JPH04212146A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To wind a photographic film around a spool in a cartridge having small void volume at low humidity and to prevent the blocking of the film. CONSTITUTION:A vinylsulfone hardening agent or a hardening agent having an active carboxyl group is incorporated into a gelatin-contg. layer of a film 2 with photosensitive silver halide on the substrate. The resulting film 2 can be wound around a spool 1 in a cartridge 3 having <=0.25 void volume V at <=60% humidity. The void volume V is defined by an equation V=(B-A)/B [where A=(the thickness of the film)X(the length of the film) and B=(the cross-sectional area of the body of the cartridge)-(the cross-sectional area of the spool)].

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photosensitive material. More specifically, the present invention provides a compact photographic material that facilitates the loading of photographic film into a camera, and which improves blocking of the film wound into a roll during storage of the photographic material. Regarding photosensitive materials.

(Prior art) In conventional photographic film cartridges, the photographic film was not tightly wound around the spool inside the cartridge, but was stored in a loose state, so even if the spool was rotated in the opposite direction to the film winding direction, Photographic film could not be sent outside the cartridge. For this reason, it has been necessary for the photographer to pull out the leading end of the photographic film by an appropriate length from outside the cartridge in advance, and then load the leading end of the photographic film into the film feeding mechanism within the camera.

However, this operation is time-consuming and requires a certain degree of skill, so loading errors often occur.If a loading error occurs, there is the problem that the photographic film is taken without being wound. Ta.

Therefore, a camera that does not require such operations has been desired.

Such a camera can be realized by making it possible to feed the photographic film from inside the cartridge.If the photographic film can be fed from inside the cartridge, the leading edge of the film can be fed out to engage the film with the film feeding mechanism inside the camera. Therefore, there is no need to load the end of the film into the film transport mechanism within the camera. Therefore, instead of the conventional cartridge, a cartridge that can feed the film from inside is required.

A conceivable method for feeding the photographic film from inside the cartridge is to rotate a spool around which the photographic film is wound in a direction opposite to the film winding direction to feed the photographic film to the outside of the cartridge. As this method ages, it is necessary to reduce the free space inside the cartridge to a certain level. This is because if the free space is large, the film will turn over inside the cartridge, and the rotation of the spool will no longer act as a force to push the leading edge of the film out of the cartridge. Furthermore, the conventional cartridge main body is large, which is not suitable for downsizing the camera.

However, if the free space is reduced below a certain level, the photographic films tend to block each other within the cartridge, resulting in the photographic film not being fed out, and blocking marks remaining, resulting in the loss of highly accurate recorded information.

As a method to solve the above problem, it was considered to roll the photographic film into a cartridge at low humidity, but this caused a new problem of slow hardening of the gelatin-containing layer in the photographic film and deterioration of photographic properties.

(Problems to be Solved by the Invention) An object of the present invention is to provide a photographic light-sensitive material that has a small void law and that improves the deterioration of photographic properties of a photographic film rolled up in a cartridge at low humidity.

(Means for Solving the Problems) An object of the present invention is to provide a photographic film having at least one layer of photosensitive silver halide on a spool, a support that is wound in a roll around the spool with one end latched to the spool. and the cartridge body, and the porosity inside the cartridge is V
(defined below) is 0.25 or less, the photographic film is rolled up inside the cartridge body at a humidity of 60% or less, and at least one of the gelatin-containing layers of the photographic film is vinyl sulfone-containing. The present invention will be described in more detail below, which is achieved by a silver halide photographic light-sensitive material characterized by containing a hardening agent or a carboxyl group-activated hardening agent.

A conceivable method for feeding the photographic film from inside the cartridge is to rotate a spool around which the photographic film is wound in a direction opposite to the film winding direction to feed the photographic film to the outside of the cartridge. In this method, it is necessary to reduce the free space inside the cartridge to a certain level. This is because if the free space is large, the film will turn over inside the cartridge, and the rotation of the spool will no longer act as a force to push the leading edge of the film to the outside.

According to the void law V defined under the free space inside the cartridge, the film cannot be stably fed unless it comes out. Here, A is the winding cross-sectional area of the film, and B is the cross-sectional area inside the cartridge, which are defined as follows.

A = (thickness of film) * (length of film) B = (cross-sectional area of cartridge body) - (cross-sectional area of spool) All dimensions are measured at a temperature of 25° C. in an atmosphere of 50%. The length of the film is the length from the leading edge of the film to the trailing edge. If the leading edge of the film is not straight, use the most protruding end as the leading edge. When the end of the film is inserted into the spool, the insertion opening of the spool is the end of the film. The thickness of the film is the sum of the thicknesses of all components such as the film support and the gelatin layer containing the emulsion.
electric Eo. Electronic manufactured by Ltd.
It is determined by measuring the thickness at 10 arbitrary points using a micrometer and averaging the thickness. The spool cross-sectional area refers to the cross-sectional area of the portion of the spool around which the film is wound. The cross-sectional area of the cartridge body means the cross-sectional area of the inside of the cartridge, not at the upper or lower ends of the cartridge, but at the cross-section of the portion where the film is accommodated. If there is a protrusion (rib) provided inside the cartridge for the purpose of controlling the position of the film or improving the slippage, the cross-sectional area of the inner side of the protrusion is used. In the case of a method in which the winding appearance of the film is adjusted using a flange or the like other than the cartridge body, the inner cross-sectional area of the protrusion of the flange that defines the position of the outermost periphery of the film is used.

