JPH0473744A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the material having a magnetic material layer which is excellent in flaw resistance and wear resistance by specifying the coercive force of the transparent magnetic material layeeyr to a specific value or above and using a radiation curing resin for the binder of the transparent magnetic material layer. CONSTITUTION:The coercive force of the transparent magnetic material layeeyr of this photographic sensitive material is specified to >= 400Oe and the radiation curing resin is used as the binder of the transparent magnetic material layer. Ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metallic powder, ferromagnetic alloy powder, barium ferrite, etc., are usable as the ferromagnetic fine powder to be used for the transparent magnetic material layer. An origoacrylate and monofunctional and multifunctional acrylate monomers, etc., are used alone or in combination as the radiation curing resin. Thereby, the flaw resistance and wear resistance of the magnetic material layer provided on the photosensitive material are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material having a transparent magnetic layer (hereinafter referred to as a photographic material, a photosensitive material, or a photosensitive material). More specifically, the present invention relates to a photographic material having a transparent magnetic layer with good abrasion resistance and scratch resistance.

(Prior art) By appropriately selecting the amount, size, etc. of magnetic particles contained in a magnetic layer, it is possible to have the transparency required for a silver halide photographic light-sensitive material without adversely affecting the granularity. Providing a magnetic layer on the back side of a silver halide photographic material having a transparent support is disclosed in US Pat. Nos. 378,294, 4,279,945, and 4,302,523.

In addition, various magnetic binders have been known so far, but when applied to the photosensitive material of the present invention,
The following problem occurred. Before being processed, photographic materials rub against various substances.For example, films rub against each other between cartridges, rub against a pressure plate inside a camera, and rub against rollers inside a processing machine. There is a problem in that the magnetic layer provided on the photosensitive material is easily damaged due to rubbing, and the scratches impair highly accurate magnetic recording and image recording. There is also the problem that the magnetic layer wears out due to friction with the magnetic head, causing clogging of the magnetic head and deteriorating the magnetic properties.There are no known single-layer binders that satisfy both conditions. There wasn't.

(Problems to be Solved by the Invention) An object of the present invention is to provide a photographic material having a magnetic layer with excellent scratch resistance and abrasion resistance.

(Means for Solving the Problems) A photographic light-sensitive material having a light-sensitive silver halide emulsion layer on at least one side of a support, which has at least one transparent magnetic layer on at least one side of the photographic light-sensitive material. This is achieved by a composition having a coercive force of 400 Oe or more, and in which the binder of the transparent magnetic layer is made of a radiation-curable resin, particularly preferably by a composition in which the radiation-curable resin contains at least urethane acrylate and polyfunctional acrylate. It was done.

The present invention will be explained in detail below.

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

An example of a ferromagnetic metal powder is one in which the metal content is 75 wt% or more, and 80@t% or more of the metal content is at least one ferromagnetic metal or alloy (FeC).

Ni, Fe-Co, Fe-N+, Co-NiCo-Fe
-Ni, etc.), and other components (AI, Si, S, Sc) with less than 20 wt% of the metal content.

Ti, V, Cr, Mn, Cu, Zn, Y, M.

Rh, Pd, Ag, Sn, Sb, B, Ba, Ta.

W, Re, Au, Hg, Pb, 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 is not particularly limited and can be used in a wide range of six shapes, including needles, rice grains, spheres, cubes, and plates, but needles and plates are preferred from the viewpoint of electromagnetic characteristics. There are no particular restrictions on the crystallite size or non-surface area, but the crystallite size is 400A or less, and the S BET is 20A.
30 n(/g LLI or higher) is preferable, and 30 n(/g LLI is particularly preferable.) The pH 1 surface treatment of ferromagnetic powder can be used without particular restrictions (the surface treatment is performed with a substance containing elements such as titanium, silicon, aluminum, etc.). Alternatively, it may be treated with an organic compound such as an adsorbent compound having a nitrogen-containing heterocycle such as carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester, benzotriazole, etc. Preferred pH range In the case of 0 ferromagnetic iron oxide fine powder in which is 5 to 10, it can be used without any particular restriction on the ratio of divalent iron/trivalent iron.

The content of ferromagnetic fine powder per transparent support 1 is 4
X 10-' to 3 g, preferably 104 to 1 g, more preferably 4X10-'' to 10-'g.

Next, the radiation-curable resin used in the present invention is not particularly limited, but preferred are the following general formulas (AI), (A-I
t), (A-m), (A-IV), etc. refers to oligomers modified by reacting acrylic groups with oligoacrylate molecular weights of about 200 to 10,000), monofunctional, and polyfunctional. Acrylate monomers may be used alone or in combination.

