DE1932882A1 - Photographic light-sensitive material and photographic reproduction process - Google Patents

Description

TELEPHONE: 555476 8000 MO N CH E N 15, ^ '· * JUni 1309 TELEGRAMS. CARPATENT N USSB AUMSTRASSE 10

W.14348 / 69 13 / de

Fuji Photo PiIm Co., Ltd. Kanagawa (Japan)

Photographic light-sensitive material and photographic reproduction process

The invention "relates to photographic materials and particularly to high contrast photographic silver halide emulsions.

It is well known that a photographic image with a high edge gradient is obtained when a certain silver halide photographic light-sensitive material is treated with a special developer, a so-called infectious developer, which mainly contains hydroquinone with a low sulfite content and a high pH value .aufweist (see. eg. B. Yule, JAC "Pormaldehyde-Hydroquinone Developers and Ifectious Development" J. Prank Inst. 1945 239 221.) However, the specific ingredients or additives are contained in a silver halide emulsion is sometimes the Entwioklungsgeschwindigkeit in treatment

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significantly delayed with the infectious developer. For example, requires a silver chlorobromide emulsion with a high content of silver bromide has a long development time for the achievement of a certain "Kon-, trastes, compared to another silver chlorobromide emulsion, that have a lower silver bromide content having. The addition of polyalkylene oxide derivatives that commonly known as coating agents leads to a remarkable decrease in the extent or the rate of infectious development. It is therefore when using an infectious developer of this type important to speed up development and the length of time required to achieve one to shorten a certain density or a certain contrast.

The object of the invention is to create a halogen silver emulsion, which use high contrast in a relatively short development time of the infectious developer.

The aforementioned purpose can according to the Er-v Finding can be achieved by having at least one layer consisting of a halosilver emulsion layer or a layer adjacent thereto, a compound of the general terms given below Formula clogs

R ₁ -SSCN

• f

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in which E ₁ -an alkyl group with 1 - 5 carbon atoms _t Hydroxyälkylgruppe with 1-5 carbon atoms, letrafurfuryl group or aralkyl group with 7-12 carbon atoms, R ₂ and R, each a hydrogen atom, an alkyl group with 1 -5 carbon atoms or a Group of atoms that form a ring via a bond of. Rg and R, is capable, for example, of a morpholine group or piperidine group and Q represents a sulfur atom or an imino group.

Examples of compounds useful in accordance with the invention are given below.

Compound I
B-Benzylsulfenyldithiocarboxydimethylamine

-CH ₂ -SSCN ^ P 96-98 ° C

Compound II
N-Cs-BenzylsulfenyldithiocarboxyVpiperidine

ο 103-105 C

Compound III

1-chlorophenyl-4- (s-benzylsulfenyldithiocarboxy) piperazine

116-117.5 ° C

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Connection IY
β-4-isopropylbenzylsulfenyldithiocarboxyinorpholine

^0H K / -ν ₂₂

K / -ν .CH ₂ -OH ₂ V

^ CH- ^ VcHg-S-S-C-H ^ yO P 79-81 ° C

Connection Y

N- (s-ß-Hydroxyäthyleulfenyldithiocarboxy) -morpholine

-C-Nf
N

HIGH ₂ CH ₂ -SSC-Nf ^ O P 64-66 "C

«N) H ₂ -CH ₂ /

Connection YI

N- (s-tert-butylsulfenyldithiocarboxy) piperidine

(CH ₃ ) ₃ CSSCN ^ - - "^ CH ₉ P 59-60 ° C

S CH ₂ -CH

Compound VII

N- (s-tert-butylsulfenyldithiocarboxy) morpholine

(CH,), C-S-S-C-n: ^ O P 63-65 "C

\ CHp-CH ^

Compound VIII
s-Benzylsulfenylisothiourea hydrochloride

• HC1 P 145-148 ° C

NH

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Compound IX
s-furfurylsulfenylisothiourea hydrochloride

1-CH ₉ -SSO-IIH ₉ -HCl P 123-125 ° C

.Il

0 NH

Connection X

8-4-18-propylbenzylsulfenylisothiourine-hydrochloric

H ₂ -SSC-NH ₂ .HCl

Compound XI
s-ß-Hydroxyethylsulfenylisothiourea hydrochloride

HIGH ₉ CH ₀ -SSC-NH ₀ -HCl P 106-107 ° C

Il

NH

The preparation of these compounds, e.g., Compound X and Compound IV, is carried out according to the following procedures carried out, but is not limited to this.

