DE3029132A1 - METHOD FOR PRODUCING A COLORED IMAGE AND PHOTOGRAPHIC RECORDING MATERIAL FOR IMPLEMENTING THE METHOD - Google Patents

Description

The invention relates to a method for producing a Dye image and also a photographic recording material for carrying out such a procedure. More particularly, the invention relates to photographic enhancement Recording materials with at least one ballast group having at least one electron accepting, nucleophilic displacement compound with a peroxide.

It is known for the production of photographic recording materials, such as image transfer units to use a variety of image dye providing compounds. Among the known image dye-supplying compounds include, inter alia, those that are initially immobile in a photographic recording material, such as, for example the initially immobile compounds, those of a redox reaction and a splitting caused by alkali subject, as a result of which a diffusible dye residue is split off. Such connections are for example known from US-PS 4,076,529. Compounds that provide image dyes of this type are known as Pedox compounds that provide dyes or P-edox dye-splitter, in Anglo-Saxon Often referred to in the literature as RDP. Compounds become. Pearlescent compounds have been found to be extremely advantageous, but their uses are becoming quite general bestowed by the fact that the dye is in a direct Relation to imagewise oxidation is released. This means that a direct positive silver halide emulsion or other inversion mechanisms must be used if a positive transfer image is to be produced.

Immobile connections that work positively, those that work with negates Silver halide emulsions for the purpose of making positives Images that can be used are known, for example, from US Pat. Nos. 4,139,379 and 4,139,389. With these connections are ballast group compounds that undergo an intramolecular nucleophilic displacement reaction subject to the release of a diffusible residue. The compounds contain a precursor for a nucleophilic group that must take up at least one electron before the

130002/0894

3P29132

binding is subject to an intramolecular nucleophilic displacement reaction. These compounds v, ^{r are} referred to as nucleophilic displacement coripounds containing electron-accepting groups, abbreviated to RENP compounds, for "ballasted electron-accepting nucleophilic displacement coripounds". It is known from US Pat. No. 4,139,379 that such compounds can be advantageously used in photographic silver halide recording materials with an electron transfer agent and an electron donor (ie a reducing agent) which supplies the electrons necessary for the compound to be reduced to a form. ground, which is subject to an intramolecular nucleophilic displacement reaction, can develop.

When used in such a photographic material or processes react (BEND) compounds with the electron donor to form a nucleophilic group, the in turn enters an intramolecular nucleophilic displacement reaction, with displacement or elimination of a diffusible one Compound of the starting compound, for example a diffusible dye. However, there where none Electrons are transferred to the electron-accepting nucleophilic precursor compound, the compound cannot Split off diffusible connection. An imagewise distribution of an electron donor appears in the photographic material by oxidizing the electron donor in an imagewise fashion before the compound reacts with the (BEND) compound has achieved, whereby non-oxidized electron donor remains distributed, which transfers electrons to (BEND) compound « can. An image-wise distribution of oxidized electron donor is achieved by reaction of the electron donor with oxidized electron transfer agent present in imagewise distribution, which in turn is obtained by reaction a uniform distribution of electron transfer agent with imagewise developable silver halide. at the development of an imagewise exposed photographic recording material having a (BEND) compound the following reactions lead to an imagewise distribution of diffusible dye: in exposed areas it becomes developable Silver halide developed by electron transfer agents,

1 30008/0894

-Xf-

generating oxidized electron transfer medium, which in turn reacts with oxidized electrons-Honor, whereby \ r is prevented that a reaction with the (ΒΕΝΠ) -compound can take place. In the unexposed areas where no developing hard silver halide is present, there is no electron transfer agent nor flektronen-nonor oxidized. As a result, the electron donor reacts with the (BENP) compound under Release or splitting off of a diffusible dye.

In other embodiments of the method according to the invention v: no electron transfer agent is used. Tt trap this The electron ponor used is one embodiment Silver halide developer compound and imagewise distribution of oxidized electron donor v; is produced as a result of the Reaction of the electron ponor with your in an image-wise distribution present developable silver halide achieved.

It is known that an oxidized electron transfer agent can be generated imagewise by reaction with a cobalt (ITI) complex or a peroxide compound on a Pedox catalyst center. In one embodiment of this method, the catalyst center can be represented by developed silver. In this embodiment, the amount of electron transfer agent oxidized is not stoichiometrically limited by the amount of silver that is developed or can be developed. Image forming systems of this type have become known as so-called. Reinforcement systems for dye images, since the ^M is not limited close of dye formed by the amount of silver present (or other redox catalyst} Pie using split off from a dye nedoxverbindungen in an amplification system for dye images inbem a cobalt (III) complex is used as an oxidizing agent is known, for example, from US Patents 3,862,842 and 3,862,855. The use of dye-releasing or dye-releasing redox compounds in intensifying systems for dye images in which a peroxide compound is used as an oxidizing agent for example from US Pat. Nos. 3,822,129 and 3,834,907 and GB patent application 2005431 A, published April 19, 1979.

130008/0894

The present invention relates to dye image enhancement using a peroxide oxidizing agent used in the development of photographic recording materials can be used that contain dye-providing (BEND) compounds, increasing photographic sensitivity, with minor amounts of silver halide if desired can be used. The applicability of peroxide dye image intensification image-providing method using (BEND) compounds is unexpected as peroxide compounds, such as, for example, hydrogen peroxide is known and expected as a powerful oxidizing agent it had to be that these donate electrons spontaneously and uniformly would oxidize preventing the release of a dye. Surprisingly, however, it was found that this Assumption does not apply.

The invention is a method for producing a A dye image and also a photographic material for the image transfer process as set out in the claims Marked are.

An exposed photographic recording material is thus according to the invention with a support and at least one light-sensitive silver halide emulsion layer applied thereon with a developable latent image as well as in the emulsion layer or in a hydrophilic layer adjacent thereto Colloid layer - one that supplies a dye, has at least one ballast group and accepts electrons nucleophilic displacement compound (BEND) compound of the following formula:

(ENup) _w

> 2. ... _V 1

'n-1

'm-i

—U

130008/0894

in which:

w, χ, γ, ζ, η and m are each positive numbers of 1 or 2;

HNuP an electron accepting or electrons

accepting nucleophilic precursor group;

R is a cyclic organic group to which

ENuP and E are bound;

9 3

R "and P. bivalent or zi-finished organic group

pen with 1 to 3 atoms in the bivalent or divalent bond;

E and Q are the atoms that make an electrophile

Form a cleavage-capable group, with the proviso that

E represents an electrophilic group and Q a divalent or divalent amino group or an oxygen, selenium or

Sulfur atom forming a monatomic bond

2 between E and X and those of

E is displaceable by the nucleophilic group provided by ENuP;

X is a substituent on at least one of

Groups R ¹ , » ² and R ³ ,

9 where it applies that one of the groups X or QX is a ballast group of sufficient size to make the compound immobile in an alkali-permeable layer of a photographic recording material and it also applies that one of the groups X ¹ and QX ² e:
supplying group is

a) developed with either:

Groups X and Q-X represent a diffusible image dye

130008/0894

1) an electron ponor, the pine silver halo "enidentwi el compound" is or

2) an electron transfer agent, which is a silver balogenide developer compound, is hosted by an electron donor, with the release or elimination of a diffusible dye from the (BFNP) - which has an inverse function to silver development, where ° rf indungsgcnäß the development in f.enenwart a peroxide Οχΐ dationsnittels durchp.efiilirt v.-ird that, ^ ejrenüber a Oxi dati ons-reduction reaction of ¹ r.it F.lektronen'ibertrafTun ^ sTnittel dep and electron donor in Absence of a silver catalyst is inert or practically inert and

b) Obertrapung the released diffusionsffihi ^ s dye to form a visible or detectable dye image of at least eineir of the two, that is, the ^1-diffusible dye and (BEND) compound.

To carry out the method according to the invention, a alkaline medium produced by a photographic recording material is contacted with developable silver halide and a dye providing (BEND) compound wit an electron ponor, which is a silver halide developing compound or with an electron transfer agent that represents a silver halide developer compound and a Electron donor, in the presence of a peroxide oxidizing agent. The evolution of the silver halide to silver produces oxidized electron donors either directly or as a result of one PV reaction between oxidized electron transfer agent and electron donor. The developed silver serves as a catalyst center or catalytic zone for a Pedox reaction between Peroxide oxidizing agent and non-oxidized electron donor

or electron transfer agents to generate additional oxidized electron donor.

BATH ORIGINAL

Mt

The lilPktronen donor dr> r was oxidized vornan- r = it dor (BF ^ P) Vt? Rl · J · ηJuii 'nic ^ t to release f? To respond ines · \\ ffusi ons Fibigen dye. As a result, a pattern of diffusional dye or dye precursors is produced, and is proportional to the close proximity of the electron donor that has been oxidized. The diffusive dye can be produced This can be transferred into an image receiving layer or by means of a receiver to produce a transfer image. Alternatively, the diffusible dye can also be removed from the recording material or element. Regardless of whether the diffusible dye is used to produce a transfer image or not, the remaining (ΒΕΜΓΐ) -VerLindunrf from which no dye released v: is orden, be used for an image [a so.q. retained image) to generate Alternatively, \ ^r, the (BEND).. -A ^r erb in thin: brought into contact with another non-oxidized electron donor v / ground with the release or splitting off of diffusible dye, which like de run leads to the generation of a! "'Bert raguncfsbildes Averden can.

