DE941765C - Photographic film and method of making it - Google Patents

Description

The invention relates to photographic firms and their manufacture. In particular, it relates to a method to improve the bond between a hydrophobic film base or base and a colloidal silver halide layer. The invention is primarily concerned with a method of improvement the association or arrest between i. one consisting of an oriented polyester film photographic film base which bears a coating on at least one surface that from a copolymer of vinylidene chloride, an acrylic acid ester and itaconic acid, and 2. one water-permeable colloid layer, the invention also including the obtained photographic film includes.

Attempts are constantly being made in phototechnology to improve the anchoring of photographic emulsions on hydrophobic base films. When using synthetic polymer flaps, the usual, z. B. applied to the cellulose ester films Procedure not always appropriate. It has been proposed to make photographic films in this way.

make sure that you have an orientable, highly polymeric Esters of a dicarboxylic acid and a dihydric alcohol, e.g. B. a polyethylene terephthalic acid ester with an aqueous dispersion, one off

■ 5 vinylidene chloride, an acrylic acid ester and itaconic acid existing copolymer covers, intestine the coated carrier film in the direction of both Axes oriented and then a water-permeable colloid layer is applied. It has, however

ίο shown that if the with such a copolymer coated polyester carrier film not shortly after the mixed polymer layer has dried are coated with layers of water-permeable colloids, the adhesive strength between the carrier and the colloid layer decreases more and more with increasing time. That is the case even if a water-permeable, colloidal auxiliary layer is also applied to the mixed polymer layer.

Since the application of the photographic emulsion layers is not always immediately after production of the carrier film, it is in the art It is generally customary to use the carrier film provided with the mixed polymer layer in roll form until it is used to store and to keep an appropriate supply of it ready. On the same type of carrier film then emulsions of the most varied types must be drawn up, with the application after the special requirements that are placed on various photographic prints. the A progressive decrease in the adhesive strength as polyester films age is therefore a problem for the film industry pose a serious problem.

However, the invention is not to use limited to a polyester film base, which is coated with a layer of a vinylidene chloride-acrylic acid ester-itaconic acid copolymer although this is the preferred embodiment. Rather, the anchoring of a water-permeable, -colloidal silver halide emulsion layer on other types of film bases or Support films can be improved in the same way by applying a layer of an organic Polyisocyanate or polyisothiocyanate before applying a water-permeable colloid layer and / or a water-permeable, colloidal silver salt emulsion layer. The film foundation or the carrier film can also consist of a hydrophobic cellulose derivative, e.g. B. cellulose acetate, cellulose propionate, Cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, polyvinyl chloride, a Super polyamide (e.g. nylon), etc. are made. It can also be used with a carrier Copolymer of vinylidene chloride with a

■ other polymerizable vinyl compound, e.g. B. acrylonitrile ,. Isobutylene, styrene, vinyl chloride, Vinyl acetate and methyl methacrylate are coated, as well as carriers from the USA patent 2,491,023 known composition.

The invention relates to a method for anchoring colloidal silver salt emulsion layers hydrophobic carrier films. It also relates to a method for improving adhesive strength between a photographic. Film base and. a water-permeable silver halide emulsion, wherein the photographic base comprises an oriented polyester support film and a substrate coating from a copolymer of vinylidene chloride with an acrylic acid ester and itaconic acid consists. Another object of the invention is to provide a method which can be used with the conventional equipment used for film production can be carried out and both economically is as well as working with common chemicals. The invention also relates to photographic films of the above type, which have a novel anchoring substrate. Further objects of the invention can be seen from the description below.

