DE2354790A1 - PHOTOGRAPHIC SILVER HALOGENIDE EMULSION - Google Patents

Description

The invention relates to an improved photographic silver halide emulsion, which contains a silver halide that too at least 40 Hol-% consists of silver chloride, the silver halide particles have an average diameter of no more than 0.8 microns; it concerns in particular described a silver halide photographic emulsion formed in a lith type light-sensitive material with an improved Sensitivity in the initial stages of an infectious Development process and with an increased edge gradient the image copy made with it can be used. Under the term "edge gradient" as used herein, is . Degree of change in optical density in relation to the vertical direction to that as the contact line between the blackened ones and non-blackened portions of the developed photographic copy image. in the In general, it can be said that the higher the edge gradient, the clearer or sharper the image copy is.

-4098 19/09 3 3

A photosensitive material with an increased edge gradient is advantageously used, for example, as used lith-type photosensitive material like it is used in collotype printing or collotype printing, using a glass grid or a contact grid Line cross images are generated. It is known, that in a photosensitive material of this type to ensure simple and easy handling of the Edge gradient increases, the sensitivity improves Graininess must be kept to a minimum and the development speed must be accelerated. It is also known that when the development is carried out under severe conditions, the fatigue of the developing liquid delayed, i.e., the tolerance and the like must be increased in order to minimize the deterioration in image quality.

In order to obtain an image copy with a high edge gradient, one is usually used for collotype printing lith type photosensitive material using an infectious development process.

The "infectious development procedure" generally involves the development with a developer containing hydroquinone as main developing agent contains along with a much lower amount of a sulfite, an inorganic alkali metal salt or an organic amine, using a pH of 9 ₅ 5 or higher. However, development using an infectious developer is associated with the following disadvantages: low sensitivity, low initial developing speed, uneven quality of the copy image obtained after each development process, and poor graininess of the copy image and the like as compared with another type of developer in which the main developing agent is a developing agent is combined. that can deliver a super additive effect, such as

& 0981 9/0933

_ 3 -

wise in the commonly used '^ etol hydroquinone developer, Metol pyrazolidone developer and the like. In addition becomes a SiI overhalide emulsion as a lith type photosensitive material used, die.ein polyoxyalkylene oxide derivative to increase .infectious development and suppress the non-infectious developability. By adding such a polyalkylene oxide derivative however, the initial development speed becomes strong degraded; That means with others. Words that. in such Emulsions require a longer development time, to an infectious development with a sufficiently high Ensure contrast ·. When the .infectious development once started, the polyoxyalkylene oxide derivative strengthens developing exceptional, strong, being it high contrast. results to initiate the infectious However, far too long a period of time is required for development so that it is possible that in the meantime gradations with an extremely low contrast and a extremely high contrast exist at the same time, as a result of which the "foot cutting" _ (cutting off the lower part) is intensified.

In addition, photosensitive materials are dated Lith-type often applied a spectral sensitization, to increase the sensitivity in a specific wavelength range. Most sensitizing dyes however, have the tendency to reduce infectious development at a noticeable rate ■ Deterioration of the "foot cutting".

When the so-called infectious development for development of a photosensitive material from. Lith type applied will occur due to the presence of various ^ Additions from the silver halide emulsion and due to Substances that are used during the development process of a are subject to chemical change, many more components,

4098 19 / 09.3 3

which affect the development performance more than when using conventional, non-infectious developers.

Additives that are usually used effectively in a non-infectious black and white developer such as e.g. D-16, D-19 and D-72 (these developers and their compositions are known per se), are not always equally effective for the infectious developer. You. Guide rather, a decrease in the land gradient due to its disappearance the infectious developability, to one Fogging and promoting developer fatigue and like adverse influences.

The aim of the present invention is therefore to provide a photo- indicate a graphic emulsion in which all the disadvantages described above are eliminated or considerably reduced are. In particular, it is an object of the invention to provide a photographic emulsion which satisfies the following criteria suffices: (1) increasing the initial development speed, (2) Achieving a high sensitivity within the shortest possible development time, (3) Achieving a high edge gradients within the shortest possible development time, (4-) maintaining an excellent Graininess while maintaining high sensitivity, (5) maintaining high earth gradient after a high degree of development and (6) maintaining a satisfactory tolerance. goal of The invention is also to provide a process for the preparation of silver halide emulsions, which in a large Dimensions meet the above requirements at the same time.

It has now been found that the above objectives can be achieved with a photo-. 409819/0933

graphic silver halide emulsion containing a silver halide which is at least 4-0 mol% consists of silver chloride, and in which the average particle diameter of the silver halide particles is not larger than 0.8 microns, which is characterized in that it is also a combination of (1) a polyalkylene oxide compound and. (2) an organic compound having at least one hydroxy group and at least one amino group having a tertiary nitrogen atom (especially one which which can promote infectious development) contains ».

Further. Objects, features and advantages of the invention emerge the following description in conjunction with the enclosed Drawings. The following mean: ■

Figures 1 and 2 each are diagrams showing the relationship between development time and relative sensitivity explain * These figures give in a relative way the Development speed;

Fig. J shows a voltage-current curve (polarograph) from which the Oxidation potential (E ~) is determined. The points a * and b represent the points at which three single segments meet cross each of which line is connected by the Center of the Kutven runs in the ordinate direction, which indicates the current value.

In particular, the organic compound should have at least a 'hydroxy group' and at least one 'amino group with a tertiary nitrogen atom to the oxidation product (i.e. * to the semiquinone) that occurs during development the main developer compound (e.g. hydroquinones) forms a specific reducing activity. At this specific compound is an aromatic one

4098 19/0933

Compound or a heterocyclic compound (among these two compounds, an aromatic compound is preferred) with an oxidation potential (which is defined in more detail below) (E _Q ) of about 0 to about -200 millivolts (mV), preferably of up to -160 millivolts, or precursors (regardless of their oxidation potential) of these compounds. Particularly preferred compounds are those of the general formula

XO-A-N.

where 'mean:

A- a bivalent aromatic or heterocyclic group (e.g. a benzene, naphthalene, pyrimidine, triazine group), where A can be substituted by substituent groups in such a way that the required value of E _{Qx is} obtained (e.g. alkyl, such as methyl, ethyl, Propyl, butyl and the like., Alkoxy such as methoxy, 'ethoxy and the like., Hydroxy, halogen such as chlorine, bromine and the like., Alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl and the like., Quaternary aminoalkyl, aralkyl such as benzyl, phenethyl and the like, aryl such as phenyl and the like, and the like);

ή * and Rp individually each used to form a tertiary

Amino group with the nitrogen atom required group, preferably an alkyl group, such as a methyl, ethyl, butyl, hydroxyalkyl, e.g. hydroxyethyl, Aminoalkyl, e.g. trimethylaminoethyl group and the like, an alkenyl group such as an allyl group, an aralkyl group, like a benzyl ", p-hydroxypheny! -substituted Alkyl group and the like, or an ary group such as a Phenyl, hydroxyphenyl, acetoxyphenyl, alkoxycarbonyloxyphenyl group '-and the like, or together one closed

409819/0933

a (saturated or unsaturated) ring;

X is a hydrogen atom, or a group associated with a inorganic or organic base can be dissociated therefrom, e.g., acetyl, benzoyl or the like Acyl group, an acetoxy or similar acyloxy group .. The compound: to which these dissociable groups are attached is referred to as the "precursor", the releases its dissociable group under the developmental conditions, the compound behaving as if X had originally been a hydrogen atom.

The compound of the general formula I is usually in a stable state in the form of a "Lewis acid-base salt" with an inorganic or organic acid (e.g. hydrochloric acid, sulfuric acid, nitric acid, ■ sulphurous Acid, oxalic acid, p-methylbenzenesulfonate and sulfuric acid and the like.), so that they stabilized in such a Shape can be used. Particularly preferred compounds of the general formula I given above are such the general formula ■.

XO-B-N

(I-a)

where B denotes an aromatic ring group of the bivalent benzene type and X, R ^ and R _{2 are} each defined as given in the above general formula I. · · "...

