DE2150137A1 - Process for producing a photographic material - Google Patents

Description

PATENT LAWYERS

DR. E. WIEGAND DIPLIN'3. W. NIEMANN DR. M. KÖHLER DIPL-ING. C. GERNnARDT Monks Hamburg 9 1 R Π 1 ^ 7

TELEPHONE: 555476 8000 MDNCHEN 15,

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

7th October 1971

W. 4o 754/71 13 / HS

5 \ i, ji Photo Film Co., Ltd. Ashigara-Iiamigun, Kanagawa (Japan)

Process for the preparation of a photographic material

The invention relates to a "method of manufacture." a photographic material,

So far, baryta paper has been used as a carrier for various photographic. materials, e.g., photographic scfc.es Paper and diffusion transfer photographic paper are used. Barvt paper is produced in that nan a paper made from paper pulp or pulp a jish coated or coated by gluing of finely divided barium sulfate, a small ivlenge

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a binder such as gelatin and water.

Such a carrier, however, suffers from various shortcomings and disadvantages including elongation and Contraction due to changes in humidity, in particular Shrinkage caused after the development treatment with a long period of time for drying is required after development and poor resistance to water.

According to the invention, it has been found from extensive studies that the above Problems and difficulties that occur with conventional baryta paper can be solved and eliminated.

According to the invention there is provided a method of making a photographic material in which ultraviolet rays are irradiated on a biaxially stretched polystyrene film having a roughened surface, a liquid on the resulting polystyrene film "for a sub or intermediate layer that is applied from a solution or dispersion in an organic solvent of a resin capable of bonding with a photographic emulsion, followed by a Emulsion or suspension containing gelatin is applied as a coating or coating.

The term "an emulsion or suspension containing gelatin as a binder" as used herein includes an aqueous emulsion or suspension of gelatin, optionally with an addition of silver halides, such as silver chloride, silver bromide, silver chlorobromide and, silver iodobromide, a light-sensitive diazo compound, Jnt-

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winding cores for an image-receiving element that in a halogen silver diffusion transfer process uses v / earth, or other necessary components.

The invention is explained in more detail below.

The "biaxially stretched" polystyrene film having a roughened surface "can be prepared by stretching a polystyrene film containing was previously formed from a polystyrene resin using a conventional one Process used for.-biax.ial stretching of plastics whereupon the stretched film is subjected to various ruffling treatments.

Biaxial stretching can be carried out either by stretching in both dimensions at the same time or, one after the other, stretches first in one direction and then in the other.

The roughening of the film surface can be carried out by treating the stretched film with an organic Brings solvent into contact, which the foIystyrolharz can dissolve or swell in order to cause a -> elling of the film, whereupon the swollen film with V / water or another organic solvent in Is brought into contact, which has no ability to dissolve the -i'olystyrene resin, but with that for the above ^ healing treatment used organic solvents is compatible in order to cause a roughened film surface.

typical ^ eirroielc for the first .kind of solvents are e.g. those who dissolve or swell the lOlystyrolhars,

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and tetrahydrofuran, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutylene, methyl chloride, ethylene chloride, cyclohexane, benzene, dimethylformamide and mixtures thereof. The latter type of solvents are, for example, those that are incapable of dissolving the polystyrene, but are well compatible with the first type of solvents. Typical examples of this are methanol and ethanol. The contact between ^ the film and the solvent can be carried out, Ψ by immersing the film in an organic solvent, applying the organic solvent on the film by means of roll coaters, or brushes, or the organic solvent is applied by means of atomization devices.

Roughening treatments other than those using organic solvents can also be applied, e.g. by mechanical abrasion, by adding a blowing agent which is capable of generating gas when heated, thereby causing expansion (whitening) over the entire film, or by ψ selectively dissolving a third substance mixed into the film structure prior to formation to thereby create a coarse surface. Any of the aforementioned roughening treatments can be applied without substantial degradation in accordance with the invention.

The polystyrene resin can be a white pigment, e.g. titanium dioxide, barium sulfate, calcium sulfate, barium carbonate, Lithopone, aluminum oxide white, calcium carbonate, dilicium dioxide white Or the like., and if necessary contain a colored pigment.