The process according to the invention consists quite generally in that a thin layer of an organic polyisocyanate or polyisothiocyanate is coated on a hydrophobic film base, followed by applying a layer of a water-permeable colloid and / or a water-permeable silver halide emulsion layer. The organic polyisocyanate or polyisothiocyanate can be applied to the base base from solutions in a suitable organic solvent, expediently a volatile solvent without any noticeable dissolving effect, the solution being essentially anhydrous and no reaction with the isocyanate compound should take place. After drying, an aqueous solution of a water-permeable colloid, e.g. B. gelatin, and then an aqueous dispersion of photosensitive silver halides in an aqueous solution of a water-permeable colloid are applied, with z. B. the gelatin is applied to the dry, photosensitive colloid substrate. If the latter substrate is omitted, the aqueous dispersion of the silver halides can be applied directly to the polyisocyanate or polyisothiocyanate layer. The colloid layer is then heated to, for example, 50 to 150 ^0th

In the preferred embodiment of the invention, an orientable hydrophobic film is first provided with a thin coating of a vinylidene chloride-acrylic ester-itaconic acid mixed polymer prior to application of the polyisocyanate layer according to the invention, the hydrophobic film made of a polyester of a dicarboxylic acid with a divalent one Alcohol of the type described in Carothers DSA. Patent 2,071,250 and expediently consists of high-melting, sparingly soluble, usually microcrystalline, cold-stretchable, linear, high-polymer esters of terephthalic acid and glycols of the general formula HO (CH ₂ ) # 0H. In the formula, η is an integer between 2 and 10. These esters are known from US Pat. No. 2,465,319. The coated film is biaxially oriented in the manner described in U.S. Patent 2,627,088. The resulting film is dried out, whereupon it can be rolled up and stored.

The initial relative proportions of the amounts used for the preparation of the

■ the copolymers used in the monomers should be in the following areas:

Monomeric compound

Vinylidene chloride
Acrylic acid ester.
Itaconic acid

area

35.0 to 96.0% 3.5 to 64.5% 0.5 to 25.0%

Preferred area

75 to 95% 4 to 20% ibis 5%

The acrylic acid esters suitable for the preparation of the copolymers are the alkyl esters of acrylic and Methacrylic acid with 1 to 18 carbons in the alkyl group (e.g. methyl methacrylate, ethyl methacrylate, Butyl methacrylate, octyl methacrylate, n-dodecyl methacrylate, Methacrylic acid n-octadecyl ester), acrylic acid methyl ester, Ethyl acrylate and propyl acrylate; Vinyl chloride, acrylonitrile and methacrylonitrile.

/ 2o The monomers can be copolymerized by various processes. For example, the interpolymerization can be carried out in an aqueous dispersion which contains a catalyst and activator, such as ammonium persulfate and

-25 contains sodium bisulfite and an emulsifying and / or dispersing agent. The copolymers according to the invention can, however, also be obtained by block polymerization of the monomeric constituents without the addition of diluents, or the monomers can be reacted in suitable organic solvents as reaction media. The total concentration of the catalyst activator should generally be between about 0.01 and about 2 percent by weight, based on the amount of monomers, and expediently between about 0.1 and ι percent by weight. Improved solubilities and viscosities are achieved if the polymerization is carried out in the presence of mercaptans, such as ethyl mercaptan, lauryl mercaptan, t-dodecyl mercaptan, etc., which reduce the branching of the copolymers. In general, the concentrations of the mercaptans should be 0.1 to 5 percent by weight, based on the weight of the polymerizable monomers present in the batch.

After drying, and when a photographic silver halide emulsion or dispersion is based on the in described in the two preceding paragraphs. Basis is to be applied, is according to the invention the layer of polyisocyanate and polyisothiocyanate and water-permeable colloid and / or water-permeable colloidal silver halide dispersions, as described above, applied and dried. The process is illustrated in more detail by the following examples.

Example I.

A sample of a polyethylene terephthalic acid ester film with a melting point above 200 ° and a ■ 60 true viscosity of about 0.50 in a mixture of 2, 4, 6-trichlorophenol and phenol (70: 100 parts by weight) was first with an aqueous dispersion of a Coated mixed polymer of vinylidene chloride, acrylic acid ester and itaconic acid of the type described in US Pat. No. 2,627,088. After drying at 50 °, the film was biaxially stretched to about three times its original dimensions and according to the invention with a i ° / _o solution of methylene bis (4 phenylisocyanate ") coated in methylene chloride. After drying at 50 ⁰ a was / applied gelatin layer of a 2 ° _o aqueous solution of the diisocyanate, the film dried for 2 minutes at ioo ° heated again at 50 °. on the gelatin substrate was then an aqueous gelatin chlorobromide emulsion up ■ carried containing 5, 6 weight percent chloride, 4 percent by weight of gelatin and 0.4 weight percent formaldehyde (as a 35 to 4o ° / ₀ solution) was prepared. After drying was the compound of the gelatin-silver halide layer well with the film base. After exposure, the film was treated as follows:

1. it was developed for 5 minutes at 20 ^° C. in the following solution:

N-methyl-p-aminophenol hydrosulfate .. 5.0 g ^8s

Hydroquinone 31.4 g

Sodium sulfite 151.0 g

Potassium carbonate 104.3 g

Sodium hydroxide 6.6 g

Water up to a total of 4.0 1

2. Rinsed in water for 5 minutes,

3. Fixed for 10 minutes at 20 ° C in the following solution:

Sodium thiosulphate 350.0 g ^ 5

Sodium sulfite 15.0 g

Sodium acetate 18.0 g

Potassium aluminum sulfate 32.0 g

Citric acid 8.0 g

Water up to a total of 2.0 1

4. The film was then washed in water for 10 minutes and tested for the adhesive strength of the layers. The wet and dry strengths were excellent.

Example II

The whole procedure of Example I was repeated, only with the exception that the diisocyanate used there is replaced by toluene-2,4-diisocyanate became. The result was similar.

Example III

The entire procedure of Example I was repeated except that used there Diisocyanate was replaced by the dimer of toluene-2,4-diisocyanate. The results were similar.

Example IV

A sample of a polyethylene terephthalic acid ester film with a melting point above 200 ⁰ and a true viscosity of about 0.50 in a mixture of 2, 4, 6-trichlorophenol and phenol (70: 100 parts by weight) was first with an aqueous dispersion ines vinylidene chloride copolymer of the above U.S. Patent 2,627,088 described

benen type coated. After drying at 50 °, the five was biaxially stretched by three times its original dimensions and treated according to the invention with a 10% solution of methylene bis (^ - phenyl isocyanate) in methylene chloride. After drying at 50 ⁰ , a solution of the mixed m- (benzoylacetamido) -benzaldehyde-sodium- ο -sulfobenzaldehyde-polyvinyl acetal of the following composition was applied:

mixed m- (Benzoylacetamido) -benzaldehyde-sodium-o-sulfobenzaldehyde-

polyvinyl acetal 1.5%

Boric acid 1.9%

Diisopropanolamine 1.3%

Acetone 40.0%

, 95% ethyl alcohol,. 55.3%

The film was then dried at 50 °, heated to 100 ° for 5 minutes and treated with a dye containing a color former Coated polyvinyl acetal silver halide emulsion, which is 1.77 percent by weight of a mixture of bromine and iodized silver, which is about 99.1% from silver bromide and 0.9% from Silver iodide consists and in the polymeric color former (4.12 weight percent of the total emulsion) was dispersed. The color former is from Example I. U.S. Patent 2,513,190 known. After this After drying, the anchoring of the acetal-silver halide layer on the carrier film was good. The film was then exposed and treated as follows:

1. One developed. 10 minutes at 20 ° C in the following solution:

p-Amino diethylaniline hydrochloride 2.5 g

. . Sodium sulfite 10.0 g

Sodium Carbonate 46, $ g

Potassium bromide; 2.0 g

Water up to 1.01

2. Rinse in water for 30 seconds.

3. It was fixed for 5 minutes at 20 ° C. in the following Solution:

Sodium thiosulfate 240.0 g

Sodium sulfite, 15.0 g

Sodium tetraborate 18.0 g

Glacial acetic acid 12.0 g

KaHum-aluminum sulphate , ... 20.0 g

Water up to 3.01

4. Rinse in water for 5 minutes. 5. Bleached for 5 minutes at 20 ° C in the following Solution:

Potassium ferricyanide 100.0 g

Boric acid 'ΐο, οg

Sodium tetraborate 5.0 g

Water up to 1.01

6. Rinse in water for 5 minutes.

7. It was fixed for 5 minutes at 20 ^° C. in the following solution:

Sodium thiosulfate 200.0 g

Water except for,, 1.01

8. Rinse in water for 10 minutes.

Even after the exposure and wet treatment described the adhesive strength was satisfactory in both the wet and dry states.

