JP2979031B2 - Silver halide photosensitive material with improved adhesion of coating layer - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide light-sensitive material, and more particularly to a silver halide light-sensitive material having improved adhesion of a coating layer.

[Conventional technology]

When the photosensitive material is wet, for example, during development, the adhesiveness between the support and the coating layer on the support in the wet state is not affected by any photosensitive material while the photosensitive material is wet. It is desirable to maintain strength. However, this adhesiveness is liable to be changed by various factors.
For example, as described in JP-A-2-11039, by adding a water-soluble polymer compound to a layer adjacent to the support or a layer close to the support, the adhesiveness changes simultaneously. I will. By including a water-soluble polymer compound in the layer, it is possible to enhance the adhesiveness, but this means has an effect on photographic performance, and there is a limit to using it alone as a control means. .

[Object of the invention]

The purpose of the present invention is to reduce the impact on photographic performance,
An object of the present invention is to provide a silver halide photographic material having sufficiently improved adhesion between a support and a coating layer on the support.

[Configuration of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material having a photographic component layer containing at least one light-sensitive layer on a support, in which 5 m
To at least one of the constituent layers existing between
A water-soluble polymer compound which is a polymer having a repeating unit represented by the following general formula [I] is added in an amount of 0.00
This has been attained by a silver halide photosensitive material containing from 2 g to 0.2 g and having a water absorption represented by the following formula (1) of from 170% to 230%.

Equation (1) [In the formula (1), A: weight of the photosensitive material at 23 ° C. and 55% RH temperature and humidity control B: Under the same temperature and humidity conditions as A, immerse the photosensitive material in a 38 ° C. developer for 3 minutes 15 seconds Weight of photosensitive material after coating Under the same temperature and humidity conditions as C: A, weight of photosensitive material after coating layer has been peeled off Hereinafter, the present invention will be described in more detail.

In the present invention, the water-soluble polymer compound is a polymer compound other than a polymer compound (eg, gelatin) used as a binder, and specifically, the Photographic Society of Japan, Vol. 29, No. 1,
P17 to 21 (1966) Any polymer compound can be used as long as the turbidity of the silver halide obtained by using the polymer compound by the method described in (1966) is smaller than that obtained by using photographic inert gelatin. In the present invention, a polymer having a repeating unit represented by the following general formula [I] is used as a high-molecular compound.

General formula [I] In the above formula, R ¹ represents a hydrogen atom or an alkyl group,
Q represents any one group selected from the group consisting of the following (a) to (d).

In these groups (a) to (d), R ² represents a methyl group or an ethyl group, R ³ represents a hydrogen atom, a methyl group or an ethyl group, and A represents a mere bond, or Represents an alkylene group.

Z represents an atom group forming a 5- or 6-membered lactam ring or oxazolidone ring. The most preferred value for Q is when it represents a pyrrolidone residue.

Examples of the monomer for deriving the repeating unit represented by the general formula [I] include N-methyl-N-vinylacetamide, N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide and the like. Can be.

The polymer having the repeating unit represented by the general formula [I] may be not only a homopolymer but also a copolymer.
Examples of the ethylenically unsaturated compound forming the copolymer include, for example, acrylic esters, methacrylic esters, acrylamide acid, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, vinyl heterocyclic compounds, Styrenes, maleates,
Examples include fumaric esters, itaconic esters, crotonic esters, and olefins. Specific examples thereof include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, octyl acrylate, 2-chloroethyl acrylate,
-Cyanoethyl acrylate, N- (β-dimethylaminoethyl) acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl acrylate; methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 3-sulfopropyl methacrylate; allyl Butyl ether, allyl phenyl ether; methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, (2-dimethylaminoethyl) vinyl ether, vinyl phenyl ether, vinyl chlorophenyl ether; acrylamide, methacrylamide, N-methylacrylamide, N- (1,1-dimethyl-3-oxobutyl Acrylamide, N-(1,1-dimethyl-3-hydroxybutyl) acrylamide, N, N-dimethylacrylamide; acryloyl hydrazine; N- methoxymethyl methacrylamide, N-(1,1-
Dimethyl-3-hydroxybutyl) methacrylamide,
N-hydroxymethylacrylamide); vinylpyridine, N-vinylimidazole, N-vinylcarbazole, vinylthiophene; styrene, chloromethylstyrene, p-acetoxystyrene, p-methylstyrene; p-vinylbenzoic acid, p-vinylbenzoic acid Methyl; crotonamide, butyl crotonate, glycerin monochromate; methyl vinyl ketone, phenyl vinyl ketone; ethylene, propylene, 1-butene, dicyclopentadiene, 4-methyl-1-hexene, 4,4-dimethyl-
1-pentene, etc .; methyl itaconate, ethyl itaconate, diethyl itaconate, etc .; methyl sorbate, ethyl maleate, butyl maleate, dibutyl maleate, octyl maleate, etc .; ethyl fumarate, dibutyl fumarate, octyl fumarate And the like; halogenated olefins such as vinyl chloride, vinylidene chloride, and isobrene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile. If necessary, two or more kinds can be used.

Among them, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, and the like are preferable in terms of the hydrophilicity of the produced polymer.
Sulfopropyl acrylate, acrylamide, dimethylacrylamide, 2-acryloylamino-2-methylpropanesulfonic acid, hydroxyethylacrylamide, methacrylamide, methyl vinyl ether, sodium styrenesulfonate, sodium styrenesulfinate, N
-Vinyl-3,5-dimethyltriazole, maleic anhydride and the like.

The molecular weight of the polymer compound used in the present invention is usually about 2000
The above is preferable, and those having about 5000 to 2,000,000 can be used widely, and there is no particular restriction on the molecular weight.

In the present invention, the water-soluble polymer compound can exert the effects of the present invention in the above-mentioned amount constituting the present invention, but the polymer compound (such as gelatin) serving as a binder of the layer to which the polymer compound is added is used. 0.01g based on solid content
More preferably, it is used in an amount of 0.1 g or more.

Next, preferred specific examples of the polymer compound used in the present invention will be described, but the present invention is not limited thereto. (The numbers outside the parentheses represent the molar ratio of comonomer in%.) In the present invention, the layer containing the water-soluble polymer compound may be at least one of the constituent layers existing up to 5 μm from the support surface, and more preferably 3
This is a layer existing within μm.

The compound may be diffused from the constituent layer to which the water-soluble polymer compound is added, but the water-soluble polymer compound contained in the layer may remain in an amount within the range of the present invention. If there is no problem, the effect can be exhibited.

In the present invention, the layer containing the water-soluble polymer compound is preferably a so-called antihalation layer. The antihalation layer preferably contains black colloidal silver.

The black colloidal silver is described, for example, in U.S. Pat.
And German Patent No. 1,096,193.

When black colloidal silver is used in the light-sensitive material of the present invention, the black colloidal silver particles are preferably composed of a polydisperse having a diameter of 30 to 200 μm, and the optical characteristics vary depending on the preparation conditions of the colloidal silver. In terms of sharpness, the spectral transmission density of colloidal silver, when the value at 550 nm is 1.00, the relative value at 450 nm is preferably 0.50 to 1.50, and the relative value at 650 nm is preferably 0.60 or more, more preferably at 550 nm. When the spectral transmission density value is 1.00, the relative value at 450 nm is 0.70
The relative value at 相 対 1.00 and 650 nm is particularly preferably 1.00 or more.
If these values are shown as specific values, it is particularly preferable that the transmission density at 550 nm is 0.50 to 0.90, the value at 450 nm is 0.35 to 0.90, and the value at 650 nm is 0.50 or more.

The coating amount of the black colloidal silver is preferably calculated in terms of silver.
A 0.05~0.40g / m ^2, particularly preferably 0.10~0.30g / m ²
It is.

In terms of desilvering property in the development process, antihalation ability, and furthermore, from the viewpoint of data clarity when forming the shooting date and time by optical exposure from the back side of silver halide color photographic photosensitive material etc. The above-mentioned range is preferable.

In the present invention, the water absorption is a value obtained by the above equation (1). The water absorption obtained by this equation is not the water absorption of only the coating layer. However, the present inventors have confirmed that the water absorption of the support itself is only about 1/100 of that of the coating layer by the same measurement. Therefore, in the present invention, the water absorption obtained by the formula (1) is obtained. Is substantially the water absorption of the coating layer.

The water absorption in the present invention is preferably 180% or more and 220%
Or less, more preferably 190% or more and 210% or less.

The water absorption in the present invention can be determined by immersing a sample in a developer under specific conditions. The composition of the developer used for this is described in Example 1 below as a developer for measuring water absorption.

The effect of the present invention, if the structure of the present invention, the type of support, binder, type of gelatin, and type of hardener,
It can be obtained irrespective of the addition amount, etc., but as the type of hardener, it is desirable to use a combination of a vinyl sulfone hardener and an active halogen hardener. When a combination of a vinyl sulfone type and an active halogen type hardener is used, the amount of the vinyl sulfone type hardener is determined based on the total amount of the gelatin in the coating layer. 7.0mg-13.0m as hardener amount of all coating layers per 1g
g, the active halogen type hardener is preferably 4.0 mg to 8.0 mg.

The photosensitive material of the present invention may have at least one photosensitive layer. When a full-color photosensitive material is used, generally,
It is preferable to have a constitution having a red-sensitive, green-sensitive and blue-sensitive photosensitive layer. The photosensitive layer can be composed of a silver halide emulsion, and as the silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The following table shows the locations.

In the present invention, the silver halide emulsion constituting the photosensitive layer is generally subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are Research Disclosure No. 17643, No. 18716 and No. 308119 (hereinafter referred to as RD17643, RD18716 and RD30, respectively).
8119).

 The following table shows the locations.

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure. The following table shows relevant descriptions.

When the light-sensitive material of the present invention is a color light-sensitive material, various couplers can be used, and specific examples thereof are described in the above-mentioned Research Disclosure. The following table shows relevant descriptions.

The additives used in the present invention can be added by the dispersion method described in RD308119XIV or the like.

In the present invention, the aforementioned RD17643 page 28, RD18716 647-
The support described on page 8 and XIX of RD308119 can be used.

The light-sensitive material of the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119VII-K.

The light-sensitive material of the present invention can have various layers and constitutions such as a normal layer, a reverse layer, and a unit constitution described in the aforementioned RD308119VII-K.

When the present invention is applied to a color light-sensitive material, it can be applied to various color light-sensitive materials represented by a color negative film for general use or a movie, and a color reversal film for a slide or a television.

The light-sensitive material of the present invention is described above as RD17643 pages 28 to 29, RD18716.
Development can be carried out by a usual method described on page 647 and XIX of RD308119.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Hereinafter, in all Examples, the amount of addition in the silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver. Further, the sensitizing dye was represented by mol / silver.

Example 1 On a triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample-101.

Sample-101 1st layer; Anti-halation layer (HC-1) Black colloidal silver 0.2 UV absorber (UV-1) 0.23 High boiling point solvent (Oil-1) 0.18 Gelatin 1.4 The above-mentioned particularly preferable range).