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.. 5 -

The hanging or clouding of the film in accordance with the procedures outlined above gives the off photographic formed from the resin produced in this way Material a satisfactory picture scene.

Polystyrene resin usually has excellent properties in terms of water resistance, Dimensional stability, rigidity or the like. Accordingly, the film treated as above is superior Whiteness and superior turbidity and is therefore used as a base material for photographic materials particularly desirable.

On the other hand, polystyrene resin poses another problem that when the polystyrene support used as such is hydrophobic and chemically inactive, coated with a hydrophilic, gelatin-containing emulsion v / ird, the adhesion between the coating film and the polystyrene support is very poor.

In the case of using transparent polystyrene as the photographic support, an improved one has therefore been made Process proposed in which a liquid that can dissolve or swell the polystyrene and which by dissolving or dispersing a resin, which resin is attached to a photographic emulsion, e.g. Gelatin, can adhere (this liquid hereinafter referred to as "liquid for the auxiliary or intermediate layer" denotes v; ird) as a coating or coating applied to the surface of a polystyrene carrier in this way to create one or more auxiliary or intermediate layers through which the adhesion between the foil

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styrofoam carrier and the photographic emulsion layer is guaranteed.

Process for applying auxiliary or intermediate coatings for transparent polystyrene films are described in a number of patents such as U.S. patents 2,872,318, 2,875,056, 3 olo 838, British patent 819 592 and the like.

Ψ To achieve satisfactory adhesion for me

between the transparent polystyrene support and the photographic one Emulsion layer in the above process for applying auxiliary or intermediate coatings however, it is necessary to use a large amount of a strong solvent for polystyrene, e.g. toluene, ethylene dichloride, Ethylacetate, acetone or the like. To use what again due to a serious deterioration in the transparencies and the mechanical strength of the support the creation of a large number of very small hoops on the surface of polystyrene substrates (so-called "solvent cracking") · For this reason

W , the kind and the composition of the solvent intended for practical use as a solvent for the auxiliary or intermediate layer are limited within a very narrow range.

According to the invention, a particularly good adhesion between the poly-styrene carrier and a gelatin containing can be achieved Emulsion or suspension can be achieved using a process in which one (1) the surface a biaxially stretched polystyrene support, (2) irradiating the support with ultraviolet rays to thereby to activate the surface, and (3) apply a liquid to it for an auxiliary or intermediate coating.

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"that brings an organic solvent and a resin with an affinity for gelatin, whereupon finally a 'coating or a coating of a gelatin containing emulsion or suspension is applied. It is not possible to have adequate adhesion between the wearer and the. photographic smulsion coating layer to be obtained if any of the working methods or working stages (l), (2) and (3), such as indicated above, is omitted,

After the method according to the invention it is now possible to use a wide variety of solvents for the auxiliary or intermediate coating, compared to the previous working methods for applying) auxiliary or intermediate coatings, with neither a Roughening nor ultraviolet irradiation is carried out, and because of this result it is also possible to use an intermediate coating liquid containing a solvent that is less Has solubility to polystyrene, or to use an intermediate layer that only has one small amounts of a soluble solvent contains what. in turn leads to the fact that the creation of new fits on the surface of the carrier is avoided and that prevents mechanical strength from being prevented while at the same time ensuring good adhesion,

• As in the method according to the invention, the effect of roughening the surface of the polystyrene film base material in cooperation with the 'effect of ultraviolet radiation are exercised, good adhesion can only be obtained if the above-described three i. '. levels (1), (2) and (3) are used together reach.

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To obtain such an adhesive force, a hydrophobic polymer should be used on the surface of the Polymer can generally be made hydrophilic with the aid of or by applying some surface treatments, usually by the decrease in the contact or contact angle of the polymer can be observed with water. However, it is completely unexpected that the improvement in adhesiveness after with the method according to the invention, even though there is no change in the contact angle with water is present, which corresponds to the degree of the moist state of the polystyrene carrier, this at the time is observed before or after irradiating the support with ultraviolet rays.

