JP2684230B2 - Photographic element with protective layer - Google Patents

Description

FIELD OF THE INVENTION This invention relates to photographic elements having a protective coating layer. More specifically, the present invention relates to photographic elements having a transparent, flexible, scratch-resistant layer having good adhesion to a support.

(Prior Art) A silver halide photographic light-sensitive material may be scratched during handling to impair excellent recording with high accuracy. Further, with the rapid autoloading of cameras and the speeding up of development processing, scratches are likely to occur during handling, and improvement is required. Therefore, many photographic material protective coatings have been developed so far.

For example, the pentaerythritol triacrylate monomer, the pentaerythritol tetraalkylate monomer, and the photopolymerization developer protective coating described in JP-A No. 61-172144 cannot provide sufficient scratch resistance. Further, the protective coating layers described in U.S. Pat. No. 4,092,173 and U.S. Pat. No. 4,333,998 provided scratch resistance, but had insufficient adhesion to the support. In addition, JP-A-61-201248 and JP-A-61-20
The protective coatings described in 1250, JP-A-61-201249, JP-A-61-201251 and the like have good adhesion to gelatin but insufficient adhesion to the support.

(Problems to be Solved by the Invention) An object of the present invention is to provide a photographic element having a protective coating layer having excellent scratch resistance and adhesiveness.

(Means for Solving the Problems) The present invention provides a photographic element having at least one image-bearing layer on a triacetyl cellulose support and a protective coating layer on the opposite side of the image-bearing layer. And a composition containing a triacetyl cellulose swelling organic solvent to coat a part of the composition on the surface of the triacetyl cellulose support, and then the composition is cured by irradiation to form a protective coating layer. Achieved by a photographic element having a protective coating layer characterized by being formed.

The first essential component of the radiation-curable composition used in the protective coating layer of the present invention is urethane acrylate. Here, the urethane acrylate refers to an acrylate ester having a urethane bond in the same molecule. The urethane acrylate may be any of a monomer, an oligomer, a polymer or a mixture thereof. Urethane acrylate is a known substance and has hitherto been used in radiation-curable compositions. Urethane acrylates readily form crosslinks upon appropriate irradiation. In a preferred embodiment of the present invention, the urethane acrylate is
It is prepared by reacting a diisocyanate with a polyol and further reacting with a hydroxyacrylate or hydroxymethacrylate. Examples of the diisocyanate include, but are not limited to, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate. More preferably, the diisocyanate is an aliphatic or alicyclic diisocyanate, and examples thereof include hexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), trimethylhexamethylene diisocyanate and isophorone diisocyanate. Examples of polyols include, but are not limited to, butanediol, neopentyl glycol, ethoxylated bisphenol A, ethoxylated bisphenol S spiroglycol and the like. Examples of hydroxy acrylate or hydroxy methacrylate include, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxymethacrylate pentaerythritol triacrylate, and the like.

The second essential component of the radiation-curable composition used in the protective coating layer of the present invention is a polyfunctional acrylate. Polyfunctional acrylates are acrylic monomers that have at least two acrylic ester groups. Such monomers act to increase the hardness of the protective coating layer, increase the adhesive strength and promote rapid curing in the radiation-curable composition. Specific examples include the following (a) to (e), but are not limited to these.

(A) Tripropylene glycol diacrylate (TP
GDA) (B) Bisphenol A diglycidyl ether acrylate (C) Pentaerythritol triacrylate (PET
A) (D) Trimethylolpropane triacrylate (TM
PTA) (E) pentaerythritol tetraacrylate By adding a triacetylcellulose swelling organic solvent to the composition used for the protective coating layer of the present invention, the leakage of the protective coating layer onto the support when the protective coating layer is coated on the support Can be improved and the adhesiveness can be improved. In particular, when the support is triacetyl cellulose, the organic solvent can cause a part of the composition of the protective coating layer to penetrate into the surface of the support (anchoring effect) to further improve the adhesiveness. The triacetyl cellulose swelling organic solvent may be any organic solvent that swells triacetyl cellulose, preferably acetone, methylene chloride, methyl ethyl ketone, methyl acetate, methyl cellosolve acetate, nitromethane, more preferably acetone. , Methylene chloride.