Typical compounds of the general formula I, the invent The following can be used as intended specified compounds., However, the invention is in no way restricted to these compounds and it .may also

40 9 8.19 / 09 3 3.

other compounds used in the German Offenlegungsschrift 2,153,632, 2,153,633, 2,153,571, 2,153,572, 2,161-431, and the like.

(i-a)

N (C ₂ H ₅ )

(i-b)

(i-c)

HO

CH

• 3

(i-d)

.HC-ß

N (CH) ₂ .HC-ö "

40981 9/0933

(if) .HO

CH

(i-g)

CH-

HO

Ή Cn, C ₄ H ₉ ) ₂ ·. HC #

CH-

CH-

HO

CH-

(i-i)

HO

, .HC-0

^t " ^C 4 ^H 9

rv

CQ-O

F (CH ₃₎ 2 ¹ ZS-H ₂ SO ₄

-409819/0933

(I-k)

C ₂ Hc-O-CO-O

I ₅ ) ₂ . HC ^

(i-i)

CH

HO

(C ₂ H ₅ ) ₂

(in the)

N (C ₉ H ₁ -) _O .HO0

HO

^S0 3 ^H

CH-

HO

OH·,

C ₀ H ₇₁ OH

409819/093

(I-P)

(i-q)

(i-r)

₅ ) ₂ .HC-0

N (C ₂ H ₅ ).

OCH ₃ \ -N (C ₂ H ₅ ) HO - CH ₃ (I-s) CH ₃

N (C ₂ H ₅ ).

The compounds (J-j) and (I-k) "are examples of "Precursor" Compounds. '- ■

The development process is an oxidation-reduction * -

409819/09

To understand reaction processes between the silver halide and the developing agent.

Of the compounds according to the invention described above, those used as part of the emulsion of the invention the most advantageous compounds for achieving the objects of the present invention have the specific oxidation potential (Eq), as already stated above The value of the oxidation potential (Eq) can easily be determined as described below Voltammetry can be determined.

First, a Britton-Robinson buffer solution is adjusted to. a pH of 11.0, prepared by mixing 825 cc of a 0.20 η Hatriumhydroxydlösung with 1 1 of solution containing 39 ₅ 2 g of orthophosphoric acid, 24-, O g of glacial acetic acid and 24.7 g of boric acid dissolved contains (the Solution has a pH of 11.0 at 25 ° C). Nitrogen gas is then introduced into the buffer solution produced in this way in order to completely displace the air, after which the samples to be measured are dissolved in it

—'S
preparing a 1 χ 10 molar solution of each sample.

After inserting a mercury dropping electrode into this solution, a voltage-current curve is recorded at 25 ° C. using a saturated calomel electrode (SCE) as a reference electrode. The oxidation potential (Eq _x ) is determined from this curve by the commonly used graphic method by determining a half-wave potential.

A number of the measured values sometimes exhibits a difference of about 100 millivolts, depending upon the effect of the salt of the compound, although compensation in the liquid-liquid contact potential, the electric resistance and the like., Which are specific to the apparatus, ^q urch suitable Settings in the electrical circuit of the polar

409819/0933

graphic apparatus of the tripolar type occasionally be performed. However, if only one connection is measured e.g. in the case of measurement with hydroquinone, the reproducibility of the value of the oxidation potential can be obtained by comparing the measured value against a standard of -150 +2 millivolts and .adjusts. - -

The term "oxidation potential" as used herein stands ^ for the electrical potential at which the sample is oxidized at the anode. Methods for measuring the oxidation potential are described in the most diverse publications, e.g. P. Dehalhay, "New Instrumental Methods in Electrochemistry", Interscience Publishers, 1954-, Ί.Μ. Kolthoft and J.H. Lingane, "Polarography", 2nd edition, Interscience Publishers, -1952, L. Meites, "Polarοgraphic techniques", 2nd edition, Interscience Publishers, 1965, and the like. The one used here The term "oxidation potential" refers to that which relates to the form in which a proton is dissociated from the organic compound, and therefore the measurement is preferably carried out in a solution with a sufficiently high pH value. In this case it takes place the measurement of the oxidation potential of the organic compound of the general formula I expediently within about 1 hour » after preparing the alkaline solution, since the organic compound has a tendency to be in an aqueous solution with a pH greater than about 10 decomposition, for example to be subject to deamination. '■

t -

In the case of the polyalkylene oxide compound that is used in accordance with the invention can be, it is a connection that at least one partial structure or units of a polyalkylene oxide which of the increase. of the infectious Development effect when using a photographic Silver halide emulsion is used, for example in US Pat

4098 19/0933

U.S. Patents 2,400,552, 3,294,537, 3,294,540, 3 516 830, 3 56? 458 and 3 34-5 175 and the like (The last three US patents mentioned correspond to French patents 1,491,805 and 1,596,673 or the published Japanese patent application Hr. 23 466/65).

Examples of suitable polyalkylene oxide compounds include an addition polymer of ethylene oxide, propylene oxide and similar alkylene oxides with a compound, such as water, aliphatic alcohols, aromatic alcohols, glycols, aliphatic acids, organic amines and a hexitol dehydration compound, a condensate of a Polyalkylene oxide with one of the above-mentioned group of compounds or a block copolymer with varying. different alkylene oxides (e.g. ethylene oxide and propylene oxide).

The polyalkylene oxide compounds used according to the invention have a molecular weight within the range of from about 500 to about 25,000, preferably from 1,000 to 20,000 and this includes, for example, the following connections:

(b) HO-CH ₂ CH ₂ O (CH ₂ CH ₂ O) ^ CO (CH ₂ ) (c) HO (CH ₂ CH ₂ O) _a (CHCH ₂ 0

409819/0 9 33

where a, "b and c mean integers, where b is an integer Number from 14 to 55 and a + c is an integer from 4 to 210 mean. "_ ·

A number of different commercial products meet the above requirements for the most varied of values for a, b and c and with the most varied of molecular weights. These products are currently under the trade names Pluronic L-44, L-61, L-62, L-64, L-68, L-81, P-65, P-75 and 3Γ-88 (products of Wyandotte Chemical Co.). For example, L-68 has a molecular weight of 8750 with b = 32 and a + c = 159, P-75 has a molecular weight from 4100 b.ei b = 37 and a + c ■ * 51, F-88 has a Molecular weight of 11,250 with b = 41 and a + c = 204.

(d) HO-CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₅₀ CH ₂ CH ₂ OH

C ₁₂ H ₂₅ COO-CH -CH-O- (CH ₂ CH ₂ O) ₁₁₁ H

■ C (CH ₂ CH ₂ O) _n H

(J + m + n = about: 20) ^

( -ρΛ unnu ου Α / Ήτΐ πχτ γ \\ —— / ι > \ _ Π TT f + ^

'(g) C ₁₇ H ₃₅ COO (CH ₂ CH ₂ O) ₃₀ H _., * ■

. . (CH ₀ CHpO) Ή :: ■ / ■ ■■■■■

98 19/09 3 3.

The silver halide emulsion used in the present invention contains particles of silver chloride, silver bromide, silver iodide or mixtures thereof, and they preferably consist of at least about 40 mol% silver chloride and less than 5 mol% of silver iodide or silver bromide. According to the invention Silver halide particles used can have a uniformly distributed halogen composition in the interior of the particles or the particle surface may have a composition different from that of the interior to have. The method according to the invention can not only on usual? Surface-sensitive negative emulsions but also on emulsions of the latent internal image type, direct-positive emulsions with a chemically obscured one Surface as well as other emulsions are applied, as obtained for example by the method described, for example, in U.S. Patents 2,592,250, 2,996,382, 3,607,278, and 3,367,778, and the like are.

If the average diameter of the silver halide particles is more than 0.8 microns, the graininess of the image obtained after the infectious development becomes much coarser than that obtained after the usual non-infectious development. The average diameter of the silver halide particles is determined by customary methods. These methods of determining particle size are described by Trivelli and Smith, "Photographic Journal"., Volume 79, pages 330-380 (1939), Trivelli, Eighter and Sheppard, "Photographic Journal", Volume 62, pages 407-410 (1922) , PF Utt and KP Leverington, "The Determination of Silver Halide Crystal Distribution in Photographic Emulsion with the Zeis-Endter Particle Size Analyzer", 1966 Particle Size Analysis Conference Report, pages 45-55 (published in "Soc. Anal. Chem. ¹¹ ) ', and the like.