A certain improvement in the adhesion was observed _a uch in a sample, the non-roughened by irradiation with ultraviolet rays of a, polystyrene transparent under the following coating with the above-described intermediate coating liquid obtained as compared with the case where no irradiation with ultraviolet rays was carried out, however, no satisfactory result was obtained.

The resin to be used according to the invention includes synthetic high molecular compounds in their Side chain at least one of the following groups

- CO _n
- COOII, ^ O, - SO ₇ K (la = r / hydrogen or

" ⁰⁰ alkali metal),

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_ 9 -

(where R ₁ and R ₂ each have a water

hydrogen atom or an alkyl group with up to 4 carbon atoms represent) contain, and have an affinity for gelatin and in an organic solvent dispersed or dissolved, as well as gelatin or casein.

Specific examples of such resins are cellulose acetate malate, Vi ^ / lmischpolymerisat with a content of maleic anhydride, copolymers of acrylamide with methacrylic acid, a mixture of polyvinylpyrrolidone with polyacrylic acid or the like.

Preferred solvents that are in the composition of the intermediate coating liquid to be used include water, alcohols, ketones, phenols, carboxylic acid esters, chlorinated paraffins, aromatic hydrocarbons or the like, e.g. methanol, ethanol, isopropanol, Butanol, acetone, methyl ethyl ketone, phenol, o-chlorophenol, p-chlorophenol, methyl acetate, butyl acetate, methylene dichloride, Ethylene dichloride, chloroform, benzene, toluene, xylene or the like., A mixture of two or several of these solvents can be used.

Da3 photographic material in which a roughened and interlayered polystyrene support showed sufficient one high adhesion between the film base and the coating layer both in the dry state and in the wet state Condition during winding treatment, and the strength

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- Io -

the adhesion was not lowered at all even after a long period of storage. The photographic material after produced by the process of the invention has very desirable photographic performance or performance due to fogging and a decrease in sensitivity which are particularly disadvantageous the use of a white and cloudy or opaque photographic support is eliminated can be, with good adhesion according to the method according to the invention without the addition of a foreign substance this can be obtained.

The invention is explained in more detail below with the aid of examples. Testing the bond strength between the polystyrene film and the coating layer as in given in the following examples, was carried out in the following procedure.

(1) Adhesion test for dry state.

An oil triacetate film 0.14 mm thick was adhered using an epoxy resin type W adhesive on the coated surface of a sample obtained by coating a polystyrene film support with an emulsion containing gelatin as a binder. The so bonded or adhered film was allowed to stand ITacht under conditions of a temperature of 23 ⁰ C and a relative humidity of 6 £ 7 ^, then c to strips of 1: n cut Greite and 15 cm length!. The cellulose triacetate film was then pulled at a peel speed of 7 _? 38 cm peeled off in a minute, the craft of the peeling resistance being measured with the help of an expansion or tension gauge.

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In the examples below, the indication denotes "good adhesion" means the case in which the sample had a peel resistance of above 8 g / mm, where this is sufficient adhesive strength for practical use as a photographic material.

(2) Wet condition adhesion test.

The same sample was bound or glued after developing, fixing or washing while under it in a wet state, the sample being coated on its surface with a cellulose triacetate film using a cyanoacrylate type adhesive in In a similar way to that described above for procedure (1), connected or glued, then determines the peel resistance. In this case, the term "good adhesion" refers to the case in which the The peeling resistance of the sample exceeds 2 g / mm, which is the same as that given above Method (l) is defined.

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

example 1

A biaxially stretched polystyrene support with a thickness of 0.1 mm was immersed in a solvent for 3 seconds from 7 'parts of ^ ethyl acetate and 1 part of ethanol immersed and then immersed in methanol for ^ o minutes, am the pilrc. became white and cloudy.

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The resulting film with a roughened surface was exposed to ultraviolet rays using three 1 kW mercury quartz lamps arranged in parallel at intervals of 50 cm along the direction of projection of the film carrier and at a position 13 cm above the carrier with the imprinting device with a demonstration speed of 3 m / min, irradiated. The film base was then coated with an interlayer liquid having the composition W shown below and then dried at room temperature.

