JP3442129B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material having improved adhesion resistance and dry unevenness, and particularly improved dry unevenness by improving wettability of the back layer with water and elution from the back layer. The present invention relates to a photographic light-sensitive material in which insoluble precipitates in a processing solution based on a product are prevented.

[0002]

2. Description of the Related Art In recent years, the use and processing of photographic light-sensitive materials have been diversified due to higher sensitivity and faster processing, and the light-sensitive materials themselves have been subjected to more severe handling than ever before. There is.

One of them is adhesion failure in a high temperature and high humidity atmosphere. To solve the problem of adhesion failure, for example, Japanese Examined Patent Publication (Kokoku) No. 57-6577, the use of a cellulose ester as a binder for the back layer prevents the back layer from adhering to the emulsion layer or intermediate layer during coating, and protects the back layer from the adhesive. It is well known that it is effective in preventing adhesion of layers.

On the other hand, static electricity tends to accumulate in the manufacture and use of photographic light-sensitive materials, and this accumulation of static electricity causes many obstacles. This charging is caused, for example, by friction between the support surface and the emulsion surface or peeling during contact between the photographic light-sensitive material and the roller in the manufacturing process or during winding-up and rewinding of the photographic light-sensitive material. In this case, peeling between the support and the emulsion surface when the light-sensitive material is exposed to high humidity enough to cause adhesion, or the case where a movie camera, automatic development of X-ray film, or the like is used.

As a method for preventing charging failure and the above-mentioned adhesion failure, Japanese Patent Publication No. 57-56059 discloses a back layer containing a polymer binder and further adjoining the outermost layer. Discloses an antistatic method containing an ionene-type polymer having a dissociative group in the polymer main chain as an antistatic agent.

However, when such a photographic light-sensitive material is processed by an automatic developing machine, there is a problem that spotted unevenness of the back layer occurs. The main cause of this problem is that after processing such as development, fixing and washing, water is repelled onto the back layer in the process of drying to form water drops, and the photosensitive photographic emulsion layer on the side opposite to the part where the water drops adhere is dried. Is delayed to cause spot-like uneven drying.

To solve this problem, Japanese Examined Patent Publication No. 5-67938 discloses that the outermost surface layer of the back layer contains acrylic acid or methacrylic acid and acrylic acid ester or methacrylic acid ester, and the sum of the repeating units is a copolymer. It is disclosed that by using at least 55 mol% of a copolymer mixed with a hydrophobic polymer, particularly a cellulose ester polymer, the adhesion resistance and the drying unevenness are improved.

The inventors of the present invention have described the above Japanese Patent Publication No. 5-67938.
When a polymer containing 12 to 20 mol% of acrylic acid or methacrylic acid, which is specifically described in No. 1, is applied to the outermost surface layer of the back layer together with diacetyl cellulose,
The spot-like drying unevenness due to the delay in drying the emulsion layer at the water drop adhesion portion is greatly improved, but the wettability of the surface of the back layer is not always at a sufficient level, and white unevenness due to the remaining fixer component and It was found that minute unevenness such as unevenness due to the traces of water droplets remained. This type of unevenness is not as large a problem as drying unevenness due to the unevenness of the drying delay of the emulsion layer described above, but it is a drawback that the commercial value is impaired particularly in the recent high-image-quality light-sensitive materials.

On the other hand, when the content of acrylic acid or methacrylic acid in the polymer is increased in order to further improve the surface wettability, the polymer having a weight average molecular weight of 60,000 or less is accompanied by an increase in the acid content. Rather, the surface wettability of the back surface is deteriorated and the drying unevenness is deteriorated. When the average molecular weight of the polymer exceeds 60,000, the wettability of the back surface is improved with the increase of the acid content, but the developer or The problem arises of forming insoluble precipitates (scums) in the fixer.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photographic light-sensitive material which is extremely excellent in drying unevenness, does not generate scum in a developing solution or a fixing solution, and has excellent adhesion resistance. is there.

[0011]

The above objects of the present invention have been achieved by the following means.