The photographic emulsion used in the present invention can

409819/09 3 3

using standard, known procedures, as described, for example, by C.E.K. Mees and T.H. James in "The Theory of the Photographic Process", 2nd and 3rd edition, are described, be sensitized, for example by sulfur sensitization (as in the ■ US patents

1 574 944 _} 2 378 94-7, 2 440 206, 2 410 689 ,. 3,189,458.

3,415,649 and the like), by reduction sensitization (as in U.S. Patents 2,518,698, 2,419,974,

2 983 610 and the like), by raising awareness under Use of precious metal ions (e.g. gold compounds, platinum compounds and. the like, as described in U.S. Patents 2,540,085, 2,597,856, 2,597,915, 2,399,083, and the like), other metal ions than silver, e.g. from ions of the metals of groups VIII and II of the Periodic Table of the Elements.

Typical examples of chemical sensitizers are Thiourea, sodium thiosulfate, cystine and the like Sensitizers containing sulfur, potassium chloroaurate, Gold (I) thiosulphate, potassium chloropalladate and similar precious metal sensitizers, Tin chloride, phenylhydrazine, reductone and the like reducing sensitizers and the like. Es Other sensitizers such as polyoxyethylene compounds can also be used (as, in U.S. Patent 2,716,062 described), PQlyoxypropylenverbindungen with a Qxonium- or ammonium group (as in US Patents 2 27 "Ί 623, 2,288,226 and 2,334,864). In addition, if desired, an increase in the contrast (an increase in gradation), a stabilization, a Fog inhibition or super-sensitization and the like * be applied.

Suitable examples are antifoggants such as nitrobenzenes, e.g. ITitrobenzimidazole (such as "in British Patent 403 789), platinum salts such as ammonium chloroplatinate

I * Ö9 & 1 9/0933

(as in U.S. Patents 2,566,263 and 2,566,245 described) and the like, stabilizers such as 4-hydroxy- 6-methyl-1,3 »3a, 7-tetrazaindene, thiazolium salts (as in U.S. Patents 2,131,038 and 2,694,716), Azaindenes such as 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (as in U.S. Patents 2,886,437 and 2,444,6O5 described), urazoles, as described in US Pat. No. 3,287,335), sulfo-catechols (as "in the U.S. Patent 3,236,652), oximes, mercaptotetrazoles (as in U.S. Patents 2,403,927, 3,266,897 and 3,397,987), lemon, polyvalent ^ Metal salts (as described in US Pat. No. 2,839,405), thiuroniums al ze (as described in US Pat 3,220,839) and salts of metals such as palladium, platinum and gold (as in U.S. Patents 2,566,263 and 2,597,915).

The photographic emulsion usable in the present invention Can be used as protective colloid gelatine and acylated gelatine derivatives, such as phthalated and malonated gelatine, «cellulose derivatives, such as hydroxyethyl cellulose, carboxymethyl cellulose; hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, Polyacrylamide, polystyrene sulfonic acid and the like; Dimensional stabilization plasticizers, polymeric latices, like polyester hy lmetliacrylat, polybutylmethacrylat, and matting agents, such as silica and the like.

The photographic emulsion usable in the present invention can also accelerate development, such as oniura compounds, Hydroquinone derivatives, 3-pyrazolidone derivatives and cationic derivatives surfactants; Stabilizers like those in common photosensitive materials such as 4-hydroxy-1,3,3a, 7-tetrazaindene derivatives; Fog inhibitors such as mercaptotetrazole and lipoic acid; Harder, e.g. inorganic and organic compounds, such as formal

4098 19/093 3

dehyde, other aldehydes, chrome alum, mucochloric acid, sodium ~ 1-hydroxy-3,5 ~ dichlorotriazine, Glyoxal, dichloracrolein, Aziridine and the like; surfactants such as Saponin, Hat riumalky Ib enz oil sulfonate, anionic or surface-active Agents as described in U.S. Patent 3,415,649 are described; anionic, nonionic or amphoteric surfactants, such as those commonly used as coating auxiliaries can be used, such as the alkylarylsulfonates described in U.S. Patent 2,600,831, those described in U.S. Patent 3,133,816 amphoteric compounds; Radiation inhibiting dyes, such as 'merocyanine dyes, oxonol dyes, styryl' dyes, naphthoquinone dyes and the like, contain.

The layer of the photographic material used in the present invention Emulsion can be made either on its top side or on its bottom side with at least one layer; one Colloid that has been colored to prevent halation (Halation) to prevent or a pilter effect to achieve. The silver halide photographic emulsion can be prepared using various methine dyes such as

they from CE.K. Mees-in “The Theory of the Photographic Process”, revised edition MacMillan, by Prances M. Hamer-in “The Cyanine Dyes And Related Compounds”, Interscience Publishers, are described, for example using cyanine dyes, merocyanine dyes, hemicyanine dyes, complex merocyanine dyes , Styryl dyes, neutrocyanine dyes and the like., Be spectrally sensitized. The use of sensitizing dyes of the general forms given below in IJ and III is particularly advantageous %

40 9 819/0933

235-4

General formula II

where mean: · ■.

Zxj to form a heterocyclic ring, for example a tetrazole, pyrrolidine, pyridine, thiazole, thiazoline, selenazole, selenazoline, oxazole, Oxazoline, imidazole, imidazoline, and indolenine — unites required atom grouping;

L ^ j and Lp each have a methine chain, e.g. a methine, methyl methine, Ethyl methine, phenyl methine and 2-hydroxyethyl methine chains and the like. "

Y ^ an oxygen atom, a sulfur atom or a group = N-IL-, where IL- is an aliphatic group, e.g. a saturated aliphatic group or an unsaturated aliphatic group (e.g. an unsubstituted alkyl group or a substituted alkyl group with preferably up to 5 carbon atoms in the alkyl radical ), e.g. an alkyl group (such as a methyl, ethyl or propyl group), a cyanoalkyl group (such as a cyanoethyl group), an allyl group (such as a vinylmethyl group), a carboxyalkyl group (such as a carboxymethyl or carboxyethyl group), an aminoalkyl group (such as a dimethylaminoethyl group ), an Aia.lk3 ^r l group (such as a p-carboxyphenylmethyl group), a hydroxyalkyl group (such as a hydroxyethyl group), a

40981 9 / 09.33

_r 235

(wi # © ine FhenyjU od & s? $

a the 2a & t -0 €>& ea? ■

Be
t

© (z, l ,. tine

ρ des? ice «sut> öti; tuiepte Alifeflgruppe with feis. to §; carbon atoms in space ^ riyest), z * B,, ei Alk.y.lg3? Uppe (y / ie a methyl or ethyl group), a

e "(-like., © ine; Oaxbo ^ nnethyl ^ · or öarb- · ■". ',' 'a-SuIfoglkylgruppe (-y / ie. a SuIf o " -one. AllyXgcuppe. (. Like some yi .g3? i3Lpp.e) - j-- an AminQall £ ylg3? lJppe (like a " g2? uppe) V a Asgto ^ alkyigaiuppg · (like gina prppjlgimppe), §ing Aq? alkyl group (like a 'benzyl group),

(like. a phenyl-, p-öar'boxyphenyl'- ■

oops) *.

