DE1138316B - Photographic material containing an azopyrazolone dye, optionally in the form of a color photographic material, for the silver dye bleaching process - Google Patents

Description

The silver dye bleaching process for producing colored photographic images is the observation based on the fact that numerous azo dyes with which the layer formers, especially gelatine, are colored, depending on the amount of photo image present in the layer. That Image silver is usually created by exposing, developing and fixing the elements in the colored layers existing, light-sensitive, optionally sensitized silver halides.

The process can be applied to colored layers, whereby the layer former is applied before Generation of the layer or the finished layer on its base with azo dyes. It can be also apply to multilayer material.

For example, it can be on a transparent or white-pigmented layer carrier and on baryta-coated Paper three layers of color can be applied. Immediately on the carrier material are z. B. a dyed with green-blue dye, selectively red-sensitized silver bromide emulsion, over it a purple-colored, selectively green-sensitized silver bromide emulsion and finally a yellow-colored, selective blue-sensitive layer. By copying a colored original picture using a usual light source, e.g. B. tungsten light bulbs (integral or additive copy), or partial color separations with selectively colored copying light, the silver bromide is in the required places in the assigned partial layers exposed. After exposure, developing into image silver with the usual For developers and for fixing, the colored layers each contain the associated partial color separation as a negative silver image in the homogeneously colored individual layers.

The requirements imposed on those in the photographic material in the silver dye bleaching process Dyes are made are extremely versatile. In addition to the one for the silver dye bleaching process required easy bleachability, such dyes must have good water solubility, must be resistant to diffusion in gelatine or other layer-forming colloids and the photographic ones must be allowed Properties of the halide silver emulsions in which they are embedded, not disadvantageous influence. They must be lightfast and have pure color nuances.

Among those who have become known for the silver dye bleaching process yellow azo dyes, the pyrazolone dyes occupy an important place. Lots of dyes this group have the property in oxidizing baths such. B. in ferricyanide photography,

containing an azopyrazolone dye Material, if necessary as a color photo

graphic material formed,

for the silver dye bleaching process

Applicant:
CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dr.-Ing. F.Wuesthoff, Dipl.-Ing. G. pulse and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Claimed priority:
Switzerland of March 25, 1960 (No. 3377)

Dr. Paul Dreyfuss, Basel (Switzerland),
has been named as the inventor

bath to be destructible, which may increase their value as filter dyes, but which does their utility as image dyes for the silver dye bleaching process is reduced.

The invention now relates to a photographic material containing pyrazolone dyes, which surprisingly differ from the pyrazolone dyes already proposed for the purpose mentioned Advantageously, they differ on the one hand depending on the amount available Let image silver fade according to the usual methods, but on the other hand with oxidizing baths, such as Potassium ferricyanide baths or strongly acidic copper salt baths, are not destroyed.

The new photographic material is characterized in that it contains at least one dye the formula

R-NH-C-B-N = N-Py (1)

contains, wherein B is a monocyclic, in the m- or p-position to the - CO and the - N = N group bonded benzene radical, R an aromatic radical and Py a bonded in the 4-position to the azo group 5-pyrazolone radical means.

209 677/280

The dyes of the formula (1) can contain one or more than one pyrazolone radical bonded to an azo group and optionally more than one remainder of the composition

R -NH-OC-B

contain. Dyes that contain at least one of these radicals more than once in the molecule can be Manufacture by making tetrazo compounds, which are the remainder of the formula

- R - NH- OC- B -

contain, coupling with pyrazolones or by monoazo dyes which correspond to the formula (1) and contain at least one reactive substituent, preferably an H ₂ N group, with suitable agents, e.g. B. phosgene or cyanuric chloride linked together.