(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and a back layer on the side of the support opposite to the silver halide emulsion layer. In, the outermost surface layer of the back layer is the following (a), (b), (c)
A silver halide photographic light-sensitive material comprising at least one polymer each. (a) A cellulose ester polymer soluble in an organic solvent. (b) An organic solvent-soluble polymer having a weight average molecular weight of 70,000 or more and 2,000,000 or less, containing 20 to 50 mol% of a monomer unit containing at least -COOH group as a repeating unit. (c) An organic solvent-soluble polymer containing 1 to 35 mol% of a monomer unit containing at least —COOH group as a repeating unit and having a weight average molecular weight of 1,000 or more and 60,000 or less.

Preferred embodiments of the silver halide photographic light-sensitive material of the present invention are the following (2), (3) and (4).

(2) In (b) and (c), the total amount of the monomer unit containing a —COOH group and the acrylic acid ester or the methacrylic acid ester is at least 55 mol% as a repeating unit in the copolymer. The silver halide photographic light-sensitive material as described in (1) above.

(3) The difference between the content (mol%) of the monomer unit containing —COOH group in (b) and the content (mol%) of the monomer unit containing —COOH group of (c) is −10 to 3
The silver halide photographic light-sensitive material as described in (1), which is in the range of 0%.

(4) In the polymer on the outermost surface of the back (b)
The ratio of (c) to (c) is 30:70 to 90:10, and the silver halide photographic light-sensitive material described in (1) is characterized.

The present invention will be described in detail below. In order to more completely overcome the problem of uneven processing of the light-sensitive material, the content of acrylic acid or methacrylic acid specifically described in Japanese Patent Publication No. 5-67938 is insufficient.
It is necessary to increase the content of the acid component monomer. However, the surface wettability cannot be sufficiently improved only by increasing the acid content, and in order to achieve effective surface wettability, the monomer unit containing —COOH group is contained in an amount of 20 mol% or more, and the weight average molecular weight is increased. It is necessary that the polymer is 70,000 or more (polymer represented by (b)).

On the other hand, when such a polymer having a high acid content and a high molecular weight is applied together with the cellulose ester polymer (the polymer represented by (a)), there arises a problem of scum in the developing solution and scum in the fixing solution. It was The present inventors have responded to these problems by adding the polymer represented by (c) in addition to the polymer represented by (a) and the polymer represented by (b). It has come to overcome all the problems of fixer scum.

The polymer of the present invention will be described in detail below. Examples of preferable cellulose ester polymer represented by (a) include cellulose diacetate, cellulose triacetate, and cellulose acetate butyrate, and among them, cellulose diacetate and cellulose triacetate are particularly preferable.

The polymer represented by (b) contains 20 to 50 mol% of a monomer unit containing at least a --COOH group as a repeating unit and has a weight average molecular weight of 70,000 to 200.
It is a copolymer that is soluble in organic solvents of not more than 10,000.

Among them, as the monomer containing -COOH group, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride (the ring is opened after the completion of the polymerization to form a repeating unit of -COOH), vinylbenzoic acid, 2- Acrylamide acetic acid, 3-methacrylamidopropionic acid, 6-acrylamido-hexanoic acid, 11-acrylamidoundecanoic acid, 4-acrylamidobenzoic acid, 4-methacrylamidobenzoic acid, 2-acrylamidobenzoic acid,

[0022]

[Chemical 1]

And the like. These -CO
Among the OH group-containing monomers, acrylic acid, methacrylic acid, itaconic acid, and -COOH-substituted acrylic ester and methacrylic acid ester are preferable, and acrylic acid and methacrylic acid are particularly preferable.

In the copolymer represented by (b), --CO
Substituted or unsubstituted alkyl acrylate or alkyl methacrylate is preferable as the monomer to be copolymerized in addition to the OH group-containing monomer.

Specific examples of the alkyl acrylate and alkyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate.
Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, benzyl Acrylate, methoxybenzyl ac

Relate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 5
-Hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-Methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, methyl methacrylate

, Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-
Butyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2
-Butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate , Stearyl methacrylate

Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl. Methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate and the like can be mentioned.

Of these, linear or branched unsubstituted alkyl ester acrylates or methacrylates having 1 to 4 carbon atoms are particularly preferable.

Further, the polymer represented by (b) may be copolymerized with acrylic acid or methacrylic acid and other copolymerizable monomer other than the above alkyl acrylate or alkyl methacrylate.

Examples of such a monomer include acrylamide and methacrylamides (eg, acrylamide, methacrylamide, N, N-diethylacrylamide, N).
-Acryloylmorpholine, Nt-butyl acrylamide, Nt-octyl acrylamide, diacetone acrylamide, Nt-butyl methacrylamide, etc.),
Vinyl esters (eg vinyl acetate, vinyl laurate), acrylonitrile, methacrylonitrile, dienes (eg butadiene, isoprene), aromatic vinyl compounds (eg styrene, divinylbenzene and its derivatives such as vinyltoluene, vinylacetophenone and sulfostyrene). ), Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg

Vinyl vinyl ether), maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- and 4-vinyl pyridine, ethylene, propylene, 1-butene, isobutene, etc. Can be mentioned.

In the polymer represented by (b) of the present invention, the proportion of the --COOH group-containing monomer is 20 to 50 mol%, preferably 20 to 45%, and particularly preferably 25 to 40 mol%. In addition, the polymer represented by (b) is copolymerized with an acrylic ester or a methacrylic ester in terms of compatibility with the cellulose ester polymers (a) and (c). preferable. In such (b) -COOH
The sum of the proportions of the group-containing polymer and the acrylic or methacrylic acid ester is preferably 55.
It is at least mol%, particularly preferably at least 70 mol%.

The weight average molecular weight of the polymer represented by (b) of the present invention is 70,000 to 2,000,000, preferably 70,000 to 1,000,000, particularly preferably 80,000 to 700,000. If the molecular weight is too small, the polymer (b) will dissolve in the alkaline treatment liquid, resulting in insufficient surface wettability,
If the molecular weight is too high, the viscosity of the polymer coating solution will increase,
This causes a problem that the compatibility with the polymer (a) deteriorates.

Typical examples of the polymer (b) of the present invention are shown below together with the weight average molecular weight (Mw), but the present invention is not limited thereto. The composition ratio in parentheses indicates the mole percentage ratio of each monomer component.

B-1 methyl methacrylate / methacrylic acid copolymer (75/25) Mw = 150,000 B-2 methyl methacrylate / methacrylic acid copolymer (70/30) Mw = 80,000 B-3 methyl methacrylate / methacrylic acid copolymer Polymer (70/30) Mw = 120,000 B-4 Methyl methacrylate / methacrylic acid copolymer (70/30) Mw = 250,000 B-5 Methyl methacrylate / methacrylic acid copolymer (70/30) Mw = 350,000

B-6 methyl methacrylate / methacrylic acid copolymer (60/40) Mw = 300,000 B-7 methyl methacrylate / styrene / methacrylic acid copolymer (40/30/30) Mw = 150,000 B-8 methyl methacrylate / 2-Hydroxyethyl methacrylate / methacrylic acid copolymer (45/20/35)
Mw = 250,000 B-9 ethyl methacrylate / methacrylic acid copolymer (70/30) Mw = 140,000 B-10 n-butyl acrylate / methyl methacrylate / methacrylic acid copolymer (30/25/45) Mw = 550,000

B-11 methyl acrylate / methacrylic acid copolymer (70/30) Mw = 120,000 B-12 methyl methacrylate / acrylic acid copolymer (75/25) Mw = 150,000 B-13 methyl methacrylate / acrylic acid copolymer Polymer (70/30) Mw = 180,000 B-14 Methyl acrylate / Methyl methacrylate /
Acrylic acid copolymer (35/35/30) Mw = 95,000 B-15 ethyl acrylate / acrylic acid copolymer (70
/ 30) Mw = 280,000

B-16 methyl acrylate / t-butyl methacrylate / methacrylic acid copolymer (20/50/30)
Mw = 120,000 B-17 methyl methacrylate / acrylic acid / methacrylic acid copolymer (65/15/20) Mw = 150,000 B-18 methyl methacrylate / methacrylic acid / vinyl benzoic acid copolymer (70/20/10) Mw = 75,000 B-19 methyl methacrylate / 3- (acryloyloxyethoxycarbonyl) propionic acid copolymer (65/3
5) Mw = 180,000 B-20 methyl acrylate / t-butyl acrylamide / 3-acrylamide propionic acid copolymer (45/25 /
30) Mw = 120,000

The polymer represented by (c) contains 1 to 3 monomers containing at least --COOH groups as repeating units.
An organic solvent-soluble polymer containing 5 mol% and having a weight average molecular weight of 1,000 or more and 60,000 or less.

