JP2750857B2 - Roll photosensitive material - Google Patents

Description

Description: TECHNICAL FIELD [0001] The present invention relates to a roll-shaped photosensitive material integrally wound with a light-shielding packaging material, and more particularly to a film and a light-shielding property during camera operation and development processing. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a roll-shaped photosensitive material that prevents the occurrence of a discharge phenomenon (discharge phenomenon occurring between a light-shielding packaging material and a film) that occurs when separating packaging materials.

[Prior art] As a roll-shaped photosensitive material having a light-shielding packaging material, a film and a light-shielding packaging material are simultaneously wound and contained in a cartridge. Photosensitive material,
A so-called 120-size film in which a film is fixed with adhesive paper at approximately the center of the entire length of the light-shielding packaging material and both the light-shielding packaging material and the film are wound on a spool, and a leader light-shielding packaging material and a film at the leading end of the film. There is a so-called 220-size film or the like to which a trailer light-shielding packaging material is attached with adhesive paper or the like at the end, and the present invention is applied to all roll-shaped photosensitive materials using these light-shielding packaging materials.

In order to provide light-shielding properties, the commonly used light-shielding packaging materials need to be coated or laminated with black-colored paper or colored paper with incomplete light-shielding properties or white paper with a resin dispersed with carbon black as a light-shielding agent. It has a great light-shielding effect. In addition, printing is performed as necessary to increase the value of characters and symbols necessary for the function and other commercial values.

[Problems to be Solved by the Invention] When a roll-shaped photosensitive material using such a resin-processed light-shielding packaging material is developed, the light-shielding packaging material and the film necessarily separate when developed. The problem is that at the time of this separation, static electricity is generated on the film due to the separation between the film release surface and the light-shielding packaging material, and static marks are often generated on the film by discharge.

When the static mark enters the screen, it becomes a fatal defect, and when the film is printed, a branch-like, cloud-like, or lightning-like pattern appears on the screen, and the value as a print is completely lost. Especially when using 120 size film, if the static mark is entered on the film taken for portraits and weddings, it will be irreplaceable, so development is very careful. It is.

On the other hand, in order to suppress the generated static electricity, various antistatic agents may be added to the back and front surfaces of the film to prevent the film itself from being charged. In addition, Japanese Patent Publication No. 61-36
No. 216, a light-shielding paper using an aluminum layer, as described in JP-A-60-35728, a combination of a high-density polyethylene and a low-density polyethylene in a certain range, and charging from single use. Is improved.

JP-A-59-68238 discloses a light-shielding paper in which an antistatic agent is added to an interlayer of a packaging material obtained by laminating a thermoplastic resin, and JP-B-51-49205 discloses an acrylate ester and a methacrylic acid. There is described a light-shielding paper which reduces the influence of static electricity by containing carbon black in at least one of an acid ester and an ethylene copolymer.

The light-shielding paper described in JP-B-51-49205 is
Carbon black having an average particle size of 50 μm or less is dispersed in the resin layer. Certainly, the addition of carbon black is effective in preventing static charge, but in recent years, with the increase in sensitivity of color light-sensitive materials, the situation is not sufficient in the range of the technology described in these publications. In particular, ISO160
In the case of a high sensitivity film of ISO 3200, conventional antistatic technology is not sufficient. Therefore, there has been a demand for the development of a technique that has an effective antistatic effect and is easy to manufacture.

As a result of intensive studies, we have found that by setting the back surface of the light-shielding packaging material to a certain surface specific resistance or less, there is a dramatic effect on antistatic.

[Means for Solving the Problems] In order to solve the above-mentioned problems, a roll-shaped photosensitive material of the present invention comprises a film and a light-shielding packaging material having one or both surfaces processed with a resin layer. In the material, the surface in contact with the film back surface of the light-shielding packaging material has an oil absorption (ml / 100 g) of 100 or more and a specific surface area (m ² / g).
A resin layer containing 150 or more carbon blacks, characterized in that its surface resistivity is 10 ⁵ Ω or less.

