DE2135412B2 - LIGHT-SENSITIVE, PHOTOGRAPHIC RECORDING MATERIAL WITH AT LEAST ONE SILVER HALOGENIDE EMULSION LAYER SPECTRALLY SENSITIZED BY MEROCYANINE - Google Patents

Description

1. The sensitizer mixture used must have the extremely high contrast that the emulsion from Lith-type supplies, do not change.

2. The sensitizer mixture should help to improve the good dot quality without the To worsen the sharpness of the raster image.

3. The sensitizer mixture must not have any residual color densities or color haze after high-contrast development leave behind on the recording material

Furthermore, it is desirable that the converted Sensibilisalui mixture have a high spectral sensitivity without desensitization of the inherent sensitivity of the emulsion (none disadvantageous influence on the sensitivity to blue). It is also necessary that it be sharp and good Dot quality is obtained within a relatively short development time (2 to 3 minutes). the known supersensitization methods, however, are mainly based on conventional silver iodobromide emulsions applied, a satisfactory supersensitization in the above sense can thus im In the case of the high contrast lith type silver chlorobromide emulsion cannot be obtained.

It is an object of the present invention to provide a light-sensitive photographic recording material with at least one silver halide emulsion layer that is supersensitized in this way has been found to meet the above requirements.

Furthermore, the present invention is based on the object of providing light-sensitive, photographic, to find silver halide recording materials in which no disadvantageous Interactions between the sensitizers and the photographic additives involved in this Material is present, entered and whose photographic properties remain unchanged, even if the material is stored for a long time.

The subject matter of the invention is based on a light-sensitive photographic recording material with at least one silver halide emulsion layer which is substituted by at least one acidic Benzoxazole - Thiohydantoin - Dimethine merocyanine is spectrally sensitized and is characterized by that the silver halide emulsion layer is a mixture of at least one benzoxazole-thiohydantoin-dimethine merocyanine the formula

(CH ₂ ) W ₁ OH

= CH-CH = C-N

O = C-N

= S

(CH ₂ Jm ₁ SO ₃ M ₁

wherein Y _{1 is} hydrogen, a lower alkyl group, a lower alkoxy group, a phenyl group or a

Halogen atom means, R _{1 represents} a saturated or unsaturated lower K-Ohlenwasserstofikette, a phenyl group or a substituted phenyl group, W _{1 represents} 2, 3 or 4, n _{x represents} 1, 2 or 3 and M represents a hydrogen atom, an alkali metal atom or represents a group of the formula - HX (in which X is an inorganic base), and at least one benzoxazole-thiohydantoin-dimethine merocyanine of the formula

(CH ₂ ) M ₂ COOH
CH-CH = C-Ns

Y ₂ IO = CN

(CH ₂ ) Mi ₂ SO ₃ M ₂ I.
R,

UD

wherein Y ₂ , R ;. m ₂ . n ₂ and M _{2 has} the same definition as Y _1, R ₁ / M _1, n, and M are in the general research _J0 mel 1 ₁ includes.

In the context of the present invention, the term “lower” denotes groups with particular 1 to 6, preferably 1 to Λ carbon atoms.

The invention achieves that when using a mixture of at least one compound of the above general form! 1 with at least of a compound of the above formula 11 in a silver halide emulsion is remarkable Increase in spectral sensitivity can be achieved. In addition, the gradation of the lith-type emulsions are not changed. Especially when the mixture is spectrally sensitizing merocyanines according to the present invention applied in a lith-type emulsion that with an aldehyde-containing lith developer containing hydroquinone as the main one Component to be treated, one achieves the advantage that a sharp point image with extremely high contrast can be obtained and in the recording material after development no residual color remains.

Typical examples of compounds of the general formulas 1 and 11 are given below.

