JP2000214555A - Photographic substrate and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic substrate with an undercoat layer excellent in coatability by using a deionized gelatin binder, to obtain a silver halide photographic sensitive material excellent in adhesiveness to the substrate by disposing a photographic sensitive layer on the undercoat layer excellent in blocking resistance by coating with good coatability and to further obtain the silver halide photographic sensitive material excellent in transfer resistance and scuffing resistance. SOLUTION: The photographic substrate has an undercoat layer using a deionized gelatin binder obtained by ion-exchanging anions in gelatin for hydroxide ions (OH-) and cations for hydrogen ions (H+) so as to attain <=400 ppm calcium ion (Ca2+) content and <=8,000ppm sodium ion (Na+) content based on the dry gelatin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The first field of application of the invention is:
The present invention relates to a photographic support, and more particularly to a photographic support having excellent undercoat coating properties and blocking resistance obtained from an undercoat coating solution having good solubility or dispersibility. The second field of application relates to a silver halide photographic light-sensitive material in which the photographic light-sensitive layer provided on the undercoat layer has good coatability and excellent adhesion. Further, the present invention relates to a silver halide photographic material having excellent transfer resistance and scratch resistance.

[0002]

2. Description of the Related Art In general, a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) is provided on a support such as glass, paper, plastic film, or paper coated with plastic, and a silver halide emulsion layer and a silver halide emulsion layer. Accordingly, non-photosensitive layers such as an intermediate layer, a protective layer, an antihalation layer, and an antistatic layer are coated in various combinations.

Hitherto, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polystyrene, polycarbonate and the like have been widely used as photographic supports because of their excellent transparency and plasticity. It is very difficult to uniformly coat a photographic photosensitive layer composed of a hydrophilic colloid mainly composed of gelatin on a support made of such a high molecular substance and to firmly adhere it. In order to overcome such difficulties, it is necessary to provide an undercoat layer on the surface of the hydrophobic support.

[0004] Gelatin has been used as the main binder of the undercoat layer from the viewpoint of adhesion to the photographic photosensitive layer. As a solvent for the undercoat coating solution, water is suitable because of the solubility of gelatin.However, water has a large drying load and a large surface tension. Cannot be maintained, resulting in coating defects such as repelling. Therefore, an organic solvent which can be dried at a low temperature and has good wettability is introduced into the undercoat coating liquid system.

Accordingly, the solvent of the undercoating coating solution is mainly composed of water and a low-boiling organic solvent. However, when these low-boiling organic solvents are used as a part of the undercoating coating solution, many solvents such as metal ions are formed. Gelatin containing inorganic ions makes the undercoating coating solution cloudy, and tends to generate aggregates. Coarse agglomerates are liable to be formed as precipitates in the undercoating coating solution, and undesirably cause coating defects such as cissing. Also, when the undercoating coating solution becomes cloudy without forming a precipitate, the cause of the white turbidity is that the gelatin in the undercoating coating solution is in an unfavorable state such as poor dissolution or particle coarsening, so that the undercoating layer coating surface becomes cloudy. As a result, haze increases, which is not preferable as a photographic support. For these aggregates and coarse particles, there is a method of filtering the aggregates with a filter immediately before coating, and by increasing the filterability of the filter, the aggregates and the like can be removed to the extent that they can be used as a photosensitive material. However, the frequency of filter replacement increases, which is not preferable in terms of productivity.

[0006] In recent years, in order to improve the productivity of photographic supports, the coating speed of these undercoat layers has been increased. Under rapid coating and drying accompanying high-speed coating, undercoating of organic solvents having a low boiling point is required. Introducing only into the coating liquid system is not sufficient, and may cause coating defects such as coating unevenness and cissing. In particular, it is liable to occur in a gelatin undercoating coating system comprising a low boiling point, low surface tension solvent and a high boiling point, high surface tension solvent component. In order to prevent these coating defects, a method of adding a solvent having a high boiling point and a low surface tension to an undercoat coating liquid system has been performed, but a sufficient effect has not been obtained.

Although a method using a surfactant is also common, US Pat. No. 2,240,476 and US Pat.
Nos. 202, 3,068,101, 3,220,8
In the case of the low molecular weight surfactants disclosed in Nos. 47 and 3,415,649 and the like, the amount of use is enormous in order to obtain the effect, and coating failure due to foaming of the undercoating coating solution or under high humidity Bleed out (precipitation).

It is known that a so-called blocking phenomenon easily occurs in an undercoat layer containing gelatin as a main binder when the undercoat layer is left in contact with the undercoat surfaces. This phenomenon is particularly remarkable under high temperature and high pressure. If the back side between the undercoat layer and the support contains a slipping agent such as wax, a surfactant, a matting agent, etc., these are wound up in a roll shape after the undercoating layer is applied and then blocked by a blocking phenomenon. The material is transferred to the undercoat layer side, causing serious problems such as coating defects when coating the photographic constituent layer and deterioration of the adhesiveness of the photographic constituent layer. As means for preventing this blocking phenomenon, the film thickness is limited to 0.25 to 1.0 μm by the method described in JP-A-52-119919,
There is a method in which synthetic copolymer particles having an average particle size of 0.1 to 10.0 μm and a glass transition temperature of 45 ° C. or more are contained as a matting agent. However, this method uses a matting agent, so that the transparency of the support is impaired, and furthermore, the matting agent falls off on a transport roll in the coating process before the photographic photosensitive layer is coated. There is.

In recent years, photosensitive materials have been used in a wide variety of ways, and the photosensitive materials are exposed to harsher handling conditions than ever before due to the manufacturing process, high-speed transportation in various apparatuses, and expansion of processing methods. As a result, not only the adhesion performance of the emulsion layer on the support but also the abrasion resistance of the back surface is deteriorated in the prior art, and a further improvement in performance is required.

Also, US Pat. No. 3,782,947,
In JP-A-4,279,945 and JP-A-4,302,523, by providing a transparent magnetic recording layer on the back surface of the photosensitive material, various kinds of information such as the type, serial number, manufacturer name, etc. It has been proposed to input various information at the time of shooting, such as weather, aperture, exposure conditions, etc., and the number of prints, the size of a trimming frame, development and printing conditions, etc. into the magnetic recording layer. However, since the magnetic recording layer is usually provided on the back surface, there is a problem in that if the magnetic recording layer is scratched when rubbed with a magnetic head, the magnetic recording layer appears on a printed image or an error occurs when reproducing magnetic information.

As means for solving the improvement of the scratch resistance of the back surface, for example, JP-A-50-117414 discloses an organopolysiloxane, and JP-A-1-161337 discloses a slipping agent such as a higher fatty acid or a derivative thereof. , Is disclosed on the outermost surface. However, when the layer containing these slipping agents is the outermost surface of the back surface, when the undercoat layer and the back surface are coated and stored in a roll form, the slip agent is transferred to the undercoating surface and the emulsion layer is transferred. May cause coating failure.

[0012]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a photographic support having an undercoat layer having excellent coatability using a deionized gelatin binder. A second object is to provide a silver halide photographic light-sensitive material having excellent adhesion to a support by coating a photographic light-sensitive layer with good coatability on an undercoat layer having excellent coatability and blocking resistance. It is in. Another object of the present invention is to provide a silver halide photographic material having excellent transfer resistance and scratch resistance.

[0013]

Means for Solving the Problems According to the present invention, as a result of intensive studies on the above-mentioned problems, a good undercoating coating liquid free of agglomerates and coarse particles can be obtained by using a deionized gelatin binder. It has been found that by applying this undercoating coating solution, an undercoating layer which can maintain good coating properties and prevent blocking can be obtained. Further, by coating a photographic photosensitive layer on a photographic support having an undercoat layer, good coatability of the photographic photosensitive layer and good adhesion to the support were achieved. Further, by applying the device described in the present invention to the outermost layer of the slipping agent and the binder opposite to the surface having the photosensitive layer via the photographic support, excellent transfer resistance and scratch resistance were achieved.

The present invention has been achieved by the following constitutions.

[0015] 1) A photographic support having a subbing layer, an anion of hydroxide ions in the gelatin undercoat layer (OH - ^to), and ion-exchanged cations with hydrogen ions (H ⁺⁾ The calcium ion (Ca ²⁺ ) content of the deionized gelatin binder is 400 pp based on dry gelatin.
A photographic support characterized by using a deionized gelatin binder which has been treated to have a sodium ion (Na ⁺ ) content of 8,000 ppm or less based on dry gelatin.

[0016] 2) The deionized gelatin binder of chlorine ions (Cl - ^to) content dry gelatin 5
The photographic support as described in 1) above, wherein the photographic support is a deionized gelatin binder which has been treated with a sulfate ion (SO ₄ ^2- ) content of not more than 100 ppm with respect to dry gelatin at not more than 00 ppm.

3) The above 1) or 2), wherein the undercoat layer contains a nonionic fluorine-containing surfactant.
2. The photographic support according to 1.

4) The photographic support as described in 1) or 2) above, wherein the undercoat layer contains a nonionic fluoropolymer surfactant.

5) wherein the binder is cross-linked with a vinyl sulfone type cross-linking agent.
The photographic support according to any one of the above 4).

(6) The photographic support as described in any one of (1) to (5) above, wherein the undercoat layer contains a cellulose ester.

7) The photographic support according to any one of 1) to 6) above, wherein the photographic support is cellulose triacetate.

8) On one side of the photographic support according to any one of 1) to 7), at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and A silver halide photographic material having a photographic photosensitive layer comprising a photosensitive layer.

9) A silver halide photographic material having at least one photosensitive layer on a photographic support,
The outermost layer opposite to the side having the photosensitive layer through the support contains a slipping agent and a binder, and the undercoat layer of the photosensitive layer of the support contains deionized gelatin. Silver halide photographic material.

10) In a silver halide photographic light-sensitive material having at least one light-sensitive layer on a photographic support, the outermost layer opposite to the surface having the light-sensitive layer via the support is a slipping agent. And a binder, and the undercoat layer of the photosensitive layer of the support contains gelatin and a nonionic fluorine-containing surfactant.

11) In a silver halide photographic light-sensitive material having at least one light-sensitive layer on a photographic support, the outermost layer opposite to the surface having the light-sensitive layer via the support is a slipping agent. And a binder, and the undercoat layer of the photosensitive layer of the support contains gelatin and a nonionic fluoropolymer surfactant.

12) In a silver halide photographic light-sensitive material having at least one light-sensitive layer on a photographic support, the outermost layer opposite to the surface having the light-sensitive layer via the support is a slipping agent. And a binder, and the undercoat layer of the photosensitive layer of the support contains gelatin and a vinyl sulfone type crosslinking agent.

13) In a silver halide photographic material having at least one photosensitive layer on a photographic support, the outermost layer on the side opposite to the side having the photosensitive layer via the support is a slipping agent. And a binder, and the undercoat layer of the photosensitive layer of the support contains gelatin and cellulose ester.

(14) The silver halide photographic material as described in any one of (10) to (13) above, wherein the gelatin is deionized gelatin.

15) In a silver halide photographic light-sensitive material having at least one light-sensitive layer on a photographic support, the outermost layer opposite to the surface having the light-sensitive layer via the support is a slipping agent. And a binder, and at least one of a fluorine-containing surfactant and a fluorine-containing polymer surfactant in a subbing layer of a photosensitive layer of the support, deionized gelatin,
A silver halide photographic material comprising a vinyl sulfone type crosslinking agent and a cellulose ester.

16) The silver halide photographic material as described in any one of 9) to 15) above, wherein the slip agent is a higher fatty acid ester.

(17) The silver halide photographic material as described in any one of (9) to (16) above, wherein the binder is a cellulose ester.

18) In the layer containing the binder and the slipping agent, the ratio of the slipping agent to the binder is 10: 90-4.
The silver halide photographic material according to any one of 9) to 17) above, wherein the ratio is 5:55.

(19) The silver halide photographic material as described in any one of (9) to (18) above, wherein the photographic support is a cellulose ester.

The present invention will be described in detail.

First, gelatin used as a main binder of the undercoat layer of the present invention will be described. Gelatin used in the present invention includes, in addition to acid-treated gelatin and alkali-treated gelatin, enzyme-treated gelatin and gelatin derivatives which are subjected to an enzyme treatment in the course of the production of gelatin, that is, amino, imino and hydroxyl groups as functional groups in the molecule. It may be modified by treating with a reagent having a group, a carboxyl group, and a group obtained by reacting with the group. General methods for producing gelatin are well known, for example, T.I. H. Ja
mes: The Theory of Photogr
aphic Process 4th. ed. 19
77 (Macmilllan), 55, Scientific Photograph Handbook (above), 72-75 (Maruzen), Basics of Photographic Engineering-Silver halide photography, 119-124 (Corona), etc., can be referred to.

For example, lime-processed gelatin is prepared as follows. First, ossein consisting only of collagen from which calcium phosphate has been removed is immersed (lime-soaked) in saturated lime water for 2 to 3 months, and then washed and neutralized.
Extract with hot water at 0 ° C (No. 1 extraction). Then 60-6
No. 2 extraction at 5 ° C., No. 3 extraction at 70-75 ° C., and No. 4 extraction at 80 ° C. or more. Each extract is filtered, concentrated under reduced pressure, cooled and coagulated at about 10 ° C., and then dried to obtain.

The ion exchange treatment of the gelatin of the present invention is performed immediately after the filtration treatment in the above-mentioned production process. For example, a method in which a gelatin aqueous solution is heated and brought into contact with an ion exchange resin can be used. As the ion exchange treatment, both ion exchange treatments can be used. The metal element in gelatin is usually present as a cation in many cases, and can be removed by a cation exchange resin. However, since it may be present as a negative complex salt, both ion exchange treatments are performed.

As a method of both ion exchange treatments, a method of performing anion exchange treatment after performing cation exchange treatment,
A method in which the cation exchange treatment is performed after the anion exchange treatment in the former order, or a treatment with both ion exchange resins and a chelate resin can be used. A base such as sodium hydroxide may be used as the anion exchange resin during regeneration. In this case, sodium ions (Na ⁺ ) may remain in the anion exchange resin. For this reason, it is more preferable to perform cation exchange after anion exchange to remove sodium ions (Na ⁺ ) mixed from the anion exchange resin. These methods are described in “Chemical Experiment Course 2, Basic Technology II” edited by The Chemical Society of Japan, Maruzen (1956), pp. 151-202, “New Experimental Chemistry Course 1, Basic Operation I” edited by The Chemical Society of Japan, Maruzen (1975), 463
497 pages.

The following can be used as the ion exchange resin.

Cation exchange resin: Amberlite IR-
20 (manufactured by Rohm and Haas) Anion exchange resin: Diaion SA-21A (manufactured by Mitsubishi Kasei), Dowex 1 × 8 (manufactured by Dow Chemical), etc. Both ion exchange resin and chelating resin: Diaion C
R-20 (manufactured by Mitsubishi Kasei Co., Ltd.) Many of these ion exchange resins are commercially available, and those suitable for the purpose can be easily obtained. As the resin material, not only a synthetic resin (for example, styrene-divinylbenzene copolymer) but also a natural resin (for example, a cellulose-based one) may be used. The shape of the resin is
It may be in the form of granules, powders, films, etc., and may be appropriately selected to be easily handled.

Further, Japanese Patent Application Laid-Open No. 7-270982 discloses a method for controlling aggregates by adjusting the content of calcium ions (Ca ²⁺ ). However, the inventor did not merely adjust the amount of calcium ions (Ca ²⁺ ),
It has been found that by exchanging cations in gelatin for hydrogen ions (H ⁺ ) and anions for hydroxide ions (OH ⁻ ), the effect of suppressing aggregates can be further improved. Due to the deionization treatment, the amount of calcium ions (Ca ²⁺ ) in the cations contained in the gelatin is 400 ppm or less based on the dry gelatin, and the amount of sodium ions (Na ⁺ )
The amount is preferably 8000 ppm or less based on the dry gelatin, the amount of chloride ion (Cl ⁻ ) in the contained anion is 500 ppm or less based on the dry gelatin, and the amount of sulfate ion (SO
_The amount of ^42- ) is preferably 100 ppm or less based on dry gelatin. More preferably, the amount of calcium ions (Ca ²⁺ ) in the cation contained in the gelatin is 200 ppm or less based on the dry gelatin, and the amount of the sodium ions (N
a ⁺⁾ amount is preferably not more than 1500ppm with respect to dry gelatin, chlorine ions in the anion containing (Cl ^-)
The amount is 300 ppm or less based on dry gelatin, and the amount of sulfate ion (SO ₄ ²⁻ ) is 50 ppm based on dry gelatin.
It is as follows.

It is well known that gelatin is an amphoteric electrolyte. At the isoionic point where the charge is most neutralized, the repulsive force of the charge is small, so that it is difficult to swell and dissolve with water. PH of gelatin in which cations are exchanged with hydrogen ions (H ⁺ ) and anions are exchanged with hydroxide ions (OH ⁻ )
Indicates the vicinity of an isoionic point, and gelatin may be difficult to swell and dissolve, and may be difficult to handle when handled as an undercoating coating solution. As a countermeasure, sodium hydroxide may be added to gelatin after ion exchange, and it is necessary to adjust the amount of sodium ions (Na ⁺ ) introduced at this time so as to have the above-mentioned ion amount.

The deionized gelatin used in the present invention is used in an amount of 0.1 to 5.0% by weight in the undercoating coating solution.
More preferably, the coating amount is 0.5 to 2.0% by weight, and the coating amount is preferably ^{20 to} 600 mg per 1 m ² of the support.
0-300 mg is more preferred.

The nonionic fluorinated surfactant used in the present invention is represented by the following general formula [I].

Formula [I] Rf ₁ -Af-Xf wherein Rf ₁ is a fluorinated or perfluorinated substituted, unsubstituted alkyl, alkenyl or aryl group containing at least 3 fluorine atoms. Represents a group. Af
Represents a divalent linking group, and Xf represents a water-soluble group. Af preferably represents an alkyl group, an aryl group or an alkylaryl group, which is a divalent substituent interrupted by a hetero atom such as oxygen, an ester group, an amide group, a sulfonyl group, sulfur, or an unsubstituted linking group. It may be.

Xf is a hydrophilic group, for example, of the general formula-
(Bf-O) _af -R ₄ polyoxyalkylene group (Bf here -CH ₂ CH ₂ - or -CH ₂ CH (OH)
CH ₂ - represents, af is the number of 1 to 50 represent the average degree of polymerization of the polyoxyalkylene group. R ₄ represents a substituted or unsubstituted alkyl group or aryl group).

Specific examples of the nonionic fluorine-containing surfactant represented by the general formula [I] are shown below, but it should not be construed that the invention is limited thereto.

[0048]

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The nonionic fluoropolymer surfactant used in the present invention is represented by the following general formula [II].

[0050]

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In the general formula [II], R ₁ is a hydrogen atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.

Rf ₂ has 1 to 30 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, preferably 1 to 30 carbon atoms.
20 represents an alkyl group, an aralkyl group, an aryl group or an alkylaryl group, of which a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group,
Perfluorohexyl group, perfluorooctyl group,
2,2,3,3-tetrafluoropropyl group, 2,2
3,3,4,4,5,5-octafluoroamyl group,
2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,4 4,4-heptafluorobutyl group, 1,1,1,3,3,3-hexafluoro-
2-propyl group, 1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl group, 1,1,2,2
A 2-tetrafluoro-2-hydroxyethyl group, a p-fluorophenyl group, a p-trifluoromethylphenyl group, a 3,3,4,5,6-pentatrifluoromethylphenyl group and the like are preferable.

Yf is

[0054]

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Represents Here, R ₂ represents an alkylene group having 1 to 100 carbon atoms, an arylene group or an alkylene group.
L is -O- group, -S- group, -N (R ₃₎ - group, -CO-
Group, -OCO- group, -SCO- group, -CON (R ₃₎ -
Group, —SO ₂ — group, —N (R ₃ ) SO ₂ — group, —SO ₂ N
(R ₃ ) — represents a —SO— group, and R ₃ represents an alkyl group having 1 to 4 carbon atoms. pf represents 0 or 1.

If is an integer of 0 or an integer of 1 to 4, preferably 0 or 1.

Mf is an integer of 5 to 50, preferably 5 to 20. nf is 0 or an integer of 1 to 20,
Preferably it is 0-10.

Zf represents an alkyl group having 1 to 24 carbon atoms, preferably an alkyl group having 4 to 18 carbon atoms. Zf is
For example, hydrogen atom, methyl, ethyl, butyl, dodecyl,
A linear or branched alkyl group such as tetradecyl and hexadecyl groups; an alkenyl group such as oleyl group; an alkylphenyl group such as pentylphenyl group and octylphenyl group.

The molecular weight of the copolymer used in the present invention is 30
00 to 200,000, preferably 5000 to 5
0000.

X: y = 10: 90-80: 20
(Mol%), preferably from 20:80 to 50:50.
It is.

Specific examples of the nonionic fluorine-containing polymer surfactant represented by the general formula [II] are shown below, but are not limited thereto.

[0062]

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[0063]

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In the present invention, the application amount of the nonionic fluorinated surfactant and the nonionic fluorinated polymeric surfactant is preferably 0.001 to 0.05% by weight, more preferably 0.001 to 0.05% by weight in the undercoating coating solution. Is 0.005 to 0.03% by weight,
Preferably 0.01~9.0mg in content per support 1 m ^2, in particular 0.05~3.0mg is more preferable.
Hereinafter, nonionic fluorine-containing surfactants and nonionic fluorine-containing polymer surfactants are also collectively referred to as fluorine-containing surfactants.

The solvent used in the undercoat coating solution of the present invention will be described. As a solvent of the undercoat coating solution of the present invention, water for swelling gelatin and an organic solvent having miscibility with water can be used to maintain wettability at the time of coating on a support.
Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol and butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; glycol ethers such as methyl cellosolve and ethyl cellosolve; and amides such as N, N-dimethylformamide and formamide. And the like.

In preparing the undercoat coating solution of the present invention, an organic solvent having good wettability to a support is often a poor solvent for gelatin, and cannot swell gelatin. In addition, when an organic solvent is added after swelling gelatin with water, or when gelatin swelled with water in an organic solvent is added, gelatin is rapidly mixed with a poor solvent to generate gelatin aggregates. Absent. Therefore, it is necessary to introduce an acid into the coating liquid system in order to disperse the gelatin in a solvent containing an organic solvent. Acids used at this time include formic acid, acetic acid, propionic acid, phthalic acid,
Salicylic acid, citric acid, oxalic acid, phosphoric acid and the like can be used.

In the present invention, it is preferable to use a crosslinking agent in order to improve the adhesion of the undercoat layer. Examples of the crosslinking agent that can be used in the present invention include aldehyde compounds, ketone compounds, compounds having a reactive halogen, compounds having a reactive olefin, N-methylol compounds,
Aziridine compounds, acid derivatives, epoxy compounds,
Examples thereof include halogen carboxaldehydes, chromium ban, zirconium sulfate, and a carboxyl group-active crosslinking agent.

In the present invention, it is preferable to use a vinyl sulfone type crosslinking agent as the crosslinking agent. As the vinyl sulfone type crosslinking agent used in the present invention, the following general formula (III)
The crosslinking agent represented by is preferred.

Formula (III) (CH ₂ ＣＨCHSO ₂ ) _mh Lh In the formula, Lh is an MH-valent group having at least one hydroxyl group, and mh is 2, 3 or 4;
In I], Lh is mh value, each having 1 to 10 carbon atoms.
A 5- or 6-membered heterocyclic group containing a nitrogen, oxygen or sulfur atom, a 5- or 6-membered alicyclic group, or an aralkylene group having 7 to 10 carbon atoms.

Further, among the vinyl sulfone type crosslinking agents used in the present invention, it is more preferable to use the crosslinking agents represented by the following general formulas (IV) and (V).

[0071]

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In the formula, Xh represents a vinyl group and Ah represents a divalent group, but need not be present. The divalent group is preferably a cyclic or acyclic hydrocarbon having 1 to 10 carbon atoms, of which 1 to 3 may be substituted with a heteroatom such as nitrogen, oxygen, sulfur, etc., more preferably Is carbon number 1
A chain hydrocarbon having from 5 to 5 carbon atoms, and having 2 to 5 carbon atoms may be branched or linear. This chain may have a substituent such as an alkoxy group such as methoxy and ethoxy, a halogen such as chlorine and bromine, a hydroxy group and an acetoxy group. Rh ₁ is hydrogen or carbon number 1
It represents 4 hydrocarbons, Rh ₁ which present two to in one molecule is not necessarily the same.

