DE1073306B - Image receiving material for use in the silver salt diffusion transfer photographic process and process for its manufacture - Google Patents

Description

GERMAN

The invention relates to the production of photographic images, being a halosilver image during development by diffusion is transferred image-by-image to a FoHe or the like that takes over the image, and in particular it relates to the composition or structure of such a film.

The process by which the remaining halogen silver of a negative silver image is used to create a positive image on an image-receiving material is known as silver salt diffusion transfer method known and z. As described in U.S. Patent 2,352,014. According to the method described in this patent specification, the material to be copied used to form an image on a photosensitive halogen silver emulsion, which for the sake of simplicity can be referred to as the negative material. The ones struck by the light A latent negative image is created in the areas of the negative material, while the areas which are not exposed to light have been taken, a positive picture from unexposed! Halogen silver included. The exposed negative material is then treated with a developer mix that includes a halogen silver solvent and a Halogen silver developing agent contains, followed by the wet, exposed negative material with an image receiving material is brought into contact, which consists of a sheet of paper or a film which is a concealing agent and halogen silver solvents.

The latent negative image is developed on the negative paper by the developer mixture; the silver halide solvents in the developer mixture react with the unexposed silver halide to form soluble silver complex compounds, which are transferred to the image receiving material by diffusion and there with the concealment agent contained therein are implemented, whereupon the halosilver complexes mentioned in metallic silver or silver compounds of high optical density are converted.

Although the silver salt diffusion transfer method has become widely used, it has however, there are certain disadvantages, in particular with regard to the previously used image receiving material. Many of the commercially available image receiving materials have a cloudy or after processing mottled appearance, a property which is particularly objectionable when using transparent image receiving materials be used. Another disadvantage is a noticeable yellow discoloration of the background of the images obtained on aging. These also have image receiving or transfer films after processing a very sticky surface, which is particularly noticeable when the finished copy is damp Touched fingers or processed under high humidity conditions.

Image receiving material
for use in photographic

Silver salt diffusion

transmission method

and method of making it

Applicant:

General Aniline & Film Corporation,
New York, NY (V. St. A.)

Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:
V. St. v. America 7 May 1958

Clifford Ernest Herrick Jr., Chenango Forks, N. Y., Floyd Joseph Lafreniere, Johnson City, N. Y.,

and Douglas Straw, Binghamton, N.Y. (V. St. A.),

have been named as inventors

The image receiving materials of the above U.S. patent are prepared by using gelatin from a aqueous solution is applied to a carrier. Requires the use of water as a solvent however, long drying times at fairly high temperatures, and those with such takeover materials any existing high stickiness is most likely due to their gelatin layer.

Another type of acquisition material is described in U.S. Patent 2,579,587. Although the The products described here do not contain gelatine, but they are due to the processing method required and the substances used for use in simple office use Not suitable for copiers.

According to the present invention, there has now been made one for the silver salt diffusion transfer contract process Developed suitable transfer material that does not have any of the disadvantages of previous commercial products.

According to the invention, a plastic film used as a carrier, for example made of cellulose acetate, is made of polystyrene Od. Like., Coated with a solution that consists of

909709/410

3 4

organic solvents and a copolymer __ - production of further reproductions z. B. by means of the diazo from maleic anhydride and an alkylyinyl ether, copying process or for use as an intermediate normally hydrophobic polymer such as cellulose for the production of printing plates for photolose acetate, vinyl acetate or the like. That of developing agents such as hydroquinone or p-amino-5 U.S. Patent 2,772,972 is very suitable.
phenol, a halogen silver complex-binding substance, such as "By using the wet, organic Lö-2-Oxyäthylallylthiourea, and a water-soluble solvent-using process, after which the silver salt, such as silver nitrate, silver acetate, silver citrate is coated according to the invention, or the like., which is very likely to accelerate the nucleation or nucleation which is also necessary for the production of dense images, and consequently the costs of nucleation will also contribute.

Coating solution also includes small amounts of one of the anion of the In addition to the above novel properties and advantages

water-soluble silver salt corresponding acid, such as has the novel takeover material according to the invention

Nitric acid, acetic acid, citric acid or the like, also all properties and possible uses

puts. This acid is supposed to prevent the silver ion from passing through 15 of the previously known takeover materials. So can

the developing agent is reduced before the over on the transfer material according to the invention

drawn film has been dried. generated photographic images all common photographic

The graphic aftertreatment such as reinforcement, used polymer mixture used to coat the film used as a carrier is normally hydro-weakening, tinting, color development, build-up of color phob and is therefore subjected to the images used for processing by silver bleaching and the like, aqueous Developer solution not evenly wetted. The invention is illustrated by the following examples. Such hydrophobic coatings, however, if they are explained in more detail,
with certain hydrolytic agents, such as. B. _. . ,.
a moist nitrogenous base, are treated, "

converted to hydrophilic films (cf. USA. Patent 25 A solution A was prepared by adding 50 g of poly-

2 756 163). After the copolymer vinyl methyl ether-maleic anhydride of a specific

from alkyl vinyl ether and maleic anhydride containing viscosity of 1.0 to 1.5 in 2-butanone at 20 ° C and

Coating has been rendered hydrophilic, taking 25 g of a low-viscosity cellulose acetate, the 56 ° / ₀

Foil coating contained the unbound acetic acid applied after exposure, in a mixture of

winder mixture slightly. 3 ° 3000 ecm acetone and 250 ecm ethylene glycol monomethyl

Due to the hydrolysis of the surface of the coating from ether acetate were dissolved.

the alkyl vinyl ether-maleic anhydride mixed polymer. Solution B contained 1750 ecm of methanol, 1.75 ecm Risat with a water-soluble, nitrogenous base nitric acid, 5.0 g of hydroquinone and 2.5 g of 2-oxyethylwird also any allylthiourea present in the coating. 2.5 g of silver mineral acid were added to this solution neutralized and the formation of the smallest nitrate, which was dissolved in 5.0 ecm of water, was added. The solution B was added to the solution A and the is required. mixture obtained by reverse contact immersion

To allow the rolling of the carrier film and the formation of a cellulose strip used as a carrier

To prevent stains on the back, the like acetate film can be applied that a concentration of about

Above coated film was also obtained on its 40 0.5 ccm / 100 cm ² .

The reverse side can be coated with a solution that. After drying, the film was treated with a 10 ° / ₀ igen

Copolymer of the alkyl vinyl ether and maleic aqueous solution of monoethanolamine coated,

acid anhydride and the hydrophobic polymer. wherein the reverse contact dipping process with a

For the process according to the invention suitable alkyl speed of about 1.65 m / min used and

vinyl ether-maleic anhydride copolymers are 45 the film was kept moist for about 1 minute before it

for example in U.S. Pat. No. 2,772,972 was sent to a drying chamber. Then it was

wrote. Such copolymers consist of a - the back of the film by means of the reverse contact-

on the one hand from maleic anhydride and on the other hand z. B. from the immersion process coated with a solution, the addition of

Methyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, composition corresponded to solution A, but in addition

2-methoxyethyl vinyl ether and the like 50 still contained 1750 ecm of methanol. This coating was

Instead of the maleic anhydride mixed poly- also, as described above, with 10% mono-

cellulose-ethanolamine coated as a hydrophobic resin.

Acetates can also be found in the USA. Patent A sheet of halogenated silver negative paper was made

2,772,972 using an opaque original

become, such as B. cellulose propionate, cellulose butyrate, ge 55 reflectographically in a conventional reflectography

mixed esters such as cellulose acetate propionate, cellulose exposure device wetted. After the exposure were

acetate butyrate, polyvinyl acetals, such as polyvinyl butyral, the negative paper and the above-described transfer

Polymethyl acrylate, polymethyl methacrylate and the like accepted film through a developing device.

Instead of the mentioned halogen silver complex sent through. In the developing device were

Formers can also use the exposed negative and the transfer film in US Pat. No. 60

2 755 185 described complexing agents are used Presence of a developer solution that contains a halogen

the, such. B. N-allyl-4-morpholinothiocarbamate, 1-allyl silver developing agent and a fixing agent such as

3-ethyl-2-thiourea, l-benzyl-3- / 3-oxyethyl-2-thio-sodium thiosulfate, with the layer sides facing

urea and the like pressed together. A few seconds after

The new transfer film according to the invention provides 6 g of the two films emerging from the developing device In a surprisingly short time, the image transfer from the negative to the copying was positive, rich in contrast Finished taking material from originals with completely clear background, and the two slides were and free from yellow discoloration. Separated from each other after editing. The only slightly damp takeover is the moist film was completely tack-free and when it dries, the inner film contained a completely clear black and white half a few seconds to a copy, which is used to make a positive image of the opaque original.

A developer mixture suitable for use in the above developing device has e.g. B. the the following composition:

Hydroquinone "13.0 g

Sodium sulfite _ 40.9 g

Sodium thiosulfate 21.5 g

Potassium bromide 2.5 g

1-phenyl-3-pyrazolidone 1.0 g

Sodium hydroxide 10.0 g

Water about 800.0 ecm

Example 2

A transfer film was produced according to Example 1, However, the low-viscosity cellulose acetate of solution A used there by a vinyl acetate resin was replaced. The vinyl acetate used had an inherent viscosity in cyclohexanone of 0.11 at 20 ° C.

After exposure and processing as in Example 1, excellent, sharp black-and-white positive images were obtained of the opaque copied material.

Example 3

The procedure of Example 1 was repeated, except that the maleic anhydride copolymer was 50.0 g Poly-2-chloroethyl vinyl ether-maleic anhydride is used became.

Example 4

The procedure of Example 1 was repeated, but using polyethylene vinyl ether-maleic anhydride became.

Example 5

The procedure of Example 1 was repeated, wherein however, instead of cellulose acetate, 25.0 g of a vinyl acetate resin with an inherent viscosity of 0.11 in cyclohexanone at 20 ° C used as a hydrophobic resin became. When the obtained sheet was processed by following the procedure of Example 1, they became about the same Results obtained as in Example 1.

Example 6

Using 25.0 g of a low viscosity polyvinyl butyral with a low hydroxyl content and a viscosity of 23 cP (5% in ethanol) instead of the cellulose acetate, a cellulose acetate transfer film was produced, exposed and exposed as in Example 1 developed. A clear black and white positive image of the opaque copy material was obtained.

Example 7

The procedure of Example 1 was repeated, but the maleic anhydride copolymer through Polybutyl vinyl ether maleic anhydride was replaced. Practically the same results as in Example 1 obtained.

Example 8

The procedure of Example 1 was repeated except that polyvinyl isobutyl ether-maleic anhydride was used became. Practically the same results as in Example 1 were obtained.

Example 9 ' ^6s

The procedure of Example 1 was repeated, using poly-2-methoxyethylvinylether-maleic anhydride was used. The same results as in Example 1 were obtained.

Claims (10)

Patent claims: 1. Image receiving material for photographic use Silver salt diffusion transfer process consisting of a carrier and one on top of it arranged water-absorbing layer made of a copolymer of alkyl vinyl ether and maleic anhydride, a compatible hydrophobic resin, a halogen silver developing agent, a silver halide complexing agent and a water-soluble silver salt. 2. A method for producing the material according to claim 1, characterized in that the layer is treated with alkali, in particular with a water-soluble, nitrogen-containing base, until it becomes water-accepting has become. 3. Material according to claim I _1, characterized in that the carrier consists of a transparent plastic. 4. Material according to claim 3, characterized in that the carrier consists of a cellulose triacetate consists. 5. Material according to claim I ₁ - characterized in that the alkyl vinyl ether-maleic anhydride copolymer consists of a copolymer of vinyl methyl ether and maleic anhydride. 6. Material according to claim 1, characterized in that the hydrophobic resin is made of cellulose acetate consists. 7. Material according to claim 1, characterized in that the water-soluble silver salt consists of silver nitrate consists. 8. Material according to claim 1, characterized in that the silver complexing agent consists of a THourea derivative consists of one nitrogen atom is linked by a methylene group to a carbon atom grouping, the one immediately contains> C = C <radical bonded to said methylene group, and the other Nitrogen atom, due to its chemical structure, in which the nitrogen atom is either by a aliphatic radical is substituted or forms part of a saturated heterocyclic ring, is strongly basic. 9. The method according to claim 2, characterized in that the coating is an acid, the anion thereof corresponds to the anion of the water-soluble silver salt, added and the layer by treatment with is made water-absorbent with an alkali. 10. Material according to claim 8, characterized in that that the thiourea derivative it contains has the following formula: CH ₂ = CH-CH ₂ -N _n HIGH ₂ CH ₂ -N © 909 709/410 1.60