Example V

A sample of a polyethylene terephthalic acid ester film base with a melting point above 200 ⁰ and a true viscosity of about 0.50 in a mixture of 2,4,6-trichlorophenol and phenol (70: 100 parts by weight) was treated with a 1 "/" solution treated with methylene bis (4-phenyiisocyanate) in methylene chloride, dried at 50 °, heated to 100 ° for 2 minutes and coated with a gelatin-silver halide emulsion In the manner described in Example I, the adhesive strength in dry and wet conditions was so satisfactory.

Example VI

A sample of the polyethylene terephthalic acid film described in Example V. was treated as in Example V, with the exception that. the film before the application of the solution of methylene bis (4-phenyl isocyanate) has been biaxially stretched. The adhesive strengths of the layers were after coating with a gelatin-silver halide emulsion and a treatment as in Example I as well as in the remaining cases.

Example VII.

A sample of biaxially stretched polyethylene terephthalic acid ester of the type described in Example V was, as indicated there, with a solution of Treated methylene bis (4-phenyl isocyanate). After drying, a Gelatin dispersion of the following composition applied:

Gelatin: 1%

Glacial acetic acid 4%

Methanol 40%

Acetone 55% ^l0 *

The treated film was heated to 100 ° for 2 minutes heated and coated with a gelatin silver salt emulsion. After the wet treatment according to the example I the wet and dry bond strength of the 110th layers was good.

Example VIII

A sample of 'biaxially stretched Polyäthylenterephthalsäureester · the type described in the Beispiel'V "was treated with a i ° / _o solution of methylene bis (4-phenylisocyanate) are treated as in Example V. After drying, the following solution was applied to the Diisocyanatschicht :

mixed m- (Benzoyl-acetamide) -benzaldehyde sodium-o-sulfobenzaldehyde-

polyvinyl .. 1,5 ° / ₀

Boric Acid! .9 ⁰ Zo

Diisopropanolamine! .3 ⁰ Zo

Acetone .- 40.0 ⁰ Z ₀ 125.

Ethyl alcohol (95 ° / ₀ ) 55.3%

The film treated in this way was on 100 for 2 minutes heated and with a polyvinyl acetal color former silver salt emulsion coated which is 1.5 percent by weight of about 1.3 percent silver iodide and 98.7 percent silver bromide contained existing silver iodobromide. The silver salt was in the polymeric color former dispersed, which made up 3.8 percent by weight of the total emulsion (the color former is from the U.S. Patent 2,513,190 known). After this After drying, the emulsion adhered well to the carrier film. It was exposed and with the following solutions treated:

i. Developer (10 minutes at 20 ° C): ■ '

p-aminodiethylaniline hydrochloride. 2.5 g

Sodium stufite 10.0 g

Sodium carbonate 46.8 g

Potassium bromide 2.0 g

Water up to 1.0 1

• ao 2nd water rinse: 30 seconds.

3. Fixing bath (5 minutes at 20 ^° C.):

Sodium thiosulfate ·. 240.0 g

Sodium sulfite - 15.0 g

Sodium tetraborate 18.0 g

^a5 glacial acetic acid 12.0 g

Potassium aluminum sulfate 20.0 g

Water up to 3.01

4. Water rinse: 5 minutes.

5. Bleaching (5 minutes at 20 ° C):

Potassium ferricyanide ... ^ Γ. ΐοο, ο g

Boric acid 10.0 g

Sodium tetraborate 5.0 g

Water up to 1.0 1

6. Water rinse: 5 minutes.

7. Fixing bath (5 minutes at 20 ^° C.):

Sodium thiosulphate ... 200.0 g

Water up to 1.0 1

8. 10 minute water rinse.

After these treatments, both the wet and dry bond strength of these layers was satisfactory.

Example IX

Example VII was repeated, with the exception that instead of methylene bis (4-phenyl isocyanate) Toluene-2,4-diisocyanate was used. Man achieved similar results.

Example X

Example VII was repeated with the modification that instead of methylene bis (4-phenyl isocyanate) Hexamethylene diisocyanate was used. Similar results were obtained.

. . Example XI

Example VII was repeated, only with the exception that instead of methylene bis (4-phenyl isocyanate) the dimer of toluene-2, 4-diisocyanate is used became. Similar results were obtained. From the foregoing it can be seen that according to the invention previously unknown layer combinations can be obtained through the novel anchoring substrate. The diisocyanate or diisothiocyanate layer is very thin, but the other layers have their usual thickness. In the case of carrier films made of polyethylene terephthalic acid ester with a layer of a copolymer of vinylidene chloride, acrylic acid ester and itaconic acid can be the thickness of the various Layers may be the same as those in U.S. Patent 2,627,088.

Instead of the isocyanates described in the preceding examples, it is possible to use the same amounts of the polyisothiocyanates, polyisocyanates, diisothiocyanates and diisocyanates and mixtures of two or three or more such cyanates described above and below. Examples of these compounds include polymethylene diisocyanates and diisothiocyanates, such as. B. ethylene diisocyanate, trimethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate and the corresponding diisothiocyanates; Alkylene diisocyanates and diisothiocyanates, such as. B. propylene-i, 2-diisocyanate, 2,3-dimethyltetramethylene diisocyanate and diisothiocyanate, butylene-i, 2-diisocyanate, butylene-i, 3-diisothiocyanate and butylene-1,3-diisocyanate; Alkylidene diisocyanates and diisothiocyanates, such as. B. ethylidene diisocyanate (CH ₃ CH (NCO) ₂ ) and heptylidene diisothiocyanate (CH ₃ (CHa) ₅ CH (CNS) ₂ ); Cycloalkylene diisocyanate and. diisothiocyanates, such as. B. i, 4-diisocyanatocyclohexane, cyclopentylene-i, 3-diisocyanate and cyclohexylene-i, 2-diisothiocyanate; aromatic 'polyisocyanates and polyisothiocyanates, such as. B. m-phenylene diisothiocyanate, p-phenylene diisocyanate, p-phenylene diisothiocyanate, i-methyl-phenylene-2,4-diisocyanate, naphthylene-1,4-diisocyanate, o, o'-toluene diisocyanate, diphenyl -4, 4'-diisothiocyanate and diisocyanate, benzene-i, 2,4-triisothiocyanate, 5-nitroi, 3-phenylene diisocyanate, xylylene-i, 4-diisocyanate, xylylene-i, 3-diisocyanate, 4, 4 '-Diphenylene methane diisocyanate, 4,4'-diphenylene propane diisocyanate and xylylene-1,4-diisothiocyanate; aliphatic-aromatic diisocyanates and diisothiocyanates, such as. B. Phenylethylene diisocyanate (C ₅ H ₆ CH (NCO) CH ₂ NCO); Diisocyanates and diisothiocyanates containing heteroatoms, such as. B. SCNCH ₂ OCH ₂ NSc, SCNCH ₂ -CH ₂ OCH ₂ CH ₂ NSC and SCN (CBy ₃ -S - (CH ₂ ) ₃ -NSC; i, 2, 3, 4-tetraisocyanatobutane, butane-i, 2, 2-triisocyanate, i-isocyanato-4-isothiocyanatohexane, and 2-chloro-1,3-diisocyanatopropane, Mixtures of two or more of these compounds can also be used.

Have the preferred diisocyanates, diisothiocyanates, and mixed isocyanate-isothiocyanates the general formula ZCN-R - NCZ, in which R is a divalent hydrocarbon radical and Z is an iao Means chalcogen with an atomic weight below 33.

Instead of those described in the examples Solvents can also be other solvents for the cyanate compounds or mixtures thereof are used, which exert a slightly dissolving effect on the carrier film used and with

Polyisocyanates or polyisothiocyanates do not react. Such solvents include Hydrocarbons, Ethers, esters and chlorinated hydrocarbons. The polyisocyanate or polyisothiocyanate can be 0.10 to ίο and expediently make up 0.25 to 4 percent by weight of the solution. Such other solvents are i.a. Benzene, toluene, xylene, hexane, heptane, dioxane, methylene chloride, chloroform, trichlorethylene, Tetrachloroethane, carbon tetrachloride, methyl acetate, ethyl acetate, and mixtures of the two or more of these solvents.