Synthesis example

A mixture of 2.4 g of p-isopropylbenzyl chloride, 32.6 g of thiourea and 99 ml (#) ethanol were boiled for 3 hours and concentrated to dryness. A solution of 100 g. Sodium hydroxide in 400 ml of water was added, and the mixture was stirred for 3 Boiled for hours while blowing nitrogen gas. To The mixture was cooled and acidified with hydrochloric acid

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extracted about 1 liter of ethyl acetate, washed with water and dried. The ethyl acetate was then distilled off and the residue was fractionated, 64 g (yield 90% ) of p-isopropylbenzylmorcaptan having a melting point of 116-117.5 ° C. being obtained.

A mixture of 10 g of p-isopropylbenzyl mercaptan, 5.5 g of thiourea, 9 ml of concentrated hydrochloric acid, 9 ml of water and 130 ml of ethanol were added while cooling with ice stirred and kept at 5 * ■ 10 ° C, including 7.5 g of "50 jU i; '· - · -. Hydrogen peroxy d was added dropwise. After the dropping, the mixture became during further Stirred for 3 hours, filtered and proportioned with ethanol washed. The filtrate and washing solution were collected and placed under reduced pressure to dryness concentrated. To this, ethanol was added, heated, and the insoluble (soluble) material was separated off, to which ether was then added to deposit crystals. Recrystallization from a mixed solvent of ethanol and ether was repeated, leaving 11.7 g (yield 70 #) of s-4-isopropylbenzylsulfenylisothiourea hydrochloride (Compound X) having a melting point of 154-155 ° C were obtained.

2.0 g of potassium morpholine dithiocarbamate were dissolved in 20 ml of a 5% solution of sodium bicarbonate and with vigorous stirring and cooling with ice with a solution of 2.8 g of p-isopropylbenzylsulfenylisothiourea hydrochloride mixed in 30 ml of 50% ethanol. The mixture immediately became whitish-cloudy, viscous and difficult to stir. The reaction mixture was allowed to stand for a short period of time, filtered and removed from methanol recrystallized, with 2.5 g (yield 77 ^) of the

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-Compound "-17 with a melting point of 79-81 ° C. The elemental analysis of the compound IV gave the following results:

Analysis (C ₁₅ H ₂₁ ROS ₃ )

^: CHS

calculated 55.00 6.46 29.37

found 55.17 6.40 28.58. .

The amounts of the compounds that make the photographic Emulsions to be added vary according to the kinds of the emulsions and the compounds. In general, a proportion of 0.05 "to 10 g of the compounds per 1 mole of the amount used in the photographic Silver halide contained in the emulsion was added.

The preparation of a photographic emulsion is usually carried out in three steps, namely (1) precipitation and digestion of silver halide, i.e. physical digestion, (2) removal of excess Salting by washing with water and (3) chemical digestion, i.e. after ripening to increase sensitivity. The compound according to the invention can be added to the emulsion in any state, wherein however, an optimal result can be obtained when adding after and before chemical digestion the coating takes place. The compounds are in solvents, which have no adverse effect on the emulsion, dissolved, for example in water, a lower alcohol such as methanol or ethanol, ketones such as acetone, and are then added to the emulsion. These chemicals are usually added directly to the emulsion, but they can if desired a photographic layer adjacent thereto

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is added, for example a protective layer, in order to penetrate through this to the emulsion layer.

The photographic emulsion which can be used according to the invention is a chlorosilver, bromosilver, Silver chlorobromide, silver iodobromide, and silver chloroiodobromide emulsions. In addition, a direct reversal emulsion, for example from the Herschel effect or Type of solarization.

The emulsion can be chemically sensitized according to procedures well known in the art, wherein one or more of the unstable sulfur-containing compounds, e.g., aranonium thio-sulfate and aryl thio-urea (cf. P.Glafkide's "Chemie Photographique" II. edition, pages 297 to 299 (1957)) and gold compounds, e.g. a complex of monovalent gold and rhodan

acid
hydrogen / (cf. «Ie page 3ol) can be used. The emulsion may also by addition of sensitizing dyes such as cyanine dyes ^ or Herocyariinfarbstoffen ( 'See, Shinichi Kikuchi, "Kagaku Shashin Binran (Handbook of Scientific Photography)", pages 15 to 24, published by Maruzen Co., 1959), are optically sensitized . ' In addition, the emulsion can be stabilized by adding heterocyclic compounds, for example benzotriazole or 1-phenyl-5-mercaptotetrazole. In addition, the emulsion can be hardened by hardeners such as formaldehyde or chloromuconic acid (mucochloric acid) and may contain surface-active materials, e.g. E.g., saponin, to facilitate coating or coating.