Specific examples and preferred examples of the monomer containing a --COOH group in (c) are the same as those described in the polymer (b). Moreover, in (c), -COOH
Substituted or unsubstituted alkyl acrylates or alkyl methacrylates are preferable as monomers to be copolymerized in addition to the group-containing monomers, and specific and particularly preferable examples thereof are the same as those mentioned above in the polymer (b). Can be mentioned. Further, in the polymer represented by (c), the specific examples of the monomer which may be copolymerized with the monomer containing a —COOH group other than the alkyl acrylate and the alkyl methacrylate are the same as those described in the polymer (b). I can list things.

In the polymer represented by (c) of the present invention, the proportion of the monomer containing —COOH group is (c).
Depending on the structure of, it is 1 to 35 mol%, preferably 3 to 30 mol%, particularly preferably 5 to 30 mol%.

The polymer represented by (c) is --COOH.
Copolymerization of a group-containing monomer with an acrylic acid ester or a methacrylic acid ester is preferable from the viewpoint of preventing treatment liquid scum when combined with the polymers represented by the cellulose ester polymers (a) and (b) . Therefore, as in (b), in (c), the sum of the proportions of acrylic acid or methacrylic acid and acrylic acid ester or methacrylic acid ester is preferably 55 mol%.
More preferably, it is 70 mol% or more.

Further, the molecular weight of the polymer represented by (c) of the present invention has a weight average molecular weight of 1,000 or more and 60,000 or less from the viewpoint of achieving both good surface wettability and prevention of treatment liquid scum.
Preferably 3000 or more and 50,000 or less, particularly preferably 50
It is from 00 to 40,000.

Typical examples of the polymer (c) of the present invention are shown below together with the weight average molecular weight (Mw), but the present invention is not limited thereto. The composition ratio in parentheses indicates the mole percentage ratio of each monomer component.

C-1 methyl methacrylate / methacrylic acid copolymer (95/5) Mw = 25,000 C-2 methyl methacrylate / methacrylic acid copolymer (90/10) Mw = 7,000 C-3 methyl methacrylate / methacrylic acid copolymer Polymer (90/10) Mw = 23,000 C-4 methyl methacrylate / methacrylic acid copolymer (90/10) Mw = 38,000 C-5 methyl methacrylate / methacrylic acid copolymer (80/20) Mw = 27,000

C-6 methyl methacrylate / methacrylic acid copolymer (70/30) Mw = 50,000 C-7 methyl methacrylate / vinyl acetate / methacrylic acid copolymer (50/30/20) Mw = 9,500 C-8 methyl Methacrylate / styrene / methacryl
Acid copolymer (65/20/15) Mw = 15,000 C-9 ethyl methacrylate / methacrylic acid copolymer (90/10) Mw = 48,000 C-10 n-butyl acrylate / methyl methacrylate / methacrylic acid copolymer Combined (50/40/10) Mw = 12,000

C-11 methyl acrylate / methacrylic acid copolymer (95/5) Mw = 18,000 C-12 methyl methacrylate / acrylic acid copolymer (90/10) Mw = 35,000 C-13 methyl methacrylate / acrylic acid copolymer Polymer (80/20) Mw = 25,000 C-14 Methyl acrylate / Methyl methacrylate /
Acrylic acid copolymer (45/45/10) Mw = 20,000 C-15 ethyl acrylate / acrylic acid copolymer (70
/ 30) Mw ＝ 26,000

C-16 methyl acrylate / itaconic acid copolymer (95/5) Mw = 8,000 C-17 methyl methacrylate / acrylic acid / methacrylic acid copolymer (75/10/15) Mw = 22,000 C-18 methyl Methacrylate / methacrylic acid / vinyl benzoic acid copolymer (85/10/5) Mw = 15,000 C-19 methyl methacrylate / 3- (acryloyloxyethoxycarbonyl) propionic acid copolymer (75/2
5) Mw = 13,000 C-20 methyl acrylate / t-butyl acrylamide / 3-acrylamide propionic acid copolymer (55/35 /
10) Mw = 27,000

In the present invention, as long as the good performance of each polymer represented by (a), (b) and (c) can be obtained, (b) and (c) the monomer containing a --COOH group is used. The proportion of units is 20 to 50 mol% in (b) and 1 in (c).
It can be freely set in the range of 35 to 35 mol%, but in order to obtain better drying unevenness prevention ability and treatment liquid scum prevention ability, "the proportion of the -COOH group-containing monomer in (b) (mol%)
"(C) minus the proportion (mol%) of the -COOH group-containing monomer" is preferably in the range of -10 to 30%, particularly preferably in the range of -5 to 20%.

In the present invention, the amount of the binder used in the outermost surface layer of the back layer may vary depending on the type, form or coating form of the photographic light-sensitive material, but 0.01 to 2 g / m 2 as the total binder in the outermost surface layer. ² is preferable, and 0.05 to 1 g / m ² is particularly preferable. The total amount of the polymers represented by (b) and (c) is 0.001 to 1.6 g / m ²
Is preferable, and 0.005-0.4 g / m ² is particularly preferable.

In all binders of the outermost surface layer, (b)
And the proportion of the polymer represented by (c) is 5 to 80 by weight.
% Is preferred and 10-40% is particularly preferred.

In the present invention, the ratio of the polymer represented by (b) to the polymer represented by (c) in the outermost surface layer is not particularly limited, but the mass ratio is preferably 30:70.
To 90:10, particularly preferably 50:50 to 8
It is within the range of 5:15.

In the present invention, the polymer constituting the outermost surface layer may be any one of the above-mentioned polymers (a), as long as it does not impair the surface wettability of the obtained coating and the ability to prevent the scum of the treatment liquid.
An organic solvent-based polymer other than the polymer (b) and the polymer (c) may be used. Preferred examples of such a polymer include an alkyl acrylate that does not include a -COOH group,
Alkyl methacrylate homopolymer or copolymer (for example, polymethyl methacrylate, polyethyl methacrylate, polymethyl methacrylate-co-ethyl acrylate, etc.), styrenes (polystyrene, polystyrene-
co-methylmethacrylate), and the like.

However, the addition of such a polymer is not essential, and the addition amount is 0 to 30 in all binders.
Mass % is preferred.

In the back layer of the present invention, the layer adjacent to the outermost surface layer of the back layer is the above-mentioned polymer (a), polymer (b), polymer (c) or a synthetic polymer such as polymethylmethacrylate or a mixture thereof. Etc. can be used. Further, it may be a layer of the ionene type polymer disclosed in JP-B-57-50659 alone or in a mixture with the binder. Further, the adjacent layer may contain a dye or a crosslinking agent in addition to these binders.

Particularly when the adjacent layer is an ionene type polymer layer or a layer comprising an ionene type polymer and a hydrophilic binder, the coatability is good, the adhesion between the outermost surface layer and the adjacent layer is good, and conversely, the outermost surface layer. It is possible to obtain a photographic light-sensitive material having good adhesion resistance between the silver halide emulsion layer side and the light-sensitive layer or protective layer on the silver halide emulsion layer side, and having excellent scratch resistance and antistatic property.

The outermost surface layer of the back layer of the present invention may contain an antistatic agent, a matting agent, a slip agent, a dye, a crosslinking agent, etc., if necessary.

The method of applying the outermost surface layer of the backing layer containing the polymer of the present invention to a photographic light-sensitive material is as follows. The polymer is an organic solvent (for example, methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, dioxane, dimethylformamide, Formamide, dimethyl sulfoxide, methyl cellosolve, ethyl cellosolve, methylene chloride, etc.) or a mixed solvent of organic solvents and sprayed, coated or dipped in the solvent and dried.