This procedure has been made with reference to a simple Photographic recording material described which consists of a support and a silver halide emulsion layer that is assigned a dye-delivering (BEND) compound. The development of such a recording material can be effected by bringing the recording material into contact with a suitable aqueous alkaline solution and transferring by contacting the recording material during or after development with a separate image receiving material with transfer of the dye or by washing out the recording material with an aqueous solution for Purpose of dye removal. The method can, however, also be used using drawing materials, which contain an image receiving part and all or a part of the components required for development. Such Recording materials are in the field of color diffusion transfer processes known and are described in numerous patents. Advantageously contains such a

130008/089

ORIGlNAL BATHROOM
JAHfOiftO GaI

.Aufzeichnungsmaterial means from which an alkaline Entv.'icklungsflüssigkeit is ejected with one or more components required for the development under the unwinding Chung ^M aterials, whereby a Farbstofffreisetzune and Hbertracumg of the dye occurs in the image-receiving element. Particularly advantageous recording materials of this type are constructed in such a way that the only work step that is required is to release the alkaline developer or developing liquid. In the case of some recording materials, it is also necessary to separate the image receiving part from the rest of the recording material.

Accordingly, a photographic recording material according to the invention has for performing an image transfer process on:

a) a photographic recording part. or element having a support and at least one photosensitive layer applied thereon A silver halide emulsion layer to which a (BEND) compound of the following formula is assigned:

(ENuP) _w

* · -Ίη-1

wherein

19 7 2

w, x, y, z, n and m as well as ENuP, P., Γ ¹ ", P, E, O and X have the given meaning;

BATH ORIGINAL

b) an image receiving layer and

c) either i) an electron donor which is a silver halide developing agent or ii) an electron donor in combination with an electron transfer agent which is a Is silver halide developing agent,

wherein the recording material is a peroxide oxidizing agent contains, the opposite of an oxidation-deduction with the electron transfer agent and the electron donor is inert or virtually inert in the absence of a silver catalyst.

accordingly a particularly advantageous embodiment of the invention the recording material also contains an alkaline developer composition or developer liquid, for example in a splittable container from which the mass or liquid in which material can be distributed.

In the foregoing, the invention has been described using the example of the use of dye-providing (BEND) compounds. As for example, from US Pat. Nos. 4,139,379 and 4,139,389, however, the (BEND) compound can also be used for this purpose to release a photographic reagent, such as an antifoggant, a development inhibitor, instead of a dye, a development accelerator, a developing agent, a fixing agent, a silver halide solvent or a toner compound. In the case of photographic recording materials containing such photographic Reagent-releasing or supplying (BEND) compounds can be a dye image by means of a dye Generate image-forming (BEND) compound, as described above, or by using others a dye supplying compounds known to be capable of supplying dyes by peroxide amplification techniques, For example, so-called PDR compounds or couplers that provide dyes (RDR compounds are so-called dyes releasing To understand redox compounds).

130008/0894

The photographic recording materials according to the invention for the image transmission ancestor belong accordingly also those recording material which are composed of:

a) a photographic Aufziehunrsnateri al or Aufzoici- ¹ -nungteil with a Tr; 'irer fit at least one applied thereon for alkali perneal layer with a light-sensitive silver halide emulsion, which is assigned an image dye-providing compound and a (BEND) compound of following formula:

(ENuP) ₁ , 2 ^

-1

/ "γ-Ί_ί

_Λ .2.

fP ³ ")

m-1

where mean:

w, x, y, ζ, η and m are positive numbers of 1 or 2;

ENuP

an electron accepting or accepting nucleophilic precursor group;

R ² and R ³

E and Q

a cyclic organic group to which ENuP and E are bound;

divalent organic groups with 1 to 3 atoms in the divalent bond;

the ^ ome, which is an electrophilic, splittable Form grouping in which

E represents an electrophilic group and Q a divalent amino group, an acid

130008/0894

BATH ORIGINAL

represents material, selenium or sulfur atom, with BiI dun "a monatomic bond between Γ and X "and that of Π by the nucleophilic group formed by ENuP becomes, is dilutable;

X a substitute in at least one

of groups P, ^ and ¹ ^ "and

1 2
one of the groups \ "or QX is a ballast group of such a size that is sufficient to form the compound in an alkali-permeable layer of a photographic recording material

1 to make 2 immobile and i - obei one of the groups X and Q-X of the plague a photographic reagent;

b) a uild receiving layer and

c) either i) an electron donor that is a silver halide developing compound is or ii) an El electron ponor in combination with an electron transfer agent, the one Is filber halide developing agent, with the proviso that the recording material contains a peroxide oxidizing agent, that against an oxidation induction with the electron transfer agent and the electron donor is inert or virtually inert in the absence of a silver catalyst.

According to a particularly advantageous embodiment, the recording material also contains an alkaline developer for example an alkaline developer liquid, e.g. within a splittable container from which the mass or liquid can be distributed in the material.

The peroxide oxidizing agents used to carry out the invention Process and for the production of the invention Recording materials can be used from the. customary known peroxide oxidizing agents are selected, Many marriages require the presence of a catalyst to oxidize an electron donor or electron transfer agent. to be able to ren, i.e. the opposite to an oxidation-reduction in

130008/0094

BAD OR1GIN ^AL

In the absence of a catalyst, they are inert or practically inert. In the absence of a catalyst, the oxidizing agent and reducing agent are thus in a state in which they are kinetically are practically stable, i.e. the kinetic reaction is so slow (or practically nonexistent) that they are necessary for the Overall procedure is not significant.

The peroxide oxidizing agent and the electron donor or the electron donor and the electron transfer agent are preferably selected such that when test samples thereof are dissolved in 0.01 molar concentration in an inert solvent at 20 ^° C., practically none for at least 10 minutes Redox reaction does not take place, preferably for several hours. Peroxide oxidizing agents of this type include water-insoluble compounds having a peroxide group, such as inorganic peroxide compounds or salts of peracids. Examples include perborates, percarbonates and persilicates and, in particular, hydrogen peroxide, which can be used as peroxide quidation agents for carrying out the process according to the invention, as well as organic peroxide compounds, for example benzoyl peroxide, percarbamide and addition compounds of hydrogen peroxide and aliphatic acid amides, polyalcohols, amines, acyl-substituted ones Hydrazines, etc. The use of hydrogen peroxide has proven to be particularly advantageous because this compound is highly active in the presence of a silver catalyst and can easily be handled in the form of aqueous solutions.

The silver halide emulsion layer or silver halide emulsion layers of a recording material according to the invention can consist of customary known silver halide emulsion layers, such as those from Research Disclosure, No. 17643, Section 1, December 19 ¹ B (published by Industrial Opportunities Ltd., Homewell Ilavant Hampshire, POQ 1EF , Great Britain) are known. The emulsions which are used to produce the recording materials can be negative-working or positive-working emulsions, it being possible for either latent surface images or internal grain images to be produced when the emulsions are exposed. In the event of

U0008 / 0894

- χΤ-

v; ending of dye-supplying (BE \ T>) compounds bat es proved particularly advantageous to use negative-working silver halide emulsions. In case of use of Photographic Reagent Providing (BBND) Compounds the preferred silver halide emulsion used depends on the type of the dye-supplying compound used. For example, it has been found particularly advantageous to use positive working silver halide emulsions when as dyes supplying compounds, so-called Pedox compounds which split off dyes (RDP. Connections) used to invelchep trap positive images may have been produced. When using such Emulsions are called a dye from the RDR compounds direct function of silver halide development and a photographic R.eagenSj for example an antifoggant or a development inhibitor can be released from the (BEND) compound as an inverse function of silver halide development.

The emulsions used to prepare the recording materials can, for example, cover 17643 as described in the already cited Research Disclosure, no., Chemically sensifailisiert (Section III) spectrally sensitized or desensitized (Section I ^v), cured (Section X), and / or contain stabilizers and antifoggants (Section VI) and / or other conventionally known photographic additives.

The electron donors, electron transfer agents and (BEND) compounds, those for the production of recording materials according to the invention and which can be used in the context of recording materials according to the invention are, for example from US Pat. Nos. 4,139,379 and 4,139,389 already cited. Reference is hereby expressly made to these patents.

According to an advantageous embodiment of the invention, the electron donor is the one in coordination with the (BFND) compounds used is able to develop silver halide. As a result, the electron donor becomes by reacting with the in image-wise distribution destroys the developable silver halide present. In general, in this embodiment, the

1 30008 / 089A

⁵ A

-η -

Invention use any I-lcktronen-Ponor, who by a faster reaction rate with the exposed silver halide as marked with the (BE ^ - 'P) -VerMndurp. Typically suitable electron ponors for this are for example ascorbic acid, trihydroxynyriridines, z.H. 2-methyl-4, 5, δ-trihydroxypyriridine and hydroxylamines such as bobeispielsv.'eise Diethylhydroxyl ani η.

In an advantageous manner, the P. octrononor can in certain advantageous configurations in combination with one. Pick-up transmission means (hereinafter referred to as yit VS ''' ) can be used. Full allce ^ log läP.t the I: ¹ "" ¹ ρIs a ^Tr erhindung indicate that a much better ^c i lberhalocrcnidentwi CV ^ lun snittel under the conditions of ^T: represents ntvi cklunosprozesses than is rionor lilektronen-of and in the areas in which the electron ponor is unrepentant or neutrally ineffective with regard to a development of the filber halide, the EÜM serves to develop the silver halide and to generate an electron donor that is oxidized in a corresponding imagewise distribution because the oxidized Ef ^{| M} easily absorbs electrons from the electron donor. In general, the peeinneten EO) "s have at least one proFere ^ ilberhalotrenidentwiclclun.es.qeschv.'indigkeit under the conditions of the development process, when the combination of pick donor and the" ΡΗ ^Λ · ^! Is used, compared to Development speed when using the electron ponor without the electron drooping agent.