The base paper of the light-shielding packaging material used in the present invention may be any of ordinary natural pulp paper, synthetic fiber, or synthetic paper using a synthetic resin film.
Natural pulp paper containing wood pulp as a main component, such as hardwood pulp and softwood hardwood mixed pulp, is advantageously used. Papermaking of these papers may be performed by any of the generally known round net forming method and fourdrinier forming method.

These base papers containing natural pulp as a main component can contain various polymeric compounds. For example, cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol, gelatin, etc. as a dry paper strength enhancer, fatty acid salts, rosin derivatives, dialkylketin dimer emulsions, petroleum oils as sizing agents Resin emulsions, ammonium salts of styrene-maleic anhydride copolymer alkyl esters, etc., as pigments such as clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc., as wet paper strength enhancers, melamine resins, lactic acid resins, ethoxy Polyamide resin as a fixing agent, polyvalent metal salts such as aluminum sulfate and aluminum chloride, cation-modified polymers such as kaolin-modified starch, etc., pH adjusters, caustic soda, sodium carbonate, hydrochloric acid, etc., inorganic electrolytes, salt, Glauber, etc. Other dyes can be incorporated in combination fluorescent whitening agents, such as latex carbon an appropriate.

As a resin for processing the back side of the base paper, Japanese Patent Publication No. 51-4920
No. 5, JP-A-48-22020, JP-A-50-67644, JP-A-5
5-140835, JP-A-58-17434, JP-A-58-186744
Nos. JP-A-59-68238, JP-A-60-35728 and resins having low density, medium density, high density, linear low density, various polyolefins such as polyethylene and polypropylene, and polyvinyls such as ethylene vinyl acetate. Acrylic, such as ethylene ethyl acrylate and ethylene methyl acrylate,
Examples include rubbers such as styrene-butadiene, simple substances such as ionomers, blends, polymer polyamides, polyethylene terephthalate, polymethylpentene, and ethylene vinyl alcohol copolymer.

 The above layer may be provided with two or more layers.

When laminating these resins on the base paper, an anchor agent may be used to further enhance the adhesiveness. Examples of the anchor agent include organic titanium-based, isocyanate-based,
Polyethyleneimine, polybutadiene and the like can be mentioned.

The carbon black used in the present invention may be produced by any of a furnace type, a channel type, an acetylene type and a thermal type.

When the carbon produced by such a production is used for a light-shielding packaging material, any carbon black can be used as long as it simply gives light-shielding properties. It has been found that it is necessary to use a carbon black having a certain range of physical properties from among these carbon blacks in order to obtain the required specific surface resistivity or lower.

In order to obtain the surface resistivity required for the light-shielding packaging material of the present invention, the carbon black required to have an oil absorption (ml / 100 g) of 100 or more and a specific surface area (m ² / g) of 150 or more It was found that having physical properties was a necessary condition.

Hereinafter, typical examples of the carbon black effective for the present invention will be described. Of course, it is not limited to these carbon blacks. MA-, manufactured by Mitsubishi Chemical Industries, Ltd.
600, # 650B, # 40, # 3150, # 3250, # 3750, # 395
0, MA-100, CABOT carbon VULCAN XC-72R, BLAC
Pearls700, manufactured by VUCAN P-Lion Akzo Co., Ltd., Ketjen Black EC manufactured by Asahi Carbon Co., Ltd., Asahi HS-500 Other factors that affect the conductivity of carbon black include surface conditions (less impurities) ), Although the graphitization is progressing (a commercially available product is sufficient), but it is an incidental performance, and the oil absorption and the specific surface area basically determine the conductivity. It is an important item.

Using carbon black outside the range we found,
In order to keep the specific surface resistance below a certain level on the back surface of the light-shielding packaging material, it can be obtained by increasing the amount of addition.

However, the problems when the addition amount is unnecessarily increased are as follows: (1) The resin film processed into the light-shielding packaging material becomes brittle or hard. When processed with such a resin, the flexibility of the light-shielding packaging material is lost as a result. When a roll film using such a light-shielding packaging material is used for a camera, there is a disadvantage that the winding torque of the camera is heavy and operability is deteriorated. In addition, in the camera of the automatic winding type, the consumption of the battery is increased.

(2) Since more carbon black is used than necessary, the dispersing time is long and the cost is high overall.

