JPS5824774B2 - Dry imaging material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION In the present invention, before an image is recorded, it is preheated to become a photosensitive state (hereinafter referred to as activation), exposed to light in this state, and then heated. This relates to a dry image forming material that can form a visible image by being developed (hereinafter referred to as a post-activated dry image forming material). The present invention relates to a post-activated dry image forming material which has increased spectral sensitivity without impairing the characteristics that it is capable of producing, and which has excellent image quality.

The feature of being able to handle and preserve materials before use in a bright room is to photograph information on a desired part of the material to form an image, and then apply the material to a duplicator such as a duplicator, copier, or printer. This means that after creating a copy, additional visible images can be recorded by photographing and developing new information in the unused blank space.

Although the present invention is spectrally sensitized and has high sensitivity enough to photograph colored originals and colored objects, it has stability before use (raw stability) to the extent that additional recording is practical. and the image quality is excellent.

Conventionally, as a silver salt image forming material that can obtain a visible image only by dry processing, a material consisting of an organic silver salt oxidizing agent, a reducing agent for silver ions, and silver halide as a catalyst component has been used, for example, in Japanese Patent Publication No. 43-4924. proposed in No.

In addition, a post-activation type dry image forming material was published in Japanese Patent Application Laid-Open No. 48-5
1626, Special Publication No. 53-2687, Special Publication No. 53-4
No. 1967 and Japanese Patent Publication No. 54-5685, these specifications indicate that a spectral sensitizing dye is added.

However, in the materials proposed so far,
When the material is placed under light irradiation or exposed to high temperatures even in the dark, the photographic properties deteriorate significantly, so-called poor biostability, or low sensitivity makes it difficult to take photographs. had the disadvantage of insufficient sensitivity.

In other words, with conventional post-activated dry imaging materials, improving the biostability lowers the sensitivity, and conversely increasing the sensitivity deteriorates the biostability. Currently, there is no active dry imaging material.

This phenomenon consists essentially of an organic silver salt oxidizing agent and /'% silver halide as a reducing agent and catalytic component for the silver salt, and is a dry image that can be obtained by thermal development alone. Because the image forming mechanism and composition of the forming material are different from those of silver halide photographic materials that are developed by wet processing to produce visible images, knowledge and techniques related to wet silver halide photographic materials, such as knowledge about additives, can be applied to dry images. This shows that the problem cannot be solved only by applying it to the forming material.

In particular, post-activated dry imaging materials are similar to wet silver halide photographic materials and regular dry imaging materials in which the material before use is not exposed to light, since the material before use is exposed to the presence of light. It is completely unpredictable whether suitable additives can be applied to post-activated dry imaging materials.

That is, wet silver halide photographic materials and conventional heat-developable dry imaging materials are commonly used in these materials because they are not exposed to light or heated before use. Spectral sensitizing dyes do not necessarily need to be stable against light irradiation during storage or heating before use; in fact, many dyes themselves are used that are unstable against these steps.

Therefore, simply applying the sensitization techniques applied to wet-type silver halide photographic materials and conventional dry-type imaging materials to post-activated dry-type image-forming materials will degrade the biostability.
Generally, these conventional techniques cannot simply be applied to post-activated dry imaging materials.

For example, Special Publication No. 49-25498, USP39335
In No. 07, even in a system consisting of an organic silver salt oxidizing agent and a reducing agent that does not contain photosensitive silver halide, photosensitivity is imparted for the first time by incorporating a spectral sensitizing dye, making it possible to form ordinary dry images. It is stated that it can be used as a material.

As can be seen from this example, adding a spectral sensitizing dye acts in the direction of imparting photosensitivity as long as the dye is not destroyed. Simply applying these spectral sensitizing dyes to post-activated dry imaging materials, which are required to have no deterioration of photographic properties and no fogging even when heated, will not promote fogging. , resulting in a marked deterioration of biostability.

As in these examples, the spectral sensitizing dyes commonly used in wet silver halide photographic materials and conventional heat-developable dry imaging materials are simply applied to post-activated dry imaging material systems. This means that the biostability of the post-activated dry image forming material may be deteriorated by causing fog during the preheating stage before exposure, or by increasing the fog during development heating, or by spectral sensitization. Either the dye itself is destroyed or bleached in the system and cannot exhibit its spectral sensitizing ability from the beginning, or it rapidly loses its spectral sensitizing ability during storage of the raw film, and the spectral sensitizing ability is lost when the post-activated imaging material is used. Sensitization was usually not feasible.

Furthermore, spectrally sensitized imaging materials are generally more affected by halation and irradiation than non-spectrally sensitized imaging materials.

Therefore, in order to obtain high resolution and excellent image quality with spectrally sensitized image forming materials, anti-halation and anti-irradiation treatments are usually applied.

However, as mentioned above, post-activated dry image forming materials are exposed to more severe conditions in terms of biostability than wet silver halide photographic materials or ordinary dry image forming materials. It has been difficult to apply processing methods suitable for photographic materials and conventional dry imaging materials.