"Epic suitable ΕΠΜ-compounds are, for example, Ilydroquinone compounds, for example hydroquinone, 2,5-pichlorohydroquinone, 2-chlorohydroquinone and the like, aroinopheno! 5-dibromaminophenol and the like; pyrocatechol compounds, such as pyrocatechol, 4-cyclohexylpyrocatechol, 3-methoxypyrocatechol and 4- (N-octadecylanino) pyrocatechol; phenylenediamine compounds, for example N, ^ I-diethyl-p-methylphenylenediamine, S-diethyl-p-methylphenylenediamine, -p-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, N, N, N ¹ , N'-tetramethyl-p-phenylenediamine and the like.

130008/0894

BATH ORIGINAL

In a particularly advantageous embodiment of the invention, a 3-pyrazolidone compound is used as the EÜM, for example: 1-phenyl-3-pyrazolidone, 1-phenyl-4, 4-diI! ^ ethyl-3-pyrazoliclon, 4-rydroxymethyl- 4-methyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-i- (3, 4-dimethylphenyl) -3-pyrazolidone, 1-m-tolyl-3-pyrazolidone, 1-p-tolyl- 3-pyrazolidone, 4-hydroxyethyl-4-methyl-1-p-tolyl-3-pyrazolidone, 1-phenyl ^ -methyl ^ -nyrazolidone, 1-phenyl-S-ii'etiiyl-3-pyrazolidone, 1-phenyl-4 , 4-bis (hydroxymethyl) -3-pyrazolidone, 1 ^ -dimethyl-S-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1 - (3-chlorophenyl) -4-methyl -3-pyrazolidone, 1-C4-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (3-chlorophenyl) -3-pyrazolidone, 1 - (4-clilophenyl) -3-pyrazolidone, 1- (4 Tolyl) -4-methyl-3-pyrazolidone, 1 - (2-tolyl) -4-methyl-3-pyrazolidone, 1 -C4-tolyl) -3-pyrazolidone, 1 - (3-tolyl) -3-pyrazolidone , 1 -C 3-tolyl) -4,4-dircethyl-3-pyrazolidone, 1-C2-trifluoroethyl) -4,4-dinethyl-3-pyrazolidone or 5-ethyl f ^T l-3-pyrazolidone.

Combinations of different electron

Use transmission means such as in the US-PS 3 039 869. The electron transfer medium which is favorable in individual cases depends on the electron donor and the (BEND) compound used in the individual case, as well as the for the development conditions applied to the development of the recording material .

In those cases in which a particularly high image resolution is desirable is, for example, in the case of multicolor photographic recording materials, it has been found to be particularly advantageous proved to be an alkali-labile electron-donor precursor compound to use. In general, the hydrolysis of the electron precursor compound proceeds at a limited rate and when the electron donor is generated, it reacts rapidly with the oxidized electron transfer agent, which during generated by the silver halide development reaction or with the developable silver halide.

Advantageously, the alkali-labile electron donor precursor compound have sufficient ballast groups to support the

130008/0894

To make connection practically immobile, in particular when in a multicolor photographic material is used.

The alkali-labile electron-ion precursor compound can advantageously be used correspond to the following formula:

where mean:

A to form an aromatic ping with 5 to 6 atoms and preferably those needed to create a carbocyclic aromatic ring required atoms;

R is hydrogen or one or more groups, e.g. one, two or three groups with 1 to 30 carbon atoms and preferably a size that dip Compound in the alkali-permeable layers of a photographic recording material at least makes semi-immobile, for example groups of 8 to 30 carbon atoms, e.g. N-substituted carbamoyl groups, such as N-alkylcarbamoyl groups, also alkylthioether groups, N-substituted sulfamoyl groups, e.g., N-alkylsulfamoyl groups or alkoxycarbonyl groups and the like as well

R is an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted one Aryl group having 6 to 30 carbon atoms, preferably a methyl group.

Typical compounds which can be used according to the invention and which under the general formula given are:

130008/0894

ED-I

- yr-

3 *

H ₂ So ₂ NHC ₁₈ π ₃₇

O = C

O = C-

N-CH

ED-2

OH

O = C

C ₁₈ H ₃₇ NG CII

CII,

■ \

ED-3

(CH,), CCOCHCONH

NHSO ₉ C ₁ , II ,, I ι ο 33

130008/0894

-yC-

^Π! 3 CONCH ₂ CH ₂ NI

O = C-

O = C

CH ₇ NCH ₉ CH ₇ So ₉ NHC _1Q H__ j Δ £ ■ / loo /

<f ^H 3

0 =

• Ν

■ Ν

O = C

SO ₂ NHC ₁₂ H ₂₅

130008/0894

- yes -

I '-' citerhin can! -. Example circles in the Pahpen of other ^ us ^ estaltunpen of the process according to the invention, other hydrolysing fibers are used ! '', at spiclsveipe:

CH

Γ H ₃₇ NHSO ₂ (CII ₂ ) ₃

3 ^IT 7

0 C = O

1 30008/0894

(CII ₃ ) ₃ CC-CHCONH OCOCIU

N-CH ₂ C

^OC 14 »29

CH CH,

\ n /

C = O

In further embodiments according to the invention, the electron donor can present in the keto form, for example in the form of a protohydroquinone, which in a base to form a Electron donors are enolized. An example of a connection of this type is the following connection:

5CH ₇ CH ₇ CH ₉ So ₉ NIIC

i i L L

130001/0104

In further embodiments according to the invention, electron ions can be used are used which are not precursor compounds, but are preferably at least semi-immobile in the Are layers of the photographic material. Typical compounds of this type are the following:

F.O-16

C-OH C-OII CII
CHOII

15 ^ΤΙ 31

GD-17

CONIICh ₂ CIIO

^C 15 ⁿ 31

ED-18

ED-19

CONH (CII ₂ ) ₄ -0

OCH

, -SO ₂ NII (CH ₂ ) ₄ 0

(CII ₃ ) ₂ CH ₂ C (CII ₃ )

CH ₂ C (CH ₃ ),

^C 15 ^H 31

130008/089;

it

Hn-20

ED-21

]; ie already stated, show the erf i η dun ^ s like. "'^ usable (BEND) compounds have the following structural formula:

Ce:. 'UP) " Ct -.- i

L,

-1

X ¹ .

In this formula, the electron accepting nucleophile can be Forerunner group represented by ENuP, for example be a precursor group for a hydroxylanino group, e.g. a nitroso group (NO), a stable free mitroxyl radical (M-O ^ or preferably a nitro group (λ "" ^) or else the For example, grouping the formula ENuP can be a precursor group be for a hydroxyl group, e.g. an oxo group (= 0), or an inine group which in alkaline Tlrifrebun "· to a Hydrolyzed oxo group.

130008/0896

gRJf

Under the through Γ. Cyclic organic groups shown include groups "with pines" with bridging bonds, polycyclic groups and the like, preferably with 5 to 7 members in rinp to which IiNuP and H peHinden are. Preferably, stands for an aromatic pin / r H ¹ It 5 to 6 " and preferably P is a carbocyclic pine, for example a benzenoid group or else a heterocyclic finger, including non-aromatic ^p inge, in which PNuP is part of the ring, (for example in which OuP is a nitroxyl group with the nitrogen atom in the ring). P preferably has fewer than 50 atoms and in particular fewer than 15 atoms.

2 3
The ^{divalent organic groups represented by D} and P. rit 1 to 3 / tones in the divalent bond, can be, for example, alkylene, oxyalkylene, thia ^ kylene or azaalkylene groups or an alkyl or aryl-substituted nitrogen atom, and the like, it being possible for large or larger groups to be present in the side chains of the bond which take over the puncture of ballast groups, for example groups with at least 8 carbon atoms, these groups being able to represent X when X is a ballast group. Advantageously, P. can also be or have a dialkyl-substituted ethylene bond, for example a dimethylalkylene bond, which can be particularly advantageous when Q is an oxygen atom and P and E \ ^T uP form a quinone.

In the electrophilic cleavage group formed by Π and Q, E preferably stands for a carbonyl group (-CO-) or thiocarbonyl group (-CS-) or a sulfonyl group. The monatomic bond represented by Q preferably consists of a nitrogen atom which provides a divalent amino group. The third valence of the nitrogen atom can be saturated with a hydrogen atom, an alkyl group having, for example, 1 to 20 atoms, preferably 1 to 10 carbon atoms, including substituted carbon atoms and carbocyclic groups, or an aryl group having, for example, 6 to 20 carbon atoms, including a substituted aryl group and a group _; which is bonded to X to form a cyclic group containing 5 to 7 atoms.

