.02 2.0 100 137 0.03 2.7 120 155 0.03 2.0

Table IV shows that the sample to which the sensitizing dye was added exhibited greater stability during the development process than that without this addition

Example 5

This sample was prepared in the same manner as in Example 4 using Compound 23 dye. The silver halide emulsion used was a mixture of two monodisperse emulsions with peaks in the grain size gradient curve at 0.015 μm and 0.035 μm. 20th

The results are shown in Table V below Table V

Table V shows that sufficient effects cannot be obtained when the grain size distribution goes beyond the scope set by the invention, d. that is, the composite silver halide emulsion used in this example is outside the scope of the invention.

17th

Claims (3)

Patent claims: 1. Light sensitive photographic spectrally sensitized silver halide recording material of the lith type with a substrate and at least one silver halide emulsion layer applied thereon, wherein the silver halide has an average grain size of 0.1 to 0.8 μm, at least 80% of the silver halide grains in the range 0.7 to 1.3 times the average grain size and the silver halide of silver chloride bromide or silver chloride iodobromide with at least 50 mol% of silver chloride, characterized in that the recording material is a Tetrazolium compound of the general formulas (I) to (III) R ¹ -N-N-R ³ N N i. x ^e R <- N - N - D - N - N - R ³ N N A. I Il N N A. R »—Ν — Ν — R ' Il I N N R ¹⁰ —Ν — Ν — R " I Il N N ^N c ^/ contains, where mean: R ¹ , R ³ to R ³ and R ⁸ to R "each represent an aryl group or a heterocyclic group,
R ² , R ⁶ and R ⁷ each represent a hydrogen atom, an aryl, alkyl or hydroxyl group, a heterocyclic group, a carboxyl group or a salt thereof, or an amino, mercapto or nitro group, D an arylene group, E is an alkylene, arylene or aralkylene group, and
Χ ^Θ an anion that is omitted in the betaine structure. 2. Silver halide recording material according to claim 1, characterized in that it is a tetrazolium compound 2,3,5-triphenyl-2 H-tetrazolium chloride, 2,5-diphenyl-3-ar-naphthyl-2 H-tetrazolium chloride ^, S ^ -triphenyl ^ H-tetrazolium isopropylnaphthalene sulphonate or S-ip-hydroxyphenyO-S-methyl ^ -phenyl -2 Contains H-tetrazolium chloride. 3. Silver halide recording material according to claim 1 and 2, characterized in that it is as Sensitizing dye one of the formulas CH = C- (CH ₂ ) j SOf (CH ₂ ) JSO ₃ HN (C ₂ H ₅ ), C ₂ H ₅ CH = C-CH = (CHj) ₃ SOj (CH ₂ ) j SO ₃ HN CH = CH- (CH ₂ J ₂ CHSOf CH ₃ (CH ₂ ) ICHSO ₃ Na
CH ₃ IO and