DE1960730B2 - PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

wherein R is a Wasserstonatom or Kernsubstituent, Z represents a nonmetallic atom group required for completing a 5- to 6-membered heterocyclic ring, R, and R ₂ are each a Alkylgrappe having 1 to 5 carbon; ₀ atoms of substance or an alkyl group which is substituted by a hydroxyl, acetoxy, sulfate (S0 ₄ H), carboxyl, carboxyalkoxyl, sulfo, hydroxysulfo or alkoxysulfoalkoxy radical, m is the number 1 or 2, X is an anion and ρ denotes the number i or 2, and contains a hypersensitizing compound (II), characterized in that the hypersensitizing compound (II) is at least one condensation product of formaldehyde and a substituted or unsubstituted polyhydroxybenzene of the general formulas below

(OH), * (OH) " ₂ ^OH

3S

40

2. Recording material according to claim 1, characterized in that the carbocyanine dye contains at least one quinoline nucleus which as substituents R halogen atoms, an alkyl group with 1 to 8 carbon atoms, an Alkosylgnippe or may contain a hydroxyl group.

3. Recording material according to claim 1, characterized in that the formalin condensation product has a degree of polymerization of 2 to 10 units and a molecular weight of 300 to 800.

4. A recording material according to Claim i, characterized in that the carbocyanine dye are present in a concentration or amount of 0.002 contain the formalin condensation product in a concentration or amount of 0, ¹ to 5.0 g / mole of silver halide to 0.2 g / mol silver halide, and .

5. Recording material according to claim 1, characterized in that the concentration or quantity ratio of carbocyanine dye to formalin condensation product is in the range from 1: 5 to 1: 500.

where R ₃ and R ₄ each contain one of the radicals OH, OMe, OR ₆ , NHR ₆ , NH ₂ , N (R ₆ J ₂ , NHNH ₂ , NHNHR ₆ (where R _{6 is} an alkyl group having 1 to 8 carbon atoms , an aryl group or an aralkyl group and Me represents an alkali metal or alkaline earth metal), R _{5 represents} a hydroxyl group or a halogen atom, and n ¹ and n ¹ each represent 1, 2 or 3.

The invention relates to a photographic recording material with a spectrally oversensitized photographic film applied to a layer support Silver halide emulsion containing a sensitizing mixture of a carbocyanine of the formula I.

R ₁ -N

-CH = CH-C = (CH-CH) _n = JEf = NR ₂

rin R is a hydrogen atom or a core substituent,: a non-metallic atomic group which is necessary for the completion of a 5- to 6-membered heterocyclic ring, R ₁ and R ₂ each have a; yl group with 1 to 5 carbon atoms or a: yl group which is replaced by a hydroxyl -, acetoxy, fat (SO ₄ H) -, carboxyl, carboxyalkoxyl, sulfo-, droxysulfo- or alkoxysulfoalkoxy radical substituted m the number 1 or 2. X is an anion and ρ is the number 1 or 2, and from a supersensitizing active compound (II) contains.

It is known that by adding an additive, which does not use the photographic emulsion in the same wavelength range as the sensitizing

sensitizing dye, along with the sensitizing dye to the photographic silver halide emulsion at least a part of the wavelength range, in which the dye sensitizes, inten-

is more sensitized than when the dye is Emulsion alone is added. This phenomenon is usually called "supersensitization" (oversensitization) denotes and other compounds that the photographic emulsion is not in the same Wavelength range like that of the sensitizing dye sensitize, are called "supersensitizers".

For example, US Pat. No. 2,158,883 describes photographic silver halide emulsions, the one oversensitizing combination of at least one ^ -carbocyanine dye of the general formula

Y <> R '

C = CH-CH = CH-C N

N ^X X

wherein A is a divalent aryl group, in particular a phenylene or nyphthylene group, R and R 'are alkyl groups. Y is oxygen, sulfur or selenium and X is an acid residue with at least one pseudocyanine or contain isocyanine dye.

The sensitizer mixtures used lead to panchromatic sensitization, and are therefore for selectively red-sensitive emulsions such as those used in color photographic recording materials are necessary, poorly usable, since these emulsions have an undesirable, intense have spectral sensitivity within a wavelength range of about 480 to 530 ΐημ.

The object of the invention is therefore a spectrally oversensitized silver halide photographic emulsion indicate in which only the sensitivity to red is increased without, however, any Increase in the sensitivity to green and the formation of fog.

The object of the invention is based on a photographic recording material with a Spectral hypersensitivity applied to a layer support th photographic fusion of silver halide, which is a sensitizing mixture of a Carbocyanine of formula I.

R ₁ -N / = CH- CH = CH- C = (CH-CHl =

NR ₂ (X);

where R is a hydrogen atom or a core substituent, Z is a non-metallic atomic group which is necessary for the completion of a 5- to O-membered heterocyclic ring, R ₁ and R _{2 are} each an alkyl group with 1 to 5 carbon atoms or an alkyl group which is replaced by a hydroxyl, Acetoxy-, SuIfUt (SO ₄ H) -, carboxyl-, carboxyalkoxyl-, sulfo-, hydroxysulfo- or alkoxysulfoalkoxy radical is substituted, »ι the number 1 or 2, X an anion and ρ the number 1 or 2, and from one oversensitizing compound (II) contains, and is characterized in that as the oversensitizing compound (II) at least one condensation product of formaldehyde and a substituted or unsubstituted polyhydroxybenzene of the following general formulas

OH) "4

OH) "2

OH

where R ₃ and R ₄ each contain one of the radicals OH, OMe, OR ₆ , NHR ₆ , NH ₂ , N (R ₆ ); ,, NHNH ₂ , NHNHR ₆ (where R _{6 is} an alkyl group with 1 to 8 Carbon atoms, an aryl group or an aralkyl group and Me represents an alkali metal or alkaline earth metal), R _{5 represents} a hydroxyl group or a halogen atom, and n ¹ and n ² represent 1, 2 or 3, respectively.

The 4-quinoline nucleus contained in the above general formula (I) can, for. B. be substituted by halogen atoms, alkyl groups with 1 to 8 carbon atoms, alkoxyl groups or hydroxyl groups. Examples of the heterocyclic ring completed by Z are 4-quinoline nucleus, 2-quinoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazole nucleus, oxazole nucleus, benzoimidazole nucleus, 3,3-dialkylindoles. Examples of the radicals represented by Ri and R ₂ are methyl, ethyl, propyl and similar Al-

alkyl groups and substituted alkyl groups, e.g. B. β - hydroxyethyl, β - acetoxyethyl, ethyl sulfate - (- C ₂ H ₄ SO ₄ H), carboxymethyl, β - carboxyethyl, γ - catboxypropyl, 2 - (2 - carboxyethoxy) - ethyl, β - sulfoethyl,> ■ - sulfopropyl, 2 - hydroxy -1 - sulfopropyl or 3 - methoxy - 2 - (3 - sulfopropoxy) - propyl groups. The chemical structural feature of such sensitizing dyes can be seen in the fact that they contain at least one 4-quinoline nucleus. Typical examples of the compounds of the general formulas IIa, lib and Hc given above are: p-dihydroxybenzene, o-dihydroxybenzene, ρ - hydroxybenzoic acid, ρ - hydroxybenzenesulphonic acid, m - hydroxybenzoic acid, η - hydroxybenzenesulphonic acid, a-resorcinic acid, / i-resorcic acid, ; · - Resorcic acid. 3,5 - dihydroxybenzenesulfonic acid, 2,4-dihydroxybenzenesulfonic acid, 2,6-dihydroxybenzenesulfonic acid, 2,5 - dihydroxybenzoic acid, 3,5 - dihydroxybenzoic acid, 2,5 - hydroxybenzenesulfonic acid,

Pyrogallol carboxylic acid - (5), pyrogallol carboxylic acid - (4), pyrogallol sulfonic acid - (5), pyrogallol sulfonic acid (4), and their alkali salts (Li ₅ Na, K. or dgL) and their alkaline earth salts (Mg, Ca or the like). Further examples effectively used in accordance with the invention are the amides or hydrazides of the aforementioned carboxylic acids or sulfonic acids, and amide compounds or hydrazide compounds of these N-alkyl (1 to 8 carbon atoms) or N-aralkyl or N-allyl derivatives. The esters of the above-mentioned carboxylic acids or sulfonic acids can also be effectively used according to the invention.

The condensate of the above-mentioned optionally substituted polyhydroxybenzenes and formaldehyde can be used in the usual way for the production of novolak-like phenol-formaldehyde resin getting produced. In general it is made in the following way: The polysubstituted Hydroxybenzoi is dispersed in water. and after adding concentrated hydrochloric acid and 37% Formalin, the dispersion is stirred at 100 ° C. for 30 to 60 minutes. After that, if necessary Hydrochloric acid is added and heating and stirring are continued. After the reaction has ended the product is poured into cold water and the precipitate is collected and purified to the To get condensate.

Another example is explained in more detail below. For example, 415 parts of p-hydroxybenzoic acid in 1000 parts of water under vigorous Stir dispersed and 25 parts of a 35 "oigen or more concentrated hydrochloric acid and 245 parts of 37% formalin is added to the dispersion. Then the reaction mixture is left for 30 minutes stirred at 100 ° C. and after further addition of 20 parts of concentrated hydrochloric acid, the system becomes reacted for a further 30 minutes.

At the end of the reaction, 20 parts are more concentrated Hydrochloric acid is added to the reaction product and the system is stirred while the reaction solution becomes cloudy and white. After stirring for about 90 minutes, the stirring is stopped and the reaction mixture is stopped poured into 3000 parts of cold water with stirring. The product so precipitated will separated off by filtration, redissolved in 1000 parts of methanol, the product not yet dried and then precipitated again by adding water. The product is filtered through recovered and dried to obtain the desired condensate. When other substituted or unsubstituted polyhydroxybenzenes are used in place of the abovementioned p-hydroxybenzoic acid can be the method described above or a slightly modified method to reach the condensate effortlessly to use. That after the one described above Process obtained condensate has like the usual novolak resin about 2 to 10 units in a condensation unit (degree of polymerization).

The invention achieves that the red sensitivity of spectrally oversensitized photographic Silver halide emulsion is greatly increased without increasing the green sensitivity and fogging.

If, according to the invention, a formalin condensate is added to a silver halide emulsion which has the Sensitizing dye of the specified form! (I) contains, excellent supersensitization can be obtained, and moreover, fogging tendency can be reduced can be remarkably lowered as compared with the case where the sensitizing dye was added to the emulsion alone. Some of the sensitizing dyes contemplated above Formula (I) when incorporated into the photographic light-sensitive materials have Disadvantages that the sensitivity thereof is reduced during storage, however, such Lowering of sensitivity during storage can be prevented by working according to the invention incorporated the dye of the emulsion together with the formalin condensate.

According to a further embodiment of the invention, a formalin condensation product with a Degree of polymerization from 2 to 10 units and in particular a degree of polymerization from 2 to 5 units and a molecular weight of 300 to 8 (X) preferred, with a particularly good sensitivity probability distribution is achieved.

The concentration of the sensitizing dye of the invention in the silver halide emulsion fiee 'preferably in the range from 0.002 to 0.2 g per mole of silver halide, and the concentration of the formalin condensate in said emulsion is preferably in the range from 0.1 to 5.0 g per mole of silver halide. The particularly effective concentration ratio of sensitizing dye to formalin condensate is preferably in the range from 1: 5 to 1: 500.

The sensitizing dye can be the emulsi .. after any suitable way of working that has been got in the field. be admitted. That Formalin condensate can be the halide silver emulsion in the form of a solution in water or in an organic Solvent, for example methanol or ethanol, are added. The Incorporated sensitizing dye and formalin condensate into the E. emulsion prior to coating.

The sensitizing dye can be added to the emulsion either before or after the addition of the formalin condensate or a mixture of the sensitizing dye and the formalin condensate can be incorporated into the emulsion. In addition, the two components of the emulsion not only be added immediately before coating, but also during ripening can be added to the emulsion after washing.

In the emulsion according to the invention, gelatin is usually used as the binder of the silver halide emulsion used, but also other binders, such as resinous materials or Cellulose derivatives which do not adversely affect the photographic light-sensitive materials can be used.

The inventive composite photographic emulsion can be a gelatin-chlorosilver, Gelatin-bromide-silver. Gelatin-iodobromide silver. gelatin - Silver chlorobromo or gelatin - silver iodochromobromo emulsion.

The silver halide emulsion composed according to the invention can also contain customary additives, z. B. a chemical sensitizer. an antifoggant, a stabilizer, a hardening agent, a wetting agent, a plasticizer, a development accelerator, a toner, a fluorescent whitening agent, an anti-air fogging agent, and a

Cuppler. The silver halide emulsion can according to The sensitivities used according to the invention

: in the usual procedure on a suitable sizing dyes of the above form

questioners, e.g. B. a glass plate, a cellulose derivative (I) are listed below, for example,

him, a synthetic resin film, or a barite - but not limited to those specified

3paper can be applied. 5 examples are provided:

H ₅ C ₂ -N

CH-CH = CH

N
I.
C ₂ H ₅

H, C, -N

' ^CH ~ ^{CH = CH} \

N
C ₂ H ₅

H ₅ C ₂ -N

/ r

- CH-CH = CH -4,

H ₅ C ₂ -

CH ₃ CH ₃

CH- CH = CH- <, T

I.
C ₂ H ₅

H ₅ C ₂

C ₂ H ₅

(ο

ίο

V V

H ₅ CN> = CH-CH =

Cl

H "C, -N) = CH-CH = CH

/ YV

Y, -V

H ₃ CO- <
H ₅ C ₂ -N

= CH-CH = CH

YV

N
ι QH ₅

HX- <

H, C ₇ -N; -CH-CH =

VA <' ^:

H, O-N> = CH-CH = CH-S

V-

H ₅ QN

CH- CH = CH- <f

> - SO

CH-CH = CH- ^. jl j Br "

C ₂ H ₊ COOH

CH-CH =

Br "

H ₅ C ₂ -N

CH-CH = CH

HcC ₂ -N

CH-CH = CH

The invention is explained in more detail below with the aid of examples.

Examples

In various proportions of a halogen silver emulsion of the same approach, (1) only one sensitizing dye of those given above general formula (I) and (2) a combination of a sensitizing dye of the general Formula (I) and a formalin condensate were added and each portion was placed on a cellulose acetate pad upset. When the pH is lowered by the addition of the formalin condensate to the emulsion the pH was adjusted by adding alkali. After drying, it was coated in this way Recording material through a filter that emits light with a wavelength greater than 590 πΐμ let through, exposed and then developed.

The sensitivity is determined by the reciprocal value of the exposure required to achieve an optical Density of veil +0.1 is necessary, shown the sensitivity in the case of incorporating the sensitizing dye alone in the Emulsion is defined as 100 and the sensitivity in the case of incorporation of the formalin condensate together with the sensitizing dye in the emulsion compared with that so defined Sensitivity is represented.

In the case of incorporating the novolak-like condensate of the optionally substituted polyhydroxybenzene and formaldehyde alone into the emulsion, no sensitizing effect on the emulsion or a very low sensitizing effect was obtained, so that its numerical value is not shown. The emulsions used in the comparative batches were of the same batch, but different emulsions from different stock batches were used in different batches. The results are listed in Table I below, a chlorobromide silver emulsion from the same batch being used in Examples 1 and 2, and a bromo-silver emulsion from the same batch being used in the Examples! and 2 was used, a silver bromide emulsion from the same formulation was used in Examples 3 to 10, and a silver chlorobromide emulsion from the same formulation was used in Examples 11-18. The photographic photosensitive elements prepared in Examples i and 2 and 11 to 18 were developed for 2 minutes at 20 ° C in a developer having the composition shown in Table II below, and those in Examples 3 to 10 The photographic photosensitive elements produced were developed for 4 minutes at 20 ^° C. in a developer having the composition given in Table III below

1-8 (35).
1-8 (35) -J
1-8 (35) - Table I. and
and Formalin
Formalin (350) ....
(480) .... Sensation
opportunity veil example
No. Additive (mg / mole silver halide) 100
120
135 0.16
0.06
0.06 (b)
(C) h Condensation product of / 3-resorcic acid
h Condensation product of γ-resorcic acid

13th

continuation

14th

Example

Addition Img: mol of silver halide!

1-8 (35) + condensation product of 4-hydroxybenzoic acid hydrazide and

Formaldehyde (350)

1-8 (35) 4- Condensation product of 3,5-dihydroxybenzoic acid hydrazide

and formaldehyde (2800)

1-8 (35) 4- condensation product of p-chlorophenol and formaldehyde (700) 1-8 (35) + · condensation product of sodium hydroxybenzenesulfonic acid

and formaldehyde (350)

1-8 (35) + condensation product of p-hydroxybenzoic acid

and formaldehyde

1-8 (35) + condensation product of o-hydroxybenzoic acid

and formaldehyde (1400) ''.

1-6 (40)

1-6 (40) + condensation product of m-hydroxybenzoic acid
and formaldehyde (2800)

1-7 (39)

1-7 (39) + condensation product of o-hydroxybenzoic acid
and formaldehyde (2800) '

1-4 (78)

1-4 (78) + condensation product of o-hydroxybenzoic acid
and formaldehyde (1400) '

1-2 (72)

1-2 (72) + condensation product of o-hydroxybenzoic acid
and formaldehyde

1-3 (38)

1-3 (38) + condensation product of o-hydroxybenzoic acid
and formaldehyde (2800)

1-5 (34)

1-5 (34) + condensation product of hydroquinone and formaldehyde (1400)

1-7 (70)

1-7 (70) 4- Condensation product of o-hydroxybenzoic acid
and formaldehyde (700)

1-8 (70) + condensation product of gallic acid and formaldehyde (2800)

1-9 (42)

1-9 (42) + condensation product of m-hydroxybenzoic acid

and formaldehyde (2800)

1-10 (84)

1-10 (84) + condensation product of m-hydroxybenzoic acid and formaldehyde (5600)

1-11 (41)

1-11 (41) + condensation product of m-hydroxybenzoic acid and formaldehyde (2800)

1-12 (41)

1-12 (41) + condensation product of m-hydroxybenzoic acid and formaldehyde (2800)

1-13 (45)

1-13 (45) + condensation product of m-hydroxybenzoic acid and formaldehyde (1400)

1-14 (40)

1-14 (40) + condensation product of o-hydroxybenzoic acid and formaldehyde (2800)

sensitivity

veil

120

120
190

120
130

250
100

180
100

130
100

140
100

150
100

130
100
290
100

120
100
150
100

! 90
100

120
100

130
100

140
100

200
100

170

0.08

OJl 0.08

0.12 0.06

0.08 0.08

0.06 0.07

0.04 0.0ή

0.05 0.06

0.04 0.06

0.06 0.06 0.06 0.06

0.06 0.11 0.06 0.04

0.04 0.04

0.04 0.04

0.04 0.04

0.04 0.04

0.04 0.04

0.07

Continued 16

example Additive (mg / mole silver halide)

sensitivity

veil

(m ')
(n ')

1-15 (38)

1-15 (38) + condensation product of m-hydroxybenzoic acid and formaldehyde (2800)

1-16 (37)

1-16 (37) + condensation product of o-hydroxybenzoic acid and formaldehyde (2800)

1-17 (35)

1-17 (35) -1- condensation product of o-hydroxybenzoic acid and formaldehyde (2800)

100

210
100

250
100

170

0.07

0.04 0.09

0.04 0.06

0.04

Table Il

N-methyl-p-aminophenol sulfate 3.1 g

Sodium sulfite 45.0 g

Hydroquinone 12.0 g

Sodium carbonate (anhydrous) 67.5 g

Potassium bromide 1.9 g

Water rest on

1.01

Table III

N-methyl-p-aminophenol sulfate 2.2 g

Sodium sulfite 96.0 g

Hydroquinone 8.8 g

Sodium carbonate 48.0 g

Potassium bromide 5.0 g

Water rest on

1.01

586/517

Claims (1)

Patent claims: 1. Photographic recording material with a spectrally oversensitive coating applied to a layer support photographic silver halide emulsion comprising a sensitizing mixture of a Carbocyanine of formula I. CH-CH = CH -C = (CH-CH) = NR ₂ (X);