DE2165034A1 - Process for the manufacture of photographic material - Google Patents

Description

PATENT LAWYERS

DR. E. WIEGAND DIPL-JNG. W.NIEMANN 2lDOÜo4

. DR. M. KOHLER DIPL.-ING. C GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55547 «8000 MDN CH EM 15,

TELEGRAM ₁ CARPATENT NUSSBAUMST * ASSE1O.

December 28, 1971 ¥ 40 925/71 - Ko / DE

Fuji Photo PiIm Co. ltd., Ashigara-Kamigun, Kanagawa / Japan

Process for the manufacture of photographic material

The invention is concerned with a method for Manufacture of photographic material.

So far, the photographic carriers -. for example, for photographic printing papers and photographic Diffusion transfer papers generally consist of one Baryta paper is made, which by absorbing an aqueous mixture, the fine particles of barium sulfate and a binder, such as gelatin, which is kneaded with water had been made on a paper made from a paper pulp. These carriers however, there are often various errors including expansion and contraction due to variations in humidity, especially shrinkage after the development process, need a longer drying period aur

209828 / TOQS

BAD ORiGINAL

Evaporation of the developing liquid and have a poor resistance to water.

To overcome these errors, papers coated with polyethylene resins, so-called waterproof papers, recently used for this purpose, which, however, are not favorable for practical use as they Errors show such as fluid drainage from the edge of the paper, poor sharpness in cutting and the need for an additional step to coat the paper with the polyethylene resin. ".... _:

In particular, the present invention is characterized in that an aqueous gelatin solution or dispersion in an organic solvent is applied as an undercoat to a high molecular film having a roughened surface, the undercoat to a surface by heating. Temperature in the range from Tg -40 ⁰ G up to Tg +40 ⁰ C is dried, whereupon an emulsion or suspension continues

Contains gelatin as a binder.

The term "roughened surface" according to the invention

means the surface with a large number of open pores or indentations, i.e. about 1o ² to 1O ⁸

Pores per 1 cm · The pores are formed by erosion of a solvent or a swelling agent and have a diameter of 0.1 to 100 to and are about 0.1 / u deep. Jk The upper limit of the depth is such that the shape of a support can be obtained and varies with the number of pores, the diameters of the pores and the thickness of the supports. Due to the presence of the pores, the surface is intricately porous. The term "Tg" used here denotes the glass transition temperature of the corresponding high-molecular film. The term "emulsion or suspension containing gelatin as a binder" denotes aqueous emulsions or aqueous suspensions of gelatin which, with or without the addition of silver halides such as silver chloride, silver bromide, silver chlorobromide and silver odbromide, / light-sensitive diazo compound, substance for the formation of development centers image receiving material used in the silver halide diffusion transfer process and other substances that provide the necessary components - 209028 / 100J_,. ■

BADORI & ÜÄ \

The "stretched high molecular weight film with roughened Surface ", which is used in the method according to the invention, can be produced by stretching a previously formed Film made of a high molecular weight polymer either .in uniaxial or biaxial direction according to the known plastic stretching process and treatment of the obtained stretched film with. a variety of surface roughening treatments get v / earth.

In the case of biaxial stretching, stretching can be carried out either simultaneously or sequentially will.

The process of stretching films and enlarging them of stretching are known and are described in "Plastic Film," edited by PLASTIC FILM RESEARCH ASSOCIATION, and published by SIHO DO, Japan, described / · '

The roughening of the film surface can be achieved by contacting of the film with a dissolving or swelling.

. timid Eosungsmxttels,

film-forming resin under swelling of the film γ subsequent weiterefKontaktierung swollen film with water or another organic solvent which is not capable of dissolving the film-forming hard, but ieischbar with the solvent used in the swelling stage organic solvent _T vein compatible osltv sA-a & ß a. Roughening

Λϊΐβ Ύϊΐ USr PatentsC-Trift 35 ι? In this case, the film may be contacted with the solvent by a variety of methods including immersing the film in an organic solvent, applying the organic solvent using a roller coater, a paint brush, or a sprayer.