130008/0894

BATH ORIGINAL

1 2 3 ^

The groups represented by R, R and P 'are selected so that ENuP and E are so close to each other that an intramolecular nucleophilic cleavage of Q from E is possible, the groups preferably being selected such that 1 or 3 to 5 atoms lie between the atom that represents the nucleophilic center of the nucleophilic group and the atom that represents the electrophilic center, the compound being able to form a 3- or 5- to 7-membered ring, in particular a 5 - or 6-membered ^p .ing with intramolecular nucleop]
Group.

nucleophilic displacement of group Q-X from electrophilic

In the case of the dye-supplying (BEND) compounds the dye providing compound produced by X or Q-X, preferably from a preformed dye or a so-called "shifted" dye. Dyes of this type are well known. They include, for example Azo dyes, including metallizable azo dyes and metallized azo dyes, azomethine (imine) dyes, Anthraquinone dyes, alizarin dyes, merocyanine dyes, Quinoline dyes, cyanine dyes and the like.

The so-called shifted dyes include those compounds whose light absorption characteristics are hypsochromic or bathochromic be moved if they are exposed to a different environment, for example when the pw / value changes Reaction with a compound to form a complex, e.g., with a metal ion, upon removal of a group e.g. a hydrolyzable acyl group bonded to an atom of the chromophore, and the like. The one dye The supplying moiety can also be a chelating dye group which when released into an image-receiving layer diffuses with a content of metal ions and forms a metal complex dye there.

In an advantageous manner, the splittable group can also be present as a substituent on a "displaceable" dye in order to achieve the To control the resonance of the dye. If the dye is released

130008/0894

a bathochromic or hypsochromic shift occurs. In this case, any dye can be used which has an ionizable nitrogen atom, oxygen atom, sulfur atom or selenium atom, which affects the resonance of the dye. The dye is bound to the compound in such a way that that the ionizable group is the "leaving group" in the electrophilic cleavage group.

On the other hand, the compound providing a dye can also be an image dye precursor compound. The expression As used herein, "image dye precursor compound" refers to such Compounds which undergo reactions in photographic imaging systems to produce an image dye, for example, color couplers, oxichromogenic compounds and the like.

In the case of (BEND) compounds which provide photographic reagents, the plague which supplies the photographic reagent, represented by X or Q-X have the definition given above or the reagent can, for example, also be a silver complexing agent, a hardening agent, a masking agent, a sensitizer, a desensitizer or an oxidizing agent

1 2 be medium. In other words: X and Q-X can do one represent any radical which, in combination with a hydrogen atom, provides a photographic reagent upon splitting. When the photographic reagent is a development inhibitor or an antifoggant, Q is preferably composed of an active nitrogen atom or an active silice atom, e.g. in a benzotriazole, benzimidazole or a mercaptotetrazole, wherein the compound is blocked prior to release and becomes active when released.

The nature of the ballast groups in the compounds described is not critical as long as the portion of the compound on the ballast side of E is primarily responsible for the immobility of the compound. The other part of the Holeküls on the remaining side of E has generally sufficiently solubilizing groups, to make the molecule after cleavage diffusible mobile and in an alkaline ^u edium. So

130008/0894

for example, X can be used for a comparatively small group

■ ti 3
because the remainder of R, P "and P contribute sufficiently to the insolubility of the compound and its immobility, but if X or -X" has a ballast function, they generally have long-chain alkyl residues on or aromatic Peste of the benzene or naphthalene series. Typical suitable groups which have a ballast function contain at least 8 carbon atoms, preferably at least 14 carbon atoms. ^! " ^! If X has a ballast function, X can consist of one or more.

12 3 groups exist by which Γ, V or IV are substituted and which contribute to the desired immobility or cause this. For example, two comparatively small groups, for example groups with 5 to 12 C- ^ toroes, can be used for this purpose.

how v / ends be to achieve the same immobility / a long Ballast group with 8 to 20 carbon atoms. Will be several If ballast groups are used, it can optionally be advantageous be a bond with an electron withdrawing group between the bulk of the ballast group and an aromatic ping to which it is bound, especially if the electron accepting or electron accepting nucleophile Precursor is a nitro substituent of the ring.

As used herein, the term "nucleophilic group" refers to an atom or group of atoms that includes Has electron pair that is able to create a covalent bond. Groups of this type are sometimes ionizable Groups that react like anionic groups. The term "electron accepting or electron accepting nucleophiles Precursor group "refers to a precursor group that, upon acceptance of at least one electron, i.e. in the course of a Reduction reaction forms a nucleophilic group. The electron accepting or accepting nucleophilic precursor groups have a less nucleophilic character than the corresponding reduced groups or have a structure that adversely affects the short distance or proximity of the nucleophilic center with respect to the electrophilic center.

130008/0894

BAD ORiGJNAL

The nucleophilic group can only have one nucleophilic center, for example an oxygen atom of a hydroxyl group or it can have more than one atom that can represent the nucleophilic center, for example in the form of a hydroxylamino group, in which either the nitrogen atom or the oxygen atom can be the nucleophilic center. Is more than a nucleophilic center in the nucleophilic group of the intramolecular nucleophilic displacement compound occurs the nucleophilic attack and the displacement generally by the center that form the most favorable ring structure able. This means that when the oxygen atom is the hydroxylamino group would form a 7-membered ring and the nitrogen atom would form a 6-membered ring, the active nucleophilic center would generally be the nitrogen atom.

The term "electrophilic group" refers to an atom or group of atoms that is capable of accepting a pair of electrons while bonding. Typical electrophilic groups are sulfonyl groups (-SO ₂ -), carbonyl groups (-C0-) and thiocarbonyl groups (-CS-) and the like, in which case the carbon atom of the carbonyl group represents the electrophilic center of the group and can receive a partial positive charge. The term "electrophilic cleavage group" as used herein refers to a group (-EQ-) in which E represents an electrophilic group and Q a "leaving" group, vrelche one

2
monatomic bond between E and X forms. This exiting

Group is able to take up a pair of electrons after it has been released by the electrophilic group.

According to an advantageous embodiment of the invention, the (BEND) compounds used according to the invention constitute ballast groups comprising compounds of the following formula:

^ rNE -f- QR ⁹ -X ³ )

130008/0894

where mean:

Pune an electron accepting nucleophilic precursor _re st for a nucleophilic hydroxyl group including the imino group and, preferably, oxo group;

G is an imino group including an alkylinino group or a sulfonimido group, a cyclic one Group with the participation of R or P or one of the groups specified for ENuP, whereby the G group is preferably in the para position to the group ENuP;

E is an electrophilic group, for example a carbonyl group (-C0-) or a thiocarbonyl group (-CS-); preferably a carbonyl group;

Q is a divalent amino group, an oxygen, sulfur or selenium atom that is a monatomic bond between E and R bring about, v / whether ei in the case where Q is a trivalent atom, this by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms including a substituted alkyl group, or by an aromatic group having 5 to 20 carbon atoms, including one optionally substituted Aryl group, may be substituted;

R is an alkylene group having 1 to 3 carbon atoms in the bond, including a substituted alkylene group and preferably an alkylene group with a carbon atom in the divalent bond, e.g., a methylene group or a dialkyl or diaryl substituted Methylene group;

η = 1 or 2;

R is an aromatic group of at least 5 atoms, preferably 5 to 20 atoms, including a heterocyclic group Group, for example a group with a nucleus, for example a pyridine, tetrazole, benzimidazole, Benzotetrazole or isoquinoline nucleus or a

130008/0894

carbocyclic arylene group, which preferably has 6 to 20 carbon atoms and which preferably consists of a phenylene group or a naphthylene group, the phenylene or naphthylene group being

may optionally be substituted or R "represents an aliphatic hydrocarbon group, for example an alkylene group having 1 to 12 carbon atoms which may optionally be substituted;

R is an alkyl group having 1 to 40 carbon atoms including a substituted alkyl group and a cycloalkyl group, an aryl group having 6 to 40 carbon atoms including a substituted one Aryl group or the substituent X;

5
R, R and each a substituent consisting of one atom,

R for example a hydrogen or halogen atom or preferably a group consisting of several atoms, for example an optionally substituted alkyl or cycloalkyl group with 1 to 40 carbon atoms, an alkoxy group, an optionally substituted / ryl group with 6 to 40 carbon atoms, a carbonyl, sulfamyl group or sulfonamido group, or the radicals R, ^. and R can each be the substituent X ¹ _{(where the} following applies: P ⁶ and R ⁵ or R and R, if they are located in adjacent positions on the ring, can together form a 5- to 7-membered ring, namely with the remainder of the molecule, whereby this ring can optionally also have a bridge bond, with the rule that if P. represents an aliphatic hydrocarbon group, for example an alkylene group, R and R must represent substituents composed of several atoms

and furthermore where P is preferably a substituent made up of several atoms and furthermore where holds that if G is an electron accepting nucleophile Precursor group, as indicated for ENuP,

4 6

the substituent represented by R or R adjacent to C can also be a group of the following formula can:

130008/0894

R ⁸

^y nl ^v * ■

to form a compound having multiple groups or multiple groups represented by a nucleophilic displacement reaction can be released or split off;

X is provided in at least one of the substituted positions and both X and (QIV -X ) can each represent a ballast group of sufficient size to render the compound immobile in an alkali-permeable layer of a photographic recording material, or they can be photographically useful or photographic advantageous

Represent groups, provided that one of the groups X and

9 3
- (- QR "-X) is a ballast group and the other group is one

photographically useful group, for example a photographic one Reagent or a dye providing group and

R a group which has a suitable spacing or the required Proximity of the nucleophilic group to E ensured, so that an intramolecular nucleophilic cleavage of Q from E takes place can, \\ robei R is preferably a group consisting of 3 to 5 atoms, between the atom that is the nucleophilic center of the nucleophilic group and the atom that is the represents the electrophilic center of the electrophilic group, the compound being able to form a 5- to 8-membered ring, Preferential rates a 5- or 6-membered ring at intramolecular

q τ nucleophilic displacement from the group (Q-P / -X) from the electrophilic group.