Examples of compounds of general formula 1:

CH ₃ CH ₂ OH

CH = C-N

O = C-N

(CH ₂ I ₃ SO ₃ Na

55

CH ₂ CH ₂ OH
CH-CH = C-Ns

O = C-N '

CH ₃

CH ₂ CH ₂ CH ₂ OH

N = CH-CH = CN _x

V I> = S (3)

i O = C-N '

(CH ₂ I ₃ SO ₃ Na

CH ₂ CH ₂ OH

O _x I

VCH-CH = CN _x N ⁷ ! V = S (4)

O = CN ⁷

(CHj) ₃ SOjHN. j

CH ₃ O

CH ₂ CH ₂ OH CH-CH = C-Ns

(CH ₂ ) ₃ SO ₃ Na

O = C-N

(5)

CH ₂ CH ₂ OH

> CH-CH = C-Ns

N ⁷ IV = S (6)

IO = CN ⁷

(CH _{2 I 3} SO ₃ Na I.

CH ₂ CH = CH ₂

> CH-CH = C-N

N ⁷ I.

IO = C-N

(CH _{2 I 3} SO ₃ Na I.

CH ₂ CH ₂ OH

S (7)

Examples of formula II:

for connections of general

CH ₂ CH ₂ COOH

60

(2)

= CH-CH = C-Ns

I O = C-N '

I.
(CH ₂ J ₃ SO ₃ H

CH ₃

CH ₃ O

CH ₂ COOH
O \ I

> CH-CH = CN \
N ^X I> = S

I O = C-N /

(CH ₂ ) ₄ SO ₃ H

(CH ₂ ) ₃ SO ₃ Na

CH ₂ COOH
CH-CH = C-Nx

(H)

(CH ₂ J ₃ SO ₃ N ?.

(CH ₂ ) ₃ SO ₃ Na

According to a preferred embodiment, the silver halide emulsion layer contains the photosensitive Photographic recording material of the invention a mixture of at least one of the Compounds Nos. 1 to 7 given above and at least one of those given above Compounds No. 8 to 14.

According to further preferred embodiments, the super halide emulsion layer contains a mixture of Compound No. 5 and Compound No. 11, a mixture of the compound No. 1 and the compound No. 10, a mixture hus of Compound No. 6 and Compound No. 9, a mixture of Compound No. 2 and the Compound No. 8, a mixture of Compound No. 2 and Compound No. 11, a mixture of Compound No. 4 and Compound No. 8, a mixture of the compound No. 4 and Compound No. 9, a mixture of Compound No. 5 and Compound No. 9, a mixture of the compound no. 5 and the ίο compound no. 10, a mixture of the compound No. 4 and the compound No. 10 or a mixture of the compound No. 2 and the compound No. 9.

The above advantages are not only obtained with lith-type photographic emulsions, but also if the sensitizer mixtures according to the application contain other light-sensitive, photographic materials containing silver chloride, silicon chloride bromide or contain silver iodobromide, d. H. common black and white photographic materials, color photographic materials, color photo graphic materials for the silver dye bleaching process and photographic recording materials for image transfer processes.

The sensitization ranges and the sensitivity maxima of the spectrally sensitized according to the invention Silver halide emulsions vary depending on the kind and amount of the sensitizing dyes of the general formulas 1 and II, they can therefore suitably depending on the intended use can be selected. The spectral sensitizing merocyanines can to be added to a silver halide emulsion after being in an optional water miscible organic solvents such as methanol or ethanol have been dissolved. In this case either solutions for each of the individual compounds or a solution for a combination of the connections are added.

The timing of adding these sensitizing dyes can be at any stage during the preparation of the emulsion. That is particularly preferred Addition after the end of the second ripening process.

The amount of the compounds to be added varies depending on the kinds of the compounds and the silver halide emulsion. In general, the total amount of the sensitizing dyes is the Formulas 1 and II in the relatively wide range of about 1 to 200 mg per kilogram of the Silver halide emulsion. In this case, the mixing ratio is between the sensitizing dyes of formula 1 and the sensitizing dyes of formula 1! preferably between 1: 5

and 5: 1 by weight.

The emulsions used according to the present invention can be treated with a noble metal sensitizer, a sulfur sensitizer or a polyalkylene oxide compound as a contrast enhancing agent Funds have been transferred. In addition, the emulsions can be visible all over the place Area color sensitized by using the compounds mentioned in combination with another sensitizing dye,

z. B. a carbocyanine or merocyanine dye. Especially if you are sensitive to red if desired, the additional use of thiacarbocyanine dyes is advantageous. the

Emulsions can also contain customary pholographic additives such as stabilizers, hardeners and coating auxiliaries.

The above-described pholographic silver halide emulsions, which have been mixed with the compounds according to the present invention are, are on a suitable support, e.g. B. made of glass, cellulose triacetate, polyester or paper, applied and then dried, whereby a light-sensitive, silver halide-containing, photographic Recording material according to the present invention is obtained.

example 1

A super chloride romide emulsion of the lith type, containing 20 mole percent silver bromide was treated with a gelatin coagulant and then subjected to the second ripening process by the gold sensitization method. Then the emulsion became divided into several servings. The individual portions were with methanolic solutions of the compounds given in Table 1 were added. The emulsions were then 20 minutes left to stand for a long time at about 40'C in order to stabilize the optical sensitization. After that they became with a suitable amount of a polyalkylene oxide derivative as a contrast enhancing agent and mixed with a hardening agent and a coating aid, applied to a layer support and dried, whereby green-sensitive lith-type photographic recording materials were obtained. The samples thus obtained were each placed in a sensitometer with a light source of 125 Lux (2660 K) exposed through a green filter with a transmission maximum at 525 nm and then 3 minutes at 20 "C with a developer of the the following composition:

Hot water 500 ml

Addition product of formaldehyde and sodium sulfite 50 g

Hydroquinone 19 g

Boric acid 10 g

Potassium bromide 2.2 g

Water up to 1000 ml

45

The results obtained are shown in Table 1. In Table 1 is the relative sensitivity given as a calculated value assuming the green sensitivity the sample containing dye no. 1 alone is based on 100. The residual color density is a density value measured by using a color densitometer.

Table 1 link

No.

1
2
3

Amount supplied

the connection

(mg kg emulsion)

(5) 50 mg
(11) 50 mg

(5) 30 mg
+ (11) 20 mg

(1) 50 mg
(10) 50 mg

Relative Sensitivity to green I icht

90

70

120

100
80

Remaining color density (Color

veili

0.04
0.02
0.02

0.03
0.04

link
No. Amount supplied
the connection
(mg / kg emulsion) Relative
Sensitive
speed against
green light Residual color
density
(Color
veil) 6th
7th
8th
9 (1) 25 mg
+ (10) 25 mg
(6) 50 mg
(9) 50 mg
(6) 40 mg
+ (9) 10 mg 130
80
70
110 0.03
0.03
0.02
0.02

From Table 1 it can be seen that the samples according to the invention, which contain a combination of compounds according to the present invention contain very excellent properties in terms of Have a degree of color sensitivity and produce less color haze than the samples, each containing only one of these compounds.

B e i s ρ i e 1 2

A silver chlorobromide emulsion containing 20 mole percent silver bromide was added to the second Subjected to the ripening process and then divided into several servings. Each serving was made with the ones in the Table 2 compounds indicated.

A sample of the same emulsion with the known dimethine merocyanine dye was used for comparison (Control) of the formula

CH

H ₅

= CH-CH =

O = C-N

C ₂ H ₅

40 staggered. In addition, the same additives as in Example 1 were added to all of these emulsions and then applied evenly to polyester substrates to prepare samples. The samples produced in this way were exposed in the same way as in Example 1 and then developed at 20 ° C. for 3 minutes. The results obtained are summarized in Table 2. In Table 2, the sensitivity is the relative sensitivity based on the green sensitivity of the control dye, which is based on 100.

Table 2

55

10
11
12th
13th
14th
15th
16

Amount of compound added

(mg / kg emulsion)

Control dye 40 mg
(2) 20 mg + (8) 20 mg!
(2) 20 mg + (11) 20 mg j
(4) 20 mg + (8) 20 mg!

