JPH023034A - Water-based thermodevelopable photosensitive composition and thermodevelopable photosensitive material - Google Patents

Abstract

PURPOSE:To make it possible to apply the title composition as a water-based composition, and to improve the manufacturing step of the composition by dispersing a photosensitive silver halide in an oil drop. CONSTITUTION:The photosensitive silver halide which is coexisted with a hydrophilic binder and a reducing agent, is dispersed in the oil drop contd. in the hydrophilic binder. The usable oil drop is preferably chemically inactive, and a high boiling point org. solvent dispersed the photosensitive silver halide is dispersed into the oil drop in the presence of a surfactant. Thus, the thermodevelopable photosensitive material obtd. has the similar photographic characteristics such as the max. optical density and the min. optical density and the tone to those obtd. at the time of using an org. solvent, even at the time of using water as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat-developable photosensitive material that can obtain a black-white-silver image by heat physical development after exposure. In particular, the present invention relates to a heat-developable photosensitive material that can be coated using water in the manufacturing process, and a heat-developable photosensitive material using this heat-developable photosensitive composition.

BACKGROUND OF THE INVENTION Silver halide photographic materials subjected to wet development processing have excellent photographic properties such as sensitivity, gradation control, and image quality, and are widely used. However, in wet development processing, it is necessary to accurately prepare the processing solution, process temperature, and process time. There are also known heat-development acute photosensitive materials that are subjected to quick dry processing using heat development without this wet development processing. This heat-developable photosensitive material is used, for example, in the basics of photographic engineering, non-silver salt photographic WN982
pp. 242-255 of Coronasha Publishing), 1976-4
It is described in Publication No. 921, Publication No. 43-4924@, etc.

This heat-developable photosensitive material is composed of a photosensitive silver halide, a reducing agent, a V1 silver salt oxidizing agent, and a hydrophobic binder, and these compositions are dissolved or dispersed in an organic solvent and coated on a support. .

Photosensitive materials produced from this composition have various problems during production, such as the effects on humans caused by organic solvents, the risk of explosion, and the contamination of the surrounding environment. Water-based heat-developable photosensitive materials that do not use a specific solvent, use a hydrophilic binder (eg, gelatin), and can be coated using water as a solvent are also known.

For example, JP-A-52-137321M, JP-A-533161
No. 1, No. 53-116144, No. 54-46709, and Japanese Patent Publication No. 62-30414. In these heat-developable photosensitive materials, a photosensitive silver halide or an organic silver salt oxidizing agent is synthesized in a hydrophilic binder.

Materials prepared in this way have complicated manufacturing processes and high S/N compared to the above-mentioned compositions (organic solvent-based).
There were drawbacks such as not being able to obtain a ratio.

[Problems to be Solved by the Invention] The present invention solves the problems associated with the production of heat-developable photosensitive materials, which have conventionally been produced using organic solvents, such as human impact and dangers such as explosions.
It also aims to solve problems such as pollution of the surrounding environment and reduce manufacturing costs.

A first object of the present invention is to provide a heat-developable photosensitive composition that can be coated in an aqueous system and to improve the manufacturing process. A second object of the present invention is to provide an inexpensive heat-developable photosensitive material. A third object of the present invention is to provide a heat-developable photosensitive material with excellent characteristics.

[: Means for Solving Problem 1] The object of the present invention is to form a photosensitive silver halide into oil droplets in a heat-developable photosensitive composition comprising at least photosensitive silver halide, a reducing agent, J3, and a hydrophilic binder. This was achieved by dispersing the

The silver halide used in the present invention can be selected from silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, and silver iodochlorobromide. Preferably, silver bromide or silver bromide
These are silver chlorobromide, silver iodobromide, and silver iodochlorobromide, which are comprised in a ratio of 5 mol% or more. In particular, when using only silver halide as an oxidizing agent for forming a silver image in physical development, silver iodobromide is preferred.

