JPH0497335A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the adhesiveness before and after development processing and to facilitate base recovery by forming a transparent magnetic material layer which has >=400 Oe coercive force and forming a binder of at least one kind of acid, alkali or biodecomposable binders. CONSTITUTION:This photographic sensitive material is formed by having photosensitive silver halide emulsion layers on at least one side of the base 15 and has the transparent magnetic material layer 16 on at least one side of the photographic sensitive material. The coercive force of this layer is >=400 Oe and the binder of the transparent magnetic material layer 16 or the binder of at least one layer nearer the base 15 side than the transparent magnetic material layer 16 consists of at least one kind of the acid, alkali or biodecomposable binders. Then, the binder of the transparent magnetic material layer 16 itself or the layer existing on the side nearer the base 15 than the transparent magnetic material layer 16 is easily removed by the acid, alkali or biodecomposable binder, by which the transparent magnetic maternal layer 16 is liberated and removed from the base 15. The base recovery is facilitated in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention has a transparent magnetic layer (or magnetic recording layer),
The present invention also relates to a silver halide photographic material (hereinafter referred to as a photographic material or photosensitive material) which has excellent adhesion before and after development processing, allows recovery of the base, and is free from environmental pollution.

(Prior art) Conventional silver halide photographic materials (hereinafter abbreviated as "sensitized materials") are
It is almost impossible to input various information (for example, date of photography, weather, magnification ratio, number of prints, etc.) at the time of photography with a camera, and it is only possible to input the date of photography optically.

Furthermore, it is completely impossible to input information to the photosensitive material itself during printing, which is a major obstacle to high-speed processing and cost reduction.

Inputting various types of information into the photosensitive material is a very important means for improving the operability and simplifying the camera in the future. As a means for inputting information, the magnetic recording method is important and has been studied in the past because it allows arbitrary output and is inexpensive.

For example, by appropriately selecting the amount and size of the magnetic particles contained in the magnetic recording layer, it is possible to create a magnetic recording layer that has the necessary transparency for the photosensitive material at the time of photographing, and that does not adversely affect the granularity. Providing a support on the back surface of a sensitive material is disclosed in U.S. Pat.
It is described in No. 4302523, etc. Further, a method for inputting signals to the magnetic recording layer is disclosed in World Publication No. 90-4205, World Publication No. 90-04212, etc.

By providing these magnetic recording layers and input/output methods, it is now possible to incorporate various information into the photosensitive material, which was previously difficult to do. It is now possible to input and output information such as conditions, number of reprints, areas to be zoomed in, developing conditions such as mensage, printing conditions, etc. to the magnetic layer of the photosensitive material.

Furthermore, it has the potential to be applied as a signal input/output means for directly outputting images from the photosensitive material to television/video images.

However, these magnetic recording layers are generally made by coating fine particles of ferromagnetic material dispersed in a binder. The binder used at this time is preferably vinyl chloride, vinyl acetate, or polyurethane, which are generally used in video tape recorders. It is certainly possible to simultaneously satisfy excellent adhesive properties and magnetic recording properties by dispersing magnetic fine particles in these binders and applying the mixture to the back layer of a photographic material to provide a magnetic recording layer.

On the other hand, in recent years, industrial waste discharged as a result of people's production activities has caused environmental pollution and has become a major social problem. As a countermeasure against this problem, the base is recovered from the photographic material generated during the manufacturing or processing process and reused, thereby reducing the cost.

Therefore, if the binder used in conventional video tapes is used as the magnetic recording layer of a photographic material, it is impossible to easily remove the magnetic layer from the base of the photographic material, and the material is discarded as industrial waste. Photographic materials must be handled as such, which causes environmental pollution and increases costs.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a photographic material having an excellent transparent magnetic recording layer that does not impair photographic performance. A second object of the present invention is to provide a photographic material that has excellent adhesion before and after development and allows easy recovery of the base.

(Means for Solving the Problems) These objects of the present invention provide a photographic material T4 having a light-sensitive silver halide emulsion layer on at least one side of the support.
The photographic light-sensitive material has a transparent magnetic layer on at least one side and has a coercive force of 400 Oe or more, and a binder for the transparent magnetic layer or at least one binder layer closer to the support than the transparent magnetic layer. This was achieved using a photographic material characterized by comprising at least one of acid, alkali, and biodegradable binders.

In order to remove the transparent magnetic layer from the support, the present invention uses the binder of the transparent magnetic layer itself, or the layers present on the support side of the transparent magnetic layer (for example, an intermediate layer, an antistatic layer, an undercoat layer, etc.). ) can be easily removed with an acid, alkali or biodegradable binder to liberate and remove the magnetic layer from the support, thereby achieving the effects of the present invention.