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I'm a film trained to achieve a "particularly high contrast when developing under." Use of the infection developer is as a lithographic one Film known. Lithographic type photosensitive materials usually consist of one Ohlorbromsilberemulsion with a high content of silver chloride and are suitable for the production of Half tone dots with the help of a glass screen or a pane of glass or a touch screen.

If the compounds according to the invention are a Emulsion of the above-described lithographic film can be added and the film on a halftone image · exposed and developed with the infection developer is the development time that is required for the product with high density halftone dots or indications is shortened, and accordingly is the optimal one Range of development time, i.e. the development latitude increased. As a result, a Obtain optimal dot quality over a wider range of development times.

The invention is explained in more detail below with the aid of examples.

Examples

A silver chlorobromide emulsion with a content of 3o M0I.5S silver bromide, containing merocyanine dyes was optically sensitized, the above compounds were converted into those in the following Table I added amounts indicated. The resulting emulsions were used as a coating or an overcoat

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- Io -

applied to a film base and dried, whereupon the sensitometric study described below was carried out on the film samples.

Table I. sample
No. link
No. 1 no 2 III 3 III 4th IV 5 IV 6th V 7th V- 8th • viii 9 VIII

Additional amount (g) (per 1 mol of silver halide)

W χ TTT _lj5

o, 4 ■ o, 7

o, 9 o, 2 o, 2

In the sensitometric examination -.- / urden the films for Io seconds through one window at a time optical wedge with a step difference of o, l below Use of a tungsten lamp (2666 ° K) as a light source exposed and then developed in a developer of the following composition »

V / poor V / ater 5oo inl

anhydrous sodium sulfate 3o g

Paraformaldehyde 7.5 g

Sodium bisulfite 2.2g

Borax. 7.5 g

Hydroquinone '. 22.5 g

Potassium bromide 1.6 g

Water rest on 1 Li.fcer

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_ _λ1 _ 1032882

The results * the "when executing the development were obtained at 2o ° C for 2, 3 or 4 minutes, are compiled in Table II below.

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link
■ No. relative
2 ' Tabel II 2ο8 2 ' gamma
3 ¹ 4 " veil
2 »3 · ο, ο4 4 » sample
No. no 32 sensitivity
3 ¹ · 4 ¹ 218 5.5 ΐο, ΐ ΙΙ, ο ο, ο4 ο, ο4 ö, o4 1 III 6o loo 221 6, ο 11.2 Ιο, Ι ο, ο4 ο, ο5 ο, ο4 2 III 72 115 224 6.3 1ο, 8 Ιο, ο ο, ο4 ο, ο4, ο, ο5 3 IV 52 12ο 23ο 5.7 Ι2, ο 11.5 ο, ο4 ο, ο4 ο, ο4 4th IV 66 Ho 22ο 6.5 12.1 11.0 ο, ο4 ο, ο4 ο, ο4 5 V 65 123 225 6.5 11.2 11.5 ο, ο4 ο, ο4 ο, ο5 6th V 77 122 233 7.1 3.1.2 11.7 ο, ο4 0, ο4 ο, ο5 7th VIII 78 13ο 24ο 7.5 9.8 8.5 ο, ο4 ο, ο5 ο, ο5 8th VIII 83 145 7.5 ⁹ ' ⁵ 8.2 ό, ο5 ο, ο5 9 149

From the above results is

it can be seen that the addition of compounds according to Invention resulted in a considerable increase in sensitivity in a development time of 2 minutes, however leads to a small effect with a development time of 4 minutes. Thus, the addition of the compounds leads according to the invention to an increase in the initial speed of development.

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Claims (9)

