JPH0797206B2 - Light-sensitive paper for roll-shaped photosensitive material packaging - Google Patents

Description

The present invention relates to a roll-shaped photosensitive material wound with light-shielding paper, and more specifically, a roll-shaped photosensitive material which prevents loosening during operation of a camera. It is about.

[Prior art]

As a roll-shaped photosensitive material using light-shielding paper, (1) so-called cartridge type of 110 size and 126 size in which a film and light-shielding paper are overlapped and wound in a cartridge (2) film is formed in the substantially central portion of the entire length of light-shielding paper Is fixed with adhesive paper and the film is wound on the spool on the light-shielding paper.
The 120 size film and (3) there is a so-called 220 size film in which a leader light-shielding paper is attached to the leading end of the film and a trailer light-shielding paper is attached to the end of the film with adhesive paper or the like. The present invention relates to the latter 120-size and 220-size films. The light-shielding paper described below is a so-called light-shielding paper used for 120 size and 220 size films.

Generally, for light shielding, light shielding black paper or light shielding paper having a light shielding effect by coating or laminating a resin in which carbon black is dispersed as a light shielding agent on a base paper is used. Also, if necessary, characters, symbols, and other printing necessary for functional purposes are printed to enhance the commercial value. Furthermore, in order to facilitate the engagement of the light-shielding paper with the spool, the tip of the light-shielding paper is preliminarily bent.

Furthermore, specific examples of currently known light-shielding paper are: adhesion of photographic film and light-shielding paper under high temperature and high humidity, gas fog, slack winding caused by large bending rigidity, and dimensional instability due to moisture absorption. Light-shielding paper (Japanese Patent Laid-Open No. 55-140835 and Japanese Patent Publication No. 61-36216) provided with at least one aluminum layer on the support to prevent static electricity, high-density polyethylene for improving the charging property and sharpness at the time of perforation And light-shielding paper provided with a layer of low-density polyethylene (Japanese Patent Laid-Open No. 60-35728), low-temperature heat sealability, foreign matter sealability, ethylene polymer for improving sharpness, acrylic acid ester, methacrylic acid ester,
Light-shielding paper provided with a laminated film of methacrylic acid ester, vinyl acetate and ethylene copolymer (Japanese Patent Laid-Open No. 59-68238)
No.), a light-shielding paper which prevents neck-in when applying an intermediate layer and a surface layer onto a support by co-extrusion with molten steel (JP-A-58-186).
744), light-shielding paper processed on one or both sides with a layer formed of polyolefin or a mixture of polyolefins (JP-A-58-17434), which has an absorption band at a wavelength of 550 mμ or more to increase the light-shielding property. Light-shielding paper using paint
52-150016), methyl methacrylate, methacrylic acid,
Light-shielding paper coated with a copolymer such as ethyl acrylate (Japanese Patent Laid-Open No. 50-67644), light-shielding coated with a copolymer of at least one of acrylic acid ester and methacrylic acid ester and ethylene Paper (Japanese Patent Publication No. 48-22020, Japanese Patent Publication No. 51)
-49205), a light-shielding paper having a plurality of carbon black layers on a paper support (US Pat. No. T871,004), printing on one surface of the paper, and extruding and laminating a carbon black-containing polyethylene layer on the other surface. Shading paper (UK patent 1,156,302
), A light-shielding paper provided with a protective layer on the printing surface of the paper and a layer of carbon black-containing vinylidene chloride or a stellene butadiene copolymer on the opposite surface (US Pat. No. 2,646,365,
2,646,366, 2,751,309, 2,959,492, 3,0
53,779), light-shielding paper in which polyethylene containing carbon black is processed on the surface of the support by extrusion (French Patent 1,449,852, British Patent 1,071,032), ethylene /
A light-shielding paper (German Patent 1,903,378) coated with a mixture of a vinyl acetate copolymer and carbon black is disclosed.

However, the conventional light-shielding paper that has undergone these various improvements has improved considerably from the functional side of the light-shielding paper, but the overall quality of the 120-size roll film and 220-size roll film, especially in terms of camera operability. From the above, when the film is loaded into the camera and the tip of the light-shielding paper is inserted into the locking slit of the winding fpool, the light-shielding paper is loosely engaged with the locking slit, so the so-called "rolling phenomenon" is caused. Occurrence has not solved the problem of the wearability of the camera.

