DE2321217A1 - THERMAL DEVELOPMENT LIGHT SENSITIVE MATERIAL - Google Patents

Description

DR. E. WIEGAND DIPL-IMG. W. DR. M. KÖHLER DIPL-ING. C. GERMHARDT MPNCHEN HAMBURG PHONE: 55547ί «Mn ΜΠΝΓΜΡΜ 0 TELiGRAMME = KARPATENT ⁸ °°° MUNICH 2, MATH I LD E N STRAS S E T2

W 41 588/73 - Xo / DE April 26, 1973

Fuji Photo PiIm Co., Ltd. Minami Ashigara-shi, Kanagawa / Japan

Thermally developable photosensitive material

The invention "is concerned with a thermally developable photosensitive material and "relates in particular a thermally developable photosensitive material which produces a black-tinted image upon development delivers «

The invention provides a thermally viable one photosensitive material which 1) a silver salt of benzotriazole, 2) a by reaction silver halide made of an inorganic halide with the silver salt of benzotriazole, 3) a reducing agent, 4) a binder and 5) one of the blackening agents listed below.

Heretofore, photographic processes using silver halides have been widely used as they have excellent photographic properties such as speed and gradation compared to electrophotographic Process or photograpbiseben provide diazo processes.

309845/0967 ORlOiNAL INSPECTED

■ - * T © doeh must be used in such procedures ^ Silherhalide photosensitive photographic materials after imagewise exposure and development with a developer some process steps such as stop treatment, They may be subjected to fixing, washing and stabilization in order to prevent the developed image from being discolored is faded or under normal light and also to prevent that the undeveloped areas, hereinafter referred to as the background, are blackened. That's why have encountered various problems in using such silver halide light-sensitive materials, for example that these treatments require a lot of time and circumstances that pose a risk to humans due to the chemicals to be handled and that the treatment rooms and the hands and clothes of workers are contaminated or stained with the chemicals

So it would be in the photographic field of impoverishment very cheap using silver halides, to improve the materials so that they can be treated in the dry state without any solution processing and that the treated images would be stable.

Various efforts have heretofore been made for this purpose. One attempt is the so-called combined Fixing and developing processes such as those disclosed in TB Patent 2,875,048, British Patent 954 453 and the German patent specification 1 163 is described, with the two stages of development and fixing by the usual silver halide photographic process United is another attempt to change the wet processing procedures in the silver halide photographic process on dry treatments is for example in the German patent specification 1,174,159 and the British Patent specification 943 476 and 951 644, and another attempt is the use of light sensitivity

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Chen elements, the main components of which are a silver salt a long-chain aliphatic carboxylic acid, for example silver behenate, or a silver salt, for example the silver salt of saccharin, the silver salt of benzotriazole, and the like, as well as a catalytic amount of a silver halide as in Japanese Patent Publications 4921/68, 4924/68, 26582/69, 18416/70, 12700/70 and 22185/70, British Patent 1 205 500 uiiä- ■ the like is indicated.

The present invention relates to the last one above specified group, wherein the silver salt of benzotriazole and a silver halide in a photographic photosensitive Material are incorporated. ----...

However, in the previously proposed thermally developable photosensitive materials, i. using hates who like a silver carboxylate Silver behenate or a silver salt of benzotriazole, a reducing agent and a catalytic amount of silver halide contain, no images with black tone will be obtained. Therefore, in the case of a thermally developable material, which contains, for example, silver behenate, phthalazinone can still be added to the mass specified above, to get a picture of black color.

However, although phthalazinone is effective with known compositions containing silver behenate, it is not effective in im Within the scope of the invention where the silver salt of benzotriazole is included as an image-forming compound. This fact will evidenced by the comparative tests listed in the examples below.

The use of the silver salt of benzotriazole as an image-forming compound gives various advantages, for example becomes little thermal fog when heating the unexposed parts due to the excellent thermal stability of the same compared to silver behenate formed and therefore can take pictures with good contrast

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between the image areas and the background. As a result, it is beneficial for thermally viable light-sensitive materials that contain the silver salt of benzotriazole to provide a compound which provides a good image with black coloration obtain.

According to the invention, it was found that a black colored developed image can be contained if a thermally developable photosensitive material is used, which 1) the silver salt of benzotriazole,

2) a silver halide produced by reacting an inorganic halide with the silver salt of benzotriazole,

3) a reducing agent, 4) a binder and 5) at least one compound according to the following general formula

¹ E ²

HS C-N N

/ V

contains, wherein R ₁ and R _{2 represent} a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group in order to obtain the color of the developed image practically black.

They preferred radicals R ₁ and R ₂ are hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, phenyl groups or halogen-substituted phenyl groups.