There may be other roughening treatments are used as the use of organic solvents, for example, mechanical abrasion * addition of a Schäunmngs- * means, which forms gas when heated, so that so that a / \ _t roughening of the whole film is obtained, or selective dissolution of a third Substance that has been mixed into the film structure prior to formation, thereby creating a coarse roughened

209828/1008

Surface is formed, applied, - be. All above roughening treatments] without the teaching of the present invention thereby significantly influenced-wi-rd.

The forming resin can be a white pigment, for example titanium dioxide, barium sulfate, calcium sulfate, barium carbonate, lithopone, aluminum oxide white, calcium carbonate, Silica white and the like and, if necessary, colored pigments or colored pigments in an amount less than $ 60 wt. based on the Weight of the film included.

Resins such as polystyrene, polyesters, polycarbonates and polyolefins generally have excellent properties in terms of water resistance, dimensional stability, stiffness and the like. Therefore, those in the foregoing show Films treated wise a superior whiteness and opacity and are therefore suitable for use as Very suitable carrier for photographic materials. On the other hand, since these resins are inherently hydrophobic and chemical are inactive, they pose a serious problem that when coated with a hydrophilic emulsion they cause gelatin contains, result in very poor adhesion between the applied film and the "fräger".

In order to solve the above problems, there has been an improved method of increasing the adhesive strength between the coated layer of the photographic emulsion and the support in an earlier proposal procedural measures of surface activating treatments, for example proposed by corona discharge, ozone oxidation and irradiation with ultraviolet rays. These treatments however, have the disadvantage that they are specially constructed

209828/1008
BAD ORfOIHAt

and require complex devices.

According to the inventive method, a satisfactory adhesion strength between the coating emulsion layer and the support can be obtained in a simple manner> be, with only conventional Emulsionsauftragungs- or coating equipment may be used without any special devices are needed.

It has now been established that one extremely. strong adhesion between the photographic emulsion and The roughened carrier can be obtained by initially

.... roughened carrier obtained in the above manner with an undercoating liquid of 5 to 15% by weight of an aqueous solution of gelatin or a dispersion of 0.5 to 5% by weight of gelatin in an organic solvent is coated, then the undercoat is dried by heating to a temperature from Tg -ACPQ to Tg +40 ⁰ C and then a photographic gelatin-containing emulsion is applied to it. The reason of the limitation of the drying temperature in the range of Tg -40 ⁰ C to Tg +40 ⁰ C is that at temperatures below Tg -40 ⁰ C insufficient adhesion strength is obtained and that a bad flatness "under excessive contraction of the carrier in . temperatures above Tg is obtained +40 ⁰ C.

It is of course possible to obtain a good adhesion and a satisfactory flatness even at temperatures above Tg +40 ⁰ C, the heat treatment is provided while fixing the carrier and thereby prevent a conditional übermäßgen contraction is effected.

The hot drying treatment can either be done directly after after drawing up the undercoating liquid or after gelation be carried out by cooling the undercoating liquid, with similar effects in the case of the present invention

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Procedures are obtained.

The reason why this improvement in adhesive strength is achieved by the method of the present invention is likely to be due to the following occurrences: ".

1) it becomes the penetration of the undercoating liquid all tiny pores' of the roughened surface of the carrier

■ gers to a considerable extent due to the degradation of the

Of gelatin subbing coating and the drop of the W surface tension favors viscosity by heating and

2) the so-called "anchoring effect" is due to the shrinkage achieved in the region of the glass transition point of the biaxially stretched film.

In fact, a complete lack of adhesion strength between the photographic emulsion and the support is found when the same undercoating liquid a, uf. , a non-roughened and transparent high molecular weight ffatzplwy is applied and then dried at an elevated temperature within the above range. If the drying treatment is ^{carried out at temperatures below Tg -4O 0} C, the adhesive strength is too low to be suitable for use in a photographic material suitable for practical use.