In addition, 2-(2'-hydroxyphenyl)benzotriazoles are disclosed in USP3004896 and USP3189.
As described in Japanese Patent Publication No. 615, it is known to act as an ultraviolet absorber and used as a photodegradation inhibitor for polymers, and as described in Japanese Patent Publication No. 44-29620, wet halogenation for color photography is known. Used when exposing silver photographic materials to prevent undesirable exposure to ultraviolet rays, which would make the blue color too strong and disrupt the color balance, and used as a filter layer on the photosensitive layer to prevent fading and discoloration of color photographic images. This is a substance known to be effective.

However, certain 2-(2'-hydroxyphenyl)benzotriazoles, which are ultraviolet absorbers that do not absorb light at wavelengths above 450 nm, are
It prevents deterioration of image quality due to the effects of halation and irradiation, which occur due to an increase in spectral sensitivity toward longer wavelengths of 50 nm or more, and can be used in dark places or at 450 nm.
It was not even expected that it would have an effective effect on storage stability under light irradiation of m or more.

An object of the present invention is to provide a spectrally sensitized post-activated dry image forming material which is excellent in both sensitivity and biostability and is usable for practical use.

Another object of the present invention is to provide a post-activated dry image forming material that is spectrally sensitized and has excellent image quality.

As a result of intensive research to achieve the above object, the present inventors have found that, unlike wet silver halide photographic materials and ordinary dry image forming materials, they contain an appropriate oxidizing agent to form a strong oxidizing atmosphere. , and found a cyanine dye having a specific structure and a 2-(2'-hydroxyphenyl)benzotriazole having a specific structure, and by using them together, an epoch-making effect was obtained, and the present invention I came to the conclusion.

That is, the present invention provides (a) a silver salt of a long chain fatty acid having 16 or more carbon atoms, (b) a reducing agent for the silver salt, and (C) a silver halide containing silver iodide or the silver halide. (d) a free silver layer oxidizing agent, (e) a photoreactive halogen oxidizing agent, (f) a toning agent, and (b) a binder; and (h) the following compound (1). , (■) and (i) the following compounds (nD, (IV), (V
), (Vl) and (7) is contained in the same layer as component (a).

(In the formula, R is hydrogen, C1-C3 alkyl, C1-C4
Alkoxy, phenyl, and halogen are listed.

) (wherein, X is H, CHa, Cl, C6H5, O
CH3 or CH3C0NH, Y is H2C river or C
2H5, Z and Z' are Se, S or O, W and W are Se or S, A is C2-C4 alkylene, M is H7HN(C2H5)3. HN3) or Na
k respectively.

) The silver salt of a long-chain fatty acid having 16 or more carbon atoms as component (a) used in the post-activated dry image forming material of the present invention includes:
Examples include silver palmitate, silver margarate, silver stearate, silver araxinate, silver behenate, silver cerotate, silver melisinate, and the like.

Among these, silver behenate is particularly useful.

The amount of these long-chain fatty acid silver used on the support is about 0.1~
509/lri'', and a particularly preferred amount is l-101
It is 1/m'.

Component (b), the reducing agent used in the dry imaging material of the present invention, is a reducing agent which, after activation and exposure, is catalyzed by the free silver generated from the silver halide in the exposed area, and when further heated, it becomes non-reducing. By reducing the photosensitive organic silver salt oxidizing agent,
An organic reducing agent with suitable reducing power to form a silver image is used.

Suitable reducing agents include various monohydroxybenzenes, polyhydroxybenzenes, naphthols, hydroxybinaphthyls, methylenebisphenols, phenylenediamines, aminophenols, sulfonamidophenols, β-pyrazolidones, and ascorbic acids. can be mentioned.

The reducing agent preferably used is selected depending on component (a), and phenols are preferred.

Among these, particularly preferred are inhibited phenols having a structure in which a sterically high group is bonded to the carbon adjacent to the carbon to which the hydroxyl group is bonded, thereby sterically inhibiting the hydroxyl group.

stomach.

Inhibiting phenols are particularly preferred for post-activated dry imaging materials because of their high photostability.

Such inhibitory phenols include, for example, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol).

methylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,6-methylenebis(2-bitroxy-3-t-butyl-5-methylphenyl)-4-methylphenol, 2 .4,4-)limethylpentylbis(2-human.

Roxy3,5-dimethylphenyl)methane, 2゜2'
-methylenebis[4-methyl-6-(1-methylcyclohexyl)phenol] and 2,5-di-tert-butyl-4-methoxyphenol may be mentioned.

The appropriate amount of the reducing agent to be used is usually 0.1 to 3 mol per 1 mol of component (a).

The silver halide referred to as component (c) suitable for the present invention must contain silver iodide, but in order to fully exhibit the properties of silver iodide, the silver halide must contain at least 30 molar proportion of the silver halide. is preferably silver iodide.

Furthermore, it is more preferable that 50 or more moles of silver halide be silver iodide.

Silver iodide may be used as 100 mol% of silver halide, but from the viewpoint of sensitivity, silver bromide or silver chloride other than silver iodide is contained in silver halide at a ratio of 2 or more moles. is preferred.

On the other hand, from the viewpoint of biostability, it is preferable that silver bromide is contained rather than silver chloride.

Therefore, the most preferred silver halide 1 for the present invention
consists of silver iodide and silver bromide.