The silver halide of the present invention can be prepared by a known method. A particularly preferred method of preparation is in an organic solvent or in an organic solvent with an oil-soluble binder as a protective colloid. This preparation method is described, for example, in U.S. Patent No. 3,706,565;
No. 3,713.833 Specifications, Special Publication No. 1971-1
No. 567, No. 52-17415, JP-A-57-186
No. 745, 58-139135@, 58-2179
No. 27, No. 59-52236, and the like. A part of the organic silver salt is used as photosensitive silver halide.
It can also be used after converting it to silver 1genide, but
Particularly preferred is the photosensitive silver halide described in JP-A-57-186745 and the like, which is obtained by reacting long-chain fat 11111 with an equimolar or more amount of halogen ions.

The silver halide used in the present invention can be chemically sensitized, e.g.
Sensitization may be carried out by sulfur sensitization, reduction sensitization, noble metal sensitization, or the like. In addition, spectral sensitization can be performed using a sensitizing dye. The sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes, and preferably cyanine dyes, merocyanine dyes, complex cyanine dyes, and complex merocyanine. It is a pigment.

In the present invention, along with photosensitive silver halide, an organic gold a salt,
In particular, organic silver salt can be present to promote physical development. Examples of organic silver salts include aliphatic carboxylic acid silver salts such as silver behenate, silver stearate, and silver palmitic acid; silver aromatic carboxylic acid salts such as silver benzoate and silver 2,4-dicoO benzoate; 3-mercapto-4-phenyl-1
, 2,4-1-riazole silver, 2-mercaptobenzimidazole silver, mercaptide silver salts such as 2-mercaptobenzothiazole silver, penzotriazole silver, 5-chlorobenzotriazole silver, 1.2.4-h riazole Examples include imino silver salts such as silver and saccharin silver.

These organic silver salts may be allowed to coexist with the photosensitive silver halide in the oil droplets, or may be made to exist in the hydrophilic binder. The same or different organic silver salts may be present both in the oil droplet and in the hydrophilic binder.

lf1 photosensitive silver halide or 11 used in the present invention
The amount of photosensitive silver halide including silver salt used is 0.1 to 4.0 y/rd in terms of metal 1a. In the present invention, when a photosensitive silver halide is used in combination with a total silver salt, both compounds can be used in any mixing ratio as necessary, but preferably the photosensitive silver halide is a total silver salt. 3 mol% or more.

In the present invention, photosensitive silver halide is dispersed in oil droplets in a hydrophilic binder. The oil droplets used are preferably chemically inert, high-boiling organic solvents with a boiling point of 200° C. or higher. Specific examples include phthalic acid esters such as dibdeltthalate and didodecyl phthalate, triphenyl phosphate, tricresyl phosphate, and
Phosphorus II esters such as I-thylhexyl phosphate, 2
- Ethylhexylbenzony 1~, benzoic acid airs such as dodecyl benzoate, high boiling point alcohols such as ylstearyl alcohol, aliphatic carboxylic acid esters such as dibdeltatalate and isostearyl lactate, Examples include hydrocarbons such as baratuin and dodecylbenzene. In the present invention, in addition to the high-boiling solvent, an auxiliary organic solvent having a boiling point of about 30 to about 100°C can be used. Specific examples include dichloromethane, 1-recurne, l1ill ethyl, ethyl propionate, methyl L thyl ketone, cyclohexanone, cyclohexane, and the like. The amount of the high boiling point g1 solvent used in the oil droplets of the present invention is 0.2 to 20 g, preferably 0.5 g, per photosensitive silver halide or photosensitive halide containing organic silver salt. ~10g. If the amount is outside this range, that is, if it is less than 0.2 g, problems will occur in the dispersibility of silver halide, and if it is more than 20 g, a so-called sweating phenomenon will occur, in which high-boiling organic solvents come out of the photosensitive material.

