US3475193A - Method of subbing a photographic film - Google Patents

Description

Oct 28, 1969 man@ TAKENAKA ETAL 3,475,193

METHOD OF SUBBING A PHOTOGRAPHIC FILM Filed Sept. 9, 1965 HARUO TAKENAK. SEICH/ 008A 7Z'PPE/ /KED SHYN/CH ADACHIHRRA ,6MM www THE/R HTTdRN' YS United States Patent O METHOD OF SUBBING A PHOTOGRAPHIC FILM Haruo Takenaka, Odawara-shi, Seichi Ooba, Tokyo, and

Teppei Ikeda and Shynich Adachihara, Ashigarakamigun, Kanagawa-ken, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kamigawa-ken, Japan, a corporation of Japan Filed Sept. 9, 1965, Ser. No. 486,044 Int. Cl. B44d I/06, l/092 U.S. Cl. 117-34 5 Claims ABSTRACT oF THE DIscLosURE A process for subbing a photographic film, which comprises radiating ultraviolet rays having a wave length of l800-3200 A. for up to 3 minutes upon a film support of biaxially oriented, crystallized linear polyester containing aromatic carbonyl groups, in the presence of at least one member selected from the group consisting of oxygen and ozone, and then applying to the radiated surface a subbing solution containing gelatin or an organic solvent-soluble hydrophilic resin, said gelatin and resin being in a mixed organic solvent containing 1-25% by weight of a .member selected from the group consisting of solvents and swelling agents for the polyester, whereby adhesiveness between the film support and the emulsion layer or the backing layer of the photographic lm is remarkably improved.

This invention relates to a method for the production of a photographic film, and more particularly, to a method of subbing a photographic film.

In general, photographic film is produced by applying a hydrophilic light sensitive emulsion layer and a hydrophilic back layer to a hydrophobic film as support.

It is required that the adhesion of the emulsion layer or back layer to a film support be strong enough not to be stripped during the production, processing, and use of the photographic film under dry and wet conditions. For this purpose, an adhesive layer called a subbing layer is ordinarily provided between the film support and the emulsion layer and back layer (bath being designated as the emulsion layer hereinafter).

Up to this time, it has been usual that when a film support consisting of cellulose ester is used, such subbing layer is formed by applying a solution or dispersion of hydrophilic resin in a solvent capable of dissolving or swelling the support to the surface of the support.

However, in order that the subbing layer is formed on a film support consisting of biaxially orientated, crystallized linear polyester containing aromatic carbonyl group by the method as described above, a large amount of an expensive solvent having high polarity and high boiling point must be incorporated in a subbing solution as the solvent for swelling or dissolving the polyester. In such case, a high temperature and long time are required for drying the subbing layer, so the expansion of the support and the lowering of the elasticity modulus occur during the intial stage of the drying and thereafter, the GOntraction of the support occurs, which results in wrinkles. Moreover, when a dispersion of gelatin, as widely used as hydrophilic resin, is used as a subbing solution, it is unavoidable that the gel strength of the gelatin lowers and the adhesive strength under a wet condition after coated with a photographic emulsion is inferior.

As the solvent or swelling agent of the polyester as described above are used aldehyde or ketones having aromatic or partially saturated aromatic group and aldehydes having heterocyclic group containing nitrogen (U.K.P. 772,600), carboxylic acids represented by the general formula: R-COOH or R-X-COOH in which y 3,475,193 Patented Oct. 28, 1969 substituted alcohols, ketones, carboxylic acids and their esters (U.K.P` 797,425), benzyl alcohol whose aromatic nucleus is substituted with -NO2 or -Cl U.S.P. 2,830,- 030), chloral hydrate (German Patent 1,020,457) and pyrol (German Patent 1,092,653). Illustrative of the solvents as lmentioned above are benzoic acid, salicylic acid, salicylic acid ester, monochloroacetic acid, dichloroacetic acid, trichloroacetic aid, trifluoroacetic acid, 2-nitropropanol, `benzyl alcohol, benzaldehyde, acetonyl acetone, acetophenone, benzamide, benzonitrile, benzylamine and methyl nicotinate. Further, phenol, o-chlorophenol, cresol and other phenol derivatives are known as the solvent or swelling agent for polyesters.

As it has been difiicult hitherto, as mentioned hereinbefore, to form a subbing layer by applying a solution or dispersion of hydrophilic resin to a biaxially orientated, crystallized polyester, the subbing layer must be formed -by the method of applying a hydrophobic resin having a good adhesiveness and solubility to a polyester support, drying and applying a hydrophilic resin thereto. In such subbing method, however, two layers must be provided and therefore, it is not favourable from an economical point of view.