In that case, the silver halide may be a mixture of silver iodide and silver bromide, or may be a mixed crystal.

The molar composition ratio of silver iodide and silver bromide is 30 silver iodide/silver bromide.
/70 to 98/2 is preferable, and 50150 to 951
The range of 5 is more preferable.

A suitable amount of silver halide is 0% relative to the organic silver salt oxidizing agent.
．． 1 to 20 mol % is preferable. Silver halide can be added to the dry image forming material of the present invention by the following method.

The first method, as described in US Pat. No. 3,152,904, is a method in which silver halide is prepared in advance and mixed with a separately prepared silver salt of a long-chain fatty acid.

The silver halide used in this method may be made by methods known in the photographic field.

The second method involves reacting a pre-prepared silver salt of a long chain fatty acid with an appropriate halogenating agent as described in U.S. Pat. This is a method of converting silver halide into silver halide.

The silver halide is preferably formed by reacting an organic silver salt oxidizing agent with a suitable halogenating agent.

Examples of the halogenating agent suitable for the present invention include an organic halide compound of an element of Group I, Group II or Group II of the periodic table with an atomic number of 14 or more, a halogen molecule, a complex with a halogen molecule, -
〇〇NX-(Tazoshi, X is Cl.

Br or ■.

N-halogenamides, arylhalomethanes or metal halides containing units of ) may be mentioned.

Among these, from the viewpoint of biostability, halogen molecules, complexes with halogen molecules, and N-halogenamides are preferred.

complex of triphenylphosphite and iodine, p-
Complex of dioxane and bromine, N-halogenophthalimide,
N-halogenoacetamide, N~halogenophthalazinone, N-halogenoacetamide, N-halogenoacetamide, α-halogenodiphenylmethane, CoX2, N
tX29MgX2 tBaX2. RbX, C5X,
TeX2. TeX4. AsX3 and the like (wherein X is C11, Br or Engineering).

From the viewpoint of biostability and sensitivity, the halogenating agent for forming silver iodide is particularly preferably iodine or N-iodosuccinimide.

Furthermore, an iodine complex is also preferably used as an iodine source.

Examples include a complex of triphenylphosphite and iodine, or a complex of p-dioxane and iodine.

N-iodosuccinimide is preferably prepared in advance in an alcoholic (methanol, ethanol, etc.) solution and added to the emulsion for the imaging material.

Also, from the viewpoint of biostability and sensitivity, bromination. As the halogenating agent for forming silver, N-promosuccinimide, cobalt dibromide or nickel dibromide is particularly preferred.

The amount of halogenating agent used may be equivalent to or greater than the desired amount of silver halide.

- Component (d) of the present invention has the effect of oxidizing free silver and contributes to improving biostability.

Examples of component (d) include divalent mercury ion compounds, trivalent iron ion compounds, trivalent cobalt ion compounds, divalent palladium ion compounds, and sulfinic acid compounds.

Examples of compounds that provide divalent mercury ions include mercuric aliphatic carboxylates such as mercuric acetate and mercuric behenate, mercuric benzoate, mercuric m-methylbenzoate, and mercuric acetamidobenzoate. Examples include mercuric aromatic carboxylic acids, mercuric halides such as mercury bromide, mercury iodide, mercuric benzotriazole, mercury phthalazinone, and the like.

Particularly preferred compounds are mercuric acetate, mercury bromide, and mercury iodide.

Examples of the trivalent iron ion compound include acetylacetone complex salts, bipyridyl complex salts, and the like.

Examples of the trivalent cobalt ion compound include complex salts of acetylacetone and complex salts of 0-phenanthroline.

Examples of the divalent baladium ion compound include complex salts of acetylacetone.

Examples of the sulfinic acid compound include n-octylsulfinic acid and p-toluenesulfinic acid.

Particularly preferred is a divalent mercury ion compound as component (d).

The preferred amount of component (a) used is 0.01 to 10 molar relative to the organic silver salt oxidizing agent.

Component (e), the photoreactive oxidizing agent, is component (a).
By oxidizing the free silver produced during raw film storage, it becomes a reduced state itself, but it can be returned to its pre-reduced state under light irradiation.

Suitable photoreactive halogen oxidizing agents for the present invention as component (e) are halogen compounds capable of generating halogen free radicals upon irradiation with light.

Preferred such halogen compounds are halogenated compounds in which a carbon atom and a bromine atom or an iodine atom are bonded.

The following method is suitable for determining whether a selected halogen compound is suitable for the present invention.

1 mole of silver behenate (which is at least 1 mole having 3 to 8 carbon atoms)
It is suitable that the compound is synthesized in a solvent in which an alcohol that is soluble or partially soluble in the seed water is mixed with water at a ratio of 1:5 to 5:1.

), 1 mol of polyvinyl butyral, and 0.25 mol of a photoreactive oxidizing agent in a mixture of methyl ethyl ketone and toluene:
A layer formed in the form of a film is prepared by a conventional casting method using a mixed solvent of 1 ml.

A film using this film that satisfies the following two criteria is suitable for the present invention.