Gelatin 1.4 g

7th

Water 3.6 cnr

Methanol 164 cm *.

Methylene chloride 3o cur

Salicylic acid 0.5 g

Formalin (2o? & Lge aqueous solution) 0.5 cnr

The one thus provided with the auxiliary or intermediate layer Film was further coated with a photographic silver halide emulsion having the following composition

k drew, where the amount is given for 1 m of the film is.

Silver chlorobromide 3.5 g

Gelatine (binder) 13, ο g

Formalin (hardener) o, l g

Saponin (wetting agent for

Coatings) o, o3 g

I water to bring the emulsion to 130 cm- '.

For comparison purposes, it was used photographic rlalogensilveremulsion with the abovementioned Composition on jev / eils a piece of another i'ilms

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i.e., (A) a transparent polystyrene film having no roughened surface at all, (B) one Polystyrene film coated with the above-described interlayer liquid after being was subjected to irradiation with ultraviolet rays, (G) a polystyrene film in which only a roughening treatment had been carried out; and (D) a polystyrene film similar to the above described interlayer liquid was irradiated without prior irradiation with ultraviolet

applied

Rays / .JJie results of the experiment are in the following Table (I) compiled.

• Tabel : AWAY (g / mm) C. D. E. O o, 5
0 0 , 6
, 2 1.1
o, 5 Peel resistance O
O Dry state
Jcup state According to the
invention 2o, o
4.5

Y / ie can be seen from Table I above, became satisfactorily good adhesion in both the dry state and the wet state achieved by the method according to the invention. No reduction in bond strength was observed after a period of 6 months found.

Example 2

A biaxially stretched polystyrene film with a thickness of 0.1 mm was in toluene and then immersed in methyl isobutyl ketone for 5 seconds

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and then immersed again in methanol for 30 seconds to a white and cloudy (roughened) support with a fine porous layer on its surface to give «This roughened polystyrene film was exposed to ultraviolet rays under the same conditions as as described in Example 1, and then irradiated with an interlayer liquid of the type described below Composition coated and then dried at room temperature.

gelatin 1 , 4 e water 3 , 6 cnr Methanol 114 CBT Methylene chloride 3o cmr Methyl acetate 5o cur Salicylic acid O , 5 S. Formalin (2o; aqueous solution) O , 5 cnr

The one thus provided with the auxiliary or intermediate layer Film was further processed with a photographic silver halide emulsion, as used in Example 1, coated to form a photographic material with good adhesion in an extent above 20 g / mm in the dry state and 4.5 g / mm or above in the wet state, neither of which amounts decreased after a long period of time.

However, there was poor adhesion between the The above-mentioned photographic emulsion and the support are obtained when the above-described interlayer liquid applied to a transparent polystyrene film after irradiation with ultraviolet rays became.

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Example 3

A biaxially stretched polystyrene film having a thickness of 0.2 mm was mixed into a one for 3 seconds Solvent consisting of 1 part acetone and 1 part methyl ethyl ketone, and then for 30 seconds immersed in methanol to form a white and cloudy (roughened) film with a fine porous layer on it to surrender to its surface. Using the roughened film thus prepared as a support: this was among the the same conditions as described in Example 1, with irradiated ultraviolet rays, and then the interlayer liquid, which had the following composition, applied to the irradiated PiIm.

gelatin 2.5 g water 3o cnr Methanol 7 ο cm ⁵ toluene 12.5 cm ⁵ Salicylic acid o, 6 g Formalin (2o $ aqueous solution) o, 3 cnr

The film thus obtained was further used to form an image-receiving layer of an image-receiving material for use in the silver salt diffusion transfer photographic process with a coating liquid coated, which has the following composition:

Gelatin (binder) 3 g

colloidal silver sulphide

(Development cores) ο, οοΐ g

Phenyl mercaptotetrazole

(Color former) o, ol g

Saponin (wetting agent) o, o2 g

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A sample with this image receiving material showed satisfactory adhesion both in dry and in wet condition, which is necessary for the use of a silver salt diffusion transfer photographic process was enough. However, only poor adhesion was achieved if the coating liquid was applied directly to the polystyrene carrier, which had only been subjected to a surface roughening treatment was applied.

Example 4

A polystyrene sheet containing 22.5% by weight of powdery titanium dioxide became biaxial in the lateral and longitudinal directions stretched at an amount of elongation of 1.5 times to form a white polystyrene film base with a ■ ^ icke of 0.1 mm to get. This polystyrene film carrier was immersed first for 3 seconds in methyl ethyl ketone and then for 30 seconds in methanol, with a roughened polystyrene support containing a titanium dioxide pigment was obtained. This film was exposed to radiation with ultraviolet rays in the same manner as described in Example 1, subjected and then with the Interlayer liquid, which had the same composition as described in Example 2, coated and then dried at room temperature.

The film thus obtained was coated with a silver halide color photographic composition as shown below
Film is specified.

leads, coated, the amount in each case for 1 m of the

Silver chlorobromide 3 »o g

Gelatine 3 »5 g beniioylaceto-2-chloro-5-dodecyloxy-

carbonylanilide (yellow coupler) 14, ο g

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Triethylene phosphoramide

($ Acetone solution) 3> o ml

Polyvinylpyrrolidone 0.7 g

The peeling test revealed that the above-mentioned Mim coated with the coloring emulsion was sufficient Adhesion strength in both dry and wet states as required for the color photographic material is required.

However, there became very poor adhesion between the support and the above color photographic Emulsion layer observed on the samples, one of which by irradiating the same film support with ultraviolet Blasting without prior roughening treatment, followed by coating of the above intermediate coating liquid and the other by coating the above-mentioned interlayer liquid on the roughened film without ultraviolet irradiation.

Example 5

A polystyrene film, which had a roughened surface and in a similar manner, -as described in Example 1, was irradiated with ultraviolet rays, with an interlayer liquid became the following specified composition coated and dried at 8o C for 2 minutes.

Copolymer, consisting of 209816/1417 25th G 1 part maleic anhydride and 5oo cm 1 part vinyl acetate 25o cm Methanol 5o cm acetone 2, 5 g. n-butanol Chromium acetate

The film provided with the auxiliary or intermediate layer was further coated with a photographic silver halide emulsion, as described in Example 1. The peeling test of the resulting emulsion-coated sample showed that the film had sufficient adhesive strength between the support and the emulsion layer in both dry and wet states, as required for the photographic material ψ .

However, there was very poor adhesion between the support and the photographic emulsion to the samples observed one of which was obtained without roughening treatment and the other obtained without irradiation with ultraviolet rays became.

Example 6

An interlayer liquid with the following composition was applied to the polystyrene support, that described in a similar manner to that described in Example 2 ", roughened and with ultraviolet rays irradiated, applied and then dried at 80 ° C for 5 minutes.

Copolymer, consisting of 2nd Floor 2 parts of acrylamide and 45o cm 1 part methacrylic acid 2o cm ⁵ Methanol 2nd Floor Isopropanol 1.5 g phenol Chromium acetate

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The auxiliary or intermediate layer thus formed was further coated with a photographic silver halide emulsion, as described in Example 1, coated. The resulting emulsion-coated film was then subjected to a peeling test and showed excellent adhesive strength between the support and the emulsion layer both dry and wet, which are suitable for use in a photographic material was sufficient.

However, the adhesive strength was very poor in the cases where the film was exposed after the ultraviolet irradiation Blasting and coating with the interlayer liquid listed above had been obtained, but not subjected to surface roughening treatment and when the film is after the surface-roughening treatment followed by the application of the above said interlayer liquid, but without ultraviolet irradiation.

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Claims (1)

- 2ο - Godfather ηta n β pruch A process for the preparation of a photographic material, characterized in that roughening a biaxially stretched polystyrene film support, irradiating the carrier with ultraviolet rays, then the surface of this Mlras an intermediate layer of at least one solvent capable of dissolving the polystyrene or swell, and a resin having an affinity for gelatin and then a photographic layer consisting of an emulsion or suspension containing gelatin as a binder is applied to the intermediate layer. 209816 / U17