Claims 1. Photographic light-sensitive material, characterized in that it is as a coating or Coating on a support at least one halogen silver emulsion layer which has a compound of the general formula below / 2 R _n -SSG-- N (I) contains, where R, an alkyl group with 1 to 5 carbon atoms, a hydroxyalkyl group with 1 to 5 carbon atoms, a tetrafurfuryl group or an aralkyl group with 7 to 12 carbon atoms, R ₂ and R, each a hydrogen atom, an alkyl group with 1 ₁ to 5 carbon atoms or an atomic group capable of forming a ring by bonding R 2 and R 1, and Q represents a sulfur atom or an imino group. 2. Photographic, photosensitive material according to claim 1, characterized in that the compound in an amount of 0.05 to 10 g per 1 mol of silver halide is present in the emulsion layer. 3. Photographic light-sensitive material according to Claim 1 or 2, characterized in that the compound of s-benzylsulfenyldithiocarboxydimethylamine, N- (s-benzylsulfenyldithiocarboxy) piperidine, l-chlorophenyl- ^ is-benzylsulfenyldithiocarboxyJ-piperazine, s- ^ isopropylbenzylsulfenyldithiocarboxymorpholine, N- (8-ß-Hydroxyäthylsüifenyldithiocarboxy) -mörpholin, N-Cs-tert-butylsulfenyldithiocarboxyJ-piperidine, 909883/1283 K- (s ~ tert-Butyilsulf enyldithioearboxy '-) ^ -morpholine, s-Benzy Isulf eny Hs othiours toff -hydrochloride, or s-B-Hydroxya ^ hylsiilfeiiylisotMoharnst ^ i: * ^ rid - 4. Phötographisöhes, lichitempfiildlielies i $ atema; l. according to claim x _f, characterized in that ejs has on a support as a coating or coating at least one halogen silver emulsion layer which is a compound of the general formula below R - S - S - C - N ^ά - ^{: <L} X) .Q contains! wherein R, an -Alky! group with 1 "to 5 material atoms, a hydroxyalkyl group with 1 to 5 carbon atoms, a tetrafurfuryl group or an aralkyl group with 7 to 12 carbon atoms and Q is a sulfur atom or represent an imine group. 5. Photographic light-sensitive material according to claim 4, characterized in that the compound in an amount of 0.05 to 10 g per 1 mole of silver the emulsion layer is present. 6. Photographic light-sensitive material. according to claim 4 or 5, characterized in that the compound of s-4-isopropylbenzylsulfenyldithio-. carboxymorpholine, N- (s-ß-hydroxyethylsulfenyldithiocarb'oxy) morpholine or N- (s-tert -butylsulfenyldithiocarboxy) mprpholine consists. . ·. 909883/1283 7 »Photographiocheo, photosensitive material according to claim 1, characterized in that it is at least as a coating or coating on a carrier a silver halide emulsion layer and a photographic layer adjacent thereto, the adjacent layer the compound of claim 1 given formula I contains. 8 β Photographic, light-sensitive material according to claim 7, characterized in that the compound in the adjacent layer is in an amount of 0.05 to 10 g per 1 mol of silver halide is present. 9, Photographic light-sensitive material / Or 8 according to claim 7 / characterized in that the compound of s-benzylsulfenyldithiocarboxydimethylamine, N- (s-Benzylsulfenyldithiocarboxy) -piperidine, 1-chlorophenyl-4- (s ~ benzylsulfenyldithiocarboxy) -piperazine, s-4-isopropylbenzylsulfenyldithioearboxymorpholine, N-Cs-ß-Hydroxyäthylsulfenyldithiocarboxy) morpholine, j N- (s-tert, -ButylsUlfenyldithiοcarboxy) -piperidine, N- (s-tert-butylsulfenyldithiocarboxy) -morpholine, s-Benzylsulfenylisothiourea hydrochloride, · s-furfurylsulfenylisothiourea hydrochloride, s-4-isopropylbenzylsulfeny! isothiourea hydrochloride or ß-ß-Hydroxyäthylsulfeny! isothiourea hydrochloride consists, · ' 10. Photographic light-sensitive material according to claim 7, characterized in that it is in the adjacent layer contains a compound of the general formula II given in claim 4. 1.1. Photographic light-sensitive material according to claim 8 / characterized in that the compound in an amount of 0.05 to Io g per 1 mole of syllable: halide is present. 909 883/1283 12. Photographic, light-colored material according to claim 10 or 11, characterized in that the compound of s-4-isopropyl'benzylsulfenyldithio- carioxynorpholine, N- (s-ß-Hyciroxyäthylsulfenyldithioc ar "boxy} -morpholine or IT- (s-tert-butylsulfenyldithiocarboxy ) -r.; orpholin consists. 13. iieProduktionsverfahren, characterized in that m ... r. βία photographic, light-sensitive material, aas u ? a carrier as a coating or covering has a halo-emulsion layer and an adjacent photographic layer, with one of these layers being a compound of the following general formula ;? -SSCN ¹ "N, ent .: ilt, v / orin R-, an alkyl group with 1 to 5 carbon atoms, a hydroxyalkyl group with 1 to 5 carbon atoms, ^ ine tetrafurfuryl group or an aralkyl group with 7 to 12 carbon atoms, "R ₂ and R, each a hydrogen atom , an alkyl group having 1 to 5 carbon _{atoms or an atomic group suitable for forming a ring by joining R 2} and R, and Q represents a sulfur atom or an imino group, and the exposed photographic material is developed with an infection developer containing hydroquinone. 9 0 9883/1283