JPH03132755A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photogrpahic sensitive material good in slidability and scratch resistance and capable of preventing uneven drying after development processing by incorporating a higher fatty acid amide or ester and a partial ester of a higher fatty acid and a polyvalent alcohol in the outermost surface layer of a backing layer. CONSTITUTION:The outermost surface layer of the backing layer contains the fatty acid amide or ester, preferably, represented by general formula I: R1COR2, preferably, in an amount of 1-500 mg/m<2> of the photosensitive material, and the higher fatty acid partial ester of the polyvalent alcohol leaving one or more free hydroxyl groups, preferably, represented by general formula III-VII, preferably, in an amount of 0.1-60 wt.% of the higher fatty acid amide or ester.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material with improved slipperiness, scratch resistance, and drying unevenness after processing. It is.

[Prior Art] Silver halide photographic materials are manufactured through manufacturing processes such as coating, drying, processing, and winding during photographing, development, and printing.
Various devices,
The following serious adverse effects often occur due to contact friction with machines, cameras, etc., contact between the front and back surfaces of the silver halide emulsion layer due to overlapping of photosensitive materials, ItiTlln, or adhesion.

In other words, scratches may occur on the surface of the support on the side of the silver halide emulsion layer or the surface of the back layer, deterioration of the drive performance of the photosensitive material in various devices such as cameras, and film peeling of the photographic constituent layers due to adhesion. be.

In particular, in recent years, photosensitive materials have become more popular than ever due to the expansion of usage and processing methods for photosensitive materials (e.g., rapid imaging and rapid processing) and the diversification of usage environments such as use in high temperature and high humidity environments. As a result, various types of failures are likely to occur, particularly contact friction and contact failures involving the surface layers on both sides of the photosensitive material.

In order to solve these problems, it is well known that the back layer contains a slip agent.

[Problems to be Solved by the Invention] As such a slip agent, there is a method of using a higher fatty acid or an ester thereof as described in JP-A-1-161337. However, although this method provides good slipperiness, it has the disadvantage that the surface of the photosensitive material becomes extremely water-repellent, which tends to cause uneven drying during development.

Therefore, an object of the present invention is to provide a silver halide photographic material that has good slipperiness and scratch resistance and can prevent uneven drying after development.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to provide a silver halide emulsion layer having at least one silver halide emulsion layer on a support, and In a silver halide photographic light-sensitive material comprising at least one back layer on the side opposite to the silver halide emulsion layer with respect to the support, the at least one
What is achieved by providing a silver halide photographic material characterized in that the outermost surface layer of the back layer contains an amide or ester of a higher fatty acid and a partial fatty acid ester of a higher fatty acid or a polyhydric alcohol. I found out.

The present invention will be explained in more detail below.

In the present invention, as the higher fatty acid amide or ester contained in the outermost layer of the back layer, those represented by the following general formula [I] are preferably mentioned.

General formula [I] R+ C0R2 [wherein R1 represents a saturated or unsaturated linear aliphatic hydrocarbon group such as an alkyl group or alkenyl group having 12 or more carbon atoms, R2 is -NH2 group or -0R3 group, R3 represents a saturated or unsaturated straight chain aliphatic hydrocarbon group such as an alkyl group or alkenyl group having 12 or more carbon atoms, and R2 is preferably a 10R3 group, that is, an ester of a higher fatty acid. . Further, at least one of R1 and R3 represents a saturated or unsaturated straight-chain aliphatic hydrocarbon group such as an alkyl group or an alkenyl group having preferably 20 or more carbon atoms, more preferably 25 or more carbon atoms. Preferred specific examples of the higher fatty acid amide or ester represented by the above general formula [I] used in the present invention are listed below, but the present invention is not limited thereto.

(1) C,, H3jCONH2 (2) C,,H,,C0NH.

(3) C2,H,,C0NH.

(4) Cl9H,,C00C,. H6(5)C
l7H C00C,,H,.

<6) Cz+H43COOC1? H3S (7)
C2, H4, C00C,,H,.

(8) C25H5,C00C,. )ts+(9)
C27H5SCOOCISH33 In the present invention, the amide or ester of the higher fatty acid is preferably contained in an amount of 1 to 500111 g, particularly preferably 5 to 100 mg, per 112 of the light-sensitive material.

Moreover, as the higher fatty acid used in the present invention, a compound represented by the general formula [ff] is preferably mentioned.

General formula [ff] R4C0OH [wherein R4 represents a saturated or unsaturated straight-chain aliphatic hydrocarbon group having 12 or more carbon atoms. ] Preferred specific examples of the above-mentioned higher fatty acids are listed below, but the present invention is of course not limited to these.

(10) C,,H,,C00H (11) CI 7 H3s C00H(12)
C,,H,,C00H (13) C2,8,3COOH (14) C,4H,,Cool-1(15) C
2,8550008 Next, the partial fatty acid ester of a polyhydric alcohol used in the present invention is a partially esterified product obtained by esterifying a polyhydric alcohol with one or more hydroxyl groups remaining, and preferably has the general formula [ 1ff], [IV co, [V
], [VI co or cvir.

General formula CTU] HOCH2CH,0COR5 General formula [1V] General formula (V) (19) 1-10(jl,cH20COC,,H.

HOCH2CH20(-0C21H43HOCH2CH
,0COC2,H,.

(20) General formula (Vl) General formula [■] (21) (22) [In the formula, R5 to RI2 each represent a saturated or unsaturated straight chain aliphatic hydrocarbon group having 12 or more carbon atoms, and R6
and R7, R8 and R9, and any one of R+o, R++ and R+2 may be the same or different, respectively. ] Preferred specific examples of the above-mentioned partial fatty acid esters of polyhydric alcohols are listed below, but the present invention is of course not limited to these.

(23) CH20COCffi, H,.

(24) Cl, ococ, TeHko5 (25) (26) (27) CI-120COC,, H4゜HOH2C-C-CH20H CH, ○COC21H-3 CH20COC, tH3S HOH2C-C-CH20COC, □HzsCIl ,0
COC,,H,.

CH,0COC2,H4゜H(]-]12C-C-CH20COC2,H43CI
I=○C0C2,H,.

The content of the above-mentioned higher fatty acid or partial fatty acid ester of polyhydric alcohol in the light-sensitive material is 0.1 to 60% in terms of the ratio of 0.1 to 60% of the content of the amide or ester of higher fatty acid.
, particularly preferably 1 to 40%.

In the present invention, amides and esters of the above-mentioned higher fatty acids,
Higher fatty acids and partial fatty acid esters of polyhydric alcohols include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as methylene chloride and carbon tetrachloride; ethers such as diethyl ether and dioxane. Class: Used by dissolving in a solvent such as aromatic hydrocarbons such as benzene and toluene.

The above-mentioned amides or esters of higher fatty acids and partial fatty acid esters of higher fatty acids or polyhydric alcohols may be used alone, but they are often used in combination with a binder. Examples of binders that can be used in combination include polymers or copolymers such as polystyrene, polymethyl methacrylate, polyvinylidene chloride, polyacrylonitrile, and polyvinyl acetate, cellulose diacetate, cellulose triacetate, cellulose nitrate, ethyl cellulose, and cellulose propionate. Examples include cellulose derivatives such as Nate, and acetals such as polyvinyl formal, polygonyl acetal, and polyvinyl benzal, but are not limited to the above as long as they have film-forming ability and are soluble in solvents. .

In the silver halide photographic material of the present invention, a layer containing an antistatic agent is usually provided on the support side of the outermost layer of the back layer. Such antistatic agents include, for example, ionene-type polymers as disclosed in Japanese Patent Publication No. 57-56059 and vinylbenzyl quaternary ammonium salts as disclosed in Japanese Patent Publication No. 61-223736 in the polymer position. Cross-linked polymer, Tokuko Sho 5
Examples include an alumina sol having an electrolyte as disclosed in Japanese Patent Application Laid-open No. 7-12979, and crystalline metal oxide fine particles as disclosed in Japanese Patent Application Laid-open No. 143431/1983.

In particular, when the above-mentioned ionene type polymer is used as an antistatic agent, the resistance to aqueous processing solution compositions is poor;
Scum may occur in the photosensitive material, but when the layer containing the amide or ester of higher fatty acid of the present invention and a silicone compound having a hydrophilic group is used as the outermost layer of the back layer, this outermost layer becomes ionene. The above-mentioned problem can be improved since it has the effect of suppressing the leaching of the type polymer into the developing solution.

In addition, when using alumina sol or crystalline metal oxide fine particles having the above-mentioned electrolyte as an antistatic agent, it is necessary to ensure that the outermost layer on the back side has good coating properties and that there is a gap between the outermost layer and the layer containing the antistatic agent. A photographic material with good adhesion, excellent scratch resistance and slipperiness, and improved drying unevenness can be obtained.