Correspond in further advantageous embodiments of the invention the (BEND) compounds of the following formula:

130008/0894

BAD ORIGINAU

--X ²

v.'orin mean:

ENuP is an electron accepting precursor or group of precursors for an electron accepting Hydroxylamino group, for example a nitroso group (NO), a stable nitroxyl radical and preferably a nitro group

Λ the one to complete a 5- or 6-section aromatic ring required atoms, including a polycyclic aromatic ring structure, wherein the aromatic ring or the aromatic ring structure is carbocyclic or heteroyclic Can be ring and optionally can have an aromatic onium group in the ring, where A is preferably for represents the atoms necessary to complete a carbocyclic ring system, for example a benzene or naphthalene ring;

W is an electron withdrawing group with a positive Hammett sigma value, for example a cyrano-, nitro-, Fluorine, chlorine, bromine, iodine, trifluoromethyl, trialkylammonium, Carbonyl, N-substituted sulfamyl ester group and the like;

R is a hydrogen atom or an optionally substituted alkyl group having 1 to 30 carbon atoms or a optionally substituted aryl group having 6 to 30 carbon atoms;

130008/0894

R is a divalent organic group with 1 to 3 atoms in the divalent bond, for example an alkylene, oxaalkylene, thioalkylene or iminoalkylene group or an alkyl or aryl-substituted nitrogen atom, preferably an alkylene bond with at least a dialkyl or diaryl substituted methylene group in the bond;

m and q = 1 or 2;

ρ and r are each a number of 1 or more, with the proviso that ρ is preferably a number from 3 to 4, where ^ "(R) V. ^r 27 * - can be a substituent in any position of the aromatic ring structure of A. ;

E and Q atoms or groups that form an electrophilic cleavage group in which E represents an electrophilic center and is preferably a carbonyl group or thiocarbonyl group or a sulfonyl group and in which Q is a Is group that is a monatomic bond between E and

2
X represents, wherein the monoatom can consist of an oxygen, sulfur or selenium atom or also a nitrogen atom which forms an amino group and the like and wherein Q is preferably an amino group which has a substituent consisting of an alkyl group with 1 to 20 atoms, inclusive a substituent consisting of a substituted alkyl group or a substituent consisting of one or more optionally substituted alkyl groups attached to

2
X are attached to form cyclic groups such as piperidine groups and the like;

η = 1, 2 or 3, preferably 1;

2
X together with Q is either an image dye-providing group, an image dye-providing precursor group, or a photographic reagent-providing group;

130008/0894

X ^{1 is} a ballast group, preferably an optionally substituted alkyl group with 8 to 30 carbon atoms or an optionally substituted aryl group with 8 to 30 carbon atoms, including the necessary links or linking groups to the aromatic ring, with the proviso that at least one of the

ι ίο
Group ^ X or R is present in the compound and is a group of sufficient size to make the (BEND) compound immobile and non-diffusing in the alkali-permeable layers of the photographic material, ie preferably at least one of the groups X is ode
Carbon atoms.

,
of groups X or Π ^ a group with 12 to 30

It should be noted that if there are several groups in the compound, as indicated in the above formula, they can have an identical or different structure. This means that, for example, ρ has the meaning of 3, every ι
can.

each of the groups (R -Vf-) have a different structure

The electron withdrawing groups of the compounds of the specified Formulas are generally groups with a positive Hammett sigma value and preferably groups with a sigma value of more than 0.2 or groups with a combined effect of more than 0.5 as substituents of the aromatic ring, The Hammett sigma values can be determined using methods as described in the book "Steric Effects in Organic Chemistry", published by John Wiley and Sons, Inc., 1956, Pages 570-574 and the book, "Progress in Physical Organic Chemistry ", Volume 2, Interscience Publishers, 1964, pages 333 to 339.

Typical suitable electron withdrawing groups with positive Hammett sigma values are, for example, cyano, nitro, fluorine, Bromine, iodine, trifluoromethyl, trialkylammonium, carbonyl, N-substituted Carbamoyl, sulfoxide, sulfonyl and N-substituted Sulfamoyl ester groups.

1 30008 / 089A

The expression "aromatic hung with a." Electron withdrawing substituents "refers to onium groups in the ring and on those groups by which the finger is substituted, which bonds for other groups, for example Represent ballast groups.

According to a further advantageous embodiment of the invention the (BEND) compound has the following formula:

E-n-x '

ι ο
E, Q, X and X have the meaning already given,

Typical dyes which can be used according to the invention provide (BEND) connections are for example:

BEND-1

CH ₉ N-CO

^SC 12 ^H 25 * - NHSO

N CH, SO, NH N

OCOCH-CH.

ti Δ J

130008/0694

BEND-2

BEND-3

CH, SO ₉ NH "3 2,

COCH ₉ CH it L

BEND-4

^N " ^C 6 ^H 5

130008/0894

BEND-5

R-

■ ^C 16 ^H 33

-CH ₇ NCO CH,

-rs

NHSO

(CII ₃ )

CvH ₁ . "65

BEND-6

^C 16 ^H 33

-CH ₉ NCO ₉

130008/0894

BEND-7 OH

SO ₂ NII

C ₁₂ H ₂₅ SO, -

0 CH ₃ SO ₂ C-NCH ₂ CH ₂ N-CII ₃ Ό-

° 2 ^C 12 ^H 25

BEND-8

NO.

Cl-

// - C-NCII ₇ CH-NSO., // ti ι ^ ^ ₁ Z

O CH ₃ CII ₃

^C 18 ^H 37 ^SO 2

IH

SO ₂ CII ₃

NO

BEND 9

NO ₉

^SO 2 ^C 12 ^H 25 OH

CH ₃ SO ₂ NH

CH ₃ CH ₃ SO ₂ NCH ₂ CH ₂ N-

130008 / 089A

BEND-1O

^C 12 ^H 25 ^S ° 2

P =

no

BEND-11

^C 12 »25 ^SUN

NO,

^SO 2 ^C 12 ⁿ 25

CII

NII R

= -SO

CN

BEND 12 ^C 12 ^H 25 ^{S (} Y

-N (CII ₂ ).

-SO

N-

O OC

BEND 13 ^C 12 ^H 25 ^SO 2

CH

-N (CH ₂ ) ₃ NH-R

^S ° 2 ^C 12 ^H 2S

O
0-CC ₆ H ₅

130008/0894

BEND 14

/ ^SO 2 ^NHCII 2

^SO 2 ^C 12 ^H 25

BEND 15

^C 12 ^H 25 ^5O 2

^SO 2 ^C 12 ^H 25

IIC (CII ₃ )

BHND 16

NO.

^C 12 ^H 2S ^SO 2 "

CON NSO

^SO 2 ^C 12 ^H 25

NHSO ₉ ^ (/ V

O ₉ N

SO ₉ CH,

OH

130008/0894

BATH ORIGINAL

J * 57

BEND 17

SO ₂ NHC (CH ₃ )

° 2 ^C 12 ^H 25

CH ₃ SO ₂ NH N = N

BEND 18

RO-C-N-CH

It I

0 CH,

CH ₂ MCOH CH ₃

^C 16 ^H 33

NHSO

BEND 19

^C 12 ^H 25 \

RO-C-N-CI CH

CH, C 1 3 if

H ₂ -N C-OR

N = N

SO ₀ N-CH-COOH

130008 / 089A

■■ - ■■ - -υ ■ ^; -. ■ "■ -.

-X- st

BEND ZO

NO

OH

^C 12 ^H 25 N ₉ ^S0 = N NIISO ₂ CH ₃

O ^V II

^J 2 ■ '2

BEND 21

N—

_A CII, _y N-N

S-CNCH

NCH,

-CH ₂ NC-S-

* υ Ο ^ -H Ί6 ^η 33

^C 6 ^H 5

BEND 22

^C 12 ^H 25

R.
^C 12 ^H 25

CH ₃ R = -CH ₂ N CO

30008/0894

- Sä

BEND 23

2 ^H 25

CH ₇

I ³ Il

-CH "N C-O

N = N-Q

O ₇ NCH ₉ COOH

Ί ^z

CH,

BEND 24

R ^C 16 ^H 33

CH ₃

R - -CH.

N— C-O- / \ -N-N-

NO,

130008 / 089A

- C (T

3Q29132

BEND 25

R.
^C 16 ^H 33

CH.

-CH ₂ N-

: —Ο

N = N- / V-

NO,

SO ₂ N

SO ₂ NH ₂

Typical (BEND) compounds which can be used according to the invention and which provide photographic reagents are, for example:

BEND 26

SCH ₂ CH ₂ CN j

CH,

I '

CH,

° 2 ^C 12 ^H 25

130008 / 089A

BEND 27

CH.

O = CN-CH ₀ -C-

² I.

^C 12 ^H 25 ^SO 2

° 2 ^C 12 ^H 25

CH-

I ²

CH ₂

CN

BEND 28

^C 6 ^H 5

BEND 29

130008 / 089A

A photographic product developable by the process of the invention In the simplest case, recording material can consist of a support with a silver halide emulsion layer applied thereon that contains a (BEND) compound or is in contact with a layer with such a compound.

