DD160787A3 - PHOTOGRAPHIC MATERIAL BASED ON HALOGEN SILVER EMULSIONS - Google Patents

Abstract

Claim 1: photographic material based on silver halide emulsions, characterized in that in at least one layer at least one diffusion-resistant compound of an acid-substituted dye and a mordant of the general formula (formula) in which n = 4 to 12, the substituents R ind R 2 and R ind 3 are alkyl radicals having 1 to 4 carbon atoms and may be identical or different.

Description

The invention _; ' relates to photographic materials based on', halogen-based over-emulsions containing dyes which have been made non-diffusible by mordants, in particular filter dyes.

It is known to protect photosensitive emulsion layers of photographic materials from unwanted light of certain wavelength ranges by staining these layers or an adjacent layer with selectively absorbing substances. As light absorbers, e.g. molecularly dissolved organic dyes, pigments or colloidal dispersions (e.g., colloidal silver). Such dyes can be used for color separation, Därbab mood or to reduce the reflection and / or diffusion Lichthofes. All such compounds are to be summarized below as filter dyes.

The following requirements are to filter dyes that: An intended use exactly matched, selective light absorption, diffusion resistance, residue-free Entfernbarkelt or decolorizability in photographic processing gear, photographic reactivity and easy production with consistent quality and the lowest possible cost ·!.

In particular, diffusion resistance is not achieved by most organic dyes. Although pigments and silver sols are diffusion-resistant, they exacerbate the sharpness of photographic images as scattering layers. Material and are therefore unaffected by most modern color materials.

189 1 5d_

useful. In order to obtain diisocyanates solid organic acid-substituted dyes, the pickling with basic substituted compounds, eg basic substituted polymers, biguanides of aromatic diamino compounds or similar substances has been repeatedly proposed. However, such substances have a number of disadvantages. In particular, the resulting dye-mordant salt is often at high concentrations per unit weight. Gelatin is no longer completely decolorizable or it precipitates in the form of crystals. It is particularly disadvantageous, that the light absorption of certain dyes - before pl learning from the class of oxonols - adversely affected by mordant is. The selectivity of the absorption is largely lost with simultaneous density loss' in the absorption maximum, thereby, the effect of the. Dye substantially reduced. Furthermore, known mordants often cause an undesirable influence on horizontal swelling or hardening. ;

It is the object of the invention to provide photographic materials with better sharpness and improved color rendering. The object of the invention is to provide photographic materials which contain filter dyes which have been rendered non-diffusible by mordants and which do not alter the properties of the photographic material into physical -mechanical still negatively influence in photographic terms, have a selective high absorption in the desired spectral range and can be decolorized completely in photographic processing or, can be removed.

The object is achieved according to the invention by using a photographic material based on PIA-based emulsions which, in at least one layer, comprises at least one diffusion-resistant compound of an acid-substituted filter dye and a mordant of the general

189 1 56 -

my formula

P,

C = O

ο.

/in

: ^R 3 V ·. ;;

in which η = 4 to 12, the substituents R, R ₉ .. uη5 R- AlkyIreste having 1 to 4 carbon atoms and may be identical or different, contains.

The acid-substituted dyes may have one or more acidic groups in the molecule. In particular, dyes from the classes of the oronol dyes, merocyanines, dialkylacin compounds or azo dyes are suitable. It. also dye mixtures can be pickled.

D: e preparation of the inventive mordant is carried out by padding isation of the corresponding acrylic acid. - (N.Ii.TI, trialkyl-ammonlurrO-ethyl-salz'e · ^';.:.

They form fprblrse, clear, viscous liquids which ^s: .ch readily dissolve in water and an aqueous solution, react approximately neutral, but they are also stable in moderately acidic to alkaline pH range (pH 4-9).. Such compounds exhibit antistatic properties and are known as antistatic agents in textile chemistry; their beneficial. Application for the production of dif ferentiated filter fibers is unrelated to this and could not be predicted.

189 1 56

_The: use of erfinduhgsgemäßen mordant is carried out as an aqueous solution of 1 to 10 weight percent. More concentrated solutions are: possible, but more difficult to handle due to their higher viscosity.

It has proven to be particularly advantageous to carry out the preparation and purification of the diffusion-resistant compound of acid-substituted filter dye and a mordant according to the invention in a special carrier gel and then add it to the photographic casting solution.

, · ,,:. The optimal ratio

from dye to mordant is suitably determined in a preliminary experiment. , _:

The advantage of the invention is that photographic materials are obtained whose properties, such as e.g. Sharpness and. Color rendering, by incorporation, diffusion-resistant .Filterfarbstoffe or filter layers are significantly improved and retained after passing through the usual photographic processing sganges no residual staining.

