JPH05241276A - Silver halide photographic sensitive material improved in curl tendency - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material small in the curl tendency in a state of raw film and superior in handling. CONSTITUTION:The silver halide photographic sensitive material is obtained by creating one side of a support with at least one photosensitive silver halide emulsion layer and the other side with at least one nonphotosensitive hydrophilic colloidal layer, and it is wound with the silver halide emulsion layer in the outside at the time of manufacture, it undergoes seasoning in a state of a roll, and then, it is rewound with the emulsion layer in the inside and packed. The support is the plastic film on which an antistatic layer containing an ionic polymer and/or a matal oxide is laminated, and a layer containing polyvinylidene chlorude is formed between the antistatic layer and the plastic film. It is preferred that the dry gelatin weight on the side of the support of the silver halide emulsion layer and that on Line side of the nonphotosensitive hydrophilic colloidal layer are each <=2.5g/m<2>.

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 a photographic light-sensitive material for printing plate making excellent in curling 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 sheet of a certain size. At present, the roll film is more widely used in terms of price and the like.

However, this roll film has a major drawback. It is a phenomenon called curling curl. This is a curl that occurs when the film is wound around the core, as can be seen from the reading, and it occurs to the extent that the roll film has a certain degree of difference, but it does occur.

The curling curl has been regarded as a problem for a long time, but the curling curl elimination property after the development treatment is as described in JP-A 1-244446 and the like, an aromatic dicarboxylic acid having a metal sulfonate. Techniques such as using a copolyester film containing as a copolymer component are known, but uncured curl curl of a so-called raw film has been reached without effective measures.

[0005]

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material in which the curling curl of a raw film is particularly small.

[0006]

The above object of the present invention is to provide at least one photosensitive silver halide emulsion layer on one side of a support, and
A silver halide light-sensitive material comprising at least one non-photosensitive hydrophilic colloid layer coated on the other surface of the support, wherein the silver halide emulsion layer is outside during the production of the silver halide photographic light-sensitive material. The silver halide photographic light-sensitive material wound into a roll is seasoned in the state of a roll, and then the silver halide emulsion layer is rewound so that it is on the inside and packaged. This is achieved by a photographic light-sensitive material.

The support is a plastic film on which an antistatic layer containing an ionic polymer and / or a metal oxide is laminated, and between the antistatic layer and the plastic film. , A layer containing poly (vinylidene chloride), and the dry weight of each of the photosensitive silver halide emulsion layer coated on the support and the non-photosensitive hydrophilic colloid layer side is 2.5 g / It is preferably m ² or less. Hereinafter, details of the present invention will be described.

In the present invention, seasoning is synonymous with the passage of time, and under the conditions of the present invention, it is preferable to carry out the treatment between 15 and 35 degrees Celsius for 1 to 7 days, particularly preferably.
It is a seasoning of 30 degrees or more for 3 days.

The vinylidene chloride copolymer in the present invention is a vinylidene chloride-containing copolymer, and is disclosed in JP-A-51-135.
Copolymer of vinylidene chloride / acrylic acid ester / vinyl monomer having side chain alcohol as described in No. 526, Copolymer of vinylidene chloride / alkyl acrylate / acrylic acid as described in US Pat. No. 2,852,378, US Pat. No. 2,698,235 And the vinylidene chloride / acrylonitrile / itaconic acid copolymers, and the vinylidene chloride / alkyl acrylate / itaconic acid copolymers described in US Pat. No. 3,788,856.

A preferred embodiment of vinylidene chloride is
30 to 94 parts by weight of a copolymer (A) containing 80 to 94% by weight of vinylidene chloride as a resin component, 3 to 50 parts by weight of a copolymer (B) containing 94 to 100% by weight of vinylidene chloride as a resin component,
A vinylidene chloride copolymer mixed latex obtained by mixing 3 to 20 parts by weight of a copolymer (C) containing 40 to 80% by weight of vinylidene chloride as a resin component in a latex state or mixing in the same latex. is there.

The following are specific examples of the compound.

All numbers in parentheses represent weight ratios.

Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (86: 12: 2) Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (82: 10: 8) Vinylidene chloride: hydroxydiethyl methacrylate ( 9
2: 8) copolymer vinylidene chloride: butyl acrylate: acrylic acid (94:
4: 2) Copolymer Vinylden chloride: Butyl acrylate: Itaconic acid (75:
20: 5) copolymer vinylidene chloride: methyl acrylate: itaconic acid (90:
8: 2) copolymer vinylidene chloride: methyl acrylate: methacrylic acid
(93: 4: 3) Copolymer Vinylidene chloride: Itaconic acid monoethyl ester (96: 4)
Copolymer of vinylidene chloride: acrylonitrile: acrylic acid (95: 3.
5: 1.5) copolymer vinylidene chloride: methyl acrylate: acrylic acid (90:
5: 5) copolymer vinylidene chloride: ethyl acrylate: acrylic acid (93:
5: 2) copolymer vinylidene chloride: methyl acrylate: 3-chloro-2-hydroxypropyl acrylate (84: 9: 7) copolymer vinylidene chloride: methyl acrylate: N-ethanol acrylamide (85: 10: 5) ) Copolymer of vinylidene chloride: methyl acrylate: acrylic acid (98:
1: 1) copolymer vinylidene chloride: methyl acrylate: itaconic acid (97:
1: 2) copolymer vinylidene chloride: acrylonitrile: acrylic acid (99: 0.
5: 0.5) copolymer vinylidene chloride: ethyl acrylate: acrylic acid (98:
1: 1) copolymer vinylidene chloride: methyl acrylate: acrylic acid (65:
34: 1) copolymer vinylidene chloride: methyl acrylate: itaconic acid (70:
29: 1) copolymer vinylidene chloride: acrylonitrile: acrylic acid (70: 2
9: 1) copolymer vinylidene chloride: ethyl acrylate: acrylic acid (68:
The method of coating the vinylidene chloride layer on the copolymer support of (31: 1) is not particularly limited, but for example, Japanese Patent Application No. 2-1818
The method described in No. 53 can be used.

In addition, various treatments can be applied to give a strong adhesive force. For example, 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, or acid treatment. Component, hydroxyl group component, epoxy group component, N-alkanol group component, diolefin monomer component, polymer latex component etc. by a method of applying an undercoat layer containing a single or a plurality of components selected is there. In the present invention, it is preferable that an antistatic layer is coated on the vinylidene chloride copolymer layer.

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

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group. The conductive group needs to be 5% by weight or more per polymer molecule. Hydroxy group, amino group, epoxy group, aziridine group, active methylene group, in the water-soluble conductive polymer,
It may contain a sulfinic acid group, an aldehyde group, or a vinyl sulfone group.

The molecular weight of the polymer is 3,000 to 100,000, preferably 3500 to 50,000.

Examples of the compound of the water-soluble conductive polymer used in the present invention are shown below, but the invention is not limited thereto.

[0019]

[Chemical 1]

[0020]

[Chemical 2]

[0021]

[Chemical 3]

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

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

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

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 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 curing agents and vinyl sulfone curing agents.

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

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

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

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

Numbers in parentheses () indicate epoxy equivalents.

[0033]

[Chemical 7]

[0034]

[Chemical 8]

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

Next, a method of forming a conductive layer using a metal oxide will be described.

Crystalline metal oxide particles are preferable as the metal oxide, but those containing oxygen defects and those containing a small amount of different atoms forming a donor to the metal oxide used are generally used. In terms of high conductivity, it is particularly preferable. Particularly, the latter metal oxides containing a small amount of different atoms forming a donor are particularly preferable because they do not cause fog in the silver halide emulsion.

Examples of metal oxides include ZnO ₂ , TiO ₂ and Sn.
_{O 2, Al 2 O 3,} In 2 O 3, SiO 2, MgO, BaO, M 0 O 3, V 2 O 5 or the like, or composite oxides thereof are preferable, and ZnO _2, TiO _2, Sn
O ₂ is preferred.

As an example containing different kinds of atoms, for example, addition of Sb or the like to SnO ₂ or addition of Nb or Ta to TiO ₂ is effective. The addition amount of these different kinds of atoms is preferably in the range of 0.01 to 30 mol%, and particularly preferably in the range of 0.1 to 10 mol%.

The metal oxide particles used in the present invention are
It has conductivity and its volume resistivity is 10 ⁷ Ωcm.
It is particularly preferable that it is 10 ⁵ Ωcm or less.

Regarding this oxide, JP-A-56-143431
No. 56-120519 and No. 58-62647.
The metal oxide particles are used by being dispersed or dissolved in a binder. The binder that can be used is not particularly limited as long as it has a film forming ability.

Particularly, gelatin (lime-processed gelatin, acid-processed gelatin, oxygen-decomposed gelatin, phthalated gelatin, acetylated gelatin, etc.), acetyl cellulose, diacetyl cellulose, triacetyl cellulose, polyvinyl alcohol, polyvinyl acetate, polybutyl acrylate, Polyacrylamide and dextran are preferred.