The monoazo dyes produced by coupling diazo compounds with pyrazolones which can be coupled once obtained by coupling diazo compounds on both sides with two couplable Dipyrazolones or by coupling ίο tetrazo compounds on both sides with pyrazolones which can be coupled once and those by linking monoazo dyes to a single reactive group available dyes are uniform dyes of the formula

-Py-N = N - / - B-C-HN- \

J Jc-

-R-NH-C-B-

Ii ο

(m-i) (2-m)

-N = N-Py- -Py-N = N-B-C-HN-R-

-H

in which B, R and Py have the meaning given and k, tn and η each denote an integer with a value of at most 2.
As already mentioned, these dyes can do the

(OT-I) (fi-l)

Pyrazolonxest bound to the azo group contain once (m = V). However, the dyes which contain this residue more than once, e.g. B. twice, and thus which of the formula

-Py-N = N-> -HN-N -R-NH- -C-
Il -B- N = N-Py- ( J Il
O <a - »> '-B- Y L. -C-
Il 11
O

-Py-N = N-B-C-HN-R-

(71-1)

correspond, in which B, R, Py, k and η have the meaning given.

Dyes of the formula (3) can thus be obtained as follows:

a) Coupling a doubly couplable dipyrazolone with a diazo compound of an amine formula

R-NH-OC-B-NH ₂ or 2 molecules of a monoazo dye of the formula are linked

R-NH-OC-B-N = N-Py

which contains a group capable of linking in the pyrazolone radical, with one another and arrives in this way to a dye of the formula

R —NH-C-B-N = N-Py-Py-N = N-B - C —HN-R (4)

Il Il

ο ο

b) A tetrazo compound of a diamine of the formula is coupled

H ₂ NB-CO-HN-R-NH-OC-B-NH ₂

on both sides with a pyrazolone and receives a dye of the formula

Py-N = N-B-C-HN-R-NH-C-B-N = N-Py

(5)

With a suitable composition of the radical R, e.g. B.

65

these dyes can also be obtained by linking monoazo dyes to the remainder of the diazo component build up, for example by adding a diazo compound of an amine of the formula

H ₂ NB —C —HN-R '—NO ₂ (7)

Ij O

wherein R 'denotes a benzene radical, couples with a pyrazolone, the nitro group to the amino group reduced and treated the aminoazo dye obtained with phosgene.

c) By coupling tetrazo compounds of diamines on both sides of the formula

H ₂ NR-NH-OC-NH ₂

pyrazolones lead to dyes of the formula

Py-N = N-R-NH-C-B-N = N-Py

(8th)

In the formulas listed under a) to c) and also in the following formulas, B, R and Py always have the meaning given above, unless otherwise stated.

Dyes suitable for the present purpose, which are characterized by particularly good diffusion fastness can also be produced if the for

Py-N = N- / B-C-HN-A-R-NH-C-B-N = N-Py

Preparation of the component serving for the dye to be used for the photographic material have two reactive sites. This is the case when you have tetrazo compounds with twofold pyrazolones which can be coupled or if azo dyes are used with two identical linkable Substituents linked together in the molecule, e.g. B. Diaminoazo dyes treated with phosgene. In the case of the coupling of tetrazo compounds, one can also use a molecular ratio work, which is different from 1: 1, where appropriate an excess of the pyrazolone is used. In this way it is possible to obtain dyes, which have both sufficient water solubility and good diffusion resistance.

Apparently the products obtainable in this way do not represent uniform compounds, but mixtures of Bodies of different molecular weights and can be represented by the formula

'fc-1

where / c is an integer with a value of at most 2 and χ is an integer greater than 1 means.

As can be seen from the above, the pyrazolone dyes suitably contain acidic, water-solubilizing groups, e.g. B. carboxylic acid groups and / or preferably sulfonic acid groups. These can be present at any point on the dye molecule, due to their good accessibility but with advantage in the pyrazolone residues or in the aromatic residues R.

The rest

-N = N-B-C-

jl

preferably correspond to the formula The pyrazolone radicals are advantageously the radicals the formula

HO

C-N-R ₉

—C:

C = N

R ₁

-N = N-

—C—

- H

(10)

where ρ is an integer with a value of at most 2. This radical can thus be a benzene radical bonded in the 1-position to the azo group, further substituted in the 6-position by a methyl group or not further substituted in the 3- or 4-position to the - CO group, preferably the radical of the formula

-N = N

into consideration, wherein R _{1 is} a z. B. low molecular weight alkyl group, in particular a methyl group or a free or optionally functionally modified carboxylic acid group, e.g. B. a carboxylic acid ester _{or carboxamide group, and R 2 is} an aromatic radical of the naphthalene series or preferably the benzene series. The already mentioned several times the point of attachment of two pyrazolone radicals, as they are, for. B. occurs in the dyes of the formula (4), is conveniently located on the radicals R ₂ . So z. B. the phenyl radicals of a 1-phenylpyrazolone can be connected to one another directly or via a bridge member such as a —CH = CH group, a urea or triazine bridge.

The radicals R are also advantageously radicals of the benzene or naphthalene series, which z. B. a contain a single naphthalene nucleus or one or two benzene nuclei.

The diazotization components are expediently by acylation of an aromatic amine with a Nitrobenzoyl chloride and subsequent reduction prepared in a known manner. The tetrazotization components are obtained in a corresponding manner from nitrobenzoyl chloride and aromatic diamines. Here you can either react 1 mole of the diamine with 2 moles of nitrobenzoyl chloride and receives a symmetrical tetrazotization component after the reduction. But you can also preferably use an unsymmetrical tetrazotization component, as can be obtained by acylation of 1 mole of a diamine with 1 mole of a nitrobenzoyl chloride

or obtained by acylation of a nitroaniline with nitrobenzoyl chloride and subsequent reduction.

Suitable diazotization components are, for. B.

N- (3-aminobenzoyl) -l-naphthylamine, N- (4-aminobenzoyl) -sulfanilic acid, N- (3-methyl-4-aminobenzoyl) -2-naphthylamine-4,8-disulfonic acid.

Suitable tetrazotization components are, for. B.

N, N'-bis- (3-aminobenzoyl) -benzidine-2,2'-disulfonic acid,

l-Ammo-3- (meta-aminobenzoylamino) -benzene-6-sulfonic acid,

l-Amino-3- (para-aminobenzoylamino) -benzene-6-sulfonic acid.

Suitable pyrazolones are, for. B.

l-phenyl-S-methyl-S-pyrazolone, l-phenyl-S-methyl-S-pyrazolon ^ '- sulfonic acid,

l-phenyl-S-pyrazolon-i-i-carboxylic acid ethyl ester-4'-sulfonic acid,

l- (3'-aminophenyl) -5-pyrazolone-3-carboxylic acid,

particularly good lightfastness; where even higher lightfastness is required, it can do Treatment with metal donors can be improved.

The dyes to be used according to the invention can be mixed with a silver halide emulsion in gelatin or used in another colloid; you can z. B. also in droplets high-boiling crystalloid material or in

ίο a special colloid layer, which is the halogen silver layer to be incorporated; they can be diffusion-resistant per se or through additives in one diffusion-resistant form are brought. On the other hand, you can also, as is the case for certain transmission methods is desirable to be capable of diffusion. The dyes according to the invention can be used in Cast in single layers or in multilayer materials or in package emulsions; you can serve to generate transparent or reflective images.

In German Patent 892 860, azo dyes are used as dyes for the silver dye bleaching process have been described whose diazonium radical are derived from primary aromatic amines and a

UHDiphenylen- (4,4 ')] - bis (3-methyl-5-pyrazolone), _{a5 residue with a long} phosphatic chain. The Pyrl, l '- [2,2'-disulfo-diphenylene- (4,4')] - bis (3-methylazolone dyes of this patent are the de-

5-pyrazolone),

l, l '- [2,2'-Disulfo-diphenylene- (4,4')] - bis (5-pyrazoIon-3-carboxylic acid,

It is noteworthy that the dyes to be used according to the invention are bleached to pure white and that the whites produced by bleaching do not yellow even when the pictures are stored for a long time.

The lightfastness of speaking pyrozolone dyes of the formula (1) is superior. In addition, German Patent 902 581 describes individual azo dyes 30 for the silver dye bleaching process which contain pyrazolone residues and residues of 4,4'-diaminodiphenyl-2,2'-disulfonic acid. Compared to these dyes, the corresponding dyes of the formula (1) containing aminobenzoyl radicals have the advantage. This is the case even when large molecular weight substances have the significantly better diffusion resistance.
Pyrazolones, e.g. B. those that are followed by a larger figure below under A to F information about

radical bonded in the 1-position to the pyrazolone ring the preparation of a number for the present are complained to apply. The pyr- purpose of suitable dyes. In this information and azolone dyes of the groups given at the outset, the following example denote the parts settlement are characterized by pure light yellow shades, 40 unless otherwise noted, parts by weight, Particularly good permeability for light from the waves - the percentages percentages by weight, and the temperatures length over 500 ηιμ and very good lightfastness. are given in degrees Celsius.

Because of their complete bleachability and their special- A. 422 parts of N- (meta-aminobenzoyl) -2-naphthyl-

The amine-4,8-disulfonic acid to be used according to the invention (obtainable by reduction The dyes are particularly suitable for non-reflective images of the acylation product of 2-naphthylamine-4,8-dinet. They are well compatible with silver bromide emulsion. sulfonic acid and 3-nitrobenzoyl chloride) are diazo dies diffusion-resistant representative, ie especially dosed and in a weakly alkaline solution with 219 parts those from tetrazotization components and / or l- (m-aminophenyl) -5-pyrazolone-3-carboxylic acid ge-bispyrazolones are made to be used. The dye is isolated and turned into neutral preferred for use in multilayer materials. Lots of 50 buffered aqueous solution exhausting with phosgene the dyes according to the invention are characterized by treated. The obtained dye of the formula

SO.H

NH-CO-

N = N-HC

Il

HO-C

C-COOH

Il

SO, H

-NH-

: co

colors gelatin in a pure yellow shade. It is practically almost free of diffusion, is compatible with silver bromide emulsion and bleaches in the presence of metallic
Silver.

B. 291 parts of N, N'-bis (meta-aminobenzoyl) benzidine-2,2'-disulfonic acid (obtainable by reducing the acylation product from 1 mol of benzidine-2,2'-disulfonic acid and 2 moles of 3-nitrobenzoyl chloride)

HoC-C

C-N = N

C-OH

can be combined in a strongly alkaline aqueous solution with aqueous gelatin solution, then rendered neutral and mixed with a silver bromide emulsion in gelatin. It is diffusion-proof and for use suitable in multi-layer castings.

C. By coupling 291 parts of N, N'-bis (meta-aminobenzoyl) -benzidine-2,2'-disulf onic acid with 219 parts of 1 - (meta-aminophenyl) -5-pyrazolone-3-carboxylic acid and exhaustive treatment with phosgene

tetrazotized and coupled in alkaline solution with 174 parts of l-phenyl-3-methyl-5-pyrazolone. The received, very pure light yellow dye of the formula

CO —HN-

HO ₃ S

a diffusion-resistant yellow dye of golden yellow hue is obtained.

D. 307 parts of 1-amino-3- (meta-aminobenzoylamino) -benzene-6-sulf onic acid (produced by acylating 1 mol of 1,3-phenylenediamine-4-sulfonic acid with 1 mol meta-nitrobenzoyl chloride and reduction of the obtained Product) are tetrazotized and coupled with 438 parts of 1- (m-aminophenyl) -5-pyrazolone-3-carboxylic acid. The yellow dye of the formula obtained

HOOC - C C

= N-

-NH-CO-

N ^ C-OH

N '

HO, S-I.