The value of porosity V is 0<V≦0.25, but 0.04≦
More preferably, V≦0.22, and 0.08≦V
Most preferably, ≦0.22.

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

In forming the plastics of the present invention, a plasticizer is mixed into the plastics as necessary. Examples of the plasticizer include 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 plastic materials used in the present invention are listed below, but the invention is 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 methacrylic resin, vinyl formal resin, Examples include vinyl butyral resin, polyethylene terephthalate, nylon, phenol resin, and melamine resin.

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

Furthermore, the cartridge of the present invention may contain various antistatic agents. The antistatic agent is not particularly limited, but carbon black, the metal oxide particles of the present invention, nonionic, anionic, cationic, betaine-based surfactants, nonionic, anionic, cationic, betaine polymers, and the like can be preferably used. As these antistatic cartridges, Japanese Patent Application Laid-open Nos. 1-312537 and 1-31253
It is stated in No. 8.

Cartridges are usually manufactured using plastic mixed with carbon black or pigments to provide light-blocking properties.

Furthermore, although the current size of the cartridge may remain unchanged, it is effective to make the camera smaller if the diameter of the cartridge, which is currently 25 m/m, is set to 22 m/m or less, preferably 20 m/m or less, and 14 m/m or more. The volume of the cartridge case is
It is preferably 30 cm2 or less, preferably 25 cm2 or less, and more preferably 20 cm2 or less. The weight of the plastic used for the cartridge and cartridge case is 1 g or more and 25 g or less, preferably 5 g or more and 15 g or less.

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

Next, the form of the cartridge containing the color sensitive material described in the present invention will be described.

Examples of the cartridge of the present invention are shown in FIGS. 1A and 1B. The photographic film cartridge 20 consists of a spool 1, a photographic film 2 which is wound into a roll with one end secured to the spool 1, and a cartridge body 3. The spool 1 is rotatably attached to the inside of the cartridge body 3 around an axis, and can be rotated from outside the cartridge body 3. The cartridge body 3 is provided with a photographic film drawer opening 4 for pulling out the photographic film 2.
A light shielding member 4A is attached to the inner surface of the photographic film drawer opening 4 to keep the inside of the cartridge body 3 in a light shielding state.

In the photographic film cartridge 20 of this enforcement order,
A pair of ribs 8 extending in the circumferential direction along the inner surface of the cartridge body 3 and having a width of about 15 to 20% of the film width are provided at both ends of the film 2 in the width direction. The rib 8 opens in the direction of the film outlet 4 so that the photographic film 2 can be pulled out from the film outlet 4. The ribs 8 press the film 2 from the outermost surface to maintain the film 2 tightly wound around the spool 1. The cartridge body cross-sectional area in this case is the area inside the rib 8.

The outer diameter of the spool 1 is determined as follows. As described above, it is difficult to tightly wind the film 2 around the spool 1 in a roll shape while keeping the innermost peripheral surface 2A of the film in contact with the outer periphery of the spool 1. For this reason, it is unavoidable that a gap is formed between the innermost circumferential surface of the film 2A and the spool 1. In order to prevent the formation of such gaps, it is necessary to set the porosity V to 0.25 or less. Furthermore, if the distance H between the innermost circumferential surface of the film 2A and the spool 1 is too large, a reversal phenomenon of the film 2 as shown in FIG. 2 will occur. For this reason, the outer diameter of the spool 1 is such that when a gap is created between the innermost film surface 2A and the spool 1, the distance H between the two is 2.
It is desirable to make it less than mm. That is, the outer diameter of the spool is A, the inner diameter of the cartridge body is B, the thickness of the rib is T,
If the thickness of the film is C, and the number of rolls that changes depending on the length of the film is D, then B/2=A/2+H+C*D+T, so A/2=B/2-T-H-C *D. The interval H is H=B/2-A/2-C*D-T, so the outer diameter A of the spool when H≦2mm
becomes B/2-R-C*D-2≦A/2.

By setting the interval H to 2 mm or less, the spool rotation torque can be reduced to 0.8 Kgf. If it is set to less than cm, the reversal phenomenon of the photographic film 2 can be prevented. The ribs 8 do not need to be provided along the entire circumferential direction along the inner surface of the cartridge main body 3, but may be provided only on a part of the circumferential direction of the inner surface of the cartridge main body 3. Further, instead of being provided only at both ends of the film 2 in the width direction as in this embodiment, it may be provided over the entire width of the film 2.

Other preferred embodiments of the cartridge include Japanese Patent Application No.
-172594, US4,883,235, US4,8
83,236, US4,887,112, US4,91
3,368, US 4,834,306, US 4,846,418, US 4,880,179, etc.

A preferred vinyl sulfone hardener of the present invention is represented by the following general formula.

(General formula I) X1-SO2-L-SO2-X2 In the above general formula, X1 and X2 are either -CH=CH2 or -CH2CH2-Y, and X1 and X2
may be the same or different. Y represents a group that can be substituted by a nucleophilic reagent (nucleophilic group) or can be eliminated in the form of HY by a base.

L is a divalent linking group and may be substituted.

The hardener of the present invention represented by general formula (I) will be explained in more detail. X1 and X2 represent -CH=-CH2 or -CH2CH2-Y (Y is a group that is substituted or eliminated by the action of a nucleophile or a base), and preferred specific examples thereof include the following. be able to.

-CH=CH2, -CH2CH2-Cl-CH2CH2
-Br, -CH2CH2-OSO2CH2-CH2CH
2-OSO2C6H5, -CH2CH2-OSO2C6
H4-CH3-CH2CH2-OSO3Na, -CH2
CH2-OSO2K-CH2CH2-OCOCH3, -
CH2CH2-OCOCF3-CH2CH2-OCOC
HCl2 Among these, especially -CH=CH2, -CH2CH2-Cl-CH2CH2
-Br, -CH2CH2-OSO2CH3-CH2CH
2-OSO3Na and -CH2CH2-OSO3K are preferred, and -CH=CH2 is most preferred.

The divalent linking group L is an alkylene group (including a cycloalkylene group), an arylene group (including a heteroaromatic ring group), or a group thereof, -O-, -NR1-, -SO2-, -
SO3-, -S-, -SO-, -SO2NR1-, -C
O-, -COO-, -CONR1-, -NR1COO-
, -NR1CONR- is a divalent group formed by combining one or more bonds represented by -NR1CONR-. R1 represents a hydrogen atom, or an alkyl group, aryl group, or aralkyl group having 1 to 15 carbon atoms.

Also -NR1-, -SO2NR1-, -CONR1-,
When two or more bonds represented by -NR1COO- or -NR1CONR- are included, those R1's may be bonded to each other to form a ring. Furthermore, L may have a substituent, and examples of the substituent include a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, a halogen atom, an alkyl group, an aralkyl group, Examples include aryl groups. Moreover, the substituent may be further substituted with one or more groups represented by X3-SO2-. X3 has the same meaning as X1 and X2 described above.

Representative examples of L include the following. However, a to k in the examples are integers from 1 to 6. Only e may be 0, preferably 2 or 3. e of a~k
1 or 2 is preferable, and 1 is particularly preferable. In the formula, R1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

-(CH2)a- -(CH2)b-O-(CH2)c- -(CH2)d-CONR1-(CH2)e-HR1C
O-(CH2)f--(CH2)g-SO2-(CH2
) The h-carboxyl group-activated hardener is a compound that activates the carboxyl group of a hydrophilic binder, and is generally called a condensing agent. As a preferable example, the following general formula (2
) to (8) can be mentioned.

General formula (2) In the formula, R11 and R12 are alkyl groups having 1 to 10 carbon atoms (
For example, a methyl group, an ethyl group, a 2-ethylhexyl group, etc.), an aryl group having 6 to 15 carbon atoms (such as a phenyl group,
naphthyl group, etc.) or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.), and may be the same or different from each other. Also R11,
It is also preferred that R12 be bonded to each other to form a heterocycle together with the nitrogen atom. Examples of rings that form a ring include a pyrrolidine ring, a piperazine ring, and a morpholine ring.

R13 is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, a sulfamino group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a dialkyl-substituted amino group having 2 to 20 carbon atoms. Represents a substituent such as a group.

When R13 is an alkoxy group, an alkyl group, a dialkylamino group, or an N-alkylcarbamoyl group, these groups may be further substituted, and examples of these substituents include a halogen atom, a carbamoyl group, a sulfo group, Examples include sulfoxy group, sulfamino group, and ureido group. X- represents an anion and serves as a counter ion of the N-carbamoylpyridinium salt. When the substituent of R13 includes a sulfo group, sulfooxy group, or sulfamino group, an inner salt may be formed and X- may not be present. Preferred examples of anions include halide ions, sulfate ions, sulfosate ions, εO4-, BF4PF6-, and the like.

A detailed description of the carbamoylammonium salt hardener represented by the general formula (2) can be found in Japanese Patent Publication No. 56-12
No. 853, No. 58-32699, JP-A-49-519
For details, refer to publications such as No. 45, No. 51-59625, and No. 61-9641.

General formula (3) R11, R12, R13 and X- are defined by general formula (I
I-1) and these compounds are detailed in Belgian Patent No. 825,726.

General formula (4) R14, R15, R16 and R17 have 1 to 20 carbon atoms
Alkyl group (e.g. methyl group, ethyl group, butyl group,
2-ethylhexyl group, dodecyl group, etc.), carbon number 6-
20 aralkyl groups (e.g. benzyl group, phenethyl group, 3-pyridylmethyl group, etc.), or 5 to 20 carbon atoms
are aryl groups (for example, phenyl group, naphthyl group, pyridine group, etc.), and may be the same or different. Further, R14, R15, R16 and R17 may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, and a 6 to 20 carbon atoms.
Examples include an aryloxy group, an N,N-disubstituted carbamoyl group, and the like.

It is also preferable that any two of R14, R15, R16 and R17 combine to form a ring.

For example, examples of R14 and R15 or R16 and R17 bonding together to form a ring with a nitrogen atom include a pyrrolidine ring, a piperazine ring, a perhydroazepine ring, a morpholine ring, and the like.

Examples of R14 and R16, or R15 and R17 bonding together to form a ring with two nitrogen atoms and a carbon atom sandwiched between them, include an imidazoline ring, a tetrahydropyrimidine ring, and a tetrahydrodiazepine ring. There are cases where this is done.

X represents a group that can be eliminated when the compound represented by the general formula (4) reacts with a nucleophilic reagent, and preferred examples include a halogen atom and a sulfonyloxy group.

Y- represents an anion, such as halide ion, sulfonate ion, sulfate ion, εO4-, BF4-, P
F6- etc. are preferred.

When Y- represents a sulfonate ion, X, R14
, R15, R16 or R17 to form an inner salt.

The amidinium salt hardener represented by the general formula (4) is described in detail in JP-A-60-225148.

General formula (5) In the formula, R18 is an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, 2-ethylhexyl group, etc.), a cycloalkyl group having 5 to 8 carbon atoms (e.g., cyclohexyl group, etc.), or a carbon atom. R19 represents an alkoxyalkyl group having 3 to 10 carbon atoms (eg, methoxyethyl group) or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.) in addition to the group defined in R18.

A group represented by is preferred. R20 represents an alkylene group having 2 to 4 carbon atoms (eg, ethylene group, propylene group, trimethyl group, etc.). R21 and R22 each represent an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, etc.), which may be the same or different. In addition, R21 and R22 are combined together with a nitrogen atom to form a heterocyclic ring (e.g., pyrrolidine ring, piperazine ring, morpholine ring, etc.)
It is also preferable to form R23 is an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, butyl group, etc.)
represents, but it is also preferable that it be substituted. Preferred examples of the substituent include substituted or unsubstituted carbamoyl groups and sulfo groups. X- represents an anion, such as halide ion, sulfonate ion, sulfate ion, εO
4-, BF4-, PF6-, etc. are preferred. Also R23
When is substituted with a sulfo group, an inner salt is formed and X- may not be present.

These tarbodiimide hardeners are described in Japanese Patent Application Laid-open No. 1983
-126125 and 52-48311 for details.

General formula (6) In the formula, R24 is an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, butyl group, etc.), an aryl group having 6 to 15 carbon atoms (e.g., phenyl group, naphthyl group, etc.), or Represents an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.). These groups may be substituted, and examples of the substituent include carbamoyl group, sulfamoyl group, and sulfo group. R25, R
26 represents a substituent such as a hydrogen atom, a halogen atom, an acylamido group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and may be the same or different. good. It is also preferable that R25 and R26 combine to form a condensed ring together with the pyridinium ring skeleton.

X represents a group that can be separated when the compound represented by the general formula (6) reacts with a nucleophile, and preferable examples include a halogen atom, a sulfonyloxy group, or an OP(OR
27) A group represented by 2 (R27 represents an alkyl group or an aryl group) can be mentioned. When X represents a sulfonyloxy group, it is also preferable that X and R24 are bonded.

Y- represents an anion, such as halide ion, sulfonate ion, sulfate ion, ClO4-BF4-, P
F6- etc. are preferred. Further, when R24 is substituted with a sulfo group, an inner salt is formed and Y- does not need to be present.

Regarding these pyridinium salt type hardeners,
No. 8-50699, JP-A-57-44140, JP-A No. 57
-46538 has a detailed description.

General formula (7) In the formula, R11 and R12 are defined as R in general formula (1).
11, is exactly the same as the definition of R12, and R23 is an alkyl group having 1 to 10 carbon atoms (e.g. methyl group, ethyl group, butyl group, etc.), an aryl group having 6 to 15 carbon atoms (e.g. phenyl group, naphthyl group, etc.) , or an aralkyl group having 7 to 15 carbon atoms (for example, a benzyl group, a phenethyl group, etc.). X- is an anion, a halide ion,
Sulfonate ion, sulfate ion, ClO4-, BF4
-, PF6-, etc. are preferred.

The pyridinium salt hardener represented by the general formula (7) is described in detail in JP-A-52-54427.

General formula (8) In the formula, R29 is an alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, 2-ethylhexyl group, etc.) or an aryl group having 6 to 15 carbon atoms (e.g., phenyl group, naphthyl group, etc.) , or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.), which may be substituted or unsubstituted. Examples of substituents include halogen atoms, carbamoyl groups, sulfo groups, sulfoxy groups, ureido groups, alkoxy groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and dialkyl-substituted amino groups having 2 to 20 carbon atoms. There is.

Z represents a nonmetallic atom group necessary to complete the nitrogen-containing heteroaromatic ring, and preferred examples include a pyridine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, an oxazole ring, etc., and benzo-fused rings thereof.

R30 is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, a ureido group, and has 1 to 10 carbon atoms.
represents a substituent such as an alkoxy group, an alkyl group having 1 to 10 carbon atoms, and a dialkyl-substituted amino group having 2 to 20 carbon atoms. When R30 is an alkoxy group, an alkyl group, a dialkylamino group, or an N-alkylcarbamoyl group, these groups may be further substituted, and examples of these substituents include a halogen atom, a carbamoyl group, a sulfo group, Examples include sulfoxy group and ureido group.

X- represents an anion. When R29, R30 or their substituents contain a sulfo group or a sulfooxy group,
Forming an inner salt, X- may be absent. Preferred examples of anions include halide ions, sulfate ions, sulfonate ions, εO4-, BF4-, PF
6- etc.

In addition to the compounds represented by the above-mentioned general formulas (2) to (8), examples of carboxyl group-activated hardeners used in the present invention include JP-A-50-38540 and JP-A-52-9347.
0, W090/02357, US4,877,724,
JP-A-56-43353, JP-A-58-113929,
Compounds such as those described in US 3,321,313 are also preferred. Particularly preferably, the carboxyl group-activated hardener used in the present invention is represented by the general formula (2).

Typical examples of vinyl sulfone hardeners used in the present invention are listed below from A-1 to A-12, and typical examples of carboxyl group-activated hardeners are listed from B-1 to B-85. However, the present invention is not limited to these examples.

In the present invention, the amount of hardening agent used can be arbitrarily selected depending on the purpose. Usually 0.0 for dry gelatin
Proportions ranging from 1 to 20 weight percent can be used. Particular preference is given to using proportions ranging from 0.05 to 15 weight percent.

In the present invention, the photographic layer using a hardener is not particularly limited as long as it is a gelalan-containing layer, and includes silver halide emulsion layers as well as non-photosensitive layers such as undercoat layers, back layers, filter layers, intermediate layers, and overcoats. It can be used in any gelatin-containing photographic layer, such as a layer.

The above hardeners may be used alone or in combination of two or more. It may also be used in combination with other hardening agents known so far. Known hardeners include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl urea), and 2-hydroxy-4,6-dichloro-
1,3,5-triazine, etc. U.S. Patent No. 3,28
No. 8,775, No. 2,732,303, British Patent No. 9
Compounds containing reactive halogens such as those described in No. 74,723 and No. 1,167,207, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine , other compounds containing reactive olefins such as those described in U.S. Patent No. 3,635,718, U.S. Pat. Patent No. 2,732,316,
N-methylol compounds described in US Pat. No. 2,586,168, isocyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017
, No. 280, No. 2,983,611, etc., U.S. Patent No. 2,725,294
No. 2,725,295, etc., epoxy compounds described in U.S. Pat. No. 3,091,537, and halogencarboxaldehydes such as mucochloric acid. I can do it. Alternatively, inorganic compound hardeners include chromium alum and zirconium sulfate. In addition, compounds in the form of precursors instead of the above compounds, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitro alcohols, mesyloxyethylsulfonyl compounds, chloroethylsulfonyl It may be used in combination with other compounds. When using a carboxyl group-activated hardener and another hardener in combination, the ratio of the carboxyl group-activated hardener to be used can be selected as desired depending on the purpose and effect, but it should not be less than 50 mol%. It is preferable that

Furthermore, a compound that accelerates the hardening of gelatin can also be used together with a hardening agent. For example, in the system of carboxyl active group hardener and vinyl sulfone hardener,
For example, a polymer containing a sulfinic acid group described in No. 6-4141 is used in combination as a hardening accelerator.

Gelatin, which can be used as a hardening agent, is manufactured by
Before gelatin extraction, so-called alkali-treated (lime-treated) gelatin is immersed in an alkaline bath, acid-treated gelatin is immersed in an acid bath, and double-soaked gelatin that has undergone both treatments.
Any enzyme-treated gelatin may be used. Furthermore, the hardening agent can also be applied to low molecular weight gelatin which has been partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme.

Gelatin to act as a hardening agent may be partially mixed with colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, agar, sodium alginate, starch derivatives,
Sugar derivatives such as dextran, synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof, partial hydrolysates, etc. can be substituted, as well as so-called gelatin derivatives. May be used instead.

When the hardener of the present invention is used in a photographic light-sensitive material, the photographic emulsion layer and other layers may also contain a synthetic polymer compound, such as a latex-like water-dispersed vinyl compound polymer, which particularly improves the dimensional stability of the photographic material. Enhancing compounds and the like may be included alone or in admixture, or in combination with hydrophilic water-permeable colloids.

In order to reduce blocking, it is preferable to include a slip agent in the outermost layer of the bag. These slip agents are not particularly limited, but include those that do not deteriorate photographic properties and
It is preferable to use a material that does not cause trouble in the manufacturing process. Those slip agents are US 4,275,146, US 3,933
,516, Special Publication No. 1262385, Special Publication No. 55-
90633, Japanese Patent Publication No. 52-129520, etc.

Preferred specific examples of the slip agent are shown below, but the invention is not limited thereto.

Compound Example S-10 Erucic acid amide S-11C33H67COOH S-12 Liquid paraffin Furthermore, in the present invention, it is preferable to include a so-called matting agent in the outermost layer of the bag to improve blocking.
The particle size is preferably 1 to 3μ. By containing these matting agents, the average height of the convex portions on the outermost surface of the back layer is preferably 0.8 to 3 μm. These matting agents are disclosed in JP-A-64-77052 and JP-A-62-1.
4647, etc.

The coating amount is preferably 5 to 300 mg/m2.

M-8 silica (spherical) M-9 〃 (amorphous) The support for the sensitive material used in the present invention is not particularly limited, but various plastic films can be used, and preferred ones include cellulose derivatives (e.g. diacetyl,
triacetyl, propionyl, detanoyl, acetylpropionyl acetate, etc.), polyamides, polycarbonates described in U.S. Pat. -cyclohexane dimethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene, polysulfone, polyacrylate, polyetherimide, etc., and particularly preferred are triacetyl cellulose and polyethylene terephthalate.

These supports have plasticizers added to them for the purpose of imparting flexibility, etc.
Sometimes used. In particular, cellulose esters usually contain plasticizers such as triphenyl phosphate, biphenyl diphenyl phosphate, and dimethyl ethyl phosphate.

The thickness of these supports varies depending on the polymer type, but the thickness is 1
It can be used depending on the purpose, ranging from sheets of about 2.0 mm to thin films of about 20 μm, but the ones commonly used are 50 μm to 3.0 μm.
The thickness range is 00μ.

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 purposes such as neutralizing the base color, preventing light piping, and preventing halation.

Chemical treatment, mechanical treatment, After surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., photographic emulsion is directly applied to improve adhesive strength. Alternatively, a method may be used in which a subbing layer is provided after these surface treatments or without surface treatment and a photographic emulsion layer is applied thereon.

In this case, for the cellulose derivative, a single layer of a gelatin solution dispersed in a methylene chloride/ketone/alcohol mixed organic solvent is applied to provide an undercoat layer.

Chromium salts (such as chromium alum) as gelatin hardeners
, aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (
(2,4-dichloro-6-hydroxy-s-triazine, etc.), epichlorohydrin resin, and the like. These undercoating liquids can contain various additives as necessary. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids,
Anti-rash agents, etc. When using the undercoat liquid of the present invention, an etching agent such as resorcinol, chloral hydrate, chlorophenol, etc. can also be included in the undercoat liquid.

The subbing layer of the present invention may contain inorganic fine particles such as SiO2, TiO2, or polymethyl methacrylate copolymer fine particles (1 to 10 .mu.m) as a matting agent.

The undercoating liquid according to the present invention can be applied by a generally well-known coating method, such as a dip coating method, an air knife coating method,
Curtain coating method, roller coating method, wire bar coating method, gravure coating method, or U.S. Patent No. 2,68
It can be coated by the extrusion coating method using a hopper as described in the specification of No. 1,294.

U.S. Pat. No. 2,761,791, 3, as appropriate.
508,947, 2,941,898, and 3,5
Two or more layers can be simultaneously coated by the method described in No. 26,528, "Coating Engineering" by Yuji Harasaki, p. 253 (published by Asakura Shoten, 1973).

The sensitive material of the present invention is composed of a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer, etc., and these are mainly used as a hydrophilic colloid layer.

In this case, binders for the hydrophilic colloid layer include, 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. Examples include polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof and partially hydrolyzed dispersions, dextran, polyvinyl acetate, polyacrylic ester, rosin, etc., as required. Mixtures of two or more of these colloids may also be used.

Among these, gelatin or its derivatives are most used, and gelatin here refers to so-called lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin.

In the present invention, anionic, nonionic, cationic, and betaine fluorine-containing surfactants can also be used in combination.

These fluorine-containing surfactants are disclosed in JP-A-49-10722, British Patent No. 1,330,356, and JP-A-53-84.
No. 712, No. 54-14224, No. 50-11322
No. 1, U.S. Patent No. 4,335,201, U.S. Patent No. 4,347
, 308, British Patent No. 1,417,915, Japanese Patent Publication No. 52-26687, No. 57-26719, British Patent No. 59-
No. 38573, JP-A-55-149938, JP-A No. 54-
No. 48520, No. 54-14224, No. 58-200
No. 235, No. 57-146248, No. 58-1965
No. 44, British Patent No. 1,439,402, etc.

Preferred specific examples of these are described below.

In the present invention, a nonionic surfactant may be used.

Specific examples of nonionic surfactants preferably used in the present invention are shown below.

Compound Examples The layer to which the fluorine-containing surfactant and nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material, such as a surface protective layer, emulsion layer, intermediate layer, or lower layer. Examples include a coating layer and a backing layer.

The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention may be 0.0001 g to 1 g per square meter of the photographic material, more preferably 0.0005 to 0.5 g, Particularly preferred is 0.00
05g to 0.2g. Moreover, two or more types of these surfactants of the present invention may be mixed.

Also, ethylene glycol, propylene glycol, 1,
1,1-trimethylolpropane, etc., JP-A-54-89
Polyomal compounds such as those shown in No. 626 can be added to the protective layer or other layers of the present invention.

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

In addition, in the present invention, lubricating compositions such as U.S. Pat. No. 3,079,837, U.S. Pat. Modified silicones such as those shown in No. 537 and JP-A-52-129520 can be included in the photographic constituent layer.

The photographic light-sensitive material of the present invention has a photographic constituent layer in which U.S. Pat.
No. 411,911, No. 3,411,912, Special Publication No. 4
5-5331 and the like.

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

Representative examples of silver halide color photographic materials particularly preferred in the present invention include color reversal films and color negative films.

In particular, a general color negative film is a preferred color photographic material.

The following description will be made using a general color negative film.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is 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, the above-mentioned arrangement order may be reversed, or the arrangement order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer between each layer may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included, and a color mixing inhibitor as commonly used may be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are disclosed in West German Patent No. 1,121,470 or British Patent No. 923,045, Japanese Patent Application Laid-open No. 112751/1986,
No. 2-200350, No. 62-206541, No. 62
-206543, 56-25738, 62-6
No. 3936, No. 59-202464, Special Publication No. 55-3
No. 4932 and No. 49-15495.

Silver halide grains include those with regular crystal shapes such as cubes, octahedrons, and dodecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with crystal defects such as twin planes. or a combination thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No. 17643
(December 1978), pp. 22-23 “I. Emulsion Production (
Emulsion preparation andt
ypea)” and No. 18716 (November 1979), p. 648, P. Glafkides, “Physics and Chemistry of Photography”, published by P. Glafkides, C.
hemicet physique photogra
phique, Paul Montel, 1967],
Dahuin Chopsticks ``Photographic Emulsion Chemistry'', published by Focal Press (
G. F. Duffin, Photographic Em
ulsion Chemistry (Focal Pr.
ess, 1966), Zelikman et al., "Manufacture and Coating of Photographic Emulsions," published by Focal Press (V.L. Zeli
kman et al. , Making and Co.
ating Photographic Emulsi
on, Focal Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and. Engineering (Gutoff, Photographic Science
nce and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,4
No. 34,226, No. 4,414,310, No. 4,43
3,048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The efficiency of the present invention is particularly noticeable when emulsions sensitized with gold compounds and sulfur-containing compounds are used.

Additives used in such processes are listed in Research Disclosure No. 17643 and the same No. 1871
6, and the relevant sections 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 descriptions are shown in the table below.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411,987 and US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No. No. 17643, VII-C-G.

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

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters, esters of phosphoric acid or phosphonic acid, benzoic acid esters, amides, Examples include alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives, and hydrocarbons. Further, as a co-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, -Ethoxyethyl acetate, dimethylformamide and the like.

Specific examples of latex dispersion processes, effects, and latexes for impregnation include U.S. Pat. It is described in.

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 rate T1/2 is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T1/2 can be measured according to a method known in the art. For example, Photographic Science and. It can be measured by using a swell meter (swell meter) of the type described in Photogr. Sci. Eng., Vol. 19, No. 2, pp. 124-129, and T1/2 can be measured using a color developer at 30°C. The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is processed for 3 minutes and 15 seconds, and is defined as the time required to reach the film thickness of T1/2.

The membrane swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.

Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula: (
It can be calculated according to the maximum swelling film thickness - film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention includes the above-mentioned RD. N
o. 17643, pages 28-29, and the same No. 187
16-615 left column to right column can be used for development processing.

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 processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound No. 7, No. 3,342,59
No. 9, Schiff base-type compounds described in Research Disclosure No. 14,850 and Research Disclosure No. 15,159, Research Disclosure No. 1
No. 3,924.

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

Example 1 A back layer having the composition shown below was provided to serve as a base for a photosensitive material.

First layer triacetylcellulose 0.1g/m2 Ethylene glycol 0.08g/m2 0.05g/m2 Second layer diacetylcellulose 0.32g/m2 Aerosil 0.
02g/m2 (n)C15H31COOC48H81(n)0.02
g/m2 Poly(methyl methacrylate/styrene) (molar ratio 95:5, average particle size 2.0μ) 0.01 g/m2 Next, each layer of a photosensitive material having the composition shown below was applied in layers to create a multilayer color effect. I created the material.

The numbers corresponding to each component indicate the coating amount in g/m2, and for silver halide, the coating amount in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

1st layer; antihalation layer black colloidal silver silver 0.18 gelatin 0.40 2nd layer; intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) ) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, coefficient of variation with respect to particle size 0.15) Silver 0.55 Sensitizing dye I 6.9×10−5 Sensitizing dye II 1.8×10−5 Sensitizing dye III 3.1×10−4 Sensitizing Dye IV 4.0×10-5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 4th layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion ( Silver iodide 10 mol%, average grain size 0.7μ, average aspect ratio 5.5, average thickness 0.2μ
) Silver 1.0 Sensitizing dye I 5.1 x 10-5 Sensitizing dye II 1.4 x 10-5 Sensitizing dye III 2.3 x 10-4 Sensitizing dye IV 3.0 x 10-5 EX -2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 16 mol%, average grain size 1. 1
μ) Silver 1.60 Sensitizing dye IX 5.4×10−5 Sensitizing dye II 1.4×10−5 Sensitizing dye III 2.4×10−4 Sensitizing dye IV 3.1×10−5 EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (middle layer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 Gelatin 0.80 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 6.0, average thickness 0.15) Silver 0.40 Sensitizing dye V 3.0 x 10-5 Sensitizing dye VI 1.0 x 10-4 Sensitizing dye VII 3.8 x 10 -4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 8th layer (second green feeling Emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0)
．． 7μ, coefficient related to particle size 0.18) Silver 0.80 Sensitizing dye V 2.1×10-5 Sensitizing dye VI 7.0×10-5 Sensitizing dye VII 2.6×10-4 EX-6 0.180 EX-8 0.010 EX-1 0.008 EX-7 0.012 HBS-1 0.160 HBS-4 0.008 Gelatin 1.10 9th layer (3rd green emulsion layer) Musty odor Silver emulsion (silver iodide 12 mol%, average grain size 1.0
μ) Silver 1.2 Sensitizing dye V 3.5×10-5 Sensitizing dye VI 8.0×10-5 Sensitizing dye VII 3.0×10-4 EX-6 0.065 EX-11 0. 030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.74 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.05 EX-5 0.08 HBS-3 0.03 Gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 5.7, average thickness 0.15) Silver 0.24 Sensitizing dye VII 3.5 x 10-4 EX-9 0.85 EX-8 0.12 HBS-1 0.28 Gelatin 1 .28 12th layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.8 μ, coefficient of variation regarding grain size 0.16) Silver 0.
45 Sensitizing dye VII 2.1×10-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 Gelatin 0.46 13th layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide 14 mol%, average grain size 1.3
μ) Silver 0.77 Sensitizing dye VII 2.2×10−4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (first protective layer) Silver iodobromide emulsion (iodide Silver 1 mol%, average particle size 0.07
μ) Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.00 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0. 54 S-1 0.15 S-2 0.05 Gelatin 0.72 The hardener shown in Table 1 was added to make up 2.5% by weight of the total gelatin amount, and samples 1-1 to 1-3 were prepared. Created. Additionally, a surfactant was added.

EX-11; Same as EX-1 except R=H HBS-1; Tricresyl phosphate HBS-2;
Dibutyl phthalate HBS-3; Bis(2-ethylexyl) phthalate sensitizing dye (sample processing) Samples 1-1 to 1-3 were cut into a 24-shot film having a width of 135 mm and the format shown in Figure 1. The porosity V when the film was wound inside the cartridge body was 0.05. Table 2 shows the atmosphere when the film was rolled up.

(Sample evaluation) The samples prepared above were evaluated by the method shown below.

The results are shown in Table 2.

(1) A comparative sample for the number of days when the degree of swelling became constant was stored in the cartridge body, and after a certain number of days, the sample was taken out from the cartridge body and the degree of swelling was determined by the calculation shown below. The degree of swelling was determined by measuring the increment in film thickness when the film was immersed in distilled water for 3 minutes at 25 degrees Celsius using a swelling film thickness meter, and the number of days in which the film remained constant within experimental error was determined.

(2) Number of days for which the characteristic curve becomes constant The sample was stored in the cartridge body, and after a certain number of days, it was exposed to light, developed as described above, and the curve was determined by sensitometry, and the number of days during which the curve was almost the same was determined. .

(3) Blocking resistance With the sample stored in the cartridge body, 40 degrees and 80 degrees
%RH for 3 days, and the blocking properties of the samples were evaluated in three grades: ○, △, and × in order from the sample that did not adhere to each other.

As is clear from Table 2, both blocking resistance and photographic properties were improved by the present invention.

Example 2 A support was prepared in exactly the same manner as in Example-1.

JP-A-2-854, Example 1, Sample 101 on the support.
The reversal color emulsion layer described was coated. However, gelatin dura required A-5. Also, cartridge retraction is 2
The test was carried out at 5 degrees and 50% RH, and was designated as sample 2-1.

Sample 2-1 of the present invention has excellent blocking resistance, and
There was no deterioration in photographic characteristics.

[Brief explanation of the drawing]

FIG. 1(A) is a sectional view of the cartridge body of a small cartridge, and FIG. 1(B) is a drawing seen from the direction of FIG. 1A. FIG. 2 is a diagram when a film reversal phenomenon occurs. (Explanation of symbols) 1: Spool 2: Film 3: Cartridge body 4: Light shielding member 6: Film drawer opening 8: Rib 20: Film cartridge

Claims (4)

[Claims] Claim 1: A photographic film comprising a spool, a photographic film having at least one layer of photosensitive silver halide on a support which is fixed at one end to the spool and wound around the spool in the form of a roll, and a cartridge body. In a photographic light-sensitive material having a porosity V (defined below) of 0.25 or less, the photographic film is wound inside the cartridge body at a humidity of 60% or less, and at least one of the gelatin-containing layers of the photographic film is A silver halide photographic material comprising a vinyl sulfone hardener or a carboxyl group-activated hardener. 2. The photographic light-sensitive material according to claim 1, wherein the photographic light-sensitive material is a color photographic light-sensitive material, and the rolling humidity is 50% or less. Claim 3: 5￣300 of a matting agent with an average particle size of 1￣3μ
The photographic light-sensitive material according to claims 1 and 2, which contains mg/m2 on the back side and has a surface roughness of 0.8 to 3μ. 4. The photographic material according to claims 1 to 3, which contains a slip agent and a fluorine-containing surfactant. V = (B-A) / B where A = (cross-sectional area of the film) = (thickness of the film) * (length of the film) B = (cross-sectional area inside the cartridge) = (cross-sectional area of the cartridge body) - (spool cross-sectional area)