In order to use the metal oxide more effectively and lower the resistance of the conductive layer, it is preferable that the volume content of the metal oxide in the conductive layer is high, but the strength as a layer is sufficient. Since at least about 5% of a binder is required to have the metal oxide, the volume percentage of the metal oxide is preferably in the range of 5 to 95%.

[0044] The amount of the metal oxide is preferably 0.05 to 10 g / m ^2, more preferably 0.01-5 g / m ^2. This provides antistatic properties.

[0045]

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

Example 1 A sample was prepared as follows.

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

(Support B) Support B is a support on which polyvinylidene chloride is not laminated.

Corona discharge was applied to the surface of the above support at 10 W / (m ² · min), and then the following composition was applied using a roll-fit coating pan and an air knife. Drying is 90 ℃, overall heat transfer coefficient is 25Kcal (m ² · hr ・ ℃)
Parallel flow drying conditions for 30 seconds, followed by 140 ° C. for 90 seconds. The film thickness of this layer after drying was 1 μ, and the surface resistivity of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0050]

[Chemical 9]

Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 600) 6 g / l Curing agent 12 g / l

[0052]

[Chemical 10]

(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 in an aqueous solution of gelatin at the same time for 25 minutes at 40 ° C. to obtain an average particle size. Diameter 0.20μ
A silver chlorobromide emulsion of m was prepared. To these emulsions was added 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer, followed by washing with water and desalting. 60 mg of this 6
After addition of -methyl-4-hydroxy-1,3,3a, 7-tetrazaindene, it was sulfur sensitized. After dividing it into three equal parts,
The required amount of gelatin was added to each as shown in Table 1, and 6-methyl-4-hydroxy-1,3,3a, 7 was added as a stabilizer.
An emulsion was prepared by adding tetrazaindene and then making up to 260 ml with water. (Preparation of latex (L) for emulsion addition) 0.25 kg of KMDS (dextran sulfate sodium salt) manufactured by Meito Sangyo Co., Ltd. and 0.05 kg of ammonium persulfate were added to 40 l of water while stirring at a liquid temperature of 81 ° C. and a nitrogen atmosphere. Below n-butyl acrylate 4.51Kg, styrene 5.49Kg and acrylic acid 0.
1 kg of the mixed solution was added over 1 hour, 0.005 kg of ammonium persulfate was then added, and the mixture was stirred for 1.5 hours, cooled, and adjusted to pH 6 with ammonia water.

The obtained latex liquid was used as GF manufactured by Whotman.
A monodisperse latex (L) having an average particle size of 0.25 μ was prepared by separating the mixture 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 to the above emulsion solution as a bactericide,
Adjust the pH to 6.5 using 0.5N sodium hydroxide solution,
Next, 360 mg of the following compound (T) was added, and further, 5 ml of a 20% saponin aqueous solution, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenztriazole, and 80 mg of 5-methylbenztriazole were added per 1 mol of silver halide. ) Was added to 60 mg of the following compound (M), and 280 mg of a styrene-maleic acid copolymer aqueous polymer as a thickener was sequentially added, and the mixture was made up to 475 ml with water to prepare an emulsion coating solution.

[0058]

[Chemical 11]

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, it was dissolved at 40 ° C. Then, as a coating aid, 60 cc of 1% aqueous solution of the following compound (Z), filter dye The following compound (N) (5.3 g), amorphous silica (1 g) as a matting agent, and the following compound (B) (300 mg) are sequentially added, and the pH is adjusted to 6.0 with citric acid solution, and then latex (L) (80 ml) is added and water is added. To 1 liter to prepare an emulsion protective film coating solution.

[0061]

[Chemical 12]

(Preparation of Backing Coating Solution B-1) Gelatin 36 g
Is swelled in water, heated and dissolved, then
(C-1) 1.6 g, (C-2) 310 mg, (C-3) 1.9 g,
2.9 g of the compound (N) was added as an aqueous solution, and then 11 ml of a 20% saponin aqueous solution was added.
5 g of (C-4) was added, and 63 mg of the following compound (C-5) was added as a methanol solution. As a thickener to this liquid,
Styrene-maleic acid copolymer 800g of water-soluble polymer was added to adjust the viscosity, pH was adjusted to 5.4 using citric acid aqueous solution, and finally 144mg of glyoxal was added, and 960ml of water was added.
To prepare BC coating liquid B-1. Also, backing layer coating liquid B- in which only gelatin was reduced to 27 g and 18 g
2, B-3 was also prepared.