The high-boiling organic solvent in which the photosensitive silver halide of the present invention is dispersed is dispersed in the above-mentioned hydrophilic colloid in the presence of a surfactant. As a dispersion method, for example, US patent 2
．． Examples include methods described in specifications such as No. 739.888 and No. 3,352.681. Specifically, the photosensitive silver halide is dispersed in a high boiling organic solvent, such as tricresyl phosphate, and a co-solvent, such as vinegar MJ til, along with other additives if necessary. Thereafter, it can be prepared by mixing it into an aqueous solution of a hydrophilic colloid containing a surfactant, such as gelatin, and emulsifying it with a mixer, colloid mill, etc.

When the reducing agent used in the present invention is heated, it reduces silver ions using the image nuclei of silver halide as a catalyst, and itself is oxidized to participate in silver image formation. In the present invention, various known compounds can be used as reducing agents. Specific examples include IJ21fgla used in ordinary silver halide photosensitive materials, such as hydroquinone, methylhydro[]quinone, chlorohydroquinone, methylhydroxynaphthalene, N,N--diethyl-Pfurylene diamine, and aminophenol. , ascorbic acid, 1
~Phenyl-3-pyrazolidone etc. can be mentioned,
In addition to these, 2.2-1methylenebis(6-t-butyl-4-methylphenol), 4.4-butylidenebis(6-t-butyl-3-methylphenol), 4.
4'-diobis(6-t-butyl-3-methylphenol) and other bisnaphthol reducing compounds described in JP-A-46-6074, Belgian Patent No. 802
Examples include sulfone-7 midophenol compounds such as 4-benzenesulfonamidophenol described in No. 519.

In addition, in order to create a dye image, JP-A-59-48764@
Compounds described in publications and the like that have a reducing property against silver halide and release a hydrophilic dye can be used. U.S. Patent No. 3,531,286, U.S. Patent No. 3,7
Dye images can be created by combining various phenol developers and couplers described in Belgian Patent No. 61.270, Belgian Patent No. 4.021,240, Belgian Patent No. 802.519, and the like. Hydrophilic leuco color charts described in U.S. Pat. Nos. 3,985,565 and 4,022,617 can be used.

As for the method of adding the reducing agent used in the present invention, it can be made to coexist in the oil droplet together with the photosensitive silver halide. Further, it can be dissolved in a hydrophilic binder or dissolved in oil droplets separate from the photosensitive silver halide and dispersed, or it can be dissolved in the binder and oil droplets simultaneously.

A preferred method of addition is to coexist in oil droplets together with photosensitive silver halide. The amount of the reducing agent used is about 0.05 to about 5 mol per ml of gold silver of photosensitive silver halide or photosensitive silver halide and Ill salt,
Preferably it is about 0.2 to about 2 moles.

The hydrophilic binder used in the present invention is a transparent or semi-transparent hydrophilic colloid, and specific examples include gelatin, gelatin derivatives, carboxymethylcellulose, hirulose derivatives such as methylcellulose, polysaccharides such as Denkuron and gum arabic, Synthetic water-soluble polymers such as polyvinyl alcohol, polyvinylbiolidone, and acrylamide polymers can be mentioned. Two or more of these hydrophilic binders can be used in combination. To further increase dimensional stability, latex-type dispersed vinyl compounds can be added. The amount of hydrophilic binder used may be any amount that protects the oil droplets and does not impair heat resistance during thermal development.

At least 0 for 1111 parts by weight of high boiling point 4'i solute
0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Amounts outside this range, i.e. less than 0.01 parts by weight, will cause problems with oil droplet dispersion and protection; If the amount exceeds 1 part, preferable heat developability cannot be obtained.

The hydrophilic binder used in the present invention can be crosslinked and hardened, if necessary, to improve water resistance and heat resistance. As the compound (liIIIll agent) for this purpose, known compounds can be used.