Other radiation-curable components may be added to the protective coating layer of the present invention. For example, ethyl acrylate, 2-
Viscosity modifiers of compositions such as ethylhexyl acrylate, N-vinylpyrrolidone, isobornyl acrylate are included.

The composition ratio of the protective coating layer of the present invention may be any ratio, and urethane acrylate is 5 to 95 wt%, preferably 10 to 90 wt%.
%, Polyfunctional acrylate 95 to 5 wt%, preferably 10 to 9
0 wt%. The thickness of the protective coating layer is preferably 0.1
˜20 μ, more preferably 3 to 10 μ.

As the radiation used in the present invention, conventionally known ultraviolet rays, electron beams and the like can be used, and the irradiation may be performed under a vacuum in the atmosphere, an inert gas atmosphere.

The support of the light-sensitive material used in the present invention is not particularly limited, but various plastic films can be used, and preferred are cellulose derivatives (for example, diacetyl, triacetyl, propionyl, decanoyl, acetylpropionyl-acetate), polyamide Polycarbonate described in US Pat. No. 3,023,101, Japanese Patent Publication No. 48
Polyester described in No. 40414 (for example, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene,
Polysulfone, polyacrylate, polyetherimide and the like are preferable, and triacetyl cellulose and polyethylene terephthalate are particularly preferable.

These supports may be added with a plasticizer and used for the purpose of imparting flexibility. Particularly in the case of cellulose ester, plasticizer-containing substances such as tolphenyl phosphate, biphenyl diphenyl phosphate and dimethylethyl phosphate are usually used.

These supports vary depending on the polymer type, but the thickness is
From 1 mm sheet to 20 μm thin film, it can be used properly depending on the application, but is usually 50 μm to 300 μm
Is the thickness range.

The molecular weight of these support polymers is preferably 10,000 or more, more preferably 20,000 to 800,000.

The support may contain a dye for the purpose of neutralizing the base color, preventing light piping, preventing halation, and the like.

Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high-frequency treatment for firmly adhering a photographic layer (for example, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, etc.) on these supports. After performing surface activation treatments such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a photographic emulsion may be directly applied to obtain an adhesive force, or these surface treatments may be performed once. Or a method in which an undercoat layer is provided without surface treatment, and a photographic emulsion layer is coated thereon.

At that time, a single layer of a gelatin solution dispersed in a methylene chloride / ketone / alcohol mixed organic solvent is applied to the cellulose derivative to provide an undercoat layer.

Examples of gelatin hardening agents include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), epichlorohydrin. Resin etc. can be mentioned. These undercoat liquids can contain various additives as necessary. Examples include surfactants, antistatic agents, dyes for coloring antihalation agents, pigments, coating aids, antifoggants and the like. When the undercoat liquid of the present invention is used, an etching agent such as resorcin, chloral hydrate, chlorophenol and the like can be contained in the undercoat liquid.

In the underlayer of the present invention, inorganic fine particles such as SiO ₂ and TiO ₂ or polymethyl methacrylate copolymer fine particles (1 to
10 μm) as a matting agent.

The undercoating liquid according to the present invention may be prepared by a well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or U.S. Pat.
It can be applied by an extrusion coating method using a hopper described in the specification of 1,294. U.S. Pat.Nos. 2,761,791, 3,508,947, 2,94
Two or more layers can be simultaneously coated by the method described in Nos. 1,898 and 3,526,528, Yuji Harazaki, "Coating Engineering", page 253 (1973, published by Asakura Shoten).

The light-sensitive material of the present invention comprises a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer and the like, and these are mainly used in a hydrophilic colloid layer.

In that case, as a binder of the hydrophilic colloid layer,
For example, proteins such as gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N-vinylpyrrolidone, Polyacrylic acid copolymer, polyacrylamide or derivatives and partial hydrolysates thereof, dextran, polyvinyl acetate, polyacrylic acid ester, rosin, etc. may be mentioned, and if necessary, in a mixture of two or more of these colloids. May be used.

Among them, gelatin or a derivative thereof is most used, and the gelatin mentioned here refers to so-called lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin.

In the present invention, an anion, a nonion, a cation,
A betaine-containing fluorine-containing surfactant can be used in combination.

These fluorine-containing surfactants are described in JP-A-49-10722, British Patent No. 1,330,356, JP-A-53-84712 and JP-A-54-1422.
No. 4, No. 50-113221, U.S. Pat.No. 4,335,201, No. 4,34
No. 7,308, UK Patent No. 1,417,915, JP-B-52-26687
No. 57-26719, No. 59-38573, JP-A-55-149938
No. 54-48520, No. 54-14224, No. 58-200235,
Nos. 57-146248, 58-196544, UK Patent No. 1,439,40
No. 2, etc.

 These preferred specific examples are described below.

I-1 C ₈ F ₁₇ SO ₃ K I-2 C ₇ F ₁₅ COONa In the present invention, a nonionic surfactant may be used.

Hereinafter, specific examples of the nonionic surfactant preferably used in the present invention will be shown.

Compound example N-1 C ₁₁ H ₂₃ COOCH ₂ CH ₂ O ₈ H N-3 C ₁₆ H ₃₃ COCH ₂ CH ₂ O ₁₂ H The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of a photographic light-sensitive material. For example, a surface protective layer, an emulsion layer,
Examples include an intermediate layer, an undercoat layer, and a back layer.

The amount of the fluorine-containing surfactant and the nonionic surfactant used in the present invention may be 0.0001 g to 1 g per square meter of the photographic light-sensitive material, and is more preferably 0.000 g to 1 g.
5 to 0.5 g, particularly preferably 0.0005 to 0.2 g. or,
Two or more of these surfactants of the present invention may be mixed.

Also, ethylene glycol, propylene glycol, 1,
A polyomal compound such as 1,1-trimethylolpropane as disclosed in JP-A-54-89626 can be added to the protective layer of the present invention or another layer.

Other known surfactants may be added alone or as a mixture to the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, sensitization and other improvements in photographic properties.

Also, in the present invention, lubricating compositions, for example, U.S. Pat.Nos. 3,079,837, 3,080,317, 3,545,970,
Modified silicones and the like described in JP-A-3,294,537 and JP-A-52-129520 can be contained in the photographic constituent layers. Further, higher fatty acid esters are also effective.

The photographic light-sensitive material of the present invention contains U.S. Pat.
Polymer latexes described in 411,911, 3,411,912 and JP-B-45-5331 can be included.

The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened by various organic or inorganic hardeners (alone or in combination).

In particular, color reversal films and color negative films can be mentioned as typical examples of preferred silver halide color photographic light-sensitive materials in the present invention. In particular, a color negative film for general use is a preferred color photographic light-sensitive material.

 Hereinafter, a general-purpose color negative film will be described.

The light-sensitive material of the present invention comprises at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support.
The number of layers and the order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as the layers are provided. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, even if the arrangement order is reversed, the installation order in which different photosensitive layers are sandwiched between the same color-sensitive layers can be replaced.

Non-light-sensitive layers such as intermediate layers of the respective layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, No. 61-20038, a coupler as described in the specification, a DIR compound may be contained, and a color-mixing inhibitor as commonly used is included. You can leave.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No., JP-A-57-112751, JP-A-62-200350, JP-A-62-2065
No. 41, No. 62-206543, No. 56-25738, No. 62-63936
No. 59-202464, Japanese Patent Publication No. 55-34932, No. 49-15495
It is described in the specification.

Silver halide grains have crystal defects such as those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, and twin planes. Or a composite form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparation
and typea) ”and ibid. No. 18716 (November 1979), 648
P.Glafkides, Chemicet Phisique Photographiq, Ph.D.
ue, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Vorcal Press (VLZelikman et al., Making and Coating Pho.
tographic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide such as silver rhodane or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The efficiency of the present invention is:
This is particularly noticeable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such a process are described in Research Disclosure Nos. 17643 and 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, Examples thereof include alcohols or phenols, aliphatic carboxylic esters, aniline derivatives, and hydrocarbons. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, propionate, methyl ethyl ketone, cyclohexanone, and 2-hexanone. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling speed T1 / 2 is preferably 30 seconds or less. Film thickness is 25 ° C relative humidity
It means the film thickness measured under 55% humidity control (2 days), and the film swelling rate T1 / 2 can be measured according to a method known in the art. For example, A.Gree
n) et al. Photographic Science and Engineering (Photogr.Sci.Eng.), Volume 19, 2
No., pages 124 to 129, serometer (swelling meter)
And T1 / 2 is 30% with color developer.
90% of the maximum swollen film thickness reached when treated at ℃ for 3 minutes and 15 seconds
Is defined as the saturated film thickness, and is defined as the time required to reach the film thickness of T1 / 2.

The film swelling speed T1 / 2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 15
0-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) /
It can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
The development can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, the compounds are described in U.S. Pat. Nos. 3,342,597, indoaniline compounds, 3,342,599, and Schiff base compounds described in Research Disclosures 14,850 and 15,159, and 13,924.

Next, the cartridge used in the present invention is mainly composed of synthetic plastic.

In molding the plastic of the present invention, a plasticizer is mixed with the plastic as required. As the plasticizer, for example, trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone,
Representative examples include di-n-octyl succinate, bromonaphthalene, and butyl palmitate.

Specific examples of the plastic material used in the present invention are shown below, but are not limited thereto.

Specific examples include polystyrene, polyethylene, polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, methyl methacryl resin, vinyl formal resin, There are vinyl butyral resin, polyethylene terephthalate, Teflon, nylon, phenol resin, melamine resin and the like.

Particularly preferred plastic materials for the present invention are polystyrene, polyethylene, polypropylene and the like.

Further, the cartridge of the present invention may contain various antistatic agents. Antistatic agent is not particularly limited, carbon black, metal oxide particles of the present invention, nonionic, anion, cation, betaine surfactant, nonionic,
Anions, cations, betaine polymers and the like can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538.

Usually, the cartridge is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties.

Furthermore, the shape may be the same as the current size, but the diameter of the cartridge at present 25 m / m is 22 m / m or less, preferably 20 m / m or less.
It is effective to reduce the size of the camera if it is less than m / m or more than 14 m / m. Further, in the current cartridge, the leading end of the spool on the side that engages with the film drive unit of the camera is protruding, which is an obstacle to miniaturization of the camera. Therefore, it is preferable to eliminate this portion. As a result, the volume of the cartridge, which is currently about 35 cm ³ , can be reduced. The volume of the cartridge case is 30 cm
³ or less, preferably 25 cm ³ or less, more preferably 20 cm ³
It is preferable to set the following. Plastics used for cartridges and cartridge cases weigh more than 1g
It is 25 g or less, preferably 5 g or more and 15 g or less.

The ratio of the volume of the cartridge case to the plastic used for the cartridge and the cartridge case is 4
0.70.7, preferably 3-1.

In the case of the cartridge incorporating the 135 color photosensitive material in the present invention, the total weight of the plastic used for the cartridge and the cartridge case is usually 1 g or more and 25 g or less,
Preferably it is 5 g or more and 15 g or less.

Next, the form of the cartridge incorporating the color photosensitive material described in the present invention will be described.

The form of the cartridge of the present invention is not particularly limited, but it is preferable that it be compatible with commercially available cameras. Furthermore, the present invention may be applied to a new camera compatible with a cartridge incorporating the color photographic material of the present invention. First example of these concrete cartridges
Figures (further internal structures are shown in FIGS. 2 to 4).

(Examples) The present invention will be described in more detail with reference to Examples below, but the invention is not limited thereto.

〔Example〕

(1) Preparation of base The composition described below was applied on a support with a wire bar, dried at 60 ° C, and then irradiated with UV (some samples differ). UV irradiation was performed using a 120 w / cm high-pressure mercury lamp in an N ₂ atmosphere for 5 seconds to prepare a base for a light-sensitive material.

