JP3122794B2 - Silver halide photographic material with improved curl - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for printing plate making and, more particularly, to an excellent photographic light-sensitive material for printing plate making having a small curl.

[0002]

BACKGROUND OF THE INVENTION In the printing and plate making industries, there are two types of films, a roll film in which a long sheet is wound around a core, and a sheet film cut into a fixed size sheet. At present, roll films are used more in terms of cost, price and the like.

[0003] However, this roll film has a major drawback. It is a phenomenon called curl. This is a curl caused by the film being wound around the core, as in the case of reading characters, and it occurs more or less, although there is a difference in the degree of the roll film.

[0004] Although curl curl has been regarded as a problem for some time, curl curl resolving properties after development processing are described in Japanese Patent Application Laid-Open No. 1-244446. Although a technique of using a copolymerized polyester film having a copolymer component as is known, there is no effective countermeasure against untreated, so-called raw film curl.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which has a small roll curl of a raw film.

[0006]

The above object of the present invention DETAILED DESCRIPTION OF THE INVENTION, light-sensitive silver halide emulsion layer of at least one layer on a polyester support and the support relative to a light-sensitive silver halide emulsion layer
A silver halide photographic material comprising coated with a non-light-sensitive hydrophilic colloid layer at least one layer on the other side, said supporting
The carrier has an antistatic layer containing an ionic polymer substance.
Between the antistatic layer and the support.
A layer comprising vinylidene, said light-sensitive silver halide emulsion layer side and the amount with the respective non-light-sensitive hydrophilic colloid layer side of gelatin which is coated on the support is located at 2.5 g / m ² or less When the silver halide photographic light-sensitive material was produced, the silver halide emulsion layer was wound and wound so that the silver halide emulsion layer side was wound outward .
Seasoned sensitive light material in the form of a roll, then the product
During shipment, the emulsion layer side is achieved by a silver halide photographic light-sensitive material characterized that you packaging rewinding so as to be inside.

[0007]

Hereinafter, the present invention will be described in detail.

[0009] a time synonymous the seasoning in the present invention, the conditions of the present invention, rather preferably carried out from 1 day between 35 degrees 15 degrees Celsius for 7 days, particularly preferably at 30 degrees or more Seasoning for 3 days or more .

[0010] The vinylidene chloride copolymer of the present invention
Is a copolymer containing vinylidene chloride, JP-A-51-135
No. 526 vinylidene chloride / acrylate / side
Copolymerization of vinyl monomer having alcohol in chain
, Vinylidene chloride / al as described in US Patent 2,852,378
Kill acrylate / acrylic acid copolymer, USA
Patent 2,698,235 Vinylidene chloride / acrylonitrile
/ Itaconic acid copolymer, US Pat. No. 3,788,856
Described vinylidene chloride / alkyl acrylate / itaco
And a copolymer composed of an acid.

Preferred embodiments of vinylidene chloride include:
A copolymer (A) containing 80 to 94% by weight of vinylidene chloride was prepared.
30 to 94 parts by weight as fat, 94 to 100 parts by weight of vinylidene chloride
% Of the copolymer (B) containing 3 to 50 parts by weight as a resin component,
Preparation of copolymer (C) containing 40 to 80% by weight of vinylidene chloride
Mix 3-20 parts by weight of fat in latex state, no
Salt obtained by mixing in the same latex
It is a vinylidene fluoride copolymer mixed latex.

The following are specific examples of compounds.
It is.

All figures in parentheses indicate weight ratios.

Vinylidene chloride: methyl acrylate:
Copolymer of droxyethyl acrylate (86: 12: 2).

Vinylidene chloride: ethyl methacrylate:
Copolymerization of hydroxypropyl acrylate (82: 10: 8)
body.

Vinylidene chloride: hydroxydiethyl meta
Copolymer of acrylate (92: 8).

Vinylidene chloride: butyl acrylate:
Copolymer of crylic acid (94: 4: 2).

Vinylidene chloride: butyl acrylate:
Copolymer of taconic acid (75: 20: 5).

Vinylidene chloride: methyl acrylate: a
A copolymer of taconic acid (90: 8: 2).

Vinylidene chloride: methyl acrylate:
Tacrylic acid (93: 4: 3).

Vinylidene chloride: monoethyl itaconate
A copolymer of steal (96: 4).

Vinylidene chloride: acrylonitrile: ac
Copolymer of lylic acid (95: 3.5: 1.5).

Vinylidene chloride: methyl acrylate:
Copolymer of crylic acid (90: 5: 5).

Vinylidene chloride: ethyl acrylate:
Copolymer of crylic acid (93: 5: 2).

Vinylidene chloride: methyl acrylate: 3
-Chloro-2-hydroxypropyl acrylate (84: 9:
7) Copolymer.