The support to which the present invention can be applied includes, for example, polyolefin such as polyethylene, polystyrene, a cellulose derivative such as cellulose triacetate, a film such as polyester such as polyethylene terephthalate or baryta paper, synthetic paper or both surfaces of the paper. And the like, which consist of a sheet coated with the polymer film of 1.

The photographic light-sensitive material of the present invention (hereinafter referred to as "sensitivity"
"Abbreviated as" material ") is an ordinary black-and-white silver halide light-sensitive material (for example, a black-and-white light-sensitive material for photographing, a black-and-white light-sensitive material for roentgen, a black-and-white light-sensitive material for printing, etc.), a normal multi-layer color light-sensitive material (for example, color reversal). film, a color negative film, various photosensitive materials such as color positive films, etc.).

In the silver halide photographic light-sensitive material of the present invention, the silver halide grains in the emulsion may have a regular crystal form such as a cube or an octahedron, or may have a spherical shape, a plate shape or a potato shape. Irregular (irreg
It may have a regular crystal form, or may consist of a mixture of grains of various crystal forms.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, JP-A-2-685.
It is possible to use those described in the following relevant parts of Japanese Patent Publication No. 39. Item This section 1. Silver halide emulsions and JP-A-2-68539, page 8, lower right column, line 6 from the bottom or from its manufacturing process, page 10 upper right column, line 12 2. Chemical sensitization method, page 10, upper right column, line 13 to left lower column, line 16 3. Antifoggant / stabilization Page 10, lower left column, line 17 to page 11, upper left column, line 7 and agent and page 3, lower left column, line 2 to page 4, lower left column 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column, 5. Surfactants / antistatics Page 11, upper left column, line 14 to page 12, upper left column, line 9 Antistatic agent 6. Matting agent, slip agent, page 12, upper left column, line 10 to upper right column, line 10 14th plasticizer Page 10, lower left column, line 10 to lower right column, line 1 7. Hydrophilic colloid, page 12, right upper column, line 11 to left lower column, line 16 8. Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 9. Support, page 13, upper right column, lines 7 to 20 10. Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9 11. Development processing method JP-A-2-03037 Gazette, page 16, upper right column, line 7 to page 19, lower left column, line 15 And JP-A-2-115837, page 3, lower right column, line 5 to page 6, upper right column, line 10

[0064]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, "part" in an Example shows a " mass part."

Example 8 g of an ionene-type polymer having a molecular weight of 10,000 and consisting of the repeating units shown below was dissolved in 10 ml of water, and a coating solution diluted with a mixed solvent of 650 ml of methanol and 350 ml of acetone was coated on the cellulose triacetate film support. The amount is 50mg / m ² and applied 1
It was dried at 00 ° C. for 3 minutes.

[0066]

[Chemical 2]

Then, a back coating solution 101-120 for the outermost surface layer shown in Table 1 was coated thereon with a coating amount of the compound (a) of 120 mg.
/ M ² and then dried at 90 ° C. for 3 minutes to form the outermost surface layer of the back layer to obtain a corresponding back layer-coated film.

[0068]

[Table 1]

[0069]

[Table 2]

Gelatin 4 g / m ² , silver iodobromide (iodine content 2 mol%) 5 on the side opposite to the back layer of the obtained film.
Silver halide emulsion layer containing g / m ² and 1 g of gelatin
Films 201 to 220 for indirect radiography provided with a protective layer containing / m ² were produced. The obtained X-ray films 201 to 220 were developed by using an automatic processor RU-II (manufactured by Fuji Film Co., Ltd.) to develop developer RD-3 (manufactured by Fuji Film Co., Ltd.) and fixer Fuji-F (Fuji Film (manufactured by Fuji Film Co., Ltd.). Manufactured by K.K.) with a total processing time of 90 seconds. At this time, the drying temperature is 3
It was 5 ° C.

The treated film was observed with the naked eye to see the degree of occurrence of uneven dryness. The dry unevenness on the emulsion layer side was defined as "occurrence" when thin uneven spots were observed on the surface of the emulsion layer side. The dry unevenness on the back layer side was defined as "occurred" when white unevenness due to the residual fixing liquid component remaining on the surface of the back layer, unevenness due to the traces of water droplets, and the like were observed.
The results of the above unevenness of drying are shown in Table 2.