The present invention will be described in detail below.

First, the magnetic material used in the transparent magnetic material of the present invention will be described.

The ferromagnetic fine powder used in the transparent magnetic layer of the present invention includes ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder, and ferromagnetic alloy powder. , barium ferrite, etc. can be used.

An example of a ferromagnetic alloy powder is one in which the metal content is 75 wt% or more, and 80 wt% or more of the metal content is at least one ferromagnetic metal or alloy (Fe, Co, Ni, Fe-
Co, Fe-N15Co-Ni.

Co-Fe-Ni, etc.), and the metal content is 20wt%
Other components (AffiXS i, S, Sc, Ti,
V, Cr, Mn, Cu, Zn, Y, Mo.

Rh5Pd, Ag, Sn, Sb, B, Ba, Ta.

W, Re5Au, Hg, Pd, P, La, Ce.

Pr, Nd, Te, Bi, etc.) can be mentioned. Further, the ferromagnetic metal component may contain a small amount of water, hydroxide, or oxide.

Methods for producing these ferromagnetic powders are known, and the ferromagnetic powder used in the present invention can also be produced according to known methods.

The shape and size of the ferromagnetic powder are not particularly limited and can be widely used. The shape may be needle-like, rice-grain-like, spherical, cubic, plate-like, etc., but needle-like and plate-like are preferable from the viewpoint of electromagnetic conversion characteristics. There are no particular restrictions on crystallite size or non-surface area, but if the crystallite size is 400 Å or less and S RET is 20
i/g or more is preferable, and 30 nτ/g or more is particularly preferable. The pH 1 surface treatment of ferromagnetic powder can be used without particular restrictions (the surface may be treated with a substance containing elements such as titanium, silicon, aluminum, etc., or with a substance containing elements such as carboxylic acid,
may be treated with an organic compound such as an adsorbent compound having a nitrogen-containing heterocycle such as sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester, hensitriazole, etc.), and the preferred pH range is 5 to 10. In the case of zero ferromagnetic iron oxide fine powder, it can be used without any particular restriction on the ratio of divalent iron/trivalent iron. Regarding these magnetic recording layers, Japanese Patent Application Laid-open Nos. 47-32812 and 53-10960
It is stated in No. 4.

The content of ferromagnetic fine powder per 1M of transparent support is 4
X I O-'~3g, preferably 104-1g, more preferably 4X10-'~4X10-'g.

Next, the acid/alkali or biodegradable binder used in the present invention will be described.

First, as an acid- or alkali-decomposable binder, its solubility rapidly improves when treated for a long time (1 hour or more) under acidic or alkaline conditions (generally in an aqueous solution or a water-miscible organic solvent), and it is released from the support. It is not particularly limited as long as it can be chemically decomposed and released from the support under acidic or alkaline conditions.

Preferred among these binders are cellulose derivatives IJ (monoacetylcellulose, diacetylcellulose, propionylcellulose, hydroxyethylcellulose, methylcellulose, etc.) and poly(meth)acrylic acid esters! ! (For example, as ester residues hydroxyalkyl or allyl groups (e.g. hydroxyethyl, hydroxyethylphenyl), carboxyalkyl or allyl groups (e.g. carboxyethyl, carboxyphenyl etc.), aminoalkyl or allyl groups (e.g. aminoethyl, (aminoethylphenyl, etc.), poly(
Examples include meth)acrylamides (eg, poly(N,N-dihydroxyethylacrylamide)).

The next most preferred biodegradable binder is poly (
Examples include poly(3-hydroxyalkanoate), polycaprolactone, starch, starch-containing polymers (polyethylene, polypropylene), and more preferred are poly(3-hydroxyvalate), poly(3-hydroxybutyrate), poly( 4-hydroxybutyrate), starch-containing polyethylene, and starch-containing polypropylene.

These are described in detail in Biodegradable Plastics - Overseas Employment Survey Report (published by the Bioindustry Association of Japan, June 1989).

When removing the magnetic layer comprising the acid/alkali or biodegradable binder of the present invention or the binder layer forming one layer on the support side from the photographic material and recovering the support, the solubility and decomposition of the binder In order to promote the properties, it is preferable to cut the photographic material into fine pieces in advance, and it is also preferable to appropriately heat, stir or blow air into the processing bath for decomposition. At this time, when processing a photographic material containing an acid, alkali or biodegradable binder, a processing liquid is generally used, but the solvent used is not particularly limited, and for example, water,
Alcohols (methanol, ethanol, propatool, etc.) and ketones (acetone, methyl ethyl ketone, acetophenone, etc.) are preferred, and mixed solvents thereof may also be used.

In addition, the compounds imparting acidity/alkalinity used in the present invention are preferably acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and acetic acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and ammonia. Among these, hydrochloric acid, sulfuric acid, sodium hydroxide, and potassium hydroxide are particularly preferred.

Furthermore, a method for decomposing a photosensitive material using a biodegradable binder will be described.

In the present invention, the recovered photosensitive material is first cut into small pieces, and if there is a gelatin emulsion, it is treated with a gelatin-degrading enzyme (for example, amylase) to remove the gelatin emulsion layer, and then activated sludge is used to remove the magnetic recording layer. It is preferable to decompose it inside. The activated sludge used at this time is not particularly limited, but for example, standard activated sludge from the Chemical Safety Center (CBC) of the Japan Chemical Inspection Association can be used.

These can be decomposed faster by drawing in air and keeping the temperature between 20 and 35°C.

The longer the time required to decompose the biodegradable polymer of the present invention by the above method, the better; however, in the present invention, in consideration of recovery efficiency, it is from half a day to 20 days, more preferably from 1 day to 7 days.

A crosslinking agent may be added to the magnetic layer of the present invention made of an acid, alkali, or biodegradable binder or to the constituent layer on the support side of the magnetic layer, for example, an epoxy-based, isocyanate-based, or silane coupling-based crosslinking agent. agents can be used.

The thickness of the magnetic layer is 0.1n to 10p1, preferably 0.
It is 2-5μ, more preferably 0.5-3n.

The magnetic recording layer of the present invention is preferably provided on the back surface of the photosensitive material. The magnetic recording layer can be provided on the back surface of the transparent support by coating or printing.

Further, a transparent support having a magnetic recording layer is prepared by co-casting a solution of the degradable polymer of the present invention in which magnetized particles are dispersed and a solution of a polymer for forming a transparent support (for example, triacetyl cellulose). In this case, it is preferred that the two types of polymers have substantially the same composition.

The magnetic recording layer may also have functions such as improving lubricity, curl iFI knots, preventing static electricity, and preventing adhesion, or another functional layer may be provided to provide these functions. If necessary, a protective layer may be provided adjacent to the magnetic recording layer to improve scratch resistance.

By calendering the back surface of the transparent support having the magnetic recording layer, smoothness can be improved, and the S/N ratio of the magnetic signal can be improved. In this case, it is preferable to apply a photosensitive layer on the transparent support after calendering.

Methods for applying the magnetic recording layer onto the support include air doctor coating, blade coating, air knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating, kiss coating, cast coating, and spray coating. can be used, and other methods are also possible, and detailed explanations of these can be found in R Coating Engineering, pages 1253-277, published by Asakura Shoten.
(published on March 20, 1972).

By such a method, the magnetic layer coated on the support is immediately subjected to a treatment to orient the magnetic powder in the layer while drying, if necessary, and then the formed magnetic layer is dried. The conveying speed of the support at this time is usually 10 m/min to 500 m/min.
m/min and the drying temperature is 20°C to 120°C.
controlled by The magnetic recording medium of the present invention is manufactured by subjecting the magnetic recording medium to surface smoothing if necessary. These are, for example, Japanese Patent Publication No. 40-23625, Japanese Patent Publication No. 39-28
No. 368, US-Japan Patent No. 3,473,960, and the like. Furthermore, the method disclosed in Japanese Patent Publication No. 41-13181 is considered to be a basic and important technique in this field.

In order to reduce errors in input/output signals of the magnetic recording layer of the present invention, it is preferable to include a slipping agent in the outermost layer of the magnetic recording layer.

These slip agents are not particularly limited, but are preferably those that do not deteriorate photographic properties or cause trouble in the manufacturing process.

These lubricants are disclosed in U.S. Patent No. 4,275.146, U.S. Pat.
No. 58-90633, No. 52-129520, etc.

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

Compound example S-1co.

(Si-0), CH3 S-2CH3CH.

(S i -OS i -0) q.

((jlzt'iOCH,CHztnHC)+3S
3 C+sH:++C00C+6H,13
S -4(n)C1sH3,C00CaoHs+ (n
)S 5 (n)CzJssCOOCso
H+o+(n)S 6 (iso)C+J
ssCOOCsJiq(iso)S-7(iso)C
+JxsCOOC4oHs+(n)S 8
Coo-Cz4H4q(iso)(CHz)s Coo-C1sH4w(iso) (iso)CzJssCOO(CHz) 40cOcB
Hss(iso)S-10 Erucic acid amide S 11 Cs5HitCOOH5-12 Liquid paraffin Furthermore, in the present invention, it is preferable that a so-called matting agent be included in the outermost layer of the magnetic layer in order to improve the adhesion resistance, and its particle size is preferably 1 to 3μ; if it is too large, errors in magnetic properties will occur, and if it is too slim, the adhesion resistance will be poor.

By containing these matting agents, it is preferable that the average height of the convex portions on the surface of the magnetic layer is 0.8 to 3 On.
No. 7052, No. 62-14647, Special Publication No. 4B-59
No. 66, No. 39-11501, No. 46-1796,
Spherical or amorphous inorganic or organic matting agents described in JP-A-47-18004, JP-A-55-33747, JP-A-53-7231, and JP-A-60-153722 are preferred. Further, the amount of the matting agent used in the present invention is 5 to 30
0+ng/rrf is preferable, more preferably 10-3
It is 00■/po.

Specific examples of the matting agent are shown below, but the matting agent is not limited thereto.

CH3 (CL-ChT port average particle size 2.1pmCO
OCH.

CL Hs M-7 (under CHz CHa - Average particle size 2.4n 2, 2n Average particle size 2.2n M-8 Silica (spherical) N2.4nM-9
(Amorphous)〃2.3μ Other constituent factors of the present invention will be described below.

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 (for example, triacetyl, propionyl, butanoyl, acetylpropionyl acetate, etc.), Polyamide, U.S. Patent No. 3
, 023, 101, the polycarbonate described in Japanese Patent Publication No. 1973
8-40414 etc. (e.g. polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene, polysulfone, polyarylate, polyetherimide, etc. Preferred are triacetylcellulose and polyethylene terephthalate.

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

These supports vary depending on the type of polymer, but the thickness is 1
It can be used depending on the purpose, ranging from a sheet about the size of a cabinet to a thin film of about 20μ, but 50μ to 30μ is commonly used.
The thickness range is 0μ.

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 haze color, preventing light piping, and preventing halation.

In order to firmly adhere photographic layers (e.g., photosensitive silver halide emulsion layer, intermediate layer, filter layer, transparent magnetic layer and conductive layer of the present invention, etc.) to these supports 1-, chemical treatment and mechanical treatment are performed. 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 and bonded. Alternatively, a method may be used in which a subbing layer is provided and a photographic emulsion layer is coated on the undercoat layer after the above surface treatment or without any surface treatment.

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-3-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 SiO□ and Ti1t 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 using generally well-known coating methods such as dip coating method, air knife coating method,
Curtain coat method, roller coat method, wire bar code method, gravure coat method, or U.S. Patent No. 2,68
Coating can be carried out by the extrusion coating method using a hopper as described in the specification of No. 1,294.

If necessary, U.S. Patent No. 2.761.791, 3.
508 947, 2,941.898, and 352
6 Specification No. 528, “Coating Engineering” by Yuji Harasaki
Two or more layers can be coated simultaneously by the method described on page 253 (published by Asakura Shoten, 1973).

The sensitive material of the present invention is composed of a silver halide emulsion layer, a hack layer, a protective layer, an intermediate layer, an antihalation layer, etc., and these are mainly used in the 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; II 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, poly7IJ/l[F ester, rosin, etc.] If necessary, a mixture of two or more of these colloids may 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 surfactant sides are disclosed in JP-A-49-10722, British Patent Box No. 1.330,356, and JP-A-53-84.
No. 712, No. 54-14224, No. 5 (1-1132)
No. 21, U.S. Patent No. 4,335°201, U.S. Patent No. 4,34
No. 7,308, British Patent Box No. 1.417,915, Special Publication No. 52-26687, No. 57-26719, No. 59
-38573, JP-A-55-149938, JP-A No. 54
-48520, 54-14224, 5B-20
No. 0235, No. 57-146248, No. 581965
No. 44, British Patent Box 1,439.402, etc.

Preferred specific examples of these are described below.

1-1' CsF+tSOJ 1 2 CJ'+5COONa1-3
C.J.