Vinylidene chloride: methyl acrylate: N
-A copolymer of ethanolacrylamide (85: 10: 5).

Vinylidene chloride: methyl acrylate:
Copolymer of acrylic acid (98: 1: 1).

Vinylidene chloride: methyl acrylate: a
Copolymer of taconic acid (97: 1: 2).

Vinylidene chloride: acrylonitrile: ac
Copolymer of lylic acid (99: 0.5: 0.5).

Vinylidene chloride: ethyl acrylate:
Copolymer of acrylic acid (98: 1: 1).

Vinylidene chloride: methyl acrylate:
Copolymer of crylic acid (65: 34: 1).

Vinylidene chloride: methyl acrylate: a
Copolymer of taconic acid (70: 29: 1).

Vinylidene chloride: acrylonitrile: ac
Copolymer of lylic acid (70: 29: 1) vinylidene chloride: ethyl acrylate: acrylic acid (68:
31: 1) Coat vinylidene chloride layer on copolymer support
There are no particular restrictions on the method used, but for example,
The method described in Japanese Patent Application No. 2-81853 can be used.

In addition, various treatments can be applied to give a strong adhesive force. For example, the surface may be subjected to surface treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and acid treatment. Component, hydroxyl group component, epoxy group component, N-alkanol group component, diolefin monomer component, polymer latex component, etc. is there. The present invention
An antistatic layer on the vinylidene chloride copolymer layer.
Is painted.

As the antistatic layer, a layer containing an ionic polymer substance is preferably used. Also, specifically, as the ionic polymer compound used in the present invention,
JP-B-49-23828, JP-B-49-23827, JP-B-47-28937: Anionic polymer compounds: JP-B-55-734,
JP-A-50-54672, JP-B-59-14735, JP-B-57-18175,
Ionene-type polymers having a dissociating group in the main chain, such as those found in JP-A-57-18176 and JP-A-57-56059: JP-B-53-1
No. 3223, No. 57-15376, JP-A-53-45231, No. 55-14578
No. 3, 55-65950, 55-67746, 57-11342, 5
And cationic pendant polymers having a cationic dissociating group in the side chain, such as those described in JP-A-7-19735 and JP-B-58-56858. The antistatic layer is preferably made of a reaction product of a water-soluble conductive polymer, a hydrophobic latex, and an epoxy-based curing agent.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups. The conductive groups require at least 5% by weight per polymer molecule. In the water-soluble conductive polymer, hydroxy group, amino group, epoxy group, aziridine group, active methylene group,
It may contain a sulfinic acid group, an aldehyde group and a vinyl sulfone group.

The molecular weight of the polymer is from 3000 to 100,000, preferably from 3500 to 50,000.

The following are examples of compounds of the water-soluble conductive polymer used in the present invention, but the invention is not limited thereto.

[0039]

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[0040]

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[0041]

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Further, A-1 to A-21 on pages 35 to 40 of Japanese Patent Application No. 2-226971 can also be used.

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are composed of a so-called latex which is substantially insoluble in water. This hydrophobic polymer is obtained by polymerizing a monomer selected in any combination from styrene, a styrene derivative, an alkyl acrylate, an alkyl methacrylate, an olefin derivative, a halogenated ethylene derivative, a vinyl ester derivative, and acrylonitrile. In particular, at least styrene derivatives, alkyl acrylates and alkyl methacrylates
It is preferably contained at 30 mol%. In particular, 50 mol% or more is preferable.

[0044]

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[0045]

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[0046]

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Further, B-1 to B-26 described in Japanese Patent Application No. 2-226971, pages 49 to 55, can also be used. Next, the epoxy-based curing agent in the present invention is not particularly limited as long as it has an epoxy group, and can be used in combination with a plurality of curing agents such as aldehyde-based and vinylsulfone-based curing agents.

Preferred epoxy compounds are those containing a hydroxy group or an ether condensation. In the present invention, the epoxy equivalent is a value represented by the following general formula.

Epoxy equivalent = molecular weight / the number of epoxy groups in one molecule. This value can be determined by colorimetry, for example, by the method of New Experimental Chemistry Course 13 (1) Organic Structure P58 (published by Maruzen).

The epoxy equivalent is preferably from 50 to 300, more preferably from 80 to 210. If it is more than 300, the curing is weak, and if the amount is increased, the coating property deteriorates. If the curing is weak, scratches are likely to occur. When the epoxy equivalent is less than 50, the curing is strong, but the haze and the residual color are deteriorated, and even if the amount is reduced, it does not improve.

Specific examples of the epoxy compound of the present invention will be given.

The numbers in parentheses indicate epoxy equivalents.

[0053]

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[0054]

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The addition amount of the epoxy curing agent is 5 mg / m ^{2 to 1} g / m.
² is preferred.

[0056]

EXAMPLES Examples of the present invention will be specifically described below, but it goes without saying that the present invention is not limited to these examples.

Example 1 A sample was prepared as follows.

(Support A) Vinylidene chloride / ethyl acrylate / itaconic acid =
An aqueous dispersion of the copolymer at a ratio of 86.8 / 11.1 / 2.0 / 0.3 wt% was applied and dried to a thickness of 1.2 μm, and the support on which the polyvinylidene chloride layer was laminated was used as support A.

(Support B) A support in which polyvinylidene chloride is not laminated on the support A is referred to as a support B. The following undercoat layer was coated on one side of each of the above supports, then a silver halide emulsion layer was coated, and an emulsion protective layer was coated thereon.

On the other side, a backing layer was applied to form Samples 1 to 6 as shown in Table 1.

(Preparation of Emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows.

An aqueous solution containing 71.7 mg of pentabromorhodium potassium salt, sodium chloride and potassium bromide per 180 g of silver nitrate and an aqueous solution of silver nitrate were stirred simultaneously in an aqueous gelatin solution at 40 ° C. for 25 minutes, and each was averaged. Silver chlorobromide emulsions each having a particle size of 0.20 μm were prepared. 6-Methyl-4-hydroxy-1,3,3 as a stabilizer in these emulsions
After 600 mg of a, 7-tetrazaindene was added, the mixture was washed with water and desalted. 60 mg of 6-methyl-4-hydroxy-1,3,3a, 7
Sulfur sensitization after addition of tetrazaindene. After dividing this into three equal parts, first add the necessary amount of gelatin to the first
As shown in the table, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and the emulsion was prepared by finishing to 260 ml with water. (Preparation of latex (L) for adding emulsion) 0.2 g of KMDS (dextran sulfate sodium salt) manufactured by Meito Sangyo in 40 l of water
5Kg and 0.05Kg ammonium persulfate added liquid temperature 81 ℃
N-butyl acrylate under a nitrogen atmosphere while stirring at 4.
A mixture of 51 kg, styrene 5.49 kg and acrylic acid 0.1 kg was added over 1 hour, and then ammonium persulfate was added at 0.005 Kg.
g was added, and the mixture was further stirred for 1.5 hours, cooled, and adjusted to pH 6 with aqueous ammonia.

The obtained latex solution was washed with Whotman GF.
A monodisperse latex (L) having an average particle size of 0.25 μm was prepared by filtering with a / D filter and finishing with water to 50.5 kg.

The following additives were added to the above emulsion to prepare a silver halide emulsion coating solution as follows.

(Preparation of Emulsion Coating Solution) After adding 9 mg of a mixture of the following three components A, B and C as a bactericide to the emulsion solution,
Adjust the pH to 6.5 using 0.5N sodium hydroxide solution,
Next, 360 mg of the following compound (T) was added, 5 ml of a 20% aqueous solution of saponin per mole of silver halide, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenztriazole, and the latex liquid for emulsion addition (L ) Was added, followed by the addition of 60 mg of the following compound (M) and 280 mg of a styrene-maleic acid copolymer aqueous polymer as a thickener, followed by finishing with water to 475 ml to prepare an emulsion coating solution.

[0066]

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Next, an emulsion protective film coating solution was prepared as follows.

(Preparation of Coating Solution for Emulsion Protective Film) Pure water was added to various amounts of gelatin, and after swelling, dissolved at 40 ° C. Then, as a coating aid, a 1% aqueous solution of the following compound (Z), as a filter dye the following compound (N), non-amorphous silica as a matting agent, and sequential addition of the following compound (B), after the pH6.0 further with citric acid solution, an emulsion protective layer coating solution by raising Specifications Te in water .

[0069]

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Next, an antistatic solution having the following composition was applied to the side opposite to the side on which the emulsion layer was applied.

Ammonium sulfate 0.5 g / l Polyethyl oxide compound (molecular weight 600) 6 g / l Mixture of curing agents E1, E2, E4 12.0 g / l Then, the backing coating solution used for coating the backing lower layer is as follows: Prepared.

(Preparation of Backing Coating Solution B # 1) Gelatin
After swelling 36 g in water and heating to dissolve, 1.6 g of the following compound (C # 1), 310 mg of (C # 2) and 1.9% of (C # 3) are used as dyes.
g, 2.9 g of the compound (N) was added in the form of an aqueous solution, 11 ml of a 20% aqueous solution of saponin was added, 5 g of the following compound (C 物 4) was added as a physical property modifier, and the following compound (C 63 mg of (5) was added. A styrene-maleic acid copolymer water-soluble polymer was added to this solution as a thickener.
Add 0 g and adjust the viscosity.
Glyoxal, and add 144 mg of glyoxal, and add 96
Finished to 0 ml to prepare a BC coating solution B # 1. In addition, backing layer coating solution B in which only gelatin was reduced to 27 g and 18 g
-2 and B-3 were also prepared.