Composition (B) Same as composition (a) except that pentaerythritol triacrylate described in composition (a) is replaced with pentaerythritol tetraacrylate.

(C) Same as the composition (a) except that the acetone described in the composition (a) is removed.

(E) Same as composition (a) except that Sartomer 9505 (urethane acrylate) described in composition (a) was replaced with 10 g of Aronix M1200 (urethane acrylate: manufactured by Toagosei Co., Ltd.).

(2) Preparation of Photosensitive Material On the opposite side of the base prepared above, an undercoat containing gelatin as a main component is applied, and each layer having the composition as shown below is multilayer-coated thereon to prepare a sample which is a multilayer color photosensitive material. It was made.

A photosensitive layer was prepared in the same manner as the photosensitive layer described in Example 1 of JP-A-2-93641.

However, a fluorine-containing surfactant was added to the second protective layer as shown in Table 1.

(3) Processing of sample The sample was cut into a film having a width of 135 mm and having the format shown in FIG. Development of these samples was performed as follows.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5 g Water added 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium sulfate 10.0 g Water added 1.0 pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0 pH6.6 Stabilizer Holimarin (40%) 2.0ml Polyoxy Ethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3g Water added 1.0 (4) Scratch resistance evaluation (i) Scratch strength Sample back surface before development processing (surface not coated with photosensitive material) , Vertically apply a diamond needle with a tip of 0.025 mmR,
Apply a continuous load and scratch the sample back surface at a speed of 60 cm / min. (25 ° C., 60% RH) The sample after being scratched was placed on a Schaukasten, and the load at which scratches began to be seen through transmission was defined as the scratching strength.

(Ii) Surface rubbing test A Kikuron eagle cut into 1 cm squares was loaded with a load of 500 g and rubbed once at a speed of 60 cm / min to examine the extent of scratches visible by reflected light. Evaluation was made in three stages of ○, Δ, and × in order from those that are hardly damaged to those that are easy to damage. (twenty five
(° C, 60% RH) (iii) Put 10 samples after development on (a) Schaukasten, and check the number of scratches seen by transmitted light, (b) The number of scratches seen by reflected light on sample back surface It was (○: No scratch, ×: Scratch) (5) Adhesion evaluation When the back surface of the photosensitive material after development processing is scratched in a cross shape with a cutter knife, an adhesive tape is attached, and the tape is peeled off. Then, it is checked whether or not the protective coating layer applied to the back surface remains. (○: All remained, △: 5
0% or more remained, x: less than 50%) The results are shown in Table 2.

From Table 2, the protective coating layer of the present invention improves the scratch resistance, and when the composition containing acetone is applied (2-2, 2-3, 2-6), the adhesion is also improved. I understand.

(Effects of the Invention) The protective layer of the present invention is cured by irradiation with radiation, whereby scratch resistance and adhesion resistance are remarkably improved.

[Brief description of the drawings]

FIG. 1 is a perspective view of a photographic film cartridge according to the present invention, FIG. 2 is a plan view showing a state of a leading end portion of the photographic film, FIG. 3 is a sectional view of the cartridge, and FIG. FIG. [Description of Signs] 1 ... Photo film cartridge 2 ... Spool 3 ... Photo film 4 ... Patrone main body 5 ... Film drawer 7 ... Perforation 8 ... Protrusion 9 ... Protrusion 10 ... Hole 11… Notch 12 …… Drawer passage 13 …… Step

Claims (1)

(57) [Claims] 1. A photographic element having at least one image-bearing layer on a triacetylcellulose support and a protective coating on the opposite side of the image-bearing layer from a urethane acrylate, a polyfunctional acrylate and a triacetylcellulose swellable organic material. Protective coating characterized by coating a composition containing a solvent, permeating a part of the composition onto the surface of the triacetyl cellulose support, and then curing the composition by irradiation to form a protective coating layer. A photographic element having a coating layer.