CsP + qsOJ-CIl□C00XC3H? (:eF+, sO□N-4:CIIzCHCHzO)
r(C!Izh asO3Nai1 5Hq CsF + , 5OzN (C)IzCIhOMC1h
asOJaCsHt O CJ+tSOJCHzCHzO-P-ONaNa ■-7 C++F+vCHzCH*0OC-CHzCsH+JO
C-CH-3OJa 1-8 C13N CsF + ysO□NCH2CII zcHz (O
CR2CH2) J-CH2COOθC11°C+J3zC00(CHzC11□Oh if CHz-CH
-CJ)r(CHzC1120 卜, HH C@F, 7SOZNCH1CH2N-C1131eut C+JzJ(CthCllzO) +□Hr-11c,
. H21 CsF1. ．． 5OJ(CHzCHzO)-+bH 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 example N I C++l (!5COOiCHzCHzO
'P J 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, for example, a surface protective layer, an emulsion layer, an intermediate layer, Examples include an undercoat layer and a bank 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-) Limethylolpropane etc. JP-A-54-896
Polyomal compounds such as those shown in No. 26 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 applied for other purposes, such as emulsion dispersion, enhancement, and other improvements in photographic properties.

Also, 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. Furthermore, higher fatty acid esters are also effective.

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).

Particularly representative examples of silver halide color photographic materials preferred in the present invention include color reversal films and color halide films.

In particular, a general purpose 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 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 sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the photosensitive layer is generally a unit photosensitive layer. 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 order of installation may be reversed, or the order of installation 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, British Patent No. 923.045, Japanese Patent Application Laid-open No. 57112751, and Japanese Patent Application Publication No. 1986-62.
-200350, 62-206541, 62-
No. 206543, No. 56-25738, No. 62-63
No. 936, No. 59-202464, Special Publication No. 55-34
No. 932 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 about 0 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) Th17643
(December 1978), pp. 22-23, “1. Emulsion preparation and
8716 (November 1979), 648 pages, Graphic ``Physics and Chemistry of Photography'', published by Paul Montell (P, GIafkidesCh
emicet Ph1sique Photogr
aphique, Paul) lontel,
1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G.P. Duffin, Photo
graphicεa+ulsion Chea+1sL
ry (Focal Press, 1966))
, Zelikman et al. [Production and coating of photographic emulsions], published by Focal Press (ν, L. Zelikman et al.
,,Makingand Coating Photo
graphic Emulsion, Focal Pr
ess.

(1964) and others.

U.S. Patent No. 3,574,628, U.S. Patent No. 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 Gutoff, Photographic Science and Engineering.
nce and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,4
34゜226, 4,414,310, 4,43
3. No. 048, No. 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

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 a process are described in Research Disclosure 17643 and 18716, 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.

1111IJ! J! -LFLL7643R
D18716-1 Chemical sensitizer page 23 64
8@Right column 2 Sensitivity enhancer Same as above 3
Spectral enhancers, pages 23-24, page 648, right column - supersensitizers, page 649, right column 4 brighteners
Page 24 5 Antifouling agent Pages 24-25 Page 649 Right column ~
and stabilizer 6 light absorber, fu pages 25-26 page 649 right column ~
Ilter dye, page 650 left column UV absorber 7 Stain inhibitor page 25 right column page 650 left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column lO binder page 26 Same as above If Plasticizer, lubricant page 27 page 650 right column 12 Coating aid,
Pages 26-27 Page 650 Right Column Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, reacting with formaldehyde as described in U.S. Pat. No. 4,411,987 and No. 4,435,503 It is preferable to add a compound that can be immobilized to the photosensitive material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) m17643, ■-C to 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 point 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, and amino acids.゛, alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives,
Examples include hydrocarbons. In addition, as an auxiliary solvent,
Boiling point is about 30℃ or higher, preferably 50℃ or higher and about 160℃
The following organic solvents can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. Are listed.

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 T% is preferably 30 seconds or less.

The film thickness can be measured by ejecting the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate Tz can be measured according to a method known in the art. For example, Photography Inc. Science and Engineering (A. Green) et al.
Photogr, Sci, 14 pagesg, ), vol. 19, 2
It can be measured by using a swellometer (swelling film) of the type described in No. 1, pp. 124-129, and T'A is the maximum swollen film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. The saturation film thickness is defined as 90% of T'A, and is defined as the time required to reach the film thickness of T'A.

The film swelling rate Tz 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 swelling film thickness under the conditions mentioned above.
It can be calculated according to (maximum swelling M thickness - film thickness) / HQ thickness.

The color photographic material according to the present invention is described in the aforementioned RD, No. 17643, pages 28-29, and No. 18716, No. 6.
15. Development processing can be carried out by the usual methods described in the left column to right column.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up 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
3.942.

Next, a preferable form of the photosensitive material of the present invention is a roll-shaped film that allows signals to be easily input to the transparent magnetic recording layer when the film is transported in a camera or printer. In this roll-shaped film, the image exposure section 1
The area of the piece is 350 mr (more than 1200 mrrr), and the magnetic information recordable space is
It is preferable that the area is 15% or more of the area of the piece. Specifically, it is preferable that the number of perforations per screen is less than 135 formats. It is particularly preferable that the number of perforations per frame is 4 or more.

Information can also be optically input into the magnetic information recordable space using a light emitter such as an LED. It is also preferable to input the magnetic information and the optical vibration fμ in the same space. Magnetic recording format is world public 9O
- (It is preferable to follow the method disclosed in No. 14205.

When the photosensitive material of the present invention is used in the form of a roll, it is preferably stored in a cartridge.The most common cartridge is the current 135 format cartridge. Other Cartrits proposed in the following patents can also be used. (Jitsukai Showa 5111-6
No. 7329, JP-A No. 181035, JP-A-58
-182634, Utility Model Application No. 195236/1982, U.S. Patent No. 4221479, Japanese Patent Application No. 57785/1983, Japanese Patent Application No. 183344/1983, Japanese Patent Application No. 325638/1983
Japanese Patent Application No. 121862, Japanese Patent Application No. 125362, Japanese Patent Application No. 1-30246, Japanese Patent Application No. 1-20222, Japanese Patent Application No. 1-21863, Japanese Patent Application No. 1-37181, Japanese Patent Application No. 1999 -33108, Japanese Patent Application No. 1-85198, Japanese Patent Application No. 1
No. 172595, Japanese Patent Application No. 1-172594, Japanese Patent Application No. 1
(No. 172,593, US Pat. No. 4,846,418, US Pat. No. 4,848,693, US Pat. No. 4,832,275) Particularly preferred are cartridges having means for controlling the attitude of the cartridge within the camera. (Patent application Hei 1-2148
No. 95) Next, the cartridge used in the present invention is mainly composed of synthetic plastic.

In molding the plastics of the present invention, a plasticizer is mixed with the plastics as necessary. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl tucrate, diethyl sebacate, methyl amyl ketone, nitrohenzene, γ-valerolactone,
Representative examples include di-n-octyl succifutate, 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 1, Teflon, 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. Antistatic agents are not particularly limited, but include carbon blanks, metal oxide particles, nonions, anions, cations, hetain surfactants, nonions, anions,
Cationic and betaine polymers can be preferably used. These antistatic cartridges are described in Japanese Patent Application Laid-open Nos. 312537 and 312538.

Cartries and jis are usually manufactured using plastic mixed with carbon blanks and 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. Furthermore, in current cartridges, the tip of the spool that is engaged with the film drive section of the camera protrudes, which is an impediment to miniaturization of cameras, so it is desirable to eliminate this portion. As a result of this, currently approximately 35
d The volume of some cartridges can be reduced. The volume of the cartridge case is preferably 3 pci or less, preferably 251 cd or less, more preferably 20 cd or less. The weight of the plastic used for the cartridge and cartridge case is Ig or more and 25g or less, preferably 5g or more and 15g or less.

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

In the case of the cartridge containing the 135 color photosensitive material according to the present invention, the total weight of the plastic used for the cartridge and the cartridge case is usually 1 g or more and 25 g or less, preferably 5 g or more and 15 g or less.

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

The cartridge of the present invention is not particularly limited in its form, but is preferably compatible with commercially available cameras. Furthermore, the present invention may be used in a new camera that is compatible with Cartlitz and incorporates the color photosensitive material of the present invention. Specific examples of these cartridges are shown in FIG. 1 (further, the internal structure is shown in FIGS. 2 to 4, and the film magnetic track is shown in FIG. 5).

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

Example 1 l-1) Creation of hese Co-casting of a tope solution and cellulose triacetate dope solution consisting of the binder shown in Table 1 in which r-FezO* (specific surface area 25n (/g manufactured by Pfizer Inc. (USA)) was dispersed. Then, thickness 2
A film base having a total thickness of 122μ with a transparent magnetic recording layer of μ was prepared.

The coating pattern of r −F e=03 was 0.14 g/m. Note that sample 1-1 (control) is r-FezOx
It does not contain.

A coating layer having the composition shown below was provided on this hese to prepare a hese for photosensitive materials. Note that the surface having the magnetic recording layer was used as a hack layer.

(Back layer composition) Layer - Cellulose triacetate o, tg/m Ethylene glycol 0.08SnO□/5b20J/5
i02 (weight ratio 0.290/10/1, average particle size 0, 12 μm) 2nd layer cellulose diacetate Q, 32 g/m completed Rosil 0.02 Compound example S-40,01 M-50,04 Co( "D to

1-2) Preparation of photosensitive material After applying corona bi-electric treatment to the side opposite to the hack layer of the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers. A sample of a multilayer color photosensitive material was prepared.

(Photosensitive layer composition) JP-A-2-93641 Example IG A photosensitive layer was prepared in exactly the same manner as the photosensitive layer described here.

(Processing of Sample) The sample was cut into a 24-shot film with a formant of 135 ts width as shown in FIG. 1.

These samples were developed as follows.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe Fixed 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene 1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g Potassium iodide hydroxylamine sulfate 4-(N-ethyl-N-β hydroxyethylamino) Add 2-methylaniline sulfate solution 1.3wg 2.4g 4.5g 1.01 pH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100, 0g Ethylenediaminetetraacetic acid disodium salt Ammonium nitrate Add water and add 10゜50゜10゜1゜H6 Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 1,0g 4, 0g ammonium thiosulfate aqueous solution (70% > 175.(1++f
fi Sodium bisulfite 4.6g Add water 1.01pi (6,6 Stable liquid formalin (40%) 2.0w + 1
Add 0.3 g of polyoxoethylene-p-monononylphenyl ether (average degree of polymerization 10) to 1.0 liters of water (1) Transmittance. The total light transmittance was measured.

Sample 1-1 (control) was set as 100, and relative values relative to that were shown in Table 1 as relative transmittance.

Note that the total light transmittance was measured according to ASTM D-1003.

(2) Adhesion The completed sample was heated for 2 hours in an atmosphere of 25°C and 50% RH.
After leaving it for a week, an adhesion test was conducted using the method described below. The surface tested here is the hex side.

(b) Dry film adhesion test method On the surface to be tested, make 36 squares by making 7 cuts at 5 mm intervals vertically and horizontally, and apply adhesive tape (
For example, attach knit tape (manufactured by Nitto Electric Industry ■),
Quickly draw in 180° direction. In this method, if the unstripped portion is 90% or more, it is graded A, if it is 60% or more, it is graded B, and if it is less than 60%, it is graded 0. Adhesive strength sufficient for practical use as a photographic material is one that is classified as grade A of the above three-level evaluation. Testing was done on the hack side.

(b) Wet film adhesion test method At each stage of development, fixation, and water washing, scratch the film at the X mark using an iron pen in the processing solution, and then scratch it firmly with the tip of your finger.
Adhesive strength was evaluated based on the maximum peeling 11 that occurred along the x line when rubbed twice.

A case where the constituent layers do not peel off more than scratches is given as A grade, a case where the maximum peeling is within 5 dragons is graded as B grade, and other cases as 0 grade.

Adhesive strength sufficient for practical use as a photographic material is one classified as B or higher, preferably grade A, of the above three-level evaluation. The evaluation was performed on the Hetsuku side.

(3) Coercive force The coercive force was measured from the magnetic recording layer side.

(4) Evaluation of output errors in magnetic recording Using the signal manual method disclosed in the above-mentioned World Publication No. 90-04205, output operations were performed 500 times from the bank side to the magnetic material, and the error occurred. It shows the number of times. Note that this output error evaluation was also performed for sensitive materials that were subjected to magnetic input and then developed.

(5) Base recovery ability After removing the emulsion layer side of the undeveloped photographic material with an aqueous sodium hyponitrite solution, it was cut into small pieces (1 mm x 11 mm).
0. IN hydrochloric acid aqueous solution or 0.1N sodium hydroxide aqueous solution?
8 solution or activated sludge aqueous solution (by blowing air) was left for 20 hours at room temperature with stirring. After thoroughly washing the treatment solution with water, the resulting base was dried to create a base with a thickness of 1 um again, and its transmittance was measured.

The relative i3 transmittance was determined by assuming that the control sample without a magnetic layer had a transmittance of 100%.

The lower the transmittance, the worse the base recovery performance.

Comparative compound A; Cellulose triacetate B; Vinyl chloride/butyl acetate copolymer Samples 1-2 to 1-4 using the binder of the present invention as shown in Table 1
was excellent in i3 pass rate, adhesion, coercive force, magnetic output error, and base recovery performance. On the other hand, samples 1-5 to 1-10 using comparative compounds were significantly inferior in terms of base recovery.

From the above, it can be seen that the present invention is superior to conventional techniques.

Example 2 2-1) Preparation of support Cellulose triacetate dope was cast to a thickness of 105 μm.
created a film base.

The following hack layer was applied to one side (hack layer) of this base.

(a) Hack first layer binder Listed in Table 2 (0.1 g/m) Sn (Jt/
5b203/5rOz particles (molar ratio 90/] 0/1, average particle size o, 12 μm) o.

(b) Pack second layer Butyl acetate/vinyl chloride polymer (50150) 2 Cobalt tope iron oxide mold powder (However, sample 2-1 (control) does not contain cobalt tope iron oxide fine powder) 0.20 g /n((c)Pack 3rd layer polymethyl meccrylate 0.
32g/m Aerosil 0.02 Poly (methyl mecrylate/divinyl styrene) (molar ratio 95:5) (average particle size 2.2μm) 0.04 C+sHs+COOCC00C+ 2g/n (5g/rrf 0,005 2-2) Preparation of Material Layer A photosensitive material layer was applied to the layer on the opposite side of the hack of the support prepared in 2-1) in exactly the same manner as in Example 1-2).

The prepared samples were evaluated as shown in Table 2.

As can be seen from Table 2, samples 2-2 to 2-24 of the present invention were satisfied in all respects. On the other hand, comparative sample 2
-5 to 2-10 were thick (inferior) in terms of base recovery.

Example 3 A support and a back surface were prepared in exactly the same manner as in Example 2-1 except that the thickness of the cellulose triacetate was changed to 115 μm. On the surface opposite to the hack surface of the support, JP-A No. 2-854 was applied. Example 1 A reversal color emulsion layer as described in Sample 101 was coated. However, the fluorine-containing surfactant used in Example 2 was added to the outermost layer (protective layer) of the emulsion layer in exactly the same manner.

The development process used was CR-56 color reversal process manufactured by Fuji Photo Film Co., Ltd.

Among the obtained samples 3-1 to 3-10, sample 3 of the present invention
-2 to 3-4 were excellent in all of permeability, adhesiveness, coercive force, magnetic properties, and base recovery.

On the other hand, comparative samples 3-5 to 3-10 could not satisfy all the above performance points.

[Brief explanation of drawings]

Fig. 1 is a perspective view of a photographic film cartridge according to the present invention, the second lever is a plane view showing the state of the leading end of the photographic film, Fig. 3 is a sectional view of the cartridge, and Fig. 4 shows the inside of the cartridge. FIG. Also, Figure 5 15-1)
, (5-2)) are plane and cross-sectional views of the magnetic recording track layer. [Explanation of symbols] 1... Photographic film cartridge 2... Spool 3... Photographic film 4... Patrone main body 5... Film drawer lower... Perforation solenoid 8... Raised portion 9...・Protrusion 10 ・ Hole 11 ・ ・ Notch 12 ・ Film extraction passage 13 ・ Step 14 ・ Emulsion constituent layer 15 ・ Support 16 ・ Transparent magnetic layer 17...Antistatic layer + scratch resistant layer + lubricating layer 18...1
Frame 19...Perforation 1-0~t-1...Magnetic recording trunk f00~f29
...

Claims (7)

[Claims] (1) In a silver halide photographic material having a light-sensitive silver halide emulsion layer on at least one side of the support,
The photographic light-sensitive material has a transparent magnetic layer on at least one side and has a coercive force of 400 Oe or more, and the binder of the transparent magnetic layer or the binder of at least one layer closer to the support than the transparent magnetic layer is an acidic material. 1. A silver halide photographic material comprising at least one of , an alkali binder, and a biodegradable binder. (2) The silver halide photographic material according to claim 1, wherein the photographic material is a color photographic material. (3) The ferromagnetic material used in the transparent magnetic layer is ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic alloy fine powder, ferromagnetic The silver halide photographic material according to claims 1 and 2, which is a fine metal powder and barium ferrite. (4) The silver halide photographic material according to claims 2 and 3, wherein the acid- or alkali-decomposable binder is a polymer having an ionic dissociative group or a derivative thereof. (5) The biodegradable binder is 3-hydroxyvalate,
The photographic light-sensitive material according to claims 2 and 3, which is a polymer selected from a copolymer mainly composed of 4-hydroxybutyrate or a starch-containing polyethylene. (6) 5 to 300 mg of a matting agent with an average particle size of 1 to 3 mm
/m^2 Contained on the back side and has a surface roughness of 0.8 to 3.
The silver halide photographic material according to claims 4 and 5, which has a particle diameter of 0 μm. (7) The silver halide photographic material according to claim 6, which contains a slip agent and a fluorine-containing surfactant.