Criterion 1: Examining the X-ray diffraction of this film, 2θ=12.10° peak intensity of silver behenate is 100.
31. Oo silver bromide peak or 2θ-23,7°
No silver iodide peak is observed (peak intensity approximately less than 10).

Standard 2: Next, this film was exposed to light from a black lamp (0.5 mW/cII) under conditions of 50°G and 80% RH.
After irradiation with L) for 1 hour, the X-ray diffraction was again examined, and the peak intensity at 2θ = 12.1° of silver behenate was 100°, whereas that of silver bromide was 2θ = 31°. Oo peak or 2θ=2
A silver iodide peak at 3.7° is observed (peak intensity is approximately 10 or more).

However, the value of 2θ is the diffraction peak value due to CuKα.

Specifically, the following compounds can be mentioned as compounds of component (1) that can be preferably used in the present invention.

1,1,1,1-0-1-tetrabromo-0-xylene, 1,1,1.1-tetrabromo-m-xylene, 1. l, l-tribromoacetic acid, l.

1.1-tribromobenzophenone, 1,1.1-tribromo-p-bromotoluene, 1,1.1-dribromo-2,2-diphenylethane, tetrabromomethane, 2
,2.2-tribromoethano-#,2,2,2-tribromoethylcyclohexylcarbamate,2,2,
2-Tribromoethylphenylcarbamate, 2,2,
2-Tribromoethylbenzoate, 2,2,2-tribromoethylcarbamate, 2-methyl-1,1,1-
Tribromo-2-propertool, bis(2,2゜2-trifluoromethoxy)diphenylmethane, 2゜2.2-t
-ribromoethyl stearate 1.2,2゜2-tribromoethyl-2-furoate, bis(2,2,2-tribromoethyl)succinate, 2t2>2-tribromoethyl phenyl sulfonate, 2,2. 2-) Ribromoethoxytrimethylsilane, 2,2,2-tribromo-1-phenylethanol, 2,2,2-tribromoethyldiphenylphosphate, 1,2-short ethane, iodoform, and the like.

Bromine compounds are preferable because they improve the quality of raw wheat and cause less coloring of the material.

Especially 1,1,1,1-atrabromo〇-xylene, 1
, 1,1.1-7trabromo-m-xylene, 1,1.
1-Tribromoethyl acetate, l,l,1-tripro-p-bromotoluene, 1,1,1-tribromoacetophenone, 1,1.1-tribromo-2,2-diphenylethane, 2,2,2 -tribromoethanol, men-
1,2,3,4-tetrabromomethane is a preferred compound.

More preferably l. i, t/, t/-tetrabromo-〇-(or m)xylene.

The preferred amount of component (e) used is 2.5 to 40 moles relative to component (a).

The toning agent (f) is used to develop a black image, and those known in the art can be used.

For example, phthalazinone and phthalic anhydride described in USP 3080254, 2-pyrazolone-5-ones described in USP 3846136, cyclic imides such as phthalimide, N-hydroxy; and mercapto compounds described in JP-A-49-5020;
Alternatively, oxazinediones described in JP-A-49-91215, phthalic acid as described in USP 3847612, or a combination of phthalamic acid and imidazole, or phthalazine and aromatic acid as described in JP-A-52-33722, or Examples include acid anhydrides.

Suitable amounts used range from 1 to 100 moles relative to component (a).

Examples of the binder for component (b) include polyvinyl butyral, polyvinyl formal, polymethyl methacrylate, polystyrene or copolymers thereof, cellulose acetate, polyvinyl acetate, cellulose acetate propionate, cellulose acetate butyrate, acrylic resins and polystyrene. Examples include organophilic film-forming polymer compounds that are soluble in organic solvents, such as those containing blended or copolymerized acrylic acid ester resins.

In particular, polyvinyl butyral is preferred as the binder for forming the layer contained in component (a)'.

Two or more of these can be used as a mixture.

These amounts are approximately 10:1 by weight relative to component (2).
~1:2 is appropriate.

Component (h) is a characteristic component of the present invention, and is an element that greatly improves the raw quality of the dry image forming material, and is expressed by the following formula (I
), (If).

(Tazoshi, R is H, C1-C8 alkyl, C1-C4
represents alkoxy, phenyl or halogen.

) If R is alkyl of C8 or more or alkoxy of C6 or more, the solubility is poor and the effect is lowered, so it is not preferable.

Specific examples of component <h) include, but are not limited to, those shown below.

The appropriate amount of component (h) to be used is 1 x 10-2 to 6 x 1 O-1 per mole of silver salt oxidizing agent of component (a).
mole, and a particularly preferable range is 3 x 10-2 to 3
X 10-1 mol.

In addition, component (f) needs to be contained in the same layer as component (a) in order to interact with the silver salt oxidizing agent.

The spectral sensitizing dye of component (i) suitable for the present invention has the general formula (
2) A compound represented by (g) or (b) on two sides.

The amount of the compound (i) to be used is preferably 0.001 to 1 mole per 1 of component (a).

(In the formula, X is H, CH3, CA!, C6H5, OC
H3 or CH3C0NH, Y is H, CH3 or C
2H5, Z and Z' are Se, S or 0, W and W are Se or S, A is C2 to C4 alkylene, M is H, HN(C2H5)s, HN) or N
a respectively.