Purely to be used as an undercoating liquid Gelatin dispersion in an organic solvent makes it beneficial to use methanol as the solvent because of this "Stability as a dispersant and stability to to be used by the carrier. The solvent can also be used to dissolve the film-forming resin, if necessary contain suitable solvents, for example in the Pail of the use of polystyrene as a film-forming resin, tetrahydrofuran, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, Methyl isobutyl ketone, methyl chloride, ethylene chloride,

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Cyclohexane, benzene, dimethylformamide and the like.

That obtainable by the process according to the invention photographic material has excellent properties in terms of adhesive strength between Support and the photographic emulsion coating layer, water resistance and dimensional stability in the moist state, so that considerably the period of development, Fixation, water washing and similar processes can be shortened and accelerated, especially the Drying period.

The following examples are provided for further explanation the invention. The attempt to determine the adhesive strength between the carrier and the raised Layer was carried out in the examples in the following way:.

1 · Adhesion test in the dry state

A cellulose triacetate film 0.14 mm thick was applied using an epoxy type resin adhesive to the coated surface of a film sample which was passed through Drawing up a high molecular weight film with a ^ v ^ fjigg-g

elatine was developed as a binder / The bonded film was left to stand for 24 hours at a temperature of 23 ^° C. and a relative humidity of 65 $, then cut into rectangular strips 1 cm wide and 15 cm long. The cellulose triacetate film was then stripped off at a suction rate of 7.38 cm / min, the force required for stripping being determined by means of a tension measuring device.

In the following examples, the term "good adhesion" refers to the case where the sample withstood a scrape of more than 8 g / mm, which is usually sufficient for practical use as a photographic material is. ''

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2. Adhesion test when wet

The same sample as above was after development, Fixation of dull water washing while it was still in the wet state on its surface with a Cellulose triacetate film bonded using a cyanoacrylate type adhesive in the same way as under 1 and then the stripping resistance is determined. In this Pail means the term "good adhesion" to a stripping-off resistance of the sample greater than 2 g / mm, determined in the same way as in method 1 above.

In the examples, parts are based on weight, unless otherwise stated.

example 1

A biaxially stretched polystyrene carrier of one Thickness of 0.1 mm was immersed for 3 seconds in a solvent composed of 7 parts of ethyl acetate and 1 part of ethanol, then immersed in methanol for 30 minutes until the film turned white and opaque.

The obtained film had a roughened surface and became the following with an aqueous gelatin solution Composition coated:

Gelatin 10 g

Formalin (20 $ aqueous solution) ^

(Hardener) 4 cm *.

Water 190 cm ³

The film coated with the above solution was immediately ^{dried at 80 °} C. for 10 minutes, then further coated with a photographic silver halide emulsion of the following composition, the amount being given for 1 square meter of the film?

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Silver chlorobromide 3.5 g,

Gelatin 13 ", above

Formalin (hardener) 0.1 g

Saponin (wetting agent for pull-up) 0.03 g

Water in a quantity to a total dough solution of 130. cm

The Abstreifversuch of the coated film with the emulsion showed excellent Haf tungs.f estigkeit in the dry state of 17 g / mm and in a wet ä

Condition of 6 g / mm.

On the other hand, when the undercoated film was dried in a stream of air at room temperature and then coated with the introductory photographic emulsion, only poor adhesion, that is, an adhesion strength of 1 g / mm in the dry state and practically 0 in the wet state, was obtained. Furthermore zeigiß the Emulsionsüberzugsschieht / no bond to the substrate and peeled off by itself when the Yergleichsprobe was prepared by drawing the sub-coating liquid on a transparent polystyrene film which had not been treated for the surfaces on roughening, ybei 80 ⁰ C for 10 minutes, dried and further with the previous *

standing photographic emulsion was coated.

Example 2

In the same manner as in Example 1, an undercoating liquid having the following composition was prepared applied to the roughened carrier:

Gelatin water methanol formalin (20 μl aqueous solution)

Salicylic acid (dispersant) 1.4 g.