Further, Japanese Patent Application Laid-Open No. 55-140835 discloses a technique of providing a single aluminum layer on the light-shielding paper in order to prevent "roll slack" due to expansion and contraction of the light-shielding paper due to absorption and desorption of moisture. Certainly, the provision of the aluminum layer is excellent in terms of moisture resistance, and it is effective for "roll slack" caused by expansion and contraction of the light-shielding paper after being taken up on the spool due to absorption and desorption of moisture. However, according to the results of the examination by the present inventors regarding the "roll slack", the "roll slack" phenomenon is more likely to occur when the film is set on the camera rather than after the film is wound on the spool and the light-shielding paper tip is inserted on the spool. Upon raising, it became clear that it was due to the relationship between the locking slit of the spool and the shape of the tip of the shading paper and the rigidity of the shading paper. It has also been clarified that these phenomena are particularly important as the light-shielding paper becomes thinner, the physical properties of the light-shielding paper and the matching process between the shape of the locking slit of the spool and the shape of the light-shielding paper.

In recent years, the thinning of light-shielding paper is becoming more and more important due to the improved camera operability (rolling up) of roll-shaped film and the advent of 220-size film, but when simply thinned, the rigidity is insufficient and the spool is poorly engaged. It gives the cause of "Burmaki", and the solution is urged.

[Object of the Invention]

It is an object of the present invention to provide a means for preventing "winding" that occurs when operating a camera loaded with 120 and 220 size roll films.

In particular, the purpose is to present the physical properties and form of the light-shielding paper which is effective in preventing "rolling".

[Structure and Action of Invention]

The above-mentioned object of the present invention is a roll-shaped photosensitive material packaging light-shielding paper having a resin layer on one side or both sides of the base paper, the flexibility of the light-shielding paper is 10 to 40 g, and the The ratio of the thickness of the resin layer on one side of the base paper is 0.11 to 0.
83, or the ratio of the resin weight of the resin layer on one surface of the base paper to the weight of the base paper is 0.01 to 0.5.

In the embodiment of the present invention, when the tail portion of the light-shielding paper is inserted into the locking slit in the diameter direction of the spool winding shaft and the tail portion is supported, both ends of the light-shielding paper may contact the inside of the spool flange. The tail shape is preferable.

In addition, the rigidity of the light-shielding paper is 10 to 40 in terms of flexibility to prevent "winding".
It is required to be g, more preferably 15 to 30 g.

The so-called "flexibility" in the present invention is to use light-shielding paper to make a round circle having a diameter of 25 mm as a strip of 20 mm, overlap both ends of the strip by 3 mm and bond them with double-sided adhesive tape, put them in a load cell, and 40 mm / min from the diameter direction. Press at the speed of
Read the repulsive force applied to the load cell when it becomes 2, and use this value as the flexibility.

As a method of imparting flexibility (rigidity) to the light-shielding paper, resin processing is applied to the base paper, and mainly laminating and coating methods are used.

Further, it is preferable that the resin processing is performed under the condition that rigidity is secured and the locking slit of the spool is liable to be bent in order to ensure reliability of locking to the spool.

It is considered that the thickness of the resin layer and the thickness of the base paper, or the balance between the weight of the resin coating and the weight of the base paper is an important factor that determines the conditions in which the degree of softness and the tendency to crease easily occur. The result turned out.

The thickness of the base paper used is preferably 60 to 95 μm,
It is more preferably 70 to 85 μm, or as a basis weight, preferably 40 to 100 g / m ² , and more preferably 65 to 80 g / m ^2.
Is.

The resin amount with respect to the base paper is preferably 10 to 50 μm, and more preferably 10 to 30 μm, if the thickness is displayed conveniently for the laminating method. Alternatively, when it is difficult to determine the thickness due to the permeation into the paper quality due to the difference in solvent, concentration, etc., it is preferably 1 to 20 g / m ^{2 and more} preferably 1 to 8 g / m ² in terms of coating weight.

Therefore, the balance between the base paper and the resin amount is 0.11 to 0.83 as a thickness display, more preferably 0.11 to 0.
43, or 0.01 to 0.5 for weight display, and 0.013 to 0.12
Is preferred.

In this range, the habit of twisting can be easily achieved. Further, if this ratio is exceeded, the flexibility is too stiff to invite unwinding, which easily causes unrolling.If this ratio is not satisfied, the winding shape has no self-correcting force and the edges of the light-shielding paper are deformed. Invite.

If you use light-shielding paper that has physical properties such as flexibility and crease habit as described above, you can avoid the "winding" to a considerable extent, but the light-shielding paper rear end on the side (trailer side) to be inserted into the locking slit of the spool It has become clear that the shape of the tail of the and the geometrical relationship between the spool flange and the locking slit are the important factors for the winding.