N = N-HC
HO-C

C -COOH

, / -NH ₂

is largely resistant to diffusion and can be used for multi-layer castings to be treated using the silver dye bleaching process Find use. By treatment with phosgene, it can be converted into transformed into a completely diffusion-resistant dye.

E. A tetrazo solution of 307 parts of 1-amino-3 - (meta - aminobenzoylamino) - benzene - 6 - sulfonic acid ', -NH ₂

(1 mol) becomes a neutral solution of 506 parts by weight of 1,1'- [2,2'-disulf o-diphenylene (-4,4 ')] - bis (3-methyl-5-pyrazolone) (1 mol) is added dropwise, and the pH is adjusted by the simultaneous addition of sodium carbonate solution held at 7. The polyazo dye, which probably consists essentially of units of the formula

HO

OH

C — N -

C = N

HO ₃ S SO ₃ H

-N-C

N = CC - N = N- (\ - CO - NH- / \ —Ν = Ν

H _a C

CH ₃

is isolated in a salt-free form. Similar dyes are made from the same starting materials produced in other proportions, e.g. B. from 307 parts of the tetrazotization component and 1012 parts of the pyrazolone component (molecular ratio 1: 2). All these dyes are of pure, spectrally identical, greenish-yellow tone. The solubility of the dyes in water and also the Diffusion increases as the amount of pyrazolone increases. During the coupled in a molecular ratio of 1: 1 Polyazo dye is sparingly soluble, the dye is coupled in a molecular ratio of 1: 1.3 (307 parts by weight of tetrazo component and 658 parts by weight of pyrazolone) soluble in water and very easily completely diffusion-proof in gelatine. The dye, coupled in a molecular ratio of 1: 1.6, is also non-diffusion-proof. The readily soluble 1: 2 molecular ratio coupled disazo dye diffuses when it is poured in high concentration with little gelatin, noticeably more, but this is also dye Can be used for multi-layer castings with usual layer thicknesses and usual color densities. Preferably be Dyes of the stated constitution are used in which the molecular ratio is tetrazo component to pyrazolone component between 1: 1 and 1: 2, e.g. B. is 1: 1.2. This dye stands out

209 677/280

due to good solubility, diffusion resistance, good spectral properties, compatibility with halogen silver emulsion, complete bleachability and high lightfastness.

F. If the tetrazotization component used according to E is replaced by 307 parts of 1-amino-3- (para-aminobenzoyl-amino) -benzene-6-sulfonic acid replaced and coupled with 675 parts of the same pyrazolone component, a golden yellow dye is obtained otherwise similar properties. If the tetrazotization component is replaced by the same amount l-amino-4- (para-aminobenzoylamino) -benzene-2-sul-

H ₃ C-CO-NHOH H ₃ CO fonic acid (prepared by reducing the condensation product of para-phenylenediaminesulfonic acid and p-nitrobenzoyl chloride), an orange-yellow dye with similar properties is obtained.

example

The following layers are poured on top of one another on a cellulose acetate film in the order given:

a) A red-sensitized silver bromide emulsion containing the cyan dye of the formula

NH-OC-

SO »H

b) A green sensitized silver bromide emulsion containing the purple dye of the formula

NH-COCH ₃ H ₃ C-CO-HN

CO- / \ / V-CO

HN OH H ₃ C cn. ^CH 3 ^{H0 NH}

¹ \

> - C CH ₂

HO ₃ SI

SO ₃ H

c) A filter layer formed from colloidal silver and dye, the dye given above under F described, coupled in a molecular ratio of 1: 1.33 Dye from l-amino-4- (para-aminobenzoylamino) -benzene-2-sulfonic acid and 1,1 '- [2,2'-disulfodiphenylene- (4,4')] - bis (3-methyl-5-pyrazolone) is used.

d) An unsensitized silver bromide emulsion having the same molecular ratio as that described under E above 1: 1.2 coupled dye is stained.

The material produced in this way is processed according to the usual methods of the silver dye bleaching process. It has a sufficient sensitivity for the usual lighting conditions in all color layers. The material is exposed, for example, under a colored positive master copy, in a Metol-Hydroquinone-Developer developed, fixed and in a dye bleach bath, which is made of hydrochloric acid, Thiourea and phenazine was prepared, bleached. After removing the excess silver in a potassium ferricyanide bath and subsequent treatment in a fixer bath, an image is created in preserved natural colors.

Claims (12)

PATENT CLAIMS: 1. Photographic, an azopyrazolone dye containing material, optionally designed as a color photographic material, for the Silver dye bleaching process, characterized in that it contains at least one dye of the formula R_NH - C - B - N = N - Py Il ο contains, wherein B is a monocyclic, in the m- or p-position to the —CO— and the —N = N group bonded benzene radical, R an aromatic radical and Py one in the 4-position to the Azo group-bound 5-pyrazolone radical mean. 2. Photographic material according to claim 1, characterized in that there is at least one dye of the formula H - Py-N = N - / - B.-C-HN- \ R-NH-C-B-N = N-Py - Py-N = N-B-C-HN-R- (ro-i) (2- ») -H («1-1) (fl-l) contains, where B, R and Py have the meaning given and k, m and η each represent an integer with a value of at most 2. 3. Photographic material according to claim 2, characterized in that there is at least one Dye of the formula _Py_N = N - / - B-C-HN-Y— -R-NH-C-B-N = N-Py- -Py-N = N-B-C-HN-R- (m-l) contains, wherein B, R, Py, k and η the specified characterized in that there is at least one Have meaning. io dye of the formula 4. Photographic material according to claim 3, R -NH-C-B-N = N-Py-Py-N = N-B-C-HN-R Il Il ο ο contains, wherein B, R and Py have the meaning given.
5. Photographic material according to claim 3, characterized in that it contains at least one dye of the formula Py-N = N- B -C-HN- R-NH-CBN = N-Py Il Il ο ο contains, wherein B, R and Py have the meaning given.
6. Photographic material according to claim 3, characterized in that there is at least one Dye of the formula Py-N = N-R-NH-C-B-N = N-Py il ο contains, wherein B, R and Py the specified Be 35 characterized in that there is at least one have meaning. Dye of the formula 7. Photographic material according to claim 1, Py-N = NABC-HN R-NH-C-B-N = N-Py
O contains, where B, R and Py has the meaning given and χ is an integer of at least 2. 8. Photographic material according to claim 1, characterized in that there is at least one Contains dye obtained by coupling a tetrazotized diamine of the formula H ₂ N- / B-C-HN-AR-NH-C-B -NH ₂ wherein B, R and k have the meaning given, was obtained with a bis-pyrazolone capable of double coupling. 9. Photographic material according to claim 8, characterized in that there is at least one Contains dye, in the manner indicated in claim 8 by coupling the tetrazo compound with the bis-pyrazolone in a mol- ular ratio between 1: 1 and 1: 2 was obtained. 10. Photographic material according to claim 1, characterized in that it contains at least one dye which is linked to the Amino groups, preferably by means of phosgene, from a dye of the formula Py-N = N-A-B-C-HN - \ - R - NH-C - B-N = N-Py was obtained in which B, R, Py and Ic have the meaning given and both pyrazolone radicals _{contain an H 2} N group. 11. Photographic material according to one of the Claims 1 to 10, characterized in that in the dyes of the specified compositions 16 C- Il ο Setting the Leftovers
-N = NB I. i - C i; 5 the formula -N = N - B. - \ the formula ii
O O
-H -N = N- <z C. 2Ϊ.-1 10 correspond. Il
O -N = N— correspond to, where ρ is an integer in the value of Documents considered: means at most 2. 15 German Patent Specifications No. 892 860, 902 581; 12. Photographic material according to claim 11, Werner Schultze, »color film and color photo characterized in that the remainders graphie ", 1953, p. 94.