DE2135412C3 - Light-sensitive, photographic recording material having at least one silver halide emulsion layer spectrally sensitized by merocyanines - Google Patents

Description

(CH ₂ ) H ₁ OH

N = CH- CH = < · /

15th

(CH ₂ ) Zn ₁ SO ₃ M ₁

O = C-N

R.

= s

(D

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, Ui _{1 is} 2, 3 or 4,? t, represents 1, 2 or 3 and M _{1 represents} 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 ) H ₂ COOH
I.

I.
CH-CH = CN

35

O = C- (CH ₂ ) Wi ₂ SO ₃ M ₂

= s

I. R2

(II)

40

wherein Y ₂ , R ₂ , m ₂ , n ₂ and M _{2 have} the same definition as Y ₁ , R ₁ , m _{1, M 1} and M ₁ in the formula I, respectively.

45

It is known for the spectral 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 achieved when the compounds are added individually. This effect will called supersensitization. There are many such supersensitizing mixtures of sensitizers known.

Special requirements are placed on the spectral sensitivity 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:

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 reacted sensitizer 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.

The present invention is based on the object of a photosensitive 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-Dimethinemerocyanin is spectrally sensitized, and is characterized by that the silver halide emulsion layer is a mixture of at least one Benz oxazole-thiohydantoin-di .nethinmerocyanin of For mel

(CH ₂ ) H ₁ OH

= CH-CH = CN
O = CN

(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

Represents halogen atom, R _{1 represents} a saturated or unsaturated lower hydrocarbon chain, a phenyl group or a substituted phenyl group, Wi _{1 represents} 2, 3 or 4, Ji _{1 represents} 1, 2 or 3 and M _{1 represents} 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 merocyanirj of the formula

(CH ₂ ) n ₂ COOH
CH-CH = C-Nv

O = CN
(CH ₂ Jm ₂ SO ₃ M ₂

= S

(H)

wherein Y ₂ , R ₂ , m ₂ , n ₂ and M _{2 have} the same definition as Y ₁ , R ₁ , Wi 1, n or M ₁ in general formula I, contains.

In the context of the present invention, the term “lower” denotes groups with particular 1 to 6, preferably 1 to 4 carbon atoms.

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

Typical examples of compounds of the general formulas I and II are given below.

Examples of compounds of the general formula I:

(D

50 CH ₃

CtI ₂ Ui

N = CH-CH = CN \ N ^x I> =

O = C-N /

CH ₂ CH ₂ CH ₂ OH S (3)

(CH ₂ I ₃ SO ₃ Na

CH ₂ Ut

VcH-CH = C-Nv O = C-N '

CH ₂ CH ₂ OH

S (4)

(CH ₂ J ₃ SO ₃ HN

CH ₂ CH ₂ OH

CH ₃ O

S (5)

(CH ₂ I ₃ SO ₃ Na

VcH-CH = C-Nv

n / I V =

O = C-N /

(CH ₂ I ₃ SO ₃ Na

CH ₂ CH ₂ OH

S (6) CK ₂ CH = CH ₂

CH ₇ CH ₂ OH

CH-CH = C-N

H = C-N \

O = C-N /

(CH ₂ ) ₃ SO ₃ Na

Examples of compounds of the general formula II:

CH ₂ CH ₂ OH

Λ / CK I

T V = CH-CH = C-Ns

vA </ ■!

I O = C-N '

(CH ₂ ) ₄ SO ₃ Na

(2)

CH ₂ CH ₂ COOH

M = CN _x

> = S (8) O = CN ^X

CH ₇ COOH

x!

> CH-CH = C-N \ O = C-N /

CH ₃ O

(CH ₂ J ₄ SO ₃ H

CH ₂ COOH ^ CH-CH = C-Nn

CH ₂ CH ₂ COOH CH-CH = C-Ns

O = C-N

(CH ₂ I ₄ SO ₃ Na

(12)

CH ₂ CH ₂ COOH CH = CH-CN

H = C-N \

IV = O = CN ⁷

(13)

(CH ₂ ) ₃ SO ₃ Na

QH ₇ CH ₂ COOH

CH-CH = C-Nn

O = C-N

(14)

(CH ₂ ) ₃ SO ₃ Na

CH ₇ CH = CH,

According to a preferred embodiment, the silver halide emulsion layer contains the photosensitive photographic recording material of the invention is a mixture of at least one of the above specified compounds No. I to 7 and at least one of the above Compounds No. S to 14.

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

The above advantages are not only obtained with photographic emulsions of the lith type, but also if the sensitization 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 photographic 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 I 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 the individual compounds or a solution for a combination of the connections are added.

The timing of adding these sensitizing dyes may be at any stage during manufacture of the emulsion. It is particularly preferred to add it 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 I 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 the formula I and the sensitizing dyes of the formula II 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 furthermore contain customary photographic additives such as stabilizers, hardeners and coating auxiliaries.

The above-described silver halide photographic 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 lith type silver chlorobromide emulsion containing 20 mol% of silver bromide was treated with a gelatin coagulant and then subjected to the second ripening process by the gold sensitization method. Then the emulsion was divided into several portions. The individual portions were mixed with methanolic solutions of the compounds listed in Table 1. The emulsions were then left to stand at about 40 ^° C. for 20 minutes in order to stabilize the optical sensitization. Thereafter, they were added with an appropriate amount of a polyalkylene oxide derivative as a contrast-enhancing agent, a hardening agent and a coating aid, coated on a support and dried to obtain green-sensitive lith type photographic materials. The samples thus obtained were each (2660 ⁰ K) nm exposed in a sensitometer with a light source of 125 lux by a green filter having a transmission maximum at 525 and then developed for 3 minutes at 2O ⁰ C with a developer having 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 of the sample containing dye No. 1 alone as follows 100 is used as the basis. The residual color density is a density value measured by using a color densitometer.

Table 1

connection Amount supplied
the connection Relative
Sensitive Residual color
density No. (mg / kg emulsion) speed against
green light (Color
veil) 1 (5) 50 mg 90 0.04 2 (11) 50 mg 70 0.02 3 (5) 30 mg 120 0.02 + (11) 20 mg 4th (1) 50 mg 100 ■ "" 0.03 5 (10) 50tng 80 0.04

55

60

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

From Table 1 it can be seen that the samples according to the invention, which contain a combination of compounds contain according to the present invention, quite 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.

Example 2

A silver chlorobromide emulsion containing 20 mol 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.

For comparison, a sample of the same emulsion with the known dimethine merocyanine dye (Control) of the formula

C ₂ H ₅

= CH-CH = C-N

I> =!
O = CN /

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 100-based green sensitivity of the control dye.

Table 2

Amount of compound added Relative rest Sensation color density sample opportunity (Color No. (mg / kg emulsion) against veil) Control dye 40 mg green '. (2) 20 mg + (8) 20 mg light 0.04 10 (2) 20 mg + (11) 20 mg 100 0.03 Il (4) 20mg + (8) 20mg 110 0.02 12th (4) 20 mg + (9) 20 mg 130 0.03 13th (5) 20 mg + (9) 20 mg 120 0j02 14th (5) 20 mg + (10) 20 mg 130 0.03 15th 130 0.03 16 120

309 644/3

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, green-sensitive photographic Lith type recording media 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 contact screen, exposed and developed using the same procedure as for the sensitometric investigation. Then the obtained point images were microscopically evaluated. The point spreadsheets were assessed with grades 5 to 1, with a grade of 5 being given to an image which contained the sharpest points, while the rating 1 was given to the image which had a number of interference showed. The results obtained are summarized in Table 3.

Table 3

15th 17th Amount of compound added Relative Point- 18th Sensation beurle- sample zo 19 opportunity lung No. 20th (mg / kg emulsion) against 21 (4) 40 mg green 22nd (9) 40 mg light 3 25 23 (4) 20 mg + (9) 20 mg 100 3 (10) 40 mg 80 5 (4) 20 mg + (10) 20 mg 130 2 to 3 (2) 40 mg 90; 4th (2) 20 mg + (9) 20 mg 120 4th 80 5 130

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

Claims (1)

Claim: Photosensitive photographic recording material with at least one silver halide emulsion layer, which is replaced by at least one acid-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