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4th S. cm ⁵ 10 S. -.a* 500 1t 5

Provided with the Dnterüberzug Piim was UEN indirectly dried at 60 ⁰ C for 10 minutes, then with a-o to form an image recording layer on a photographic wherein the silver salt & iffusionsübertragungsverfahren suitable image receiving material suitable liquid of the following composition coated: ■

Gelatin 3 g

Silver sulfide colloid

(Development nuclei) - - 0.001 g of phenyl mercaptotetrazole
(Hue modifier) 0.01 g

Saponin (wetting agent) 0.02 g

The peel test with this image receiving material showed a dry peel resistance of 18 g / mm and in the wet state of 5 g / mm. on the other hand became a . Adhesion strength of 3 g / mm in the dry state and 1 g / mm in the wet state with a Another sample obtained by drawing up the Uhtertiberierungslösung and subsequent drying in air at room temperature.

Example 3

A polystyrene sheet containing 22% by weight of titanium dioxide particles was biaxially stretched at 12QPG both in the lateral direction and in the longitudinal direction, each with an elongation of 1.5 times, and a white polystyrene carrier with a thickness of 0.1 mm was obtained. This polystyrene support was immersed in methyl ethyl ketone for 3 seconds and dried in an air blower for 10 seconds, then immersed in methanol for 30 seconds, and a white roughened polystyrene support, the

209828/1003

Containing titanium dioxide. This support was coated with the XJnterüberzugsflüssigkeit according to Example 1, wherein 5 ¹ E allowed to stand for 10 minutes to solidify and then at 80 ⁰ C for 20 minutes / getrocknet- Piim this was coated with a silver halide emulsion farbphotographisehen the following composition per square meter Piim!

Silver chlorobromide "3.0 g

Gelatin 5.5 g

an aqueous gelatin dispersionj

containing BenzofLaeeto ~ 2-chloro- (

5-dodecyloxycarbonylanilide

(Yellow coupler) manufactured as below HjO g

Polyvinylpyrrolidone 0.7 g

(Molecular weight 200,000)

When Abstreifversuch with the above coated with the color emulsion T ilm was? Satisfactory adhesion strength in both the dry and in the wet state, as required for farbphotographisehe materials obtained _f ie 17 g / mm respectively, 5 g / mm in each state.

The above-mentioned dispersion was made by fresh 1 part of 5 wt .- ^ aqueous solution of sulfonic acid, 10 Parts of 10 wt .- ^ aqueous gelatin solution, 1 part dibutyl ( phthalate, 1 part of the above-mentioned coupler, 2 parts of ethyl acetate and 0.5 part of methanol solution of 20 wt .- ^ anionic active means produced under vigorous Eükren.

Example 4
on the other hand

the undercoat peeled off by itself, if the PiIm equipped with the undercoat at room temperature with an air vessel after the "solidification during Was dried for 10 seconds at 5Έ.

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A .Polycarbonate film with a thickness of 0.2 mm, the uniaxial at 190 ⁰ C to an elongation of 1.8-. After it had been stretched, it was immersed in dimethylformamide for 3 seconds and then immersed in methanol for a further 30 seconds, and a white powder with a roughened surface was obtained. Dieser.Film was coated with an aqueous gelatin solution of Example 1 and then at 150 ⁰ C for 2 minutes getrocknet..Auf the obtained film has a silver halide photographic emulsion was coated according to Example. 1 In the stripping test, extremely strong adhesion between the emulsion layer and the support was obtained and there was no peeling. On the other hand, a peel strength of at most 10 g / mm was obtained when the silver halide photographic emulsion was coated on a roughened polystyrene film after it was coated with the above gelatin aqueous solution and dried at room temperature in an air blower.

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Claims (1)

Claim Process for the production of photographic material, characterized in that first an aqueous gelatin solution or a dispersion of gelatin in an organic solvent is drawn onto a stretched high-molecular film with a roughened surface as an undercoat, then the film obtained at temperatures in the range of Tg -4O ⁰ C to Tg + 4O ⁰ C is heat-treated, and then a gelatin is applied as a binder emulsion or suspension containing the film, wherein Tg represents the glass transition temperature of the film-forming resin used. 209828/1008