) Specific examples of component (i) include the following compounds.

In addition to the above-mentioned components, a sensitizer can be used if necessary.

Of the 5 substances that increase sensitivity, those that significantly impair the quality of raw wheat are not preferred for the present invention.

Examples of compounds that are preferably used in the present invention and substantially increase the sensitivity include amide compounds such as 1-methyl-2-pyrrolidone described in JP-A-51-7914, or JP-A-54-156525. The general formula described in No. 1 (where R1+ R2, R3t R4, R5t R6 is hydrogen, phenyl or naphthyl unsubstituted or substituted with methyl, methoxy or halogen, straight chain or branched alkyl of 01 to CIO, C1 ~C4 alkoxy, unsubstituted or substituted with methyl, methoxy or halogen, benzyl or phenethyl, hydroxy, cyano, carboxy, C2-C5 alkoxycarbonyl,
It represents nitro, amino or carbamoyl, and X represents hydrogen, hydroxy or amine.

) or JP-A-55-320
No. 15, the following general formula (wherein R1 is hydrogen, C1 to C5 straight chain or branched alkyl, unsubstituted or substituted phenyl, or unsubstituted or substituted C3 to C3 cycloalkyl, R2 is C1 ~C
5 straight-chain or branched alkyl, unsubstituted or substituted phenyl, or unsubstituted or substituted C2-C8 cycloalkyl, R3, R4 are hydrogen, C1-C6 straight-chain or branched alkyl, unsubstituted or Substituted phenyl, or C1
~C5 straight-chain or branched alkyl, unsubstituted or substituted phenylalkyl.

) 3-pyrazolin-5-ones can be mentioned.

Specific examples include 2-phenyl-3-pyrazolin-5-one, 1-(p-iodophenyl)-2,3-dimethyl-
3-Birapurin-5-one, 2) 3 p 4 F
diphenyl-3-pyrazolin-5-one, ■-phenyl-2,3-dimethyl-3-pyrazolin-5-one, 1
．． 3-diethyl-2-phenyl-3-pyrazoline-5-
one, 2,3-dimethyl-1-ethyl-4-isopropyl-3-pyrazolin-5-one, 2o-1lyl)-3-
Methyl-4-ethyl-3-viraprin-5-one, 2-
Cyclohexyl-3-pyrazolin-5-one, 2-methyl-1,3-diphenyl-3-pyrazolin-5-one,
Examples include l-cyclohexyl-2,3-dimethyl-3-pyrazolin-5-one.

The appropriate amount of these to be used is 5 to 50 moles relative to component (a).

The dry image forming material of the present invention is produced, for example, as follows.

Component (a), a silver salt of a long-chain fatty acid, is dispersed into the binder-forming polymer stream of component (f) by means of a ball mill, homogenizer, mixer, sand mill, or the like.

Necessary ingredients are added to this to prepare a photosensitive material composition.

This is applied onto a support such as a plastic film, paper, glass layer, metal layer, etc., and dried.

Examples of plastic films include polyethylene terephthalate film, cellulose acetate film, polyamide film, polyethylene film, and polypropylene film.

The dry thickness of the applied image forming layer is in the range of 1 to 100 microns, with a more preferred range of 3 to 20 microns.

The components of the image forming composition may be contained in one layer, or may be contained in two or more layers.

Furthermore, a top coat layer may be provided thereon.

When producing a post-activated dry image forming material, it is not necessary to prepare, apply and dry the photosensitive material components in a dark room, but good properties are achieved if the temperature is below 50°C. It is preferable for this purpose.

The sheet material produced in this way does not lose its image forming ability even under normal indoor light and can be handled in a bright room.

By heating desired areas of this sheet material in the dark, it can be brought into a light-sensitive state from which an image can be recorded.

The preheating conditions for activation are usually preferably in the range of 90-130°C.

If the heating temperature is set high, the heating time may be shortened accordingly.

A visible image is obtained by imagewise exposure of the portion rendered photosensitive by heating and subsequent heat development.

The heating conditions for development are usually preferably in the temperature range of 90 to 150°C.

Preheating and development heating time are usually 1 to 30 seconds.

The heat development time is usually the same as or longer than the preheating time to prepare the image for recording.

In this way, with the image forming material of the present invention, it is possible to selectively record visible images only in desired areas, not only from black and white originals, but also from various color originals, and furthermore, to record the latest information in other areas as desired. Additional recording can be performed selectively.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 15 and Comparative Examples 1 to 16 3 g of silver behenate was added to 20 g of toluene-methyl ethyl ketone mixture (weight ratio 1:2), and a uniform silver behenate suspension was created by ball milling for about 18 hours. .

For 1.59 of silver behenate suspension, the following ingredients (4)
was added to prepare a coating composition.

This composition was uniformly applied onto a polyethylene terephthalate film having a thickness of 100μ through a lOOμ orifice, and was dried by air drying at room temperature (approximately 20°C).

The coating amount of silver behenate was about 4 min/d.

Next, as a second layer on top of this, about 2 p' of a reducing agent-containing solution consisting of the following component (6)! Apply it evenly through an i75μ orifice and air dry at room temperature (20°C).
A dry imaging material was prepared having a thickness of approximately 12 microns with the emulsion layer.