[0073]

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[0074]

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Next, a protective film coating solution B # 4 was prepared as follows for coating the protective film layer of the backing layer.

(Preparation of Coating Solution B # 4) Gelatin 50
g in water, and after heating and dissolving, add 2-sulfonate-bis (2-ethylhexyl) succinate sodium salt to 340
mg, polymethyl methacrylate as matting agent
1.7 g (average particle size of about 0.4μ) and 3.4 g of sodium chloride
Further, 1.1 g of glyoxal and 540 mg of mucochloric acid were added, and finished to 1000 ml with water to prepare a coating solution B # 4 for a protective film.

[Preparation of Evaluation Samples] Each of the above coating solutions was applied to both surfaces of a polyethylene terephthalate film (100 μm thick) provided with a subbing layer in Example # 1 of JP-A-59-19941 one by one. Evaluation samples shown in Table 1 were prepared.

At this time, the backing lower layer was coated on one surface of the support provided with the undercoat layer using a B-1 coating solution so that the dry weight of gelatin became 2 g / m ² , and at the same time, Then, a backing protective film layer was coated and dried using a protective film solution B-4 so that the dry weight of gelatin became 1 g / m ² . Then, the emulsion layer was placed on the other side of the support at a dry gelatin weight of 1st.
So that the table, also like coating amount of silver was coated so as the 4.3 g / m ^2, the emulsion protective layer thereon using the protective film liquid gelatin dry Weight a value of Table 1 Was coated and dried simultaneously with the emulsion layer while adding formalin as a hardener.

Similarly, using B-2 and B-4, the amount of gelatin added on the backing layer side was 2.5 g / m ² , and the dry weight of gelatin was 2.5 g / m ² without changing the coated silver amount on the emulsion layer side. ² and B-3 and B-4, the amount of gelatin on the backing layer side was 2.0 g / m ² and the dry weight of gelatin was 2.0 g without changing the amount of silver on the emulsion layer side. Evaluation samples 1 to 6 applied so as to obtain g / m ² were prepared.

Next, the curl of curl was evaluated by the following method. (Evaluation Method of Rolling Curl) The obtained Samples 1 to 6 were divided into two, and one of them was wound around a core having a diameter of 7.5 cm with the emulsion surface inside to obtain Samples 1 to 6. The other was wound with the emulsion side outward. These samples were 1 "to 6".

Wrap samples 1 ″ to 6 ″ in a vinyl sheet,
After leaving at ℃ for 3 days, the emulsion was turned back and the emulsion surface was turned inside. After leaving these 1 to 6 and 1 ″ to 6 ″ at 25 ° C. for one month, they were removed from the core, and the evaluation was made based on how the portion near the core was curled.

(1) First, a sample cut into a size of 30 cm × 30 cm in the length direction and 25.2 cm in the horizontal direction is prepared.

(2) The sample is placed on a horizontal surface with the convex direction facing downward.

(3) The distance from the lower surface of each of the four corners of the arc-warped sample was measured, and the curl was measured by using the average value.

In this evaluation method, the smaller the distance from the lower surface, the better the curl.

The results are shown in Table 1.

[0087]

[Table 1]

From the results shown in Table 1, it is clear that the sample of the present invention has excellent curl.

Example 2 Rolling and curling were evaluated in the same manner as in Example 1 except that the vinylidene chloride copolymer in Example 1 was replaced with 100% vinylidene chloride, and similar results were obtained.

[0090]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has a small curl in a raw film state and is excellent in handling.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-310343 (JP, A) JP-A-54-52523 (JP, A) JP-A-51-16358 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03C 1/81 G03C 3/00

Claims (1)

(57) [Claims] 1. A photosensitive halo comprising at least one layer on a support
The photosensitive halide is applied to the silver gemide emulsion layer and the support.
At least one non-light-sensitive parent layer on the side opposite to the silver halide emulsion layer
For silver halide light-sensitive materials coated with an aqueous colloid layer
Wherein the support is a band containing an ionic polymer substance.
An antistatic layer is laminated, between the antistatic layer and the support.
Has a layer containing polyvinylidene chloride, on the support
Coated photosensitive silver halide emulsion layer and non-photosensitive hydrophilic
Gelatin with the amount of each sex colloid layer, 2.5 g / m ² or more
Below, so that the emulsion layer side is wrapped around during the production of the photosensitive material.
And roll the photosensitive material into a roll
And then, at the time of product shipment, the emulsion layer side
The silver halide photographic light-sensitive material characterized that you packaging rewinding so as to be side.