Next, in order to check the stains generated in the developing layer and the fixing layer, X was used under the same processing conditions using the above-mentioned automatic developing machine.
After continuous treatment of 39 m ^{2 of} ray film (18 cm width × 215 m), insoluble precipitates generated in the developer and fixer layers were observed. When a deposit (scum) was generated, it was defined as "occurred". The results of scum are shown in Table 2.

Next, in order to check the adhesion resistance, the obtained untreated X-ray film was cut into a size of 35 mm × 35 mm, left in an atmosphere of 25 ° C. and 80% relative humidity for 24 hours, and then, two sheets each. Five sets were stacked and left for 24 hours under the same atmosphere with a load of 2 kg. Then, this was taken out, the film was peeled off, and the adhesion area between the back layer and the protective layer was examined. At this time, A is the case where the adhesion area is 0 to 5%, B is the case where it is 6 to 10%, and C is the case where it is 11 to 20%.
21 to 30% was evaluated as D, and 31% or more was evaluated as E. Table 2 shows the results of adhesion. Next, in order to examine the antistatic ability, two unexposed X-ray films 201 to 220 were used.
After leaving it in an atmosphere of 5 ° C and a relative humidity of 30% for 24 hours,
A rubber roller was rotated on the surface on the side of the photosensitive layer to generate static, which was developed by the above-mentioned automatic developing machine and observed. The results are shown in Table 2.

[0074]

[Table 3]

As shown in Table 2, the films 210, 21
From comparison of 1, 212, 216, and 218
As described in No. 938, good adhesion resistance can be obtained by applying a cellulose ester and a low-COOH content methyl methacrylate / methacrylic acid copolymer (90/10 to 80/20) to the outermost surface of the back. Although it is obtained and the drying unevenness on the emulsion layer side is improved, the unevenness on the back layer side remains a problem.

On the other hand, a film 2 composed of a high molecular weight polymer B-4 having a high --COOH content and a cellulose ester.
Nos. 09 and 213 have sufficient drying unevenness, but scum during development and fixing is a problem. Further, even if the content of -COOH is high, the film 214 composed of only the low molecular weight polymer C-6 and cellulose ester causes not only insufficient drying unevenness but also a problem of scum during development.

[0077]

The film 201 in which the cellulose ester polymer (a) of the present invention, the high molecular weight -COOH polymer (b), and the low molecular weight -COOH polymer (c) are combined is used.
-208 is adhesion resistance, static mark, uneven drying,
It shows extremely excellent performance against any of the scums. In addition, the films 215 and 21 using other materials or combinations of materials for the composition and molecular weight of the -COOH polymer.
Nos. 7, 219 and 220 show insufficient performance in terms of uneven drying or scum, and it is clear that only the combination of the polymers of the present invention is the best one satisfying all the performances.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Norimasa Sato No. 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Shashin Film Co., Ltd. (56) References JP-A-60-87323 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/76 502

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on a support and a back layer on the opposite side of the support from the silver halide emulsion layer. , The outermost surface layer of the back layer is (a), (b),
At least look at containing the polymer of each one of (c), tail (b)
Content of the monomer unit containing -COOH group (mol%)
And (c) the content of monomer units containing -COOH groups (see
(%)) ((B) content minus (c) content)
Is 5% or more, and the ratio of (b) and (c) is 30:
A silver halide photographic light-sensitive material characterized by being 70 to 90:10 . (a) A cellulose ester polymer soluble in an organic solvent. (b) The repeating unit contains 25 to 40 mol% of monomer units containing at least -COOH group and has a weight average molecular weight of
80,000 700,000 following organic solvent-soluble polymer. , 1 to monomeric units containing at least -COOH groups as (c) repeating units 3 comprise 0 mol%, weight average molecular weight
5000 or 50,000 or less of an organic solvent-soluble polymer. 2. In (b) and (c) of claim 1,
The silver halide photographic light-sensitive material according to claim 1, wherein the total amount of the monomer unit containing a COOH group and the acrylic acid ester or the methacrylic acid ester is at least 55 mol% as a repeating unit in the copolymer.