In addition, the outermost layer of the back side containing the amide or ester of higher fatty acid and the partial fatty acid ester of higher fatty acid or polyhydric alcohol, or the layer containing an antistatic agent, may further contain a matting agent, a surfactant, etc., if necessary. It can contain agents, dyes, etc.

As the matting agent, fine particles of silica dioxide having an average particle size of 0.01 to 10 μm are preferred. There are no particular restrictions on the various additives mentioned above and the various additives in the photosensitive silver halide emulsion layer on the side opposite to the back surface of the support.
You can refer to the description in December 2008).

Further, another layer, for example a binder layer, may be provided between the outermost layer of the back layer and the layer containing an antistatic agent.

Examples of the support used in the silver halide photographic material of the present invention include films such as polyolefins such as polyethylene, polystyrene, cellulose derivatives such as cellulose triacetate, polyesters such as polyethylene terephthalate, baryta paper, synthetic paper, etc. Included are supports made of sheets such as paper coated on both sides with these polymer films, and the like.

The layer containing the amide or ester of a higher fatty acid and the partial fatty acid ester of a higher fatty acid or a polyhydric alcohol of the present invention can be formed by, for example, curtain coating, reverse roll coating, fountain air doctor coating, slide hopper coating,
The coating can be applied using various known coating or infiltration methods such as extrusion coating and dip coating.

For example, in the case of a color photosensitive material, the silver halide photographic material of the present invention includes a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a yellow coupler. In addition to a silver halide emulsion layer such as a blue-sensitive emulsion layer, an intermediate layer, a filter layer, etc. may be provided as necessary.

As the magenta coupler contained in the green-sensitive layer, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, and 17 nM acylacetonitrile couplers can be preferably used.

As the cyan coupler contained in the red-sensitive layer, naphthol couplers and phenol couplers can be preferably used.

Furthermore, as the yellow coupler contained in the blue-sensitive layer, for example, acylacetanilide couplers can be preferably used. l
-Anilide and baloylacetanilide compounds are preferred.

Next, the silver halide emulsion forming the silver halide emulsion layer will be explained. In the silver halide emulsion, any silver halide used in ordinary silver halide emulsions can be used, but silver iodobromide is particularly preferred. The silver halide emulsion may be an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion).
These emulsions may be used alone or in combination, and polydisperse emulsions and monodisperse emulsions may be used as a mixture, but monodisperse emulsions are preferred. Here, a monodisperse emulsion is defined as a grain size distribution of silver halide grains contained in the emulsion.
It refers to an emulsion whose coefficient of variation is 22% or less, preferably 15% or less.

Further, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = Standard deviation of particle size distribution Average particle size × 100% Average particle size = . , -r Here, ri represents the particle size on each side of the particle, and ni represents the number thereof.

In addition, the average grain size r is the length of one side in the case of cubic silver halide grains, and the average value of the length of one side when converted into a cube in the case of spherical grains. It is expressed by the above formula when the particle size is ri and the number is ni.

Note that the above particle size can be measured by various methods commonly used in the technical field.

Typical methods include Loveland's "Particle Size Analysis Method J,"
A, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122, or "Theory of the Photographic Process", co-authored by Mies and James, 3rd edition, published by McLamin Publishing Co., Ltd. (1966), No. 2 described in the chapter.

Various additives can be added to the various photographic constituent layers constituting the silver halide photographic light-sensitive material of the present invention, and various photographic additives such as wetting agents, film property improving agents, coating aids, etc. can be added depending on the purpose. Agents etc. can also be added. Furthermore, other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, A development speed regulator, matting agent, etc. may also be used.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent fading of dye images due to short-wavelength actinic rays.

In addition to gelatin, a suitable gelatin derivative can be used as a protective colloid or a binder in the silver halide emulsion layer depending on the purpose, and other hydrophilic binders can also be included depending on the purpose. It can also be added to photographic constituent layers such as emulsion layers, intermediate layers, protective f71 layers, filter layers, backing layers, etc., depending on the purpose.Additionally, suitable plasticizers can be added to the hydrophilic binder according to the purpose. , a wetting agent, etc. may also be contained.

Further, the constituent layers of the above-mentioned photographic light-sensitive material can be hardened with any suitable hardening agent.

The non-photosensitive layer constituting the silver halide photographic light-sensitive material of the present invention includes a matting agent such as colloidal silica and polymethyl methacrylate, a high boiling point solvent (for example, tricresyl phosphate, dioctyl phthalate, etc.), an ultraviolet absorber, and an oxidizing agent. It can contain inhibitors, lipophilic components such as hydroquinone derivatives, coating aids such as surfactants, gelatin hardeners, and the like.

Gelatin is generally used as a binder for the above-mentioned non-photosensitive layer phase, but in place of some or all of the gelatin, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives, or synthetic binders may be used. Water-soluble polymers, gelatin derivatives, gelatin graft-copolymerized with monomers having polymerizable ethylene groups, etc. may be used.

The silver halide photographic light-sensitive material of the present invention includes a normal black-and-white silver halide light-sensitive material (for example, a black-and-white light-sensitive material for scanning, a black-and-white light-sensitive material for X-ray, a black-and-white light-sensitive material for printing and tilling, etc.), a normal multilayer Various silver halide photographic materials such as color light-sensitive materials (for example, color reversal films, color negative films, color positive films, etc.) can be mentioned.

[Example] The present invention will be explained in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 A multilayer color photographic material sample was prepared by sequentially forming each layer having the composition shown below on a triacetylcellulose film support from the support side.

1st H: Antihalation layer Gelatin layer containing black colloidal silver.

Gelatin 2.2Q/+' 2nd layer: middle layer 2.5-di-t-octyl hydroxide A gelatin layer containing an emulsified dispersion of non-alcoholic acid.

Gelatin 1.2Q/l' 3rd layer: low sensitivity red-sensitive silver halide emulsion layer average grain size o,
30 urn XAgI 6. AgB containing o mol%
Monodisperse emulsion consisting of rI (emulsion I)...silver coating! 11.8 (1/v2 sensitizing dye process... 6 x 10-5 mol sensitizing dye for 1 mol of silver... 1.Ox 10-5 mol cyan coupler (C-1 >... 0.06 mol per mol of silver Colored cyan coupler (CG-1)... 0003 mol per mol of silver DIR compound (D-1>... 0 mol per mol of silver .0015 mol DIR compound (D-2>... 0.002 mol gelatin 1.4 g/f for 1 mol silver 4th layer: High sensitivity red-sensitive silver halide emulsion layer Average grain size 0.
5 μm, monodisperse emulsion (emulsion ■) consisting of AgBr1 containing 7.0 mol% of Ag1...Silver coating: 1.3G/f Sensitizing dye processing.
... 3 x 10-5 moles of sensitizing dye per mole of silver...
- 1.0% per mole of silver. OX 10-5 mol cyan coupler (C-1)... 0.02 mol per mol of silver Colored cyan coupler <cc-i>... 0.0015 mol DIR compound (D -2)... 0.001 mol gelatin 1.0 g/f for 1 mol silver 5th layer: Same gelatin layer as the second intermediate layer.

Gelatin i, og/f 6th W1: Low sensitivity green sensitive silver halide emulsion layer Emulsion ■...
・Amount of coated silver 1.5 g/v" Sensitizing dye m... 2.5X 10-5 mol sensitizing dye m per 1 mol of silver ・
... 1.2X i Q-5 mole magenta coupler per 1 mole of silver (M-1>... O, (150 mole per mole of silver) colored magenta coupler (CM-1>... silver 1 0.009 mol to mol DIR compound (D-1)... 0.0010 mol to 1 mol of silver DIR compound (D-3)... 0.0030 mol to 1 mol of silver Gelatin 2 .0g/v+2 7th layer: High-sensitivity green-sensitive silver halide emulsion layer Emulsion・・・
・Coated silver amount 1.4g/l' sensitizing dye ■... 1.5X 1Q-5 mol sensitizing dye ■・ per 1 mole of silver
... 1 mole of silver. ox 10-5 mol Magenta coupler (M-1)... 0.020 mol per mol of silver Colored magenta coupler (CM-1)... 0.002 mol DIR compound (D -3) ... 0.0010 mol gelatin per 1 mol silver (1/f 8th layer: yellow filter layer emulsified dispersion of yellow colloidal silver and 2.5-di-t-octylhydroquinone) gelatin layer containing.

Gelatin 1.5 (1/m' 9th layer: low sensitivity blue-sensitive silver halide emulsion layer average grain size o,
48 μm, AgBr containing 16Ele% AIJ
Monodispersed emulsion consisting of I (emulsion ■)...silver coating amount 0.9
g/i2 Sensitizing dye V... 13 x 10-5 mol per mol of silver Yellow coupler (Y-1)... 0.29 mol per mol of silver Gelatin 1.9 g/w' 10th layer: High-speed blue-sensitive emulsion layer Monodispersed emulsion (emulsion ■) consisting of A(]3r I containing 15 mol% of A(l I) with an average grain size of 0.8 μl...
・Silver coating amount 0.5!11. /l' Sensitizing dye V...1. OX 10-" mol Yellow coupler (Y-1)... 0.08 mol to 1 mol of silver DIR compound (D-2)... 0.0015 mol to 1 mol of silver Gelatin 1.6 ( 1/f No. 1111J: First protective layer silver iodobromide (Ag 11 mol% average grain size 0.07 μa+)...Silver coating m O,5+1 /f Gelatin layer containing ultraviolet absorbers UV-1 and UV-2 Gelatin 1.2g/f 12th W1: Second protective layer Ca F17S Oa K (F -1) ---
2omo/f and polymethyl methacrylate particles (
average particle size 3.5 μm), ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average particle size 2.5 μm), and formalin scavenger (HS
-1) gelatin layer containing gelatin 1.20/,'.

In addition to the above ingredients, each layer contains 10% of gelatin.
Polyethylene acrylate latex (average particle size 0.07 μm), gelatin hardening agent <H-1>, and surfactant were added in the following proportions.

Further, layers having the following compositions were sequentially formed on the back surface of the support from the support side.

Back side 1st layer 20 ml + 2/* of the following antistatic layer coating liquid composition
' and dried at 80'C for 5 minutes.

Back surface second layer The compositions for the second layer shown in Table 1 below were applied to the above antistatic layer at a concentration of 25 nI2/f, and
Samples No. 1 to 6 were prepared by drying for a minute. Furthermore,
The compounds contained in each layer of Table 1 except for the second layer on the back surface are as follows.

Sensitizing dye: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide Sensitizing dye ■: Anhydro-9-ethyl-3°3'- Di(3-sulfopropyl)-4,5,4',5'-dibenzodeacarbocyanine hydroxide sensitizing dye 11[:Anhydro5,5'-diphenyl-
9-Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■: Anhydro-g-ethyl-3°3'-di(3-sulfopropyl) 5.6.5 ',6'-dibenzoxacarbocyanine hydroxide sensitizing dye V: anhydro-3,3'-di(3-sulfobrovir)-4,5-benzo5'-methoxythiacyani-1-2 C-1- 3-1 4-1 CH.

CM-1 H3-1 (,σ 4-1 V-2 The dynamic friction coefficient and scratch resistance of the sample prepared as above were measured by the following method, and the above sample was developed with the following processing solution. After applying this, the coefficient of dynamic friction and scratch resistance were examined in the same manner.The results are shown in Table 2.

Dynamic friction coefficient: Measured by JIS method using steel balls.

Scratch resistance: A sapphire needle with a tip of 0.1 mm (radius) is crimped onto the sample surface, and the load is continuously changed in the range of 0 to 200 g while moving the membrane surface in parallel at a rate of 1 CIo per second. The needle load at which damage occurred to the membrane surface of the sample was determined.

Processing process (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixed
Arrival 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment liquid used in each treatment step is as follows.

[Color developing solution] [Bleaching solution 1 Table 2 [Fixing solution] [Stabilizing solution] As is clear from Table 2, the combination of carnauba wax with higher fatty acids or partial fatty acid esters of polyhydric alcohols provides excellent slipperiness. It was also possible to improve drying unevenness after development while maintaining scratch resistance.

Example 2 Multilayer color photographic material samples Nos. 088 to 14 were prepared in the same manner as in Example 1, except that the composition of the coating liquid for back surface phase 1H was changed as shown below.

Back surface first layer (ionene type polymer) Samples Nos. 8 to 14 prepared as above were developed in the same manner as in Example 1, and then the degree of uneven drying and staining was visually evaluated. . The results are shown in Table 3.

As is clear from Table 3, when the second layer on the back side does not contain higher fatty acids or partial fatty acid esters of polyhydric alcohols as in comparative samples No. 126 and 13,
There was uneven drying on the sample after the development process, and comparative sample N
In the case where the second layer on the back surface is not provided as in case o and 14, dirt occurred on the surface of the first layer on the back surface, whereas,
In all of the samples Nos. 48 to 11 of the present invention, no uneven drying or staining was observed after the development process.

[Effect of the Invention 1] As explained in detail above, the present invention can provide a silver halide photographic material that has good slipperiness and scratch resistance and can prevent uneven drying after development. .

Claims (1)

[Claims] A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on a support and at least one back layer on the opposite side of the silver halide emulsion layer to the support. . A silver halide photographic material, characterized in that the outermost layer of the at least one back layer contains an amide or ester of a higher fatty acid, and a partial fatty acid ester of a higher fatty acid or a polyhydric alcohol.