FIG. 1 shows a state in which the tail is inserted into the locking slit. In the figure, 1 is a light-shielding paper, 10 is a belt portion at the rear end of the light-shielding paper having a width D ₁ , 11 is a tail, 112 is an insertion piece, 111 is a belt portion 10 and an insertion piece 11
The narrowed portion located between 2 and the one-dot chain line XX ′ is the center line of the shading paper.

In addition, 2 is a spool, 21 is a flange, 22 is an internal method between flanges.
D ₂ is a winding shaft, 23 is a locking slit bored in the center in the width d of containing axial diameter of the winding shaft.

Further, A means the length of fitting of the intersection point (introduction point of the band) 114 of the edge of the band 10 and the edge of the narrowed portion 111 into the flange. In the figure, the introduction point 114 is not yet fitted in the flange. Further, B represents a locking gap from the slit butt 231 to the edge 113 of the tail (stenosis portion or insertion piece). In the figure, the edge 113 is not abuttingly supported by the slit butt 231.

The tail 11 is bent around the edge of the engaging slit and is wound around the winding shaft so that the light-shielding paper 1 can be smoothly wound up on the spool when the film is loaded in the camera.

At this time, the edge 113 is not abutted and supported by the slit bottom 231 and B> 0.
Center aligned with a central cross-sectional circle of which the center line XX 'and the position of the D _2/2 of the winding axis of the backing paper in a difficult, Izure or edges of the band portion 10押窄or cleaved inside the flange It causes the edge deformation. If it is wound in this state, it is naturally impossible to carry out a uniform laminated winding, which causes a blunt winding and causes light leakage.

On the other hand, when the edge 113 and the slit butt 231 are brought into contact with each other and winding is performed with B = 0, and when the introduction point 114 is not fitted into the flange and A> 0, the winding is still performed with the center line XX ′ of the shading paper. Center misalignment with the central cross-section circle of the shaft is often unsuccessful, and a slight misalignment in the early stages of winding soon refers to winding that results in edge deformation of either edge of the shading paper.

Further, when the tail 11 is sufficiently inserted into the winding opening of the slit 23 and the insertion piece 112 sticks out from the other end of the slit for a long time and the rigidity of the light-shielding paper is large, the laminated winding becomes non-circular and causes a cause of the blunt winding. In addition, the number of weights of the light-shielding paper and the film may be partially different, and pressure fog may occur in a portion where the lamination pressure is high.

Therefore, according to the present invention, regarding the shape of the tail, when the tail is inserted into the slit, with respect to the insertion length A and the supporting gap B, B = 0, that is, when the tail edge is abutted and supported by the slit butt, ≦ 0, that is, the above-mentioned introduction point gives a size and shape in which the introduction point abuts on the inside of the flange or is already fitted into the inside of the flange.

The present invention will be described in more detail below.

The base paper used in the present invention may be any of ordinary natural pulp paper, synthetic fiber or synthetic paper using synthetic resin, but mainly contains wood pulp such as softwood pulp, hardwood pulp, and mixed softwood pulp. Natural pulp paper is advantageously used. Papermaking of these papers may be performed by either of the conventionally known round net papermaking method and fourdrinier papermaking method.

The base paper containing these natural pulps as a main component may contain various polymer compound additives. For example,
As a dry paper strengthening agent, cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol, gelatin, etc., as a sizing agent, fatty acid salt, rosin derivative, dialkylketin dimer emulsion, petroleum resin emulsion, Styrene
Clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc. as pigments such as aluminum salt of maleic anhydride copolymer alkyl ester, and melamine resin, urea resin, epoxidized polyamide resin, fixing agent as wet paper strength enhancer. As, aluminum sulfate, polyvalent metal salts such as aluminum chloride, cation-modified polymers such as cationized starch, as a pH adjusting agent, caustic soda, sodium carbonate, hydrochloric acid, etc., as an inorganic electrolyte, salt, mirabilite, etc., other dyes, An optical brightening agent, latex, carbon black and the like can be contained in an appropriate combination.

Further, as a resin in which a resin layer is provided on one side or both sides of a base paper, Japanese Patent Publication No. 51-49205, Japanese Unexamined Patent Publication No. 48-22020, 50-67644
No. 55, No. 55-140835, No. 58-17434, No. 53-186744, No.
59-68238, 60-35728, etc. low density, medium density,
High density, linear low density various polyolefins such as polyethylene and polypropylene, polyvinyls such as ethylene vinyl acetate, alklus such as ethylene ethyl acrylate and ethylene methyl acrylate, rubbers such as styrene-butadiene, simple substances such as ionomers, Examples thereof include graft polymer polyamide, polyethylene-terephthalate, and polymethylpentene ethylene-vinyl alcohol copolymer. The above resin may be provided as two or more layers.