■■ * ■

.B ₇ -:

A a Wa ^ s'e ^ gtgif / ä ^ oih or an IJiedrig & llfcyliriAppe 'with nieht in @ hr al§ 3 Kohien ¹ '

■ \ _ ■■ \ · c · f

and % ** in each case the 'zur Billing · ein'atOmatiiiciieh Hinges

irom benzene * or jfp? uppation;

^ 3 each one oxygen atom, one sulfur atom, " a selenium atom, a £ h? uppe «B-Eq, where Eq is an ali- phatic group, e.g., a saturated aliphatic group

. Or - an unsaturated one. aliphatic group "" ■ (ζ, e.g. an unsubstituted alkyl group or a substituted alkyl group with preferably "up to 5 carbon atoms in the alkyl radical), eg an alkyl group (such as a methyl, ethyl, isopropyl group and the like), an allyl group (v / ie a vinyl methyl group), an acetoxyalkyl group (such ^as: Acetoxyäthylgruppe), a Gyanoalkylgruppe (\ vie a Gyanoäthylgruppe.) oedeutet, or a group of the Forme 1 '' - - '■ ■

= C ^ ■, where B ^ _0. And "B ^ are each an alkyl group,

E ₁₁ ■■■■■, .... - ■: v ---:: ■

for example mean a methyl or ethyl group. 'The aromatic ring formed by Zy, and Zo may also by an aryl group (ζ.B. durch'Phenyl and ^dglv'); a halogen atom (ZB. chlorine, Bröm UNAE ^r 'the like.), an Al-'kylgruppe (eg methyl, Ithyl and -dgl.) j an alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), an alkoxy group (eg methoxy, ilthoxy, propoxy and the like), an irifluoromethyl group, an alkylsulfonyl group (e.g. methylsulfonyl, ethylsulfonyl. and the like) may be substituted. The optionally formed heterocyclic nuclei can, for example, be heterocyclic nuclei (Eihge) such as ^ -phenyl- ■ benzoxazole ^ 5-chlorobenzoiazole, 5-methylbenzoxazole, 5-methoxycarbonyibenzoxazole, 5-chlorobenzthiaezole, 5- ■ \ methoxj ^ benzthiazbl, J-öhlor-G-methylbenzthiazol, ■: ..- .. ß-Naphthothia2öl, ß ', ß' -Näphthöthiazol, 5-Methylbenz- 'selenazol, Benzselenazol, 5,6-Dichlorbenzimidazol,

4 O 9 8 1 9 / Ö i i 3 "■ ' ^{i: 1;!}

■. '. - 23 -. -. ν-. ; ; . 235479Ö

5ί ^ -Diehlorbenzimidazo1, 5-trifluoromothylbenzimidazole, 5 ^ -chloro-6-methylsulfonylbenzimidazole, 5-methoxycarbonylbenzimidazole, maphthoimidazole-1,1 ^f -dimethylindolenine and the like, · -. ;;

R, -, and Eg each denote an * alkyl group '(e.g. an ethyl, propyl group and the like), a substituted alkyl group (e.g. a prop.enyl, hydroxyalkyl group, vi ± e a hydroxyethyl group, an amidoalkyl group, such as an amidoethyl group , an aralkyl group such as a p-carb- "oxyphenylmethyl group, a carboxyalkyl group such as a carboxyinethyl, carboxyethyl and .garboxybutyl group, an alkyl group containing a sulfo group, such as a sulfopropyl, 3-sulfobutyl group, a 2- [2- ( 3-SuIfopropoxy)] ethoxyethyl group and the like. In addition to the above-mentioned substituents, this also includes those substituents described by E.Ji, Poppe in "Zeitschrift für Scientific Photographic", Volume 63, Pages 149-1 ^ 8 (1 "" 969), are described-, _ "■ '.. ·

2P _t is an organic or inorganic anion as verv ends v / ith the general in. A cyanine dye /, for example a bromide ,. Iodide, p-toluenesulfonic acid, perchloric acid ion and the like.

ρ means .the number 1 or 2 $ but if ρ ■ = ■ 1, forms the Link; an intramolecular salt.

The meta dyes of the formulas II and III given above can either alone .or. in the form of a combination of two or more dyes that come from. the group of dyes of formulas II and III can be selected. In addition, it is possible to use the dye general formula II. with a dye of the general

409 8 1 9/09 3 3

Combine Formula III. Examples of the invention Dyes which can be used are the compounds listed below, to which, however, the invention is not restricted is. .

Compounds of the general formula II:

(Il-a)

NaO ₃ S (CH ₂ ) ₄ -N

(Il-b)

S.
C = C ^ C = S

τ ■ /

(CH ₂ ) ₃ SO 3 ITa

Λ0 98 1 9/0933

(ίΤ-c)

ί - \ / C = S. IN C = C ■ - / C. / V ^N C ₂ H ₅ ^H 3 ^C / :: C ■ _.
ρ 2 ^H 5 (Il-d)

■ ^x c = c ..,. "c = s

C-N

(CHg) ₃ Sun

O 'C ₂ H ₅

(H-e)

^l 2 | -

I ₂ A _x

C = CH-C = C-A = S

0 "GH ₂₁ COOH

(H-f)

If. C = CH-

C ₂ H ₅ .

^ = S

OC ₂ H ₅

(Ιΐ-β)

CH

CH,

CH,

C = S

-JN

2 ^Η 5

C - Ν

(ii-fr).

(Il-i)

QOOH ] f ^H 2

N '

'C = CH-CH = CC ^ C = S

C = CH-CH = C. . C = S

. . C CN

C-N

₃ H.

4098 197 09 3 3

(ii-.i)

CH ..

"■

H ₃ C-,

'C = CH-CH = C

CH-

(Il-k) ■ "

S.

■ C = CH-C = C

^ N

, P-

^ C = S

/ ■ "■ -

C ₂ H ₅ 7 η

CH

CH-

C = CH-CH = C. C = S '

■ ■ ■■

09819/093

Compounds of the general formula III ^:

(Ill-a)

S.

CH-

C = CH-C-CH-G

I-

C ₂ H ₅

(Ill-c)

B CH ₃

C = CH-C = CH-

/ Br

(CH ₂ ) ₃ S0 ₃

AO9819 / 093 3

ν -j 'T

(Ill-d)

(CH ₉ ), SO, ⁰

(Ill-e)

. (Ill-f)

CH ₀ CH = CH

\ C — GH = CH — CH ^ = O ι

(CH ₂ CH ₂ O) _{2 (CH2)} 3SO

; CH ₂ ) ₃ S0 ₃ Na

0 9ca: ie

a 0 a

(iii-g) (Ill-h)

, Se j

C-CH = C-CH-C

■■

C-CH = C-CH =

COOCH-

(CH ₂ ) ₃ SO_ (CH ₂ ) ₃ SO 3 HF (C ₂ H ₅ ) 3

(Ill-i)

k 0 9 8 1 9/0 9 3 3., ..,

(in-, i)

(ill-k)

C-CH = CH-CH = C /

(CH ₂ ) ₃ SO ₃ °

(iii-i)

C = CH-C = CH-C

(CH ₂ ) 3

A09819 / 0933 '

Examples of other connections are as follows:

s.

CH-CH = C

The polyalkylene oxide compound which can be used in the present invention is used in a for .the! promotion of .infectious development Adequate amount added, expediently in an amount from Oj.01 to 1 g per mole of silver halide. Which as an indispensable Organic compound used in the invention is preferably used in an amount of 10 "" ° to 10 moles per mole of silver halide was added. The sensitizing dye usable in the present invention is in a sensitizing amount, preferably in an amount of 10 to 10 ^ mol per mol of silver halide added sufficient to determine the sensitivity by usual sensitometry to improve.

These additional compounds are in the form of solutions using "solvents, such as water, or a suitable, water-miscible solvent, which the photographic properties of the silver halide are not "impaired, such as an alcohol (e.g. methanol, ethanol, Methyloellosolve and the like), a ketone ■ (e.g. acetone and like.), added. The compound of general formula I is preferably in the form of a neutral or acidic, aqueous Solution of the same added.

409819/0933

• - - 33 -.

These additional compounds can be made using the usual " Methods such as those made famous in Japanese Patent Application No. 8231/1970 (which corresponds to US Patent Application ITr. 11,1501), and in the published U.S. Patent No. Japanese 'patent applications ITr. 27555/1969, 23 -389/1969, 22 948/1969 (corresponding to US Patents Nos. ^, 3 ^ 57f 630, 3,585,195, 3,482,981 'and 3,469,987) and the like. are described. The finished emulsion is preferred at. a pf-value below 6.8, especially below 6.5.