In particular, the condition (1) is a fatal drawback when a roll film is used and is a condition that must be avoided in order to lower the commercial value. Along with these, as a light-shielding packaging material, a material having high flexibility is generally used at present. That is, the functions required as the light-shielding packaging material include high flexibility, light-shielding properties, and excellent charging characteristics.

It is clear from the above description that the carbon black used is an absolute requirement in order to satisfy three or more.

Normally, in order to make a resin-processed light-shielding packaging material using carbon black, a so-called masterbatch in which carbon black is contained in a thermoplastic resin such as a polyethylene resin using a normal melt kneader such as a Banbury mixer kneader is created. Then, dilute it with the diluted resin to the required ratio and adjust it, or adjust the so-called compound, which contains the required amount of carbon black from the beginning in the resin, or disperse the resin. It is generally known to control the dispersion of carbon black in a latex liquid using a dispersant.

At this time, in addition to the carbon black, a fatty acid metal salt such as zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, sodium palmitate, calcium palmitate, sodium laphrate and an antioxidant are also used. can do.

The amount of carbon black required at this time differs depending on whether the resin is directly mixed in the resin or in the case where the resin is mixed with a latex liquid in a dispersed state.

That is, when directly mixed into the resin, the content is preferably in the range of 3 to 20% by weight, and particularly preferably in the range of 5 to 15% by weight, based on the resin composition.

When mixed with a latex liquid, the content is preferably in the range of 10 to 40% by weight, particularly preferably 15 to 30% by weight, based on the resin composition.

Means for processing the resin containing the light-shielding substance on the surface of the base paper include reverse roll method, blade method, air knife method, rod method, extrusion method, gravure roll method or dry lamination, wet lamination, and solution coating. It can be applied using a method.

In addition, an adhesive layer may be interposed, these known techniques can be used, and the present invention is not limited thereto.

The letters and symbols necessary for the function are printed on the surface of the light-shielding packaging material, or printed to increase the commercial value,
As the ink used for these printings, generally used offset printing ink, gravure printing ink, or UV ink can be used.

Typical types of synthetic resins used in these inks include salt vinyl acetate, nitrified cotton, polyester, polyamide urethane, polyacryl, rosin-modified maleic acid, ethylene vinyl acetate, vinyl ether, urethane vinyl acetate, and salt. Vinyl acetate urethane resin, modified alkyd resin, modified phenol resin, alkali-soluble resin (rosin-modified maleic resin, styrene maleic resin, styrene acrylate resin, acrylate acrylate resin, methacrylate acrylate resin), Hydrosol type resin (styrene maleic acid resin, styrene acrylate resin, α-methyl styrene acrylate resin, acrylate acrylate resin, methacrylate acrylate resin), emulsion type resin (styrene resin,
Styrene acrylate resin, acrylate copolymer resin, methacrylate copolymer resin) and the like. As resins for UV inks, polymers having acrylic unsaturated groups are generally used, and typical examples are polyester / acrylate, polyester / urethane resin / acrylate, and epoxy resin / acryl. Acid esters, pentaerythritol triacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and hydroxyethyl methacrylate.

A commonly known coloring agent is used in combination with these inks. As the coloring agent used, Japanese Patent Application No.
189425 Various pigments and azo pigments (azo lakes; carmine 6B, red 2B, insoluble azo;
Monoazo yellow (PY-1, -3), Disazo yellow (PY-12, -13, -14, -17, -83), Pyrazolo orange (PO-B, -34), Vulcan orange (PO-16) Chromophthal yellow (PY-93, -95), Chromophthal red (PR-144, -166), polycyclic pigment (phthalocyanine; copper phthalocyanine blue (PB-15,-)
15-1, -15-3), copper phthalocyanine green (PG-
7), dioxazine type; dioxazine bioresist (PV
-23), isoindolinone type; isoindolinone yellow (PY-109, -110), sulene type: peryleneperinone,
Flavanthrone, thioindigo, lake pigments (malachite green, rhodamine B, rhodamine G, Victoria blue B, and inorganic pigments (oxides: titanium dioxide, bengalara, sulfate; precipitated barium sulfate, carbonate; precipitated calcium carbonate, Silicate; hydrous silicate, anhydrous silicate,
Metal powder: aluminum powder, bronze powder, zinc dust carbon black, graphite, navy blue and the like. In addition, oil-soluble dyes, dispersible dyes and the like are also used. Various solvents, dispersants, etc.
Additives such as wetting agents, defoamers, leveling agents, thickeners, stabilizers, crosslinking agents, waxes, driers and the like are used.

Further, a varnish may be applied to protect the gloss on the surface and the printed portion on the surface. As the type of varnish used at this time, acrylic resin, cellulose resin such as cellulose acetate, urethane resin, epoxy resin, polyester resin,
Appropriate resins such as ionomer resins, EEA resins, various polyethylene resins (low density, high density, linear low density, polyethylene, etc.), and polypropylene resins can be used. Also, wax and the like can be used.

The film used in the present invention is also important from the viewpoint of antistatic and camera operability. That is, the thickness of the film base is preferably 11 μm or less, and the film is easy to slip from the viewpoint of the operability of the camera, and the slipperiness in contact with the light-shielding packaging material becomes important. In order to impart such slipperiness, Japanese Patent Application Nos.
The lubricant described in -129883 may be used, and the backside is similarly configured.

[Action] In the present invention, the light-shielding packaging material processed on one or both sides with a resin layer is made of carbon black having an oil absorption (ml / 100 g) of 100 or more and a specific surface area (m ² / g) of 150 or more. Since the surface resistivity of the compounded resin layer is 10 ⁵ Ω or less,
It has high flexibility, has light-shielding properties, and has significantly improved charging characteristics. For this reason, the light-shielding packaging material is suitable as a light-shielding member for the roll-shaped photosensitive material, and furthermore, when the light-shielding packaging material is separated from the film, a discharge phenomenon occurring between the light-shielding packaging material and the film is prevented. In addition, static marks generated on the film can be suppressed.

[Effects of the Invention] According to the present invention, in a roll-shaped photosensitive material having a film and a light-shielding packaging material processed on one or both sides with a resin layer, light-shielding packaging processed on one or both sides with a resin layer materials fee, oil absorption (ml / 100 g) is 100 or more, the surface specific resistance of the specific surface area (m ² / g) is a resin layer containing a combination of more than 150 carbon black is less than 10 ⁵ Omega.

Thus, the light-shielding packaging material has an oil absorption (ml / 100 g) of 1
By using a resin layer containing carbon black having a specific surface area (m ² / g) of 150 or more, the surface resistivity of the
It has a simple structure with a predetermined set value of 10 ⁵ Ω or less, has high flexibility, has a light-shielding property, is suitable as a light-shielding member for a roll-shaped photosensitive material, has a remarkably improved charging property, and has a large distance from a film. In this case, a discharge phenomenon occurring between the light-shielding packaging material and the film can be prevented, and static marks generated on the film can be suppressed.

Therefore, as in the past, to prevent static electricity, various antistatic agents are added to the back and front surfaces of the film to prevent the film itself from being charged, and even if an antistatic agent is added to the intermediate layer in the packaging material, In recent years, the range of these technologies is not enough with the increase in sensitivity of color photosensitive materials, but by setting the surface resistivity of the light-shielding packaging material to 10 ⁵ Ωcm or less,
It has a dramatic effect on antistatic properties, and the manufacturing method is extremely easy.

[Example] Hereinafter, an example of the present invention will be described, but of course, the present invention is not limited to this example.

Example 1 The following light-shielding packaging material was prepared.

In addition, the base paper of the light-shielding packaging material used was formed using a fourdrinier method. At this time, 7% by weight of carbon black (Mitsubishi Kasei Carbon # 45) was mixed to hold the light-shielding packaging material.

At this time, the thickness of the base paper was 75 μm, the weight of the base paper was 70 g / m ^2, and ethylene-vinyl acetate copolymer (EVA) (vinyl acetate content: 15 mol%) was used as the resin for backside processing. After melt-kneading using a Burley mixer, coating was performed by a melt extruder to a thickness of 25 μm. The amount of carbon black added was 8% by weight.

After the backside resin processing, various designs were printed on the front surface with an ink composed of vinyl chloride grease and an acrylic resin by a gravure printing method, and then an acrylic resin was applied for surface protection to obtain a finish.

Using these light-shielding packaging materials, a 120-size roll film (ISO200) was prepared. The films used at this time are shown below.

Transparent cellulose triacetate film thickness 100
The following layers were sequentially formed on a support having a thickness of μm to form a multilayer color negative photosensitive material.

First layer: Antihalation layer An aqueous gelatin solution containing black colloidal silver was applied at a rate of 0.3 g / m ² of silver to a dry film thickness of 3.0 μm.

Second layer: Intermediate layer An aqueous solution of seratin was applied to a dry film thickness of 1.0 μm.

Third layer: Red-sensitive low-sensitivity silver halide emulsion layer A silver iodobromide emulsion (an average grain size of 0.45 μm, a silver iodobromide emulsion containing 4 mol% of silver iodide) is chemically sensitized with a gold and sulfur sensitizer. Further, as a red-sensitive sensitizing dye, anhydrous 9-ethyl-3,
3'-di- (3-sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide; anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3 -Sulfoptyl) thiacarbocyanine hydroxide; and anhydrous 5,5 '
-Dichloro-3 ', 9-getyl-3- (4-sulfobutyl) oxythiacarbocyanine hydroxide, followed by 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.0 g, 20.0 mg of 1-phenyl-5-mercaptotetrazole was added to prepare a red-sensitive low-sensitivity emulsion. Further, 1-hydroxy-N- [δ- (2,4-di-t-amylphenoxy) is used as a cyan coupler per mole of silver halide.
Butyl] -2-naphthamide 50 g, 1-hydroxy-4- [4- (1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2 , 4-Di-t-amylphenoxy) butyl] -2-naphthamide disodium salt 4g, 2- (1-phenyl-5-tetrazolylthio) -4-octadecylsuccinimide-1 as a DIR compound
1.7 g of indanone and 0.3 g of dodecyl gallate are added, 65 g of tricresyl phosphate and 136 of ethyl acetate
The mixture was dissolved by heating and added to 550 ml of a 7.5% aqueous gelatin solution containing 5 g of sodium triisopropylnaphthalenesulfonate. A dispersion emulsified and dispersed by a colloid mill was added to prepare a red-sensitive low-sensitivity emulsion. μm, coated silver amount 3
It was coated so as to 0mg / dm ^2. (Including 100 g of gelatin per mole of silver halide) Fourth layer: Red-sensitive high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 0.80 μm, containing 7 mol% of silver iodobromide) was mixed with gold and silver. Chemically sensitized with a sulfur sensitizer, and as a red-sensitive sensitizing dye, anhydrous 9-ethyl-3,3'-di-
(3-Sulfonpropyl) -4,5,4 ', 5'-dibenzothiacarbocyaniline humanoxide, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfobutyl) After addition of thiacarbocyanine hydroxide; and anhydrous 5,5'-dichloro-3 ', 9-diethyl-3- (4-sulfoptyl) oxythiacarbocyanine hydroxide.
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.0 g and 1-phenyl-5-mercaptotetrazole
10.0 g was added to prepare a red-sensitive high-sensitivity emulsion. Further, as a cyan coupler per mole of silver halide, 1-hydroxy-N- [δ-, (2,4-di-t-amylphenoxy)
Butyl] -2-naphthamide 10 g, 1-fudoxy-4- [4- (1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2 , 4-Di-t-aminophenoxy) butyl] -2-naphthamide disodium salt 4 g, DIR compound 2- (1-phenyl-5-
Tetrazolthio) -4-octadecylsuccinimide-
1.6 g of 1-indanone and 0.5 g of dodecyl gallate were added, 20 g of tricresyl phosphate and 60 m of ethyl acetate were added.
The mixture is heated and dissolved, and 7.5 ml of a 7.5% gelatin aqueous solution containing 1.5 g of sodium triisopropylnaphthalenesulfonate is dissolved.
A red-sensitive high-sensitivity emulsion was prepared by adding a dispersion emulsified and dispersed by a colloid mill, and coated so as to have a dry film thickness of 2.0 μm and a coated silver amount of 20 mg / dm ² . (Silver halide 1
Contains 100 g of gelatin per mole. Fifth layer: Intermediate layer Same as the second layer Sixth layer: Green-sensitive low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodobromide emulsion containing 8 mol% of silver iodide) ) Is chemically sensitized with a gold and sulfur sensitizer, and further, as a green-sensitive sensitizing dye, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfobutyl) oxacarbocyanine hydroxy 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfobutyl) anhydride
Oxacarbocyanine hydroxide and anhydrous 9-ethyl-3,3'-di- (3-sulfopropyl) -5,6,5 ', 6'-
Dibenzoxacarbocyanine hydroxide was added, followed by 1.0 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 20.0 mg of 1-phenyl-5-methylcaptotetrazole, resulting in green-sensitive low sensitivity An emulsion was prepared.
Further, as a magenta coupler per mole of silver halide,
1- (2,4,6-trichloro) phenyl-3- [3- (2,4
-Di-tert-aminophenoxy) acetamide] benzamide-5-pyrazolone 50 g, as a colored magenta coupler, 1- (2,4,6-trichlorophenyl) -4-
(1-Naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone 10
g, as a DIR compound, β- {4- [1- (p-nitrophenyl) -4- (1-phenyl-5-tetrazolyl} thiomethyl-3-undecyl-5-pyrazolyloxy]-
1.5 g of 1-hydroxy-2-naphthamide｝ proonic acid was added, a mixture of 60 g of tricresyl phosphate and 200 m by weight of ethyl acetate was dissolved under heating, and the mixture was added to an aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate to give colloid. A green-sensitive low-sensitivity emulsion was prepared by adding a dispersion emulsified and dispersed in a mill, and a dry film thickness of 4.0 μm and a dry silver amount of 20 m were prepared.
g / dm ² (1 per mole of silver halide)
00g gelatin).