(4) 20 mg + (9) 20 mg j

(5) 20 mg + (9) 20 mg j
(5) 20 mg + (10) 20 mg

Relative
Sensation
opportunity
against
green >>
light Rest-
farhdichK
(Color
veil) 100 n, 04 HO 0.03 130 0.02 120 0.03 130 0.02 130 0.03 120 0.03

It can be seen from Table 2 that the samples according to the present invention are excellent Color sensitivity and less color haze result.

Example 3

In the same way as described in Example 1, the compounds mentioned in Table 3 were incorporated either alone or in combination in the same emulsion as in the example 1 was used. After sufficient stabilization of the color sensitivity of the emulsion were Given amounts of the additives were added, and immediately afterwards the emulsions were applied to a polyester film support and then dried, with green-sensitive pholographic Lith type recording materials were obtained. The photographic recording materials were subjected to the same sensitometric investigations as described in Example 1 and then developed with a developer containing hydroquinone as a main ingredient. The relative The sensitivities of the photographic materials were measured. For evaluation A visual method was applied to the point spreads such that the sample was in close contact with it brought to a copact screen, exposed and developed was carried out using the same procedure as in the sensitometric study. Then were the point images obtained assessed microscopically. The point images were assessed using the Grades 5 to 1, with a grade of 5 given to an image containing the sharpest points, while c rating 1 was given to the image showing a number of interferences. The result obtained thereby The results are listed in Table 3.

Table 3

sample

Amount of compound added (mg / kg emulsion)

(4) 40 mg
(9) 40 mg

(4) 20 mg + (9) 20 mg (10) 40 mg

(4) 20 mg + (10) 20 mg (2) 40 mg
(2) 20 mg + (9) 20 mg

Relative sensitivity

against green

light

100 80

130 90

120 80

130

Scoring

2 to 3 4 4 5

From Table 3 it can be seen that the samples gemüi of the invention have high green sensitivity and excellent dot quality.

Claims (1)

Claim: Photosensitive photographic recording material with at least one silver halide emulsion layer through at least one acidic substituted benzoxazole-thiohydantoin-dimethine merocyanine is spectrally sensitized, characterized in that the SiI overhalide emulsion layer a mixture of at least one benzoxazole-thiohydantoin-dimethine merocyanine the formula (CH ₂ ) H ₁ OH I.
= CH-CH = CN R ₁ 15th = s (CH ₂ Jm ₁ SO ₃ M ₁ (1) where Y _{1 is} hydrogen, a lower alkyl group, a lower alkoxy group, a phenyl group or a halogen atom, R _{1 is} a saturated or unsaturated lower hydrocarbon chain, a phenyl group or a substituted phenyl group, Wi _{1 is} door 2, 3 or 4, η is 1, 2 or 3 and M _{1 is} a hydrogen atom, an alkali metal atom or a group of the formula - HX (in which X is an inorganic base) and at least one benzoxazole - thiohydantoin - dimethine merocyanine of the formula (CH ₂ ) Zi ₂ COOH CH-CH = C-N O = C ^- N
(CH ₂ Jm ₂ SO ₃ M ₂ 35 = s (Π) 40 wherein Y ₂ , R ₂ , m ₂ , H ₂ and M _{2 have} the same definition as Y ₁ , R ₁ , Wi ₁ , n or M ₁ in the formula I, contains. 45 It is known for the specific sensitization of light-sensitive silver halide emulsion layers to use acid-substituted benzoxazole-thiohydantoin-dimethine merocyanines (Belgian patent 831). It is also known that the sensitizing effect of sensitizer dyes, including merocyanines, can be increased by adding other compounds. It is also known that by using a mixture of one of the aforementioned sensitizing dyes with certain Types of other sensitizing dyes or organic compounds in silver halide emulsions a photosensitivity can be achieved which is greater than the sum total of the photosensitivities which is reached in wmJ when the compounds are each added individually. This effect will called supersensitization. There are many such supersensitizing mixtures of sensitizers known. Special requirements are placed on the spectral sensitization of a silver chlorobromide emulsion of the so-called lith type. It is necessary that a mixture of sensitizers is used not only increases the sensitization effect, but also meets the following requirements will: