DE2165371C2 - Color photographic recording material - Google Patents

Description

CH,

R.

wherein

Ri is an alkyl, alkenyl, aryl, alkoxy, alkenoxy, aryloxy, acylaminoalkyl or acylaminoaralkyl group with not more than 18 carbon atoms and

R _{2 represents} a hydrogen atom, a halogen atom, an alkyl, alkenyl or alkoxy group

mean.

2. Color photographic recording material according to claim 1, characterized in that it as a UV absorbing compound

methyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-t-butyl-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-t-amyl-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-n-octyI-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-n-pentadecyl-

4,4,4 ', 4'-tetramethyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-diphenyI-4,4,4 \ 4'-tetra-

methyl-bis-2,2'-spirochroman, 6.6'-dihydroxy-7,7'-diallyl-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-dimethoxy-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman, 6.6'-dihydroxy-7,7'-diethoxy-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-diphenoxy-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-diallyloxy-4,4,4 \ 4'-tetra-

rnethyl-bis-2,2'-spiföchroman, 6,6'-dihydroxy-7 _t 7'-di-jff-acetylaminopropyl-

4 _< 4,4 ', 4'-Utramethyl-bis-2,2-spirochroman, fi.o'-dihydroxy ^ J'-di- ^ p-acetylamino phenyI) -ethyl-4,4.4 ', 4'-tetramethyl-bis- 2,2'-spirochroman,

6,6'-dihydroxy-4,4,4 \ 4 ', 5,5', 7,7 \ 8,8'-deca

metbyl-bis-2 ^ '- spirocbroman contains

3. Color photographic recording material according to claim 1 or 2, characterized in that that it contains the UV absorbing compound in an amount of 0.05 to 5 moles per mole of 5-pyrazolone magenta coupler.

4. Color photographic recording material according to claim 1 to 3, characterized in that it in addition

2,5-di-t-octylhydroquinone, 2,5-di-n-octylhydroquinone, 2-methyl-5-t-octylhydroquinone or 2-methyl-5-n-octyl hydroquinone

contains as alkylhydroquinone

5. color photographic Aufnahmnuugsmaterial according to claim 1 to 4, characterized in that it additionally as UV absorbing compounds

a stilbene derivative,

a 2-arylimino-3-aΓylmethyIen-thiazoIin,

a 2-arylimino-3-alkyI-5-heteromethylene

thiazoline or a 2-benzotriazolyl-4-alkylphenol

contains

The invention relates to a color photographic recording material which, in at least one silver halide emulsion layer, has a 5-pyrazolone magenta coupler which has at least one hydrophobic group Has 8-30 carbon atoms and contains a UV absorbing compound.

In DE-OS 15 47 684 are color photographic Recording materials described, the special 6-hydroxychromane as UV-absorbing compound gen included. This is intended to result in an end in the materials bleaching of the dyes formed during color development can be prevented.

The object of the invention is to create color photographic recording materials that combine fertilize with a greater UV absorption.

The task is solved with a color photo

graphic recording material in at least a silver halide emulsion layer a 5-pyrazo

Ion-purple cup! He, of at least one hydrophobic

Has group with 8-30 carbon atoms, and contains a UV-absorbing compound, the characterized in that the UV absorbing compound corresponds to the following formula OH

"R ₁

bis-2,2'-spirochroman or

wherein Ri is an AlJc. " ¹ -, alkenyl, aryl, alkoxy, alkenoxy, aryloxy, acylaminoalkyl or acylaminoaralkyl group having not more than 18 carbon atoms and R _{2 is} a hydrogen atom, a halogen atom, an alkyl, alkenyl or Mean alkoxy group,

As can be seen from the following examples and comparative examples results, the dihydroxyspirochromanverbindungen used according to the invention are wide more effective than UV absorbing compounds for color photographic materials. in

Preferred examples of such UV absorbing compounds are

15th

Compound II

CH ₃

C ₄ H ₉ (O

CH ₃

HO

CH ₃

CH,

C ₄ H ₉ (I)

6,6'-dihydroxy-7,7'-di-t-butyl-4,4,4 ', 4'-tetramethyl-bis-2 ^' - spirochroman

methyl-bis-2,2'-spirochroman (I), 6,6'-dihydroxy-7,7'-di-t-butyl-4,4,4 \ 4'-tetramethyl-bis-2,2'- spirochioman (II), Vei binding III

CH ₃

methyl-bLs-i ^ '- spirochroman (III),

methyl-bis-2,2'-spirochroman (IV), ö.o'-dihydroxy ^ J'-di-n-pentadecyM ^ / l '^' - tetra-

methyl bis-2,2'-spirochroman (V), 6,6'-dihydroxy-7,7'-diphenyi-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman (VI), o.o'-dihydroxy ^ J'-diallyMA ^ / l'-tetramethyI-bis-2,2'-spirochroman (VII).

CH ₃

C ₅ H _n (I)

CH ₃

25 6,6'-Dihydroxy-7,7'-di-t-amyI-4,4,4 ', 4'-tetramethyl-bis-2,2'-spJ: ochroman

methyl-bis-2,2'-spirochroman (VIII), 6,6'-dihydrox; -7,7'-diethoxy-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman (IX), 6,6'-dihydroxy-7,7'-diphenoxy-4,4,4 ', 4'-tetra-

methyl-bis-2,2'-spirochroman (X), 6,6'-dihydroxy-7,7'-diallyloxy-4.4,4 ', 4'-tetra-

methyl bis ^^ '- spirochroman (XI), 6,6'-dihydroxy-7,7'-di-jS-acetylaminopropyl-4,4,4 ', 4'-tetramethyl-bis-2,2'-spiro-

chroman (XII),
6,6'-dihydroxy-7,7'-di-j8- (p-acetylaminophenyl) -äthyM ^^ '^' - tetramethyl-bis ^^ '- spirochroman (XIII),

Compound IV

HO

CH ₃

C, H _l7 (n)

6,6'-dihydroxy-7,7'-di-n-octyl-4,4, - <', 4'-tetramethyl-bis-2,2'-spirochroman

Compound V

2,2'-spirochroman (XIV) or .o'-dihydroxy ^^^ '^' ^^ 'J ^' ^ bis-2,2'-spirochroman (XV)

CH ₃

contains. The compounds I to XV listed above correspond to those given below Formulas.

CH ₃

CH ₃

C ₁₅ H ₃₁ (n)

'i, 6'-Dihydroxy-7,7'-di-n -pentadecyl-4,4,4', 4'-tetramethyl-bis-2,2'-spirochroman

Compound I

₃ - Compound VI

CH ₃

OH

OH

CH,

methyl-bis-2,2'-spirochroman

CH,

6,6'-dihydroxy-7,7'-dipheny 1-4.4> 4'.4'-tetramethyl-bis-2,2'-spirochroman

Compound VII

HO

CH ₃

CHjCH = CH ₂

° H 5 compound X

6,6'-dibydroxy-7,7'-dietboxy-4,4,4'.4'-tetramethyl-bis-2,2'-spirocbroman

CH,

CH ₃

CH ₂ = CHCH ₂

6 6'-dihydroxy-7,7'-dialyI-4,4,4 ', 4'-tetramethyl-bis-2,2'-spirochroman

Compound VIII

CH ₃

OCH ₃

CH ₃

HO

OH

CH ₃

CH ₃

CH ₃ O ö.o'-dihydroxy ^ J'-dimethoxy ^. ^ '/ T'-tetra-

methyl-bis-2,2'-spirochroman compound IX

CH ₃

CH ₃ HO - <f S

OC ₂ H ₅ Ο - <\ / - OH

H ₅ C ₂ O compound XII

10

15th

20th

CH ₃

H

6,6'-dihydroxy-7,7'-diphenoxy ~ i, 4,4 ', 4'-tetramethyl-bis-2,2'-spirochroman

Compound XI

CH ₃

CH ₃

JO

J5

HO

methyl-to-2,2'-spirochroman

CH ₃ OCH ₂ CH = CH ₂

CH ₃ CHjCHNHCOCH ₃

CH ₃ CH ₂ CHnHCOCH ₃

CH, ^^^ '^' - tetra m; thyl-bis-2,2'-spirochrornan

Compound XIII

CH

HO

CH ₃ CH ₃ CONH- ^ ^ -CH ₂ CH ₂

6,6'-Dihydroxy-7,7'-dt-Xp-acetylaminophenyl) -ethyl-4,4,4 ', 4'-tetramethyl-bis-2,2'-spirochroman

Compound XIV

CH ₁

CH,

CH,

OH

CH ₃

CH ₃

6,6'-dihydroxy-4,4,4'.4'.7,7'.8.8 ^: -octamethy! -Bis-2,2'-spirochronian

Compound XV

CH.

HO

CH,

V-OH

CH,

CH,

CH, Cl

methyl-bis-2,2'-spirochroman

in

The color photographic recording material preferably contains the UV absorbing compound in an amount of 0.05 to 5 moles, preferably 0.1 to Moles, per mole of 5-pyrazolone purple coupler. The color photographic Recording material preferably contains, as silver halide, silver chloride, silver bromochloride, Silver bromide or silver iodobromochloride.

In a special form of training, this includes color photography Recording material as well

2,5-di-t-octylhydroquinone,
2,5-di-n-octyl hydroquinone.
2-methyl-5-t-octy! Hydroquinone or
2-Me thy l-5-n-octy! Hydroquinone

as alkyl hydroquinone.

In a further embodiment, this includes color photography Recording material as well

a stilbene derivative,

a 2-aryiimino-J-aryimethylene-thiazoline,

a 2-arylimino-3-alkyl-5-heteromethylene

thiazoline or
a 2-benzotriazolyl-4-alkylphenol

as UV absorbing compounds.

The above-mentioned dihydroxyspirochroman compounds are new compounds and they can be made by Condensation of hydroquinone derivatives with acetone is produced:

C)
2ΗΟ-ΛΛ-ΟΗ + 3CH ₃ CCH ₃

R ₁ R ₂

HO

OH + 3H ₂ O

CH ₃

CH ₃

R, R

For a more detailed explanation, a synthesis example -to (1) for the preparation of the new dihydroxyspirochroman compounds are given below.

Synthesis example

Sequentially 620 g (5.0 mol) of methylhydroquinone, 1500 cc of glacial acetic acid were charged into a controller with a stirrer and a Rückflußküh- Ai provided 5-1 three-necked flask. 580 g (10.0 mol) of acetone and 850 ecm of concentrated (2) hydrochloric acid were added. The mixture warmed slightly melted gradually 5 <> evenly and wu ^r de lightly brown. Then, it was heated under reflux in an oil bath with stirring, and the reaction liquid turned black-brown in about 30 minutes. The reaction liquid was further refluxed in this state for 7 to 8 hours and then allowed to stand at room temperature. Within a few days a black precipitate separated out and about 5 days later the separated crystals were filtered (3) and, after washing well with water, recrystallized twice from bO ethanol. Colorless, needle-like crystals with a melting point of 145 to 149 ° C. were obtained in an amount of 220 g.

The dihydroxyspiro (4) used according to the invention Chromanverbindungen of the general formula I have in the color photographic according to the invention Recording materials have the following properties

The dihydroxyspirochroman compounds of the present invention significantly reduce the degree of fading (degree of fading) under the action of light to which the magenta color image obtained from the pyrazolone coupler is subjected. In comparison to the previously known dye stabilizers, they can have an equivalent effect in smaller amounts.
The dihydroxyspirochromanverbindungen according to the invention are themselves very stable and do not have the tendency to participate in the color formation reaction or during the color development using primary aromatic amine compounds and in a bleach bath that contains a strong oxidizing agent, such as. B. ferricyanide or bichromate contains, lead to discoloration. They do not give discoloration even if they are left in the color photographic material after development.
The dihydroxyspirochroman compounds according to the invention prevent the undesired change whereby the 5-pyrazolone coupler is copied out or yellowing or discoloration of the images occurs when exposed to light or heat. The dihydroxyspirochroman compounds of the present invention are easily soluble in organic solvents, and they can be easily and stably incorporated into color photographic materials.

(5) The dihydroxyspirochroman compounds of the present invention can easily be made in one step from cheap raw materials that are readily available are to be synthesized.

(6) The compounds of the present invention have no adverse photographic effect Emulsion, in which they are incorporated, and they interfere with the color formation of the 5-pyrazolone purple coupler not.

The preferred 5-pyrazolone purple couplers include / u the groups that can be represented by the following structural formulas II and III:

Structural formula II

R, -C CH-X

Il I

N C = O

Structural formula III

R, -C

CH- CH- CH- C - R <

C = O O = C N

In the above formulas means

R _{4 is} an aryl group or a substituted aryl group. A suitable substituent for the aryl group is an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio group, a halogen atom, a trifluoromethyl, cyano, acyl, sulfonyl, acylamino, sulfonamino, ureido, Amino, carboxyl, alkoxycarbonyl or carbamyl group and R ₄ preferably denotes a phenyl group substituted by these substituent groups.

R _{5 represents} an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, an amino group, a substituted amino group, an acylamino group, a substituted ureido group, a sulfonamide or alkoxy group and

R ^ means a lower alkyl or aryl group.

X represents those radicals which are produced by the oxidation product of the primary aromatic amine developer / compound can be split off, e.g. B. a hydrogen atom, a halogen atom, a cyano, arylthio, aryloxy, arylazo, heteroazo and acyloxy group.

At least one of the radicals R ₄ and R ₅ contains a hydrophobic radical with 8 to 30 carbon atoms. This hydrophobic residue has a tendency to increase the affinity between the coupler molecules as well as between the coupler molecules and the coupler-solvent molecules and keeps the coupler inside and in the vicinity of the solvent particles which are in close contact with one another. This hydrophobic residue also gives the coupler

solvent has an affinity for the dyes derived therefrom and has a tendency to enhance the effect of the coupler solvent. This hydrophobic radical is contained in R ₄ or R <, which are linked to the coupler radical directly or indirectly through a divalenlen organic radical with an amine, ether, ester, urea or sulfonamide bond. A hydrophobic radical suitable according to the invention can be selected from the group of straight-chain or branched alkyl, alkenyl, alkoxyalkyl, alkoxyaryl, aryl, aryloxyalkyl, aryloxyaryl and acylaminoalkyl groups. Specific examples of the hydrophobic residue are as follows:

.-, (i) n-CpHu -

(ii) nC _l6 H "CH = CH -
(iii) nC | ₂ H; <O (CH ₂ )., -

■ "(iv) n-C |, H" -O

(ν) nC, ₂ H ₂₅ - <;

(vi)

/ ~ \ —Q-LH ₁ -

N = /

nC ₁₅ H "
(vii) SeC-C ₅ H ,,

OCH ₂ -

sec.-

(viii) tert-C ₄ H

(ix) nC | ₂ H ₂₅

nC ₁₅ H "-C

N-CH ₂ CH ₂ -

nC ₄ H,

In practicing the present invention, a dispersion product in which a dinydroxyspirochroman compound has been separately emulsified to form a photographic silver halide emulsion, containing a diffusion-sensitive pyrazolone coupler can be added or the diffusion-sensitive Pyrazolone coupler and the dihydroxyspirochroman compound are dissolved in the same solvent to form a mixed solution, which is then dispersed in an aqueous medium and the resulting dispersion is added to the photographic emulsion.

The amount of the dihydroxyspirochroman compound used in the present invention varies depending on the purpose for which the color photographic material is used should be, depending on the type of 5-pyrazolone coupler and also an amount depending on the structure of the dihydroxyspirochroman compound to be used within the range of 0.05 to 5.0 mol per mol 5-

12th

However, pyrazolone coupler is effective, particularly one particularly preferred with the present invention Amount is 0.1 to 2.0 moles. The results can be used are Specific examples of 5-pyrazolone purple couplers include the following:

Coupler

Melting point

N == CC _n H,

C-CH,

82-84 ⁰ C

Ci

Cl

Cl

= C-

C-CH,

Il ο

N = C

C-CH,

Il ο

V-OC ₁₁ H,

OC ₁₈ H, -

121 ° C

100-102 ⁰ C.

104-105 ⁰ C.

N = C-NH

Cl

CH ₂

N = C-NH

C-CH,

NHC OC H ₂ O

NHCOCHO

C ₂ H ₅

C ₅ H ₁₁ C

C ₅ H ₁₁ (I)

C ₅ H ₁₁ (I)

174-175 ° C

172 ° C

13th 14th

Ιοί Iscl / uni!

Coupler

Melting point

N = C-NHCOCH, -CH, - Ν

COC ₁₁ H ₂₃

CH, (n)

125 ° C

Cl

LI <' 1 IN

Cl

C-CH ₂

N = C-NHCOCHXH ₂ N

C-CH,

COC ₁₅ H ₃ ,

LjH,

* - '* "*? Vi r ~> χ τ ι ι / * ■ * f \ r ^ ι ι / ~ \ // \ ν

CH ₃

N = C-NHCOCHO

CH,

C ₁₅ H ₃₁ (Ii)

96-98 ° C

Cl

-CH ₂

K Cl

Cl

y ν

Cl

Cl

Cl

Cl

Cl

N = C -NHCO-

C-CH, 0

N = C-NHC0

C-CH ₂ O

N = C-NHCO

C-CH,

N = C-NHCO

NHCOCH ₂ O- ^ ^ -C <H ,, (sec)
C ₅ H _n (SeC)

140-142 ⁰ C.

NHCOCH ₂ O-

<f

C ₅ H _n (I)

176-177 ° C

C ₅ H _n (I)

C ₅ H _n (I)

141 ⁰ C

C ₅ H _n (I)

M Cl

C ₂ H,

Cl

C-CH,

Il ο

123 ° C

C ₁₅ H _3I (n)

15 16

Fortset / unu

Coupler

Melting point

Cl

N CH ₃ - <f% -N

N = C-NHCO

C-CH ₂

a

0 Cl NHCOCH ₂ O- <f \ - C ₅ H ₁₁ (O C ₅ H _n (I)

O CH ₃ O - <f> - N

N = C-NHCO

C ₂ H ₅
C.

L C-CH ₂

Cl J ₁

C ₅ H _n (O

C ₅ H _n (I)

Cl

N = C-NHCO

C ₅ H ₅
NHCOCHO- ^

CHj

C-CH ₂

C _IS H ₃₁ (n)

/ Vn

Cl

N = C-NHCONHC "Hj ₇

C-CH,

Cl

R Cl

N = C-NHCONH

C ₂ H ₅
NHCOCHO- <f

150-152 ⁰ C.

175 ° C

106-108 ⁰ C.

103 ⁰ C

-C ₅ H ₁₁ (O

129-131 ° C

Cl

Ci

C-CH ₂

C ₅ H ₁₁ (O

N = C-NHCONH

S CH ₃ - <> --N

i, C-CH ₂

Cl _{| (}

Cl

T CHjO

4 \

= C-NHCONH

Cl

C-CH ₂

Il ο NHCOCH ₂ O- ^ Vc ₅ H ₁₁ (O C ₅ H ₁₁ (O

C ₂ H ₅

C ₅ H ₁₁ (O

¹⁶² ° ^C

308 125/10

17th

18th

continuation

Coupler

Melting point

Cl

U Cl

N = C-NHCO

NHCOCH ₂ O ^^

Cl

Cl

C-CH

Il I λ \.

0 N = N- <f> -OCH ₃

V CH ₃ O

4th
\

N = C-

C ₅ H _n (I)

C ₅ H ₁₁ (O

Cl

C-CH

Il I

O N = N

NHCOCH ₂ O -OCH ₃

150-153 ° C

5H ₁₁ (O

175-177 ° C

C ₅ H ₁₁ (O- / V-OCH ₂ CONH

C ₅ H _n (O

CONH —C CH-

Il I

N C =

N Cl I Cl

Cl

CHCH ₃

C ₅ H ₁₁ (I)

OCH ₂ CONH

C ₅ H ₁₁ (O

CONH —C CH-

Il I

N C =

N Cl I Cl

Cl

163-166 ° C

186-188 ° C

CH-

COOH

= CC ₁₇ H ₃₅

C-CH ₂

171-175 ⁰ C.

continuation

Coupler

Melting point

N = C = CHC NHCOCHCh ₁

CH ₂ COOH

C-CH ₂

Il ο

N = C-NHCO

NHCOCHCH = CHC ₁₆ Hj ₃ CH ₂ COOH

= C-NHCO

NHCOCHCH = CKe ₁₆ H ₃₃ CH ₂ COOH

N ~ C -NHCO

C-CH ₂

NHCOCHCH = CH-C ₁₆ H ₃₃ CH ₂ COOH

196-199 ° C

The dihydroxyspirochroman compounds of the above given structural formula I have a clear stabilizing effect on the incorporated by the Azomethine dyes derived from couplers having a 5-pyrazolone ring and sometimes also have them has a stabilizing effect on color images produced by magenta couplers with other structures, e.g. B. 5-pyrazolobenzimidazoles, indazolones or 2-cyanoacetylchromanes. In addition, wise the invention to be used Dihydroxyspirochromanverbindungen the effect that they Improve light fastness even in color images which are impaired by yellow color couplers consisting of acylacetanilides and by cyan color couplers consisting of phenols or α-naphthols.

The dihydroxyspirochroman compounds of the present invention are easily soluble in many organic compounds Solvents. These compounds are finely dispersed in an aqueous medium after being in have been dissolved in an organic solvent. The emulsion thus obtained is then used to photograph: - see emulsion added. An embodiment of the Invention consists in adding the dihydroxyspirochromanverbindungen with oil-soluble 5-pyrazolone couplers mix and then disperse the mixture in the medium or the dye stabilizer and the To separately add couplers in the form of a solution or a dispersion to the emulsion.

For the purpose of adding the coupler and the invented

UV-absorbing compound used according to the photographic emulsion can various organic solvents are used; are particularly suitable for this purpose however, the solvents described below:

(1) Practically water-insoluble and non-volatile solvents with a boiling point at normal atmospheric pressure of not less than 200 ^° C., e.g. B. di-ß'butyl phthalate, tri-o-cresyl phosphate, tri-n-hexyl phosphate, Ν, Ν-diethyl caprylamide, di-n-butyl succinate, p-nonylphenol and chlorinated paraffins;

(2) partially water-soluble and volatile solvents with a boiling point at normal atmospheric pressure of not higher than 120 ⁰ C; this type of solvent is completely removed during the manufacturing process of the photographic material, e.g. B. ethyl acetate, cyclohexyl alcohol and cyclohexanone;

(3) water-miscible solvents; this type of solvent is used during manufacturing Process of photographic material removed by washing or dialysis, e.g. B. methanol, Ethanol, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethyl sulfoxide, dimethyl formamide, hexamethyl phosphorylamide and methyl cellosolve.

This in an aqueous medium for photographic

phiscbe purposes dispersed dibydroxyspirochromane compounds are not soluble in water and, moreover, in none of the others for photography Development used, developer solutions containing developer compounds with a high pH soluble and does not happen to be lost by leakage during development or that they diffuse other layers of the photographic material.

In practicing the invention, one type of those represented by general formula I may be used Dihydroxyspirochroman compound either individually or in groups of the same structural formula can be used in combination. It can also be connected by using the connection with a different dye stabilizer than such of the general formula I the dye stabilizing effect according to the invention can be increased even further. For example, those described in US Pat. Nos. 23 36 327, 24 03 721 and 27 28 659 are suitable Alkylhydroquinones for use in conjunction with dihydroxyspirochromes by general Formula I. As a result, not only the purple color image produced by the pyrazolone coupler becomes clear made lightfast but also that remaining in the color photographic material after development Pyrazolone coupler can be effectively prevented from yellowing or discoloration (Staining) when exposed to heat or light. For specific examples of include such connections

2,5-di-t-octylhydroquinone,
2,5-di-n-octylhydroquinone,
2-methyl-5-t-octyl hydroquinone and 2-methyl-5-n-octyl hydroquinone.

The use of an acid buffer solution as a final bath for developing the photographic of the present invention Material is preferred to further improve the durability of the BiHes. This is in Japanese Patent application 82 769/1970 described in more detail.

For the color development of the dihydroxyspirochroman compounds according to the invention The usual general methods can be used for the photographic material containing the material. Removing the Silver is preferably done with a bleach bath that contains a weak oxidizing agent. It is beneficial that the color photographic material of the invention with aldehydes such as formaldehyde, either treated during or after color development. This not only serves to make the hydrophilic film hardening of the color photographic material, but also improves the heat resistance of the color image. It is advantageous if the color photographic material according to the invention is in the final stage of the Color development process is treated in a stabilizing bath. This bath contains an acidic substance, a water-soluble substance having an effect of stabilizing the color image, an ultraviolet absorbent and a fluorescent collector. As a color image stabilizer, that can be added to the stabilizing bath, hydroquinone or his are suitable substituted derivatives, urea or its substituted derivatives and p-alkoxyphenol or its substituted ones Derivatives. The dihydroxyspirochromic compound used according to the invention prevents in particular effective fading of the color image protected by the UV absorbing means by the Light. Stilbene derivatives have proven to be particularly suitable as additional UV-absorbing agents (See e.g. the known Japanese patent applications 9 585/1970 and 9 586/1970), 2-arylimino-3-arylmethylene thiazolidone or 2-arylimino-3-alkyl-5-heteromethylene thiazolidone (See the published Japanese patent application 29 627/1969) and the 2-benzotriazolyl-4-alkylphenols, as they are for example ! 0 wise in the well-known Japanese patent application 19 299/1968 are described.

example 1

is 17 g of 1- (2 ', 6'-dichloro-4'-methoxy) phenyl-3- [3 "{ir- (2'", 4 '"- di-t-amylphenoxy) butylamide} benzamide] -5 -pyrazolon (example compound O) as magenta couplers listed in the following Table UV-absorbing compounds in the quantities also specified and a solution obtained by heating 34 g of tricresyl phosphate and 30 ml of ethyl acetate were mixed with an aqueous solution of 50 ⁰ C, m ' e containing 1.0 g of sodium dodecylbenzenesulfonate and 25 g of gelatin, mixed and subjected to strong mechanical agitation in a high speed mixer to finely disperse them.

To the obtained coupler dispersion product, 500 g of a photographic emulsion containing 36.7 g Silver iodobromide and 45 g gelatin was added.

15 ml of an acetone solution of 3% triethylenephosphamide were added as a hardening agent. The mixture obtained in this way was applied to baryta paper to a dry layer thickness of 5 microns. This color photographic paper was exposed to light using a sensitometer through a step wedge with green light and developed as indicated below at 30 ⁰ C.

Color development Color developer 7 minutes ⁴⁰ 1. Stop-fix bath 2 minutes 2. Water 2 minutes 3. Bleach solution 2 minutes 4th To wash 2 minutes .. 5. Hardening and fixing bath 2 minutes ⁴ⁱ 6. Water 2 minutes 7th dry 8th.

Each of the treatment solutions described above had the following composition:

Color developer
(Treatment 1)

Sodium metaborate 25.0 g

Sodium sulfite 2.0 g

Hydroxylamine sulfate 3.0 g

Potassium amide 0.5 g

bo 6-nitrobenzimidazole nitrate 0.02 g

Sodium hydroxide 4.0 g

Benzyl alcohol 15.8 ml

Diethylene glycol 20.0 ml

4-amino-3-methyl-N-ethyl-8.0 g

bj N - (, / 5-methyhulfonamidäthyl) aniline
3 / 2H ₂ O- H ₂ SO ₄

Water ad 1 I.

pH 10.6

Stop-fix bath ad 120.0 g (Treatment 2) 20.0 g Ammonium thiosulfate 10.0 g Sodium metabisulfite 1 I. Glacial acetic acid water pH 4.5 Bleach bath 25, floor (Treatment 4) 20.0 g Potassium nitrate ad 8.0 g Potassium ferricyanide 5.0 g Potassium bromide 2.5 k Boric acid I 1 Boron; ix water pH 7.2

Hardening and fixing bath
(Treatment 6)

Ammonium thiosulfate ad 120.0 g Sodium sulfite 5.0 g Boric acid 2.5 g Formalin (38%) 40 ml water 1 I. pH 9.5

These developed samples were filtered through a filter that removes virtually all ultraviolet rays for 10 days at a wavelength of less than 400 microns with a daylight fluorescent lamp exposed. The luminous intensity of the emitted light at this point in time was 10,000 lux. Changes in Oriin density (fading of the purple dye image) and those of blue density (yellowing of the bright image areas) became before and after the exposure measured. The results obtained are given in the table below.

Table I.

Changes in the developed samples upon exposure to light

rehearse

UV-absorbing compound Type

lot

(G)

Fading of the
Purple dye image
(Decrease in green light density, initial density = 1.0)

Contamination or discoloration in the
bright picture frames (increase in blue light dichotomies)

Duration of light exposure

5 days 10 days 10 days

Comparative sample not added 0 0.35 0.67 0.10 I. according to the invention Verb. 1 3.4 0.09 0.18 0.08 2. according to the invention Verb. Il 3.4 0.09 0.17 0.08 Comparative sample known connection *) 3.4 0.10 0.21 0.09 Comparative sample known connection *) 6.8 0.10 0.20 0.09

*) 2.2,4-Trimethyl-7-t-octyl-6-hydroxychroman (DE-OS 15 47 e> 84. Compound 7).

From the results given in the table above, it can be seen that the invention Compounds ir are able to effectively prevent fading of the magenta dye image and their The improvement effect exceeds that of the known UV-absorbing compounds. Also can the compounds according to the invention effectively prevent the formation of the dye image unused residual couplers cause yellowing or staining on exposure or heating (Discoloration) and this shows that they extend the shelf life of color photography and the Dye image stabilizers can improve.

Example 2

On a paper carrier that is on a surface that had been made hydrophilic, had a polyethylene layer on it, was in the form of a first layer (with a dry film thickness of 4 microns) an α- {4-methoxybenzoyl) - [2'-chloro-5 '- (2 ", 4" -di-sec.-amyIphenoxyacetamido)] acetoanilide as a blue-sensitive emulsion layer containing yellow couplers and in the form of a An intermediate layer made of gelatin is applied to a wide layer (1 micron).

One obtained by melting by heating to 55 ° C. the mixture of 32 g of the purple coupler 1- (2 ', 4', 6'-trichlorophenyl-3- [3 "{ff- (2" ', 4 "' - di-t -amylphenoxy) butylamide) benzamide] -5-pyrazolone (Compound example L), 63 ml of tri-n-hexyl phosphate, 50 ml of ethyl acetate and the The solution obtained below indicated dye stabilizers was 700 ml of a 45 g Gel'Mne and 3.0 g of aqueous solution containing sodium dodecyl sulfate were added and the mixture was stirred. They were in one High speed mixer vigorously mechanically agitated for 30 minutes. This made the coupler and the dye stabilizer is finely dispersed in the solvent. All of the emulsified dispersion solution was added to 1 kg of a green-sensitive photographic emulsion containing 0.27 ml of silver iodobromide and contained 70 g gelatin. After adding 50 ml of an acetone solution of 3% triethylenephosphamide as a hardening agent, the third layer photographic emulsion was added to the above color photographic paper applied to form a dry film thickness of 3 microns. On the The above layer became the fourth layer as a 2-benztriazo-4-sec.-butyl-6-t-butylphenol as an ultraviolet absorbent containing gelatin layer to a dry film thickness of 2 microns and then a 1-Hy-

2ft

droxy ^ -chlor ^ -dodecylnaphthamide as a cyan coupler containing red sensitive emulsion layer to a dry film thickness of 3 microns and thereafter a 1 micron thick layer of gelatin as a protective layer to complete the color photographic Paper applied.

This color photographic paper was exposed to green light through a step wedge and on

Table Il

similar manner to Example 1 of color development was subjected to a magenta dye image having a gradually varying dye density exhibited. These developed samples were exposed directly to the light of a daylight fluorescent lamp exposed to a light intensity of 10,000 lux and the results obtained are as follows Table II indicated.

Fading of the purple images and discoloration (staining) of the highlight areas when the developed areas are irradiated Samples with light

UV absorbing compound Type

Amount of fading of the
Purple color picture
(Decrease in the (irünlichtdichle for a
initial density
from 1.0)

Contamination of the highlight areas (increase in blue light density) (thereby
it is about the
Absolute value of blue density measured by a
Blue filter)

Ie) duration of light exposure

10 days 20 days 20 days

Comparative sample

Comparative sample

not added according to the invention. Verb. I according to the invention. Verb. Il known compound 7 (DE-OS 15 47 684)

0 0.31 0.45 0.25 6.4 0.09 0.17 0.14 6.4 0.08 0.17 0.14 12.8 0.10 0.20 0.17

As can be seen from the above results, the compounds of the invention are both in able to effectively prevent fading of the magenta dye image as well as more effective improvement than with the known UV absorbing compound. It was found that the Compounds according to the invention effectively prevent the highlight areas of the color copy when Exposure to turn yellow.

Example 3

For the preparation of the dispersion solution with the emulsifying coupler, that of the green-sensitive emulsion to be added in the manner indicated in Example 2, except for the coupler, the Solvent and the UV-absorbing compound, the hydroquinone derivatives given below admitted. The above example was repeated for all other points, and those obtained thereby Results are given in Table III below.

Tabel Days) lot Dihydroxyspirochroman derivatives I. lot and hydroquinone derivatives Discoloration (fleece : III UV absorbing compound education) the high Hydroquinone drugs Fading of the light districts United improvement effects through Type Purple dye (Increase in (Light exposure time 20 (G) Type (G) image (decrease Blue light dichle) sample 6.4 3.2 the green light density at one 6.4 3.2 initial 0.10 according to the invention Density of 1.0) Compound I 6.4 2,5-di-t-octyl- 3.2 0.14 0.11 according to the invention hydroquinone Compound II 6.4 the same 3.2 0.14 0.12 5 according to the invention Compound I 2.5-di-n-octyl- 0.12 0.13 6th according to the invention hydroquinone Compound II the same 0.13 7th 8th

When these results are compared with those of Table II, it can be seen that when the compounds of the present invention, namely, the dihydroxyspirochroman compounds, are used in combination with the alkylhydroquinone, they are effective in preventing the fading of the magenta dye image and at the same time effectively preventing the light image areas from being stained . _n . ·,,
Example 4

The sodium salt was applied as the first layer to a film base made of cellulose triacetate red-sensitive emulsion layer containing l-llydroxy-4-sulfo-2-octadecylnaphlhoamide as a cyan coupler to a dry film thickness of 5 microns and a 1.5 micron gelatin intermediate layer as the second layer applied one after the other.

The solution obtained by dissolving the specified in the following Table IV UV absorbing compounds and Hyurochinonuerivaie in iOrni Tri-G-Mcsyipiiuspuai and 1.0 ml of ethyl acetate at 5O ⁰ C was added to 200 ml of a 15 g of gelatin, 0.5 g sodium p-dodecylbenzenesulfonate and 0.5 g of aqueous solution containing sodium bisulfite was added and the mixture was stirred. They were finely dispersed by vigorous mechanical stirring using a high speed mixer for 30 minutes. The entire emulsified dispersion solution was added to 1 kg of a green-sensitive emulsion containing 0.27 mol of silver iodobromide and 70 g of gelatin. It was then added to an aqueous solution containing 21.8 g of 1-phenyl -3 - (3 '- (ff-oleylsuccinamide) benzamide (-5-pyrazolone (compound example A') and 1.5 g of sodium hydroxide) and the pH the emulsion was adjusted to 6.0 using an aqueous solution of 5% acetic acid, and to this solution was added 20 ml of an aqueous solution of 4% sodium salt of 1-hydroxy-3,5-dichloro-S-triazine as a hardening agent , which was then applied to the above-mentioned color film base as a third layer up to a dry film thickness of 5 microns. A gelatin layer containing a yellow colloid was also applied to the third layer of the film up to a dry film thickness of 2 microns, one of the 2-sodium salt of <7- ( 4-Oleylsuccinamidobeniuyl) -2'-rncil'iuXy-5 - (. AiuLiAj'dtciuaMiMÜ al »Gciukuppiei containing blue-sensitive layer as a fifth layer up to a thickness of 6 microns and a high molecular weight ultraviolet absorbent with the following specified S. structure-containing gelatin layer up to a thickness of 2.5 microns applied to complete the color film,

NaO ₃ S

NHSO,

SO,

SO ₁ Na

where m is a large positive number.

This film was made by a Stufenkci! exposed to green light and then developed in the color developer solution of the composition given below at 20 ^° C. for 18 minutes.

Color developing solution

Water 1000 ml

N.N-diethyl-p-phenylenediamine sulfate 2.8 g

Sodium sulfite 2.5 g

Sodium carbonate 65.0 g

Hydroxylamine hydrochloride 1.0 g

Potassium bromide 1.2 g

running water of 17 ⁰ C washed to produce a purple picture.

Bleach and fix solution

Water 1 1

EDTA-2 Ma-SaIz 35 g

Sodium hydroxide 11g

Ferric chloride 25 g

Hyposulfite 5H; O) 170g

Borax 10 g

Potassium bromide 30 g

Potassium thiocyanate 10 g

Then, 2 minutes, washed at 17 ° C, treated in a bleaching and fixing solution of the following composition for 5 minutes at 20 ⁰ C and finally for 10 minutes in

Table IV

Bleaching of the purple dye images and discoloration (staining) of the highlight areas when irradiated with light

The color developed samples were exposed to light from a xenon lamp with a luminous intensity of 50,000 Lux exposed through a heat absorbing filter for 3 days. The results obtained are in given in Table IV below.

sample UV absorbing link Hydroquinone derivative lot Fading of the Contamination of the Purple dyeF- Hochlichtb- 'i-ke Type lot Type image (decrease (Increase in the green light Blue light density) (G) density at one Initial density (G) from 1.1)

Comparative
D robe

not added

not set 0.55

0.15

i-location

Sample UV absorbing compound
Type amount

(G)

llydrochinonderiva

Type amount

■ λ: '! Bleach Je ·; Contamination of the Purple dye llochlicht districts bildcs (decrease (Increase in the green light Blue light density) density at one AnCang density of 1.1) 0.12 0.09 0.09 0.05 0.11 0.10 0.07 0.07

9 according to the invention
Compound I 2.2 2.5-di-t-octyl
hydroquinone 10 according to the invention
Compound I 2.2 the same 11th according to the invention
Connection Il 2.2 the same 12th according to the invention
Connection II 2.2 the same

From r'p.n results in the table above show that by the compounds according to the invention the fading of the purple dye image up to can be reduced to a considerable degree in that they prevent the unexposed, uncolored ones bright areas of the image turn yellow on exposure and that their effects through the common use can be further strengthened by dialkylhydroquinone.

Example 5

To 200 g of an emulsion containing 0.27 mol of silver iodobromide and 70 g of gelatin in 1 kg were the solutions given below with a dispersed magenta coupler and those given below Dispersion solutions of color stabilizers added. After adding another 3 ml of a Acetonlösur.g of 3% Triälhylenphospharnid were they on a Polyathylenterephthalatfi'm up to one Dry film thickness of 5 microns applied.

Coupler dispersion solutions: the couplers shown in Table V below were refluxed dissolved in 10 ml of tri-n-hexyl phosphate and 15 ml of ethyl acetate. The resulting solution became 70 ml of a 0.5 g Containing sodium cetyl sulfate and 5.0 g gelatin

Table V

Fading of the magenta dye images on exposure to aqueous solution was added. They were in one Homomixer mechanically stirred vigorously to disperse them.

Dispersion solutions of the dye stabilizers: those indicated by dissolving those given in Table V below UV absorbing compound in a mixed solvent of 2 ml of di-n-butyl phthalate and 5 ml of ethyl acetate were added to 30 ml of 0.1 g of sodium cetyl sulfate and 2.0 g of gelatin containing aqueous solution added. It was mixed with vigorous mechanical stirring in a homomixer dispersed.

These film samples were exposed sensitometrically and treated as indicated in Example 1 under Formation of purple dye images and through a Ultraviolet absorption filter with light from a fluorescent lamp with a light intensity of 10,000 lux 10 days long exposure to determine the fading of the dye images. The results obtained are given in Table V below.

As indicated in the following table, the dihydroxyspirochroman compounds used in the present invention make the azomethine dye compound produced from 5-pyrazolone couplers with various substituent groups lightfast.

sample Purple coupler lot UV absorbing link Fading Type Type lot (Decrease in green light (G) density at one 4.52 (G) Initial density of 1.0) Comparative sample A. 4.52 not added 0 0.27 13th A. 4.52 I. 0.5 0.09 14th A. 4.52 II 0.5 0.10 15th A. 5.80 V 0.5 0.12 Comparative sample H 5.80 not added 0 0.70 16 H 5.80 VI 0.6 0.25 17th H 5.11 IX 0.6 0.19 Comparative sample J 5.11 not added 0 0.45 18th J 5.11 II 0.5 0.10 I.
0.08 ■ 19th J VIII 0.5

continuation

sample Purple coupler UV absorbing link Fading Type amount Type lot (Decrease in green light density at one (G) (S) Initial density of 1.0)

Comparative sample

W.
W.
W.

Example 6

6.15 6.15 6.15

not added

I. V

0.6

0.6

0.51 0.15 0.18

The tests were carried out according to the procedure described in Example 2.

On a paper carrier with a polyethylene layer on its surface became the first layer Dry film thickness of 4 μΓη a blue sensitive Emulsion layer containing α- (4-methoxybenzoyi) - [2'-chloro-5 '- (2 ", 4" -di-sec.-amylphenoxyacetoamide)] - acetanilide as a yellow coupler, and as a second layer An intermediate layer of gelatin is drawn up from 1 μm strength.

The solution, which by melting at 55 ° C a

Mixture of 32 g of l- (2 ', 4', 6'-TrichlorphenyI-3- [3 "- {e- (2" ', 4 "' - di-tert-amylphenoxy) -butylamido} benzamido] - 5-pyrazolone as a purple coupler, 63 ml of tri-n-hexyl phosphate and 50 ml of ethyl acetate and each of the UV-absorbing dyes in the table below specified types and amounts was obtained, was 700 ml of an aqueous solution with a Content of 45 g of gelatin and 3.0 g of sodium dodecyl sulfate were added and the mixtures were given a strong mechanical stirring with a high speed mixer for 30 minutes. The Coupler and the UV stabilizing compound are finely dispersed in the solvent. The entire emulsified Dispersion solution became 1 kg of a green-sensitive photographic emulsion containing of 0.27 mol of silver iodobromide and 70 g of gelatin were added. 50 ml of an acetone solution containing 3% triethylenephosphoramide was added to the above photographic emulsion as a hardening agent. Each The resulting mixture was applied as a third layer to the above color photographic papers a dry film thickness of 3 μΐη drawn up.

A gelatin layer containing 2-benzotriazo-4-sec.-butyl-6-tert.-butylph.enol as a UV-absorbing layer was applied to this third layer as the fourth layer Compound applied to a dry film thickness of 2 μm, and then a red-sensitive emulsion layer containing l-hydroxy-4-chloro-2-dodecylnaphthamide as a cyan coupler was applied to a dry film thickness of 3 μm and a 1 μm thick gelatin layer was coated as a protective layer, whereby the color photographic papers were obtained.

The color photographic papers were exposed to stepwise fashion · green light by means of a sensitometer and developed at 30 ⁰ C in the following manner.

Color development treatment stages

1. Color development 7 min

2. Stop fix bath 2 min

3. Soak for 2 min

4. Bleach solution 2 min

5. Laundry

6. Hardening and fixing bath is 7. Watering

8. Drying

2 min 2 min 2min 2min

The following treatment solutions were used:

Color developer (Treatment level 1)

Natnummetaborat 25.0 g Sodium sulfite 2.0 g Hydroxylamine (sulfate) 3.0 g Potassium bromide o ^ g 6-NitrobenzimidPzol (nitrate) 0.02 g caustic soda 4.0 g Benzyl alcohol 15.8 ml Diethylene glycol 20.0 ml 4-amino-3-methyl-N-ethyl N - (/ J-methylsulfonamidoethyl) - aniline 3/2 H ₂ O H ₁ SO ₄ 8.0 g Water to 11 solution (pH = 10.6) Stop fix bath
(Treatment level 2) Ammonium thiosulfate 120.0 g Sodium metabisulfite 20.0 g Glacial acetic acid 10.0 g Water up to 11 solution (pH = 4.5) Bleach bath (Treatment level 4) Potassium nitrate 25.0 g Potassium ferricyanide 20.0 g Potassium bromide 8.0 g Boric acid 5.0 g borax 2.5 g Water up to 11 solution (pH - 7.2) Hardening and fixing bath (Treatment level 6) Ammonium thiosulfate 120.0 g Sodium sulfite 5.0 g Boric acid 2.5 g Formalin, 38% 40.0 ml Water up to 11 solution (pH = 9.5)

The developed samples were directly exposed to light with a luminous intensity of 10,000 lux from a fluorescent lamp of the daylight type.

The changes in green density (bleaching of the purple dye image) and blue density (yellowing in the highlight areas) were measured both before and after exposure to light. The results obtained are shown in Table VI below.

34

For comparison, the compounds 1,5 and 7 of DE-OS 15 47 684 with the following formulas used.

Connection 1

HO

(OC ₄ H ₉ Table VI

CH ₃

Compound 5 HO

(OC ₄ H, compound 7

HO

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

(t) C, H ₁₇

Fading of the purple dye images and staining of the highlight areas when the developed samples are irradiated with light

sample UV absorbing compound lot Fading of the Contamination of the 20 days Art Purple color stump picture Hochlict'.tbereiches (Decrease in green (Increase in blue light light density at a density) applied initial (Absolute value of density of 1.0) Blue density, measured through a blue filter) (G) Period of light exposure 10 days 20 days

comparison No addition 0 0.31 0.45 0.25 Comparison A Connection 1 12.8 0.16 0.24 0.21 Comparison B Connection 5 12.8 0.16 0.25 0.20 Compare C Connection 7 12.8 0.10 0.20 0.17 D. Compound H
according to the invention 6.4 0.08 0.17 0.14 E. Compound III
according to the invention 6.4 0.12 0.20 0.16 F. Compound IV
according to the invention 6.4 0.11 0.20 0.16

It follows from the above values that the compounds used according to the invention the fading of the dye images can be prevented to a far greater extent than with DE-OS 15 47 684 specified UV absorbing compounds. These results are even more surprising

the fact that the amounts of the compounds according to the invention used were lower than those of the comparative compounds, i.e. H. the quantities of the compounds according to the invention were only half of the comparison compounds.

Claims (1)

Patent claims: 1, a color photographic recording material which, in at least one silver halide emulsion layer, has a 5-pyrazolone magenta coupler which has at least one hydrophobic group with 8-30 carbon atoms, and a UV-absorbing Contains compound, characterized in that the UV-absorbing compound of the formula is equivalent to OH