The heating period can vary in length

depending on the temperature used, the type of colloid layer, the colloidal silver salt layer

15- etc. The heating time used in practice is between ^x / ₂ and 15 minutes.

Of course, the application of the silver salt emulsions and the subsequent drying, winding, Slitting, cutting, perforating, etc., can be performed in the absence of actinic light. Instead of the particular colloidal silver salt emulsions described in the preceding examples Various other colloidal layers can also be applied to the layer of isocyanate compounds Silver salt emulsions and water-permeable colloidal intermediate layers are applied, which do not contain photosensitive silver salts. .Other colloids applied according to the invention are polyvinyl alcohol and water-soluble Derivatives of polyvinyl alcohols in general, e.g. B. partially hydrolyzed polyvinyl acetates and mixed polyvinyl chloride acetate, hydrolyzed ^. Copolymers of vinyl acetate with unsaturated Connections, e.g. B. with maleic anhydride, acrylic acid esters, etc. Suitable colloids of the last mentioned types are known from U.S. Patents 2276322, 2276323 and 2397866. Further Colloids are, among other things, hydrophilic, partially substituted polyvinyl esters and acetals as well as the low-substituted cellulose ester of saturated aliphatic Monocarboxylic acids with 2 to 4 carbon atoms and low-substituted cellulose ethers, e.g. B. Methyl cellulose, ethyl cellulose, etc. Other natural colloids include casein, albumin, Gum arabic, agar-agar, polyglucuronic acid, etc., which by the substrates according to the invention also if. be anchored on the carrier films.

The invention can be used to make all types of photographic film including Black and white and color films for cinematography and photographic for portrait films, such for holding documents, lithographic films, medical, dental and industrial X-ray films, sound recording films, films of the United States patent 2,180,409. and the types known from US Pat. No. 2,462,503.

The great advantage of the invention is that · it is a simple and economical way to Improvement of the adhesive strength of water-permeable, colloidal silver salt emulsion layers creates hydrophobic carrier films. The invention can also be used with the usual in the manufacture of photographic film equipment used. According to the invention, 6 & a good anchoring of formaldehyde-hardened gelatin-silver salt emulsions on a hydrophobic Carrier film allows even if the same has aged for a long time. Is particularly advantageous the invention for the above-described polyester carrier films coated with a copolymer. Further advantages will be apparent from the description above.

The invention can be modified extensively without departing from its scope.

Claims (3)

PATENT CLAIMS: 1. A photographic film characterized by a hydrophobic support which is an organic Polyisocyanate or polyisothiocyanate-containing substrate and one or more water-permeable Carries colloid layers. 2. A process for the production of a photographic film according to claim 1, characterized in that a hydrophobic support is coated with a solution which contains an organic polyisocyanate or polyisothiocyanate, the layer obtained dries, or one or the layer of said isocyanate compounds applying several water-permeable colloid layers and heating the ^{film obtained to 50 to 150 0.} " 3. The method according to claim 2, characterized in that a solution is used which 95 '· contains a volatile organic solvent. 4. "The method according to claim 2 or 3, characterized characterized in that the isocyanate compound is an aromatic diisocyanate or diisothiocyanate or a mixture thereof is used. 100 · 5. The method according to claim 2 to 4, characterized marked; that one on the colloid layer an aqueous dispersion of a photosensitive Applying silver salt in a water-permeable colloid. 6. The method according to claim 5, characterized in that an aqueous gelatin solution is used as the colloid layer which is drawn onto the isocyanate layer, that the gelatin layer is dried and then coated with a gelatin 11 »silver salt emulsion layer and the film obtained ¹ Z _{Dries 2} to 15 minutes. 7. The method according to any one of claims 2 to 6, characterized in that the hydrophobic support a polyethylene terephthalic acid ester film is used, which is a coating a vinylidene chloride-acrylic acid ester - itaconic acid copolymer carries. 509 691 4.56