For example, inorganic hardening agents such as chrome alum and aluminum alum, aldehyde type hardening agents such as formaldehyde and glyogysar, N-methylol that releases aldehyde,
Acetal-type hardeners, epoxy-type hardeners, aziridine-type hardeners, mucohalogen acid-type active halogen-type hardeners, dichloro-os-triazine-type hardeners, activated olefin-type hardeners, Carbodiimide type hardeners, isoxazolium type hardeners, methanesulfonic acid ester type hardeners, active ester faecal hardeners, etc. can be used.

In the present invention, toning agents can be used.

For example, phthalazine and its derivatives described in U.S. Pat.
Cyclic imides described in JP-A-50-329
Examples include phthalazinedione compounds described in Publication No. 27.

In the present invention, a known antifoggant can be used to prevent thermal fog during development. For example, mercury compounds described in Japanese Patent Publication No. 47-11113@, Japanese Patent Publication No. 49-10724, Japanese Patent Publication No. 54-25808,
N-henogeno compounds described in each publication of No. 54-2J813, stearic acid, behenic acid, etc. described in U.S. Pat. Acid stabilizers such as 8th class fatty acids, salicylic acid, tetrabrobenzoic acid, and trimellit M can be mentioned.

In the present invention, a base or a base precursor can be used to promote the redox reaction. For example, U.S. Pat.
Amino acid compounds described in No. 1 Specification 2, salts consisting of carboxylic acids and bases described in each specification such as British Patent No. 998.949 and U.S. Patent No. 3.220.846,
Was it described in Mochima No. 50-22625? Redon 7
You can give meads.

According to the present invention, as a thermal solvent, for example, US Pat.
No. 3,347.675 Specification 1: Polyglycols and derivatives thereof, U.S. Pat. No. 3,677.95
Polar substances such as lactone of 4-hydroxybutanoic acid and methylsulnoinylmethane described in No. 9 Akira Ill, 1,1
It is possible to use 0-decanediol, bifinyl perate, etc.

In the present invention, compounds can be used to prevent photodiscoloration after image formation. For example, 3.8 for US patent
39.04 January 7-zole thione ethers, blocked azole 1,4-enes, described in Specification 1, U.S. Pat. 3. Halogen-containing organic oxidizing agent described in 707,377@Seikagata, U.S. Patent 3.
Examples include 1-carb7yl-2-tetrazolin-51ones described in the September specification of 893.859.

In the present invention, other additives such as a development accelerator, anti-oxidation agent (layer), ultraviolet absorber, fluorescent whitening agent, Noirter dye (layer), etc. can be used.

In this defense, the above-mentioned photosensitive silver halide, reducing agent, hydrophilic binder and, if necessary, 1. A heat-developable photosensitive material can be prepared by coating a heat-developable photosensitive composition containing the following additives on a support in one layer or in multiple layers. Furthermore, an overcoating polymer layer can be provided on the heat-developable photosensitive layer formed of 111 layers or multiple layers. Examples of polymers used in the polymer layer include polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, chlorinated rubber, ethyl cellulose, cellulose acetate butyrate, cellulose acetate, polyvinyl perchloride, polyvinylidene chloride, polycarbonate, and polyvinylpyrroli. oil-soluble binders such as
Or polyvinyl alcohol, gelatin, methylcellulose, polyvinylpyrrolidone, acrylamide polymer,
Examples include water-soluble polymers such as starch, dispersed emulsified vinyl polymers, and the like. Alternatively, the above polymer may be provided as an undercoat layer on a support, and a heat-developable photosensitive layer may be provided thereon.

The support used in the present invention can be selected from a wide variety of supports. For example, synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, cellulose acetate, synthetic paper, paper coated with resin films such as polyethylene, papers such as ato paper, photographic baryta paper, metal plates such as aluminum, etc. (foil), metal vaporizer, synthetic resin film with curvature, crow temporary, etc.

K (5 methods include roll coating method, air knife method,
A kiss coat method, a curtain coat method, a barcode method, a hopper coat method, etc. can be used.

The heat-developable photosensitive material obtained by applying the heat-developable photosensitive composition of the present invention is exposed to light from a light source such as a xenon lamp, a mercury lamp, a tungsten lamp, a CRT, or a laser beam.
It is then heated at a temperature of 60 to 180°C, preferably 80 to 150°C. The current 11g 1 hour is preferably about 1 to 60 seconds. The most common method for heat development is to bring the material into contact with a heated plate +- or a heated drum, but it is also possible to temporarily hold it in a heated atmosphere, or heat it with frequency heating or infrared light. You can.

[ff Effect of brightness J According to this defense, even when water is used as a solvent, a heat-developable photosensitive material can be obtained which has the same photographic properties as when using a specific solvent, that is, maximum density, minimum 111 f, and color tone. I can do it.

[Example J Example 1 Preparation of silver iodobromide Silver behenate 279 was dispersed in ethyl alcohol 600d, and polyvinyl butyral 169 was further dissolved to prepare a polymer dispersion of silver salt. While stirring this dispersion while maintaining it at 70°C, 10.8% of N-butylsuccinimide was dissolved in 120% of acetone. ? and 0.72 g of N-iodosuccinimide were added dropwise over 30 minutes. Then 40℃
The mixture was poured into 6 IJ of stirring water to precipitate polyvinyl butyral containing silver iodobromide. The precipitate was filtered and dried to obtain a solid substance 459 of polyvinyl butyral containing 3 silver iodobromide.

The grain size of this silver iodobromide was 0.08 to 0.10 μm.

Preparation and testing of photosensitive materials Solid material of polyvinyl butyral containing the above-mentioned silver iodobromide 5.
0g, tricresyl phosphate 7°0! Silver iodobromide was redispersed in J J3 and ethyl acetate 50° C. while maintaining it at 50° C., and then 2.0 g of the following reducing agent and 5η of the sensitizing dye F were dissolved.

Aqueous solution 1009 containing 3.0 g of reduced 1'11 if1 dye-sensitive gelatin and 1.0 g of sodium dodecylbenzenesulfonate as a surfactant and the above ethyl acetate solution were mixed and emulsified using an ultrasonic disperser. Ethyl acetate was removed from this dispersion under reduced pressure,
300 mg of the following base precursor was added and coated on a polyester film at a silver amount of 0.6 g/m.

A 10 second exposure to 700 lux tungsten light was applied through a base precursor grayscale wedge (Kodak Step Tablet No. 2) and heat developed for 5 seconds on a 90° C. heat block. The above operations were performed under red safety light (Examples 2 to 4 were similarly performed under red safety light). O
A dark brown image with wax of 1.0 and Qsin of 0.08 was obtained.

Comparative Example 1 A heat-developable photosensitive material was prepared according to Example 4 of JP-A-53-31611. This comparative example is an example in which photosensitive silver halide is incorporated into gelatin.

Inert gelatin 249 was dissolved in 800 Id of water at 50°C. Next, 41 g of Behen M was added and melted by heating at 85°C. Next, an aqueous solution in which 4 g of sodium hydroxide was dissolved in 100 °C of water was added, and the mixture was cooled to 30°C to prepare a dispersion containing sodium behenate and behenic acid. An aqueous solution of 17 g of silver nitrate dissolved in 100 m of water was added to this solution to prepare a silver behenate dispersion containing behenic acid and zeratin. To this dispersion was added a silver bromide emulsion (particle size: 0.09 to 0.12 μm, Φ ratio of silver bromide to gelatin -2 = 3) prepared separately using gelatin as a binder at a weight ratio of 10:1. Mix and place on a polyester film in a silver amount of 0.6g/
It was covered with heavy cloth to act as a buttocks. Roughly, the following composition was coated on this coated surface so that the amount of reducing agent was 1 g/Td.