Seventh layer: green-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.85 μm, silver iodobromide 10
Mol%), with gold and sulfur sensitizers, and further as a green-sensitive sensitizing dye, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfobutyl). Oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-
Ethyl 3,3'-di- (3-sulfopropyl) -5,6,5 ',
6'-Dibenzoxacarbocyanine hydroxide was added, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.0 and 1-phenyl-5-mercaptotetrazole 10.0 mg were added to increase the green sensitivity. A sensitivity emulsion was prepared. Further, as a magenta coupler per mol of silver halide, 1- (2,4,6-trichloro) phenyl-3- [3-
2,4-di-tert-amylphenoxyacetamide] benzamide-5-pyrazolone 5 g, 1- (2,4,6-trichlorophenyl) -4-l as a colored magenta coupler
(1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone 2.
5 g, 2,5-di-t-octylhydrozoloquinone 1.5 g, and as a DIR compound, β- {4- [1- (p-nitrophenyl) -4- (1-phenyl-5-tetrazolyl) thiomethyl- 3-undecyl-5-pyrazolyloxy]-
1-hydroxy-2-naphthamide｝ propionic acid 0.5
Is added, and a mixture of 20 g of tricresyl phosphate and 30 ml of ethyl acetate is heated and dissolved, and added to a gelatin aqueous solution containing sodium triisopropylnaphrenesulfonate,
A green-sensitive high-sensitivity emulsion was prepared by adding a dispersion emulsified and dispersed in a colloid mill, and the dried film thickness was 2.0 μm, and the coated silver amount was 15 mg / dm.
² (100 g per mole of silver halide)
Containing gelatin).

Eighth layer: Intermediate layer Same as the second layer Ninth layer: Yellow filter layer In a gelatin aqueous solution in which yellow colloidal silver is dispersed,
3-5 g of 2-5-di-t-octylhydroquinone and di-2-
Ethylhexyl phthalate 1.5g was dissolved in ethyl acetate 10ml, triisopropyl naphthalene sulfonic acid sodium 0.3g
Add a dispersion dispersed in an aqueous gelatin solution containing
This was applied at a ratio of 0.9 g / ml of gelatin and 0.10 g / m ² of 2.5-di-t-octylhydroquinone to a dry film thickness of 1.2 μm.

10th layer: Blue-sensitive low-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size: 0.6 μm, containing 6 mol% of silver iodide) is chemically sensitized with a gold and sulfur sensitizer, and further sensitized. Anhydrous 5,5'-dimethoxy-3,3'-di-
(3-Sulfopropyl) thiocyanine hydroxide was added, followed by 1.0 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 20.0 mg of 1-phenyl-5-mercaptoterazole. A blue-sensitive low-sensitivity silver halide emulsion was prepared. Further, as a yellow coupler per mole of silver halide, α-pivaloyl-α- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidin-4-yl) -2′-chloro 250 g of -5 '-[α- (dodecyloxycarbonyl) pentoxycarbonyl] acetanilide is added, a mixture of 120 g of dibutyl phthalate and 300 ml of ethyl acetate is heated and dissolved, and the mixture is added to an aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate. A blue-sensitive low-sensitivity silver halide emulsion was prepared by adding a dispersion emulsified and dispersed in a colloid mill, and the dried film thickness was 4.0 μm.
m, silver coating amount: 5 mg / dm ² (including 240 g of gelatin per mole of silver halide).

Eleventh layer: Blue-sensitive high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 1.2 μm, containing 7 mol% of silver iodide) is chemically sensitized with a gold and sulfur sensitizer, and further sensitized. Anhydrous 5,5'-dimethoxy-3,3'-di-
(3-Sulfopropyl) thiocyanine hydroxide was added, followed by 1.0 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 10.0 mg of 1-phenyl-5-mercaptotetrazole, A blue-sensitive high-sensitivity silver halide emulsion was prepared. Further, as a yellow coupler per mol of silver halide, α-pivaloyl-α- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidine-4-yl) -2′-chloro- 5 '-[α- (dodecyloxycarbonyl) pentoxycarbonyl] acetoalinide 80 was added, and a mixture of 40 g of dibutyl phthalate and 240 ml of ethyl acetate was dissolved under heating. A blue-sensitive high-sensitivity silver halide emulsion was prepared by adding a dispersion emulsified and dispersed in a mill, and a dry film thickness of 2.0 μm and a coating amount of 160 g per mol of silver halide coated so as to have a coating amount of 5 mg / dm ² were obtained. Including gelatin).

12th layer: Intermediate layer 2 g of di-2-ethylhexyl tafflate, 2 g of 2- [3-cyano-3- (n-dodecylaminocarbonyl) anilidene] -1-ethylpyrrolidine and 2 ml of ethyl acetate are mixed, and triisopropylnaphthalene is mixed. 0.6 g of sodium sulfonate
Was added to the aqueous gelatin solution, and this was applied at a rate of 1.0 g / m ² of gelatin to a dry film thickness of 1.0 μm.

Thirteenth layer: protective layer An aqueous gelatin solution containing 4 g of gelatin and 0.2 g of 1,2-bisvinylsulfonylethane per 100 m weight was applied at a rate of 1.3 g / m ² of gelatin to a dry film thickness of 1.2 μm. The obtained sample was examined for static marks generated when the light-shielding packaging material and the film were separated during the development processing, and the following results were obtained. The development processing was performed by a hanger type automatic development processor.

The presence or absence of the static mark was visually determined after the film was developed.

…: There is no static mark.

Δ: 1 to 2 weak marks in one.

×: Two or more clear marks in one.

In addition, the following resin was used in place of the resin used in this experiment, and the results of the test were the same as those of the present example.

Use resin No-1 low density polyethylene (LDPE) (density 1.918g / c
In m ³⁾ No-2 low-density polyethylene (density 0.930 g / cm ³ or less) and high density polyethylene (density 0.950 g / cm ³ or higher) in a weight ratio of
Mix at 60:40 No-3 Mix No.2 resin at a weight ratio of 40:60 No-4 Ethyl acrylate copolymer (DPD-6169 manufactured by Union Carbide, USA) No-5 Ethylene vinyl acetate copolymer (Vinyl acetate content 10 mol%) No-6 Linear low density polyethylene (LLDPE) weight ratio 60 (L
LDPE): 40 (LDPE) No-7 Linear low density polyethylene 15μm weight ratio (60 (LL
DPE): 40 (LDPE)) Low density polyethylene 15μm ² layers No-8 Linear low density polyethylene 60% by weight and low density polyethylene 40% by weight No-9 Ethylene-ethyl methacrylate (ethylene content 70mol%) No-10 Ethylene-methyl acrylate (ethylene content
75mol%) No-11 ethylene-butyl acrylate (ethylene content
No-12 Ethylene-butyl methacrylate (ethylene content: 85 mol%) No-13 Ethylene-ethyl acrylate-2-ethyl-butyl (ethylene content: 90 mol%) No-14 Ethylene-ethyl-2-acrylate- Heosyl (92 mol% ethylene content) Example-2 The following light-shielding packaging material was prepared using the carbon black used in Example 1.

Example except that the amount of carbon black added was changed.
A sample was prepared under the same conditions as in 1.

Using the prepared sample, the camera operability and the static edge when separating the light-shielding packaging material from the film were examined.

Camera used: Asahi Pentax 67 Camera operability ○: No hoisting torque.

Δ: Winding torque is slightly heavy.

×: The winding torque is heavy.

 The criterion for determining the static mark is the same as in Example-1.

Example 3 The following light-shielding packaging material was prepared.

Using the base paper: Fourdrinier papermaking method basis weight, 60 g / m ² thickness 65μm Mitsubishi Carbon Black # 4 by weight 7% mixed black base paper used resins: amorphous saturated polyester solution, Byron #
500 (manufactured by Toyobo Co., Ltd.) Resin layer thickness: 20 μm The film used was a film having a sensitivity of ISO400, and the surface treatment of the light-shielding packaging material was performed in the same manner as in Example-1. When separating the light-shielding packaging material from the film in order to develop the obtained sample (126 size film), the state of the generated static mark was visually confirmed after the development.

The light-shielding packaging material and the film were separated using a model PS-35 manufactured by Noritsu Koki Co., Ltd.

：: No static mark.

Δ: One to two weak static marks in one.

X: Two or more obvious static marks.

Example-4 The following light-shielding packaging material was prepared.

Base paper used: Fourdrinier papermaking method Basis weight 75 g / m ² Thickness 80 μm Black base paper mixed with Mitsubishi Carbon Black # 45 8% by weight Resin used: Saturated polyester resin (Toyobo Co., Ltd. Byron # 200) Coating amount (drying) After): 6 g / m ² light-shielding packaging material surface: the same as in Example 1. In addition, a 120-size film was prepared using an ISO 1600 film, and a test sample was prepared. After the photographing was completed, the light-shielding packaging material and the film were separated by hand at a normal operation speed in a dark room in order to perform a developing process by a photographing process hanger type automatic developing machine.

After the development processing, the presence or absence of a static mark generated on the film was visually confirmed.

：: No static mark.

×: Two or more obvious static marks in one.

In addition, the following resin was used in place of the resin used in this experiment, and a sample was prepared and tested. As a result, the same result as the result of this experiment was obtained.

Resin No-1 Aqueous polyethylene dispersion (solid content 40% by weight) No-2 Aqueous polypropylene dispersion (solid content 20% by weight) No-3 15% by weight ethylene / vinyl acetate copolymer toluene solution No-4 Non Crystalline saturated polyester solution (Toyobo Co., Ltd.)
No.5: Aqueous polyvinylidene chloride dispersion (Asahi Kasei Kogyo Co., Ltd .: Saran Latex L-511) No-6 Aqueous polyester dispersion (Northman Chemical: East WD size) No-7 Vinyl chloride vinyl acetate copolymer resin Denka Vinyl # 1000C Denki Kagaku Kogyo Co., Ltd.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keiji Yamaguchi 1 Konica Sakuracho, Hino City, Tokyo Inside Konica Corporation (72) Inventor Shoji Yokokoji 1-1-5 Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. (72) Inventor Shigeru Kawagishi 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. (72) Inventor Masao Nakajima 1-1-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd.

Claims (1)

(57) [Claims] 1. A roll-shaped photosensitive material having a film and a light-shielding packaging material processed on one or both sides by a resin layer, wherein the surface of the light-shielding packaging material which is in contact with the back surface of the film has an oil absorption (ml / 100 g). ) Is 100 or more, specific surface area (m ² / g)
Is a resin layer containing 150 or more carbon black, and has a surface resistivity of 10 ⁵ Ω or less.