Component (5) Polyvinyl butyral methyl ethyl ketone solution (15
Weight%) 1.3g.

Acetone solution of mercuric iodide (100m979cc)
Q, 5cc bisparamethoxyphenylterylium diaiodide
28 ~ bis-paramethoxyphenylterylium dibromite
141n91.2,3.4-Tetrabromobutanequinolin Methanol solution (i
o~/1.0CC) Q, lcc 2-(2'-hydroxyphenyl)benzotriazole compound referred to in the present invention in Table 1 35mg Component (B) Cellulose acetate 6.3g2.6
-methylenebis(2-hydroxy-5-t-phthyl-5
-methylphenyl)-4-methylphenol
3.2g acetone
83.0g; Phthalazinone
1.2g On the other hand, as Comparative Example 1-16, in place of the pigment compound according to the present invention used in composition (4) of Examples 1 to 15, the pigment compound starch a) described below was used.
(b) t (c), (d), (e) and no addition, and in place of the 2-(2'-hydroxyphenyl)benzotriazole compound according to the present invention, other compounds (a) below, Components (O), (c), ni), (e) and additive-free components were prepared separately, and a dry image forming material was prepared in the same manner as in Example 1-15.

Each sample obtained was heated in a dark room on a hot plate at 100° C. for 3 seconds, and then exposed to light from a tungsten lamp through a color filter for 1 second through a Kodak 21 step tablet.

The color temperature of the light source was 3200°, and the color filter used was a yellow filter ¥50 manufactured by Toshiba Corporation.

Next, heat development was carried out for 4 seconds on a hot plate at 1.25°C.

As a forced deterioration test to test the quality of raw wheat, each sample was tested in a dark place at a temperature of 45°C and a humidity of 80% RH.
A heat-humidity deterioration test in a dark place (left for 0 days) was adopted.

After the test, images were formed using the above method.

After measuring the density of each sample after image formation, the obtained sensitivity and 0. DIIuII (minimum optical density) is shown in Tables 1 and 2.

The sensitivity referred to in 5 is 0. 00D (0,6 higher than D-)
It is determined by the reciprocal of the exposure amount required to obtain the optical density (optical density), and is expressed as a sensitivity ratio, with the sensitivity of Example 1 being 100.

The dark heat and humidity deterioration test means a test in which the temperature is 45°C and the humidity is 80% RH in a dark place for 10 days, and the sensitivity retention rate after the test is the sensitivity after the test compared to the sensitivity before the test. It is determined by the ratio of sensitivities.

Comparative dyes (a) to (e) in Comparative Examples 2 to 6 are the following compounds.

(d) 3-aryl-5-“3-ethyl-(2-naphthoxazolidine)-ethylidene”-1-phenyl-2-
Thiobitantoin and other compounds (a) used in Comparative Examples 12 to 16
~(e) is the following compound.

From this result, the combined use of the dye compound having a specific structure of the present invention and the 2-(2'-hydroxyphenyl)benzotriazole compound having a specific structure improves the storage stability of raw film in a dark place under high temperature and high humidity. It can be seen that the film exhibits excellent initial results in maintaining sensitivity and preventing fogging, and also exhibits excellent effects in spectral sensitization.

Examples 16-19 and Comparative Examples 17-27 Examples 1-1
Silver behenate suspension 1.5 and Comparative Example 1-16.
The following component (Q) was added to 5.9 to prepare an emulsion, which was then coated as the first layer.

A reducing agent-containing solution of approximately 2Fk consisting of the following component (1) was coated thereon as a second layer and dried in the same manner as in Examples 1 to 15 and Comparative Examples 1 to 16 to prepare a dry image forming material.

Ingredients (0 Polyvinyl butyral methyl ethyl ketone solution (15
Weight%) 1.351 2nd iodide
Mercury in acetone solution (100~/9cc acetone)
Q, 5cc2.2.2-1-ribromoethanol 45rn9N-iodosuccinimide 63-cobalt dipromide
3D-methyl-2-pyrrolidone
20■ Methanol solution of the dye compound of the present invention in Table 3 (10~/IQcc)
0.2CC 2-(2'-Hydroxyphenyl)benzotriazole compound according to the present invention in Table 3 35 ingredients (cellulose acetate 6.3I2.4
,4'-t-limethylbentylbis(2-hydroxy-
3,5-)dimethylphenylmethane 2.1/phthalazinone 1.2g4t ace
83.1 As Comparative Examples 17 to 27, in place of the dye compound according to the present invention used in component (C), dye compounds (f) and (b) described below and no additives were used, and 2-2 according to the present invention was used. In place of the (2'-hydroxyphenyl)benzotriazole compound,
Other compounds described below and components without additives were prepared separately, and dry image forming materials were prepared in the same manner as in Examples 16 to 19.

Each sample obtained was subjected to the same image forming process as in Examples 1 to 15, and then the sensitivity and 0. DI! 111L was measured.

In addition, as a qualitative test for raw wheat, a dark heat and humidity deterioration test similar to Examples 1 to 15 was conducted.

The sensitivity is expressed as specific sensitivity as Example 16'1100.

The results are shown in Table 3. Other compounds used in Comparative Examples 22 to 25 are the following compounds.

Moreover, the comparative dye (f) used in Comparative Examples 26 and 27.

(b) is the following compound.

From this result, the combined use of the dye compound having a specific structure of the present invention and the 2-(2'-hydroxyphenyl]benzotriazole compound having a specific structure improves the storage stability of raw film in a dark place under high temperature and high humidity. It is clear that it exhibits excellent effects in maintaining sensitivity and preventing fog, and also exhibits excellent effects in spectral sensitization.

Examples 20-25 and Comparative Examples 28-37 Examples 1-1
Silver stearate instead of the silver behenate suspension solution in 3.5. i-) Luene-methyl ethyl ketone solution (
Using a silver stearate suspension prepared in addition to 20 g of 1:2 weight ratio, an emulsion was prepared by adding the following component (g), and the first layer was prepared in the same manner as in Examples 1 to 15. Apply and dry.

Next, as the second layer, the following component (g) was added to Examples 1 to 1.
A dry image forming material was prepared by coating and drying in the same manner as in step 5.

Ingredients (8 Polyvinyl butyral methyl ethyl ketone solution (15
Weight%) 1. :11yo
U element
8FQ triphenyl phosphite 4
mg nickel dibromide 4 mg mercury acetate methanol solution (100 m973 cc) Q,
15cc 1.1,1.1-tetrabu D-m-xylene 30r
methanol solution (10 m
y/10cc) 0.2
cc t 2- (2'-Hydroxyphenyl)benzo I-IJ azole compound or other compound shown in Table 4 5m
9 1-phenyl-2,3-dimethyl-3-pyrazolidone-
5-one 3Orn9 component (polymethyl methacrylate 6.3f12
．． 2'-Methylenebis(4-ethyl-6-1-butylphenol) 3.55 Phthalazinone 1.2.9 Methyl ethyl ketone 83.0.9-Power, Comparative Example 29
2-(2) according to the present invention used in component (g) as ~31
'-Hydroxyphenyl) benzotriazole compound was replaced with no additive, and in Comparative Examples 32 to 34, instead of the dye compound according to the present invention used in component (g), the dye compounds ch), ( i) and (j), and 2-( of the present invention used as component (g) for Comparative Examples 35 to 37).
A compound (g) generally known as an ultraviolet absorber in place of the 2'-hydroxyphenyl)benzotriazole compound.

(5,C'))'jr: Examples 16 to 19 except for using
A dry image forming material was prepared in the same manner as above.

Each sample obtained was subjected to the same image forming process as in Examples 1 to 15, except that it was exposed for 8 seconds using a monochromator (light with a wavelength of 480 nm) to improve sensitivity and 0. D7- was measured.

The sensitivity of Example 20 was expressed as 1too. In addition, in order to test the quality of raw wheat, the same dark heat and humidity deterioration test l-' as in Examples 1 to 15 was conducted.

On the other hand, for the purpose of examining the photostability of raw materials, a fade meter (Suga Test Instruments Model XG-1, xenon lamp, 200,000 Lux) was equipped with a Toshiba VY-45 filter to detect light with a wavelength of 450 nm or more. Chisel is irradiated on the raw material for 2 hours,
A light intensity side deterioration test was performed, and an image was formed using the same method as above for eggplant 1-ffl, and the sensitivity retention rate and 0. D- was measured.

The sensitivity retention rate is expressed as a percentage of the sensitivity after the forced deterioration test to the sensitivity before the forced deterioration test (sensitivity of raw film).

The results are shown in Table 4. Comparative dye compounds (h) and (i) in Comparative Examples 32 to 34.

(j) is the following compound.

On the other hand, other compounds (g) used in Comparative Examples 35 to 37
, (1), (IJ) are the following compounds.

Judging from this result, the combination of the dye compound having a specific structure according to the present invention and the 2-(2'-hydroxyphenyl)benzotriazole compound having a specific structure,
It is clear that the quality of raw wheat is significantly improved.

In addition, the 2-(2'-hydroxyphenyl)benzotriazole compound of the present invention also contains compounds (g) and (f) of comparative examples.
), (Although they do not have a light absorption band above 450 nm, only the compounds (1) and (It) of the present invention exhibit excellent effects.

From this, it is clear that compounds (1) and (n) do not improve the photostability of the raw film by acting as ultraviolet absorbers.

Examples 26-39 and Comparative Examples 38-49 Examples 1-1
The following component (G) was added to 1.59 g of the silver behenate suspension solution in Example 5 to prepare an emulsion.
The first layer was applied and dried in the same manner as above.

Next, as a second layer, the above component (F) was added to Examples 1 to 15.
A dry image forming material was prepared by coating and drying in the same manner as above.

・Component (G) Polyvinyl butyral methyl ethyl ketone solution (15
Weight%) 1.39 iodine
877v triphenyl phosphite 4 ■ Diphenyl bromomethane 4 ■ Methanol solution of mercury acetate (1009'3 CC) 0.15 CC1,1
,1,1-tetrabromo-〇-xylene 30711
g Methanol solution of the dye compound shown in Table 5 (10 /
1occ) 0.2CCt2-(2'-Hydroxyphenyl)benzotriazole compound or other compound shown in Table 5 357711i■
-phenyl-2,3-dimethyl-3-pyrazolidone-5
-On 30~Comparative Example 46~
Comparative dye compound (k) used in 48.

(IL(r'r1t is the following compound.

From these results, it is clear that the combined use of the dye compound of the present invention and the 2-(2'-hydroquinphenyl)penztriazole compound is significantly superior in both sensitivity retention and fog in Namamugi qualitative determination. .

Furthermore, using the unused samples of Examples 26 to 32, after heating for 3 seconds on a 100°C hot plate in a dark room,
I put it in a 5-point camera and took a picture using the NBS Resolution Chart National Bureau of Standards.

Next, heat development was carried out for 4 seconds on a hot plate at 125°C.

O and D min at the line with a resolution of 100 lines/degree thus obtained were measured using a microdensitometer (Sakura Microdensitometer Model PDM-5 manufactured by Konishiroku Co., Ltd.).

This 0. The smaller Dmin is, the less the influence of halation and irradiation is, and the image quality is excellent.

The results obtained are shown in Table 6. Judging from this result, the dye compound of the present invention:! It can be seen that when used in combination with the =2-(2'-hydroxyphenyl)benzotriazole compound, the effects of irradiation and halation are reduced, O and Dmin are small in high resolution areas, and image quality is improved.

Examples 40-49 and Comparative Examples 50-60 Examples 1-1
The following component (2) was added to silver behenate suspension 1,59 in Example No. 5 to prepare a coating emulsion, which was coated and dried in the same manner as in Examples 1 to 15.

Next, a solution of component (I) below was applied and dried in the same manner as in Examples 1 to 15 to prepare a dry image forming material.

Ingredients ■ Methyl ethyl ketone solution of polyvinyl butyral (15
weight%) 1.3g acetic acid 2nd
Mercury methanol solution (109■/3CC) 0.15C
C iodine 8772
1i+triphenylphosphite 4
111g diphenylbromomethane 4
η1-phenyl-2,3-dimethyl-3-pyrazoline-
5-one 30rIIg1
．． 1,1,1-tetrabromo-0-xylene 357
721i1 Methanol solution of the dye compound shown in Table 7 (
Im! i! /ICC)
0. 2-(2'-Hydroxyphenyl)benzotriazole compound or other compound 35rIIg component shown in ICC Table 7 Component (I) 90% by weight of acrylic acid methyl ester and 10% by weight of divinylbenzene in water using a potassium persulfate catalyst. 6.392.2'-methylenebis(4-ethyl-6-1-butylphenol) A blend of 40% by weight of an emulsion polymerized and partially crosslinked rubber elastic copolymer based on polymethyl methacrylate.
3.59 Phthalazinone
1.29 methyl ethyl ketone
839 Each sample obtained was incubated at 100% in the dark.
After heating for 3 seconds on a hot plate at 0.degree. C., the mixture was placed in a 35 mm camera and photographed using an NBS resolution chart (National Bureau of Standards).

Next, heat development was carried out for 4 seconds on a hot plate at 125°C.

The 0 and Dmin of the thus obtained resolution of 100 lines/tomo line were measured using a microdensitometer (Sakura Microdensitometer Model PDM-5 manufactured by Konishiroku Co., Ltd.).

This 0. The smaller Dmin is, the less the influence of halation and irradiation is, and the image quality is excellent.

The results obtained are shown in Table 7.

These results show that in spectrally sensitized dry image forming materials, the effects of halation and irradiation are reduced by the combined use of the 2-(gu-hydroxyphenyl)benzotriazole compound of the present invention, and zero , Dmin are small, and it can be seen that the image quality is improved.

Example 50 Components in Example 26 (instead of the methanol solution of mercury acetate in q, divalent palladium acetylacetone 57/
lI! and trivalent cobalt acetylacetone 57nI
! Example 26 except that 2011Ig of iodine was used.
An image forming material was prepared by the same operation as in Example 2.
When the same evaluation as Example 6 was carried out, semi-stability equivalent to that of Example 26 was obtained.

Claims (1)

[Scope of Claims] 1 (a) a silver salt of a long chain fatty acid having 16 or more carbon atoms, (b) a reducing agent for the silver salt, (C) silver iodine containing silver iodide or A system containing a silver halide forming component, (d) an oxidizing agent for free silver, (e) a photoreactive halogen oxidizing agent, (f) a toning agent, @binder, and (h) the following compound (
■). (If), and (i) the following compound (2). 1. A post-activated dry image forming material, characterized in that at least one of (V), (V) and (Vl) is contained in the same layer as component (a). (In the formula, R is hydrogen, C1-C8 alkyl, C1-C4
represents alkoxy, phenyl or halogen. )0 u3 (wherein, X is H, CH3, Cl, C6H5, OCH
3 or CH3C0NH, Y is H2CH3 or C2
H5, Z and Z' are Se, S or O, W and W are Se or S, A is C2-C4 alkylene, M is H, HN (C2H5)3. HN, > or Nat
- Represent each. )