Second layer: Intermediate layer (IL-1) Gelatin 1.3 Third layer: Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size: 0.4 μm) 1.0 Sensitizing dye (SD-1) 1.8 × 10 ^-5 sensitizing dye (SD-2) 2.8 × 10 ^-4 sensitizing dye (SD-3) 3.0 × 10 ^-4 cyan coupler (C-1) 0.70 colored cyan coupler (CC-1) 0.066 DIR compound (D- 1) 0.03 DIR compound (D-3) 0.01 High boiling solvent (Oil-1) 0.64 Gelatin 1.2 Fourth layer; Medium-speed red-sensitive emulsion layer (RM) Silver iodobromide emulsion (average particle size 0.7 μm) 0.8 Sensitization Dye (SD-1) 2.1 × 10 ^-5 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-4 cyan coupler (C-1) 0.28 Colored cyan coupler (CC -1) 0.027 DIR compound (D-1) 0.01 High boiling solvent (Oil-1) 0.26 Gelatin 0.6 Fifth layer; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Average particle size 0.8 μm) 1.70 Increase sensitive dye (SD-1) 1.9 × 10 - ⁵ Sensitizing dye (SD-2) 1.7 × 10 ^-4 Sensitizing dye (SD-3) 1.7 × 10 ^-4 Cyan coupler (C-1) 0.05 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.025 High boiling point solvent (Oil-1) 0.17 Gelatin 1.2 6th layer; Intermediate layer (IL-2) Gelatin 0.8 7th layer; Low sensitivity green-sensitive emulsion layer (GL) Iodobromide Silver emulsion (average particle size: 0.4 μm) 1.1 Sensitizing dye (SD-4) 6.8 × 10 ^-5 Sensitizing dye (SD-5) 6.2 × 10 ^-4 Magenta coupler (M-1) 0.54 Magenta coupler (M-2) 0.19 Colored magenta coupler (CM-1) 0.06 DIR compound (D-2) 0.017 DIR compound (D-3) 0.01 High boiling solvent (Oil-2) 0.81 Gelatin 1.8 Eighth layer; Medium-sensitive green-sensitive emulsion layer (GM ) Silver iodobromide emulsion (average particle size 0.7 μm) 0.7 sensitizing dye (SD-6) 1.9 × 10 ^-4 sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-8) 1.5 × ^10-5 ma Zenta coupler (M-1) 0.07 Magenta coupler (M-2) 0.03 Colored magenta coupler (CM-1) 0.04 DIR compound (D-2) 0.018 High boiling solvent (Oil-2) 0.30 Gelatin 0.8 9th layer; High sensitivity Green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size: 1.0 μm) 1.7 sensitizing dye (SD-6) 1.2 × 10 ^-4 sensitizing dye (SD-7) 1.0 × 10 ^-4 sensitizing dye ( SD-8) 3.4 × 10 ^-6 Magenta coupler (M-1) 0.09 Magenta coupler (M-3) 0.04 Colored magenta coupler (CM-1) 0.04 High boiling solvent (Oil-2) 0.31 Gelatin 1.2 10th layer; Yellow Filter layer (YC) Yellow colloidal silver 0.05 Color stain inhibitor (SC-1) 0.1 High boiling solvent (Oil-2) 0.13 Gelatin 0.7 Formalin scavenger (HS-1) 0.09 Formalin scavenger (HS-2) 0.07 No. 11 Layer: low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.4 μm) 0 .5 Silver iodobromide emulsion (average particle size 0.7 μm) 0.5 sensitizing dye (SD-9) 5.2 × 10 ^-4 sensitizing dye (SD-10) 1.9 × 10 ^-5 yellow coupler (Y-1) 0.65 yellow Coupler (Y-2) 0.24 DIR compound (D-1) 0.03 High boiling point solvent (Oil-2) 0.18 Gelatin 1.3 Formalin scavenger (HS-1) 0.08 12th layer; Highly sensitive blue-sensitive emulsion layer (BH) Silver halide emulsion (average particle size 1.0 μm) 1.0 Sensitizing dye (SD-9) 1.8 × 10 ^-4 Sensitizing dye (SD-10) 7.9 × 10 ^-5 Yellow coupler (Y-1) 0.15 Yellow coupler (Y-) 2) 0.05 High boiling solvent (Oil-2) 0.074 Gelatin 1.3 Formalin scavenger (HS-1) 0.05 Formalin scavenger (HS-2) 0.12 13th layer; 1st protective layer (Pro-1) Fine grain silver iodobromide Emulsion 0.4 (Average particle size 0.08 μm, AgI 1 mol%) UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High boiling solvent (Oil-1) 0.0 7 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.13 Formalin scavenger (HS-2) 0.37 Gelatin 1.3 14th layer; 2nd protective layer (Pro-2) Alkali-soluble matting agent (average particle size) Diameter 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Slip agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, coating aid Su-1 and dispersion aid Su-
2. A viscosity modifier, a stabilizer ST-1, and an antifogging agent AF-1 were added, and the hardeners H-1 and H-2 were added so that the water absorption became 200%.

To the first layer of Sample 101, a water-soluble polymer compound of the type shown in Table 1 was added in the amount shown in Table 1, and a hardener H-
Samples 102 to 111 having the following water absorption were prepared by appropriately changing the amount of 1, H-2. For other configurations, see Sample 101.
Is the same as The amount of the hardener H-1, H-2 was about 6.0 mg to 12.0 m / g of gelatin for the samples 103, 107 to 111 of the present invention.
g, and the active halogen hardener H-1 was also in the range of 3.0 mg to 7.0 mg (the amount of each hardener in all coated layers per 1 g of gelatin in all coated layers). ).

Here, the composition of the developer used to determine the water absorption is as follows.

<Composition of developer for measuring water absorption> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitriloacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1. (PH = 10.1) Further, with respect to Samples 101 to 111, evaluation of adhesion to a support and sensitometry was performed as follows.

(Evaluation of Adhesiveness) A developer similar to the developer used in the above-described water absorption measurement was used. Samples 101 to 111 were added to a developer adjusted to 38 ° C for 3 minutes 15 minutes.
After immersion for 2 seconds, apply a 2mm-wide grid-like scratch to the surface of the sample on which the photographic component layer was coated, immediately rub the scratched part, dry the sample as it is, and leave the surface of the coating layer The area and the like were visually evaluated. FIG. 1 shows a model of a scratched surface. The black part in FIG. 1 is the part where the photographic constituent layer of the sample is coated, and the white part is where the scratch is made.

(Evaluation of Sensitometry) After exposing samples 101 to 111 to wedges using white light,
Each of the exposed samples was processed according to the following processing steps.

Processing step [I] (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Is as follows.

The color developing solution has the same composition as the developing solution used for evaluating the water absorption and the adhesiveness.

<Bleaching solution> Ammonium iron (III) ethylenediaminetetraacetate 100g Ethylenediaminetetraacetic acid diammonium salt 10g Ammonium bromide 150g Glacial acetic acid 10ml Add water to make 1 and adjust the pH to 6.0 using aqueous ammonia.
Adjust to

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 and adjust the pH to 6.0 using acetic acid.

<Stabilizing solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1.

After performing the above processing, the blue, green, and red light transmission densities of each sample were measured to obtain sensitometry. Further, the sensitivity of the red-sensitive layer was determined from the obtained sensitometry.
The sensitivity here is the minimum transmission density of red light of each sample +
It is the logarithm of the exposure at a density of 0.3.
It was expressed as a relative value when 100 was set.

 These results are summarized in Table-2.

As shown in Table 2, in the sample of the present invention, the adhesion was excellent, and there was almost no influence on the sensitivity of the red-sensitive layer.

[Effects of the Invention] As described above, the silver halide photographic material of the present invention comprises:
The adhesiveness between the support and the coating layer on the support was sufficiently improved, and this effect was realized with little effect on photographic performance.

[Brief description of the drawings]

FIG. 1 is a diagram showing a model of a lattice flaw applied to a sample for evaluation of adhesiveness.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Atsuo Ezaki 1 Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (56) References JP-A-3-259246 (JP, A) (58) Fields investigated ( Int.Cl. ⁶ , DB name) C03C 1/053 C03C 1/30

Claims (1)

(57) [Claims] 1. A silver halide photographic material having a photographic component layer including at least one photosensitive layer on a support, wherein the silver halide photographic material is present on the side on which the photosensitive layer is coated up to 5 μm from the support surface. In at least one of the constituent layers, a water-soluble polymer compound which is a polymer having a repeating unit represented by the following general formula (I) is 0.002 g or more per 1 g of a binder.
2g or less, and the photosensitive material has a water absorption represented by the following formula (1) of 17
A silver halide photosensitive material characterized by being at least 0% and at most 230%. Equation (1) [In the formula (1), A: weight of the photosensitive material at 23 ° C. and 55% RH temperature and humidity control B: Under the same temperature and humidity conditions as A, immerse the photosensitive material in a 38 ° C. developer for 3 minutes 15 seconds Weight of photosensitive material after peeling C: Weight of photosensitive material after peeling the coating layer under the same temperature and humidity conditions as A In the above formula, R ¹ represents a hydrogen atom or an alkyl group;
Represents any one group selected from the group consisting of the following (a) to (d). In these groups (a) to (d), R ² is a methyl group,
Represents an ethyl group, R ³ represents a hydrogen atom, a methyl group, an ethyl group, and A is a mere bond, or Represents an alkylene group. Z represents an atom group forming a 5- or 6-membered lactam ring or oxazolidone ring.