[0073]

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In the formula, lh and ph represent 1 or 2, and m
h and nh represent 0, 1 or 2, but not both at the same time. Rh ₂ represents a simple bond or represents a divalent group. In this case, any divalent group may be used, but it preferably represents an alkylene group having 1 to 8 carbon atoms or an arylene group, and a part thereof may be substituted with one or two hetero atoms.

Hereinafter, the general formula [II] used in the present invention will be described.
Specific examples of the vinyl sulfone-type cross-linking agent represented by I], the general formula [IV], and the general formula [V] are shown below, but are not limited thereto.

[0076]

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[0077]

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[0078]

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In the present invention, these crosslinking agents can be used in an amount of 0 to 500 mg, more preferably 20 to 200 mg, per 1 g of deionized gelatin.

The binder used in combination with the deionized gelatin was 2 parts per 1 g of the deionized gelatin.
It is preferably used in the range of not more than g. 0.2g more
More preferably, it is used in the range of 0.9 g to 0.9 g.

The undercoat layer of the present invention may be composed of Research Disclosure (hereinafter abbreviated as RD) 17643, Item 28, RD1
Items 647 to 648 of 8716 and XI of RD308119
The support described in X can be provided on top.
Examples of the support preferably used in the present invention include polyester films such as polyethylene terephthalate and polyethylene-2,6-naphthalate, cellulose triacetate films, polycarbonate films, polystyrene films, and polyolefin films. The undercoat layer of the present invention is preferably provided on cellulose triacetate among the above supports.

The photographic support includes a matting agent, an antistatic agent, a slipping agent, a surfactant, a stabilizer, an antioxidant, a dispersant, a plasticizer, an ultraviolet absorber, an antiadhesive, a softener, You may add an imparting agent etc. Also, a phenomenon called light piping, in which light incident from the cross section of the film of the silver halide photographic material travels through the inside of the support and penetrates deep into the film, is likely to occur, and when this occurs, the commercial value of the emulsion layer is reduced. In order to prevent such a phenomenon, it is preferable to add a dye to the photographic support and to color it.

When the photographic support is a polyester film, a heat-resistant dye that can withstand the melt-forming film is preferred. In the case of a color photographic film, gray coloring is preferable.
In the case of a radiographic film, coloring in a blue tone is preferred.
The dyes may be used alone or in combination of two or more. For example, dial resin (Di) manufactured by Mitsubishi Kasei Corporation
This goal is achieved by using dyes such as ARESIN and MACROLEX from Bayer alone or in appropriate mixtures.

The support of the present invention may be provided with another functional layer between the undercoat layer and the support. This functional layer is not particularly limited as long as the adhesiveness between the undercoat layer and the support is not impaired. For example, when the polymer film is a polyester film, JP-A-59-19941 and JP-A-59-7994.
No. 7439, copolymers with diolefin monomers described in JP-A-57-128332, JP-B-43-3976, JP-A-64-538. And a vinylidene chloride copolymer described in JP-A-3-13763. Further, surface treatment may be performed on the polyester film or the functional layer in order to firmly adhere the functional layer and the support, the functional layer and the undercoat layer, or the undercoat layer and the support itself. For example, corona discharge treatment, flame treatment, ultraviolet treatment,
High-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, and ozone oxidation treatment may be used, and chemical treatment, mechanical treatment, and the like may be used on the surface of the support.

When the polymer film is a cellulose triacetate film, the binder used for the functional layer includes gelatin, polyvinyl alcohol, a partially acetalized polyvinyl alcohol, a hydrophilic resin such as a vinyl acetate-maleic anhydride copolymer, and a cellulose resin. Examples include hydrophobic resins such as diacetate and cellulose nitrate.

Solvents for coating these functional layers include water, methanol, ethanol, isopropanol,
Alcohols such as butanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; halogenated hydrocarbons such as methylene chloride and carbon tetrachloride;
Ethers such as dioxolane and dioxane, benzene,
Examples include aromatic hydrocarbons such as toluene, glycol ethers such as methyl cellosolve and ethyl cellosolve, and amides such as N, N-dimethylformamide and formamide. These may be mixed and used as necessary. preferable.

Further, a conductive material, an antihalation agent, a crossover light-cutting agent, a coloring dye, a pigment, a coating aid, an antifogging agent may be added to the undercoat layer of the support of the present invention and / or one of these functional layers. Various additives such as an agent, an antioxidant, an ultraviolet stabilizer, an etching agent, and a matting agent may be contained.

A back surface can be provided on the side opposite to the undercoat layer of the photographic support of the present invention and the support. The back surface may have layers having various functions. For example,
An antistatic layer, an ultraviolet ray preventing layer, a sliding layer and the like. In recent years, a system called APS has been put on the market, and a silver halide photographic light-sensitive material having a magnetic recording layer on the back surface has appeared (different from a magnetic stripe previously used for 8 mm movie film). May be provided.

In the present invention, any known slip agents can be used, but in the present invention, the use of higher fatty acids or derivatives thereof is preferred for the purpose of the present invention.

The higher fatty acids or derivatives thereof include:
For example, higher fatty acid amides as disclosed in U.S. Pat. No. 4,275,146, JP-B-58-33541.
No., British Patent No. 927,446, or
Higher fatty acid esters as disclosed in U.S. Pat. Nos. 3,126,238 and 58-90633; metal salts of higher fatty acids as disclosed in U.S. Pat. No. 3,933,516; An ester of a linear higher fatty acid and a linear higher alcohol as disclosed in Japanese Patent No. 50534, a higher fatty acid-higher alcohol ester containing a branched alkyl group as disclosed in WO 90108115.8 and the like can be used. . Fats and oils and oils, which are natural products, can also be used. For example, montanic acid esters, carnauba wax, beeswax and the like contain a large amount of higher fatty acid esters and are useful in the present invention.
Particularly, carnauba wax is useful. Furthermore, higher alcohols, higher fatty acids and their derivatives can also be used. Also, fatty acid esters or alcohol esters of fluorinated fatty acids or fluorinated alcohols can be used.

[0091] Particularly preferred slip agents of the present invention are higher fatty acid esters. The number of carbon atoms in the higher fatty acid moiety is 8 to
100 is preferable, and 10-80 is more preferable. When the alcohol portion of the higher fatty acid ester is a higher alcohol, the number of carbon atoms in the higher fatty acid portion may be slightly smaller. The alcohol portion preferably has 1 to 80 carbon atoms, more preferably 4 to 60 carbon atoms. When the alcohol moiety is a polyol such as ethylene glycol, glycerin, trimethylolpropane, or pentaerythritol, the fatty acid moiety esterified thereto may be a carboxylic acid having the same number of carbon atoms, or It may be different. In the case of pentaerythritol, one OH group may remain without being esterified. Further, in the case of such a polyfunctional alcohol, not only higher fatty acids but also at least one fatty acid having at least 2 carbon atoms may be used. In the present invention, these are collectively referred to as higher fatty acid esters. In the present invention, use of one or more higher alcohol esters of higher fatty acids is preferred.

Examples of typical compounds of the above-mentioned slipping agents are shown below.

[0093]

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[0094]

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[0095]

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[0096]

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The sliding agents for higher fatty acids or derivatives thereof used in the present invention include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as methylene chloride and carbon tetrachloride, It is used by dissolving in a solvent such as an aromatic hydrocarbon such as benzene or toluene, or ether such as 3-dioxolane or dioxane, or as an aqueous dispersion or a dispersion of a mixture of water and a water-miscible organic solvent. Used.
These dispersions are emulsified and dispersed in water after the higher fatty acid or a derivative thereof is heated and melted before the dispersing operation or dissolved in a water-immiscible organic solvent (for example, hydrocarbons such as toluene). It can be obtained by adding and mixing water or a mixture of water and a water-miscible organic solvent.

As a method for preparing the dispersion, various generally known methods can be used. For example, a method described in "Techniques of emulsification and solubilization" by Tsuji recommendation (Kogaku Tosho Co., Ltd. version) is used. I can do it. When used as a dispersion, a higher fatty acid or a derivative thereof is used in an amount of 1 to 1000 n.
Particles having a size of about m and dispersed in a mixture of water and a water-miscible organic solvent are preferred.

The binder used is a thermoplastic resin, a radiation-curable resin, a thermosetting resin, or another reactive resin, and these can be used alone or as a mixture.

Examples of the thermoplastic resin include cellulose resins (cellulose derivatives such as cellulose acetate and cellulose nitrate), vinyl chloride-vinyl acetate resin, vinyl chloride resin, vinyl acetate resin, vinyl acetate partial hydrolyzate, vinyl chloride Vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, maleic acid-acrylic acid copolymer Polymer, acrylic acid (including methacrylic acid) ester polymer or copolymer, polyvinyl butyral resin, saturated polyester resin, polyurethane resin, polyamide resin, amino resin, styrene-butadiene copolymer, silicone resin, fluorine resin, etc. Can be mentioned . The radiation-curable resin is a resin that is cured by radiation such as an electron beam or ultraviolet rays, and examples thereof include a maleic anhydride type, a urethane acrylic type, and an ether acrylic type.

Examples of the thermosetting resin or other reactive resins include phenol resin, epoxy resin, polyurethane-based curable resin, urea resin, alkyd resin, and silicone-based curable resin.

The binders listed above may have a polar group in the molecule. As the polar group, an epoxy group, -COOM, -OH, -N (R) ₂ , -N (R) _{3
X, -SO 3 M, -OSO 3} M, -PO 3 M 2 and -OPO
₃ M (M and M ₂ are a hydrogen atom, an alkali metal atom, and ammonium, X is an acid forming an amine salt, R
Represents a hydrogen atom or an alkyl group. ).

Of the above binders, cellulose esters are preferred. Examples of the cellulose ester include cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate benzoate. Particularly, cellulose diacetate is preferable from the viewpoints of film formability, compatibility with other substances, transparency, flexibility and the like.

The resin used for these binders can be used as an aqueous emulsion or an aqueous colloid solution.

In addition, a hydrophilic binder can be preferably used in the present invention as a binder for the aqueous dispersion of the slipping agent.
Examples of the hydrophilic binder include Research Disclosure (hereinafter abbreviated as RD) No. 17643,2
No. 6 and the same No. 18716, page 651 (hereinafter referred to as No.
RD 17643), water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters.

Examples of the water-soluble polymer include, in addition to those described above, gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, acrylic copolymers, maleic anhydride copolymers and the like.

The cellulose ethers include carboxymethyl cellulose, ethyl cellulose, propyl cellulose, 2-hydroxyethyl cellulose, 3-hydroxypropyl cellulose, 4-hydroxybutyl cellulose, 2-hydroxyethyl cellulose acetate,
-(2-hydroxyethoxyethyl) cellulose, 2-
Hydroxyethyl-3-hydroxypropylcellulose and the like can be mentioned.

Among these water-soluble polymers, gelatin is one of the preferable ones in the present invention. Gelatin includes those produced from raw materials such as ossein, pigskin and calfskin by treatments such as alkali treatment, acid treatment, and enzyme treatment, and any of the gelatins produced therefrom can be used in the present invention. Further, the above-mentioned cellulose ethers are also preferably used in the present invention in the case of an aqueous dispersion of a slipping agent.

The latex polymer may be any homopolymer or copolymer such as acrylate, methacrylate, N-substituted acrylamide, styrene, acrylonitrile, butadiene, etc., so-called emulsion polymer emulsified and dispersed in water. Can be used without.

Examples of the water-soluble polyester include aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, and isophthalic acid, and aliphatic dicarboxylic acids such as adipic acid;
A sulfo-substituted aromatic dicarboxylic acid such as a metal sulfophthalate, ethylene glycol, propylene glycol, polyethylene glycol (degree of polymerization 500), 1,
Copolyesters with diols such as 4-cyclohexanedimethanol and cyclohexanedimethanol are preferred.

To prepare the outermost layer coating solution containing the slip agent of the present invention and the binder, a solution in which the slip agent is dissolved is dissolved in an organic solvent together with the other components described above to prepare a solution of the slip agent. And a dispersion in which a slip agent is dispersed,
There is a method of preparing by uniformly dispersing in water or a mixture of water and an organic solvent miscible with water. The organic solvent used for the dispersion, water, or an organic solvent miscible with water, and another organic solvent may be arbitrarily mixed and used. These organic solvents include methanol, ethanol, isopropyl alcohol, alcohols such as butanol, ethyl acetate,
Esters such as butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ether, glycol dimethyl ether, glycol monomethyl ether, 1,3-dioxolan,
Ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, chlorinated hydrocarbons such as methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethylene chlorohydrin, N, N-dimethylformamide; Examples thereof include formamides such as formamide, hydrocarbons such as hexane and cyclohexane, and water.

In the present invention, the outermost layer on the back surface contains a slipping agent and a binder, and the weight ratio of the slipping agent to the total solid content is preferably 10% or more and 45% or less, more preferably 15% or more and 40% or less. It is.

The amount of the slipping agent is 3 to 50 m on the support.
g / m ² or less, preferably 3 to 40 mg / m ² .

Further, the outermost layer on the back surface of the present invention may contain various additives as long as the effects of the present invention are not impaired. Such additives include a matting agent, an abrasive, a surfactant and the like.

The method of applying the outermost layer on the back surface includes extrusion coating, air doctor coating, blade coating, air knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating, and kiss coating. , Cast coating, spray coating and the like can be used.

As the antistatic agent useful for the antistatic layer of the present invention, most of the antistatic agents and antistatic compositions useful for general silver halide photographic materials can be used.

For example, styrene-sodium maleate copolymers described in JP-B-47-28937 and JP-B-49-23828, sodium vinylbenzylsulfonate copolymer described in JP-A-53-82876, and 4
Anionic antistatic agents such as a polymer or copolymer of sodium styrene sulfonate described in JP-A-8-23451,
JP-A-51-42535, JP-A-54-159222,
JP-A-55-7763 and the like, an ionene polymer (for example, a polymer of triethylenediamine and xylidene dichloride), and US Pat. No. 2,882,157, for example, polymethacryloylethyldiethylammonium methylsulfonate; Japanese Patent Publication No. 60-51693
And JP-A-61-223736 and JP-A-62-9346.
No. 4), having a quaternary ammonium group in the side chain (for example, copolymer (N, N, N-trimethyl-N-vinylbenzylammonium chloride-co-divinylbenzene)); No. 5,174,572 described in JP-A-5-174572, a cationic antistatic agent for copolymer particles having an ionene polymer crosslinkable or ionene polymer side chain (for example, polyvinyl benzyl chloride and a terminal N- (polymer of a polymer of triethylenediamine and xylidene chloride; Cross-linking reaction product) having an alumina sol described in JP-B-57-12979 as a main component and JP-A-57-10493.
ZnO, SnO ₂ , TiO ₂ , Al ₂ O ₃ , I
n ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , ZiO ₂
Metal oxide antistatic agents such as V ₂ O ₅ described in JP-B-56-5982, JP-B-52-32
No. 572, a higher fatty acid phosphate antistatic agent described in JP-A-2-252726, a poly (isothianaphthene) system described in JP-A-2-252726, JP-A-2-255770 and JP-A-2-255770.
And conjugated double bond conductive polymers such as poly (thiophene) described in JP-A-308246.

In particular, among the above antistatic agents, alkali metal sulfonic acid type anionic high molecular antistatic agents such as sodium styrene sulfonate polymer or copolymer, sodium vinylbenzyl sulfonate copolymer, etc., triethylenediamine and xylidene An ionene polymer typified by a polymer made of a dihalide such as dichloride, a condensate made of a dihalide such as diamine such as triethylenediamine and a dihalide such as xylidene dichloride, or an ionene polymer serves as a crosslinking agent for a vinyl copolymer. Ionene crosslinked copolymer particles, condensates composed of diamines such as triethylenediamine and dihalides such as xylidene chloride, or quaternary trivalent ionicene side chain pendant crosslinked copolymer particles bonded to the side chains of the polymer Ethylenediamine as a component That cationic ionene polymer antistatic agent, a quaternary benzylamine cationic polymeric antistatic agents such as cross-linked copolymer particles having a benzyl trialkyl ammonium chloride group in the side chain, SnO _2, TiO _2,
Crystalline metal oxide fine particle antistatic agent mainly composed of metal oxides of ZnO ₂ , In ₂ O ₃ , MoO ₃ , WO ₃ and / or these metal composite oxides, alumina sol composition, poly- (5- Dodecylbenzothiazothiophene), poly-
(3-Dodecylthiophene), a polythiophene-based conductive polymer antistatic agent having a conjugated double bond represented by poly-methacryloylethyloxymethyl-3-polythiophene and the like are preferable, and polyfuran and polypyrrole are also useful.

It is preferable that the same binder as described above coexists in the antistatic layer according to the present invention. Particularly, as the binder, cellulose esters and gelatin are preferable. In each case, the adhesion between the magnetic recording layer and the adjacent layer is excellent.

In recent years, as described above, silver halide photographic materials having an APS magnetic recording layer have become widespread. Various information on the silver halide photographic material is input and output to the magnetic recording layer.

The magnetic recording layer according to the present invention is formed by coating a coating solution in which magnetic particles are dispersed in water with a binder or a coating solution in which magnetic particles are dispersed in a binder-soluble organic solvent on a photographic support. Any of the above is preferably used.

The magnetic particles of the magnetic recording layer according to the present invention include ferromagnetic iron oxide such as γFe ₂ O ₃ , Co-coated γFe ₂
O ₃ , Co-coated magnetite, Co-containing magnetite,
Ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like are preferably used. Among them, Co-coated ferromagnetic iron oxide such as Co-coated γFe ₂ O ₃ is preferable. The shape may be any of a needle shape, a rice grain shape, a spherical shape, a cubic shape, a plate shape and the like, but a needle shape and a plate shape are preferable in terms of electromagnetic conversion characteristics. The crystallite size and surface area are not particularly limited, but the crystallite size is 400 ° or more and the BET value is 20 m ^2.
/ G or more, more preferably 30 m ² / g or more. The saturation magnetization (δs) of the ferromagnetic material is preferably 4.0
× 10 ^{4 to} 2.5 × 10 ⁵ A / m. The preferred pH range is 5-10. 2 for ferromagnetic iron oxide fine powder
The ratio of trivalent iron / trivalent iron can be used without any particular limitation.

The amount of the magnetic powder used is preferably 4 × 10 ⁻⁴ g or more per 1 m ^{2 of} the magnetic recording medium. The upper limit is 436n
If there an optical density of m wavelength of 1.5 or less, preferably as baking transparency required for such silver halide photographic light-sensitive material, 1 m ² per 4g before and after a limit. The range of the pH of the magnetic particles is preferably 5 to 10. The iron ratio (divalent iron / trivalent iron) of the ferromagnetic iron oxide fine powder can be used without any particular limitation.

Further, the magnetic particles were prepared by the method described in JP-A-6-1610.
As described in No. 32, it may be treated with a silane coupling agent or a titanium coupling agent. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

The binders used in the magnetic recording layer include thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, acids, alkalis or biodegradable polymers, and natural products described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The glass transition point (Tg) of the above resin is -4
0-300 ° C, weight average molecular weight 2000-10
If it is 00000, it can be used without limitation. Examples of the binder resin include a vinyl copolymer, a cellulose ester resin such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate, an acrylic resin, and a polyvinyl acetal resin. Particularly, cellulose diacetate and cellulose triacetate are preferable. Gelatin is conveniently used as a binder in the aqueous dispersion.

The binder can be cured by adding a crosslinking agent such as an epoxy-based, aziridine-based, or isocyanate-based binder, which contributes not only to the hardening of the magnetic recording layer but also to the adhesion to the adjacent layer. . Of these crosslinking agents, isocyanate-based ones are preferably used. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and the reaction products of these isocyanates with polyalcohols (for example, tolylene diisocyanate). 3 moles and trimethylolpropane 1
(Mole reaction product) and polyisocyanates formed by condensation of these isocyanates. Examples of the compounds are described in JP-A-6-59357, and any of them can be used.

As a method for dispersing the magnetic particles in the binder, it is preferable to disperse and knead the mixture in a kneader, a pin type mill, an annular type mill or the like, as in the method described in JP-A-6-35092. It may be used and may be used in combination.

As the dispersant, those described in JP-A-5-88283 and other known dispersants can be used.

The thickness of the magnetic recording layer is 0.1 to 10 μm, preferably 0.2 to 5 μm, more preferably 0.3 to 3 μm.
m. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² .
g / m ^2, more preferably from 0.02 to 0.5 g / m ^2. The transmission yellow density of the magnetic recording layer is 0.01 to 0.5.
50 is preferable, and 0.03 to 0.20 is more preferable.
0.04 to 0.15 is particularly preferred. The magnetic recording layer can be provided on the whole surface or in the form of stripes on the back surface of the silver halide photographic material by coating or printing. Methods for applying the magnetic recording layer include air doctor, blade, air knife, squeeze, impregnation, reverse roll,
Methods such as transfer roll, gravure, kiss, cast, spray, dip, bar, and extrusion can be used.

Examples of the abrasive used for the magnetic recording layer include:
Nonmagnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more are preferred. Specifically, aluminum oxide (α-alumina, γ-alumina, corundum, etc.), chromium oxide (Cr ₂ O ₃ ), iron oxide ( Examples thereof include oxides such as α-Fe ₂ O ₃ silicon dioxide and titanium dioxide, and fine powders such as diamond, etc. These particles have an average particle size of 0.01 to 5.0 μm.
m is preferable, the average particle diameter of the abrasive having a small average particle diameter is preferably 0.01 to 0.6 μm, and the average particle diameter of the abrasive having a large average particle diameter is preferably 0.4 to 2.5 μm. It can be added in the range of 0.5 to 300% by weight based on the magnetic powder. The amount of the abrasive applied is 5 to 100 mg /
The range of m ² is preferable, and the range of 10 to 55 mg / m ² is more preferable.

Further, the magnetic recording layer may be the outermost layer on the back surface of the present invention.

As the silver halide emulsion of the silver halide photographic light-sensitive material according to the present invention, those described in RD308119 can be used. The places to be described are shown below.

[Items] [Page RD308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Crystal wall Normal crystal 993 IA Twin crystal 999 IA Section Epitaxial 993 I -A halogen composition uniform 993 IB non-uniform 993 IB halogen conversion 994 IC halogen substitution 994 IC metal-containing 994 ID monodispersion 975 IF solvent added Item 995 I-F Latent image forming position Surface 995 I-G Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Item Emulsion mixed 995 I Section-J Desalting 995 II-A The silver halide emulsion according to the present invention is preferably subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are RD17643, RD
18716 and RD308119. Hereinafter, the locations described in Table 1 are shown.

[0134]

[Table 1]

In the silver halide emulsion layer according to the present invention,
Known photographic additives that can be used are those described in the above RD. In the following, relevant description places are shown in Table 2.

[0136]

[Table 2]

Various couplers can be used in the silver halide color emulsion layer according to the present invention, and specific examples are described in the above RD. In the following, Table 3 shows relevant descriptions.

[0138]

[Table 3]

The additives used in the silver halide emulsion layer according to the present invention can be added by a dispersion method described in RD308119, XIV.

As the silver halide photographic constituent layer, the above-mentioned R
An auxiliary layer such as a filter layer or an intermediate layer described in D308119, section VII-K can be provided.

The photographic constituent layer used in the present invention is the same as that of the aforementioned R
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section VII-K of D308119 can be employed.

For developing processing of the photographic constituent layer used in the present invention, for example, T.I. H. James, Theory of the Photographic Process, 4th Edition (Th
eTheory of The Photograph
ic Process Fourth Edition
n) pages 291-334, and Journal of the American Chemical Society (Journal o)
f the American Chemical S
ociety), vol. 73, p. 3100 (1951), known developers can be used. Further, the color photographic constituent layer is the same as that of the aforementioned RD1764.
3 pages 28-29, RD18716 page 615 and RD
Development processing can be performed by the usual method described in 308119XIX.

[0143]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention.

Example 1 <Preparation of gelatin for undercoat layer> A lime treatment, water washing, and a neutralization treatment were carried out, and lime was removed at 55 to 60 ° C using ossein.
Extraction was performed. Thereafter, the extracted gelatin was subjected to both ion exchange using an anion exchange resin (Diaion PA-31G) and a cation exchange resin (Diaion PK-218). In order to improve the effect of ion exchange, the number of times of ion exchange treatment was changed. G-7 to G-
In No. 9, in order to more clearly show the effects of the present invention, a small amount of sodium hydroxide was added to increase the sodium ion concentration. The ion concentration of the obtained gelatin was as shown in Table 4.

[0145]

[Table 4]

<Preparation of photographic support><Preparation of TAC film support> A TAC film support was prepared as follows. That is, 15.7 parts by weight of TAC resin flakes (degree of acetylation: 60.3 to 61.6%) and T
1.6 parts by weight of PP is dissolved in 82.7 parts by weight of a mixed solvent of methylene chloride: ethanol (84:16) (this is called dope). The thickness after drying is 100μ on the endless stainless steel belt rotating the dope.
m, dried on a belt until the amount of residual solvent became 100% by weight, and after almost one rotation, the obtained dope film (hereinafter referred to as web) was peeled off from the belt and transported by a plurality of conveyors. It was heated and dried while being transported on a roll.
The residual solvent amount was 1.0% by weight.

<Preparation and Coating of Undercoat Coating Solution on Side of Silver Halide Emulsion Layer> When the residual solvent in the web became 10% or less, the following undercoat coating solution was applied to the side of the belt of the web by an extrusion coater. Coating was performed so as to be 15 ml / m ^2, and immediately thereafter, drying was performed at 100 ° C. for 15 seconds. The gelatin used was no. 101 is G-1, N
o. 102 is G-2; 103 is G-3; 1
04 is G-4; 105 is G-5; 106 is G-6; 151 is G-7; 152 is G-
8, no. 153 was designated as G-9. The sample with the undercoat layer obtained at this time was designated as Sample A.

<< Preparation of Silver Halide Emulsion Sidecoat Layer Coating Solution >> Gelatin (gelatin containing ions shown in Table 4) 1.0 g water 3.0 cc acetic acid 2.0 cc methanol 30.0 cc acetone 65.0 cc crosslinking agent I 0.05g

[0149]

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After preparing the above liquid, the turbidity of the liquid was measured, and the state of the liquid was visually observed. As shown in Table 5, although the coating liquid of the present invention was slightly cloudy, the liquid turbidity was small and no precipitation was observed. In particular, the levels 105 and 106 at which the concentrations of cations and anions are reduced
Is a stable coating liquid having a smaller liquid turbidity. In the comparative example, the turbidity was large at the level 151 where both the cation and the anion were at a high concentration, and more precipitation occurred.
It is considered that the liquid turbidity slightly decreased at the levels 152 and 153 in which the anions were reduced, but the turbidity was still large and coarse particles such as aggregates were present.

Further, after the undercoating coating solution was applied, the applicability of the undercoating layer was observed. As shown in Table 5, it is understood that the undercoat layer of the present invention has no repelling or unevenness of the undercoat layer, has a small haze value, and maintains good transparency of the support. But,
In Comparative Examples 151 to 153, repelling defects occurred frequently because precipitation was caused by aggregates in the undercoat coating liquid.

<Preparation and application of back surface side working fluid> Sample A
On the side opposite to the undercoat layer, the following antistatic layer coating solution was applied by an extrusion coater so as to be 20 ml / m ^2, and dried at 90 ° C. for 30 seconds. Subsequently, the coating liquid for the sliding layer was applied at 15 ml / m ^{2 with an} extrusion coater.
And dried at 90 ° C. for 20 seconds.
After the application of the undercoat layer coating solution for the side surface of the silver halide emulsion and the back side surface, the film was further dried at 100 ° C. for 3 minutes. This was designated as Sample B.

<< Preparation of Antistatic Layer Coating Solution >> Alumina Sol AS-100 (solid content 10%, manufactured by Nissan Chemical Industries, Ltd.) 40 g Cellulose diacetate 5 g Acetone 550 ml Methanol 450 ml << Preparation of Sliding Layer Coating Solution >> Carnauba wax (melting point 83) C) 1.0 g Toluene 700.0 cc Methyl Ethyl Ketone 300.0 cc This sample B was subjected to a blocking test. As shown in Table 5, the photographic support of the present invention had few occurrences of blocking, and good results were obtained. On the other hand, in the comparative example, blocking was observed on almost the entire surface. From these results, it can be seen that the photographic support of the present invention has both good coatability of the undercoat layer and blocking resistance.

[Measurement of turbidity of undercoat coating liquid and haze of support coated with undercoat layer] (Digital turbidity meter, integrating sphere photoelectric scattering photometer, MODEL T, manufactured by Tokyo Denshoku Technical Center)
Using -2600 DA (with haze measurement), the turbidity of the coating solution was measured by pouring the coating solution into a glass cell, and measuring the haze of the support by cutting the sample to a size of 5 cm × 5 cm. The smaller the turbidity value of the coating liquid, the better the absence of aggregates and coarse particles. As for the haze of the support, the smaller the haze value, the higher the transparency and the better.

[Observation of condition of undercoating coating solution]
100 ml was put into a 200 ml glass beaker made of a colorless and transparent hard glass, the opening was closed with a polyethylene sheet, and allowed to stand for 24 hours. After standing, the bottom of the beaker was looked at, and the presence or absence of precipitation was observed.

[Observation of coatability of undercoat layer-coated surface] The sample was observed with transmitted light under a fluorescent lamp, and the presence or absence of coating unevenness defects was observed. The sample was immersed in a 40 ° C. aqueous solution containing 1% by weight of ethyl violet for 5 minutes, and then dried. The stained sample was cut into a size of 20 cm × 2 m, and the number of occurrences of repelling failure was observed with a transmitted light on a Shakasten with a × 10 loupe.

[Blocking test] 23 ± 2 ° C., 55 ±
The sample with the undercoat layer left for 4 hours or more under 5% RH was cut into a size of 35 mm × 35 mm. Five samples are superposed so that the back surface and the undercoat layer application surface are in contact with each other, and a load of 5 kg per 35 mm × 35 mm is applied from above. This is left for 24 hours in an atmosphere of 40 ± 3 ° C. and 80 ± 5% RH. Twenty-four hours later, the weight was removed, and the surface condition of the undercoat layer-coated surface of each of the four samples in contact with the back surface was observed and evaluated as follows.

: Blocking occurs only in an area of less than 5% of the undercoating surface. △: Blocking occurs in an area of 5 to 20% of the undercoating surface. Δ: Blocking occurs in an area of 20 to 40% of the undercoating surface. Occurrence △ ×: Blocking occurred on an area of 40 to 60% of the undercoating surface ×: Blocking occurred on an area of 60% or more of the undercoating surface

[0159]

[Table 5]

Example 2 Next, on the undercoat layer of Sample B of Example 1, each layer of a silver halide photographic constituting layer as shown below was simultaneously laminated and applied. The addition amount is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (abbreviated as SD) were shown in moles per mole of silver.

<First Layer (Antihalation Layer)> Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.044 OIL-1 0.044 Gelatin 1.33 <Second Layer (Intermediate Layer)> AS-1 0.16 OIL-1 0.20 Gelatin 1.40 <Third layer (low-sensitivity red-sensitive layer)> Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 0 × 10 ^-5 SD-4 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 SD-6 3.0 × 10 ^-6 C-1 0.51 CC-1 0.047 OIL-2 0.45 AS-2 0.005 Gelatin 1.40 <4th layer (medium-speed red-sensitive layer)> Silver iodobromide c 0.64 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.22 CC-1 0.028 DI-1 0.002 OIL-2 0.21 AS-3 0.006 Gelatin 0.87 <Fifth layer (high-sensitivity red-sensitive layer)> Silver iodobromide c 0.13 Silver iodobromide d 1.14 SD-1 3.0 × 10 ^-5 SD- ²¹ 0.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.085 C-3 0.084 CC-1 0.029 DI-1 0.027 OIL-2 0.23 AS-30 0.013 Gelatin 1.23 <Sixth layer (intermediate layer)> OIL-1 0.29 AS-1 0.23 Gelatin 1.00 <Seventh layer (low-sensitivity green photosensitive layer)> Silver iodobromide a 0 .245 silver iodobromide b 0.105 SD-5 5.0 × 10 ^-4 SD-6 5.0 × 10 ^-4 M-1 0.21 CM-2 0.039 OIL-1 0.25 AS- 2 0.003 AS-4 0.063 Gelatin 0.98 <Eighth layer (intermediate layer)> M-1 0.03 CM-2 0.005 OIL-10 .16 AS-1 0.11 Gelatin 0.80 <Ninth layer (medium-sensitive green photosensitive layer)> Silver iodobromide e 0.87 SD-7 3.0 × 10 ^-4 SD-8 6.0 × ^10-5 SD-9 4.0 x ^10-5 M-1 0.17 CM-2 0.048 CM-3 0.059 DI-2 0.012 OIL-1 0.29 AS-4 0.05 AS −2 0.005 Gelatin 1.43 <10th layer (high-sensitivity green photosensitive layer)> Silver iodobromide f 1.19 SD-7 4.0 × 10 ^-4 SD-8 8.0 × 10 ^-5 SD-9 5.0 × 10 ^-5 M-1 0.09 CM-3 0.020 DI-3 0.005 OIL-1 0.11 AS-4 0.026 AS-5 0.014 AS-60 0.0006 Gelatin 0.78 <11th layer (yellow filter layer)> Yellow colloidal silver 0.05 OIL-1 0.18 AS-7 16 Gelatin 1.00 <Twelfth layer (low-sensitivity blue-sensitive layer)> Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-10 8.0 × 10 ^-4 SD-11 3.1 × 10 ^-4 Y-1 0.91 DI-4 0.022 OIL-1 0.37 AS-2 0.002 Gelatin 1.29 <13th layer (high-sensitivity blue-sensitive layer)> Silver iodobromide h 0.13 Silver iodobromide i 1.00 SD-10 4.4 × 10 ^-4 SD-11 1.5 × 10 ^-4 Y-1 0.48 DI-4 0.019 OIL-1 0.21 AS −2 0.004 Gelatin 1.55 <14th layer (first protective layer)> Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.63 Gelatin 1.32 <15th layer (second protective layer)> PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Chin 0.55 In addition to the above compositions, SU-1 (coating aid), S
U-2 (coating aid), SU-3 (coating aid), SU-4
(Dispersion aid), V-1 (viscosity modifier), ST-1 (stabilizer), ST-2 (stabilizer), AF-1 (polyvinylpyrrolidone as an antifoggant having a weight average molecular weight of 10,000) ), AF-2 (weight average molecular weight: 1,100,
000, polyvinyl pyrrolidone as an antifoggant), AF-3 (inhibitor), AF-4 (inhibitor), AF
-5 (inhibitor), H-1 (hardener), H-2 (hardener)
And Ase-1 (preservative).

The characteristics of the above silver iodobromide are shown in Table 6, and the structure of the above compound is shown below.

[0163]

[Table 6]

[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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As examples of preferred formation of silver halide grains of the present invention, preparation examples of silver iodobromide d and f are shown below.

<Preparation of seed crystal emulsion-1> A seed crystal emulsion was prepared as follows.

The following solution A1 adjusted to 35 ° C. was mixed with an aqueous solution of silver nitrate (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (iodine) using a mixing stirrer disclosed in JP-B-58-58288. 2 mol%) was added over 2 minutes by the simultaneous mixing method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) to allow nucleation. went. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was applied to a silver potential of 9 m
While maintaining V, the mixture was added over 42 minutes by the double jet method. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side ratio of 1.0% or more of 90% or more of the total projected area of silver halide grains.
~ 2.0 hexagonal tabular grains.
This emulsion is referred to as seed emulsion-1.

<< Solution A1 >> Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml <Preparation of silver iodide fine grain emulsion SMC-1> 6.0% by weight containing 0.06 mol of potassium iodide While vigorously stirring 5 liters of an aqueous gelatin solution, 2 liters of a 7.06 mol aqueous solution of silver nitrate and a 7.06 mol aqueous solution of potassium iodide were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

<Preparation of silver iodobromide d> 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH ₂ O) _m [CH (C
H ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H, (m + n =
9.77) containing 0.5 ml of a 10% ethanol solution.
700 ml of a 4.5% by weight aqueous inert gelatin solution is added to 75
C., the pAg was adjusted to 8.4 and the pH to 5.0, and then particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) A 2.1 mol aqueous solution of silver nitrate and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 8.4 and the pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
g was adjusted to 9.8. Thereafter, 0.071 mol of SM
C-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to p
Ag was added at 9.8 and the pH was maintained at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was composed of tabular grains having a halogen composition of 0.75 μm in side length, an average aspect ratio of 5.0, and a halogen composition of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 6.7 mol%.

<Preparation of silver iodobromide f> In the preparation of silver iodobromide d, the pAg was set to 8.8 in step 1), the amount of silver nitrate added in step 3) was 0.92 mol, and SMC- Silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of 1 was 0.069 mol.

The obtained emulsion had a particle size (cubic 1 of the same volume).
An emulsion comprising tabular grains having a halogen composition of 0.65 μm, an average aspect ratio of 6.5, and a halogen composition of 2 / 8.5 / X / 7 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-described sensitizing dyes were added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added, and the fog and the sensitivity were determined according to a conventional method. Chemical sensitization was applied to optimize.

Silver bromoiodides a, b, c, e, g, h, i and j were also subjected to spectral sensitization and chemical sensitization in accordance with d and f described above.

A sample coated with the above-mentioned silver halide photographic component layer and the like was designated as Sample C, and the undercoat layers had level numbers 101 to 106,
In this order, 201-2 correspond to 151-153, respectively.
06, 251-253. Here, the applicability of the photographic constituent layer was observed.

As shown in Table 7, the samples of the present invention had good coatability of the photographic constituent layers. On the other hand, in the comparative example, application unevenness was observed and the application property was unsightly. Also,
As a result of observation with a × 10 loupe, generation of countless pinhole-shaped repelling defects was observed.

Further, the adhesion test of Sample C to the support of the photographic component layer was conducted. As shown in Table 7, the adhesiveness in the developing solution was in the range of 201 to 201 which is the sample of the present invention.
205 is almost good in B rank. The result of 206 was close to the A rank, and the result was even better. On the other hand, the comparative example was inferior in the adhesiveness in the D or E rank.

Similarly, with respect to the adhesiveness before and after the development treatment, the samples of the present invention, levels 201 to 204, have almost no peeling off and are almost good. No peeling was observed in 205 and 206, which was a better result. On the other hand, in the comparative example, before and after development, almost no eyes remained, resulting in poor adhesion. In the comparative example, the coating property of the undercoat layer was poor in the first place, the uniform coating property / adhesion property of the photographic constituent layer was not obtained, and the blocking agent was poor. It is considered that the adhesiveness of the constituent layers was deteriorated. On the other hand, the reason why the adhesiveness of the photographic constituent layer is good in the present invention is as follows. Good coatability of the undercoat layer,
2. Since the blocking between the undercoat layer and the back surface of the support does not occur, it is not affected by transfer to the back surface side or from the back surface side. 3. Since the undercoat layer gelatin has a low ion content, it is near the ionic point where it is difficult to swell and dissolve, and it can be estimated that swelling of the undercoat layer by the developer is suppressed and that the adhesiveness in the developer is good.

[Observation of Coatability of Photo Constituent Layer] Under a fluorescent lamp, pinhole defects were observed from the photographic constituent layer side using a × 10 loupe. The number of defects is 20cm x sample
The number of occurrences in 2 m was taken. Further, the coatability of the photographic constituent layer adjacent to the undercoat layer was visually observed from the back surface side, and the occurrence of coating unevenness defects and the state of occurrence were observed.

[Adhesion Test of Photo Constituent Layer] The adhesion test in the photographic processing solution was performed by immersing a sample cut into a size of 35 mm × 14 cm in a color developing solution shown below at 38 ± 2 ° C.
Immediately after the elapse of the minute, the sample was pulled up, and immediately the end of the sample was repeatedly rubbed 15 times.

Color developing solution Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

Thereafter, evaluation was made based on the peeled length of the photographic component layer at the rubbed end portion of the sample.

A: No peeling occurred B: 1 mm or less peeled C: 1 to 2 mm peeled D: 2 to 4 mm peeled E: 4 mm or more peeled The undeveloped and the adhesiveness test after the developing treatment was as follows. After performing the following development process, 23 ±
The sample which had not been subjected to development was left at 23 ± 2 ° C. and 55 ± 5% RH atmosphere for 4 hours in a 2 ° C., 55 ± 5% RH atmosphere.

(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2. 0 ° C. 830 ml Stabilizing 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 55 ± 5.0 ℃ - ※ replenishing amount is a value per silver halide photographic light-sensitive material 1 m ^2.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developing solution and color developing replenisher Developer replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium bicarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N-([beta] -hydroxyethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water was added to make up to 1 liter. The color developing solution was adjusted to pH 10.06 using potassium hydroxide or 20% sulfuric acid and the replenisher was adjusted to pH 10. Adjust to 18.

Bleach and Bleach Replenisher Bleach Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water To a liter, and the pH of the bleaching solution is adjusted to pH 4 using aqueous ammonia or glacial acetic acid. In 4, adjust the replenisher to pH 4.0.

Fixer and Fixer Replenisher Fixer Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g The fixer was adjusted to pH 6.2 using aqueous ammonia or glacial acetic acid. After adjusting the replenisher to pH 6.5, add water to make up 1 liter.

Stabilizing Solution and Stabilizing Replenishing Solution Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC 0.1 g ammonia water 0.5 ml water was added to make up to 1 liter, and then the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

[0203] Razors are used to make six vertical and horizontal cuts at intervals of 3 to 5 mm in the photographic constituent layer of the sample to form 5 x 5 squares. Here, Nichiban Co., Ltd. cellotape,
It was attached at a pressure of 1 kg / cm ² . The cellophane tape was peeled off at a speed of 5 m / sec, and the number of remaining photographic constituent layers that did not peel off from the support surface was observed. It was evaluated that the larger the remaining number, the better.

[0204]

[Table 7]

Example 3 The support used in this example was produced in the same manner as the TAC support of Example 1. The following surfactant A-1 was added to the undercoat coating solution of Example 1 so as to have a concentration of 0.1%. No change was observed with Agent A-1.
Further, under the same coating film thickness and drying conditions as in Example 1, observation of the applied surface of the undercoat layer and haze measurement were performed after application, and the same results as in Example 1 were obtained. Further, the same antistatic layer coating solution and sliding layer coating solution as in Example 1 were applied, and after coating, the same blocking test as in Example 1 was performed. No change due to activator A-1 was observed.

[0206]

Embedded image

Example 4 The same silver halide photographic constituent layer as in Example 2 was overlaid on the undercoat layer of the support obtained in Example 3, and the coatability of the photographic constituent layer and the photographic constituent layer And the support were tested for adhesion. The result almost reproduced Example 2, and no change due to the surfactant A-1 was observed.

Example 5 A support similar to the TAC support of Example 1 was prepared in the same manner as in Example 3, and the nonionic fluoropolymer surfactant II-4 was added to the undercoat coating solution of Example 1. Is added so as to be 0.002%, and 507 to 512 corresponding to the levels 101 to 106 and 554 to 5 corresponding to 151 to 153 in Example 1.
56. In the same manner as in Example 1, the turbidity of the liquid was measured, and the liquid was visually observed. As shown in Table 8, the turbidity and visual results of the undercoat coating solution were almost the same as those of Example 1, and no change was observed by the nonionic fluoropolymer surfactant II-4. Thereafter, the composition was applied on a TAC support under the same conditions as in Example 1, and the undercoat layer was evaluated.

As shown in Table 8, the coatability of the undercoat layer was good as in Example 1. Further, the same antistatic layer and sliding layer as those in Example 1 were applied, and a blocking test was performed.
In the blocking test, 508 and 510 reached the △ level, and 511 and 512 achieved the レ ベ ル level. This was improved from the result of Example 1, and it was confirmed that the blocking was further improved by including the nonionic fluoropolymer surfactant.

[0210]

[Table 8]

Example 6 The same silver halide photographic constituting layer as in Example 2 was used in Example 5
Was applied on the undercoat layer of the support obtained in the above, and the coating property of the photographic constituent layer and the adhesion test between the photographic constituent layer and the support were tested.

Undercoat layer level numbers 507 to 512, 554
607 to 612 in this order corresponding to
654 to 656. Here, the applicability of the photographic constituent layer was observed.

As shown in Table 9, the samples of the present invention had good coating properties of the photographic constituent layers. On the other hand, in the comparative example, no coating unevenness was observed, but countless pinhole-shaped repelling defects were observed. Further, in the same manner as in Example 2, an adhesion test of the photographic constituent layer with the support was conducted.

As shown in Table 9, the adhesiveness in the developing solution was almost good at B for samples 607 to 610 of the present invention. 611 and 612 reached the A rank, and were more favorable results. On the other hand, the comparative example was inferior in the adhesiveness in the D or E rank. Regarding the adhesiveness before and after the development processing, the sample of the present invention had a level of 60.
Nos. 7 to 610 are few in number of peeling, and are almost good. 611, 61
In No. 2, no peeling was observed, and the results were even better. On the other hand, in the comparative example, before and after development, almost no eyes remained, resulting in poor adhesion.

[0215]

[Table 9]

Example 7 A TAC support was prepared in the same manner as in Example 1, and 0.09 g of VS-1 was used in place of the crosslinking agent I in the undercoat coating solution of Example 1.
Using. Further, the level numbers 701 to 706 and 751 to 75
No. 3 was not added with a surfactant, and had a level number of 707 to 712.
And 754 to 756, 0.002% of a nonionic fluorine-containing polymer surfactant II-4 was added. In the same manner as in Example 1, the turbidity of the liquid was measured, and the liquid was visually observed.

As shown in Table 10, the turbidity of the undercoat
The results of visual observation were almost the same as those of Examples 1 and 5, and no change due to the crosslinking agent VS-1 was observed. Thereafter, the composition was applied on a TAC support under the same conditions as in Example 1, and the undercoat layer was evaluated.

As shown in Table 10, the coatability of the undercoat layer was good. Further, the same antistatic layer and sliding layer as those in Example 1 were applied, and a blocking test was performed. In the blocking test, 701 to 704 and 707 to 709 reached the △ level, and further, 705, 706, and 710 to 712 achieved the を level, showing even better results. This is improved from the results of Examples 1 and 5, and the blocking is improved by changing the crosslinking agent from I to VS-1, and the crosslinking agent VS-1 and the nonionic fluoropolymer surface activity are improved. Further improvement was observed with the combination of agents.

[0219]

[Table 10]

Example 8 The same silver halide photographic component layer as in Example 2 was used in Example 7
Was applied on the undercoat layer of the support obtained in the above, and the coating property of the photographic constituent layer and the adhesion test between the photographic constituent layer and the support were tested.

Undercoat layer level numbers 701 to 712, 751
801 to 812 in this order corresponding to ~ 756, respectively.
851 to 856. As a result of observing the coatability of the photographic constituent layer, as shown in Table 11, the sample of the present invention had good coatability of the photographic constituent layer. On the other hand, in the comparative example, generation of countless pinhole-shaped repelling defects was observed. Also,
In the same manner as in Example 2, an adhesion test of the photographic component layer with the support was performed.

As shown in Table 11, the adhesiveness in the developing solution was at a level of 801, 802, 8 of the sample of the present invention.
07 is almost good for B. 803, 804, 808, 80
9 is B to A and improved, 805, 806, 810 to 812
Reached A rank, and the result was further improved. On the other hand, in the comparative examples, 855 and 856 show the C rank, but the other ranks become the D or E rank, resulting in poor adhesion. Regarding the adhesiveness before and after the development process,
Levels 801-804, 807-
810 is good with a small number of strips. 805, 806, 81
Nos. 1, 812 did not show any peeling, and were more favorable results. On the other hand, in the comparative example, before and after development, almost no eyes remained, resulting in poor adhesion. From these results, it was confirmed that the adhesiveness in the developing solution was particularly improved as compared with Examples 2 and 6, and further improved by changing the crosslinking agent from I to VS-1.

[0223]

[Table 11]

Example 9 A TAC support similar to that of Example 1 was prepared, and 0.7 g of diacetyl cellulose (Teijin acetate flake, manufactured by Teijin Limited) was dissolved in acetone in the undercoat coating solution of Example 1. Was added. Further, level numbers 901 to 906 and 95
No surfactant was added to Nos. 1 to 953, and Level No. 907 was used.
To 912 and 954 to 956, nonionic fluorine-containing polymer surfactant II-4 was added so as to be 0.002%. The cross-linking agent I was used at all levels. In the same manner as in Example 1, the turbidity of the liquid was measured and visually observed.

As shown in Table 12, the turbidity of the undercoat coating solution was higher than in Examples 1 and 5, but no precipitate or the like was observed by visual inspection. Since the acetone solution of diacetyl cellulose was slightly turbid, it is estimated that the turbidity of the undercoating coating liquid also increased. However, no aggregation or precipitation due to diacetyl cellulose was observed. Thereafter, the composition was applied on a TAC support under the same conditions as in Example 1, and the undercoat layer was evaluated. As shown in Table 12, the undercoat layer coatability was good. Further, the same antistatic layer and sliding layer as those in Example 1 were applied, and a blocking test was performed.
In the blocking test, 901 to 903, 907, and 908 reached the △ level, and 904 to 906, 909 to 9
No. 12 achieved the ○ level, and showed even better results. This is better than the results of Examples 1 and 5, and the addition of diacetylcellulose improves blocking, and the combination of diacetylcellulose and a nonionic fluoropolymer surfactant further blocks. It was found to improve.

[0226]

[Table 12]

Example 10 The same silver halide photographic constituent layer as in Example 2 was used, except that Example 9
Was applied on the undercoat layer of the support obtained in the above, and the coating property of the photographic constituent layer and the adhesion test between the photographic constituent layer and the support were tested.

Undercoat layer level numbers 901 to 912, 951
1001 to 101 in this order corresponding to 956, respectively.
2, 1051 to 1056.

As a result of observing the coating properties of the photographic constituent layers, Table 1 was obtained.
As shown in FIG. 3, the sample of the present invention had good coatability of the photographic constituent layer. On the other hand, in the comparative example, generation of countless pinhole-shaped repelling defects was observed. Further, in the same manner as in Example 2, an adhesion test of the photographic constituent layer with the support was conducted.

As shown in Table 13, the adhesiveness in the developing solution was 1001, 100%, which was the sample of the present invention.
2,1007 is almost good in B. 1003, 1008,
1009 is B to A and improved, 1004 to 1006, 10
10 to 1012 reached A rank, and the result was further improved. On the other hand, Comparative Examples 1055 and 1056
Although the ranks were shown, the others were ranked D or E, resulting in poor adhesion. Regarding the adhesiveness before and after the development processing, the samples of the present invention were at the level of 1001, 1
004 and 1007 to 1009 are good with a small number of peelings. 1
No peeling was observed in 003, 1005, 1006, 1010 to 1012, and the results were even better. On the other hand, in the comparative example, before and after development, almost no eyes remained, resulting in poor adhesion. The results of the adhesiveness before and after the development, particularly before and after the development, are better than those in Examples 2 and 6, and it was confirmed that the addition of diacetylcellulose further improved the results.

[0231]

[Table 13]

Example 11 A TAC support was prepared in the same manner as in Example 1, and 0.7 g of diacetyl cellulose (Teijin acetate flake, manufactured by Teijin Limited) was dissolved in acetone in the undercoat coating solution of Example 1. Was added. No surfactant is added to the level numbers 1101 to 1106 and 1151 to 1153, and the nonionic fluoropolymer surfactant II-4 is 0.002% to the level numbers 1107 to 1112 and 1154 to 1156. Was added as follows. As a cross-linking agent, 0.09 g of VS-1 was used in all levels. The turbidity measurement of the liquid as in Example 1,
Visual observation was made.

As shown in Table 14, the turbidity of the undercoat coating solution was higher than that of Example 7 as in Example 9, but no precipitate or the like was observed by visual inspection. The increase in turbidity is presumed to be due to diacetyl cellulose. Thereafter, the composition was applied on a TAC support under the same conditions as in Example 1, and the undercoat layer was evaluated.

As shown in Table 14, the coatability of the undercoat layer was good. Further, the same antistatic layer and sliding layer as those in Example 1 were applied, and a blocking test was performed. In the blocking test, although 1101 showed the △ level, 1102
１1112 achieved the ○ level and showed good results.
This is better than the results of Example 7 and Example 9,
It was confirmed that the combination of diacetyl cellulose and the crosslinking agent VS-1 improved the blocking, and the combination of the nonionic fluoropolymer surfactant further improved the blocking.

[0235]

[Table 14]

Example 12 The same silver halide photographic constituent layer as in Example 2 was overlaid on the undercoat layer of the support obtained in Example 9, and the coatability of the photographic constituent layer and the photographic constituent layer And the support were tested for adhesion.

Undercoat layer level numbers 1101 to 1112, 1
120 corresponding to 151 to 1156, respectively.
1 to 1212 and 1251 to 1256. As a result of observing the coatability of the photographic constituent layer, as shown in Table 15, the sample of the present invention had good coatability of the photographic constituent layer. On the other hand, in the comparative example, generation of countless pinhole-shaped repelling defects was observed. Further, in the same manner as in Example 2, an adhesion test of the photographic constituent layer with the support was conducted.

As shown in Table 15, the adhesiveness in the developing solution was the same as that of the samples of the present invention at levels 1201 and 1207.
Is almost good in B. 1202 is B to A and improved, 1203 to
1206, 1208 to 1212 reached the rank A, and the result was further improved. In contrast, the comparative example is 125
Although 3 to 1256 show the C rank, the other ranks became the D rank, resulting in poor adhesion. Regarding the adhesiveness before and after the development processing, the sample of the present invention had a level of 120.
4, 1207 to 1209 are good with a small number of peeling. 120
No peeling was observed in 1-11203, 1206, and 1210-1212, and the results were even better. On the other hand, in the comparative example, before and after development, almost no eyes remained, resulting in poor adhesion. In particular, the results of the adhesiveness before and after the development were better than those in Examples 8 and 10, and it was confirmed that the addition of diacetyl cellulose and the crosslinking agent VS-1 further improved the results.

[0239]

[Table 15]

From the results of the above Examples, the photographic support of the present invention, that is, the anion was converted to hydroxide ion (OH ⁻ )
The amount of calcium ions (Ca ²⁺ ) contained in a deionized gelatin binder obtained by ion-exchanging cations to hydrogen ions (H ⁺ ) is 400 pp with respect to dry gelatin.
A photographic support having an undercoat layer using a gelatin binder having a sodium ion (Na ⁺ ) of 8,000 ppm or less based on dry gelatin has excellent coatability and blocking resistance of the undercoat layer. Thus, the silver halide photographic light-sensitive material obtained from the photographic support of the present invention was excellent in the coating property of the photographic constituent layer and the adhesion between the photographic constituent layer and the support. It was found that only the present invention was able to achieve both the coatability and blocking resistance of the undercoat layer of the support and the coatability and adhesiveness of the photographic component layer.

Example 13 On one side of a cellulose triacetate film 120 μm, an undercoat layer coating solution S-1 was applied at 20 ml / m ² using an extrusion coater, dried at 100 ° C. for 20 seconds, and applied to the other side. The antistatic layer coating solution U-1 was applied at 20 ml / m ² with an extrusion coater, dried at 80 ° C. for 40 seconds, and the outermost layer coating solution P-1 was coated at 15 ml / m 2 with an extrusion coater. ² coats, 80
Drying was performed at 12 ° C. for 12 seconds and subsequently at 75 ° C. for 2 minutes.

<Preparation of Gelatin for Undercoat Layer> Lime treatment, water washing and neutralization treatment were carried out, and lime treatment was carried out using ossein.
Extraction was performed at 5-60 ° C. Next, the extracted gelatin was subjected to both ion exchange using anion exchange treatment (Diaion PA-31G) and cation exchange treatment (Diaion PK-218). Gelatin G-11 to G-1
No. 3 was produced by changing the number of times of the ion exchange treatment.

Gelatin G-11: 410 ppm of Ca ²⁺ ,
^{Na + 8200ppm, Cl - 540ppm,} SO 4 2- 1
60 ppm G-12: Ca ²⁺ 40 ppm, Na ⁺ 600 ppm, C
_{^{l - 530ppmSO 4 2- 170ppm G-}} 13: Ca 2+ 10ppm, Na + 400ppm, C
l ^- 270 ppm, the SO ₄ ^2- 30ppm <Coating Solution S-1> Table 16 according charge table 16 according to gelatin 1g Table 16 fluorochemical surfactant table 16 according according crosslinking agent 0.05g Diacetylcellulose Table 16 Amount described Water 3 cc Acetic acid 3 cc Methanol 31 cc Acetone 63 cc <Coating solution U-1> Copolymer [N-vinylbenzyl-N, N] was obtained by the method described in the lower right column (22) of page 6 of JP-A-53-45231. , N-Trimethylammonium chloride-co-ethylene glycol dimethacrylate]
(97: 3) was synthesized and designated as T-1.

T-1 0.5 g Cellulose diacetate 0.5 g Methanol 60 cc Acetone 40 cc <Coating solution P-1> nC ₁₇ H ₃₅ COOC ₃₀ H ₆₁ -n 0.12 g nC ₃₀ H ₆₁ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Diacetyl cellulose 0.2 g Xylene 58 cc Acetone 42 cc On the undercoating layer S-1, a silver halide emulsion layer of JX400 (ISO400) of 135 size standard manufactured by Konica Corp. By coating, a silver halide photographic light-sensitive material was prepared.

Further, the obtained silver halide photographic light-sensitive material was subjected to color negative development processing of CNK-4 manufactured by Konica Corporation, and evaluated before and after the development processing.

[Blocking Property] The sample before coating the silver halide emulsion layer was 35 mm in width and 1 m in length, and was heated at 40 ° C. and 8 ° C.
After conditioning for 24 hours in an atmosphere of 0% RH, the core was wound around a core having a diameter of 1 cm with a tension of 0.3 kg / cm, and allowed to stand for 3 days in the same atmosphere. After that, unwind the sample,
The surface condition of the undercoat layer surface was visually observed as follows. If the rating is B or higher, there is no practical problem.

A: No change in undercoat layer surface B: Deformation is observed in an area of less than 20% of the undercoat layer surface C: Deformation is observed in an area of 20% or more and less than 60% of the undercoat layer surface D : Deformation is observed in an area of 60% or more of the surface of the undercoat layer.

[Adhesiveness] The sample before and after the development was heated at 23 ° C.
After adjusting the humidity at 55% RH for 12 hours, a scratch made by cutting the back surface with a cutter at 90 degrees and a cut made by cutting the blade at a 45-degree angle to the front from a right angle are made in parallel with the wound. Nichiban cellophane tape 24 mm wide is applied so as to straddle these wounds, and the surface is rubbed back and forth five times with a load of 500 g. The cellophane tape was instantaneously peeled off from the front, and the peeling of the back surface was evaluated. Peeling must not occur, but in this evaluation, there is no practical problem if the rank is B or higher.

A: There is no peeling of the back surface. B: Less than 5% of the adhesive area of cellophane tape is peeled off from a scratch of 45 degrees. C: 5% or more of the adhesive area of cellophane tape is peeled off from a scratch of 45 degrees. D: 90 Most of the adhesive area of the cellophane tape has peeled off from the scratch.

[Wet Adhesion Property] The sample was immersed in the color developing solution (38 ° C., pH 10.06) of the above-mentioned development treatment for 3 minutes, and immediately after being lifted, the end of the silver halide emulsion layer surface of the sample was put on with rubber gloves. Rubbed strongly 20 times. The peeled length of the rubbed portion of the emulsion layer was evaluated. A is preferable, but if it is at B level, there is no practical problem.

A: No peeling occurred B: Peeling less than 2 mm C: Peeling not less than 2 mm and less than 4 mm D: Peeling not less than 4 mm The evaluation results are shown in Table 16.

[0252]

[Table 16]

In the case where the outermost surface of the back surface contains a binder and a slipping agent and the undercoat layer is not the gelatin of the present invention, the blocking property and the wet state and the adhesion after development are particularly poor. In the case of the constitution, it is excellent in all of the blocking property and the adhesive property.

Example 14 Example 14 was the same as Example 13 except that S-2 was used instead of S-1, U-2 was used instead of U-1, and P-2 was used instead of P-1. A silver halide photographic light-sensitive material was prepared in the same manner as in No. 13 and subjected to development processing in the same manner, and the following evaluations were made before and after development.

<Coating Solution S-2> Gelatin G-3 1 g Nonionic fluorinated polymer surfactant II-4 0.006 g Crosslinker VS-1 0.090 g Diacetyl cellulose 0.7 g Water 3 cc Acetic acid 2 cc Methanol 30 cc Acetone 65 cc <Coating solution U-2> Tin oxide-antimony oxide composite fine particles (average particle size 0.05 μm) 1 g Diacetyl cellulose 0.44 g Acetone 90 cc Cyclohexanone 10 cc <Coating solution P-2> 100 parts by weight of water heated to 90 ° C. ,
Carnauba wax 40 mixed with 4 parts by weight of polyoxyethylene lauryl ether and separately melted at 90 ° C.
After the addition of parts by weight, the mixture was sufficiently stirred using a high-speed stirring homogenizer to prepare a carnauba wax dispersion.

WAX-1 Amount described in Table 17 Binder described in Table 17 0.2 g Acetone 12 cc Water 38 cc N, N-dimethylformamide 15 cc Methanol 35 cc As a comparative coating solution, WAX was used in coating solution P-2.
Those containing no -1 and no binder (in that case, 0.1 g of WAX-1) were prepared.

[Transferability] The sample before coating the silver halide emulsion layer was 35 mm in width and 1 m in length, and was heated at 40 ° C. and 80% R
After conditioning for 24 hours in an H atmosphere, it was wound around a core having a diameter of 1 cm with a tension of 0.3 kg / cm, and allowed to stand for 7 days in the same atmosphere. Thereafter, the sample is unwound and the undercoat layer surface is immersed in a 1% by weight solution of methyl violet at 40 ° C.
After soaking for a minute, uneven dyeing was observed. A is preferable, but at B level, there is no effect on the applicability of the photographic constituent layer, and there is no practical problem. Below the C level, repelling failure occurs during application of the photographic constituent layer.

A: Uniformly dyed B: There is slight unevenness in density but no cissing (stained stain) C: In addition to unevenness in density, cissing is present in some places D: Repelling is scattered all over the surface.

[Scratch resistance] The sample after the development processing was treated with 23
After humidity control at 55 ° C. and 55% RH for 24 hours, a sapphire needle having a tip having a diameter of 25 μm is vertically applied to the back surface, and a continuous load of 0 to 50 g is applied to the surface at a speed of 10 mm / sec.
The sample after being scratched was placed on a Schaukasten, and the load-bearing strength at which flaws began to be seen through transmission was defined as flaw resistance. The larger the value, the better the scratch resistance.

[Wet Scratch Resistance] A sample was immersed in the color developing solution (38 ° C., pH 10.06) of the above-mentioned development treatment for 3 minutes, and a sapphire needle having a tip diameter of 0.5 mm was vertically applied to the back surface of the sample. 600m with continuous load of 0-200g
Scratch at a speed of m / min. Dry the scratched sample,
The sample was placed on a Schaukasten, and the load-bearing strength at which scratches began to be seen through transmission was defined as the scratch resistance. The larger the value, the better the scratch resistance.

Table 17 shows the results of the evaluation.

[0262]

[Table 17]

From the above results, even when the undercoat layer has the structure of the present invention, the scratch resistance is poor when the outermost layer on the back surface does not contain a slipping agent, and the transferability is poor when the binder does not contain a binder. On the other hand, the configuration of the present invention is excellent in all of transferability and scratch resistance.

Example 15 Polyethylene-2,6-naphthalate film 85 μm
Is wound around a stainless steel core having a diameter of 300 mm.
Heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours.

On both sides of this support, 12 W / m ² / min
Of the following coating solution S-3
Was 20 ml / m ² coated at extrusion coater, and 20 ml / m ² coated with a coating liquid B-3 on the other side by extrusion coater.

Each layer was dried at 90 ° C. for 10 seconds after the application, and after the two layers were applied, heat-treated at 110 ° C. for 2 minutes, and then cooled at 50 ° C. for 30 seconds.

<Coating solution S-3> Gelatin G-2 1 g Nonionic fluorinated surfactant I-2 0.010 g Crosslinking agent VS-1 0.090 g Water 28 cc Acetic acid 2 cc Methanol 70 cc <Coating solution B-3> Oxidation Aqueous dispersion of tin-antimony oxide composite fine particles (average particle size: 0.05 μm) (solid content: 40% by weight) 2.5 g Gelatin 0.1 g Water 27 cc Methanol 55 cc Acetone 15 cc Polyamide-epichlorohydrin resin (reaction between adipic acid and diethylenetriamine) A product obtained by reacting the product with epichlorohydrin by a conventional method) 0.01% of solid content of polyoxyethylene nonyl phenyl ether (degree of polymerization: 10) 0.01 g After coating the coating solution B-3, the following composition The magnetic recording layer coating solution M-1 was dried with an extrusion coater to a dry film thickness of 0. As will be [mu] m, 15 ml / m the following composition coating solution P-3 thereon by extrusion coater
^Two coats were formed, and each layer was dried at 80 ° C. for 40 seconds, and then dried at 75 ° C. for 2 minutes. At the same time as drying, the magnetic material was oriented in the application direction in an orientation magnetic field while the coating film was not dried, thereby achieving high output during magnetic recording and reproduction.

<Preparation of Magnetic Recording Layer Coating Solution M-1> The following magnetic substance, binder, and solvent were charged into a sand grinder and dispersed for 4 hours to prepare a magnetic substance dispersion 1.

Magnetic material (Co-γ iron oxide) 100 g Saturated copolyester urethane (weight average molecular weight: 25,000) 16 g Cyclohexanone 87 g Methyl ethyl ketone 87 g The following abrasive, binder and solvent were charged into a sand grinder and dispersed for 4 hours. Thus, an abrasive dispersion 1 was prepared.

Abrasive (Al ₂ O ₃ , average particle size 0.4 μm) 100 g Cellulose diacetate 22 g Cyclohexanone 91.5 g Methyl ethyl ketone 91.5 g Cellulose diacetate was dissolved in a solvent, and magnetic material dispersion 1 and polishing were performed. Agent Dispersion 1 was added, dispersed by a sand grinder for 1 hour, a hardener was added, and then sufficiently stirred and mixed to obtain a magnetic recording layer coating solution M-1.

Cellulose diacetate 100 g Cyclohexanone 218 g Methyl ethyl ketone 905 g Magnetic dispersion 1 20 g Abrasive dispersion 1 15 g Isocyanate hardener 20 g <Coating solution P-3> WAX-1 Amount described in Table 18 Diacetyl cellulose 0.2 g Acetone 12 cc water 38 cc N, N-dimethylformamide 15 cc methanol 35 cc fluorinated surfactant 0.006 g As a comparative coating solution, a solution containing no binder (in that case, 0.1 g of WAX-1) was prepared.

A silver halide emulsion layer was coated on the undercoat layer S-3 in the same manner as in Example 13 to prepare a silver halide photographic material. The following evaluation was performed.

The transferability of Example 14 was evaluated using the sample before the silver halide emulsion layer was coated.

[Magnetic Head, Film Stain Test] A sample was cut into a piece having a width of 2.4 cm and a length of 50 m.
A 6 KHz square wave signal was recorded at a transport speed of 100 m / s using a magnetic head capable of inputting and outputting a magnetic signal having a length of 7 mm, a head gap of 7 μm, and a number of turns of 1,000. Next, the state of the surface of the magnetic head and the state of the surface of the film back surface after the reading were observed when a test was performed using a magnetic reading head to read a square wave signal in the same direction as during recording.

A: Condition of magnetic head surface A: No dirt on head B: Slight dirt generation C: Dirt generation around head gap D: Dirt generation also on head gap E: Dirt generation on entire head surface In state, it is harmful.

Surface state of film back surface A: No scratches generated B: Marks passed by weak head C: Slight scratches generated D: Strong scratches generated In the states of C and D, there is actual harm.

The evaluation results are shown in Table 18.

[0278]

[Table 18]

The configuration of the present invention is excellent not only in transferability but also in magnetic head contamination and scratch resistance of the back surface, which are problems in the APS standard.

[0280]

BRIEF effects] photographic support of the undercoat layer to an anion of hydroxide ion (OH ^-), a cation of hydrogen ions (H ⁺⁾
By using an ion-exchanged deionized gelatin binder, an undercoating solution without agglomerates and coarse particles can be obtained, and by using the undercoating solution, the undercoat layer has excellent coating properties and excellent blocking resistance. A support can be obtained. Further, by using this photographic support, a silver halide photographic light-sensitive material having excellent coatability of the photographic constituent layer and excellent adhesion between the photographic constituent layer and the support can be obtained. Further, by applying the slipping agent and the binder of the present invention to the outermost layer located on the opposite side of the support from the photosensitive layer, excellent transfer resistance and scratch resistance can be obtained.

Claims (19)

[Claims] 1. A photographic support having an undercoat layer,
In the undercoat layer, anion in gelatin is converted to hydroxide ion (O
H ^-), the cation of hydrogen ions (H ⁺⁾ to ion exchanged with deionized gelatin binder of calcium ions (Ca ²⁺ in) 400 ppm or less with respect to content of dry gelatin, and sodium ions (Na ⁺⁾ content A photographic support characterized in that a deionized gelatin binder treated to 8,000 ppm or less based on dry gelatin is used. 2. The deionized gelatin binder has a chloride ion (Cl ⁻ ) content of 50 to dry gelatin.
2. The photographic support according to claim 1, wherein the binder is a deionized gelatin binder which has been treated with 0 ppm or less and a sulfate ion (SO ₄ ^2- ) content of 100 ppm or less based on dry gelatin. 3. The photographic support according to claim 1, wherein the undercoat layer contains a nonionic fluorinated surfactant. 4. The photographic support according to claim 1, wherein the undercoat layer contains a nonionic fluorine-containing polymer surfactant. 5. The photographic support according to claim 1, wherein the binder is cross-linked with a vinyl sulfone-type cross-linking agent. 6. The photographic support according to claim 1, wherein the undercoat layer contains a cellulose ester. 7. The photographic support according to claim 1, wherein the photographic support is cellulose triacetate. 8. A photographic support according to claim 1, wherein at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer are provided on one side of the photographic support. A silver halide photographic light-sensitive material having a photographic light-sensitive layer comprising a functional layer. 9. A silver halide photographic material having at least one photosensitive layer on a photographic support, wherein the outermost layer opposite to the surface having the photosensitive layer via the support is a slipping agent. A silver halide photographic light-sensitive material, characterized in that the silver halide light-sensitive material comprises a binder and a subbing layer of the photosensitive layer of the support contains deionized gelatin. 10. A silver halide photographic material having at least one photosensitive layer on a photographic support,
The outermost layer opposite to the surface having the photosensitive layer via the support contains a slip agent and a binder, and the undercoat layer of the photosensitive layer of the support contains gelatin and a nonionic fluorine-containing surfactant. A silver halide photographic material. 11. A silver halide photographic material having at least one photosensitive layer on a photographic support,
The outermost layer opposite to the side having the photosensitive layer via the support contains a slipping agent and a binder, and the undercoating layer of the photosensitive layer of the support contains gelatin and a nonionic fluoropolymer surfactant. A silver halide photographic light-sensitive material comprising: 12. A silver halide photographic material having at least one photosensitive layer on a photographic support,
The outermost layer opposite to the surface having the photosensitive layer through the support contains a slipping agent and a binder, and the undercoat layer of the photosensitive layer of the support contains gelatin and a vinyl sulfone type crosslinking agent. A silver halide photographic light-sensitive material comprising: 13. A silver halide photographic light-sensitive material comprising at least one light-sensitive layer on a photographic support,
The outermost layer opposite to the surface having the photosensitive layer through the support contains a slipping agent and a binder, and the undercoat layer of the photosensitive layer of the support contains gelatin and cellulose ester. Silver halide photographic light-sensitive material. 14. The silver halide photographic material according to claim 10, wherein the gelatin is deionized gelatin. 15. A silver halide photographic material having at least one photosensitive layer on a photographic support,
The outermost layer opposite to the surface having the photosensitive layer through the support contains a slipping agent and a binder, and the undercoat layer of the photosensitive layer of the support contains a fluorine-containing surfactant and a fluorine-containing polymer interface. A silver halide photographic material comprising at least one activator, deionized gelatin, a vinyl sulfone type crosslinking agent and a cellulose ester. 16. The silver halide photographic light-sensitive material according to claim 9, wherein the slip agent is a higher fatty acid ester. 17. The silver halide photographic material according to claim 9, wherein the binder is a cellulose ester. 18. The layer containing a binder and a slipping agent, wherein the ratio of the slipping agent to the binder is 10: 90-4.
The silver halide photographic light-sensitive material according to any one of claims 9 to 17, wherein the ratio is 5:55. 19. The silver halide photographic light-sensitive material according to claim 9, wherein the photographic support is a cellulose ester.