DE2515213A1 - PHOTOGRAPHIC LIGHT SENSITIVE MATERIAL - Google Patents

Description

PATENT ADVOCATES A. GRÜNECKER

DIPL-ING

H. KINKELDEY

DH-ING

W. STOCKMAIR

O C 1 R O 1 1 CH-INQAeE (CALTECH

C i »P C I >> _κ SCHUMANN

, DR BEH NAT DIPL PHYS

P. H. JAKOB

DtPL-lNG

G. BE2OLD

DR REB. IWT - DIPt-CrtM

MUNICH

E. K. WEIL

DRHEfIOEClNG

8 MUNICH 22

MAXIMILIANSTRASSE 43

April 8, 1975 P 9125

LINDAU

Photo Film Co., Ltd.

Uo. 210, Nakanuma,
Minami Ashigara-Shi,
Kanagawa, Japan

Photographic light-sensitive material

The present invention relates to silver halide photographic light-sensitive material having improved image quality and Storage stability and a method for dispersing the so-called "DIR hydroquinone derivatives".

It is known that the image quality can be improved by using certain compounds which are a development inhibitor release in image-wise distribution. Examples of such compounds include the so-called "DIR developers" or "DIR-Hydrοchinone", as they are for example in the US Pat. Nos. 3,379,529 and 3,620,746 contained in a silver halide emulsion layer, an intermediate layer, a Filthsciu.cht. a protective layer, etc. of

TELEPHONE (O89j 2228 Ö2 TELEX OB-29 38Ο TELEGRAMS MONAP

colored or black and white photographic materials can be used. Hydroquinone derivatives can, however, be oxidized by air or in some other way, so that some of them turn into photographic development inhibitors Layers of unexposed photosensitive material may give up, or some of them may if they are in the material in an oxidized state, development inhibitors release in the course of development, regardless of the strength of the exposure. This has several disadvantages For example, the progress of development is inhibited, the sensitivity is lowered, the image density is reduced is decreased, the gradation becomes uneven, the shelf life of the unexposed photosensitive material becomes uneven deteriorates, etc.

It is therefore an object of the present invention to provide photographic light-sensitive material which so-called. "DIR hydroquinone derivatives" contains, with improved Image quality and good storage stability. The aim is to create a photosensitive material for color photography - which contains a "DIR hydroquinone derivative" and which has improved color image quality and at the same time has good storage stability. According to the invention a process is to be created to "DIR hydroquinone derivatives" dispersed in a hydrophilic colloid in which the oxidation or decomposition of the DIR hydroquinone derivatives is prevented.

In addition, a fine, granular dispersion of DIR hydroquinone derivatives should be produced be created that has an improved shelf life.

The invention thus relates to a photographic photosensitive Silver halide material with improved image quality, containing at least one hydrophilic colloid layer which is at least a reducing compound, preferably with one

509842/0927

Oxidation potential below about 1.5 volts, and at least one compound of the following formula (I)

S-Z

(D

contains where

A and A ¹ , which can be the same or different, $ ei ¹ ! What s he substance atom or a group hydrolyzable under alkaline conditions mean or where A ¹ can form a ring together with R or Q,

P, Q and R, which can be the same or different, each with a hydrogen atom, an alkyl group, an aryl group, a halogen atom, a hydroxyl group, a -Y-W- group (where Y is an oxygen atom or a sulfur atom and W represents an alkyl group, an aryl group or a heterocyclic group), a -S-Z group (where Z is a heterocyclic group Group which, when bound, is essentially photographically inert) or a heterocyclic group Mean group, where at least one ballast group with at least 5 carbon atoms is present in the molecule.

The invention relates to a photographic light-sensitive Material containing at least one hydrophilic colloid layer, the at least one reducing compound and at least one compound represented by the following general formula (D.

509842/0927

s-z

(D

contains where

A and A ', which can be the same or different, each represent a hydrogen atom or an alkali-hydrolyzable group or in which A ^f can form a ring together with R or Q,

P, Q and R, which can be the same or different
can, ö ^{e a} hydrogen atom, an alkyl group, an aryl group, a halogen atom, a hydroxyl group, a -YW group, in which Y is an oxygen atom or a sulfur atom and W is an alkyl group, an aryl group or a heterocyclic group, a -SZ- A group in which Z represents a heterocyclic group which is substantially photographically inert when bound, or a heterocyclic group wherein at least one ballast group having at least 5 carbon atoms is present in the molecule.

The invention thus relates to a photographic photosensitive Material, in particular a photosensitive color material, which contains at least one hydrophilic colloid layer, the at least one reducing compound having an oxidation potential below about 1.5 volts and at least a compound of the general formula (I)

509842/0927

S-Z

(I)

contains where

A and A ^! each represent a hydrogen atom or an alkali-hydrolyzable group, or in which A ¹ can form a ring together with R or Q, and

P, Q and R each represent a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, a -Y-W- group, in which Y is an oxygen atom or a sulfur atom and W is an alkyl group, represent an aryl group or a heterocyclic group, an -S-Z group, wherein Z is a heterocyclic group, which when bound are essentially photographically inert is, represents, or a heterocyclic group, wherein at least one ballast group having at least 5 carbon atoms is present in the molecule.

The invention relates in particular to a photosensitive material, in particular a photosensitive color material, containing at least one hydrophilic colloid layer containing a dispersion prepared by a DIR developer, in particular, in a hydrophilic colloid solution those of the general formula (I), in the presence of at least one reducing compound with an oxidation potential below about 1.5 volts, preferably from about 0.5 to 1.5 volts.

1 and 2 are layer arrangements of one embodiment of the photosensitive material of the present invention.

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As described above, the photographic photosensitive ones contain Materials a compound of the general formula (I)

S-Z

(D

A and A ¹ each represent a hydrogen atom or an alkali-hydrolyzable group (for example alkylcarbonyl, alkoxycarbonyl, alkyloxycarbonylcarbonyl, etc., in which the alkyl parts of each of these groups can contain 1 to 15 carbon atoms) or A ¹ can form a ring together with R or Q (for example an oxathiazole ring, etc.) »and

P, Q and R each represent a hydrogen atom, an alkyl group (for example, one having 1 to 32 carbon atoms like a methyl, ethyl, octyl, tert.-octyl, dodecyl, Pentadecyl, octadecyl group, etc.), a halogen atom (e.g. a chlorine atom, bromine atom, etc.), a hydroxyl group, a -Y-W group (where Y is an oxygen atom or a sulfur atom and W is an alkyl group, for example one with 1 to 18 carbon atoms such as a 2-hydroxyethyl, Ethoxycarbonylmethyl, 2-ethylhexyl, n-dodecyl, n-hexadecyl, n-octadecyl group, etc.), an aryl group (e.g. phenyl, tolyl, etc.) or a heterocyclic group (e.g. tetrazolyl, thiazolyl -, quinonyl group, etc.), a -S-Z group (where Z represents a heterocyclic group which, when bonded is essentially photographically inert) or a hetero-

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cyclic group ("for example a thiazolyl, oxazolyl, Benzothiazolyl, imidazolyl, etc.) »where in the molecule has at least one ballast group with at least 5 carbon atoms. The ones described above Alkyl groups can also be substituted with substituents such as a halogen atom (e.g. fluorine, bromine, chlorine, etc.), a hydroxyl group, an alkoxy group (e.g. methoxy, ethoxy, ethoxyethoxy, hexyloxy, dodecyloxy, etc.), a Aryloxy group (e.g. phenoxy, ρ-tert-butyiphenoxy, etc.), an aryl group (e.g. phenyl, tolyl, p-tridecanamidophenyl, Naphthyl etc.), an amino group (e.g. ethylamino, dodecylamino, diethylamino, N-methyl-N-dodecylamino, anilino, Toluidino, phenethylamino etc.), an acylamino group (e.g. formamido, acetamido, pivaloylamido, lauroylamido, stearoylamido, Benzoylamido etc.), an imido group, a carboxy group, an alkoxycarbonyl group (e.g. ethoxycarbonyl, Dodecyloxycarbonyl etc.), a carbamoyl group (e.g. tert, -butylcarbamyl, Diethylcarbamyl, isooctylcarbamyl, tolylcarbamyl etc.) or a sulfonamido group. These substituents can be further substituted.

Of the DIR hydroquinone derivatives used in the present invention can be used, preferred DIR hydroquinone derivatives are those of the general formula (Ia)

(Ia)

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wherein P, Q, R and Z each have the same meanings as defined in the general formula (i) above where at least one of the groups P, Q and R is a -Y-W- group, in which Y and W are each the same Have meanings as defined in the general formula (I), where at least one of the groups P, Q or R contains a ballast group.

The photographically inert heterocyclic groups represented by Z in the general formulas (I) and (Ia) can be, for example: a tetrazolyl group (e.g. 1-phenyltetrazolyl, etc.), a triazoyl group (e.g. 4-phenyl-1,2, 4-triazol-5-yl, 3-n-pentyl-4-phenyl-1,2,4-triazol-5-yl, etc.), a thiadiazolyl group (e.g. 2-methylthio-1,3,4-thiadiazol-5 -yl, 2-amino-1,3,4-thiadiazol-5-yl etc.), an oxadiazolyl group (e.g. 2-pentyl-1,3,4-oxadiazol-5-yl etc.), a tetraazaindenyl group (e.g. 6-methyl-1,3,3a, 7-tetraazainden-4-yl _s 6-n-nonyl-1,3,3a, 7-tetraazainden-4-yl, etc.), an oxazolyl group (e.g. benzoxazol-2-yl etc.), a thiazolyl group (e.g. benzothiazol-3-yl etc.), etc.

The ballast group included in the DIR hydroquinone derivatives, the used in the present invention contains at least 5 carbon atoms, preferably of 5 to about 32 carbon atoms. Aliphatic groups, those containing from 5 to 32 carbon atoms are particularly suitable as ballast groups.

Of the DIR hydroquinone derivatives used in the present Invention can be used, are particularly preferred DIR-hydroquinone derivatives represented by the general formula (Ib) are shown

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(Ib)

P, Q and R each represent a hydrogen atom, an alkyl group (e.g. methyl, ethyl, 1,1,3 »3-tetramethyl-butyl, n-pentadecyl, 2-propenyl etc.) »an aryl group (e.g. phenyl, p-tolyl, o-carboxyphenyl, o-methoxycarbonylphenyl, p-methoxyphenyl etc.), a halogen atom (e.g. chlorine, iodine, etc.), a -Y-W- group in which Y is an oxygen atom or a sulfur atom and ¥ is a Alkyl group (e.g. 2-ethylhexyl, n-dodecyl, n-hexadecyl, n-octadecyl, Hydroxylcarbonalmethyl, ethoxycarbonyimethyl, 2-hydroxyethyl etc.),. an aryl group (e.g. phenyl, p-tolyl, o-tolyl, m-tolyl, o-methoxy, carboxyphenyl, etc.), an alkoxy or aryloxy group (e.g. methoxy, phenoxy, o-octadecyloxycarbonyl-phenoxy, etc.), a heterocyclic Represent a group (e.g. 2-benzotriazolyl, 2-imidazolyl, etc.), or mean a heterocyclic group and

M is a phenyl group, a substituted phenyl group (e.g. ToIyI, XyIyI, Acetamidophenyl etc.), or a is a lower alkyl group (e.g. one having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc.).

An essential feature of the fiction according to en DIR hydroquinone derivatives is that the reducing power or the DIR activity of the hydroquinone derivatives by the introduction of the -Y-W groups (preferably those in which W is an alkyl or an aryl group) is increased, whereas their reducing power or DIR activity is generally lowered by the introduction of the -S-Z group. Another one essential feature of the DIR hydroquinone according to the invention

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derivatives is that if an aliphatic group with at least 5 carbon atoms is present as a ballast group, "preferably in the -W group of the molecule, the molecule not only becomes non-diffusible, but that the so-called "abnormal color formation" can be prevented. The term "abnormal color formation" means a phenomenon in which the image formed by color development using a primary aromatic amine as a developer, by the blue dyes used by the DIR hydroquinones as By-products are formed, is colored blue. The abnormal color formation can also be prevented, though the DIR hydroquinone derivatives according to the invention are used, in which Q has a meaning other than a hydrogen atom, or those in which a substituent is present per se in the 4- or 5-3-position of the hydroquinone. Another feature the fiction according to en DIR hydroquinone derivatives is that they can be manufactured without much difficulty. Other features will emerge from the description below.

Some examples of DIR hydroquinone derivatives according to the invention of the general formula (I) are given below.

Compound 1-1

2-n-Dodecylthio-5- (1'-phenyl-tetrazol-5'-ylthio) -hydroquinone.
Connection 1-2

2-n-octadecylthio-5- (1'-phenyl-tetrazol-5-ylthio) -hydroquinone
Connection 1-3

2-n-Hexadecylthio-5- (1 ^f -phenyltetrazol-5-ylthio) hydroquinone
Connection 1-4

2y2 ^! , 5'-dihydroxy-6 · - (1 "-phenyltetrazole-5" -ylthio) -4 ^! - (i "', 1"', 3 " ^f , 3"'- tetramethylbutyl) -phenylthio-benzoic acid

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Connection 1-5

2- [2 ', 5 ^f -dihydroxy-6' - (1 · -phenyltetrazol-5 "-yithio) -3 '- (i"', 1 "', 3"'»3"'-tetramethylbutyl)] - phenylthio-benzoic acid compound 1-6

2- (i'-Phenyltetrazol-5 * -yithio) -3-phenylthio-6- (1 ", 1", 3 ", 3" -tetramethylbutyl) hydroquinone compound 1-7

2- (1 · -Phenyltetrazol-5 '-yithio) -3-phenylthio · ^ - (1 ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone Compound 1-8

2,5-dihydroxy-6- (1'-phenyltetrazol-5 ^f -yithio) -4- (1 ", 1", 3 ", 3" -tetramethylbutyl) -phenyl thio-acetic acid compound 1-9

2- [2 ¹ ^ ¹ -dihydroxy-3 * -n-hexadecylthio-6 '- (1 "-phenyltetrazole-5" -yithio)] - phenylthio-benzoic acid compound 1-10

2-n-Hexadecylthio-5- (i'-phenyltetrazol-5'-yithio) -6-phenylthiohydroquinone
Compound 1-11

4 - (1 «-Phenyltetrazol-5 ^f -yithio) -5-hydroxy -? - (1", 3 ", 3", 3 "-tetramethylbutyl) -benzoxathiol-2-one Compound 1-12

2- [2 ", 5'-dihydroxy-6" - (1 "-phenyltetrazol-5" -yithio) -3 ^! - (1 "', 1"', 3 "', 3"' -tetramethylbutyl)] - phenylthio-benzoic acid methyl ester
Compound 1-13

2- [2 ^f , 5'-dihydroxy-6 »- (1" -phenyltetrazol-5 "-yithio) -4 ^f - (i" «, 1» », 3" ^f , 3 "'-tetramethylbutyl)] - phenylthio-benzoic acid methyl ester
Compound 1-14

2- [2 ', 5' -dihydroxy-3 '-n-pentadecylthio-6 · - (1 "-phenyltetrazole-5" -yithio)] -phenylthio-benzoic acid methyl ester Compound 1-15

2-n-Octyloxycarbony! Methyl thio-6-phenyl-3- (1'-phenyl tetrazol-5'-yithio) hydroquinone

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Compound 1-16

2-p-nitrophenylthio-3- (1'-phenyltetrazol-5'-ylthio) -

, 3 ", 3" -tetramethyl (butyl) hydroquinone

Compound 1-17

2- (2'-Methylthio-1 ', 3', 4'-thiadiazol-5 '-ylthio) -6- (1 ", 1", 3 ", 3" -tetramethylbutyl) hydroquinone Compound 1-18

3- (2'-Methylthio-1 S3 ¹ ^ '- thiadiazole ¹ -ylthio) -6- (1 ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone compound 1-19

2,3-Bis- (2'-methylthio-1 «, 3 ', 4'-thiadiazol-5-ylthio) -6- (1", 1 ", 3", 3 "-tetramethylbutyl) hydroquinone J.

Compound 1-20

2- (3'-n-pentyl-4 »-phenyl-1 ^f , 2«, 4'-triazol-5'-ylthio) -5- (1 ", 1", 3 "» 3 "-tetramethylbutyl) - hydroquinone compound 1-21

2- (6 »-Methyl-1 ^f , 3 ', 3a ^!, 3a ^f , 7 ^f -tetrazainden-4 ■ -ylthio) 6- (i", 1 ", 3", 3 "-tetramethylbutyl) -hydroquinone compound 1-22

2,3-bis- (6'-methyl-1 ^s , 3 ', 3a ^f , 7'-tetrazainden-4'-ylthio) -6- (1 », 1», 3 ", 3" -tetramethylbutyl) - hydroquinone compound 1-23

2-n-Hexadecylthio-5- (2 »» methylthio-1 ·, 3 ', 4 * -thiadiazol-5'-ylthio) -hydroquinone Compound 1-24

2- [2 ·, 5 '-dihydroxy-6' - (2 "-methylthio-1», 3 », 4» -thiadiazole-5 "-ylthio) -3 '- (1'", 1 »·, 3 "', 3"' -tetramethylbutyl)] -phenylthio-benzoic acid compound 1-25

2- (2'-AmInO-1 '^ ¹ , 4 ^t -thiadiazol-5 ^l -ylthio) -5- (1 ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone compound 1-26

2- [2 ^f , 5'-Dihydroxy-6 ^l - (2 "-amino-1", 3 ", 4» -thiadiazol-5 "-ylthio) -4- (1» ^f , 1 "', 3" ·, 3 "'-tetramethylbutyl)] -phenylthiobenzoic acid

509842/092

Connection 1-27

2- (2'-Amino-1 ^ 3 ^!, 4 »-thiadiazol-5'-ylthio) -3-ndodecylthio-6- (1", 1 ", 3", 3 "-tetramethylbutyl) hydroquinone compound 1- 28

2- (6 * -t-Butyl-1,3,3a, 7-tetrazainden-4-ylthio) -6- (1 ", 1" t 3 " t 3" -tetramethylbutyl) hydroquinone compound 1-29

2- (6'-n-Nonyl-1 ', 3', 3a ', 7'-tetrazainden-4 · -ylthio) -6- (1 », 1", 3 ", 3" -tetramethylbutyl) -hydroquinone Connection 1-30

2- (4 'phenyl-1 ^r, 2 x 4 "-triazöl-5' -ylthio) -5- (1 ', ^{1! R,} 3"> 3 "-tetraraethylbutyl) hydroquinone compound 1-31

2- (2 ^I -phenyl-1 ', 3 ^l , 4' ~ oxadiazol-5-ylthio) -5- (i ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone compound 1-32

2- (1 ^f -phenyltetrazol-5'-ylthio) -5-n-octyloxycarbonylmethylthio-hydroquinone compound 1-33

2-t-Dodecylthio-5- (1'-phenyltetrazole-5 ^f -ylthio) hydroquinone
Compound 1-34

2- (Benzoxazol-2'-ylthio) -5-n-octydecyl-hydroquinone Compound 1-35

2- (2'-Methylphenylthio) -6-n-octadecylthio-3- (1'-phenyltetrazole-5 "-ylthio) -hydroquinone Compound 1-36

2-n-Octyloxycarbonylmethylthio-3- (i-phenyltetrazol-5'-ylthio) -6-p-tolyl-hydroquinone Compound 1-37

2-Ethoxycarbonylmethylthio-6-n-hexadecylthio-3- (1'-phenyl-tetrazol-5'-ylthio) -hydroquinone Compound 1-38

2-phenylthio-3- (1'-phenyltetrazol-5'-ylthio) -5-ndo de cylthio-hydro quinone

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Link; 1-39

2-t-octyl-5- (1'-phenyl-tetrazol-5'-ylthio) -hydroquinone
Compound 1-40

2-t-octyl-6- (1'-phenyl-tetrazol-5'-ylthio) -hydroquinone
Compound 1-41

2-n-Pentadecyl-5- (1'-phenyltetrazol-5 ^f -ylthio) hydroquinone
Compound 1-42

2-n-octadecylthio- (X), (X ¹ ) -bis- (i'-phenyltetrazol-5 ^f -ylthio) -hydroquinone Compound 1-45

2- (4 · -Methyl! Phenyl) - (X) - (1 ^! -Phenyltetrazol-5'-ylthio) -hydroquinone Compound 1-44

2-t-octyl-6- (2 »-methylthio-1 ', 3' ^ '-thiadiazol-S'-ylthio) -hydroquinone Compound 1-45

2-n-Pentadecyl-5- (2 · -methylthio-1 ^f , 3 ', 4 ^f -thiadiazol-5'-ylthio) -hydroquinone compound 1-46

2-t-octyl-5- (2 "-amino-1 ·, 3 ', 4"-thiadiazol-5'-ylthio) -hydroquinone
Compound 1-47

2-n-Hexadecylthio-5- (2'-methylthio-1 », 3 ^f , 4'-thiadiazol-5 ^f -ylthio) -hydroquinone Compound 1-48

2-t-octyl-5- (2'-n-pentyl-1 * -phenyl-1 ', 3', 4 ^f -triazol-5'-ylthio) -hydroquinone.

The DIR hydroquinone derivatives used in the present invention can be prepared by the addition reaction of mercapto compounds with benzoquinones, as described in US Pat 3,379,529.

2/0927

Exemplary manufacturing methods are explained below. Unless otherwise stated, all parts, percentages, ratios, etc. are expressed by weight.

Manufacturing process 1 (compound 1-3)

2-n-Hexadecylthio-p-benzoquinone (315 g) is added to methanol (11) and the mixture is stirred in an ice bath. To this mixture is added dropwise a solution of 1-phenyl-5-mercaptotetrazole (155 g) in methanol (800 ml). After the addition is complete, the resulting mixture is stirred for 3 hours in an ice bath and 8 hours at room temperature (ie approximately 20 to 30 ^° C.) in order to precipitate the crystals.

The crystals formed are filtered off and recrystallized from benzene. 350 g of 2-n-hexadecylthio-5- (i'-phenyltetrazol-5-ylthio) hydroquinone are obtained, Mp 129-131 ° C.

Manufacturing process 2 (compound 1-6)

2- (i-phenyltetrazol-5-ylthio) -6- (1 », 1», 3 ", 3" -tetramethylbutyl) -p-Benzoquinone (15 g) is added to methanol (150 ml). A solution of thiophenol is added to this mixture (4.5 g) in methanol (25 ml). After the addition is complete the resulting mixture was stirred in an ice bath. The crystals formed are filtered off and removed from a solvent mixture recrystallized from hexane and ethyl acetate.

2- (i'-Phenyltetrazol-S'-ylthio ^ -phenylthio-e- (1 ", 1", 3 ", 3" -tetramethylbutyl) hydroquinone is obtained (7.5 g), mp i47 ° C

Manufacturing process 3 (compound 1-20)

3-Mercapto-5-n-benzyl-4-phenyl-1,2,4-triazole (13 g) is in Dissolve methanol (200 ml) and stir the solution in an ice bath. 2- (i ', 1', 3 ', 3' ·

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Tetramethylbutyl) p-benzoquinone (12 g). After the Addition, the resulting mixture is stirred for 2 hours in an ice bath, left to stand overnight and at reduced Focused pressure. Diethyl ether is added to the residue, the precipitated crystals are filtered off and the crystals are recrystallized from ethyl acetate.

2- (3-n-Pentyl-4 ^f -phenyl-1, 2,4-triazol-5'-yl times' (i% 1 \ 3% 3 "-tetramethylbutyl) -hydroquinone (5) g, m.p. .198 ° C.

The DIR hydroquinone derivatives according to the invention of the general formula I, in particular those that are characterized by the general Formula (Ib) shown have strong DIR activities. On the other hand, they have a tendency to be oxidized especially if they are in a solvent such as ethyl acetate, ethyl butyrate, acetone, ethoxyethoxyethyl acetate, Tricresyl phosphate, dibutyl phthalate, acetyl tributyl citrate, etc. are dissolved and form a dispersion. The quinones produced by oxidation of the DIR hydroquinone derivatives possess extremely low solubility and nucleate deposits that are formed in the dispersions, and cause desensitization. These disadvantages can be avoided by the presence of the reducing compounds according to the invention be eliminated.

After adding the DIR hydroquinone derivatives of the present invention to a molten emulsion, the emulsion is preferred applied to a support as soon as possible. Through this . can affect the shelf life of the photosensitive manufactured Materials are improved, and the deterioration in photographic properties (i.e., sensitivity, gradation, fog, etc.) of the photosensitive material caused by coexistence the DIR hydroquinone derivatives and silver halide grains can be prevented.

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The reducing compounds or reducing agents used in the present invention preferably have an oxidation potential equal to or below about 1.5 volts, most preferably from 1.5 to 0.5 volts, particularly preferably from 1.2 to 0.7 volts. The oxidation potential (Eox) can easily be measured. Methods for determining the oxidation potentials are described by A. Stanienda in Naturwissenschaften, Vol. 47, page 353 and page 512 (1960), by P. Delahay in New Instrumental Methods in Electrochemistry, Interscience Publishers (1960), by L. Meits in Polarographic Techniques , Vol. 2, ibid (1965), and others. The E _QX values are measured in a 1 × 10 to 1 × 10 "" mole acetonitrile solution containing sodium perchlorate as a supporting electrolyte, using a rotating platinum electrode and a saturated calomel electrode as a reference electrode. The measured values contain errors of up to 100 mV due to the influence of the liquid-connection potential difference, the inaccuracies in the correction of the liquid resistance in the sample solution, etc. The reproducibility of the values can be ensured by using a standard sample as a comparison. The E ^ value is the potential under-

OX

that is required to transfer an electron, which occupies the highest energy level, from a reducing compound to be measured to the anode of the ·. To transfer electrode, ie the Ε _Λ value is a measure of the reducibility of a connection.

The reducing compounds that can be used in the present invention can be be either inorganic or organic compounds, and they can be selected from compounds commonly used called antioxidants. Of these compounds, the following are suitable: phenol derivatives, in particular dihydroxybenzene derivatives, e.g. pyrocatechols and tocophenols, and trihydroxybenzene derivatives, e.g. pyrogallols etc., naphthol

509842/0927

derivatives, especially dihydroxynaphthalene derivatives, trihydroxynaphthalene derivatives etc., ascorbic acid derivatives, reductones, aromatic amino compounds, hydroxyamino compounds, Tin (II) salts, dithio compounds, etc. The water-soluble ones reducing compounds used in the present invention can be added to a colloidal solution the DIR hydroquinone derivatives in the form of an aqueous solution thereof be added. Oil-soluble reducing compounds which can be used in the present invention be used together with the DIR-Hydr ο quinone derivatives, by dissolving them in an organic solvent as a dispersion medium. The reducing compounds used in of the present invention can be used with the DIR hydroquinone derivatives during manufacture or before the dispersion of the DIR hydroquinone derivatives are premixed.

The reducing compounds used in the present invention can be used can be selected from Compounds described in U.S. Patents 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659,

2 732 300, 2 735 765, 2 710 801, 2 816 082, 3 457 079,

3 069 262, 2 735 765, 3 432 300, 3 573 050, 3 574 627,

3,698,909 and 3,764,337, in published Japanese patent application 13496/68 et al.

The reducing compounds used in the present invention can also be selected from compounds disclosed by Gerald Scott in Atmospheric Oxidation and Autooxidants, Elsevier Publishing Company (1965), and by N.M. Emanuel and Yun.Lyaskovskaya, translated by K.A. Allen, in The Inhibition of Fat Oxidation Process, Pergamon Press (1967).

As indicated above, the reducing compounds used in the present invention are preferred

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an oxidation potential below about 1.5 volts. The reducing ones However, compounds can be temporarily protected by an alkaline hydrolyzable group.

As reducing compounds used in the present invention, phenol derivatives are at least contain one or two aliphatic groups which have not less than 8 carbon atoms and which are defined by the the following general formula (II) can be shown, particularly useful:

OA "
I.

Λ U «

OA "

■ R-

(H)

PL is a hydrogen atom or a straight chain or branched-chain alkyl group with 8 to 20 carbon atoms (e.g. n-octyl, t-octyl, n-decyl, n-dodecyl, 1-methylundecyl, n-pentadecyl, 1-methylpentadecyl, n-octadecyl, etc.) means,

Rp is a hydrogen atom or a straight-chain or branched-chain alkyl group with 8 to 20 carbon atoms (e.g. n-octyl, t-oetyl, n-decyl, n-dodecyl, 1-methylundecyl, n-pentadecyl, 1-methylpentadecyl, n-octadecyl, etc.) means,

A "and A"' each represent a hydrogen atom or an alkali hydrolyzable group (e.g. alkylcarbonyl, alkoxycarbonyl, alkyloxycarbonylcarbonyl, etc., in which the alkyl parts of each of these groups can contain 1 to 15 carbon atoms),

and where the benzene ring is additionally provided with an alkyl group containing 1 to 8 carbon atoms (e.g. methyl, ethyl, n-butyl, t-butyl, amyl, isoamyl, n-hexyl, n-octyl, t-octyl, etc.), a

9842/0927

Halogen atom (e.g. fluorine, chlorine, bromine etc.), an aryl group (e.g. phenyl, tolyl, methoxyphenyl, chlorophenyl, naphthyl), a hydroxyl group, a heterocyclic group (e.g. thiazolyl, oxazolyl, benzothiazolyl, imidazolyl, etc.) and similar groups can be substituted. The alkyl groups represented by IL and Rp can also be used with Substituents such as with a halogen atom (e.g. fluorine, bromine, Chlorine, etc.), a hydroxyl group, an alkoxy group (e.g. methoxy, ethoxy, ethoxyethoxy, hexyloxy, dodecyloxy, etc.), an aryloxy group (e.g. phenoxy, p-tert-butylphenoxy, etc.), an aryl group (e.g. phenyl, tolyl, p-tridecanamidophenyl, naphthyl, etc.), an amino group (e.g. ithylamino, dodecylamino, Diethylamino, N-methyl-N-dodecylamino, anilino, Toluidino, phenethylamino etc.), an acylamino group (e.g. formamido, acetamido, pivaloylamido, lauroylamido, stearoylamido, Benzoylamido etc.), an imido group, a carboxy group, an alkoxycarbonyl group (e.g. ethoxycarbonyl, Dodecyloxycarbonyl etc.), a carbamoyl group (e.g. tert-butylcarbamyl, Diethylcarbamyl, isooctylcarbamyl, tolylcarbamyl etc.) or a sulfonamido group. These substituents can be further substituted.

Some of these compounds are described, for example, in US patents 2,336,327, 2,728,659, 2,835,579 and 3,700,453 among others described.

Specific examples of suitable reducing compounds are listed below:

Compound R-1

2,5-Di-tert-octylhydroquinone Compound R-2

2-n-Octadecylthiohydroquinone Compound R-3

2-n-hexadecylhydroquinone
Compound R-4

2-n-octadecylthio-5-tert-octy / hydroquinone

5 09842/0927

Compound R-5

Hydroquinone Compound R-6

2- (3 * -Me thyxphenyl) -hydroquinone compound R-7

Ascorbic acid compound R-8

Ascorbic Acid Palmitate Compound R-9

2,3-Dihydroxynaphthalene Compound R-10

7,7'-dimethyl-6,6 »-dihydroxy-4,4,4 * 14- · -tetramethylbis-2,2'-spirochroman Compound R-11

2,3,5-trimethylhydroquinone compound R-12

Sodium bisulfite compound R-15

N-methyl-N- (ß-methylsulfonamidoethyl) -p-aminophenol compound R-14

Hydroxylamine compound R-15

Pyrogallol compound R-16

Gallic acid compound R-17 diaminodurol

The DIR-hydroquinone derivatives or the DIR-hydroquinone derivative containing the be used in the present invention, respectively, may in an organic solvent such as tricresyl phosphate, dibutyl phthalate, a fatty oil which is liquid at ordinary temperature (ie 20 to 30 ⁰ C), For example, acetyl tri- (2-ethylhexyl) citrate, tributylglycerol, N, N-diethylcapramide, etc., dissolved v / ground and in a hydrophilic colloid solution in

509842/0927

Presence of one or more reducing compounds are dispersed. Hydrophobic or oil-soluble reducing agents Compounds, e.g., compounds R-1, R-2, R-3, R-4, R-8, R-9, R-10, R-11, etc., can be used by they are dissolved in a high-boiling solvent. ¥ water-soluble reducing compounds, for example the compounds R-5, R-6, R-7, R-12, etc., can be used directly in a hydrophilic colloid used as a dispersion medium can be incorporated.

The amount of reducing compounds, preferably the hydroquinone derivatives, represented by the general formula (II) used together with the DIR hydroquinones is not critical, it is preferably from about 1 to 70 mol%, particularly preferably from 10 to 60 mol%, based on the total moles of the reducing compound and the DIR hydroquinone derivatives of the general formula (I).

The DIR hydroquinone derivatives and / or the reducing compounds, in particular, the hydroquinone derivatives represented by the general formula (II) can be found in an emulsion is incorporated using a method used for incorporating a coupler into a Emulsion used, with or without making a dispersion thereof. In the case of light-sensitive color materials, the Proportion of DIR hydroquinone derivatives of the general formula (I), which are used according to the invention are below 50 mol% and is preferably 30 to 1 mol-6 based on the amount on coupler used. After the emulsion of the DIR hydroquinone derivatives according to the invention to form a silver halide emulsion is added, a support is coated with the silver halide emulsion substantially immediately thereafter. The dispersion The DIR hydroquinone derivatives can be prepared by placing them in a high-boiling organic solvent such as tricresyl phosphate, dibutyl phosphate, a fatty oil,

50 9 8 42/0327

which is liquid at normal temperature, e.g. acetyltri- (2-ethylhexyl) citrate, Tributylglycerin etc., waxes, higher fatty acids and their esters, N-n-butyl acetanilide, Ν, Ν-Diethylcapramid and others dissolve and then the solution in a dispersed hydrophilic colloid solution such as gelatin, according to the method described, for example, in US patents 2 304 939, 2 322 027, 2 801 170, 2 801 171, 1 949 360 and in German patent specification 1 143 707 will. They can also be added according to the method described in U.S. Patent 3,379,529. They can also be dispersed in a hydrophilic colloidal solution such as gelatin by mixing together with the synthetic polymer uses an organic solvent.

The oxidation or the change in quality of the DIR hydroquinone compounds can be prevented more effectively by having at least one organic acid, especially those that have at least contain a carboxyl group, such as citric acid, tartaric acid, fumaric acid, succinic acid, salicylic acid, phthalic acid, Polyacrylic acid, glycolic acid, ethylenediaminetetraacetic acid etc. or the esters thereof (a .B. Preferably the alkyl esters having 1 to 12 carbon atoms in the alkyl parts thereof) or salts (e.g. alkali metal salts such as sodium, potassium etc., ammonium, trimethylammonium etc.), to a high-boiling organic solvent and / or a hydrophilic one Colloid solution together with the DIR hydroquinone derivatives and / or the reducing compounds, especially the Hydroquinone derivatives represented by the general formula (II) are represented, admits.

The mean particle size of the dispersion which is used according to the invention can vary within a wide range, but the mean particle size is preferably from about 0.05 to 2 / U, more preferably from 0.05 to 0.5 / u

509842/0927

Examples of hydrophilic protective colloids, which are in a hydrophilic protective colloid layer and a hydrophilic Colloid solution can be used according to the invention are in addition to gelatin, colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose etc., saccharide derivatives such as agar-agar, sodium alginate, Starch derivatives, etc., synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylic acid copolymers, Polyacrylamide or derivatives and partially hydrolyzed products thereof. If necessary, a compatible Mixture of two or more of these colloids can be used. Among these colloids, gelatin is the most common used. The gelatin can be partially or completely replaced by a so-called gelatin derivative, i.e. gelatin that has been treated or modified with a compound that contains a group linked to the amino, imino, hydroxy, or carboxy functional groups included in the Gelatin molecules are present, can react, or through a gelatin graft polymer, i.e. one gelatin, onto the other Polymer chains have been grafted on, as well as through synthetic polymers.

Examples of compounds that can be used for the preparation of the gelatin derivatives described above are the isocyanates, acid chlorides and acid anhydrides, as described in US Pat. No. 2,614,928, the acid anhydrides, as described in US Pat. No. 3,118,766, the bromoacetic acids as described in the published Japanese patent application 5514/64 are described, the phenyl glycidyl ethers, as they are in the published Japanese patent application 26845/67 are described, the vinyl sulfones, as they are in the US-PS 3,132,945 are described, the N-AlIylvinylsulfone, as described in GB-PS 861 414, the maleic amides as described in US-PS 3,136,846, the Acrylonitriles, as described in US Pat. No. 2,594,293, the polyalkylene oxides, as described in US Pat. No. 3,312,553.

509842/0327

ben are the epoxy compounds as published in the Japanese Patent Application 26845/67, the acid esters as described in U.S. Patent 2,762,639, the alkane sultones as described in GB-PS 1,033,189 are, among others

Can be used as graft polymers that are grafted onto gelatin a variety of polymers or copolymers made from monomers such as acrylic acid, methacrylic acid, or the esters, Amides or nitriles, derivatives thereof, etc., or styrene, which are generally referred to as vinyl monomers, are used will. A number of examples of these polymers or copolymers are given, for example, in US patents 2,763,625, 2,831,767 and 2,956,883, in Polymer Letters, 5, 595 (1967), in Phot.Sei.Eng., 9, 148 (1965) and in J.Polymer Sci., A-1, 9, 3199 (1971). From these connections are hydrophilic vinyl polymers which are to some extent compatible with gelatin, for example polymers or copolymers of acrylamide, methacrylamide, hydroxyalkylacrylamide, hydroxymethacrylamide, etc. are particularly preferred.

Examples of hydrophilic colloid layers which the dispersions of the present invention can contain are additional layers such as a protective layer, an antihalation layer, an intermediate layer, a filter layer, an anti-radiation layer and a layer that prevents contamination during development, as well as light-sensitive silver halide emulsions layers.

Color photographic materials in the present invention may contain a coupler. Examples of suitable couplers that can be used in The present invention may be used include 4- and 2-equivalent couplers, particularly couplers that use a form yellow color and which are represented by the following general formula (III):

509842/0 927

'J

CH-Z

(III)

R,

PU is a primary, secondary or tertiary alkyl group (e.g. methyl, propyl, η-butyl, tert-butyl, hexyl, 2-hydroxyethyl, 2-phenylethyl, pentadecyl, etc.), an aryl group (e.g. phenyl, 2,4 ~ di-tert-phenyl, etc.), an alkoxy group (e.g. methoxy, ethoxy, benzyloxy, etc.), an aryloxy group (e.g. phenoxy, etc.), a heterocyclic group (e.g. Quinolinyl, pyridyl, benzofuranyl, oxazolyl, etc.), an amino group (e.g. methylamino, diethylamino, phenylamino, tolylamino, 4- (3-sulfobenzamino) -anilino, 2-chloro-5-acylaminoaniline, 2-chloro-5-alkoxycarbonylanilino, 2-trifluoromethylamino etc.), an acylamino group (e.g. alkyl carbamido such as ethyl carbamido, Arylcarbamido, heterocyclic carbamido such as benzothiazolylcarbamido, Sulfoamido, heterocyclic sulfoamido, etc.), means an ureido group (e.g. alkylureido, arylureido, heterocyclic ureido, etc.), among others,

R ^ is an aryl group (e.g. naphthyl, phenyl, 2,4,6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl, 4-methylphenyl, 4-acylaminophenyl, 4-alkylaminophenyl, 4-trifluoromethylphenyl, 3,5-dibromophenyl, etc.), one heterocyclic group (e.g. benzofuranyl, benzothiazolyl, Quinolinyl etc.), an alkyl group (e.g. methyl, t-butyl, benzyl etc.) and

Z represents a hydrogen atom or a group that is released during color development, e.g. a thiocyano group, an acyloxy group, an alkoxy group, an alkoxycarbonyloxy group, an aryloxycarbonyl group, a disubstituted amino group, an arylazo group, a heterocyclic group Azo group, etc., as for example in the US patent

509842/0927

Writings 3,419,319, 3,252,924, 3,311,476, and 3,227,550, in U.S. Patent Applications 461,204, filed April 15, 1974, and 471,639, filed May 20, 1974, et al are}

purple forming couplers represented by the general formula (IV):

R ₅ -CO-CH-CO-NH-R ₆ (IV)

Z ₂

Rt- a primary, secondary or tertiary alkyl group (e.g. tert-butyl, 1,1-dimethylpropyl, 1,1-dimethyl-1-methoxyphenoxymethyl, 1,1-dimethyl-1-ethylthiomethyl etc.), a Aryl group (e.g. phenyl, alkylphenyl such as 2-methylphenyl, 3-octadecylphenyl etc., alkoxyphenyl such as 2-methoxyphenyl, 4-methoxyphenyl etc.), halogenated phenyl, 2-chloro-5-alkylcarbaminophenyl, 2-chloro-5- [cc- (2,4-di-tert-aminophenoxy) -butyramido] -phenyl, 2-methoxy-5-alkylamidophenyl, 2-chloro-5-sulfoamidophenyl etc.) means

R _{6 is} a phenyl group (e.g. 2-chlorophenyl, 2-halo-5-alkylamidophenol, 2-chloro-5- [cc- (2,4-di-tert-amylphenoxy) acetamido] phenyl, 2-chloro-5 - (4-methylphenylsulfoamido) -phenyl, 2-methoxy-5- (2,4-di-tert.-amylphenoxy) -acetamidophenol, etc.) and

Z ₂ denotes a hydrogen atom or a group which is released upon color development, for example a halogen atom, an acyloxy group, an aryloxy group, a heterocyclic carbonyloxy group, a sulfimido group, an alkylsulfoxy group, an arylsulfoxy group, a phthalimido group, a dioxazolidazolide group, a dioxazolidazolide group Dioxothiazolidinyl group, a dioxomorpholinyl group, etc., as described, for example, in U.S. Patents 3,227,550, 3,253,924, 3,277,155, 3,265,506, 3,408,194 and 3,415,652, in FR-PS 1,411,384, in GB-PS 994 490, 1 040 710 and 1 118 028, in DT-OS 2 056 941, 2 163 812, 2 213 461 and

509842/0927

2,219,917, filed in U.S. Patent Application 469,923 on May 14, 1974, et al .;

and cyan-forming couplers represented by the general formulas (V) and (VI) are shown

P '^ -10

(V)

(VI)

Ry means a substituent as he generally does is used in cyan couplers, e.g. a carbamyl group (e.g. alkylcarbamyl, arylcarbamyl such as phenylcarbamyl, heterocyclic carbamyl such as benzothiazolylcarbamyl etc.), a sulfamyl group (e.g. "alkylsulfamyl, arylsulfamyl such as Phenylsulfamyl, heterocyclic sulfamyl, etc.), an alkoxycarbonyl group, an aryloxycarbonyl group, etc.,

Ro is an alkyl group, an aryl group, a heterocyclic group Group, an amino group, a carbamido group (e.g. alkylcarbamido, arylcarbamido, etc.), a sulfamido group, denotes a sulfamyl group, a carbamyl group, etc.,

509842/0927

Rq, Rq and R ₁₁ each denote the groups defined under Rq and further each denote a hydrogen atom, a halogen atom, an alkoxy group, and others

Zz denotes a V / assers to ff atom or a group which can be released during color development, for example a halogen atom, a thiocyano group, a cycloimido group (e.g. maleimido, succinimido, 1,2-dicarboxyimido, etc.), an arylazo group, a heterocyclic group Azo group means as described in U.S. Patents 2,474,293, 2,521,908, 2,423,730, and so on.

To make the coupler non-diffusible, one or several groups that have a hydrophobic residue with 8 to 32 carbon atoms included, are introduced as a ballast group in the coupler molecule. The ballast group can with the The basic structure of the coupler can be connected directly or via a bond such as an ether, carbamido, suIfamido, Ureido, ester, imido, carbamoyl or sulfamony bond.

Some examples of ballast groups are described in the examples for the DIR couplers according to the invention.

Examples of suitable ballast groups are the following:

(I) Alkyl groups and alkenyl groups, _{e.g. -CH 2} -CH- (C ₂ H ₅ ) ₂ , -C ₁₂ H ₂₅ , -C ₁₆ H ₃₃ and C ₁₇ H ₃₃

(II) Alkoxyalky! Groups such as those published in the Japanese Patent Application 27563/64, e.g.

-C: H ₂ ) ₃ -O- (CH ₂ ) ₇ CH ₃ and (III) alkylaryl groups, e.g.

509842/0927

C ₂ H ₅

C, H _o (t)

and

(IV) alkylaryloxyalkyl groups, e.g.

-CHpO-

-CJL-, U)

-GHÖ- / \> - C II (t)

CH ₇

and

-CHO-

-CH ₂ O

CHz-C-CH- -> I >

(V) Acylamidoalkyl groups such as those described, for example, in U.S. Patents 3,337,344 and 3,418,129, e.g.

509842/0927

and

(VI) alkoxyaryl groups and aryloxyaryl groups, 2. B-.

- ^ GC-, H ,, (n)

and

⁰ '

¹ ^ ¹ " ⁰

(VII) Groups that have both a long chain aliphatic group contain such as an alkyl or alkenyl group as well as a water-solubilizing group such as a carboxyl group or sulfo group, e.g.

CH-CiI-CH-C ₁₆ H ₃₃

and

CH ₂ CGCI]

-CH-C-. .H-SO-, H

(VIII) alkyl groups substituted with an ester group, e.g.

COOC ₂ IL.

-CH ₂ -CIi ₂ -CDOC ₁₂ H ₂₅ ( si)

509842/0927

BATH ORIGINAL

(IX) alkyl groups substituted with an aryl group or a heterocyclic group, e.g.

CH ₂ -CH _? -y

and

COGCH ₇

(η)

(X) aryl groups substituted with an aryloxyalkoxycarbonyl group, e.g.

i ₁₁ (t)! ^1]

_ // Vv-COOCH ₂ CO

₂ CO- ^ X ^ -C

CH ₃

Typical examples of couplers used in the present invention can be used are described below. However, the invention is not limited to these examples.

Yellow coupler Y-1

α- {3- [α- (2,4-Di-tert -amylphenoxy) -butyramido] -benzoylI-2-methoxyacetanilide

509842/0927

α-Acetoxy-α-3- [γ- (2,4-di-tert-amylphenoxy) butyramido] benzoyl-2-methoxyacetanilide

N - (^ - Anisoylacetamidobenzenesulfonyl) -N -benzyl-N-toluidine Y-4

oc- (2,4-Dioxo-5,5-dimethyloxazolidinyl) -a-pivaloyl-2-chloro-5- [a- (2,4-di-tert-amylphenoxy) butyramido] acetanilide

α- (4-Carboxyphenoxy) -α-pivaloyl-2-chloro-5- [cc- (2,4-di-tert-amylphenoxy) butyramido] acetanilide Y-6

a- [3- (1-Benzyl-2,4-dioxo) hydantoin] -a-pivaloyl-2-chloro ~ 5- [ cc- (2,4-di-tert-amylphenoxy) butyramido] acetanilide

α- (4-Methoxybenzoyl) -a-3,5-dioxomorpholino) -5 - [; y- (2,4-di-tert-amylphenoxy) butyramido] -2-chloroacetanilide

Purple coupler M-8

1- (2,4,6-Trichlorophenyl) -3- [3- (2,4-di-tert-amylphenoxy-acetamido) -benzamido] -5-pyrazolone M-9

1- (2,4,6-Trichlorophenyl) -3- {3- [oc- (2,4-di-tert-amylphenoxy) -acetamido] -benzamidqf -4-acetoxy-5-pyrazolone M-1Q

1- (2,4,6-Trichlorophenyl) -3-tridecylamido-4- (4-hydroxyphenyl) azo-5-pyrazoion M-11

1- (2,4,6-Trichlorophenyl-3 - [(2-chloro-5-tridecanoylamino) aniline] -5-pyrazolone M-12

1- (2,4,6-Trichlorophenyl) -3- (2-chloro-5-tetradecyloxycarbonyl) -anilino-4- (1-naphthylazo) -5-pyrazolone

509842/0927

1- (2,4-Dichloro-6-methoxyphenyl) -3- [(2-chloro-5-tridecanoylamino) '- anilino] -4-benzyloxycarbonyloxy-5-pyrazolone Μ-14

1- (2,4,6-Trichlorophenyl) -3- £ 3 - [(2,4-di-tert-amylphenoxy) -acetamido] -benzamido} ^ -piperidino-S -pyrazolone M-15

1- (2,4,6-Trichlorophenyl) -3- ^ 2-chloro-5- [a- (2,4-di-tert-amy! Phenoxy) -butyramido] -anilinoJ-4-N-phthalimido-5- pyrazolone
M-16

1- (2,4,6-trichlorophenyi) -3- (chloro-5-tetradecylaminoanilino) -4- (3-methyl-4-hydroxyphenylazo) -5-pyrazolone

Blue ^ rünkuppler

1-hydroxy-N- {γ- (2,4-di-tert-amylphenoxypropyl)] -2-naphthamide
C-18

1-hydroxy-4- [2- (2-hexyldecyloxycarbonyl) phenylazo] -2- [N- (1-naphthyl)] naphthamide

1-Hydroxy-4-chloro-N- [γ- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide
C-2Q

5-methyl-4,6-dichloro-2- [α- (3-n -pentadecylphenoxy) butylamino] phenol
C-21

1-hydroxy-4- (2-ethoxycarbonylphenylazo) -N- (2-ethylamyl) -2-naphthamide.

The DIR hydroquinone derivatives used in the present invention can be used together with the DIR couplers described in U.S. Patents 3,227,554, 3,148,062, 3,617,291, 3,733,201, 3,632,345, 3,622,328, and so on

509842/0927

interlayer color correction couplers (ICC couplers), as described in U.S. Patent Application 454,525, filed March 25, 1974, etc. ", or with the organic compounds that act as interlayer

interaction activators can be used. Examples such compounds include the couplers of the following formula (VII):

C _p -Z ₄ (VII)

C represents a coupler moiety capable of interacting with the oxidation product of a primary aromatic amine color developer to couple, and

Ζλ means an organic group used when coupling is released with the oxidation product of an aromatic primary amine color developer and after the release can diffuse and inhibit development.

C may be selected from 4-equivalent couplers used in color photosensitive materials, for example a 5-pyrazolone couplers, a cyanoacetylcoumarone, an indazolone, a acylacetamide, a Pivaloylacetamidkuppler, a naphthol, a phenol coupler, inter alia, Zr may be a heterocyclic group containing 1 a -Triazolring or a 1-diazole is how it is in the US Patent application 454,525, filed March 25, 1974., or a residual group as described in US Patents 3,227,554, 3,617,291, 3622 528, 3,632,373, 3,620,745, 3,620,747, 5,615,506 and 3 " 617,291 described in British Patents 1,201,110, 1,261,061, 1,269,075 and 1,269,073.

The DIR hydroquinone derivatives and / or the reducing compounds, in particular hydroquinone derivatives, which by the general formula (II) can be represented, together with an organic activator compound for a; Inter-image interplay used, for example, in

609842/0927

U.S. Patent Application 484,742, filed July 1, 1974 U.S. Patents 3,536,487, U.S. Defensive Publications T 909 and T 909 023, DT-OS 2,043,943 and 2,043,944, among others will.

Examples of these compounds are described below.

ICC uncolored coupler ICC-22

α-Benzoyl-cc- (2-benzothiazolylthio) -4- [N- (γ-phenylpropyl) -N- (4-tolyl) ~ sulfamyl] -acetanilide ICC-23

1- £ 4- [γ- (2,4-di-tert-amy! Phenoxy) -butyraraido] -phenylj -3-piperidinyl-4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone ICC-24

1- (2,4,6-Trichlorophenyl) -3- {4- [α- (2,4-di-tert-araylphenoxy) -butyramido] -aniline} -4- (1-phenyl-5-tetrazolylthio) -5-pyrazolone ICC-25

1- £ 4- [cc- (2,4-di-tert-amylphenoxy) -acetamido] -phenylj-3-methyl-4- (5- or 6-bromo-1-benztriazolyl) -5-pyrazolone ICC- 26th

5-methoxy-2- [α- (3-n -pentadecylphenoxy) butyramido] -4- (1-phenyl-5-tetrazolylthio) phenol ICC-27

N- [α- (2,4-Di-tert-amylphenoxy) acetyl] - α> (1-phenyl-5-tetrazolylthio) -m-aminoacetophenone ICC-28

α-Pivaloyl-α- (5- or 6-bromo-1-benzotriazolyl) -5- [α- (2,4-di-tert-amylphenoxy) propionamido] -2-chloro-acetanilide ICC-29

a- (4-methoxybenzoyl) -a- (5- or 6-nitro-1-benztriazolyl) -5- [γ- (2,4-di-tert-amylphenoxy) butyramido] -2-chloroacetanilide

5098A2 / 0927

ICC-30

a- (4-Stearyloxybenzoyl) -cc- (5- or 6-bromo-1-benztriazolyl) -2-methoxyacetanilide ICC-31

1-Hydroxy-4- (1-phenyltetrazolylthio) -N - [(2-chloro-5-hexadecyloxy) -phenyl] -2-naphthamide.

Examples of typical organic interlayer interaction activators are the following:

IEPC-32

5- (3-Ethyl-2-benzothiazolylidene) -3-benzylrhodarain I5PC ~ 33

5- [3- (γ-sulfopropyl) ~ 2-benzoxazolylidene] -3-cyclohexylrhoammine IEPC-34

5- (3-methyl-2- benzoselenazolylidene) -3- (γ-sulfobutyl) rhodamine IEPC-35

5- [3- (ß-Hydroxyethyl) -ß-naphthoxazolylidene] ~ 1-phenyl-2-thiohydantoin IBPC-36

2-thioxo-3-ethylbenzothiazole IEPC-37

2-mercapto-5-methylbenzthiazole IEPC-38

2-Thioxo-3-n-propylbenzoxazole IEPC-39

1,3-Di-n ~ propyl-2-thioxobenzimidazole IEPC-40 N-methyl-2-thioxo-6-chloroquinoline.

509842/0927

The couplers used in the present invention can be added in the form of a dispersion, the can be prepared in a known manner, as it has already been done in connection with the DIR hydroquinones or the compounds of the general formula (II) has been described. A common surface active agent such as an anionic surfactant (e.g. sodium alkyl benzene sulfonate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfonate, sodium alkyl naphthalene sulfonate, a Fisher coupler, etc.). amphoteric surfactant (e.g. N-tetradecyl-NjN-dipolyethylene-oc-betaine etc.) and a nonionic surfactant (e.g. sorbitan monolaurate, etc.) can be used as dispersants be used.

The amount of coupler used is generally from about 0.01 to 2 moles per mole of silver halide. The ICC coupler can be used alone or together with other couplers in an amount below about 50 mol%, preferably below 20 mol% based on the total moles of the couplers used in the light-sensitive materials of the present invention will.

The organic activators for the interlayer interimage effect are usually in the form of a solution in water or in an organic solvent that is miscible with water is added such as methanol, ethanol, pyridine, methyl cellosolve, acetone, etc. The amount of activator added

-7 -3

is generally from about 10 to about 10 moles per mole of silver halide.

The silver halide grains used in the light-sensitive Layers used can be silver chloride or silver bromide and mixed silver halides such as Silver chlorobromide, silver iodobromide and silver chloroiodobromide which may be monodispersed or polydispersed. The silver halide can cover a large area of medium partial

509842/0927

particle sizes range from about 0.1 to about 3 / U, depending on the use and purposes of the photographic Materials. The silver halide emulsions can be prepared using, for example, one Single jet, double jet or controlled double jet process, and they can be made by a digestion process with ammonia, by a neutral or acidic digestion process be digested.

The silver halide emulsion used in the light-sensitive Layers can be chemically sensitized by known methods, such as gold sensitization, as described in U.S. Patents 2,399,083, 2,597,856 and 2,597,915, reduction sensitization, such as it is described in U.S. Patents 2,483,850 and 2,521,925, sulfur sensitization as described in U.S. Patents 1,623,499 and 2,410,689 uses a sensXbilization metal ions other than silver as described in U.S. Patents 2,448,060, 2,566,245, and 2,566,263; or a combination of these methods.

The silver halide emulsions used in the present invention can also be used in a known manner be spectrally sensitized and you can add other additives such as stabilizers, e.g. 4-hydroxy-1,3 »3a, 7-tetrazaindene derivatives etc., antifoggants such as a mercapto compound, a benzothiazole derivative, etc., coating aids, a hardener, a crosslinking agent, a pH regulator, e.g. citric acid, sodium carbonate, etc., and other sensitizers such as an onium derivative such as quaternary ammonium salts disclosed in US Pat. No. 2,271,623,

2 288 226 and 2 334 864 are described, and the polyalkylene oxides, those in U.S. Patents 2,708,162, 2,531,832, 2,533,990,

3,210,191 and 3,158,484 are included. The color photographic materials of the present invention can also a filter layer, an etching or fixing layer

509842/0927

and a colored layer containing a hydrophobic dye contains, included.

The photosensitive emulsions used in the present. As used in the invention, they can be coated on a variety of substrates - such as cellulose acetate films, polyethylene tetraphthalate film, polyethylene films, polypropylene films, glass plates, baryta paper, synthetic resin-laminated paper, synthetic paper, and the like. A suitable amount of silver halide coating is approximately 0 , 1 to 20 g (as silver) / m, preferably 1 to 15 g (as silver) / m ² .

According to the invention, the light-sensitive color materials can be exposed using any light sources, for example initT daylight, tungsten light etc., and they can be developed using a color developing solution which is a common p-phenylenediaradm or p-aminophenol derivative contains as a color developing agent. Examples of suitable p-phenylene derivatives are e.g. p-Araino-N-ethyl-N-ß- (methanesulfamidoethyl) ~ m-toluidine-sesquisulfate monohydrate, Diethylamino-p-phenylenediamine sesquisulfite, p-amino-NiN-diethyl-m-toluidine hydrochloride, p-Amino-N-ethyl-N-ß-hydroxyethylaniline sesquisulfate, monohydrate Other known color developing solutions suitable for the development of negative color materials, etc. can also be used. positive or negative motion picture color films, color papers, and instantly addressable color photographic materials - have been developed. "Examples of these color developing solutions are those published in Japanese Patent Application 35749/70, Japanese Patent Applications 67793/69, 13313/71 and 19516/71, by H. Gordon in British J. Photo., 558 (1954), ibid, 440 (1955), ibid, 2 (1956), from S. Horwitz, ibid, 212 (1960), by H. Gehret, ibid, 122 (1950), ibid, 396 (1965), by J. Meech, ibid, 182 (1959), in DT-OS 2 238 051 et al.

509842/0927

In the case of photographic materials for black and white photography, a developing solution containing as a developing agent: a polyhydroxybenzene such as hydroquinone, pyrocatechol, pyrogallol, etc., an N-alkylaminophenol such as N-methylaminophenol, N-ethylaminophenol, etc. can be used. , 1-phenyl-3 -pyrazolidon, for example 1 -Phenylpyrazolidon, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, ^{1-phenyl-4,4-dimethyl-f} 3-pyrazolidone, etc., or mixtures thereof.

The DIR hydroquinone derivatives according to the invention can with the reducing compound into the photosensitive emulsion layer, the intermediate layer, the filter layer, the Anti-radiation layer or the protective layer made of ordinary color photosensitive material or photosensitive Color material to be given for immediate use.

The term "photosensitive emulsion layer" includes a hydrophilic colloid layer containing silver halide grains having sensitivity in a specific spectral range contains, a photosensitive emulsion layer unit comprising a combination of at least two photosensitive Contains silver halide hydrophilic colloid layers which have essentially the same spectral sensitivity and a different sensitivity such as that disclosed, for example, in GB-PS 923 045 and DT-OS 2 322 165, a photosensitive emulsion layer unit, which is a combination of at least two photosensitive silver halide-hydrophilic colloid layers which has essentially the same spectral sensitivity and a different sensitivity and at least one non-photosensitive hydrophilic colloid layer or a photosensitive hydrophilic Colloid layer containing silver halide grains with a sensitivity in a different spectral Area separating the two layers, including, but not limited to, for example, preferred results can be obtained by using the

509842/0927

DIR hydroquinone derivatives according to the invention together with the reducing compounds as described above into the photosensitive hydrophilic colloid layer or into a single photosensitive hydrophilic colloid layer or non-photosensitive layer included in the photosensitive Emulsion unit is included, incorporated.

Examples of the ready-to-use photosensitive materials which can be used in the present invention are the diffusion transfer color photosensitive materials for making multicolor images disclosed in Japanese Patent Application Publications-! 0240/59 and 5189/59, U.S. Patents 2,983,606, 3,415,644, 3,415,645, 3,415,646, 3,594,164 and 3,594,165, among others, and diffusion transfer color photosensitive materials employing the DIR hydroquinones as they are described in GB-PS 1 066 352, among others.

The following calculations show that the oxidation of the DIR hydroquinone derivatives, which are used in the present invention by the coexistence of the reducing Connection can be prevented.

A 1 × 10 M solution of the compound 1-38 in butyl acetate is placed in a test tube and left to stand for 2 days at 25 ^° C., and then the percentage of unchanged compound is determined spectrophotometrically (UV absorption). It is found that almost "all of the compound is oxidized.

The percentage of unchanged DIR hydroquinone derivatives is determined in a manner similar to that above, with the exception that that a reducing compound according to the invention to the solution in an amount of 5 mol%, based on the mol of the DIR hydroquinone derivative, is added.

50 9 842/0927

Table I.

Connection used

Connection 1-38 E _0x d.unchanged turning. redu-

adorn
the ver
binding
(Volt) O - 75 0.821 26th 0.763 62 0.882 43 0.753 59 0.896 15th 0.795 67 1.042 58 1.086 68 1.162 65 0.934

Connection 1-38 Connection 1-38 + Connection 1-38 + Connection 1-38 + connection I-33 + connection 1-38 + Connection 1-38 + connection 1-38 + connection 1-38 + Connection 1-38 + connection 1-38 +

Connection R-1 Connection R-2 Connection R-3 Connection R-4 Connection R-5 Connection R-6 Connection R-7 Connection R-8 Compound R-9 Compound R-10

From the results it can be seen that according to the invention by the reducing compound, the DIR hydroquinone derivative, is stabilized.

The following examples illustrate the invention. Unless otherwise stated, all parts, percentages, are ratios and the like expressed by weight.

example

Sample 101-1 is prepared by sequentially cutting the Layers 1, 2, 3 and 4. a piece of transparent cellulose triacetate film as shown in FIG is. The coating solutions used for each layer are prepared in the following manner.

Layer 1 (red sensitive layer)

1 kg of a silver halide emulsion (Ag, 0.6 mol; iodine content 6 Mo 1-%) is spectrally measured using 4 χ 10 "" - * mol

509842/0927

Sensitizing Dye I as indicated below, sensitized. (1) is added to the resulting emulsion 450 g of Emulsion I, prepared by dissolving 100 g of Coupler C-17 in 100 ml of tricresyl phosphate and 200 ml of ethyl acetate and dispersion of the resulting solution in 1 kg of a 10bigen aqueous gelatin solution in the presence of 4 g sodium nonylbenzenesulfonate, and (2) an aqueous solution of 0.1 g of 2,4-dichloro-6-hydroxytriazine sodium salt.

Layer 2 (intermediate layer)

100 g of reducing compound R-1 are dissolved in 100 ml of tricresyl phosphate dissolved and the resulting solution is dissolved in 1 kg of an aqueous gelatin solution above in a manner similar to dispersed in Emulsion I described above to prepare Emulsion II. To 1 kg of a 1Obigen aqueous Gelatin solution is added to 250 g of emulsion II and the mixture is then stirred.

Layer 5 (green sensitive layer)

1 kg of a silver iodobromide emulsion (identical to layer 1) is spectrally sensitized using 2 × 10 "mol of sensitizing dye III and 6 × 10 ^J mol of sensitizing dye IV, as indicated below. 600 g of emulsion III are added to the emulsion thus obtained , made using 100 g of Coupler M-8 in a manner similar to Layer 1.

Layer 4 (protective layer)

0.2 g is added to 1 kg of an aqueous gelatin solution above Sodium nonylbenzenesulfonate.

The sensitizing dyes used in the above manufacturing processes are the following;

609842/0927

Sensitizing Dye I:

Anhydro-5.5 ^! -dichloro-3,3'-stilofopropyl-9-ethylthiacarbocyanine hydroxide pyridinium salt
Sensitizing dye II:

Aruiydro-9 ^^ 1-3,3'-di-Csulfopropyl) -4,5,4 ', 5'-dibenzocarbocyanine-hydroxide-ethylamine salt

Sensitizing Dye III:

Anhydro-9 ^f -ethyl-5,5'-dichloro-3,3'-disulfopropyloxacarbocyanine sodium salt

Sensitizing Dye IV:

Anhydro-5,6,5 ', ö'-tetrachlor-i, 1'-diethylimidazolocarbo cyanine hydroxide sodium salt.

Emulsion IV is obtained by adding 100 g of DIR hydroquinone compound 1-38 was used in place of 100 g of reducing compound R-1 in layer 2 of sample 101-1. Sample 101-2 is obtained in a manner similar to Sample 101-1 except that 503 g of Emulsion IV instead of 250 g of Emulsion II and 258 g of a 10% aqueous gelatin solution as obtained above can be used.

Emulsion V is obtained by adding a mixture of 100 g of Compound 1-38 and 7.5 g of Compound R-1 instead of 100 g of compound R-1 was used in layer 2 of sample 101-1. Sample 101-3 is processed in a similar manner to Sample 101-2 except that Emulsion V is used in place of Emulsion IV. Each emulsion is within Applied 30 minutes after adding emulsion IV or V.

Samples 101-1, 2 and 3 are gradually exposed with red light, green light or white light and developed at 38 ⁰ C in accordance with the following steps.

509842/0927

Time (min)

1. Color development x 3.25

2. Bleach 6.5

3. Wash 3.25

4. Fixing 6.5

5. Washing 3.25

6. Stabilize x 3.25

Each solution used in the above development stages has the following composition:

Color developing solution

Sodium nitrilo triacetate 1.0 g

Sodium sulfite 4.0 g

Sodium carbonate ■ 30.0 g

Potassium bromide 1.4g

Hydroxylamine sulfate 2.4 g

4- (N-ethyl-N-ß-hydroay läthylamino) 2-methylaniline sulfate 4.5 g

Water up to 11

Bleach solution

Ammonium bromide 160.0 G Ammonia (28% aqueous solution) 25.0 ml Ethylenediaminetetraacetic acid sodium iron salt 130.0 G Glacial acetic acid 14.0 ml Water up to 1.0 1 Fixing solution Sodium tetrapolypho sphat 2.0 G Sodium sulfite 4.0 G Ammonium thiosulphate (7Q% aqueous solution) 175.0 ml Sodium bisulfite 4.6 G Water up to 1.0 1

509842/0927

Stabilizing solution

Formaldehyde (38 / aige aqueous solution) Water up to

8 ml 1 1

The transmission density of the developed samples for red and green light is determined. The results obtained are in Table II given.

Sample for the

clearing green

used layer of light

Table II Relative sensitivity

gradation

red sensitive green sensitivity rotempf, Layer layer layer

101-1

101-2

101-3

green

Red

White

green

Red

White

green

Red

White

100

90

98

100

99

1.21

- 1.20 1.19 1.17 0.62 - - 0.70 0.55 0.53 0.99 - - 1.03 0.85 0.80

It can be seen from the results of Table II that a decrease in gradation and a decrease in Sensitivity in adjacent layers occurs when compound 1-38 is used alone in the intermediate layer. On the other hand, there is little reduction in sensitivity and the interlayer inter-image effect becomes reinforced against each other if the connection 1-38 and the compound R-1 can be used together. The term "interlayer interimage effect or effect" as used herein is used, means such a developing effect as to regulate the development in adjacent layers depends on the amount of exposure or the development in the layer. The color purity and color reproduction

509842/0927

availability are thus improved in the layers. It can be seen from the results in Table II that larger Differences in the gradation in the green-sensitive layer or the red-sensitive layer compared to green light or red light and the gradation in the green-sensitive layer Layer or the red-sensitive layer against white light (both, the green-sensitized layer and the red-sensitized layer are exposed simultaneously) in samples 101-2 and 101-3 than in sample 101-1 occur, indicating that the interlayer interimage effect between the green-sensitive layer and the red-sensitive layer is improved.

Samples 101-1, 2 and 3 are exposed to soft X-rays like a cutting edge and developed as described above. The sample 101-2 as well as the sample 101-3 have a granularity superior to that of the sample 101-1.

Example 2

Samples 102-1, 102-2 and 102-3 are made as follows:

Sample 102-1

This sample is produced in the same manner as Sample 101-1 in Example 1.

Sample 102-2

This sample is prepared in the same manner as Sample 101-2 in Example 1, except that 84 grams of the compound 1-2 can be used instead of 100 g of compound 1-38.

Sample 102-3

This sample is prepared in the same manner as Sample 101-3 in Example 1 except that 91.2 g of the compound 1-2 and 8.8 g of compound R-1 instead of 92.5 g of compound 1-38 and 7.5 g of compound R-1 can be used.

509842/0927

These samples are moistened as described in Example 1 and developed and the density of the samples is determined against red and green light. In sample 102-2 is the Gradation and sensitivity decreased in adjacent layers, whereas in sample 102-3 DIR effects (Interlayer interimage texture, edge effect), improved were without lowering the sensitivity in adjacent layers.

After storage for 4 days at 40 ° C and 80? Ό relative The samples were exposed to moisture and developed as described in Example 1 and their density was compared to rotund Definitely green light. In sample 102-2, the gradation and sensitivity in adjacent layers were greatly reduced, compared with the sample 102-1, whereas with the sample 102-3 and, the gradation and sensitivity deteriorate somewhat was.

Example 3

Sample 103-1 was prepared in a manner similar to that described for Sample 101-1 in Example 1, except that e. an emulsion was used in layer 1 instead of emulsion I, which was prepared from emulsion I and which do not contain silver iodobromide emulsion and sensitizing dye I and II included. Sample 103-2 was made in the same manner as Sample 103-1 except that instead of the emulsion from Coupler C-17 dispersed in the Layer 1, an emulsion was used that contains both the Coupler C-17 (90 mol%) as well as compound 1-38 (10 mol%) contained. Sample 103-3 was prepared in the same way as Sample 103-2 except that an emulsion, the additional 5 mol% of compound R-1, on a molar basis, based on Compound 1-38, was used in Layer 1, and Samples 103-4, 103-5, 103-6, 103-7 and 103-8 were in the same way that the sample 103-3 produced "with the

509842/0927

Except that the compounds R-4, R-5, R-7, R-9 and R-10 were used in place of compound R-1.

Samples 103-1 to 103-8 are gradually exposed and developed as described in Example 1. The samples are exposed relative also after storage for 4 days at 40 ⁰ C and 75% humidity as described above and escape disgust.

If part of the DIR hydroquinone compound, 1-38, is oxidized and converted to the hydroquinone form, or if part of the development inhibitor is released during emulsification, coating, or storage under high temperature and humidity conditions, development will occur in the adjacent layer (Layer 3) is inhibited and the gradation is weakened and the sensitivity is lowered. The relative sensitivity and gradation are determined by measuring the transmission density to red light. The results obtained are shown in Table III.

Table III

sample Reducing connection γ of layer 3 stored Relat.E
d.Schic mpfindl. (Coupler C-17 alone) fresh 0.80 fresh ht 3 - 0.81 0.46 100 stored 103-1 Compound R-1 0.53 0.77 88 102 103-2 Compound R-4 0.79 0.70 99 85 103-2 Compound R-5 0.70 0.72 97 100. 103-4 Compound R-7 0.75 0.71 98 96 103-5 Compound R-9 0.77 0.78 100 98 103-6 Compound R-10 0.78 0.67 101 99 103-7 0.74 97 99 103-8 98

From Table III it can be seen that the decrease in gamma and relative sensitivity in the adjacent layer (Layer 3) can be avoided if the reducing compounds are combined with the DIR hydroquinone compound

509842/0927

applies, i.e. the DIR hydroquinone compound 1-3 can be chemically are stabilized by the reducing compounds.

Example 4

Sample 104-1 is obtained by sequentially laying layers 1 and 2 on a transparent cellulose triacetate film support applied. The composition and preparation of the coating solutions required for layers 1 and 2 are the same as those of layers 1 and 4 in Sample 101-1 of Example 1 above. Sample 104-2 was obtained in a manner similar to Sample 104-1, except that an emulsion containing both the Coupler C-17 (90 mol%) as well as compound 1-38 (10 mol%) was used in place of the emulsion containing Coupler C-17 and that in Layer 1 of Sample 104-1 was used. Sample 104-3 was obtained in a manner similar to Sample 104-2 except that others 30 moles of compound R-1 based on the amount of compound 1-38, in the emulsion used in Layer 1, were present. Sample 104-4 was obtained in a manner similar to Sample 104-3 except that 20 mol% Compound R-1 and 10 mol% of Compound R-9, based on the Amount of compound 1-38, instead of using 30 mol% Compound R-1 based on the amount of Compound 1-38 were used. Sample 104-5 was made in a similar manner as obtained for sample 104-4 except that 28 mole percent is based on compound R-1 and 2 mole percent is based on compound R-9 on the amount of compound 1-38, instead of 20 mol% Compound R-1 and 10 Mo1-% Compound R-9, based on the Amount of compound 1-38 were used.

Samples 104-1, 104-2, 104-3, 104-4, and 104-5 were staged exposed with red light, like a cutting edge with soft X-rays and developed as described in Example 1. The measurement of the macroscopic and microscopic

509842/0927

Density of the samples to red light showed that: (1) For Sample 104-2, the decrease in sensitivity was significantly larger than for sample 104-1,

(2) for sample 104-3 the DIR effects (edge effect, Improvement in graininess) with a small decrease in sensitivity, and

(3) Samples 104-4 and 104-5 were · two kinds of reducing compounds were used together, thereby the DIR effects could be obtained without any desensitization will.

Example 5

A multilayered photosensitive material (Sample 105-1) was prepared by, as shown in Fig. 1, coated a piece of cellulose triacetate film with layers 1 to 11 of the following composition.

Layer 1 (antihalation layer)

A gelatin layer that contains black / white colloidal silver.

Layer 2 (intermediate layer)

a gelatin layer containing an emulsified dispersion of compound R-1.

Layer 3 (first red sensitive emulsion layer)

A silver iodine bromide emulsion (iodine content 7 mol%; average particle size 0.4 / u) layer with a silver coverage of 1.2 g / m, the "6 χ 10 ^J mol of sensitizing dye I (as described in Example 1), 1.5 x 10 moles of Sensitizing Dye II (as described in Example 1), 0.09 moles of Coupler C-17 (in the form of an emulsified dispersion) and 0.02 moles of Coupler C-19 per mole of silver.

509842/0927

Layer 4 (second red-sensitive emulsion layer)

A silver iodobromide emulsion (iodine content 6 mol%, average grain size 0.8 / u) layer with a silver coverage of 1.2 g / m, containing 3 x 10 mol of sensitizing dye I, 1.2 10 "" ^] v [ _o i Contained Sensitizing Dye II, 0.02 mole of Coupler C-17 and 0.04 mole of Coupler-C-18 per mole of silver.

Layer 5 (intermediate layer)

A gelatin layer containing an emulsified dispersion of Compound R-1.

Layer 6 (first green sensitive emulsion layer)

A silver iodobromide emulsion (iodine content 7 mol%, average particle size 0.4 / u) layer with a silver ^{coverage of 1.4 g / m 2} , the 3 χ ΙΟ "* ⁵ mol of sensitizing dye III (as described in Example 1), 1 χ ~ 10 ^-> mol sensitizing dye IV (as described in example 1), 0.06 mol of coupler M-8 per mole of silver contained and 0.015 mole of coupler ICC 25th

Layer 7 (second green sensitive emulsion layer)

A silver iodobromide emulsion (iodine content 6 mol%, average grain size 0.7 / u) layer with a silver coverage of 1 »5 g / m ² , the 2.5 10 ~ ⁵ mol of sensitizing dye III, 0.8 χ 10 ~ ⁵ Mole of sensitizing dye IV, 0.004 mole of Coupler ICC-25 and 0.013 mole of Coupler M-9 per mole of silver.

Layer 8 (yellow filter layer)

A gelatin layer containing an emulsified dispersion of Compound R-1 and yellow colloidal silver.

Layer 9 (first blue sensitive emulsion layer)

A silver iodobromide emulsion (iodine content 7 moles &, average Grain size 0.4 / u) layer with a silver covering of

5098Λ2 / 0927

1.0 g / m ² containing 0.25 moles of Coupler Y-4 per mole of silver. Layer 10 (second blue sensitive emulsion layer)

A silver iodobromide emulsion (iodine content 6 mo 1-9 $, average Grain size 0.8 / u) layer with a silver covering of

1.1 g / m ² containing 0.07 moles of Coupler Y-4 per mole of silver.

Layer 11 (protective layer)

A layer of gelatin, the polyethylene acrylate grains (average Diameter 1.5 / u).

Each layer was applied by adding a gelatin hardener and in addition to the components mentioned above a coating aid as described in Example 1 used. The above emulsions were first sensitized using sulfur sensitization.

Sample 105-2 was prepared in a manner similar to Sample 105-1 above, except that 0.01 mol and 0.009 mol of Compound 1-38 were added to layers 3 and 5, in the form of an emulsified dispersion (dispersant : Tricresyl phosphate) and that the silver coverage in layers 3 and 5 was increased to 1.5 and 1.6 g / m ² , respectively.

Sample 105-3 was prepared in a manner similar to Sample 105-2 except that 0.1 mole of Compound R-1, based on the amount of compound 1-38, were used in layers 3 and 5, in the form of an emulsion, which both Compound 1-38 as well as Compound R-1 contained.

The samples 105-1, 105-2 and 105-3 have been developed to produce a 16 mm color negative light-sensitive material. After · o relative humidity for the storage for 4 days at 40 ⁰ C and 8O? Was added to the film in a camera, exposed and developed following the steps outlined in Example 1 to produce color negatives.

S 0 9 8 4 2/0 9 2 7

The color negatives obtained from Sample 105-2 showed improved graininess and sharpness as compared to the graininess and sharpness of the negative from sample 105-1 »but the layers sensitive to red and green, in particular the former of Sample 105-2 had a tendency to be desensitized and the contrast was decreased, so that the color balance was disturbed. On the other hand, it found desensitization and attenuation in Sample 105-3 does not take place.

sample Red sensitive
layer Y Green sensitive
layer Y Blue sensitivity
layer Y RE ⁺ 0.80
0.71
0.79 RE. 0.81
0.69
0.80 RE. 0.81
0.80
0.80 105-1
105-2
105-3 100
95
99 100
96
101 100
100
99

⁺ RE = relative sensitivity

Similar results were obtained when using the compounds R-4, R-5 »R-7 or R-9 instead of the compound R-1 in sample 105-3 used.

Example 6

Sample 106-1 was prepared in the same manner as Sample 105-1. Sample 106-2 was prepared in the same manner as Sample 105-1, except that Compound 1-2 was used in place of Compound R-1 that was present in layer 5 (intermediate layer) and the silver coverage in layers 3, 4, 6 and 7 was 1.2, 1.1 ,. 1.4 and 1.5 g / m ^{2 were changed} to 1.3, 1.35, 1.45 and 1.55 g / m ² , respectively, in order to regulate the γ values of the photosensitive layers in the sample. Sample 106-3 was prepared in a manner similar to Sample 105-1 except that Compound 1-2 (70 mol%) and Compound R-1 (30 mol%) were used in place of Compound R-1 that are in layer 5

509842/0927

(Intermediate layer) was present and that the silver coverages in layers 3, 4, 6 and 7 from 1.2, 1.1, 1.4 and 1.5 g / m ² to 1.3, 1.35 , 1.4 and 1.55 g / m ² , respectively, were changed to regulate the γ value of the photosensitive layers in the sample.

Samples 106-1, 106-2 and 106-3 were developed in the same manner as described in Example 4 to produce color negatives to manufacture. The results obtained are given in the table below.

sample Red sensitive y , 85 Green sensitivity 0 Y Blue sensitive 0 y layer 0 , 70 layer 0 , 81 layer 0 , 81 RE ⁺ 0 , 80 RE. 0 , 72 RE. 0 , 79 106-1 100 0 100 , 80 100 , 81 106-2 97 97 100 106-3 100 101 101

RE. = Relative sensitivity

It is clear from the results of the table above that the desensitization and the weakening of the gradation, that by compound 1-2 during storage in high temperature and high humidity conditions caused by the addition of the reducing compound (Compound R-1) can be avoided. Farther Sample 106-3 has improved graininess, sharpness and color reproducibility compared to the graininess Sharpness and color reproducibility of Samples 106-1 and 106-2.

Similar results are obtained when using the compounds R-2, R-3, R-7 or R-9 instead of the compound R-1 in Sample 106-3 used.

Example 7

Sample 107-1 was prepared by preparing a silver iodobromide emulsion with a silver coverage of 3 x 10 "mol / m and

SG9842 / Q927

with a gelatin content of 5.5 g / m 2 on a piece of cellulose triacetate film. Sample 107-2 was on Prepared in a manner similar to Sample 107-1 except that "Compound 1-38" was prepared using tricresyl phosphate was dispersed as a dispersant. The resulting dispersion became a silver iodobromide emulsion was added (0.03 moles of compound 1-38 were used per mole of silver). Sample 107-3 was made in a similar manner prepared as Sample 107-2, except that a combination of Compound 1-38 (70 mol%) and Compound R-1 (30 mol- ^) was used in place of compound x-38.

After storage for 4 days at 40 ⁰ C and Q0% relative humidity, the samples 107-1, 107-2 and 107-3 were stepwise exposed and developed for 5 minutes at 20 ⁰ C with a developing solution having the following composition:

Methol 0.3

Sodium sulfite 40.0

Hydro quinone 6.0

Sodium carbonate 21.8

Potassium bromide 0.86

Sodium metabisulfite 1.15

Citric acid 0.7

Then, with a fixing solution of the following composition fixed, then washed and dried:

Sodium thiosulfate (anhydrous) 153.0 g

Sodium sulfite (anhydrous) 150.0 g

Glacial acetic acid 13.5 ml

Boric acid 7.5 g

Potassium alum 15.0 g

Water up to 1.0 1

509842/0927

The results obtained from density measurements
are given in the following table.

Sample Relative Humidity γ haze

107-1 100 107-2 90 107-3 98

3.08 0.06 2.10 0.04 2.31 0.05

It is clear from the results in the above table that in sample 107-2, the compound 1-38 alone
contains, desensitization takes place, while attenuation of the gradation without desensitization is obtained in Sample 107-3 which contains Compound 1-38 and Compound R-1 together. On the other hand, the
Sample 107-3 improved graininess.

Similar results are obtained when using the compounds R-2, R-3, R-5, R-8 or R-9 in place of the compound R-1 is used or when using compounds 1-2 or 1-10 used instead of compound 1-38.

42/0927

Claims (1)

Patent to s ρ r ü c h e A photographic light-sensitive material containing at least one hydrophilic colloid layer containing at least a reducing compound and at least one compound of the following general formula (I) A.
I.
O contains where A and A ^f , which can be the same or different, each represent a hydrogen atom or an alkaline hydrolyzable group or in which A ¹ can form a ring together with R or Q, P, Q and R, which can be the same or different, each with a hydrogen atom, an alkyl group, an aryl group, a halogen atom, a hydroxyl group, a -Y-W- group, wherein Y is an oxygen atom or a sulfur atom and W is a Represent an alkyl group, an aryl group or a heterocyclic group, a -S-Z group, wherein Z is a heterocyclic group Represents a group which is photographically inert substantially in a bonded state, or a heterocyclic group mean, wherein at least one ballast group with at least 5 carbon atoms is present in the molecule. S09842 / 0927 2 _β Photographic light-sensitive material according to claim 1 _y characterized _{9 in} that the reducing compound has an oxidation potential below about 1.5 volts. 3. Photographic light-sensitive material according to claim 1 or Z _9, characterized in that the reducing compound has an oxidation potential of approximately 0.5 to 1.5 volts. 4. Photographic light-sensitive material according to one of the preceding claims, characterized in that the reducing compound has an oxidation potential of Qr> 7 to 1.2 volts =. 5. Photographer! Solles light-sensitive material according to one of the preceding claims _ΰ characterized in that A and A 'denote a hydrogen atom and that the reducing compound has an oxidation potential below about 1 ₉ ' 5 volts ,, 6c photographic light-sensitive material nacli one of the "/ _P orhergelieaden claim ₉ characterized in that the connecting _s the wird- represented by the general formula (I), the general Forael (ils OK κ s, if ' I.
I. OH wherein P, Q and R each have the same meaning as in claim 1 and M is a phenyl group or a means lower alkyl group. S0 9842/0 927 7. Photographic light-sensitive material according to any one of the preceding claims, characterized in that the reducing compound is a compound which is represented by the following general formula (II): OA " JC ? 1. OA " R ,. and R ₂ each represent a hydrogen atom or a straight-chain or branched-chain alkyl group with 8 to 20 carbon atoms, A "and A" 'each represent a hydrogen atom or an alkaline one mean hydrolyzable group and the benzene ring further with an alkyl group containing no more than 8 carbon atoms, a halogen atom, an aryl group, a hydroxyl group or a heterocyclic group can. 8. Photographic light-sensitive material according to one of the preceding claims, characterized in that the reducing compound is water-soluble is. 9. A photographic light-sensitive material according to claim 7, characterized in that the reducing compound is used in a ratio of about 1 mol-? 6 to about 70 mol- ^, based on the total amount of the reducing compound and the compound represented by the general formula ( I) is expressed, is present. 509842/0927 10 «Photographic light-sensitive material according to one of the preceding claims, characterized in that the reducing compound is used in a ratio of 10 to 60 mol% _? based on the total moles of the reducing compound and the other compound represented by general formula (I). 11. Method of making a photographic Photosensitive material according to Claims 1-10, characterized that one mip "at least one reducing compound and at least one compound that is produced by the general formula (I) as defined in claim, dissolves in an organic solvent and dispersing the solution in a hydrophilic colloid solution. 12. A process for preparing a photographic silver halide photosensitive material according to claim 1-10, characterized in that at least ₉ and a reducing compound .mindestens a compound represented by the general formula (I), as defined in claim 1, an organic solvent, dispersing the solution in a hydrophilic colloid, adding the dispersion to a coating solution for a hydrophilic colloidal emulsion and the. _The coating solution obtained is applied "on a carrier" essentially immediately after the addition of the dispersion. 13. Photographic light-sensitive material according to one of Claims 1 to 10, characterized in that that the hydrophilic colloid layer is a non-photosensitive emulsion layer and contains a dispersion, which is made by 'in a hydrophilic colloid a solution . dispersed, the at least one reducing compound and at least one compound by the general formula (i) shown contains. 2/0927 14. A photographic light-sensitive material, characterized in that it contains _f: a support having thereon at least one hydrophilic colloid layer containing at least one reducing compound and at least one compound represented by the following general formula (I), S-Z (D A and A ¹ , which can be the same or different, each represent a hydrogen atom or an alkali hydrolyzable group or in which A ¹ can form a ring together with R or Q _? Pj Q uno. R that can be the same or different can, one hydrogen atom, one alkyl group, one aryl group, a halogenator, a hydroxyl group, a -Y-W group, wherein Y is an oxygen atom or a sulfur atom and W is an alkyl group, an aryl group or a heterocyclic group Represent a group, a -S-Z group, in which Z is a heterocyclic group which is essentially in the bound state. is photographically inert, represents, or represent a heterocyclic group, at least one ballat group with at least 5 carbon atoms are contained in the molecule. 5098A2 / 0927 15. Multi-layer, color photographic light-sensitive material., Characterized in that it comprises: a support and thereon a blue-sensitive silver halide emulsion layer unit containing one Yellow coupler, a green-sensitive silver halide emulsion layer unit, containing a magenta coupler, and containing a red-sensitive silver halide emulsion layer unit a cyan coupler wherein at least one compound represented by the following general formula (I) will A ' (D νιο rin A and A 'each represent a hydrogen atom or an alkali-hydrolyzable group, or in which A' together with R or Q can form a ring, and P ₅ Q and R each represent a hydrogen atom, an alkyl group ₉ a halogen atom, a hydroxyl group, a -YW group, in which Y represents an oxygen atom or a sulfur atom and W represents an alkyl group, an aryl group or a heterocyclic group, an -SZ group wherein Z is a heterocyclic group which, when bound, is essentially photographic inert, or a heterocyclic group wherein at least one ballast group having at least 5 carbon atoms is present in the molecule, and at least one reducing compound in at least one of the Silver halide emulsion layers or an intermediate layer of the aforementioned units are present. 509342/0927 16. Multi-layer, color photographic light-sensitive material according to claim 15, characterized in that that at least one of the units contains two or more emulsion layers. 509 8Λ2 / 8927 Blank page