General formula % Formula %) In the above general formulas (A-1) to (A-IV), A represents an acrylic IE (CIIZCIICO-) or a methacrylic group (CHIC(C)13)Co-), and E represents an ester bond. U is an n-valent oligomer having a urethane bond, P is an n-valent oligomer containing an alkylene oxide group (e.g., ethylene oxide group, propylene oxide group, etc.), and G is a compound containing an epoxy group. Each represents an n-valent oligomer to be derived. Further, n represents an integer of 1 or more.

A particularly preferred radiation-curable resin is a mixture containing at least one urethane acrylate (acrylate containing a urethane group) and a polyfunctional acrylate.

More details will be given below.

A particularly preferred first component of the radiation-curable resin used in the binder of the magnetic layer of the present invention is urethane acrylate. Urethane acrylates may be monomers, oligomers or polymers, or mixtures thereof. Urethane acrylate is a well-known substance that has been used in radiation-curable resins. Urethane acrylates easily form crosslinks when exposed to appropriate radiation. In a preferred embodiment of the invention, urethane acrylates are produced by reacting diisocyanates with polyols and further reacting with hydroxyacrylates or hydroxymethacrylates. Examples of the diisocyanate include, but are not limited to, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, and the like. More preferably, the diisocyanate is an aliphatic or alicyclic diisocyanate, such as hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, isophorone diisocyanate, and the like.

Examples of the polyol include, but are not limited to, butanediol, neopentyl glycol, ethoxylated bisphenol A1, ethoxylated bisphenol S spiroglycol, and the like. Examples of the hydroxyacrylate or hydroxymethacrylate include, but are not limited to, 2-hydroxyethyl acrylate, 2hydroxymethacrylate, pentaerythritol triacrylate, and the like.

A particularly preferred second component of the radiation-curable resin used in the magnetic layer of the present invention is a polyfunctional acrylate.

Multifunctional acrylates are acrylic monomers with at least two acrylic ester groups. This type of monomer is
In radiation-curable resins, it increases the hardness of the protective coating layer, increases adhesive strength, and promotes rapid curing.

Specific examples of radiation-curable resins used in the magnetic layer of the present invention are as follows:
Specific examples of polyfunctional acrylates shown in -1 to 1-15 and which are particularly preferred second compositions of radiation-curable resins are shown in 2.
-1 to 2-5.

C1, CI(.

CtHs C) I-Co-0-CtllaO+CNH; 1 (CHz) 6 N) ICO(C411,0, CNH(C1(z) 6NHCOC2H4O-CO-C
)I C11゜(C)I n=c)l -C00CHthc-CB,
00C+CHzhcOo -CHz-C-CCII t
OOC-CH=CHo).

CHz=CHCO-0-CJ40 (1N 3-10, NHCOC2H4 2-15. 0-COCIl=CHt For example!=10, n=3, etc.) ■-9 CI (n=clI-CoO(CJaO)ii-COCH
= CIIi (n-4 to 9) Tripropylene glycol diacrylate (TPGDA) ■-13 (2-2, m-2) Bisphenol A diglycidyl ether diacrylate (l = 2, m = 2) H CHz 0 ■ ( n-1:kL16) Pentaerythritol triacrylate CPET^) CHz-QC (JI=CHz CL-OCCH=CHz Trimethylolpropane triacrylate) (TMPT
A) CTo-OCCH=CHz CI! =OCCH=CH! Pentaerythritol tetraacrylate CHz-OC
CI=CH Also, in order to improve the coating properties of the magnetic layer of the present invention, it may be diluted with a solvent that dissolves the composition of the magnetic layer.

The particularly preferred composition ratio of the radiation-curable resin used in the magnetic layer binder of the present invention may be any ratio, with urethane acrylate being 5 to 95 wt%, preferably 1O to 90-t.
%, polyfunctional acrylate is 95 to 5 wt%, preferably 10 to 90 wt%.

The radiation used in the present invention may be a conventionally known ultraviolet electron beam or the like, and the irradiation may be performed in the air, in an inert gas atmosphere, or in a vacuum.

The thickness of the magnetic layer of the present invention is preferably 0.5 to 10 μm.

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. Pat. No. 4,275,146, U.S. Pat.
No. 5B-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-I CL -(-S i -0→1- C.I.

(CHzh(OCHzCLh-6HCHzC+sTo+
COOC+J3koC+sH2+COOCaoHa+(n)(n)CtJs
sCOOCsoH+ e+(n)(iso)C+Jss
COOCsJiq(iso)(iio)C+tH3sC
OOC4*Hs+(”)S 8 COO
-CzJz*(iso)8-]I (CIl□)Il Coo-CzaHnq(iso) (iso)CzJssCOO-←CL→10COCzJ
ss (iso) erucic acid amide CzJitCOOH Liquid paraffin Furthermore, in the present invention, in order to improve the adhesion resistance, it is preferable to contain a so-called matting agent in the outermost layer of the 5-300+ag/magnetic material layer, and the particle size thereof is 1 It is preferable to have a diameter of 3 μm. If it is too large, errors in magnetic properties are likely to occur, and if it is too small, the adhesion resistance will be poor. By containing these matting agents, the average height of the convex portions on the surface of the magnetic layer is preferably 0.8 to 3.0 μm.
These matting agents are described in JP-A-64-77052 and JP-A-64-77052.
2-14647, etc.

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

M L -←CH1-C-+-rIrr- 0OCH3 Average particle size 2.1 μm -←CH,C+r! +CHz 0OCHs C→]- OOH Average particle size 2.7μm Average particle size 2.2μm 1←CHt Cth-su" Average particle size 2.4um Average particle size 2.5μm Silica (spherical) (amorphous) Average particle size 2 .2 μm 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, butanoyl, acetylpropionyl acetate, etc.), polyamides, polycarbonates described in U.S. Pat. terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene, polysulfone, polyacrylate, polyetherimide, and particularly preferred are triacetylcellulose 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.

These supports vary depending on the type of polymer, but the thickness is 1
It can be used depending on the purpose, from sheets of about -20 μm to thin films of about 20 μm, but the ones commonly used are 50 μm to 30 μm.
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 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, geltaraldehyde, etc.), isocyanates, active halogen compounds (
(2,4-dichloro-6-hydroxy-5-1-riazine, 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-fogging agents, etc. When using the base coating liquid of the present invention, resorcin, chloral hydrate, chlorophenol, etc. Etching agents such as the following can also be included in the undercoating solution.

The subbing layer of the present invention may contain inorganic fine particles such as 5 iOz, Tl0g, or polymethyl methacrylate copolymer fine particles (1 to 10 μm) 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 No. 1.294.

U.S. Pat. No. 2,761.791, 3. as appropriate.
No. 508.947, No. 2,941.898, and 3°5
Two or more layers can be coated simultaneously by the method described in No. 26.528, Yuji Harasaki, Coating F, p. 1253 (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; agar, sodium alginate, and starch derivatives; Derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyro-IJF, polyacrylic acid copolymers, polyacrylamide or derivatives and partially hydrodispersed products thereof;
Examples include dextran, polyvinyl acetate, polyacrylic acid 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 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, British Patent 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. 5819654
No. 4, British Patent No. 1,439,402, etc.

Preferred specific examples of these are described below.

1 1 CsF+tSOsK1 2
CyF+5COONaCJ.

CsF,? SOJ-CHffiCOOK■ 3H7 ■ CH.

C@F+tSOJ -(-CHzCHCHzOsr-f
-CHz +r SO3NaH Hs zl17 CaF+? SOJ -(-CHzCHtO+r10GHz
+-rSOJaH2 Na Cl1H1?00CCH5OJa I3 In the present invention, nonionic surfactant 1 may be used.

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

Compound example C++HziCOO+ CHtCHtO+-T-HCl
dbscOO+CHxCH*0-h-+CHz-CH
-CL +r-+CHtCHtO71H Cl hH33GO-(-CHgCHzO+rr H 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, Examples include a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer, and a blocking 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
0.05g 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-1989-89
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 to the photographic constituent layer of the present invention, either alone or in combination.They are used as coating aids, but are sometimes used for other purposes, such as emulsification and dispersion. It is also applied to improve sensitization and other photographic properties.

The present invention also includes lubricating compositions, such as U.S. Patent 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 rehearsal films and color negative 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 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-61-43148 and JP-A-59-1.
No. 13438, No. 59-113440, No. 61-20
037 and 61-20038, such as couplers, DIR-containing metals, etc., may be included, and a commonly used color mixing inhibitor 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. 61
-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.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) NO.

t7643 (December 1978), pp. 22-23
+, Emulsion preparation
ion and typea)” and same No. 18
716 (November 1979), p. 64B, “Physics and Chemistry of Photography” by Grafkide, published by Paul Montell (P.
Glafkides.

Che+5jcet Ph1sjque Photog
Raphique, Paul Montel.

1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Duffin, Photog)
rapicEmulsion Chemistry
(Focal Press+ 1 9 6
6)), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zeliks+an
et al,+Making and Coating
Photographic E++ulsion.

Focal Press+ 1964).

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.
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4.
434゜226, 4,414,310, 4,4
33.048, British Patent 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 K17643 and Research Disclosure Nα18716, and the relevant parts 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.

/ Attachment 1” Old 1st edition RD17643 RD18
7161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancer 4 Brightener Anti-stain agent Dye Image stabilizer Hardener Binder Plasticizer, lubricant Page 24 Page 25 Right column 25 Page 26 Page 26 Page 27 Same as above Page 650 left to right column Page 651 Left column Same as above Page 650 Right column In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. 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) Nl117643, ■-C-C.

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.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters, esters of phosphoric acid or phosphonic acid, benzoic acid esters, amides, 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, propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Examples of the steps, effects, and latex for impregnation of latex dispersion methods are described in U.S. Pat.
No. 541,230, etc.

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 means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T+A can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr, Sci, Eng,), Vol. 19, by Ni Reen et al.
2, pp. 124-129 (
T+A is defined as the saturated film thickness, which is 90% of the maximum swollen film thickness reached when treated with a color developer for 13 minutes and 15 seconds at 30°C. defined as the time of

The membrane swelling rate T'/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 (maximum swelling film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, pages 28-29, and Doseki 18716
615, left column to right column.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. 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
3.924.

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
It is preferable that the area of the frame is 350m+" or more and 120012 or less, and the magnetic information recordable space is 15% or more of the area of one frame of the image exposure section. Specifically, 1
It is preferable that the number of perforage controllers per screen is less than 135 formats, and it is particularly preferable that the number of perforation controllers per frame is 4 or less.

It is also possible to optically input information into the magnetic information recordable space using a light emitter such as an LED. It is also preferable to input magnetic information and optical information in the same space, and the magnetic recording format is based on World Publication No. 90-0.
Preferably, the method disclosed in No. 4205 is followed.

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 cartridges proposed in the following patents can also be used. (Jitsukai 58-673
No. 29, JP-A-58-181035, JP-A-58-1
No. 82634, U.S. Pat.
Japanese Patent Application No. 1-21862, Japanese Patent Application No. 1-25362, Japanese Patent Application No. 1-30246, Japanese Patent Application No. 1-20222, Japanese Patent Application No. 1-21863, Japanese Patent Application No. 1-37181, Hei 1-33108, Japanese Patent Application No. 1-85198, Japanese Patent Application No. Hei 1
-172595, Japanese Patent Application No. 1-172594, Japanese Patent Application No. 1-172593, U.S. Pat. No. 4,846,418, U.S. Pat. No. 4,848,693, U.S. Pat. , (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, if necessary. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, T-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, 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. The antistatic agent is not particularly limited, but carbon blanks, metal oxide particles of the present invention, nonions, anions, cations, hetain surfactants, nonions, anions, cations, hetain polymers, and the like can be preferably used. These anti-static cartridges are used in Japanese Patent Application Publication 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. Furthermore, in current cartridges, the tip of the spool protrudes on the side that engages with the film drive section of the camera, which is an impediment to miniaturization of cameras, so it is desirable to eliminate this portion. As a result of this, currently approximately 35
CD can reduce the volume of certain cartridges. The volume of the cartridge case is preferably 30 cj or less, preferably 25 cd or less, more preferably 20 cj 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 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, it may be used in a new camera that is compatible with a cartridge containing the color photosensitive material of the present invention. Examples of these specific cartridges are shown in FIG. 1 (further internal structures are shown in FIGS. 2 to 4).

(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 1-1 Preparation of base 7-A solution consisting of the binder composition listed in Table 1 in which FetOx (specific surface area 25n?/g manufactured by Pfizer Inc. (USA)) was dispersed was placed on a triacetyl cellulose support using microgravure. Coat with a coater (manufactured by Yasui Seiki) to a dry thin thickness of 2μ, and irradiate with a high-pressure mercury lamp (120w/cm). A 122μ support was prepared. 7-Pe,
The coating amount of O was 0.14 g/cm.

1-2 Preparation of light-sensitive material After subjecting the cellulose triacetate film support coated with the undercoat described above to the opposite side of the bank layer to a claw-leaving treatment, each layer having the composition shown below is coated in a multilayer manner to prepare a multilayer color light-sensitive material. A sample was prepared.

(Photosensitive N&lI formation) The photosensitive layer described in Example 1 of JP-A No. 2-93641 and the entire (
A photosensitive layer was prepared in the same manner.

1-3 Process the sample.
It was cut into still-shot film.

These samples were developed as follows.

Color development 3 minutes 15 seconds Bleached 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゜l-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide
1. 31g hydroxylamine sulfate
2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2 monomethylaniline sulfate 4.5g Add water l, 01! pH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium chloride Ammonium bromide Ammonium nitrate Add water to 100.0g ■ 0゜l 50゜10゜l.

pH6゜Fixer ethylenediaminetetraacetic acid disodium salt Sodium ammonium thiosulfate aqueous solution (70%) Add sodium bisulfite water 1, Og 4,0g ■ 75゜4゜1゜pH6゜Stabilizer formalin (40%) 2, Od Nonylphenyl ether (average degree of polymerization 10) Add water and give 3g i, o 7! Polyoxyethylene-p-mono(1) Transmittance The total light transmittance was measured using a non-hazy sample which was developed and fixed as described in (1).

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) Scratch strength A diamond needle with a tip of 0.0025 ■R is applied perpendicularly to the sample surface, and a load is applied continuously to scratch the sample surface at 60CI.
The scratched sample was scratched at a speed of /win, and the scratched sample was placed on a Scherkasten, and the load at which scratches began to be visible in transmission was defined as the scratching strength. (25°C 160%RH) (2) Surface abrasion test
A load of 0 g was applied and the surface was rubbed once at a speed of 60 ct/sin, and the extent of scratches visible under reflected light was examined.

O1 in order from scratch-resistant to easy-to-scratch
Evaluation was made on a three-level scale of Δ and ×. (25°C, 160% RH) (4) Evaluation of output errors in magnetic recording Using the signal input method disclosed in World Publication No. 9 (No. 1-04205), the magnetic head inputs the sensitive material 1000 times from the back side. The number of times an error occurred during the output operation is shown.This output error evaluation was also performed for the sensitive material that was developed after magnetic input.

FIG. 3 is a plan view and a sectional view of a rack layer.

[Explanation of symbols]

1... Photographic film cartridge 2...
・ Spool 3... Photographic film 4... Patrone body 5... Film drawer lower... Perforation 8... Raised portion 9... ... Projection 10 ... Hole 11 ... Notch 12 ... Film draw-out passage 13 ...
... Stepped portion 14 ... Emulsion constituent layer 15 ... Support 16 ... Transparent magnetic layer 17 ... Antistatic layer + scratch-resistant layer lubrication layer 18
・・・・・・ 1 frame 19 ・・・ Perforage 5 As can be seen from Table 2, the present invention improves both scratch strength and surface rubbing, and improves both scratch resistance and magnetic output error. It was done.

Example 2 A support and a back surface were prepared in exactly the same manner as in Example 1-1. On the surface opposite to the back surface of the support, JP-A-2-854 was applied.
The reversal color emulsion layer described in Example 1, Sample 101 was coated. The developing process used was Fuji Photo Film ■Color Reversal Processing 0CR-56 process.

Samples 2-1 to 2-6 of the present invention were excellent in permeability, scratch resistance, and magnetic properties. In contrast, comparative letter #J2
-7.2-8 had poor scratch resistance and magnetic properties.

[Brief explanation of drawings]

Fig. 1 is a perspective view of a photographic film cartridge according to the present invention, Fig. 2 is a plan 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 (5-1,
5-2) are magnetic recording tracks 1-0-L r00-f29 1... Magnetic recording tracks

Claims (7)

[Claims] (1) A silver halide photographic material having a light-sensitive silver halide emulsion layer on at least one side of a support, which has at least one transparent magnetic layer on at least one side of the photographic material, and its coercive force. has 400 Oe or more,
A silver halide photographic material, wherein the binder of the transparent magnetic layer is made of a radiation-curable resin. (2) The silver halide photographic material according to claim 1, wherein the radiation-curable resin comprises a composition containing at least urethane acrylate and polyfunctional acrylate. (3) The silver halide photographic material according to claims 1 and 2, wherein the photographic material is a color photographic material. (4) 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 Claim 1, which is metal fine powder and barium ferrite;
Silver halide photographic material according to items 2 and 3. (5) From claim 1, wherein the transparent magnetic layer is on the support opposite to the photosensitive silver halide emulsion layer and is cured by radiation before coating with the photosensitive silver halide. 4. Silver halide photographic material according to item 4. (6) 5 to 300 mg of a matting agent with an average particle size of 1 to 3 μm
/m^2 Contained on the back side and has a surface roughness of 0.8 to 3.
The silver halide photographic material according to any one of claims 1 to 5, wherein the silver halide photographic material is 0. (7) The silver halide photographic material according to claim 6, which contains a slip agent and a fluorine-containing surfactant.