Sodium benzenesulfinate (0,1% methanol solution) 4mm Phthalazine 44]
Weight% methyl hydroxide “1 sorb solution”
5゜Hydroquinone (25i11ffi% acetone solution) d Polyvinyl butyral (8 overhang% acetone solution 1&)
100d more reducing agent! The photosensitive material obtained with the coloring dye was exposed to light in the same manner as in Example 1.
Heat development was performed at 30° C. for 5 seconds. Obtained tm images t, t,
[) wax was 0.5 and [) sin was 0.2.

Example 2 Polyvinyl butyral solid containing silver iodobromide obtained in Example 1 2.59. Xylene diphenyl phosphate 5
．． 0 g and 50 d of ethyl acetate were kept at 50°C to redisperse silver iodobromide, and then 2.0 g of the reducing agent below and sensitizing dye 3 below were added.
η was dissolved.

100 g of an aqueous solution containing 3.0 g of 9H19 H3 U Latin, 07 g of benzotriazole, and the following surfactants i and og, and the above ethyl acetate solution were mixed and emulsified using an ultra-A wave disperser.

Surfactant Ethyl acetate was removed from this dispersion under reduced pressure, and 300 µm of the base precursor used in Example 1 was added to polyester film 1! No, it was applied at 8 g/ba. It was exposed to light in the same manner as in Example 1, and thermally developed for 10 seconds on a heat block at 100°C.

A dark brown image with [)wax of 1.2 and [)akin of 0.10 was obtained.

Example 3 Preparation of Silver Bromide Silver Stearate 24.5! A polymer dispersion of silver salt was prepared by dispersing J in 600 d of isopropyl alcohol and dissolving 16 g of polyvinyl butylar. This dispersion, 5
Stirring product kept at 0 °C, N- dissolved in 120 d of acetone
A solution of 11.3!7 bromosuccinimide and 0.01 g of lithium bromide was added dropwise over 60 minutes. Then f to 40°C
The mixture was poured into 6 g of stirring water to precipitate polyvinyl butyral containing silver bromide. The precipitate was filtered and dried to obtain a solid substance of polyvinyl butyral containing silver bromide 459
It's 11. The particle size of this silver bromide is 0.06 to 0.07μ
It was m.

Preparation and testing of photosensitive materials F. Polyvinyl butyral solid containing silver bromide 0.7
! J, Behen IIII silver 4.0 g, behenic acid 1.5 g,
Tricresyl bosphate 7.0g vinegar/ethyl acid 50a
Silver bromide and silver behenate were redispersed using a ball mill. Next is F-Reducing Agent 3.0! J. 1.0 g of phthalazone as a color toning agent and 11 Rg of the sensitizing dye of Example 1 were dissolved.

A reducing agent, 3.0 g of gelatin, 1.09 sodium dodecylbenzenesulfonate as a surfactant, and 6 hardening agents listed in F.
Aqueous solution 1007 containing 0η was added, and the volume was made up to 1 L using a 1B sonic disperser.

Hardener Ethyl acetate was removed from this dispersion under reduced pressure, and the amount of silver was 0.5 g/T! t''c coating. Exposure and heat development were carried out in the same manner as in Example 1.

A black image with D tmax of 1.3 and Q sin of 0.14 was obtained.

Example 4 A heat-developable photosensitive material was prepared in the same manner as in Example 3, except that 1.2 g of phenol was used as the reducing agent, and exposed and thermally developed in the same manner as in Example 1.

A black image with DIiax of 1.2 and t)lin of 0.12 was obtained.

Claims (2)

[Claims] (1) A heat-developable photosensitive composition comprising at least a photosensitive silver halide, a reducing agent, and a hydrophilic binder, characterized in that the photosensitive silver halide is dispersed in oil droplets. Composition. (2) In a heat-developable photosensitive material having a heat-developable photosensitive layer comprising at least a photosensitive silver halide, a reducing agent, and a hydrophilic binder on a support, the silver halide in the heat-developable photosensitive layer forms oil droplets. A heat-developable photosensitive material characterized in that: