US 3492122 A
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1970 HARUO TAKENAKA ET AL 3,492,122
PHOTQGRAPHIC SILVER HALIDE FILM ELEMENT Filed April 15, 1966 United States Patent 3,492,122 PHOTOGRAPHIC SILVER HALIDE FILM ELEMENT Haruo Takenaka, Teppei Ikeda, Toshiaki Okiyama, Sueo Miyazaki, and Choji Hibino, Kanagawa, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kauagawa, Japan, a corporation of Japan Filed Apr. 13, 1966, Ser. No. 542,242 Claims priority, application Japan, Apr. 16, 1965, 40/ 22,147 Int. Cl. G03c 1/84 U.S. Cl. 96-84 4 Claims ABSTRACT OF THE DISCLOSURE The disclosure relates to a silver halide film element having a polyethylene terephthalate film base and coated thereon a co-polyester layer under the silver halide emulsion. To the other side of the base is applied an organic solvent solution of a mixture of a cellulose ester and a copolyester. An antihalation layer is applied which consists of a member selected from the group consisting of styrenemaleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, and a maleic anhydride copolymer denatured by a monohydric alcohol having 4 to 12 carbon atoms.
The present invention relates to a photographic silver halide material, more particularly, it relates to a photographic film comprising a biaxially oriented, crystallized polyethylene terephthalate film support having an improved anti-halation layer.
Conventionally, anti-halation layers are generally divided into two kinds according to the position thereof. One is where the anti-halation layer is positioned at the surface of a photographic film opposite to the side of a photographic emulsion layer. The other is where the antihalation layer is positioned between the support and a photographic emulsion layer. This invention relates to the former type, and the following specification is concerned with this kind of anti-halation layer, except where there is a specific designation to the contrary.
The anti-halation layer for photographic film must satisfy the following conditions:
(1) Absorb the light having wave lengths Within the entire range to which the light-sensitive material is responsive;
(2) Be completely removable, without leaving stains, a suitable treating bath, such as a pre-treating bath, a developing bath, or a water-rinsing bath;
(3) Have no undesirable effects on the emulsion;
('4) Must have sufficient mechanical properties such as wear resistance, and scratch strength, and flatness;
When the photographic element is rolled up in a state such that the anti-halation layer is in contact with an emulsion layer, the anti-halation layer should not be transferred to the emulsion layer.
An object of this invention is to provide a polyethylene terephthalate film for photography having an anti-halation layer satisfying the above-mentioned factors.
Another object of this invention is to improve the adhesion between the polyethylene terephthalate film and the anti-halation layer.
Another object of this invention is to provide, after the removal of the anti-halation layer, a substratum of the 'back surface of the photographic film, said substratum having improved mechanical properties such as wear resistance, and scratch strength, as well as improved physical properties such as transparency and flatness, and to provide further desirable properties to the film after development.
3,492,122 Patented Jan. 27, 1970 Other objects of this invention will be apparent from the following specification and drawing, in which: A biaxially oriented, crystallized polyethylene terephthalate film support has poor adhesive characteristics to other materials. Therefore, when applying an anti-halation layer directly to the surface of the film, the adhesive strength of the anti-halation layer to the polyethylene terephthalate film is insuflicient; therefore, when the film is rolled up with the anti-halation layer being in contact with the emulsion layer, the anti-halation layer is frequently transferred to the emulsion layer. This makes practical use of the photographic film very difficult.
As the results of various investigations, the inventors have found that when a layer composed of a mixture of a cellulose ester and a copoly ester of terephthalic acid and glycols is formed on the surface of a biaxially oriented, crystallized, polyethylene terephthalate film support as a substratum, and then an anti-halation layer containing a maleic anhydride copolymer binder is applied to said substratum, the anti-halation layer is adhered firmly to the film support.
The polyester used in this invention is preferably a copolyester consisting of terephthalic acid and glycols, that is, a ternary co-condensation polyester consisting of terephthalic acid, ethylene glycol and triethylene glycol, which is soluble in the solvents and mixed solvent described hereinafter. A typical example is a co-condensation product of 1 mol of terephthalic acid residual group, 0.8-0.5 mol of ethylene glycol residual group, and 0.5-0.2 mol of triethylene glycol residual group.
Further, the cellulose ester used in this invention may be one which is soluble in said solvents and mixed solvents, the compatible range of the weight ratio of the cellulose ester to the polyester being 50:50 to :15 in a preferable concentration, capable of providing a stable coating solution. Cellulose acetate, cellulose acetate propionate, cellulose butyrate and the like may be used.
The concentration of the coating solution in this invention may generally be in the range of 0.1 to 2%, but the range of 0.1 to 1.0% is preferable. There are no particular limitations about the degree of polymerization of the polyester and the cellulose ester used and it is preferable to vary the concentration of the coating solution in accordance with the degree of polymerization thereof.
The solvents used for the coating solution of this invention may be common industrial solvents. For example, there are alcohols, such as, methanol, ethanol, methyl Cellosolve, and Cellosolve; ketones, such as, acetone, methyl ethyl ketone, and cyclohexanone; esters, such as methyl acetate, ethyl acetate, and cellosolve acetate; hydrocarbons, such as, hexane, cyclohexanone, benzene, and toluene; clorinated hydrocarbons, such as, methyl chloride, ethylene chloride, tetrachloroethane, and trichloroethylene; and cyclic ethers, such as, tetrahydrofuran and dioxane. These may be used alone or in combinations thereof.
Further, it is preferable to add into the abovementioned solvent an organic solvent capable of swelling, softening and/or dissolving polyethylene terephthalate since by the addition thereof the substratum can be adhered more firm- 1y to the polyethylene terephthalate base.
Examples of organic solvents capable of swelling, softening and/or dissolving polyethylene terephthalate, are phenol, o-chlorophenol, p-chlorophenol, cresol, and other phenol derivatives, benzoic acid, salichlic acid, salicylic acid esters, monochloroacetic acid, trichloroacetic acid, trifiuoroacetic acid, 2-nitropropanol, benzyl alcohol, benzaldehyde, acetonylacetone, acetophenone, benzamide, benzonitrile, and methyl nicontinate.
For improving the coating and sliding properties of the film during the coating procedure, or after developing the film and removing the anti-halation layer, a suitable additive, for example, an anionic surface active agent, such as, sodium dodecylbenzene sulfonate, sodium laurylsulfonate, or sodium N-methyloctyl tauride may be incorporated into the coating solution comprising the polymer and the solvent.
The anti-halation layer directly coated and formed on the above-mentioned substratum according to the process of this invention, is one of a type where the layer is coated using an organic solvent. In this case, the binder for the anti-halation layer may comprise an alkali-soluble resin, that is, a copolymer of maleic anhydride and a vinyl compound co-polymerizable with maleic anhydride. For example, there is a styrene-maleic anhydride copolymer and a maleic anhydride-vinyl acetate copolymer.
The alkali-soluble resin is dissolved in the above-mentioned alcohol or ketone in a resin concentration of above and the solution is kneaded with carbon black or mixed with an anti-halation dye to provide an anti-halation mother liquid. Various additives for improving the coating property, preventing adhesion to the emulsion layer, and controlling the friction coefiicient are added. Further, a suitable solvent selected from the above-mentioned alcohols, ketones, hydrocarbons, and chlorinated hydrocarbons is added to provide the anti-halation coating solution.
By using the maleic anhydride copolymer denatured by one or more monohydric alcohols having 4 to 12 carbon atoms in the anti-halation layer, the transfer of the antihalation layer to the emulsion layer can be effectively prevented. The denature in this specification means the formation of a half ester by opening the ring of the acid anhydride group of the maleic anhydride copolymer.
In order to denature the maleic anhydride copolymer, the copolymer is dissolved by heating into the monohydric alcohol having 4 to 12 carbon atoms in an amount of 1.5 to 5 times the weight of the copolymer. After the copolymer has been completely dissolved, a low-boiling point alcohol such as methanol or ethanol, or a ketone is added into the solution in a copolymer concentration of to above 5%. The solution is then kneaded with carbon black or mixed with an anti-halation dye to provide an anti-halation coating mother liquid.
The above-prepared coating liquid is applied on the substratum composed of a mixture of polyester and cellulose ester on a polyethylene terephthalate film, and dried to provide the anti-halation layer.
An example of the photographic film having the antihalation layer prepared according to the process of this invention as described above is shown in the accompanying drawing in its cross-sectional view. On one side of an oriented polyethylene terephthalate film support, a substratum 2 composed of a polyester-cellulose ester mixture is formed. The anti-halation layer 4 is then applied. On the opposite side of film 1, a first layer 2 composed of polyester is formed. A substratum 3 or emulsion layer is formed by coating a gelatin dispersion onto first layer 2. Finally, a photographic light-sensitive emulsion layer 5 is applied to layer 3.
Since the anti-halation layer is sufiiciently adhered to the support according to the process of this invention, the anti-halation layer is not transferred by adhesion to the emulsion layer even if the film is rolled up such that the anti-halation layer is in contact with the emulsion layer. Further, since the anti-halation layer, as taught by this invention, can be removed very easily by processing, it can be completely removed during the usual de-filming procedure by adding a light-squeezing procedure. Furthermore, after the removal of the above-mentioned antihalation layer, the substratum as taught by this invention, appears on the back surface of the light-sensitive film, and, since the substratum has sufiiciently high wear resistance and scatch strength, the film can be sufliciently used in practice after development.
EXAMPLES The following will serve to illustrate the practical examples for the production of a photographic film comprising a polyethylene terephthalate support having the anti-halation layer taught by this invention. These examples, however, are merely explanatory, and should not be construed as limiting the invention.
Example 1 A polyester was formed by adding an ester exchange reaction catalyst to a mixture of 1 mol of dimethyl terephthalate, 1.7 mols of ethylene glycol, and 0.8 mol of triethylene glycol. Into a mixed solvent of parts of ethylene dichloride, 10 parts of phenol, and 10 parts of tetrachloroethane 2 parts of the above-prepared polyester was dissolved. The solution was then applied to one surface of an oriented polyethylene terephthalate film at 60 C. and dried for 5 minutes at C.
A gelatin dispersion consisting of 1.0% of gelatin, 2.0% of water, 4.0% of acetic acid, 40.0% of methanol and 55.0% of acetone was then coated into this just formed layer, and coating was dried for twenty minutes at 60 C. (second layer).
Into a mixed solvent of 52 parts of ethylene dichloride, 8 parts of methylene chloride, 20 parts of methanol, 20 parts of tetrachloroethane and 20 parts of phenol, were dissolved 0.2 part of the above-prepared polyester and 0.2 part of triacetyl cellulose, and the coating solution was applied to the opposite surface of the polyethylene terephthalate film at 80 C. and dried for six minutes at 100 C. An anti-halation layer consisting of 1 part of a styrenemaleic anhydride copolymer, 0.25 part of sodium laurylsulfonate, 70 parts of acetone, 30 parts of methanol, 10 parts of cyclohexanone, and 1 part of carbon black at 30 C. was coated onto this layer, and the coating was dried for 20 minutes at C. to provide the anti-halation layer. Onto the gelatin layer (second layer) on the polyethylene terephthalate film, was coated, as usual, a photographic silver halide emulsion, and dried. The anti-halation layer had good adhesive property to the polyethylene terephthalate film, and also good flatness.
The anti-halation layer was completely removed when the photographic film was immersed for 60 to 90- seconds in an usual defilming treating bath mainly consisting of sodium sulfate, and then rinsed with water. Also, no stain was left. Further, the transference of the anti-halation layer to the emulsion layer was not observed at a humidity of 80% RH and at a temperature lower than 20 C.
EXAMPLE 2 The procedure as in Example 1 was repeated except that a copolymer of styrene and maleic anhydride was dissolved in 3 parts of butanol by heating and the solution was used instead of the copolymer solution in Example 1. In this example, almost the same results as in Example 1 were obtained. Also, no transference of the anti-halation layer to the emulsion layer was observed at a humidity of 80% RH and at a temperature of 30 C.
EXAMPLE 3 The procedure as in Example 2 was repeated using monochloro-acetic acid instead of phenol, with substan tially the same results as in Example 2. I
EXAMPLE 4 The procedure as in Example 2 was repeated using trichloroacetic acid instead of phenol with substantially the same results as in Example 2.
EXAMPLE 5 A polyester was prepared by adding an ester-exchange reaction catalyst into a mixture of 1 mol of dimethyl terephthalate, 1.3 mols of ethylene glycol and 1.2 mols of triethylene glycol. After dissolving 15 parts of the thus prepared polyester into 1000 parts of trichloroethylene,
the solution was applied to one surface of an oriented polyethylene terephthalate film at 60 C. and dried for 5 minutes at 80 C. On thus formed layer was applied the gelatin dispersion as described in Example 1 followed by drying.
Into a mixed solvent of 52 parts of ethylene dichloride, 8 parts of methanol, 20 parts of tetrachloroethane, and 20 parts of phenol, were dissolved 0.04 parts of the polyester as described in Example 1, and 0.018 parts of cellulose acetate butyrate, and the solution was applied to the opposite side of the polyethylene terephthalate film at 50 C. and dried for 6 minutes at 100 C. On the thus formed layer was coated at 30 C., the anti-halation layer prepared by dissolving 2.5 parts of a styrene-maleic anhydride copolymer into a mixed solvent of 2.5 parts of =butanol and 2.5 parts of octyl alcohol, adding thereto 0.25 parts of sodium laurylsulfonate, 90 parts of methanol, 10 parts of acetone, 10 parts of cyclohexane and 1.0 parts of carbon black. The layer was dried for 20 minutes at 90 C.