These additional compounds can be added directly to the emulsion itself or at least one of the to the silver halide emulsion layer, adjacent ^ layers, (e.g.;. 'B. a. protective layer or an intermediate layer, · ■■ an antihalation layer or others .Silver halide emulsions passed through which the '■ Compounds migrate and convert into the silver halogens penetrate the main emulsion layer, be added *

The; fertige.Emulsion-the invention can be applied to a suitable carrier material, for example a polyethylene- '^; terephthalate film, polystyrene film, cellulose acetate film, cellulose acetate butylate film, ^as well as other plastic films, glass plates and the like ; . ■ -... ^ ■. . ■■ · -. ■ .'-.;. ·. ■ "■ -" ■ .- '· ■ ";·' ■■ _: ■■ .-.: ^:." - ■. : ■ -.-. - ■■ -

The light ^! Sensitive silver · ^ · 'halide material produced according to the invention can be used in the usual way, e.g. Use of automatic development systems in which "/ alzen", belts and similar mechanical transfer devices are used; ■ or "are developed or treated according to any of the other well-known processes. The development is carried out, for example, using an infectious developer composed principally of dihydroxybenzene (main developing agent), inorganic or organic

Bases,. A smaller amount. Sulphite salts and buffers. ■ ■: .- .; consists, the sulfuric acid and a 'smaller amount - SuIfit'. ., contain salts *, ■ -, '-.- .. ■ \, -. * ■ -, .-. ..- "·. ·:

As. Dihydroxybenzenes used as the main developer compound can be selected in a suitable manner from compounds known per se in Photographic, to which. for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-diehlorhydroquinone, 2,5-dimethylhydroc. ν can be used either individually or in form of mixtures; Developing agent can be used and a portion of the amount used can be added to the silver halide emulsion ^; , will. . "■ _; '. ■■ - · ■, -""-.-'

The sulfite ion buffer is used in an effective amount to keep the concentration of sulfite ions as low as possible ■ -... and this includes an aldehyde-alkali metal bisulfite adduct, an acetone-alkali metal bisulfite adduct, ·, .- such as · ^. a. Acetone: alkali bisulphite adduct, as well as an Oarb; on; ylbischw.ef elsäureamine- ■ condensate, such as sodium bis (2-hydroxyethya) .amino; me-feliansulfo.nat, in order to make the developer liquid "alkaline", . to. To bring them-preferably to a pH-Y / ert of more than 9.5, certain alkaline compounds, such as sodium car-. ■■; carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ITodium hydroxide, potassium hydroxide, organic bases, such as 2- ■ ■ aminomethanol, 2,2'-iminodiethano 1, triethano lamin,: 2-ethyl- ■ aminoethanol and the like. ,, the developer ' Grounded clogged. These alkaline compounds can be added: either alone or in combination. The developer liquid can also be at least one of the following, known per se. - .. · various additives, such as benzthiazole, Λ -phenyl-5-mercaptotetrazOl and similar · organic »safety inhibitors, ι polyalkylene oxides, ■ amine compounds, onium compounds and = ··. ■. -Organic solvents, /. Such as triethylene glycol imonoalkyleth ' he. and the like. ;,. χ Q ^ "·, ■: ■ _.: ^ _K , · ■ _Λ

4D9819 / 0933 ''.

■■ - ■ '■ · _.- ■ - 35 -. .. · ""

The developer liquid may be in the form of a powder made from the developer components, as used to a large extent ^{up to "1 today} .. along with the increasing _far-; widespread use of automatic -verwendetvwird developing devices ·;... ...

The methods of the invention can be used in combination with other previously known methods, such as those described in U.S. patents. ■ j 252 101, 3 345 175, 3 220'844, J 294 540, 3 447 459 _V 3 433 639,. 3,294,537, 3,516,830, 3 5ΪΒ 085, 3-6 ^ 5 524-, 3,567,458, 3,625,689, 3,600,174, 3,142,568, 3,325,286, 3,346,368, in British Patents 1 098 748. and 1 163 724 and in German patents 1 141 531 and 2 010 and the like. , -.

The invention is explained in more detail by the following examples, without being restricted to it. The parts and percentages given therein relate if nothing . otherwise stated is based on weight. '"." ·,

Example 1,. · ''

It is chemically ripened using a customary process.

Silver iodide chloride emulsion prepared. The contents of • Bromide ions and an / iodide ions were 17 mol% and 0.2 .- ' Mol% and the amount of silver per kg of the emulsion was about 1.3 mole percent. The silver halide particles had a through- ' average diameter of about 0.6 n.

The emulsion (2.5 kg) was weighed into a container and. der.Behälters was heated ^{to about 45 0} O to melt the contents. The content was then · by adding 100 ecm - / .; ■. ""'" ^: ^ 098 19/033 3, ^ -ν

a 2 χ 10 molar solution of the sensitizing dye (II -e) in methanol spectrally sensitized. Slowly add 100 cc of a 1% aqueous solution of 2-methyl-4-hydroxy-1,3 _i 3a, 7-tetrazaindene was added as a stabilizer to the resulting solution. Thereafter, the required additives were in accordance with the composition given in the following Table I with stirring at about

4-5 C added. . ·.

(1) addition of a compound from the group of polyalkylene oxide compounds,

(2) Addition of a compound from the group of compounds of the general formula I. *. ,

To each of the emulsions thus obtained, 50 ecm of a 1% aqueous solution of sodium dodecylbenzenesulfonate and 50 ecm of a 2% solution of the sodium salt of 6-hydroxy-2,4-dichloro-S-triazine 'was added and the emulsion thus obtained was applied to a glass plate and dried to form a layer with a Dry film thickness "of 10 p.

After dem'Zerschneiden into strips the light-sensitive material thus obtained a Sensito- "meters was exposed to a Färbtemperatur of 54-0O ⁰ K by an optically -tischen wedge using. The thus exposed strips was measured using a conventional-Lj ^ th developer of the composition given below 1 j 2, 3 or 4 minutes at 20 ⁰ C developed.

Composition of developer I

Water . 500 ecm

Hydroquinone 15 δ

Formaldehyde / sodium bisulfite adduct 50 S

Potassium Carbonate 35 S

Triethanolamine. 90 ecm

^ 098 19/093 3

Uatriumsulfxt; . _τ . /. ^ -.,. - -,. .. ·: -.2.5 S--. '- V- "

Ealium bromide. .'... ■ "". _r ., ....; '...' ■ .. " 2 ^ O _:: g. .... ■ -..- .." ■

Composition, of:, - Fiyierlosunp ; . ;, _: - ■■ -. · .. ,,, .. .. ,,. -,. ; What's "he."'-,. · 600

Fodium thiosulfaij '360 g.

Ammonium sulfate \ ; - ':. ; _., ... .., - ..,. "." - ■ - _6O.g;; anhydrous liatriumsulfit- ■ I.5 g..

Glacial acetic acid. ,; . . . ,, _ .... .13r5

Boric acid. '' · ■ -. 7.5-

Ealium alum. 15 g

■ The thus developed .strip "wtiiaeA- ^ acibtt.efflo & sung ^^. ILmt-orzog ^ for the production of cliäralttGristisclien Ktirven and: ilare sensitivities were calculated in the form of relative values, where. the inertia point. the after, the, infectious Development obtained Gradienteiiskaia, used as a standard, became. -. ·

Experiment with plyalkyrenoxide in ecm. Connection of the result, N (concentration = 0.5 / έ) general

". '■ - -.' . ■ .- ■■■ '- ^:. "- ■: ■ Formula · -'!; iii © ent - -

. ■. . (Concentration = "...,

lOO. - Fig. 1 Eurve 1

100 (i ^ ä;) - ^: · 40 '- * "■■." - ■ ""'' j 2

loo (i-f) 16O ·· "* 3

100 (Id) ■ 40 Fig. 2 " ^: '"; i4

1 (A) 2 II 3 ti 4th H VJI ti 6th

In the above table-.I mean:

(A) a polyethylene oxide compound with about 50 ethylene oxide units in each oieylpheno: xy group

(l-f)

(i-d)

'GH-

(a) a comparison compound

9.819 / 0933:

Die.Tersuche Hr. 1, 2, and 6 have been included for comparison purposes carried out .. The results of the experiment Mr. 5 show • clearly compared to those made by the present invention to the attempt. 6 advantages achieved. There was no infectious development: * ', ■ ■.

