DD242878A1 - Light-sensitive color photographic silver halide material - Google Patents

Abstract

The object of finding compounds which provide improved speed fogging kinetics upon high temperature processing of silver halide color photographic materials is achieved by providing a silver halide color photographic material with organic compounds of the formulas I-III wherein R1, R2, R3, R4, R5 are the same or different, H, Cl, Br, alkyl, substituted alkyl, phenyl, substituted phenyl; A heterocyclic radical or substituted heteroatom capable of carrying a positive charge; B is Cl, Br, I, ClO4, HSO3, BF4, NO2, contains. Formulas I to III

Description

V-CH -A ^a

_ιτι

in which

R ¹ , R ² , R ³ , R ⁴ , R ⁵ A

mean,

contains.

identical or different, H, Cl, Br, alkyl, substituted alkyl, phenyl, substituted phenyl; heterocyclic radical or substituted heteroatom capable of producing a positive solution

to wear;

Cl, Br, I, ClO _4, HSO _3, BF _4, NO ₂

Field of application of the invention

The present invention relates to a silver halide color photographic light-sensitive material containing, in at least one layer, high-speed fog-reducing additives under high-temperature processing conditions.

Characteristic of the known technical solutions

It is known that color images can be produced by chromogenic development of photographic silver halide emulsions in which a clutch of developers on the basis of oxidized p _y -Phenylendiaminderivaten with color couplers to indophenol, indamine, azomethine, phenoxazine dyes, and the like is carried out , For the color images prepared by such methods, the sensitometric properties characterized by sensitivity and fog are a crucial quality parameter.

As has long been known, silver halide photographic materials have an interplay between speed and fog. On the basis of a silver halide emulsion, a certain minimum fog determines a certain sensitivity. An increase in sensitivity leads to a higher fog. Veiling additives reduce the sensitivity with high efficiency. In the case of color photographic materials, the color formation process results in the so-called color haze, resulting from excess developer oxidation product and undesired redox processes.

The optimization of a color material to the given conditions of high-temperature processing is particularly difficult, since here by increased processing temperatures between 30 and 60 ⁰ C unfavorable sensitivity fogging kinetics occurs.

Although various methods are known, which are obtained by adding antifoggants better results in high-temperature processing (DE-OS 2711942, US Patent 3376310). However, they are not useful for all purposes and have significant drawbacks such as sensitivity loss and diffusion from the material.

In order to prevent color fogging, alkylhydroquinones are also used as antioxidants, particularly in the case of materials subjected to high-temperature processing (US Pat. No. 3,953,531, DE-OS 2,417,867). Although these hydroquinone compounds cause an improvement in color fog, but associated with sensitivity loss and staining.

Object of the invention

The object of the invention is to produce an improved silver halide color photographic light-sensitive material having good speed fog kinetics.

Explanation of the essence of the invention

It is an object of the invention to find compounds which provide high sensitivity, low fog, and favorable speed fog kinetics in silver halide color photographic light-sensitive materials when subjected to high temperature processing.

According to the invention the object is achieved in that a lichtempfindlcihes color photographic silver halide in at least a r Sch maybe one or meh / j | r £ qrganische compounds of the general formulas

»Ι

II

-A

III

in which

R ¹ , R ² , R ³ , R ⁴ , R ⁵

mean,

contains.

identical or different, H, Cl, Br, alkyl, substituted alkyl, phenyl, substituted phenyl; heterocyclic radical or substituted heteroatom capable of producing a positive charge

to wear;

Cl, Br, I, ClO _4, HSO _3, BF _4, NO ₂

By using the compounds according to the invention, the photographic materials thus produced have a very good sensitivity-fogging kinetics. A particular advantage is that the excellent properties of these materials particularly at processing temperatures above 3O ⁰ C, which often have unacceptable veil result with conventional materials remain effective.

The compounds according to the invention can be added to the emulsion as a solution in organic solvents, the addition being particularly advantageously carried out in a high-boiling solvent as dispersion together with the color coupler. The introduction can be carried out according to the method specified in the US-PS 2322027, or even by similar methods, as for. For example, be described in JP-PS 39853/76.

Further advantageous properties of the materials produced according to the present invention are based on the excellent compatibility of the compounds of the invention with other additives such. Stabilizers,

Antifoggants and antioxidants.

The materials produced according to the invention may contain, in addition to the basic stabilizer 5-methyl-7-hydroxy-1,3,4-triazaindolizine, as antifoggant e.g. Sulfur compounds such as 1-phenylmercaptotetrazole or its disulfide and also benzotriazoles, azoles, benzothiazolium salts, nitroimidazoles and the like. In addition, for inhibiting color fogging and dye stabilization, well-known antioxidants such as hydroquinone derivatives, aminophenols, gallic acid derivatives, ascorbic acid derivatives, hydroxychromans, and the like can be used.

The compounds according to the invention can be used in emulsions which contain, in addition to color couplers, chemical and spectral sensitizers, curing agents, wetting agents and other photochemical additives.

A comprehensive overview of color couplers used in the materials of the invention is ζ. In "Research

Disclosure ", Vol. 176, Dec. 1978, Item 17643.

Preferred compounds according to the invention are:

0 o

^F P ·

a) CH ₃

b) CH ₂ -CH = CH ₂

c) GH ₂ -

d) CH ₂

75-77

No. 138-141 136-137

113-114

i \

.N

a) H

b) Cl

c) Br

d) CH ₃

e) OCH ₃

f) COOC ₂ H ₅

g) N (CH,) _o

Fp. F ⁰ C J

113-114 140-141 158-159 130-131

115-116 131-132 173-175

Mp: 129-130 C

Mp: 144-145 C

Mp: 120-121 ^Ü C

X-CH.

Λ O

u ρ «. /

³ N. mp: 264-266 C 0

ClO

Mp: 164-166 C

ClO.

R II Mp: / " ⁰ C _? a) Cl 209-210 b) ^CH 3 240-241 c) 215-216 , 5 ono r

br

B r- ^

^H 3 ^C ClO

Mp: 171-173 C

H ₃ C Br

\ S__n /

HC Br

«Γ ¹

ClO

Mp: 143-145 C

br

Mp: 205-206 C

br

S N

NH-C

br

Fp. F o

C 7

a) H 212-214 b) Cl 228-230 c) CH ₃ 204-206 but, 216 to 217.5

H3C

C10 ^e

Mp 209-212 C

ClO

Fp. / " ⁰ C J \ 14

209-212 218-219 221-223

-R-

£ ⁰ C

a) H

b) Cl

c) OCH ₃

131-133 124-125.5 104-105

The compounds of the invention are obtained by reaction of sultans with amines to suitamen. After halogenation of the sultams (E. Fanghänel et al., Z. Chem. 24 [1984] 403; E. Fänghänel J. Prakt. Chem. 326 [1984] 545), these are reacted with suitable nucleophiles to form quaternary compounds

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

embodiments example 1

1. Synthesis of Compound 8a

0.01 mol of N-phenyl-i ^ -dibromo ^ -methyl ^ -brommethyl-buta-i ^ -diene-i ^ -sultam (DD-PS 205900) are dissolved in 40 ml of acetonitrile and 0.01 mol of pyridine was added dropwise. The mixture is refluxed for two hours and, after cooling, the solvent is removed in vacuo. The residue is mixed with a little water and a Natriumperchloratlösung added dropwise. The precipitate is recrystallized from methanol

Yield: 67% mp: 209-210 ⁰ C.

2. Synthesis of Compound 14c

0.01 mol of N- (4-methoxyphenyl) -1,3-dibromo-2-methyl-4-bromomethylbuta-1,3-diene-1 _/ 4-sultam and 0.01 mol of triphenylphosphine are dissolved in 50 ml of acetonitrile for two hours heated to reflux. After cooling, 300 ml of water are added, allowed to stand for one hour and decanted the aqueous phase. The oily residue is mixed with 15 ml of methanol and added dropwise a sodium perchlorate solution. The precipitate is recrystallized from methanol. Yield: 50% mp: 221-223 ° C

3. Synthesis of compound 15C

The reaction solution of 14c is mixed with the equimolar amount of 0.1N sodium hydroxide solution. The precipitated crystals are recrystallized from methanol

Yield: 39% mp 104-106 ⁰ C.

Example 2

A gold-ripened, stabilized with triazaindolizine silver chloride bromide emulsion and a silver content of 35g / kg emulsion and a mean grain diameter of 0.18 to 0.2 μιη is 2.5 × 10 " ⁴ mol 9-ethyl-3,3 ' bis (4-sulfobutyl) -5,5'-diphenyloxa-trimetyl cyanine monosodium salt (see DE-PS 929080) and divided into 4 parts.

These 4 parts of the color coupler is added as a dispersion. The color coupler is dispersed with dibutyl phthalate and ethyl acetate using a conventional wetting agent. For the materials B, C and D, in each case the color coupler and the compounds according to the invention are dispersed together.

The pH of the dispersion is optionally maintained in the range of 5.5 to 7.5 with 0.1 N sodium hydroxide solution.

Mat. A: Contains 0.25 mol of 1- (2-chloro-4,6-dimethylphenyl) -3- [2- (3-pentadecylphenoxy) -butyramido] -2-pyrazolin-5-one per mole

Silver and is called a type.

Mat. B: Contains color coupler according to Mat. A and additionally according to the invention 15 mmol / kg emulsion of the compound 2a.

Mat. C: Contains color coupler according to Mat. A and additionally according to the invention 5 mmol / kg emulsion of the compound 14c.

Mat. D: Contains color coupler according to Mat. A and additionally according to the invention 5 mmol / kg emulsion of the compound 8a.

After addition of conventional additives, the emulsion samples are cast on a support, coated with a protective layer, dried, exposed through a continuous and a step wedge with light of color temperature 3200 K and then

Processing. Time temperature

Prebath 10-20 "26.7 ± 1.1 X

Development 3 '36.6 ° C

Stop bath 30-40 "26.7 ± 1.1 X

Watering 30-40 "27.0 ± 3X

Fix 40 "26.7 ± 1.1X

Watering 30-40 "27.0 ± 3X

Bleaching bath 60 "26.7 ± 1.1 X

Watering 40 "27.0 ± 3 ⁰ C

Fix 40 "26.7 + 1.1 ⁰ C

Watering 60 "27.0 ± 3 ⁰ C

Stabilizing bath 10-20 "26.7 ± 1.1 ^° C

Developer:

H ₂ O 960 ml

Anti-scale agent 1.0 ml

Na ₂ SO ₃ 4.35 g;

p-amino-N, N-di-

ethyl-m-toluidine

HCI 2.95 g

Na ₂ CO ₃ 17.1 g

NaBr 1.72 g

NaOH (2n) ^

Make up to 1000ml for V-: pH = 10.53 ± 0.05 for 27X H ₂ SO ₄ (2 n) J

The processed materials are cut into strips and measured.

The sensitometric data are summarized in Table 1. The sensitivity is determined at density 0.1 over D _m j _n and given as a comparison to the type as AIg H, where positive values mean a gain in sensitivity.

Table 1

material additive 2'ECP 2 AIgH 3'ECP 2 AIgH 4'ECP 2 AIgH mmol / kg '-'min Type Dmin Type L'min Type A without (type) 0.15 Type 0.21 +0.05 0.32 +0.05 B 15 verb 0.10 0.14 0.17 2a +0.03 +0.1 +0.05 C 5 verb 0.13 0.18 0.26 14c +0.1 +0.1 +0.08 D 5 verb 0.11 0.17 0.25 8a

When using the compounds of the invention (material B to D) is a significant reduction in the fog with simultaneous sensitivity gain detectable. The materials therefore have a particularly favorable sensitivity-fogging kinetics during high-temperature processing.

Claims (1)

Invention claim: Photosensitive silver halide color photographic material for high-temperature processing, characterized in that it comprises, in at least one layer, one or more organic compounds of the general formulas τ ~ \ t CH ₂ -Α®, _Β ^β or II