DE1174160B - Process for the production of multicolor transfer images - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: G 03 c German class: 57 b -14/02

Number: 1174160

File number: J 20438IX a / 57 b

Filing date: August 22, 1961

Opening day: July 16 , 1964

In the US Pat. No. 2,983,606 processes are described in which dye developing agents, these are dyes that have both a silver halide developer function and that in the same molecule chromophoric system containing a dye can be used to produce color transfer images. Here, a light-sensitive layer is exposed to produce a latent image and the latter developed in the presence of a dye developer. An image-correct distribution of unreacted dye developer substance from which the positive image is created. At least some of them unreacted dye developer is transferred to an overlying image-receiving layer, whereby a positive image emerges on it.

In a particularly advantageous embodiment, a photosensitive layer containing a silver halide emulsion is exposed to light and then treated with a liquid developer in the dark, e.g. B. by dipping, coating, spraying or pouring treated. The exposed photosensitive layer is placed on a layer-like support which can be used as an image-receiving layer before, during or after wetting. In a preferred embodiment, the photosensitive layer contains the dye developing agent, the liquid developer being applied uniformly to the photosensitive layer when the former is placed on the image-receiving layer. The dye developing agent can also be used in the liquid developer preparation if monochromatic images are desired. The liquid developer penetrates the emulsion and initiates the development of the latent image contained therein. The dye developing agent is precipitated in the exposed areas as a result of the development of the latent image. This process is apparently at least in part a consequence of the decrease in the solubility of the dye developing agent after oxidation. In unexposed and partially exposed areas of the emulsion, the dye developer remains at least partially unreacted and, as a result of the exposure of the silver halide emulsion, results in an imagewise distribution of unoxidized dye developer dissolved in the liquid developer. At least part of this imagewise distribution of unoxidized dye developer substance is transferred to an overlying image-receiving layer by swelling, a transfer of oxidized dye developer substance being practically excluded. In the image receiving layer diffuses from the developed process for the production of
Multicolor transfer images

Applicant:

International Polaroid Corporation,

Jersey City, N.J. (V. St. A.)

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and
Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man,
Patent Attorneys, Munich 9, Schweigerstr. 2

Named as inventor:
Milton Green, Newton Highlands, Mass.,
Howard Gardner Rogers, Weston, Mass.
(V. St. A.)

Claimed priority:

V. St. v. America dated August 22, 1960 (50 851)

Emulsion the non-oxidized dye developer substance without significant impairment of it image-fair distribution, resulting in a positive color image of the developed image.

Multicolor transfer images can be made using at least various methods two differently sensitized silver halide emulsions and by developing each emulsion in Presence of a different colored dye developing agent can be obtained. There is a procedure in the use of a common photosensitive layer, as described in the German patent 1 036 640 is described. Thereafter, at least two selectively sensitized photosensitive layers are made placed on a single carrier and treated with a single developing solution and finally on a usual image receiving layer transferred. Suitable for this is z. B. a carrier with a red sensitive Silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer. Everyone of these emulsions is a corresponding cyan dye developing agent, a magenta dye developing agent and assigned a yellow dye developing agent. In a preferred embodiment of light-sensitive layers there is the dye developer in a separate one

409 630/312

alkali-permeable layer, preferably behind the light-sensitive silver halide emulsion assigned to it. The method according to the invention is particularly suitable for developing these multilayered photosensitive layers.

It has now been found that the density and the highlights of transfer images that after such dye developing processes can be greatly improved. In the process for the production of multicolor transfer images, wherein light-sensitive silver halide emulsions with Dye developers are developed and the image transfer by alkaline diffusion transfer of unoxidized dye developer

salts are mentioned as additives to developer solutions. A reduction in the sensitivity, drastic expressions in the gradation and a loss of the maximum density are expressly mentioned. Even if attempts are made to reduce these disadvantages with certain quaternary pyridinium salts, it is expressly stated that concentrations of more than 7.0 g / l, ie of 0.7% / ₀ , tend to destroy the color balance.

In addition, the increase in density in the present processes does not result in an amplified result Surface activity by the onium compounds is because, as shown below, the Onium compounds, which are usually the strongest

Improve the density of undeveloped areas of the silver halide emulsions; in general, if the development is not included in the surface-active substances, counting the photosensitive, multilayer material, according to the invention
several differently sensitized silver halide

emulsions, each with their own but different

will. It can be assumed that the increase in density is due, at least in part, to the ability of the Onium compounds, which are soluble

Contain dye developing agents, and to increase the excess 20 of the dye developing agents.

wear in the presence of a high concentration, the fact that the onium compounds in the

Reaction with the dye developers transferring these dye developers from unexposed ones Promote areas and thereby reduce the

z. B. from 1 percent by weight, preferably from 2 percent by weight, of quaternary ammonium, quaternary Phosphonium and / or tertiary sulfonium

and diffusibility of the dye developing agents is influenced.

The use of onium compounds in the

compounds, based on the developer solution. Improving 35 was also surprising. The improvement One must assume that this onium compound shines in the highlight on the ability of the to go back an intermediate onium compounds with the dye-developing substances, by salt bilreaction enter and form salts with them and that dung with the dye developers their diffusion die Improvements in density and peak performance, especially in exposed areas Lichtem at least partially control the salt formation 30.

is due and that this increases the solubility. Particularly favorable results are achieved with

Use of quaternary ammonium compounds, i.e. organic substances with a pentavalent one Nitrogen atom. As derivatives of

Photographic is known. Thus, in the United States patent 35 ammonium compounds are considered, whose writing 2,648,604 the use of non-surface 4 hydrogen atoms replaced by organic residues of active quaternary ammonium compounds as a result. The organic radicals are usually direct winding accelerators and in the USA. Patent to the pentavalent nitrogen atom via a simple writings 2 271 623, 2 271 622 and 2 275 727 the or double bond between the carbon and use of quaternary ammonium, quater- 40 bonded nitrogen atom. The expression “quaternary phosphonium and tertiary sulfonium compound ammonium compounds” also means compounds as sensitizers for silver halide genes in which the pentavalent nitrogen atom describes emulsions. Although such onium is part of a heterocyclic ring, compounds are also used as sensitizers and as well as those in which the four valences are saturated by organic sensitizers and as development-accelerating groups, as is the case e.g. B. the niger were used, are the results, especially in the case of the quaternary Tetraalkylammoniumdere is the increase in density when using compounds. As examples of quaternary ammonium-onium compounds in connection with the coloring compounds, the following general formulas are given for substance developer substances in the case of diffusion over-
transfer procedure has not yet been recognized. At the 50
known processes result in a greater silver density in the negative, but only in the exposed ones
Surfaces of the negative, suggesting the above
Ability of the onium compounds
sensitizing or developing an emulsion 55
to accelerate. With the new process, it makes
the greater density is noticeable in the positive image,
it is mainly the result of a reinforced
Transfer of the dye developer from unexposed areas of the negative. The assumption that the 60
Onium compounds with the dye developer

substances enter into an intermediate reaction and the transfer of these dye-developing substances from Strengthening unexposed areas on the negative was in no way to be expected from the literature.

For example, U.S. Patent 2,648,604 at column 1, lines 25 to 47, is expressly one of several Disadvantages of using quaternary ammonium

RN ⁺ R
R.

Cz "^

N ⁺

(1)

(2)

Z.

N +

(3)

Here R denotes an organic group, Y an anion ζ. B. a hydroxy, bromide, chloride, toluyl

5 6

sulfonate anion and Z which to complete an embodiment contains the hydrophobic chain heterocyclic ring required atoms. Examples between 4 and 16 carbon atoms and preferably Compounds of formulas (1), (2) and (3) are wise between about 4 and about 10 carbon

Tetraäthylammoniumbromid, N-Ä thylpyridinium- atoms. Examples of hydrophobic chains are penthyl,

bromide and Ν, Ν-diethylpiperidinium bromide. 5 octyl, nonyl or decyl groups. The hydrophobic

The tertiary sulfonium and quaternary Phos chain is preferably attached directly to the nitrogen,

Phonium compounds can be represented by sulfur or phosphorus atoms substituted. she can

by the formulas in some cases as with heterocyclic quaternary

CR ^ ς + Y ™ ammonium compounds are found somewhere in the molecule,

^ ' ³ ίο z. B. on the heterocyclic ring. The upper

^un ° limit for the molecular weight and length of the

(R) ₄ P ⁺ X ^ hydrophobic chain is used in these onium compounds

preferentially through the solubility and mobility

Here R is an organic group, e.g. B. speed of the complex of such compounds and the an alkyl, aralkyl or aryl radical, and X an anion 15 dye developer in the aqueous alkaline Entz. B. the hydroxy, bromide, chloride or toluyl winding solution is determined. Examples of onium verbine sulfonate anion. Examples of such substances are fertilizers with a hydrophobic chain are: 1-Octyl-Lauryldimethylsulfonium-p-toluylsulfonat, Nonyl-di- 2-methylpyridinium-p-toluylsulphonate, octyltrimethylmethylsulphonium-p-toluylsulphonate, Octyl-dimethylammonium bromide, lauryltrimethylammoniumbrosulfonium-p-toluylsulfonate, Butyldimethylsulfonium ao mid, 1-octyl-1-methylpiperidinium methosulfate, octyl bromide, Triäthylsulfoniumbromid, Tetraäthylphos- trimethylphosphoniumbromid, Octyldimethylsulfoniphoniumbromid. um-p-toluenesulfonate.

The onium compounds can be used as free base or hydrophobic substituents in the onium

can be used as salt. In the latter case, connections can prove to be particularly useful derive the anion from each acid. It is, however, to have 25, mention the aralkyls and especially the phenes, that the iodide anion has harmful effects on alkyls. Onium compounds with such substituents can have on the emulsion and therefore suitable ones are particularly suitable for significant improvement Precautions should be taken. Especially the density as well as the top lights. Particularly good results have been obtained when one as such good results are obtained when one has the Onium compounds that used bromide. If 3 ° selects phenalkyl substituents from such, at the onium compounds instead of the bromide another those of the alkyl portion of the molecule 1 to 4 carbon anion own, it has contained in some cases as material atoms, as in benzyl, phenethyl, Proven beneficial, a small amount of potassium bromide phenylpropyl and phenylbutyl groups. admit. A group of onium compounds that emerge as

In general, the influence of which onium has proven particularly useful depends on those which contain compounds on the density and highlights of a reactive methyl group, ie, one of the molecular size of the onium cation in question. Methyl group, which in alkaline medium is usually an increase in density, especially methylene base can form. Such compounds become apparent when the molecular size of the onium cation results in addition to the improvement in density and which decreases. Conversely, the clarity of the top lights - 4 ° top lights - also means better color separation, that is, lights are particularly clearly visible with increasing mole - the transfer of the dye developer is more precisely cool size. Onium cations of an average molecular size controlled by the silver halide emulsion, to which they can be assigned a particularly marked improvement. Quaternary pyridinium ammonium, both density and peak light, produce compounds with a methyl substituent in the call. In general, a cation of an onium 45 2- or 4-positions of the heterocyclic ring will have compound, from which one particularly increased has proven to be particularly expedient because it promises a density without having hydrophobic chains with reactive methyl groups. The preferred are, for example, more than 3 carbon atoms. 2- and 4-methyl-substituted pyridinium compounds Examples of onium compounds with low moles are those in which the nitrogen atom is substituted by a size: 1-ethylpyridinium-p-toluylsulphonate, 50 phenalkyl group is substituted, especially by a 1-propylpyridinium-p-toluylsulphonate, N-phenyl-phenalkyl group in which the alkyl part of the molecule Ν, Ν, Ν-trimethylammonium-p-toluylsulfonate, 1-Pro- contains 1 to 4 carbon atoms. Preferred Verbinpylpyridiniumbromid, l-ethyl-2-methylpyridinium fertilize this type are l - (^ - phenethyl) -2-methyl bromide, 1 - (ß - hydroxyethyl) - pyridinium bromide, pyridinium bromide and l-benzyl-2-methylpyridinium-1-ethyl - 2, 3 - dimethylpyridinium - ρ - toluene sulfonate, 55 bromide.

l-ethyl-2-methoxypyridinium bromide, tetraethylamine- In one embodiment of this invention,

monium bromide, dimethyldiethylammonium-p-toluyl- a combination of onium compounds used, sulfonate, 1,1-diethylpiperidinium bromide, 1-ethyl- In this way you can get a desired equal pyridazinium methosulfate, Set ethyl dimethyl sulfonium weight between the increase in density and the bromide, methyl diethyl sulfonium p-toluyl sulfonate, 60 improvement in the top lights. Such Trimethylsulfonium bromide, tetramethylphosphoni- combination includes an onium compound with umbromide, Äthyltrimethylphosphoniumbromid, Di- small molecule size, as z. B. mentioned above äthyldimethylphosphonium-p-toluylsulfonat, Propyl- and which is free of hydrophobic chains with trimethylphosphonium bromide. is more than 3 carbon atoms, with an onium

The cation of onium compounds, the particularly 65 compound, which has a hydrophobic chain of at least responsible for better headlights, one may contain 4 carbon atoms. One of the preferred hydrophobic chain of, for example, at least combinations consists of an onium compound Contain carbon atoms. In the case of a preferred one with a small molecule size and a large onium

compound as mentioned above, and which also contains a reactive methyl group. Such a one Combination is particularly effective in producing transfer images with an increased density, Desseren top lights and better color separation. A particularly useful combination is the Onium compound with the active methyl group substituted by a phenalkyl group. An example for such an expedient combination is the Verwengen arranged in the image receiving layer; during development they are released from there and transferred to the photosensitive layer so that they are present during development. At a In another embodiment, the onium compounds are in the photosensitive layer, e.g. B. in special layers or in the dye developer layers. In the latter embodiment, should one takes care that the onium compounds

The use of N-ethylpyridinium bromide in combination does not desensitize the emulsions. with N- (jS-phenethyl) -2-methylpyridinium bromide. The amount of onium compound can vary according to

ger further modification of the preferred combination a higher molecular weight onium compound, e.g. B. Lauryltrimethylammonium Jromide used. The use of higher molecular weight onium compounds further improves this

j top lights of the transmission image. In general, the ability to connect onium is

iations to improve the color separation and the

jj top lights proportional to the ease with which ao is used in conjunction with the onium compounds

these onium compounds were attached to the silver halide. The antifoggants tend to have the

To suppress fogging which occurs as a result of the ability of the onium compound to develop

be adapted to the circumstances. In general, good results are obtained when the developer solutions contain about 1 to 10% of the onium compounds. Particularly good results are obtained when the solutions contain 2 to 4% of these compounds.

The above-mentioned improvements in density were particularly noticeable when using an antifoggant

adsorbed grains of the photosensitive emulsions will.

In certain cases it may be desirable to use an aqueous alkaline anti-fogging agent in addition to onium compounds are thioacetanilide, 5-methylbenzwickler solution to use some of the at least imidazole, 5-nitrobenzimidazole, 2-aminobenzimidein contains organic, water-miscible solvent. Examples of suitable solvents for this purpose are dioxane, Ν, Ν-dimethylethanolamine, N, N-diethylethanolamine, Tetrahydrofuran and diethylamino propanediol. Developer solutions with about 10% of the organic, water-miscible solvents are used. It should be noted, however, that this percentage can be changed according to the respective requirements. 35

In the aforementioned U.S. Patent 2,983,606 it is mentioned that density, color separation and Highlights of transfer images obtained using dye developers are, can be significantly improved if the process is carried out in the presence of at least one silver halide developing agent next to the dye developing agents. The invention shows another way to bring about such improvements, however, no silver halide developing agent is required. After another Embodiment of the invention, transmission images can additionally be improved in that at least one onium compound together with at least one silver halide developer used. Examples of combinations of onium compounds and silver halide developers, which have proven to be particularly useful are the use of l - (^ - phenethyl) -2-methyl-

pyridinium bromide with trimethylhydroquinone and 55 0.4% Resoflex 296. the use of l- (ß-Phenätnyl) -2-methylpyridinium-p-toluylsulfonat with 4'-methylphenylhydroquinone.

When carrying out the process according to the invention, it is not necessary that the onium compounds are present in the photosensitive layer during exposure. As a result, the Onium compounds can occur in the process of speeding up different things. Examples of useful

azole, 1-phenyl-5-mercaptotetrazole.

The invention is illustrated in more detail by the following examples.

example 1

A photosensitive material was prepared by coating one coated with gelatin Cellulose acetate film base with the following solutions:

1. A tetrahydrofuran-acetone solution (1: 1 volume units), containing 5.5% 1,4 bis [/ S- (2 ', 5'-dihydroxyphenyl) - isopropylamino] - anthraquinone (a blue-green dye developing agent), about 0.8% of an alkyl resin plasticizer and 2% cellulose acetate phthalate ester.

2. A red sensitive silver halide emulsion.

3. An acetone solution with 2% cellulose acetate phthalic acid ester, 0.75% cellulose acetate and 0.05% 5-nitrobenzimidazole.

4. A 2% aqueous polyvinyl alcohol solution.

5. A tetrahydrofuran-acetone solution (1: 1 volume units), containing 3.5% 2- [p- (2 ', 5'-dihydroxyphenethyl) - phenylazo] - 4 - η - propoxy-1-naphthol (a purple dye developing agent), 2% cellulose acetate phthalic acid ester, and

6. A green-sensitive silver halide emulsion.

7. An acetone solution containing 2% cellulose

Way to be introduced. In one case it has proven to be particularly useful, the onium compounds to incorporate directly into the developer solution and into the light-sensitive layer together with to allow the other substances to penetrate. In another embodiment, the onium compounds are acetate phthalic acid esters, 0.5% cellulose acetate and 0.04% 5-nitrobenzimidazole.

8. A 2% aqueous polyvinyl alcohol solution.

9. A tetrahydrofuran solution containing 3% 1-phenyl-3-N-n-hexyl-carbanyl-4- [p- (2 ', 5'-dihydroxyphenethyl) -phenylazo] -5-pyrazolone (a yellow dye developer), 2% cellulose acetate phthalic acid ester and 0.4% Resoflex 296.

10. A blue sensitive silver halide emulsion.

9 10

The photosensitive material was exposed and B e i s ο i e 1 6

then with an aqueous developing solution of the following Composition treated: A photosensitive material was similar

I-phenyl-3-pyrazolidone 1.2% ^W f ^$ l ™ ^e i "x Example 1 manufactured and developed,

2,5-bis-äthylemminohydroquinone .. 0.9% ⁵ f ^{but m} / ^de f exception that an aqueous developer

5-nitro benzimidazole 0.125% ^Losu? S ^{the fol} S ^composition used

1-ethylpyridinium bromide 2.5% was:

, Sodium carboxymethyl cellulose .... 3.0% sodium hydroxide 3.0%

Sodium hydroxide 3.0% Sodium carboxymethyl cellulose .... 5.0%

¹⁰ 1,2,6-trimethylquinolinium-p-toluene-

This solution was between the photosensitive sulfonate 5 0 ° /

Layer and an image-receiving layer spread after 5-nitrobenzimidazole 10 ° / °

the layers were laid one on top of the other. The image °

Receiving layer consisted of one with cellulose acetate _. . . "

coated baryta paper with an ethanolic 15 e 1 s ρ 1 e

Solution had been coated, the 4% N-methoxy It was as in Example 1, an aqueous developer

methyl-polyhexamethylene-adipic acid amide. solution of the following composition for release

After an exposure period of approximately 3 wraps of an exposed photosensitive material

The image-receiving layer was peeled off; she uses:

contained a positive image of the photographed sodium hydroxide 40 ° /

Subject. Sodium carboxymethyl cellulose 3.0%

/ 3-hydroxyethyl trimethyl

Example 2 "ammonium chloride 8.0%

l - (/ S-phenethyl) -2-methylpyridinium-

A photosensitive material was prepared, 25 bromide 5 0 ° /

exposed and developed in a similar way as in 5-methylbenzimidazole 0 * 5 ° / °

Example 1 described, with the exception that one

aqueous developer solution of the following combination- _R. · Ι ο

Settlement was used:. e 1 s ρ 1 e

1-ethylpyridinium-p-toluenesulfonate 3.0V ₀ ³ ° An aqueous developer solution of the following additions

5-nitrobenzimidazole 0.12% composition was used to develop an exposure

Sodium hydroxide ^{30% killed fear-} sensitive material, as in Example 1

Sodium carboxymethyl cellulose '.'. '.'. 5> / _{0 is} used.

Sodium hydroxide 4.0%

Example ³⁵ Sodium Carboxymethyl Cellulose 3.0%

".,. ,,. _c ..., _Λ,. . _t,. ... .., 1-ethylpyridinium bromide 8.0%

A highly sensitive material was found in a similar l - (^ phenethyl) -2-methylpyridinium-

Made as in Example 1, exposed and entbromide 5 q <w

however, with the exception that an aqueous 5-methylbenzimidazoV ''. '.'. '. Υ.'. '.'. '.', ois%

Developer solution of the following composition 4 °

was used: " . . ,.

Example 9

Sodium carboxymethyl cellulose 5.25%. .

Sodium hydroxide ^{- 4.0% Eme water} 8 ^{e developer} solution of the following additive

i-Bnty ^ yridfnium-p-toluenesulfonate 5.0% composition was used to develop ernes behch-

45 th photosensitive material used in

_,. . ,. in a similar manner as in Example 1

^Beis P ^{ie14 is} described.

A ^ sensitive ^ material was made of Sodium Hydroxide 4.0%

and developed with a similar We ₁ Se, as in sodium carboxymethyl cellulose .... 3.0%

Example 1 described is ^ edoci wxt <the exception, 50 i-ethylpyridinium bromide 8.0%

that a wassnge Eritw ^ kbrtong of the following t - ^. phenätrryli-2-methylpyridmium-

Composition was used: «bromide 50 ° /

Sodium hydroxide 3.0% Getyltrimethylammonium bromide ... 2.0%

Sodium carboxymethyl cellulose. 5.0% 5-methylbenzimfdazoI 0.5%

l, r-Ethylen-bis (pyridinmmbromid) 5.0% ⁵⁵ Sodium thiosulfate """" 1.0 "%

. 'ic ß ^e i ^ ^s the following examples, a light-

Eg 5 sensitive material is used, which is similar

A photosensitive material was made wise like those made above

and developed in a manner as described in Example 1 60, with the exception

is described, with the exception that an aqueous that (a) the dye developing agent in one with

Developer solution of the following composition dissolved in water and immiscible solvent

was used: dispersed in gelatin and only then in a

Layer of a cellulose acetate phthalic acid ester

Sodium hydroxide 3.0% ⁶ 5 that (b) a single gelatin

Sodium carboxymethyl cellulose .... 3.0% intermediate layer instead of the layer of polyvinyl

N, N-dimethylpyrrolidinium bromide 5.0% alcohol, cellulose acetate and the cellulose acetate

5-nitrobenzimidazole 0.2% phthalic acid ester was used and that (c) the

outer, blue-sensitive emulsion was coated with a thin gelatin layer comprising about 15 mg / 0.093 m ^a 4'-methylphenylhydroquinone contained.

Example 10

A photosensitive gelatin layer, similar to that described above, was exposed and covered with a treated with an aqueous solution of the following composition:

Water 100 ml

Sodium carboxymethyl cellulose .... 4.8 g

Sodium hydroxide 4.8 g

l- (j9-phenethyl) -2-methylpyridmium-

bromide 2.4 g

5-nitrobenzimidazole 0.24 g

Hexamethylenetetramine 6.0 g

The preparation was distributed between the light-sensitive layer and an image-receiving layer, which were laid on top of each other. The image-receiving material consisted of a baryta support which had an image-receiving layer which contained a 1: 1 mixture of gelatin and poly-4-vinylpyridine and in the a small amount of l-vinyl-5-mercaptotetrazole as Antifoggant was dispersed. After an exposure period of about 3 minutes, the image receiving material separated; it contained a dense, multicolor image with much improved highlight highlights and a much better color separation compared to transfer images that were not used of onium compounds.

Example 11

A developing solution of the following composition was used to prepare an exposed photosensitive Develop material in a manner as described in Example 10.

Water 100 ml

Sodium hydroxide 4.0 g

Sodium carboxymethyl cellulose .... 2.5g

1-ethyl pyridine bromide 5.0 g

l- (jS-phenethyl) -2-methylpyridinium-

bromide 4.0 g

5-nitrobenzimidazole 0.5 g

Tetrahydrofuran 10.0 ml

Example 12

A photosensitive material as used in Example 10 was developed similarly to Example 10, but with the exception that a developer solution of the following composition was used:

Water 100ml

Sodium hydroxide 4.0 g

Sodium carboxymethyl cellulose .... 4.0 g

Sodium thiosulfate. 1.0 g

1 - (a-phenylpropyl) -3-methyl-

pyridinium bromide 1.0 g

5-nitrobenzimidazole 0.2 g

Hexamethylenetetramine 5.0 g

Example 13

The procedure of Example 10 was repeated except that a developing solution was used the following composition was used:

Water 100 ml

Sodium hydroxide 4.0 g

Sodium carboxymethyl cellulose 4.0 g

Sodium thiosulfate 1.0 g

2,3-dimethylbenzothiazolium

methosulfate 1.0 g

5-nitrobenzimidazole 0.2 g

Hexamethylenetetramine 5.0 g

Tetrahydrofuran 10.0 ml

Example 14

The procedure of Example 10 was repeated; however, the aqueous developing solution had the following Composition:

Sodium hydroxide 4.0%

Sodium carboxymethyl cellulose .... 4.0%

Tetrahydrofuran 10.0%

Cetyldimethylbenzylammonium

bromide 1.0%

5-nitrobenzimidazole 0.2%

Sodium thiosulphate 1.0%

Example 15

The procedure of Example 10 was repeated except that an aqueous developing solution was used the following composition was used:

Sodium hydroxide 4.0%

Sodium carboxymethyl cellulose 4.0%

Sodium thiosulphate 1.0%

l - (/? - phenethyl) -2-methylpyridinium-

p-toluenesulfonate 2.0%

l- (jS-phenethyl) -3-methylpyridinium-

bromide 2.0%

5-nitrobenzimidazole 0.2%

. Hexamethylenetetramine 5.0%

Example 16

The procedure of Example 10 was repeated. It became the following aqueous developing solution used:

Sodium hydroxide

Sodium carboxymethyl cellulose ..

Sodium thiosulfate

l-ethyl-2,4,6-trimethylpyridinium

p-toluenesulfonate

Hexamethylenetetramine

4.0% 4.0%

1.0%

2.0% 5.0%

B el s pieI "17

The procedure of Example 10 was repeated _{using the following aqueous developer solution, 60:}

Sodium hydroxide 4.0%

Sodium carboxymethyl cellulose .... 5.5% triphenyl-phenacyl-phosphonium-

chloride 4.4%

5-nitrobenzimidazole 0.1%

Tetrahydrofuran 10.0%

Hexamethylenetetramine 5.0%

Example 18

The procedure of Example 10 was repeated using an aqueous developing solution of the following Composition was used:

Sodium hydroxide 4.0%

Sodium carboxymethyl cellulose 3.5%

Triethyl sulfonium tosylate 4.2%

5-nitrobenzimidazole 0.5%

Shown each of the transmission images generated according to the above examples significant improvements compared to comparable transmission images without Using the onium compounds. * 5

It should be noted that in Example 4 the process was carried out in the presence of a compound which contained two quaternary ammonium groups. The term "onium compound" used here is intended to include those substances that contain one or more onium groups.

Examples of other onium compounds that have been tested in the same way and are found to be useful proven are:

p-chlorophenacylpyridinium bromide, 2-methylbenzothiazole-N- / 3-carboxyethobromide, 2-methylbenzothiazole-N-carboxymethobromide, 1 -benzylpyridinium bromide,

l-benzyl-a-picolinium bromide, 1,2-di- (2'- [N-benzyl] pyridinium) -1,2-ethanediol bromide,

1 -methylpyridinium tosylate,
l-methyl-a-picolinium tosylate, 1-methyl-y-picolinium tosylate,
Carboxymethyl triphenylphosphonium bromide, l-methyl-2,6-lutidinium-p-toluenesulfonate, 2,3,4-trimethylthiazole tosylate,
Diethyl carboxymethyl sulfonium bromide, N-methyl-2-benzylmecaptothiazoliniummethyl-

sulfate, ■ '"
N-methyl-2-methylnercaptothiazoline methyl sulfate,

l-benzyl-2-sthylpyridinium bromide, l-methoxy- ^ gicolinium methosulfate, 6-methoxy-l - (^ - phenethyl) -quinolinium bromide, N, N'-Di - ^ - phenylethyl-N, N, N ', N'-tetramethyl-

p-phenylenediammonium bromide,! - (jö-phenäthylj-a-picöliniumperchlorat, 1 -Benzyl-4-n-.propyl-pyridinium bromide, 1-ethyl-a-picoliniufnbromid, ... ,,. " l-methyl-a-picoliniujabromide, 1-n-propyl-a-picolinium bromide, ·

l-benzyl-2-benzylpyridinium bromide, l-benzyl-4-benzylpyridinium bromide, l-benzyl-2-n-amylpyridinium bromide, 1 -Benzyloxy-a-picolinium bromide, l- (p-methylbenzyl) -a-picolinium bromide, ! - (y-Phenoxypropy ^ -a-picoliriiumbromid, l- (p-nitrobenzyl) -a-picolinium bromide, 1-laurylpyridinium-p-toluenesulfonate, Trimethylphenylammonium benzene sulfonate,

rtP

35

40

45

55

60 2,6-dimethyl-1-methylquinolinium toluenesulfonate, 1-ethylpyridinium-p-toluenesulfonate,

l- (y-phenylpropyl) -2-methylpyridinium bromide,

1-methylquinolinium chloride,

N-methylquinolinium methyl sulfate,

Trimethylphenylammonium hydroxide,

Tetrabutylammonium bromide,

Tetrabutylammonium hydroxide,

Tetraethylammonium hydroxide,

Cetyldimethylbenzylammonium chloride,

Tetra-n-propylammonium hydroxide,

1 -methylpyridinium hydroxide,

Ν, Ν-dimethylpyrrolidinium hydroxide.

The effectiveness of the onium compounds in terms of improving density and color separation of the transfer images was demonstrated by tests using areas of three-color negatives such as those used in Examples 10-18 were, firstly only with blue and green light, secondly only with blue and red light and thirdly only exposed to green and red light. The transfer images were from a first negative prepared by using an aqueous developer solution which did not contain any onium compounds (Solution A), from a second negative using an aqueous solution containing the onium compounds contained (solution B), and a third negative using an aqueous developer solution, which contained both onium compounds and a water-miscible solvent (solution C). The solutions had the following composition:

Solution a

Sodium hydroxide

Sodium carboxymethyl cellulose
5-nitrobenzimidazole

4.0%
3.5%
5 ¹ V

Solution B '

Sodium Hydroxy.d .....

Sodium carboxymethyl cellulose

1äthylpyri ^ m ^ imbrpmiji.

l ^^ eth ^ pyridi

1-

jy ^

bromide ...., ' . "

5-nitrobenzirindazole

Solution C

Sodium Hydroxide ^,

Sodium Carboxymethyl Cellulose ....

., - , 1-Ethylpyridiniitrn, bi: om | d,. '.',

l - ((8-phenethyl) -2-methylpyridinium bromide .., .. ■ _

Tetrahydrofuran

3.5%
/ 5.0%

4.0%
0.5%

4.0% ^L.

5.5%

1.0%

4.0%
0.5%

10.0%

The "analytical" blue-green, purple and yellow density values the transfer images obtained were measured by reflection. In theory, the Negatives exposed to green and blue light only use cyan dye developers from the red ones and negatives exposed to blue light use only purple dye developers and only yellow dye developing agents are transferred from the negatives exposed to green and red light. the

The results are summarized in the following table:

exposure Blue green 0.16
0.16
ungB
1.05
0.34
0.24
ungC
1.31
0.20
0.12 density
purple yellow Blue and green ... Solution a
0.45 0.12 0.23 Red and blue .... 0.23
0.16
0.22
1.01
0.09
0.12
0.65
0.16 0.22
0.83
0.16
0.23
1.13
0.13
0.12
1.24 Red and green. . Blue and green ... Sol Red and blue .... Red and green. . Blue and green ... Sol Red and blue .... Red and green ...

Similar experiments in which surfaces of the negative were exposed only to blue, red and green light, also showed the ability of the onium compounds increase density and color separation.

The dye developing agents used in the process according to the invention are compounds which in the same molecule both the chromophoric system of a dye and a Contains silver halide developer function. Particularly good results have been achieved when the Onium compounds have been used in conjunction with dye developing agents containing hydroxyl groups substituted aryl-based silver halide developing groups, particularly silver halide aryl-based developing groups substituted with at least two hydroxy groups were, e.g. B. hydroquinone and catechol groups. Examples of typical dye developing agents which can be used in the new process can be found in U.S. Pat. No. 2 »3,606 and in German patent specification 1 036 640.

The aqueous solutions used in the process according to the invention are alkaline and should preferably have a pH of at least 12. Examples of alkaline substances are sodium hydroxide and potassium hydroxide. In certain cases, a developer solution containing only quaternary substances by using quaternary hydroxides such as chofin and tetramethylammonium hydroxide, can be used in place of the alkali hydroxides.

As mentioned above, in a preferred embodiment of the method according to the invention the onium compounds together with a silver halogen developing agent in addition to the dye developing agents. used. Silver halide developers, which are particularly good for this are suitable are rrydroxy-substituted aryl compounds, z. B. Toluhydroquinone, S ^ -dihydro-L ^ -naphthohydroquinone, o-toluthiohydroquinone, 5,6,7,8-tetrahydro-1,4-naphthohydroquinone, Methoxyhydroquinone and 2,6-dimethylhydroquinone.

It should be noted that the onium compounds to be used in the process according to the invention in the alkali-permeable, film-forming substances are diffusible, those in the emulsion and in others Layers of the photosensitive material are used. Many alkali-permeable, film-forming materials are available for this purpose; the choice of the material in question depends a long way Scope of the respective purpose ah. Examples of film-forming materials are gelatin, Polyvinyl alcohol and cellulose acetate phthalic acid ester. It should also be noted that the onium compounds are preferably colorless substances so that they do not change the color of the transfer image. The interaction of the onium compounds with the dye developing agents was through recognized a dye diffusion test in which the initial diffusion rate of 2- [p- (2 ', 5'-dihydroxyphenethyl) phenylazo] -4-n-propoxy-1 -naphthol (purple dye developing agent) was measured by gelatin using a developing solution, the no quaternary ammonium compound and a developer solution, the N-ß-phenethyl-ic-picolinium bromide contained. It has been found that the quaternary ammonium compound is the initial The rate of diffusion of the dye developer decreased. It can be assumed that this Decrease in the initial diffusion rate of the dye developing agent tends to prevent early transmission and thus help improve the top lights. The inventive The process is particularly suitable for film material that is recorded in a »Polaroid Land Camera« or in a similar camera such as that described in U.S. Patent 2,435,717 should be.

The method according to the invention is also suitable for application to photosensitive material of the screen type as described in U.S. Patents 2,983,606 and 2,968,554. Thereafter at least two selectively sensitized silver halide emulsions arranged in the form of a grid, and the Substances giving color are preferably located as in multilayer photosensitive material in a separate alkali-permeable layer on the back of the light-sensitive emulsion, «5 to which they are assigned.

The expression “dye developer substance is intended to include color-changing dye developer substances, as described in German patents 1129 370 and 1990.
50

Claims (12)

Patent claims: 1. Process for the preparation of multicolor transfer images, wherein Sdrt-sensitive Silver halide dissolution with color developing agents are being developed and the image transmission by alkaline diffusion transfer of unoxidized dye developer substance undeveloped areas of the silver halide emulsions takes place, by the fact that the development of the light-sensitive, multilayer material, with several differently sensitized silver halide emulsions, each containing their own but different dye developing agents, and the Transmission in the presence of a high concentration, e.g. B. from 1 percent by weight, preferably of 2 percent by weight, of quaternary ammonium, quaternary phosphonium and / or tertiary, Sulfonium compounds, based on the developer solution. 2. The method according to claim 1, characterized in that the onium compound is in the form their salts are used. 3. The method according to claim 1 or 2, characterized in that the quaternary ammonium compound a tetralkylammonium compound or a heterocyclic ammonium compound, especially in the form of a pyridine derivative, used. 4. The method according to claim 3, characterized in that there is a quaternary heterocyclic Ammonium compound is used which contains a phenalkyl group on the pentavalent nitrogen atom. 5. The method according to claim 4, characterized in that an ammonium compound is used, in which the phenalkyl group is the phenethyl group or the benzyl group. 6. The method according to claim 1 to 5, characterized in that the development in addition to the dye developer in the presence of at least one silver halide developer. 7. The method according to claim 1 to 6, characterized in that together with the alkaline Developer solution uses a water-miscible organic solvent. 8. The method according to claim 1 to 7, characterized in that the pH of the alkaline Adjust developer solution to at least 12. 9. The method according to claim 1 to 8, characterized in that the development in Carries out the presence of at least a first and a second onium compound. 10. The method according to claim 9, characterized in that the first and second onium compounds a quaternary ammonium compound is used, the cation of the first onium compound, preferably contains hydrophobic chains with not more than 3 carbon atoms and the cation of the second onium compound has a hydrophobic chain of at least 4 carbon atoms having. 11. The method according to claim 10, characterized in that that the second onium compound is a quaternary ammonium compound with 4 to 16, preferably 4 to 10 carbon atoms are used in the hydrophobic chain. 12. The method according to claim 1 to 11, characterized in that in addition to the onium compounds an antifoggant is used. Considered publications:
British Patent Nos. 804 971, 601 824;
U.S. Patent Nos. 2,983,606, 2,636,821, 403,927.2725 290; »Journal for Scientific Photographic«, 1954, Vol. 49, pp. 1 to 9. 409 630/312 7.64 © Bundesdruckerei Berlin