Example 2 ■ ''"■'

The same starting emulsion was used as in Example 1, it was weighed into a vessel in an amount of 100 g each, heated to 4-5 ° C. to melt, then by adding 100 ecm of a 1 × 10 molar solution of the sensitizing dye (II -f) spectrally sensitized in methanol. · *. "'' - '■ ^: ί ' · '-''

Following the procedure of Example 1, a. Polyalkylene oxide compound, a compound of the general formula I and 6 ecm of a 2% solution of mucochloric acid for the preparation the final solution was added and the emulsion was then applied to a polyethylene terephthalate film and forming a layer having a dry film thickness dried by about 6 u. .,

In the same way as in Example 1, sensitometri— see tests carried out - but this time, the exposure, through close contact of the film surface with one Gray Contact Screen from Dainippon Screen Manufacturing Co. (for use as a 150 line / 2.54 cm * 'positive (1 indh)). The relative sensitivity was reported with reference to the exposed surface of both the optical density of the strips obtained reached 1.50. . ...,.

409Ö1

2354790 II Composition ^ of the developer liquid 500 ecm water '15 p Hydroquinone 50 g Formaldehyde / sodium bisulfite adduct 80. g sodium 25 g Sodium sulfite 5, o p Boric acid 2.0 g Potassium bromide ad 1 1 water

409819/0933

Table- II

Ver
search
.Ur. , Polyalkylene oxide
(KonZo /} Ln ecm O ₀ 5/4 * 5 Connection of
general formula 1
(Konzo /) in ecm relatively sensitive
ability "at an Ent
development time from Min. 4! On. Qaal-i-ity of the cross
point period at eini?
Development % from Mn. 4, ISLa • • 7 «» 2 KLn "3 100 ■ 154 2 min. 3 B. B. 8th (A) ,. ■ - 43. ' 191 210 C. B. B. 9 It (1-a) 0.5 / ° 1.5 162, 210 229 A. B. B ··. 10 It (1-f) 0.5 / 0.5 '. 189 '- 145 179 " -. B. A. B. • 11 0.5 / 5 (1-1) 0.5 / 0.5 110 116 ¹ eat. ; B. B. A. 12th ti (1-d) 0.5 / 4.5 - 75 110 158 ■ B B ■ B. 13th (B) 0 "5 / o 2 _O 5 < 44 161 177 C. A. A. 14, (1-a) 0.5 / 1.5. 109 88 151 '.. ^B B,. A ■ 15th (G) 2 / o 5 '■. - '' 25th 182 .207 C. A. B. 16 tv (1-a) 0.5 / 1.5- 150 138 172 ' A C. . '.G ■ - / * 17th (D) I / o 4.5 , '- 88 210 223 'B C. c ¹ ^ O
O 18th (1-a) 0.5 / 1.5 170 10 6 160 ^Λ B. B. . · A;
■ ■ ■ · ■ i'i π 19th (E) - 45 182 ■ 215 C. B. c "■ * -3
D. (1-a) 0.5 / 1.5- 143 A. D.

Footnotes zto? Table II;

In the table above:

(E) a polyethylene oxide compound with about 30 JLthylenöxyd-

units on each oleylphenoxy group (ö) Pluronic L-35 eier Wyandotte Chemical Co,

(D) polyoxyethylene sorbitan monooleate (n = 40)

(E) polyoxyethylene laurate (n = 40)

The crosshair dot quality · was in the order of Sharpness of the line cross edge, i.e. in the order ABO, divided into three levels by comparison with that of the standard sample (strips that were used for a 3-minute development in experiment No. 7), (See the description of Japanese Patent Application No. 3037/1962, that of U.S. Patent Application Er. 319 815 is equivalent to).

Example 3

A chemically ripened one was made by a common method Silver iodochloride bromide emulsion produced. The emulsion had a bromide ion content of 17 Mo 1% and an iodide ion content of 1 mol%. The emulsion contained 80 ecm 4 χ 1G ~ "- ^ - molar solution of the dye II-a" in methanol and 50 ecm of a 1 χ 10 "molar solution of the dye H-I in methanol per kg to achieve a spectral sensitization. To the spectrally sensible view in this way Emulsion were 500 ecm of a 1% solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and a predetermined amount of a polyoxyethylene compound (A) is added, then 100 ecm were used to produce the finished emulsion 2% solution of the sodium salt of 6-hydroxy-2,4-dichloro-S-triazine admitted.

On the other hand, a colloidal coating compound was produced

409819/0933

represents, which was used for the production of a protective layer and afterwards the compound became the general Formula I mixed in.

Complete coating compound for the protective layer

Gelatin _v 50 g

Water '1000 ecm

Silicon dioxide. . 0.2 g

Sodium_14- (p-nonylphenyl) -5,8,11,14-. tetradecane-1-sulfonate (2%) 40 ecm

First, a photosensitive silver halide was applied in an Srockenfilmstär'ke of about 5 to a P- Polyäthylenterephthalatfilmträger, then λ '/ urde the layer formed with a protective layer coated, which had a η Trockenfiimstärke of about. 1

As in Example 2, the photosensitive PiIm exposed through a "crosshair grid and using a roller type automatic developer and the developing liquid I for 75, I05 and 135 seconds, respectively developed at 27 ° C.

409819/093 3

Table III

CD CO OO

Polyalkylene
oxide (A) - 35 ' link the general Formula 1 • 20th admitted to the
Colloid protection
layer in ecm
(Conc. <F ₀ ) Relative i Sensitivity 135 Se it quality «A0 the line- 135 sec. I. I. in ecm It admitted to the
Emulsion in ecm
(Conc. <Fa) 8th. _ *
75 sec. 10 5 sec. 158 k. 75. Ne3 5 sec. B. I. ti _ 15th - 36 100 .226 B. B. (A) ti (I-a) O.5 / 0 '■. - 128 181 230 * R A. B. 35 (I-f) O.5 / 0 rr 153 193 190 B. A. Il (i-ß) 0.5 / 0 - 100 149 155 ' B. A. E. It (I-a) O.5 / 0 30 40 100 207 C. B. B. - "50 142 183 230 B. A. .U - 184 212 A ' B.

Assessment levels as in Table II

K)

cn

CX) O

Instead of the specific compounds used in Examples 1, 2 and 3, it is possible to use any of the compounds of the general formulas I _t u and III given above. The optimum amount can easily be determined by test methods known to the person skilled in the art and customarily used by him.

Example 4- '. . /

_{The value of the oxidation potential (Eq x} ) 'used according to the invention was determined by the method described above. The voltage-current curve determined using hydroquinone as the standard material is shown in FIG. 3. The values for Eq of the compounds of the general formula I are given below; -

(I-a) -69 M. (I-d) -77 (i-f) -105 (I-g) -156 (I-D -155 (I-q) .-0 (a); -250 Hydroquinone -150 + 2 (Default) . '

In Fig _e 3 are the. Midpoints of the curves between the upper limit and the lower limit in the ordinate direction (the ordinate indicating the current values) connected to one another to form three elongated line segments _e Die ^; Points ₉ at which the line segments intersect are indicated as points a and b respectively ^ The center ρ of the line segment formed between the intersection point a and the intersection point b is determined the point 'ρ corresponds to _o

. ' '4 0 9 81 9/0933;

Although the invention has been explained in more detail above with reference to specific embodiments, it will be clear to those skilled in the art that these can be used in many ways
Aspects can be changed and modified without departing from the scope of the present invention.