Typically, however, the recording material consists of a multilayer, multicolor photographic recording material with a layer support on which, for example, are applied: a red-sensitive silver halide emulsion unit with a cyan image dye-providing compound in or to a silver halide emulsion layer adjacent layer, a green-sensitive silver halide emulsion unit with a magenta image dye forming compound in a silver halide emulsion layer, or an adjacent layer and a blue-sensitive silver halide emulsion unit with a yellow image dye supplying compound in a silver halide emulsion layer or a layer adjacent thereto, with the proviso that at least one of the silver halide emulsion units contains one of the described CBEND) compounds.

Each of the silver halide emulsion units can be composed of one or more layers, the various Units and layers in various orders and various relationships to one another according to conventionally known methods can be applied to the carrier. The emulsion layers can be those with a high or a comparative act low silver halide concentration. Under a high concentration of silver halide or a high silver halide coating it is meant that each emulsion layer has at least 5.0 mg silver halide / dm, based on the weight of the Silver, contains. Such recording materials typically contain 5.0 to 25 mg silver halide / dm, based on the weight of the silver. In contrast, photographic recording materials with a low silver

130008/0894

halide concentration or low silver halide coating typically 0.001 to 5.0 mg silver halide / dm, based on the weight of silver, in each emulsion layer.

The photographic recording materials can optionally have additional layers customary in photographic recording materials, for example separating layers or Spacer layers, filter layers, antihalation layers, intercepting layers and the like. The carrier can be any of the usual known substrate exist. The support typically consists of a polymeric film material Paper, including paper coated with polymers, glass, and the like.

The (BEND) compounds can be used in silver halide emulsion layers or in other layers in contact with the silver halide emulsion densities. The (BEND) connections can be incorporated into these layers, such as photographic color couplers in such layers be incorporated. Depending on the physical properties of the (BEND) compounds and their physical compatibility they can be dispersed directly in the emulsion or the binder or else with the emulsion or the binder they can be mixed with organic or aqueous solvents and then dispersed in the emulsion or the binder.

For the production of visible image recordings with the described Dye supplying (BEND) compounds are normally used in a concentration of at least 1 χ 10 moles

2 - A

/ m and preferably in a concentration of about 1 χ 10 to

-3 2
2 x 10 moles / m used. When using compounds which provide photographic reagents (BEND), the optimum concentration in the individual case depends on the individual reagent, the magnitude of the desired effect and the nature of other components or constituents in the photographic recording material.

130008/0894

The electron donor is preferably in the same layer before like the (BEND) compound, especially if it is different from the alkali-labile, semi-immobile described above Type is, although the electron donor can, however, also be accommodated in another layer, or else in a mass or solution used to develop the recording material. Becomes the electron donor in one layer used, it is preferably used in a ratio of 1: 2 to 2: 1 and preferably 1: 1 to 2: 1 moles of electron donor per -Mol (BEND) compound used.

The electron transfer agent, if used, is used is preferably used in the mass or solution used to develop the recording material, although the electron transfer agent can also be accommodated in a layer in a blocked form or a precursor form. If the electron transfer agent is used in the mass or solution intended for development, it will be preferably used in a concentration of 0.5 to 20 g / liter, in particular in a concentration of 0.5 to 10 g / liter. When used in a layer of the recording material, a corresponding precursor compound or a so-called blocked compound preferably at a concentration of

2
about 0.2 to 1.8 million pounds / m of support area, especially in one

Concentrations of 0.5 to 1.5 millimoles / m of support surface are used.

The peroxide is preferably in the developing composition or developing solution used, preferably in a concentration of 0.001 to 1.0 mol / liter. When used in a Layer, it is preferably used in a concentration of about 2 to 8 g / m 2 support area.

Become an electron donor, electron transfer agent, or peroxide housed in the photographic recording material,

130008/0894

instead of in the developing mass or solution, so the latter serves to activate the components and / or to create a madium in which there is contact with the silver halide or the (BEND) connection, or both.

The developer composition or developer solution consists of an aqueous alkaline solution of a basic component, for example a solution of an alkali metal hydroxide or alkali metal carbonate (e.g. sodium hydroxide or sodium carbonate) or an amine (e.g. diethylamine). Preferably has the developer compound or developer solution has a pH of over 11. Typical compounds for the production of such Developer compositions and developer solutions are, for example, from the literature "Research Disdosure", pages 79-80, Nov. 1976, known.

The alkaline developer composition or developer liquid is preferably used set free from a splittable container, which is so constructed that it can hold its contents during the Development process when a pressure is exerted on the container by pressure-exerting members releases, with distribution the contents of the container within the recording material. However, other common methods of introducing the alkaline can also be used Developer liquid are applied.

Typical suitable splittable containers in which the developer liquid can be accommodated are, for example, from US-PS 2,543,181, 2,643,886, 2,653,732, 2,723,051, 3,056,492, 3,056,491 and 3,152,515 are known. In general, such containers consist of a rectangular, leaf-shaped, for liquids and air impermeable material, which is folded in the longitudinal direction around itself, with the formation of two side walls that are sealed together, forming a cavity in which the developing liquid is contained.

130008/0894

A very wide variety can be used to build up the image-receiving layers, which can optionally be part of the recording materials Compounds can be used which the dyes that diffuse into the image-receiving layer, or mordant able to fix in another way. The compounds used in individual cases for the production of the image-receiving layers depend on the dyes to be stained or fixed. Optionally, the image receiving layers Ultraviolet light absorbing compounds contain the dye images from fading due to exposure protect from ultraviolet light. Brighteners and other compounds can also optionally be used in the image-receiving layer be included in order to protect the dye images produced or to increase their effect.

As stated above, the recording materials according to the invention can also contain additional layers. These include also layers that reduce the pH value, (sometimes referred to as so-called acid layers or neutralizing layers) retardation or spacer layers, opaque, light-reflecting layers, opaque, light-absorbing layers, intercepting layers and the like.

The recording materials used for carrying out the process according to the invention can have different structures in terms of their structure known recording materials for the diffusion transfer process correspond. This means that the layer arrangement in the recording materials, which are within the scope of the invention Process can be used, the layer arrangement of known recording materials for the diffusion transfer process is equivalent to. Accordingly, the image dye-receiving layer can, for example, also be on a separate Layer support be arranged on the photographic recording material can be applied or laid on after its exposure. Such image receiving layers are for example

130008/0894

from US Pat. No. 3,362,819.

According to a further advantageous embodiment of a for implementation of the method according to the invention suitable material, the image-receiving layer forms a local component with the photographic recording part and is located between the support of the lowermost silver halide emulsion layer. A Such a type of recording material is known from BE-PS 757 960, for example. In the case of such a recording material the support of the photographic recording member is transparent and has in the following order. the following layers: an image-receiving layer, a practically opaque, light-reflecting layer and also one or several photosensitive or light-sensitive layers. After imagewise exposure of the recording material a splittable container of alkaline developing liquid and an opaque worksheet on the recording material brought. By pressure-exerting members, for example in a self-development camera, the container is split open so that the developing liquid can spread in the photographic recording material, e.g. B. when the recording material is pulled out of the camera. The developing liquid develops the exposed silver halide emulsion layers and the image dyes thereby generated as a result of development diffuse into the image-receiving layer to be generated a right-side recognizable image that passes through the transparent support on the opaque reflective Background can be viewed. For further details on this particular recording material, see For an integral image receiving layer, reference is made to BE-PS 757 960.

Another type of advantageous recording material is known from BE-PS 757 959, for example. In this embodiment is the substrate of the photographic

130008/0894

drawing material or recording part transparent and has in the following order: an image-receiving layer, a practically opaque, light-reflecting layer and one or more light-sensitive layers. Between the top emulsion layer and a transparent cover sheet with a neutralizing layer and a retardation layer or timing layer, a splittable container with alkaline developing liquid and an opacifying agent is placed. Such a recording material can be exposed in a camera through the transparent cover sheet and then peeled off through the gap formed by two pressure-exerting members of a self-development camera. The container containing the developer is split open so that its contents and the opacifier are distributed over the photographic layers, initiating the development process and protecting the photosensitive layers from further exposure. The developing liquid develops, the individual silver halide emulsion layers and the image dyes formed as a result of the development process diffuse into the image receiving layer to form a right-readable image which can be viewed through the transparent support on the opaque reflecting layer as a background. For further details of this type of recording material with an integrated image receiving layer, reference is made to BE-PS 757 959 already mentioned.

Further advantageous types of recording materials which are used in the context of the process according to the invention are known, for example, from U.S. Patents 3,415,644, 3,415,645, 3,415,646, 3,647,437, 3,635,707 and 3,993,486.

The expression "non-diffusing" or "non-diffusible" as used here has the usual meaning in the field of photography and denotes compounds that are not organic in the context of normal cases used in practice

130008/0894

Complete layers, e.g. gelatin, migrate or diffuse in an alkaline medium in the photographic recording materials of the invention and preferably migrate or diffuse when developed in a medium having a pH of 11 or above. The term "immobile" has the same meaning. The term has "diffusible" the reverse meaning and identifies compounds that have the property ^r effectively V. else by colloid layers of a photographic Aufzeichnungsnaterials in an alkaline medium to diffuse. The term "mobile" has the same meaning.

The following examples are intended to illustrate the invention in more detail.

example 1

Two color photographic recording materials of the structure shown schematically below were produced. The numerical values given in brackets indicate the concentration in g / m.

Ο, 2μ AgBr emulsion / BEND compound (0.49) / electron donor (1.11) / 2,4-di-n-amylphenol (0.79) / Gelatin (3.24)

Poly (ethylene terephthalate) ////////// support //////////////////////

The concentration of silver halide (as silver) in each recording material what follows:

2 recording material g / m Ag

A and B 1.08

C and D 0.108

130008/0894

The (BEND) connection had the following structure:

The electron donor used had / the following structure:

the

O CH ₃

Each recording material was passed through a test object with neutral graduated density levels from 0 to 6 for 2 seconds exposed in a type 1B sensitometer.

The recording materials A and C were developed by splitting a container with 80 g of potassium hydroxide, 10 g of ethylenediaminetetraacetic acid, 1 g of 4-methyl-4-hydroxymethyl-i-phenyl-3-pyrazolidone, 0.1 g of 5-methylbenzotriazole and 51 g Carboxymethyl cellulose per liter of water between the recording material and the image receiving material, which had the following schematic structure;

130008/0894

Gelatin - (1, 24)

Gelatin - (2.64) / Titanium Dioxide - (16.2) Gelatin (2.29) / mordant (2.29)

Poly (ethylene terephthalate) film support

Recording materials B and D were made in the same manner develops with the exception, however, that the developing fluid contained in the splittable container, in addition to the other ingredients, 20 ml of a 30% hydrogen peroxide.

After 10 minutes, the light-sensitive materials became and the image receiving materials separated from one another and recorded sensitometric curves corresponding to the cyan dye released from the (BEND) compound and transferred into the image-receiving layers. These curves are shown in FIGS. 1 and 2.

It was found that in the case of the higher silver concentration (Figure 1), the recording material B, which was developed with hydrogen peroxide, corresponds to approximately 0.6 log E Increase in sensitivity compared to recording material Λ. In the case of the lower silver concentration (FIG. 2), the recording material D developed with hydrogen peroxide showed approximately the same sensitivity and the same image resolution as the recording material B, while the recording material C showed little or no image resolution or image distinction.

Example 2

Two other photographic recording materials became available of the following structure shown schematically. The numerical values in brackets refer to the amounts of the compounds used in g / m.

130008/0894

0.75 μ AgBr emulsion / (BEND) compound (0.27) / Electron donor (0.54) / 2,4-di-n-amylphenol CO.39) / gelatin (3.24)

Polyethylene terephthalate) film backing

The concentration of silver halide (as silver) in each recording material was as follows:

Recording material

E and F G and H

g / m Ag

1, 08
0.108

The (BEND) compound used was the same as in Example 1.

The electron donor corresponded to the following formula:

O ₂ NHC ₁₂ H ₂₅

Each recording material was as described in Example 1 exposed and developed, with the exception, however, that the recording material F developed with a developing liquid which contained 5 ml of 30% hydrogen peroxide per liter and developed the element H with a developer liquid which contained 15 ml of a 30% hydrogen peroxide per liter.

13000870894

There were sensitometric curves of the obtained blue-green dye images made in the image receiving materials. They are shown in FIGS. 3 and 4. Again there is a corresponding one Increase in sensitivity in the case of the recording material! s developed in the presence of hydrogen peroxide.

130008/0894

Claims (1)

PATENT APPLICATION Process for the preparation of a dye image, in which one an imagewise exposed photographic recording material with a layer support and at least one coated thereon Silver halide emulsion layer with a developable latent image and - in the emulsion layer or in a adjacent to this, a hydrophilic colloid layer - one which supplies a dye and has at least one ballast group Electron accepting nucleophilic displacement compound (BEND) of the following formula: (ENuP) • X ¹ . qjy in which: 1 30008/0894 w, χ, γ, ζ, n and m each = 1 or 2; ENuP an electron accepting nuUeo- phile precursor group; R is a cyclic organic group, to which / RNuP are bound; E and 3 P "and R having divalent organic groups 1 to 3 atoms in the divalent bond; E and Q are an electrophilic Cleavage-enabling group, with the proviso that E is an electrophilic group and Q is a divalent amino group or an oxygen, selenium or Sulfur atom, the one 2 monatomic bond between E and X caused and displaceable by E through the nucleophilic group formed by EMuP is; X is a substituent on at least one 12 3 of groups P, P and P., with the proviso that the substituent X or the group -H-X represents a ballast group of sufficient size to form the compound in an alkali-permeable layer of a photographic To make materials immobile and either X or -Q-X represents a group capable of providing a diffusible image dye, (a) developed with either 1) an electron donor, which is a silver halide developing agent or 2) an electron transfer agent which is a Silver halide developing agent is, in the presence of an electron donor, releasing a diffusible one Dye from the (BEND) compound in BATH ORIGINAL reverse function of. ^ ilVercntvicklunf * and (b) the released diffusing dye under Frzeugung Fnrbstoffbildos a visible from at least the dif fusions ff. hi fen ^r arb.stoff or (RIlMD) connection transmits, characterized in that one has the development in the present of a peroxide oxidizing agent, which in absent a silver catalyst inert to an oxidation-reduction reaction with the electron transfer agent and the electron donor. 2. The method according to claim 1, characterized in that the released dye capable of diffusion by diffusion in an image receiving layer is transferred in which he a visible image generated. 3. The method according to claim 1, characterized in that one a 3-pyrazolidone was used as an electron transfer agent and that the electron donor is derived from an alkali-labile electron donor precursor of the following Formula derives: where mean: A are the atoms required to complete an aromatic ring of 5 to 6 atoms; R is a hydrogen atom or one or more groups with 8 to 30 carbon atoms of such a size the sufficient to make the compound semi-immobile in the alkali-permeable layers of the photographic material to make and 130008/0894 R is an optionally substituted alkyl group 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms. 4. The method according to claim 1, characterized in that a ^u connection of the following formula is used as the (BEND) compound: , 9 _V 3 where mean: ENuP an electron accepting nucleophile Precursor group for a nucleophilic hydroxyl group ; ι 4 g G is an imino group, one formed with P or R. te cyclic group or a group as indicated for ENuP; E is an electrophilic group; Q is a divalent amino group or an oxygen, Sulfur or selenium atom which provides a monatomic bond between E and R *; R is a divalent group of 1 to 3 carbon atoms in the bivalent bond; η = 1 or 2; R is an aromatic group of 5 to 20 carbon atoms or an alkylene group with 1 to 12 130008/0894 3P29132 Carbon atoms; R is an alkyl group with 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms or the substituent X; R, R and each a hydrogen or Ilalogenatom or R is an alkyl, alkoxy, aryl, carbonyl, sulfa myl or sulfonamido group or the substituent X ¹ , except that P. ⁶ and R ⁵ or R ⁴ and P ⁵ , if they occupy adjacent positions on the ring, together also have a 5- to 7-membered channel the rest of the molecule can form under the ο
A requirement that when P "is an alkylene group represents, R and R are multi-atom groups and that when Π is an electron uptake nucleophilic precursor group, such as 4 is indicated for ENuP, the substituent P or R, which is adjacent to Π, can also be a group of the following formula: R ⁸
eR N - E-fO - R ⁹ - X ³ ) it also holds that X is at least one of the substituted positions and X and q 3 (-QR "-X) is in each case a ballast group of sufficient size to render the compound immobile in an alkali-permeable layer of a photographic recording material or a group which provides a diffusible image dye, provided that one of the radicals X ¹ and (-QR ⁹ -x ³ ) is a ballast group and the other group is a diffusible image dye-providing group. 120003/0834 5. The method according to claim 1, characterized in that one a compound of the following formula is used as the (BEND) compound: ENuP ΓτΕ-Q- :-1 -X where mean: ENuP an electron accepting precursor group for a hydroxylamino group; A to form a 5- or 6-membered aromatic Ring's required atoms; W an electron withdrawing group with a positive Hammett sigma value; R is an IV hydrogen atom, an alkyl group with 1 to Carbon atoms or an aryl group having 6 to 30 carbon atoms; R is a divalent organic group having 1 to 3 atoms in the divalent bond; m and q = 1 or 2 each; ρ and r are each numbers 1 or greater than 1; 12th ).-Ii a substituent in any position of the aromatic Ring structure A; E and Q are a group which enables electrophilic cleavage, where E represents an electrophilic center 130008/0334 and η is a group that is monatomic Bond between T: and X represents ^; = 1, 2 or 3; X together with Q is an image dye supplying group and X a ballast group of such a size that see the (BEND) compound in the alkali permeable layers of a photograph Recording material is immobile and non-diffusing najit. 6. The method according to any one of claims ¹ 1 to 5, characterized in that there is used as the peroxide oxidizing agent hydrogen peroxide. .7. Photographic recording material for the image transfer process, which can be developed with an alkaline developer, with: a) a photographic element or recording part with a support having at least one light-sensitive silver halide emulsion layer and in the emulsion layer or in a hydrophilic colloid layer adjacent thereto of a (BEND) compound of the following Formula: (ENuP) _w ³ , -0 7 f1 ^ y ' ^{v J} m-1 in which: 130008/0894 ORIGINAL BATHROOM - ο · " v;, x, y, z, n and tp each = 1 or 2; I ⁷ NuP an electron accepting nucleophile Precursor group; P. a cyclic organic group, ηη the / ENuP are bound; Γ and 2 3
P and R divalent organic groups with 1 to / tone in the bivalent bond; E and O each have an electrophilic cleavage enabling group, where it applies that E is an electrophJIe group and Q is an bivalent v \ minogroup or an oxygen, Selenium or sulfur atom, the one causes a monatomic bond between K and X and from E through that formed by ENuP nucleophilic group i ^ can be crowded; X is a substituent on at least one of Groups R ¹ , R ² and R ³ , with the proviso that the substituent X or the group -Q-X represents a ballast group of sufficient size to form the compound to render immobile in an alkali-permeable layer of a photographic material and either X or -Q-X represents a group capable of providing a diffusible image dye, (b) an image receiving layer and (c) either i) an electron donor which is a silver halide developing compound or ii) an electron donor in combination with an electron transfer agent _T which is a silver halide developing compound, 130008/0894 BATH ORIGINAL characterized in that the recording material contains a peroxide oxidizing agent which opposes an oxidation-reduction reaction with the? Electron transfer agent and the electron donor in the absence of a silver catalyst inert or practically inert. 8. Recording material according to claim 7, characterized in that it contains a (BEND) compound of the following structure: ENuP (ΐι ⁷ ) _ηΓΓ Ν — E-eQ-r— x ³ ) where mean: ENuP an electron accepting nucleophilic precursor compound for a nucleophilic Hydroxyl group; G is an imino group, a cyclic group with 4 6
R or R or one of those given for RNuP Groups;
E is an electrophilic group; Q is a divalent amino group, or an oxygen, sulfur or selenium atom which is a monoatomic Creates bond between E and R; R is a divalent group of 1 to 3 carbon atoms in the bivalent bond; η = 1 or 2; 130008/0804 R is an aromatic group containing 5 to 20 atoms or an alkylene group having 1 to 12 carbon atoms; P. an alkyl group of 1 to 40 carbon atoms, an aryl group with 6 to 40 carbon atoms or the substituent X; ^p . , P and R each represent a hydrogen or halogen atom or an alkyl, alkoxy, aryl, carbonyl, sulfamyl or sulfonamido group or the Substituent X or, on the other hand, P and P 4 5
or R and R, provided that these radicals are on Ring are in adjacent positions, together with a 5- to 7-membered ring the remainder of the molecule, with the proviso that when R is an alkylene group, R and P are polyatomic groups and that if G is an electron accepting nucleophilic precursors r group is as indicated for ENuP, the substituent R or R, adjacent to G can also be a radical of the following formula can: ϊΝ-E-6-0-R ^y n-i - it also holds that X is in at least one of the substituted positions is present and 1 9 3
X and ("QP- -X) each have a ballast group represent a size which makes the compound in an alkali-permeable layer of a photographic material ^ mobile, or a group providing a diffusible image dye, with the proviso that one of the groups X ¹ and (-QR ⁹ -X ³ ) is a ballast group and the other group provides a diffusible image dye. 130008/0894 9. Recording material according to claim 7, characterized in that that there is a (BEND) compound of the following formula contains: ENuP E-n T (R 12th where mean: ENuP an electron accepting precursor group for a hydroxylanino group; those to complete a 5- or 6-limb aromatic pinges required atoms; an electron withdrawing group with a positive Hammett sigma - '. Vert; a hydrogen atom, an alkyl group with 1 to 30 carbon atoms or an aryl group with 6 to 30 carbon atoms; a divalent organic group having 1 to 3 atoms in the divalent bond; m and q are positive numbers of 1 or 2; ρ and r positive numbers of 1 or greater than 1; Z ~ (R) «-Wjf-a substituent in a position of the ring E and Q structure A; the atoms that provide an electrophilic splitting group, where E represents an electrophilic center and Q 130008/0894 is a group that has a monatomic bond between E and υ represents; η = 1, 2 or 3; y
X "pemeinsrin with 0 a group providing a dye and ? ί a ballast group of such a size that the (BENJi) compound in the alkali-permeable Layers of a photographic recording material innobil and non-diffusing at night. 10. Photographic recording material for the image transfer process, which cannot be developed with an alkaline developer, with: a) a photographic element or recording part with a carrier and at least one coated thereon photosensitive silver halide emulsion layer, the an image dye-providing compound and a (BEND) compound are assigned to the following formula: (ENuP) ₁ , 2, -1 • rl ³ ) P.V " in which: w, x, y, ζ, η and m each = 1 or 2; ENuP an electron accepting nucleophilic precursor group; 130008/0894 R is a cyclic organic group to which E and ENuP are bound; R and R divalent organic groups with I to 3 Atoms in the bivalent bond; E and Q represent a group which enables electrophilic cleavage, with the proviso that E is an electrophilic Is a group and O is a divalent amino group or an oxygen, selenium or sulfur atom, which causes a monatomic bond between E and X and from E through the nucleophilic group formed by ENuP can be displaced; X is a substituent on at least one of the group pen R ¹ , R ² and R " ³ , 1 2 with the proviso that the substituent X or the group -O-X represents a ballast group of sufficient size to form the compound in an alkali-permeable layer of a photographic To make materials immobile and either X or -Q-X represents a group which is a photographic Able to deliver reagent, b) an image receiving layer and c) either i) an electron donor that develops a silver halide developer compound is or ii) an electron ^ onor in Combination with an electron transfer agent, the one Silver halide developing agent is characterized in that the recording material of the supernatant contains a peroxide oxidizer that is opposed to an oxidation-reduction reaction with the electron transfer agent and the electron donor is inert or virtually inert in the absence of a silver catalyst. - 13a - 130008/0894 BATH ORIGINAL 11. Recording material according to claim 10, characterized net that there is a ^ ΒΓΝΠ) compound of the following formula ent holds: before mean: FNuP is an electron accepting nucleophilic forerunner rgruppe for a nucleophilic hydroxyl group; G is an imino group, one formed with P or R. v ^r ie egpben cyclic group, or a group for HS FiNuP; E is an electrophilic group; O a divalent amino group or an oxygen, Sulfur or selenium atom which provides a monatomic bond between E and R; R is a divalent group with 1 to 3 carbon atoms in the bivalent bond; η = 1 or 2; P is an aromatic group of 5 to 20 atoms or an alkylene group with 1 to 12 carbon atoms; R is an alkyl group with 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms or the substituent X; - 13b - >', R ur.dj eve ils pin''.'a ^ serrto-T- or Ualo ^ en-iton or: ⁵ an alkyl-, Al] oxy-, "ryl-, ^r ar'or-yl-, IuI fa rcy 1- or .Sulfonamidogrup; ip or the fubstitucnt X ¹ , v; obei "ilt, da," P. * and P ^ odor P ⁴ and " ⁵ , venn they adjoining" ositioner an "ing one, together also one 5- to 7-membered ring rit the rest of the molecule can form under the Prerequisite, dal, vcnr. ^½ "'represents an alkylene group, P and P are groups consisting of several atoms and that when G is an electron receiving nucleophilic precursor group, vie 4 is given for ENuP, the surstituent R or R, which is adjacent to G, can also be a group of the following formula: P ⁸ v. where it also applies that X is at least pincr of the substituted positions and X and 9 3 (-QR -X) each is a ballast group of sufficient size, ui? the compound in a permeable alkaline layer of a photographic recording material i ^ pobil to boat or a photographic ^p eagens donating group, provided that one of X and (-QP "-X) is a ballast group and the other group a a photographic Reagent supplying group. 12. Recording material according to claim 10, characterized in that that it contains a (BEND) connection of the following structure: ENuP -13c- 130008/0894 - veil where mean: KKuP cine electron accepting ^1r orlf ^; ufergroup] "e for an i-hydroxylariino group; A those for the formation of a 5- or ole- ^ liedri o-en aromatic Pinfes Required Atoms; V an electron withdrawing group with a positive Hammett Sigma Iated; 2
R a V, ^r asserstoffatora, an alkyl group nit 1 to carbon atoms or an aryl group having 6 to 30 carbon atoms; R is a divalent organic group with 1 to 3 atoms in the bivalent bond; m and q = 1 or 2 each; ρ and r are each numbers 1 or greater than 1; (R) - U'- a substituent in any position of the aromatic Ring structure Λ; E and Q enable electrophilic cleavage Group, where E represents an electrophilic center and 0 a monatomic bond group representing between E and X; η = 1, 2 or 3; 2
X together with Q represents a group providing a photographic reagent and X is a ballast group of such a size that the compound in the alkali-permeable layers of a photographic material is immobile and non-diffusing power. - 13d - 130008/0894 13.Record.-ir - ^ material after Ansnruc ¹¹ 1 °, dadurc ' ¹ ^ el.ennzei ch- , nan,
net, dai ^ / TTo development nit oneir ¹ rittel bev.'irVt, which is a r.illierhalo ^ enidentvi cl'lerverM ndunf and a ΠΙθΐ'ΐΓοηθη-Ήοηητ and da ^. further comprising a 3ildfarbstof f supplying Ver-iindun "a ^ a Bi Idfar stof f ⁷ supplying (BF, ND) compound or a dye-providing Pedox-Verl indun ^ (^ HDP eTbJn 14. Aufzeichnun ^ sn'.aterial NACB Ansnriichen 7 or 1, ⁿ denotes characterized ge, it daH of v / Eiteren a Rehälter a nit · alkaline Hntvickler ^contains:. _V ilt from ¹ Fntwickler ir recording material can be distributed. 15. Photographer! Small recording material according to claims 7, 8 or 10, characterized in that "the peroxide oxidation medium '.'hydrogen peroxide is. 130008/0894 BAGf-ORlQHSlAL-