On. particular advantage is that the diffusion-resistant .Darbstoff Beizmitte! compounds according to the invention show a very selective absorption and high density, while reduce the selectivity and intensity of absorption in many other Beizurnitteln the pickling.

From. great advantage is also the fact that spezie.il occurs in Pentamethinoxonolen by the Beisung mit.erfindungsgemäßen pickling center in a bathochromic shift of the absorption maximum while maintaining the high density ·. Pent.amethine oxonols have their absorption maxima at. shorter wavelengths than the sensitizing maxima of the usual red .sensibilisatoren, - and a bathochromic shift of the absorption of the ^Filter: rfarbstoffe therefore improves il re significantly effect "I..

-5 -

189 1 56

A further advantage is that the etching agents according to the invention neither influence the horizontal swelling nor the hardening of photographic materials. The viscosity of the potting solution is slightly increased. -

The mordant invention can also be used there with advantage, v / o takes place the formation of the diffusion-resistant, Farbstofi mordant salt until the photographic material, such as _x it eg dye transfer process: the case (Hydrotypieverfahren). In this case, a suitable black and white material is used in a known manner, on which the yellow, purple and blue-green partial images are printed. It is known to add to improve the sharpness and color densities pickling. However, the mordants according to the invention are distinguished from other, hitherto customary, mordants in that the dyes made diffusible with them give very clear, brilliant hues. Likewise, one achieves high color densities and excellent sharpness. The mordants according to the invention may be added directly to the emulsion or may also be contained in a special gelatin layer intended to contain the dyes.

The invention will be explained in more detail with reference to the following examples;

Example : 1 ^: - \

To 100 ml of a 10% gelatin solution containing 500 mg of a., Cr Purple oxonol dye of the formula

CH ..

SO ₃ K

Ji ξ -

18 9 15 6

contains 500 mg of a mordant of the formula

--I-v> H "~~~~~~~ C I '*',

COP- - N (C ₂ H ₅ ) ₂

in the form of a follow 5 solution added (experiment A). The average molecular weight of the amide was determined to be about 1100, which gives an average value of η = 6.

As a comparison serve 100 ml of a TO $ gelatine solution, which also contains 500 mg of said dye, but no mordant (Experiment B).

Both gelatin solutions are cast on a photographic support with the same casting thickness and dried,

The resulting gelatine slices both show the same absorption profile, i. the spectral properties of the dye were not changed by the pickling

 To prove the diffusion; For example, an undyed gelatin layer (Guii thickness about 30 μm), which has been preswollen in water, is pressed onto the dry test piece and kept in close contact for 10 minutes. After separating the layers and drying, the densities of the layers are measured spectrophotometrically. , ,

receives the following densities (at A = 550 nm) j

Table 1

Experiment Sample after diffusion

. ' , :. treats donor-recipient after 60 min.

; · · : '.';; , ;. layer layer waters n

A (with stain- '.

medium) 1.02 1.02 - 1.00

B (without pickling. · ..

average) 1.02 0.32 0.69 0.41

189 156 -τ-

After passing through usual photographic processing such as Golor positive development: color negative development, color reversal development, black and white negative development, etc., both layers were always completely decolorized.

Example 2 -

The experiment of Example 1 is repeated except that the dye is a blue-green oxonol dye of the formula

used in an amount of 300 mg and in turn 500. mg of said mordant.

attempt

Table 2

Sample untreated A max max

 Α (with mordant) 655

B (without mordant) 642

0,99 0,95

After diffusion donor-receiver layer layer

0.97 0.03

0.12 0.83

after 60 min. Moire

0.96

0.20

After passing through common processing, both layers were completely decolorized.

189 1 56 -

Example 3

Trial 1 is repeated using 500 mg of tartrazine and 1000 mg of the example stated in Example 1.

Table 3

attempt

untreated \ max max

436 0.72 436 0.68

after diffusion

Donor-receiver-after-layer

60 min. Water

0.70 0.02 0.08 0.58

0.68 0.05

After passing through the usual processing steps, both layers are completely decolorized ·

Example 4

JPlor-reversed materials are prepared in known manner, as shown in FIG. Where:

a photographic base, los.Β »losetriacetat or polyester

ι, Cellu-

: a red-sensitive bromine silver emulsion containing an oily cyan coupler, as well as other common photographic additives.

12 A j a G-gelatin interlayer to improve the sharpness and color reproduction analogous experiment A of Example 1

12 B: An intermediate gelatin layer analogous to experiment B from Example 1,.

- 9 -

1 89 1 56 -a

: A green bromine silver emulsion containing a standard magenta coupler as well as other commonly used photographic additives

J is a yellow filter layer of density at maximum

(445 nm) of 0.90 from colloidal silver

A: a yellow filter layer analogous to experiment A from example 3

B: a yellow filter layer analogous to experiment B from Example 3

An unsensitized high-sensitivity bromosilicate emulsion containing a yellow coupler and the usual photographic additives.

-10 -

Table 4

Material according to FIG.

Relative b g r

min

Eontureng r sharpness number

Bemerkunger

Type

0.10 0.12 O ₁ IO 1.6 1.6 1.6

37

-0.05 = 0.10 0.13 0.10 1.6 1.6 1.6 + 0.10 + 0.15 0.09 0.12 0.10 1.55 1.6 1.6

53

Color separation cyan / pi pure improved

Color separation generally improves

Λ ¹ * -0.30 -0.05 = P, 10 0.10 0.10 1.251.6 1.6

Color separation insufficient

-0.10 -0.40 = 0.09 0.11 0.11 1.6 1.3 1.6

40

-0.05 -0.25 + 0.10 0.10 0.12 0.10 1.6 1.4 1.6

42

-0.35 -0.40-0.05 0.11 0.12 0.09 1.3 1.3 .1,

Parabentrenner insufficient

1 89156 -ι - "- ^ r ^{:: ·:::} -

The evaluation of the non-ionic test "is shown in Table 4.

The advantages of erfindungsge'mäüen, diffusion-resistant dye-mordant compounds are clearly visible on the materials of Figures 2 and 3 »; In contrast, the use of non-diffusible dyes is always associated with significant loss of sensitivity and sometimes also a deterioration of the color separation, so that such materials are unusable for photographic purposes (materials of Fig. 4 - 7) ·

Example 5 ^':; ' .-.''''..'

For the production of blank film for color transfer process is one common, stabilized in a known manner. Schwara-Weift-Positiv-Emulsion with addition of a non-ionogenic curing agent and 2.5 g of 2-Hyciroxy-4,6-dichloro-striazine per kg of emulsion as a hardening agent applied to a photographic support. (Experiment A). In a second experiment, 10 g of the mordant from example 1 are additionally added to the material. (Experiment B)

'Developing and fixing' you get the following photographic data: / ' . ,

Gradation ^E _re l ^. ~ ·; ~ Gub thickness

Trial A '. , 2,2 'type. : 0.06 9.5 / experiment B '2.3. + 0.40 0.06 '9.8yum; ,

The P2? Üf \ mg of the usability for the diffusion transfer process is carried out by printing an Iviagenta Easters of a stencil film as a template. Reviewed apply D \\ _r and the transmission factor t ^; that's the relationship

D Template _# D Acceptor. Plays (at D Original = 2, C ^{D Minor Template D} in Acceptor /;

, · '. :. ; '''''.' - ^: ΛΖ ~ . · '

189 1 56

A Max attempt [B  ', 2,15 Ve ι search 2.80

He tragunr, s factor

, 0.14 "; 0.90

The advantages of the invention are clear. Brilliance of colors - characterized by half-width

IUBJL

Pickling agent not changed.

¹ W Ina ¹ " ^{becomes durcll} ' ^daa " ~ T " L

- 13 -

Claims (6)

A photographic material based on silver halide emulsions, d _<adu rc hgeke η η ζ η et verifiable that in at least one _of: at least one layer of diffusion-resistant compound from an acid-substituted dye and a mordant of the general formula. , ί>. in which η = 4 to 12, the substituents. ß. * ^Ά ο and R _{7 are} alkyl radicals having 1 to 4 carbon atoms and may be the same or different, is included. 2. Eo to graphic a Iiämaterial according to claim 1, characterized in that dui "is used as an acid-substituted Pilterfarbstoff an oxonol dye · 3. Photographic material according to claim 1, characterized in that an acid dye is used as the acid-substituted filter dye. 189 1 56 4. Photographic material according to claim 1, characterized in that a G-emisch of several acid-substituted dyes is used. 5. Photographic material according to claim 1, to 4, characterized .- .- characterized in that the dif fusions solid compound, acid-substituted filter dye and mordant is contained in a special gelatin layer. 6. Photographic material according to claim 1, characterized .gekennzeichnet, dati the diffusion-resistant dye off-pickling. : medium compound through the pickling of image dyes in the course of the diffusion transfer process in the '. Layer is formed. /. For this 1 Selta drawings