When laminating these resins on the base paper, an anchor agent may be used in order to further improve the adhesiveness, and examples of the anchor agent include organic titanium-based, isocyanate-based, polyethyleneimine-based and polybutadiene-based.

Carbon black may be contained in these resins in order to increase the light-shielding property.

Usually, in order to make a light-shielding photographic resin-coated paper using carbon black, a so-called masterbatch (hereinafter sometimes abbreviated as MB) containing carbon black in a high concentration in a thermoplastic resin such as polyethylene resin is used. To create
It is diluted and mixed with a diluting resin in a desired ratio, and is then melt-extrusion coated on a support such as paper by a fusible extruder, or carbon black is contained in the resin at a desired composition ratio from the beginning. It is common practice to make a so-called compound and apply it to a support by means of a fusible extruder.

The carbon black used in the present invention may be one produced by any of the manufacturing methods such as the Fornes method, the channel method and the thermal method. In the present invention, the carbon black produced by the Fornes method is commonly used. Regarding the shape and particle size of carbon black, carbon black is selected so as to satisfy the quality required of the light-shielding photographic resin-coated paper, for example, hiding power. In the present invention, for example, Mitsubishi Kasei carbon black # 5, # 20, # 33, # 40, # 44,
# 45, # 52, MA8, MA100, # 900, # 1000, 2200B, # 2350, # 24
00B etc. are used.

The content of carbon black contained in MB is 5 to 50 parts by weight, preferably 5 to 30 parts by weight. When the carbon content in MB exceeds 50 parts by weight, the dispersion in the resin becomes poor at the time of MB production, and the black resin is black even if it is coated with a diluting resin having a relatively low melting index. There is a great risk of gel formation.

The carbon black-containing MB according to the present invention can be prepared by using a usual kneading machine such as Banbury mixer or kneader. In addition to polyolefin resins and carbon black, fatty acid metal salts such as zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, sodium palmitate, calcium palmitate, sodium laurate and the like can also be used. I can. The addition amount is 0. with respect to the resin composition containing carbon black.
The range of 01 to 5% by weight is preferable. In addition to these fatty acid metal salts, antioxidants can be used alone or in combination with the fatty acid metal salts.

A reverse roll method, a blade method, an air knife method, a rod method, an extrusion method or a dry lamination, a wet lamination, a solution coating, or the like is used as a means for processing the resin containing the light-shielding substance on the surface of the base paper. It can be used for coating. Also, it may be through an adhesive layer,
These known techniques can be used and are not limited thereto.

Characters and symbols necessary for the function are printed on the surface of the light-shielding paper, or printing is done to increase the commercial value.The ink used for these printings is generally selected and harmless to the photosensitive material. It can be selected from offset printing ink, gravure printing ink or UV ink.

Typical synthetic resins used in these inks are vinyl chloride-based vinyl chloride, nitrified cotton, polyester, polyamide urethane, polyacrylic, rosin-modified maleic acid, ethylene vinyl acetate, vinyl ether, urethane vinyl acetate, vinyl chloride vinyl urethane resin. ，
Modified alkyd resin Modified phenol resin, alkali-soluble resin (rosin modified maleic acid resin, styrene maleic acid resin, styrene acrylic acid resin, acrylic ester acrylic acid resin, methacrylic acid ester acrylic acid resin), hydrosol type resin (styrene maleic acid resin) Acid resin,
Styrene acrylic acid resin, α-methylstyrene acrylic acid resin, acrylic acid ester acrylic acid resin, methacrylic acid ester acrylic acid resin, emulsion type resin (styrene resin, styrene acrylic acid ester resin, acrylic acid ester copolymer resin, methacrylic acid Ester copolymer resins), polymers with acrylic unsaturated groups are generally used as resins for UV inks, and typical examples are polyester / acrylic ester, polyester / urethane resin / acrylic ester. , Epoxy resin / acrylic acid ester, pentaerythritol triacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, hydroxy Examples include cyethylmethacrylate.

A commonly known coloring agent is used in combination with these inks. The colorant used is Japanese Patent Application No. 61-189425.
Pigments and azo pigments (azo lake; carmine 6B, red 2B, insoluble azo; monoazo yellow (PY-1, -3), disazo yellow (CPY-12, -13,-)
14, -17, -83), pyrazolo orange (PO-B-34), vulcan orange (PO-16), condensed azo type; chromophthal yellow (PY-93, -95) chromophthal red (PR-144) ,
-166), polycyclic pigments (phthalocyanine type; copper phthalocyanine blue (PB-15, -15-1, -15-3), copper phthalocyanine green (PG-7), cioxazine type; dioxazine violet (PV-23 ), Isoindolinone type; isoindolinone yellow- (PY-109, −110), slene type;
Perylene, perinone, flavantron, thioindigo,
Lake pigments (malachite green, rhodamine B, rhodamine G, Victoria blue B) or inorganic pigments (oxide, titanium dioxide, red iron oxide, sulfate; precipitated barium sulfate, carbonate; precipitated calcium carbonate, silicate; hydrous silica Acid salt, anhydrous silicate, metal powder; aluminum powder, bronze powder, zinc dust, carbon black, yellow lead, navy blue, etc.).
In addition to these, oil-soluble dyes and dispersible dyes are also used. As other raw materials for ink, various solvents, dispersants, wetting agents, defoamers, leveling agents, thickeners,
Additives such as stabilizers, crosslinkers, waxes and dryers are used.

A varnish may be applied to protect the surface gloss and the printed portion of the surface. The types of varnish used at this time are acrylic resin, cellulose resin such as fibrin acetate, urethane resin, epoxy resin, polyester resin, ionomer resin, EEA resin, various polyethylene resins (low density, high density, linear low density, Appropriate resins such as polyethylene) and polypropylene resin can be used. Wax can also be used.

The film according to the present invention is naturally involved in the "winding", but since the phenomenon causing this "winding" mainly occurs in the initial stage of the operation of mounting the film on the camera, it is not the main cause but is used. Thin film is more effective than thick film, and it is usually used as a film base thickness.
It is preferably 10 μm or less. Further, from the viewpoint of the operability of the camera, the film tends to slip, and the slipperiness on the surface in contact with the light-shielding paper becomes important. To impart these slip properties, the lubricants described in Japanese Patent Application Nos. 61-129881 and 61-129883 can be used.

〔Example〕

The effects of the present invention will be shown below by examples. Of course, the present invention is not limited to this embodiment.

Example-1 The light-shielding paper Nos. 1 and 2 shown in Table 1 below were prepared.

The base paper used was made into paper by the round net paper making method, and carbon black was mixed in a weight ratio of 7% in order to maintain the light shielding property at this time. After this, add 5w of carbon black
Various resins containing t% were laminated on the back surface with an extleader.

After processing the backside resin, various designs were gravure-printed on the surface with an ink containing vinyl chloride resin and acrylic resin, and then acrylic resin was applied for surface protection to finish.

The film used at this time has the following structure.

Transparent cellulose triacetate film (thickness 100
Each of the following layers was sequentially formed from the side of the support on a support of (μm) to prepare 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 A gelatin aqueous solution was applied so as to have a dry film thickness of 1.0 μm.

Third layer: Red-sensitive low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (silver iodobromide emulsion containing 0.45 μm of average grain size and 4 mol% of silver iodide) is chemically sensitized with gold and sulfur sensitizers. , 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-sulfobutyl) thiacarbocyanine hydroxide; and anhydrous 5,
After adding 5'-dichloro-3 ', 9-diethyl-3- (4-sulfobutyl) oxythiacarbocyanine hydroxide, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.0 20.0 mg of 1-phenyl-5-mercaptotetrazole was added to prepare a red-sensitive low-sensitivity emulsion. Further, 50 g of 1-hydroxy-N- [δ- (2,4-di-t-amylphenoxy) butyl] -2-naphthamide as a cyan coupler and 1-hydroxy-4- [as a colored cyan coupler per mol of silver halide]. 4- (1-Hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2,4-di-t-amylphenoxy) butyl] -2-naphthamide disodium 4 g of salt, 2- (1-phenyl-5-as DIR compound
Tetrazolylthio) -4-octadecylsuccinimide-1-indanone (1.7 g) and dodecyl gallate (0.3 g) were added, and tricresyl phosphate (65 g) and ethyl acetate (1 g) were added.
A mixture of 36 ml was dissolved by heating and 550 ml of 7.5% gelatin aqueous solution containing 5 g of sodium triisopropylnaphthalene sulfonate.
A red-sensitive low-sensitivity emulsion was prepared by adding a dispersion emulsified and dispersed in a colloid mill, and coated so that the dry film thickness was 4.0 μm and the coated silver amount was 30 mg / dm ² (per mol of silver halide). Contains 100g gelatin).

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 iodide) is chemically sensitized with gold and sulfur sensitizers, and further red-sensitive. As a 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-sulfobutyl) thiacarbocyanine hydroxide; and anhydrous 5,5'-dichloro-3 ', 9-diethyl-3- (4-sulfobutyl) oxythiacarbocyanine hydroxy. After adding Do, 4-
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, 10 g of 1-hydroxy-N- [δ- (2,4-di-t-amylphenoxy) butyl] -2-naphthamide as a cyan coupler and 1-hydroxy-4- [as a colored cyan coupler per mol of silver halide]. 4- (1-hydroxy-8
-Acetamido-3,6-disulfo-2-naphthylazo)
Phenoxy] -N- [δ- (2,4-di-t-amylphenoxy) butyl] -2-naphthamide disodium salt
4 g, 2- (1-phenyl-5-tetrazolylthio) -4-octadecylsuccinimide-1-as DIR compound
Indanone 1.6g and dodecyl gallate 0.5g were added,
A mixture of 20 g of tricresyl phosphate and 60 ml of ethyl acetate was heated and dissolved, and added to 30 ml of a 7.5% gelatin aqueous solution containing 1.5 g of sodium triisopropylnaphthalenesulfonate, and a dispersion emulsified and dispersed by a colloid mill was added. A high-sensitivity emulsion was prepared and the dry film thickness was 2.0 μm and the coating silver amount was 20 m.
It was coated so that it would be g / dm ² (1 per mol of silver halide)
00g gelatin included).

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 containing 8 mol% silver iodide) Emulsion) was chemically sensitized with gold and sulfur sensitizers, and as a green sensitizing dye, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfobutyl) oxacarbocyanine was used. Hydroxide; anhydrous 5,5'-diphenyl-9-ethyl 3,3'-di- (3-sulfobutyl) oxacarbocyanine hydroxide and anhydrous 9-ethyl-3,3'-di-((3-sulfopropyl ) -5,6,5 ', 6'
-Dibenzooxacarbocyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.0g and 1-phenyl-5-mercaptotetrazole 20.0mg, and a green-sensitive low-sensitivity emulsion Was produced.
Further, as a magenta coupler per mol of silver halide, 1
-(2,4,6-Trichloro) phenyl-3- [3- (2,4-
50 g of di-tert-amylphenoxy) acetamido] benzamide-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -4- (1 as a colored magenta coupler
-Naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone 10 g, D
As an IR compound, β- {4- [1- (p-nitrophenyl) -4- (1-phenyl-5-tetrazolyl) thiomethyl-3-undecyl-5-pyrazolyloxy] -1-
1.5 g of hydroxy-2-naphthamido} propionic acid was added, a mixture of 60 g of tricresyl phosphate and 200 ml of ethyl acetate was dissolved by heating, and the mixture was added to a gelatin aqueous solution containing sodium triisopropylnaphthalenesulfonate and emulsified with a colloid mill. A green sensitive low-sensitivity emulsion was prepared by adding the dispersed dispersion, and the dry film thickness was 4.0 μm, and the coated silver amount was 20 mg / dm ^2.
Was applied. (100g per mol of silver halide
Including gelatin).

Seventh layer: green-sensitive high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 0.85 μm, containing 10 mol% of silver iodide) is chemically sensitized with gold and sulfur sensitizers, and further green-sensitive. As a 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-sulfobutyl) -5,6,5 ', 6'-
Dibenzooxacarbocyanine hydroxide was added, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.0 g and 1-phenyl-5-mercaptotetrazole 10.0 mg were added to give a green-sensitive high-sensitivity emulsion. Was produced.
Further, as a magenta coupler per mol of silver halide, 1
-(2,4,6-trichloro) phenyl-3- [3-2,4-di-tert-amylphenoxyacetamido] benzamide-5-pyrazolone 5 g, as a colored magenta coupler,
1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone 2.5 g, 2,5-
1.5 g of di-t-octylhydroquinone and β- {4- [1- (p-nitrophenyl) -4 as a DIR compound
-(1-Phenyl-5-tetrazolyl) thiomethyl-3
-Undecyl-5-pyrazolyloxy] -1-hydroxy-2-naphthamido} propionic acid 0.5 g, was added,
A mixture of 20 g of tricresyl phosphate and 30 ml of ethyl acetate was dissolved by heating, and the mixture was added to an aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate, and the resulting dispersion was emulsified and dispersed by a colloid mill to prepare a green-sensitive high-sensitivity emulsion. Coating was performed so that the dry film thickness was 2.0 μm and the coating silver amount was 15 mg / dm ² . (Contains 100 g gelatin per mol of silver halide).

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, 2,
3 g of 5-di-t-octylhydroquinone and 1.5 g of di-2-ethylhexyl phthalate were dissolved in 10 ml of ethyl acetate,
A dispersion prepared by dispersing 0.3 g of sodium triisopropylnaphthalenesulfonate in an aqueous gelatin solution was added, and this was added to 0.9 g / m ² , gelatin of 2,5-di-octylhydroquinone.
The coating was applied at a rate of 0.10 g / m ² so that the dry film thickness was 1.2 μm.

Layer 10: Blue-sensitive low-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 0.6 μm, containing 6 mol% silver iodide) was chemically sensitized with gold and sulfur sensitizers, and further sensitized. As a dye, anhydrous 5,5'-dimethoxy-3,3'-di- (3-sulfopropyl) thiacyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine. Denon (1.0 g) and 1-phenyl-5-mercaptotetrazole (20.0 mg) were added to prepare a blue-sensitive low-sensitivity silver halide emulsion. Further, as a yellow coupler per mol of silver halide, α-pivaloyl-α- (benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidin-4-yl) -2'-chloro-5'- [Α- (dodecyloxycarbonyl) pentoxycarbonyl] acetanilide 250g
Was added, dibutyl phthalate 120g, ethyl acetate 300ml
The resulting mixture was dissolved by heating, added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and the resulting dispersion was emulsified and dispersed by a colloid mill to prepare a blue-sensitive low-sensitivity silver halide emulsion, and the dry film thickness was 4.0 μm. , Coated silver amount 5
It was applied so as to be mg / dm ² . (Contains 240 g gelatin per mol of silver halide).

11th 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) was chemically sensitized with gold and sulfur sensitizers, and further sensitized. As a dye, anhydrous 5,5'-dimethoxy-3,3'-di- (3-sulfopropyl) thiacyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine. Denon 1.0 g and 1-phenyl-5-mercaptotetrazole 10.0 mg were added to prepare a blue-sensitive high-sensitivity silver halide emulsion. Further, as a yellow coupler per mol of silver halide, α-pivaloyl-α- (1-benzyl-
2-Phenyl-3,5-dioxo-1,2,4-triazolidin-4-yl) -2'-chloro-5 '-[α- (dodecyloxycarbonyl) pentoxycarbonyl] acetanilide 80 g was added and dibutyl phthalate was added. 40 g, ethyl acetate 24
0 ml of the mixture was dissolved by heating, added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill to prepare a blue-sensitive high-sensitivity silver halide emulsion, and a dry film thickness of 2.0 The coating amount was 5 μm and the coated silver amount was 5 mg / dm ² . (Silver halide 1
Contains 160 g gelatin per mole).

12th layer: intermediate layer 2 g of di-2-ethylhexyl phthalate, 2- [3-cyano-3- (dodecylaminocarbonyl) anilidene]-
2 g of 1-ethylpyrrolidine and 2 ml of ethyl acetate were mixed, and the dispersion prepared by dispersing in an aqueous solution of gelatin containing 0.6 g of sodium triisopropylnaphthalene sulfonate was added to the aqueous solution of gelatin to give 1.0 g / m ² of gelatin. Was applied to give a dry film thickness of 1.0 μm.

Layer 13: Protective layer An aqueous gelatin solution containing 4 g of gelatin and 0.2 g of 1,2-bosvinylsulfonylethane was coated at a ratio of 1.3 g of gelatin / m ^{2 to} a dry film thickness of 1.2 μm per 100 ml of the protective layer.

Samples 1-1 to 1-24 having the requirements shown in Table 2 were prepared using the light-shielding paper No. 1 or No. 2 and the wrapping frequency generated by the camera operation was checked. The camera used is Pentax 67.

Example-2 Next, light-shielding paper Nos. 2-1 to 2-14 coated with the following resins were prepared as shown in Table 3.

The base paper used was manufactured by the Fourdrinier method. At this time, the back surface was processed by roll coating with various resins containing 35 wt% of carbon black in order to maintain the light-shielding property. The surface was treated in the same manner as in Example-1. At this time, the same type of film as used in Example-1 was used to make 120 size and 220 size roll films.
Also, the relationship between the tail shape of the shading paper used at this time and the spool was satisfied.

A; −2mm B; 0mm However, the length of the light-shielding paper tip that comes out of the spool locking slit
8 mm.

Asahi Pentax 67 was used as a camera for the roll film, and the occurrence rate of "blur" generated was examined. The results are shown in Table-4.

Resin used No-1 Aqueous polyethylene dispersion (40 wt% solids) No-1 Aqueous polypropylene dispersion (20 wt% solids) No-3 15 wt% toluene solution of ethylene / vinyl acetate copolymer No-4 Non-crystalline Saturated polyester solution (Toyobo Co., Ltd.)
Made: Pylon # 500) No-5 Aqueous Polyvinylidene Chloride Dispersion (Asahi Kasei Kogyo Co., Ltd .: Saran Latices L-511) No-6 Aqueous Polyester Dispersion (Eastman Chemical Co .: East WD Size) No- 7 Saturated polyester resin (Toyobo Co., Ltd .: Byron # 200) No.2-7, No.2-1 resin instead of No.2-2, No.2-3,
The results using No. 2-4, No. 2-5, and No. 2-6 also showed the same results as those shown in the above table.

Example-3 Next, light-shielding paper No.3-1-No.3-11 coated with the following resin was prepared as shown in Table-5.

The base paper used was manufactured by the cylinder net making method. At this time, in order to maintain the light-shielding property, carbon black was mixed in a weight ratio of 6% at the time of papermaking. Various resins dispersed using a Banbury mixer so that the carbon black amount to 6 wt% were processed on the back surface by an extruder.

After the backside resin processing, the surface processing was performed by the same method as in Example-1.

At this time, the film uses the same film as in Example-1,
I made 120 size roll film.

The relationship between the tail shape of the shading paper used at this time and the spool was A; -1mm B; 0mm.

However, the length of the light-shielding paper tape insertion piece that comes out from the spool locking slit is 11 mm.

In the resin used No.3-1 low density polyethylene LDPE (density 0.918g./cm ³⁾ No.3-2 low density polyethylene (density 0.930 or less) and high density polyethylene (density 0.950 or higher) at a weight ratio of 60:40 Mix No.3-3 Resin is mixed in No.2 in a weight ratio of 40:60. No.3-4 Ethylene ethyl acrylate copolymer (DPD-6169 manufactured by Union Carbide) No.3-5 Ethylene Vinyl acetate copolymer (vinyl acetate content 10mol%) No.3-6 Linear low density polyethylene (L-LDPE) No.3-8 Linear low-density polyethylene 90wt% and low-density polyethylene 10wt% No.3-9 Ethylene-ethyl methacrylate (ethylene content 70mol%) No.3-10 Ethylene-methyl acrylate (ethylene content 75mol %) No.3-11 Ethylene-butyl acrylate (Ethylene content 90 mol%) No.3-12 Ethylene-butyl methacrylate (Ethylene content 85 mol%) No.3-13 Ethylene--2-ethyl acrylate- Butyl (Ethylene content 90mol%) No.3-14 Ethylene-Acrylate-2-ethyl-hexyl (Ethylene content 92mol%) Occurrence rate of "blurring" that occurs when the above roll film is used with camera Asahi Pentax 67 Were examined and shown in Table-6.

Instead of No. 3-5 resin, No. 3-2, No. 3-3, No. 3-4, N
o.3-13, No.3-14, or No.3-6, instead of No.3-1 resin
No.3-7, No.3-8, No.3-9, No.3-10, No.3-11, No.3-12
The same results as in the above table were obtained when using.

[Brief description of drawings]

FIG. 1 is a view showing a state in which the light-shielding paper tail portion is inserted into a locking slit of a spool. 1 ...... Shading paper 10 ...... Strip 11 ...... Tail 2 ...... Spool 21 ...... Flange 22 ...... Winding shaft 23 ...... Locking slit A ...... Fitting length B ...... Engagement gap

Claims (2)

[Claims] 1. A roll-shaped photosensitive material packaging light-shielding paper having a resin layer on one or both sides of the base paper, wherein the light-shielding paper has a flexibility of 10 to 40 g, and the base paper has a thickness corresponding to the thickness of the base paper. The ratio of the thickness of the resin layer on one side is 0.11 to 0.83, or the ratio of the resin weight of the resin layer on one side of the base paper to the weight of the base paper is 0.01 to 0.5. Material wrapping paper. 2. In a roll-shaped light-sensitive material packaging light-shielding paper having a resin layer on one or both sides of a base paper, the tail of the light-shielding paper is inserted into a locking slit in the diameter direction of the spool winding shaft, and the tail is supported. The rolled light-sensitive material packaging light-shielding paper according to claim 1, wherein both ends of the light-shielding paper are in the shape of a tail so that they can contact the inside of the spool flange.