Claims;

40981 9/0933

Claims (26)

1. Photographer! See silver halide emulsion containing a silver halide which is at least 40 mol% silver chloride consists, wherein the silver halide particles one average diameter not exceeding 0.8 microns characterized in that it also contains the following combination of compounds:. (1) a polyalkylene oxide compound and (2) an organic compound having at least one hydroxyl group and at least one amino group with a tertiary nitrogen atom. ■■ ", '. 2. Emulsion according to claim 1, characterized in that it contains an organic compound of the general formula 20 - Δ - S ^. . (I) ■ .- ■ .. - ^E 2 ■■ - - where mean: - A is a divalent aromatic or heterocyclic group, IL and K ₂ individually One group each required to form a tertiary amino group with the nitrogen atom, or together form a ring, X is a hydrogen atom or one with an inorganic one or organic base dissociable therefrom or group 409 8 19/09 3 a precursor of the organic compound of the general Formula I, where the compound of general formula I has an oxidation potential within the range from 0 to -200 millivolts. 3. Emulsion according to claim 2, characterized in that it contains an organic compound of the general formula XO-B-H (I-a) wherein. B denotes an aromatic ring group of the bivalent benzene type and X, R ^ and R _{2 have} the meanings given in claim 2. 4 ·. Emulsion according to Claim 2, characterized in that in the general formula I A is an unsubstituted or substituted one Benzene, naphthalene, pyrimidine or triazine group denotes, where the substituents are each alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary Are aminoalkyl, aralkyl, or aryl groups; R ^ and E ^ individually each represent an alkyl, alkenyl, aralkyl or aryl group or together a saturated or unsaturated group Form ring; X is a hydrogen atom. an acyl or acyloxy group means. 5. Emulsion according to claim 2, characterized in that it is a polyalkylene oxide compound having a molecular weight within the range of about 500 to about 25,000 contains. ■ 6. Emulsion according to claim 5 »characterized in that it contains a compound of the formula as the polyalkylene oxide compound 409819/0933 (a) 'Cb) Cc) CH ₂ CH ₂ O ^H 3 v; orin a, b and c are integers, where b is an integer Number from 14 to 55 and .a + c an integer from 4 to 210 mean; . (d) HO-CH ₂ CH ₂ Of-CH ₂ CH ₂ O CHI I 2 j coo - ch. .ch-q - "^ G/ CH-CH ₂ OCCH ₂ CH ₂ O) Ji " J * i. G (OH ₂ CH ₂ O) _n H. wotin 1 + m + n = about 20; (f) (g) C ₁₇ H ₃₅ COO (OH ₂ CH ₂ O) ₃₀ H. or (n) _p H <CH ₂ CH ₂ 0> Ή ", where. P + q = 40 19/09 3 7. Emilsion according to Claim 2 _r, characterized in that it contains a compound of the formula I as the organic compound of the general formula I HO Π TI • Hol, HO HCl N (CH) - ₂ - Hd GH. HO. • 'CH, CH HO CH, N (C ₂ H ₅ ) ₂ -BGl 409 8-19 / 0933 HO HO / Λ V '/ C ₂ H ₅ -O-CO-O- / ~ \ H (C ₂ H ₅ ) ₂ -HCl HO -HCl ~ r 4098 19/093 3 SO "H 5 CH ₅ 'HCl ₄ - OH HO oc: IT (CH) -HCl 2Γ5 ' 2 Cl HO Cl or -HCl 409819/0933 8. Emulsion according to claim 1, characterized in that that they have at least one sensitizing dye general formula where Z _{1 is} an atomic grouping required to form a heterocyclic ring, L ₁ and L ^ are each a metal chain, X _{1 is} each an oxygen atom, a sulfur atom or a group = N-1L-, where Rg is an aliphatic group or an aryl group, η "the number 0 or / ί, R ^ and R ^ each represent an aliphatic group or an aryl group, - ■ and the general formula contains (III) wherein Λ represents a hydrogen atom or a lower alkyl group with no more than 3 carbon atoms, Zg and Z ^ jevieils an atom grouping required to form a benzene or naphthalene ring, Tp and I, each an oxygen atom, a sulfur atom, a selenium atom, a group = N-Rq, wherein Rq is an aliphatic group, or a group = C, where R ^ q and R _x ,, - 'are each an alkyl group be-R ₁₁ . 409819/0933 interpret, Rr ₇ and Eg each an aliphatic group,. X is an anion and ρ is the number 1 or 2, ρ = 1 if the compound forms an intramolecular salt. 9. Emulsion according to claim 8, characterized in that Z ^ is a tetrazole, pyrrolidine, pyridine, thiazole, thiazoline, selenazole, selenazoline, oxazole, oxazoline, imidazole, iraidazoline or indolenine ring means and that the heterocyclic ring formed by Z ^ and Z ^ is each a ring of 5-pheny! "benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-methoxycarbony! benzoxazole, 5-chlorobenzothiazole, 5- ^ ethoxybenzthiazole, 5- ^G chloro-6-methylbenzthiazole, ß-naphthothiazole, ß, ß'-haphthothiazole _s 5-methylbenzselenazole, benzselenazole, ^ iS-dichlorobenzimidazole, 5-trifluorinethylbenziniidazole, 5-chloro-6-ynethylsulfidazolimidazole, 5-chloro-6-ynethylsulphonylbenzimidazole, 5-chloro-6-ynethylsulfidazoleimidazole, 5-chloro-6-ynethylsulfidazolimidazole -dimethylindolenine. 10. Emulsion according to claim 1, characterized in that R ^, and Rj- each represent an alkyl- _s Oarboxyalkyl-, SuIfο ~ alkyl, allyl, aminoalkyl, acetoxyalkyl, aralkyl or aryl group and R ^ and Rg J ^ew sil ^s mean an alkyl, alkenyl, hydroxyalkyl, amidoalkyl, aralkyl, carboxyalkyl or sulfoalkyl group. 11. Emulsion according to claim 10, characterized in that that It ₁ and L ₂ each have a methine, methyl methine, ethyl methine, phenylmeihin and 2-hydroxyethyl methine chain, Rg an alkyl, cyanoalkyl, allyl, oxyalkyl, aminoalkyl, aralkyl, hydroxyalkyl or Aryl group, Rg an alkyl, allyl, acetoxyalkyl, cyanoalkyl group or a group = C! and R ^ _1n and H _{-1 Λ} each represent an alkyl group. ■ ^R 11 409819/0933 12 »Emulsion according to claim Λ ^ characterized in that it contains at least one dye from the group Cl C = C \ == S ■ w VC ^ "- s.n tr . ° 2 ^H 5 G. / "f TT / η H ₂ C / ■ - ■ \ 409819/0933 GH ₂ COOH CH \ C .S; CrCH-CH == < I Vh, 2 5 f2 CH ₉ CH-CH = ^ ^ = S ■ 0-3