[0063]

[Chemical 13]

[0064]

[Chemical 14]

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

(Preparation of protective film coating solution B-4) Gelatin 50
After swelling g in water and dissolving with heating, 340% of 2-sulfonate-bis (2-ethylhexyl) succinate ester sodium salt was added.
mg, and polymethylmethacrylate as matting agent
(Average particle size of about 0.4μ) 1.7g, add sodium chloride 3.4g,
Further, 1.1 g of glyoxal and 540 mg of mucochloric acid were added, and the mixture was made up to 1000 ml with water to prepare a protective film coating solution B-4.

[Preparation of Evaluation Sample] Each of the coating solutions described above was applied to both surfaces of the supports A and B one by one to prepare evaluation samples shown in Table 1.

At this time, a backing lower layer was coated on one surface of the support coated with an undercoat layer with the B-1 coating solution so that the dry weight of gelatin was 2 g / m ² , and at the same time, the upper portion thereof was coated. Then, the backing protective film layer was coated and dried using the protective film solution B-4 so that the dry weight of gelatin was 1 g / m ² . Then, an emulsion layer was coated on the other side of the support so that the dry weight of gelatin was as shown in Table 1 and the coated silver amount was 4.3 g / m ^2, and the emulsion protective layer was provided on top of it. The protective layer solution was applied and dried simultaneously with the emulsion layer while adding formalin as a hardening agent so that the dry weight of gelatin would be the value shown in Table 1. At this time, the dry weight of gelatin per unit area in the emulsion layer and the emulsion protective film layer was set to 1: 1 and the evaluation sample No.
1, 4 were produced.

Similarly, using B-2 and B-4, the amount of gelatin on the backing layer side was 2.5 g / m ² , and the dry weight of gelatin was 2.5 g / m ² on the emulsion layer side without changing the coated silver amount. gelatin with the amount of the backing layer side using a sample No.15 coated at ² and B-3 and B-4 is at 2.0 g / m ^2, gelatin dry without changing the coating amount of silver in the emulsion layer side Evaluation sample No. 3 applied so that the weight was 2.0 g / m ² was prepared.

Next, curl curl was evaluated by the following method. (Rolling curl evaluation method) The obtained sample Nos. 1 to 6 are 2
Samples Nos. 1 to 6 were prepared by winding the emulsion surface inside on a core having a diameter of 7.5 cm. The other was wrapped with the emulsion side facing outward. These samples are No. 1 "~ 6"
And

Samples 1 "to 6" were wrapped in a vinyl sheet and 30
After leaving it for 3 days at ℃, it was rewound and the emulsion surface was placed inside. These 1 to 6 and 1 ″ to 6 ″ were left at 25 ° C. for 1 month, then removed from the core, and evaluated by curling the portion near the core.

(1) First, a sample is prepared which is cut into 30 cm × 30 cm in the length direction and then cut into 25.2 cm in the lateral direction.

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

(3) The curl was measured by measuring the distances from the lower surface at the four corners of the sample which was curved in an arc shape and using the average value thereof.

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

The results are shown in Table 1.

[0077]

[Table 1]

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

Example 2 The same result was obtained when the curling curl was evaluated in the same manner as in Example 1 except that the vinylidene chloride copolymer of Example 1 was replaced with 100% vinylidene chloride.

Example 3 (Preparation of Support Having Conductive Layer) Supports A and B
After corona discharge on top, a conductive layer having the following constitution was applied. Gelatin 35mg / m ² SnO ₂ / Sb (8/2) (particle size 0.3μm) 250mg / m ²

[0081]

[Chemical 15]

This was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. A sample was prepared in the same manner as in Example 1 by providing an emulsion layer, an emulsion protective film layer, a backing layer, and a backing protective film layer. The obtained sample was used to evaluate curling curl. As a result, the same effect as in Example 1 was obtained.

[0083]

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

Claims (3)

[Claims] 1. A support having at least one light-sensitive silver halide emulsion layer coated on one side thereof, and at least one non-light-sensitive hydrophilic colloid layer coated on the other side of the support. In the silver halide light-sensitive material obtained by winding the silver halide photographic light-sensitive material so that the silver halide emulsion layer is on the outside during the production, the wound silver halide photographic light-sensitive material is seasoned in a roll state, Then, the silver halide photographic light-sensitive material is characterized in that the silver halide emulsion layer is rewound so as to be placed inside and packaged. 2. The support is a plastic film on which an antistatic layer containing an ionic polymer and / or a metal oxide is laminated, and between the antistatic layer and the plastic film. 2. The silver halide photographic light-sensitive material according to claim 1, further comprising a layer containing polyvinylidene chloride. 3. The dry weight of gelatin on each of the photosensitive silver halide emulsion layer side and the non-photosensitive hydrophilic colloid layer side coated on the support is 2.5 g / m ² or less. A silver halide photographic light-sensitive material according to claim 1 or 2.