Finally, a gelatino silver halide photographic emulsion was coated as usual, on the gelatin layer of the polyethylene terephthalate film, and dried.
The anti-halation layer had thus formed high adhesive strength to the polyethylene terephthalate film base, and also good flatness.
EXAMPLE 6 A polyester was prepared by adding an ester-exchange reaction catalyst to a mixture of 1 mol of dimethyl terephthalate, 1.5 mole of ethylene glycol, and 1 mol of triethylene glycol. After dissolving 0.7 parts of this polyester and 1 part of cellulose nitrate into a mixture of 150 parts of ethylene dichloride, 50 parts of acetone, 13 parts of phenol and 15 parts of tetrachloroethane, the solution was applied to one side of an oriented polyethylene terephthalate film at 50 C. It was then dried for 10 minutes at 210 C.
Thereafter, a gelatin dispersion consisting of 1.0 part of gelatin, parts of water, 4 parts of acetic acid, 55 parts of ethylene dichloride, 10 parts of acetone, and parts of methanol was applied to the above layer, and dried for 20 minutes at 100 C.
Further, 0.2 parts of the above-prepared polyester and 0.4 parts of triacetyl cellulose were dissolved into a mixture of 52 parts of ethylene dichloride, 8 parts of methylene chloride, 20 parts of methanol, 20 parts of tetrachloroethane, and 10' parts of phenol, and the solution was applied on the opposite side of the film at C. and dried for 10 minutes at 100 C.
Into a mixture of 2 parts butanol and 4 parts of lauryl alcohol was dissolved a vinyl acetate-maleic anhydride copolymer by heating and the solution was mixed with 2 parts of carbon black, parts of acetone, 20 parts of ethanol, and 10 parts of Cellosolve to provide an anti-halation layer coating solution. The coating solution was applied on the above-formed layer at 30 C. and dried for 20 minutes at 95 C. to form an anti-halation layer.
On thus formed gelatin layer on the polyethylene terephthalate film was coated a gelatino silver halide emulsion followed by drying.
The thus obtained anti-halation layer had high adhesive strength to the polyethylene terephthalate base, and exhibited good flatness characteristics.
These examples conclusively illustrate the advantages of this invention. Having thus described our invention, we claim the following:
What is claimed is:
1. A photographic silver halide light-sensitive element which consists essentially of:
(A) a support consisting of a biaxially oriented, crystallized polyethylene terephthalate film having a photographic silver halide emulsion layer coating thereon;
(B) a substratum on the emulsion side of the film support, said substratum consisting of a copolyester;
(C) a substratum on the opposite side of the filrn support, said substratum having been formed by coating an organic solvent solution of a mixture of cellulose ester and a copolyester which consists of a cocondensation product of 1 mol of terephthalic acid residual group, 0.8 to 0.5 mol of ethylene glycol residual group, and 0.5 to 0.2 part of triethylene glycol residual group, the weight ratio of cellulose ester to polyester being 50:50 to :15, and over said substratum;
(D) an anti-halation layer having incorporated therein, as a binder, a member selected from the group consisting of styrene-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, and a maleic anhydride copolymer denatured by a monohydric alcohol having 4 to 12 carbon atoms.
2. The photographic silver halide light-sensitive element as described in claim 10, wherein the binder is maleic anhydride copolymer denatured by a monohydrio alcohol having 4 to 12 carbon atoms.
3. The photographic silver halide element as described in claim 10 wherein said maleic anhydride copolymer is selected from the group consisting of styrene-maleic anhydride copolymer and vinyl acetate-maleic anhydride copolymer.
4. The photographic silver halide element as described in claim 10 wherein said denatured maleic anhydride copolymer is obtained by dissolving by heating said maleic anhydride copolymer into said monohydric alcohol in an amount of 1.5 to 5 times the weight of said copolymer.
References Cited UNITED STATES PATENTS 1 3,178,287 4/1965 Sweet et a1. 9684 2,698,239 1/ 1951 Alles et al. 9 2,984,569 5/1961 Huys et a1. 96-87 FOREIGN PATENTS 626,241 4/1963 Belgium. 790,023 1/ 1958 Great Britain.
GEORGE F. LESMES, Primary Examiner M. B. WITIENBERG, Assistant Examiner US. Cl. X.R. 9687; 260-16