O ^{/ j} COOH i 0 9 8 1 9/0 9 3 3 GH- GEL C. 2. C = S- C = CH-C = CH-C 33. - ORIGINAL INSPECTED ! = CH-C = CH— Br * (ÖH ₂ ) ₃ SO ₃ ^C 0 \ I I) = CH-C = CH-C CH ₀ CH = CE ₀ , ₂ CH ₂ O) ₂ (CH ₂ ) ₃ SO, 2- UU Uü " Cl , .CH 0) "(CH _o )" S0 19 / O ₂ H ₅ I ^ON O = CH-CH = OE-o'e ^N | i Tf ■ I OH ₃ I = CH = C-CH = C C ₂ H ₅ | Γφ 0-CH = C-CH = C SO ™ ⁵ P5 ^OU 3 (0H ₂ ) ₅ H >> (0 ₂ H ₅ ) ₃ \ I. ■ '-A ■ Φ C-CH = C-CH = C (CH ₂ ) ₃ SO / OCH ₃ O ₂ H ₅ 4098 19/0933 Cl N / A . "b = CH-C = CH-C C _n E, 409819/0933 13 * LicntensenslioheS ^ Siitoerhalogenidmaterial ^ thereby characterized in that it is a photosensitive layer Layer of a photographic silver halide tilsioa according to one of claims i to 12 contains * 14 *, * Photosensitive characterized 'Siiberhalogenidmaterial according to Claim _13% that there is a orgänisölie compound of general formula XQ. "- Δ - IT (1) where mean i A is a divalent aromatic or heterocyclic group, Eyj and Ro individually ο one at a time to form a tertiary Amino group with the nitrogen atom required group or a hang together, X is a hydrogen atom or an inorganic piit barren organischen'Basedavon abdissoziierbare group barren, ■. ■ ■ a precursor of the organic compound of the general my formula I contains, where the connection of all * common formula I a Cbcydationspotential within of the range from Ö to -2ÖÖ millivolts. 15. A light-sensitive silver halide material according to claim 14, characterized in that it is an organic material Contains compound of the general formula XO-B-Mi (I ^ -a) 40981970933 . - 62 - where B is an aromatic ring group of bivalent benzene 3? Vjp and X, R, - and Rp denote in claim 2 Have meanings. 16. Photosensitive silver halide material according to claim i4, characterized in that A is an unsubstituted one or substituted benzene, naphthalene, pyrimidine or Triazine group, where the substituents are alkyl, alkoxy, hydroxy, halogen, alkoxycarbonyl, quaternary Are aminoalkyl, aralkyl or aryl groups, B ^ and Rp individually in each case an alkyl, alkenyl, aralkyl or aryl group or together a saturated or unsaturated group Form ring, X is a hydrogen atom, an acyl group or represents an acyloxy group. 17. Light-sensitive silver halide material according to claim 14-j, characterized in that it is a polyalkylene oxide compound having a molecular weight within the range of about 500 to about 25,000. 18. The silver halide photosensitive material of claim • 17, characterized in that it is used as a polyalkylene oxide compound contains a compound of the formula (a) HO-GH ₂ CH ₂ -O- (GH ₂ CH ₂ O (b) HO-CH ₂ GH ₂ - (c) HO-fGHgGHgO ^ GHCHgO ^ C ^ GH O) -H 409819/09 33 where a, b and c are integers ", where b is an integer Number from 14 to 55 and a + c an integer from 4 to 210 mean, . (d) HO-CH ₂ CH ₂ O- (CH ₂ CH ₂ ^ ₀₂₂ Λ " CH ₀ CH - CH ₀ O (CH ₉ OH 0) nH I c. J ti. <! - έ. * (e) C ₁₂ ^H 25 ^C00 " ^CH / C C (CH ₂ CH ₂ O) _n H where 1 + m + η = about 20, (f) HOCH ₂ CH ₂ O (CH ₂ CH ₂ ) ₄₉ - ^^ - C ₄ H ₉ -Ct); (g) C ₁₇ H ₃₅ COO (CH ₂ CH ₂ O) ₃₀ H _oa - _er (CH ₀ CH,) H. 2 Pn (h) CHCOR- ^ ^P where p + q = 40. 19. Silver halide photosensitive material according to claim 14, characterized in that it is a compound of the general formula 1 as an organic compound Contains formula 40981970933 HO HO • HCl HO F ^R 2— \ • HOI CE _n ^Eo ~ \ y-® ( ^GE ₃ ) ₂ ' ^Eci CH ₁ 409819/0933 CH. CH HO CO-O - / Jf- N (CH ₃ ) ₂ x 1/2 C ₂ H ₅ -O-CO-O CH. N (CH) .HCl 0 9 8 19/0933 -HCl HO OCH, Cl Cl HO or .HCl CH. 409819/0933 - ^6? ■ * - 20. Silver halide photosensitive material after. Claim 13, characterized in that the Emulsion at least one sensitizing dye the general formula. ". ν. ¹ I - ^L 2 * = ^C \> C = S ". (H) where Z ^ is an atomic grouping required to form a heterocyclic ring., 1>, and Lp each is a methine chain, -ICj is an oxygen atom, a sulfur atom or a group = 1T-Eg, "where R ^ is an aliphatic group or an aryl group, η the number O or 1, R ^ and R ₁ - each represent an aliphatic group or an aryl group, and the general formula contains A / ^Y 3 -ir · ^R 8 v <*) U wherein A is a hydrogen atom or a lower alkyl group with no more than 3 carbon atoms, Zo and Z-, gev / eils one needs to form a benzene or naphthalene ring Similar atom grouping, Tp and T ^ each an oxygen atom, a sulfur atom, a selenium atom, a group = N-Rq, wherein Rq is an aliphatic group, or_ a group = C, where Ea ₀ and R ^ * are each an alkyl group "mean, R ^ and R _ß each an aliphatic group, X 408819/0933 is an anion and ρ is the number 1 or 2, where ρ = 1, when the compound forms an intramolecular salt. 21. collotype material, characterized in that it is a silver halide photographic emulsion as claimed in claim 3 contains. , 22. collotype material according to claim 21, characterized marked t £ ate in the general given in claim 3 Formulas R ^ and R ^ individually each an alkyl · «-, alkenyl · ?, Aralkyl or aryl group or together a saturated one or unsaturated ring and X is a hydrogen atom, a Mean acyl group or an acyloxy group. 23. collotype setting material according to claim 21, characterized in that that it is a polyalkylene oxide compound having a molecular weight within the range of about 500 to contains about 25,000. 24. Lichtdrucksetzmaterial according to claim 23, characterized in that, that it contains a compound of the formula as the polyalkylene oxide compound (a) HO-CH ₂ CH ₂ -O - <CH ₂ CH ₂ O) (b) HO-CH ₂ CH ₂ O 4GH ₂ CH ₂ O ^ CQ (CH ₂ ) (c) ceo. CH, where a, b and c are integers, where b is an integer Number from 14 to 55 and a + c is an integer from 4 to 210 mean, 409819/0933 (a) HO _22225022 , * ' GEL ^ CH -GH ^ O (CHCH O ^ H _t \ .e) ι ^ j έ έ έ C ₁₀ H ₀ ^ GOO-GH GH-O- (CHGHO) ₁ H 12 2i). "^. CH, where 1 + m + a = about 20 (f) HIGH ₀ CH ₉ O (CH CH O) ■ ■ C \ C C C- (g) C ₁₇ H ₃₅ COO (CH ₂ CH ₂ O) ₃₀ H _or ■ · '(CH GH ΟΓΗ (h) Ο _ΊΊ Η_σ0Ε- ^ Γ ^ 2 2p ^{11 d>} ^^ (CH ₀ CH ₀ O) _n H,. where p + q. = 40 25 · collotype material according to claim 24, characterized in that characterized in that it contains a compound of the formula Γ as the organic compound of the general formula 4098 19/093 .7- HC1 HO • HC1 HD-Tl / • HC1 CH HCl CH. ) ₂ .HCl CH OH" 409819/0933 -C HO- CO-O YVN (CH ₅ ) ₂ , 1 / 2.H ₂ SO ₄ CH, ) ₂ -HCl OH S = / .HCl 4098 197 0933 HO SO ₃ H CH. HO • HC1 ₄ - OH HO N (CH) -HCl Cl HO N (C ₂ H ₅ ) .HCl Cl .OCH HO N (C ₂ H ₅ ) -HCl or CH HO N (CH) .HCl CH, 409819/0933 26. collotype material according to claim 21; ,,, characterized characterized in that the emulsion has at least one sensi- " bilizing dye of the general formula ΛΛ O BL 5 wherein Z _x , an atomic grouping required to form a heterocyclic ring, X ^ and Lp each represent a methine chain, T ^ j. Oxygen atom, a Sehw.efelatom or a group = N-IL ~, v / orin-Ή ^ an aliphatic group: or an aryl group, η is the integer .0 or 1 and E ^ and Rr are each an aliphatic group or an aryl group mean, and the general formula contains (III) wherein A is a hydrogen atom or a; Lower alkyl group of not more than 3 carbon atoms, Z ^ and Z ₇ , respectively. one for the formation of a benzene or haphthalene ring required, -the atom grouping, T ^ and Y ^ each an oxygen * atom, a sulfur atom, a selenium atom, a group = H-Hq, where Rq is an aliphatic group, or a group = C, v / orin R ^ ₀ and R ^ each be an alkyl group AO9819 / O933 R ₁₇ and Eg each represent an aliphatic group, Z an anion and ρ the number 1 or 2, where ρ = 1 if the compound forms an intramolecular salt. 409819/0933