The object of the present invention is to cause an emulsion layer or back layer to adhere strongly to a film support by a simple method.

That is to say, in accordance with the present invention, there is the provision of a method of forming a subbing layer, which comprises radiating ultraviolet rays upon a film support of biaxially orientated, crystallized linear polyester containing aromatic carbonyl groups in the presence of oxygen and/or ozone, and then applying a subbing solution or dispersion of hydrophilic resin in an organic mixing solvent containing 1-25% by weight of a solvent of swelling agent for the polyester to the radiated surface.

The film support used in our invention consists of biaxially orientated, crystallized linear polyester containing aromatic carbonyl groups, for example, polyethylene terephthalate, copolyester of terephthalic acid-isophthalic acid-glycol and poly-l,4-cyclohexylenedirnethyl terephthalate.

The organic solvent used in our invention should include 1-25% by weight of a solvent orv swelling agent for the polyester as described above as a component of the subbing solution. At above 25%, the planeness of the film finished is often injured, and at below 1%, the required effect is hardly given. The amount of the solvent or swelling agent for polyester may be varied with the kind of polyester support and solvent or swelling agent, and the radiating condition. Further, it may be varied with the kind of other organic solvent coexistent. Of course, two or more solvents or swelling agents for the polyester may be used. In this case, the amount thereof to be used is such that the total amount of the mixed solvent or swelling agent is to be 1-25% to the whole organic solvent.

In the subbing solution used herein may be incorporated an organic solvent-soluble hydrophilic resin, gelatin, a gelatin swelling agent, dispersing agent, an organic solvent and further additives for reinforcing the subbing layer, improving the adhesiveness between the subbing layer and the support or emulsion layer, preventing static charges and coloring the support, that is to say, a hardening agent, antistatic agent, dyestuff and another hydrophilic or hydrophobic resin. In some cases, the desired adhesiveness can be obtained by the addition of a gelatin hardening agent such as ethylene imine derivative, epoxy derivative, or a hydrophobic resin such as partially saponified copolymer of vinyl chloride-vinyl acetate and cellulose nitrate, even if radiation is applied for a shorter period of time.

The hydrophilic resins used in this invention may be synthetic high molecular compounds soluble in organic solvents and soluble in or swellable with water, said compounds containing one or more groups selected from -OH, -COOH,

A--CO cyclic amido where R1 and R2 each represents H, -CH3, -C2H5, -C3H7 or --C4Hg, -SO3M -(M represents H or an alkali metal), and nitrogen-containing heterocyclic groups. For example, there are cellulose acetate phthalate, cellulose acetate maleate, vinyl copolymer containing maleic anhydride (e.g., copolymer of vinyl acetate and maleic anhydride 1:1), acetal mixtures containing -SO3M groups derived from polyvinyl alcohol (cf. U.K.P. 894,- 509), acetal mixtures containing -COOM groups derived from polyvinyl alcohol, polyvinyl alcohol partially esterified with a divalent acid, a mixture of polyvinyl pyrrolidone and polyacrylic acid, and the like.

In the present invention, the effective wave length of ultraviolet ray is within S200-1800 A. The use of a quartz mercury lamp leads to a good result practically, and if a lter absorbing ultraviolet ray having a Wave length of less than 3200 A. is inserted between a film support to be radiated and lamp, the effect by theradiation will not be observed.

The radiation of ultraviolet ray may be varied to such an extent that the quality of a support is not deteriorated, in accordance with the kind of a light source, the distance between a light source and film support, the temperature of a film support and the kind of a medium at radiating.

The support radiated by ultraviolet ray in accordance with the invention can maintain a constant adhesive strength even if a subbing layer is applied after a long storage.

In the method of our invention, the contact with a medium containing oxygen and/ or ozone may be carried out after the radiation of ultraviolet ray in vacuo or in a gas or liquid not absorbing ultraviolet ray so much.

The surface treatment of our invention can be without the use of chemicals, and two or more subbings are not necessary, resulting in a rapid processing. Furthermore, as the radiation of ultraviolet ray may be carried out in the air, the apparatus and operation for carrying out the invention are made simple and practical.

The adhesion of an emulsion layer or back layer to a support is very tenacious in our invention and is never damaged during the production, processing, use and treatment of a photographic film.

The method of our invention is carried out in general as follows:

Ultraviolet ray is radiated upon a surface of lm support of biaxially orientated, crystallized linear polyester by the use of an ultraviolet ray lamp, a subbing solution or dispersion of hydrophilic resin in organic solvent, containing a solvent or swelling agent for the polyester in a proportion of 1-25% to the whole OFSHHC Solvent, S

applied to the radiated surface, followed by drying and an emulsion layer is applied thereto. In an embodiment of our invention, as shown in FIG. l, in which the radiation is carried out in the air, a biaxially orientated, crystallized polyester film support l of 30 cm. in width and 100 microns in thickness is fed to a radiating chamber 2, where the both sides or one side of the support is radiated by cylindrical mercury lamps 3 of quartz, l kw., 50 cm. in length and about 30 cm, in arc length, arranged apart from the support surface by about 20 cm. The radiation time differs by the radiation conditions, but 3 minutes or less is preferable. The radiated film support is then fed to an applying chamber 4 where it is dipped in an applying dish 5 and it is dried in a drying chamber 6, followed by being wound up. The temperature of the air in the radiating chamber can be controlled by supplying hot air or cold air thereto from the outside. The temperature at the radiating is not limited, but a range within 70-1 50 C. is preferred. It is observed that the radiation at a high temperature takes a shorter time.

The tests with respect to the adhesiveness between a support and emulsion or back layer, which were carried out in the following examples, are the following:

Test about the dry adhesiveness-An emulsion surface of a treated and dried film or a raw film is scratched to give squares (about 4 mm. x 4 mm.) by the use of razor, an adhesive tape, for example, a polyester tape manufactured by Nitto Electric Industry Co., Ltd., is pasted thereon and it is rapidly stripped therefrom. A good adhesiveness in this test means a case where 50% or more of the emulsion layer remains on the polyester base.

Test about the wet adhesiveness during processing.- An emulsion or back surface of a film is scratched to give a line in a processing solution by the use of an iron pen and the surface is rubbed by a finger vertically to the line. A good adhesiveness in this test means a case where the emulsion or back layer is not stripped more than the scratched line.

The present invention is further illustrated by the following examples.

EXAMPLE 1 Ultraviolet ray was radiated upon the both surfaces of Aa biaxially orientated, crystallized polyethylene terephthalate film support of 3l cm. in width and 100 micron in thickness at C. for 1 minute in the air by the use of a mercury lamp of quartz and l kw., and a dispersion of gelatin in organic solvents having the following cornposition was applied thereto, followed by drying at C. for 2 minutes and Winding up.

A gelatin-silver halide emulsion layer was applied to the one side of the resulting subbing layer and an antihalation back layer was applied to the other side. The adhesive strength of the photographic light sensitive film so produced was good under a wet and dry condition.

EXAMPLE 2 The both surfaces of a biaxially orientated, crystallized polyethylene terephthalate film support of 31 cm. in width and 75 microns in thickness were irradiated with ultraviolet ray similarly to Example l, wound and stored at normal temperature and humidity (23 C., 65% RH) for 1 month. Then, coated with a. dispersion of gelatin in organic solvents having the following composition and dried at 120 C. for 2 minutes.

Parts by weight Gelatin c 1 Water 1 Salicylic acid 0.3 Methanol 20 Acetone 60 Methylene chloride 14 IBenzyl alcohol 3 o-Chlorophenol 3 A gelatin-silver halide emulsion layer and gelatin antihalation lback layer were applied to the both sides respectively. The adhesiveness under a dry and wet condition was good.

When 0.4 part of cellulose nitrate was added to the subbing solution in this example, the subbing treatment could be carried out without any obstacle and the adhesiveness of the product film under a dry condition was improved.

EXAMPLE 3 A biaxially orientated, crystallized polyethylene terephthalate iilm support of about 1 m. width and 100 micron thickness was irradiated with ultraviolet ray at 100 C. for 1 minute in the air by the use of a mercury lamp of quartz, 3 kw., 1.35 m. in length and about l m. in arc length, arranged apart from the support lby 30 cm., immediately coated lwith the dispersion of gelatin in organic solvents, similar to Example l, dried and the both surfaces were coated with a gelatin-silver halide emulsion. The adhesiveness under a wet and dry condition was good.

EXAMPLE 4 Parts fby weight Gelatin 1 Monochloroacetic acid 2 Phenol 6 Methanol 32 Methylene chloride 60 A gelatin-silver halide emulsion was applied to the one side, a gelatin antihalation layer was lapplied to the other side and dried. The adhesiveness under a wet and dry condition was good.

EXAMPLE 5 A biaxially orientated, crystallized polyethylene terephthalate iilm support of 30 cm. in width was passed at 2.5 m./min. through a treating box, as shown in FIG. 2, of 120 cm. in length, 60 cm. in width and 50 cm. in depth whose inlet and outlet were sealed by rollers 7, where the one side of the iilm support 9 was irradiated at 120 C. in an air containing 1% of ozone by the use of cylindrical mercury lamp 8 of 1 kw., 50 cm. in width and 30 cm. in arc length, arranged apart therefrom by 15 cm. The air containing ozone was supplied from 10 and discharged from 11. The iilm support was wound up once, the radiated surface thereof was coated with the gelatin dispersion of Example 1 by the other conventional immersion coating method and dried at 120 C. for 2 minutes. Then, the subbed surface was coated with a gelatin-silver halide emulsion land dried. The adhesiveness of the product iilm under a dry and wet condition was good.

EXAMPLE 6 The -both surfaces of a biaxially oriented, crystallized polyethylene terephthalate iilm support of 100g in thickness and 31 cm. in width were irradiated by ultraviolet rays for 1 minute at 80 C. in the air using a quartz mercury lamp of 1 kw., coated immediately with a hydrophilic resin solution having the following composition, and after drying for 3 minutes at 100 C., the film support was rolled up.

Weight parts Maleic anhydride-vinyl acetate copolymer (1:1) 1.3

Methanol 45 Acetone 25 Methylene chloride 20 Monochloroacetic acid 10 Chromium acetate 0.4

On the one side of thus subbed surfaces of the film support was applied a gelatino silver halide emulsion and on the opposite an anti-halation back layer, and they were dried. The adhesiveness of thus obtained photosensitive film under wet and dry conditions was good.

EXAMPLE 7 =Parts by weight Mixed acetal of polyvinyl alcohol 1 1 Methanol 30 Acetone 60 Benzyl alcohol 5 o-Chlorophenol 5 1Polyvnyl alcohol mixed-acetalated with (I) benzaldehyde and (II) a sodium salt of benzaldehyde-Q-sulfonic acid (I, 25%; II, 45%; -OH, 30%).

On the both surfaces of the Iiilm base were coated a gelatino silver halide emulsion layer and a gelatino antihalation back layer respectively and they were dried. The adhesive property of the layers in a dry state and a wet state was good.

EXAMPLE 8 The both surfaces of a biaxially oriented, crystallized poly-l,4-cyclohexylenedimethylterephthalate film support was irradiated for 2 minutes at 100 C. in the air by a quartz mercury lamp of l kw., immediately coated with the subbing solution having the following composition, and dried for 2 minutes at 120 C.

-Parts by weight Copolymer of diethylacrylamide (66%) and methacrylic acid (34%) 1.5 Methanol 45 Acetone 35 Methylene chloride 10 o-Chlorophenol 10 Chromium acetate 0.5

On the both surfaces of thus subbed film support were coated a gelatino silver halide emulsion layer and a gelatino antihalation layer respectively, and they were dried. The adhesive property of the layers in dry and wet states was good.

What is claimed is:

1. A process for subbing a photographic film, which comprises radiating ultraviolet rays having wave lengths of 1800 to 3200 A. for a duration of up to 3 minutes upon a film support of biaxially oriented, crystallized linear polyester containing aromatic carbonyl groups, in the presence of at least one member selected from the group consisting of oxygen and ozone, applying to the radiated surface of the film support a subbing solution containing a member selected from the group consisting of gelatin and a hydrophilic organic solvent-soluble resin and also containing a mixed organic solvent containing l-25% by weight of a solvent for the polyester drying, applying a gelatino silver halide emulsion to said subbed surface and then drying.

2. The process according to claim 1, wherein the linear polyester is polyethylene terephthalate.

3. The process according to claim 1, wherein the sub- Ibing solution contains gelatin.

4. The process according to claim 1, wherein the sub- 10 bing solution contains a member selected from the group consisting of a maleic anhydride-vinyl acetate copolymer, a mixed acetal of polyvinyl alcohol and a copolymer of diethylacrylamide and methacrylic acid.

5. The process according to claim 1 wherein said subbing solution is applied to both sides of said film, and

wherein the gelatino silver 4halide emulsion is applied to one side of said subbed film, and a gelatino antihalation layer is applied to the other side of said subbed film.

References Cited UNITED STATES PATENTS 2,805,173 9/1957 Ambler 117-47 2,876,187 3/1959 Wolnski 117-47 3,337,364 8/1967 Whitbourne 1l7l38.8

MURRAY KATZ, Primary Examiner U.S. Cl. X.R.

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