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A simple test shows how effective a special Compound of the above group in a thermally developable photosensitive material results. The following experiment is carried out:

The following constituents were ground in the ball mill at about 25 ^° C. under atmospheric pressure for a few hours to produce a dispersion:

Polyvinyl butyral 6 g

Silver salt of benzotriazole 4 g of isopropyl alcohol x 40 ml

The dispersion obtained is referred to as dispersion A. Dispersion A is then made with the following ingredients mixed for the production of the coating compound:

Total amount of dispersion A produced

lot

Methanol solution with a content

of 5 wt .- ^ mercury bromide

and 8.5% by weight mercury iodide 1 ml

Acetone solution with a content of 0.2% by weight benzoxazolylidene thiohydantoin as sensitizing dye 1 ml

Methyl cellosolve solution with a

Content of 25 wt .- # ascorbic acid

monopolymer 8 ml

Methylcellosolve solution containing of 5 wt .- ^ of the compound to be examined 8 ml

The mass obtained in this way was applied to a polyethylene terephthalate carrier in an amount of 1.3 g of silver per m 2 of the carrier. The coating obtained was left to dry at about 50 to 70 ^° C. under atmospheric pressure until it practically solidified. The resulting element was imagewise exposed to tungsten light for 2 minutes, then at 130 ⁰ C for 30 seconds by Einschich-

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the element is heated between two heating plates »

The hue of the obtained image then became visual
rated to determine relative inferiority or superiority.

Comparing the images thus obtained with those obtained using phthalazinone,
a black tone image could be obtained when the compound according to the invention was used, while only a brown tone image was obtained when phthalazinone was used. Specific experiments are given in the examples.

Specific examples of compounds suitable for the present invention are given below:

Connection 1:

3,6-dimercapto-1,4-diphenyl-i H, 4H-2, 3a, 5, 6a-tetrahydro zapenta len (mp. 188 ⁰ C)

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Compound 2; 3,6-Dimercapto-i, 1,4,4-tetramethy 1-2, 3a, 5, 6a ¹ -tetra zapentalen (pp. 178 ¹ S)

^H 3 / ^H 3. ■

N ^ ^ _n C-SH

I! I Il

HS C N N

CH ₃ CH ₃

Connection 3:

1 _t 4-diethyl-1,4-dimetnyl-3,6-dimercapto-2,3a, 5,6a-tetrazapen talen (pp. 191 ⁰ C)

^CH 3 \ / ° 2 ^Η 5

N H C SH

Β I Il

HS C- N ii

Connection 4:

1,4-Dibuty1-3,6-dimercapto-1H, 4H-2,3a, 5,6a-tetrazapentalen (pp. 174 ⁰ C)

N C SH

HS-C 1 N N

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Connection 5:

1,4-Di (o-chlorophenyl) -3 »6-dimercapto-1H, 4H-2, 3a, 5,6a-tetra zapentalen (pp. 226 ⁰ C (cere.))

N N C SH

HS C

Connection 6:

1,4-diethy1-3,6-dimercapto-1H, 4H-2,3a, 5,6a-tetra zapentalen (pp. 187 ⁰ G)

IL

C SH

HS C - N

H ^ C ₂ H ₅

Connection 7:

1,4-Dimethy 1-3,6-dimercapto-1H, 4H-2, 3a, 5, 6a-tetra zapenta len (pp. 189 ⁰ C)

CH

/ V

₃ .

CH SH

HS C

H CH:

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In general, the compounds identified above can be prepared by the method of Journal of the American Chemical Society, Vol. 39, p. 1535 (1917). Specific manufacturing examples for the above The compounds listed are given below.

Preparation example 1 (compound 1)

5 g of benzalazine were dissolved in 150 ecm of glacial acetic acid and 10 g of potassium thiocyanate were added to it. The mixture obtained was heated on a water bath at 90 to 95 ^° C. at atmospheric pressure for 30 minutes and then cooled. The crystals formed were filtered off and recrystallized from ethyl alcohol. 5 g of crystals with a melting point of 188 ^° C. were obtained in this way.

Preparation example 2 (compound 2)

5 g of acetonazine were dissolved in 120 ecm of glacial acetic acid and 10 g of potassium thiocyanate were added to this. The resulting mixture was heated in a water bath for 1 hour as in Example 1 and then cooled. The crystals formed were filtered off and recrystallized from ethyl alcohol. 5 g of crystals with a melting point of 173 ^° C. were obtained in this way.

Preparation example 5 (compound 3)

10 methylethylketonazine were dissolved in 120 ecm of glacial acetic acid and 20 g of potassium thiocyanate added. The resulting mixture was heated as in Example 1 on a water bath and then cooled. The crystals formed were filtered off and recrystallized from ethyl alcohol

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11 g of crystals with a melting point of 191 ^° C. were obtained.

Preparation _example 4 (compound 4) v

6.8 g of hydrazine hydrochloride and 19.6 g of potassium thiocyanate were dissolved in 100 ecm of water and 20 ecm of glacial acetic acid were also added. Then 17 »2 g of valeraldehyde were gradually added dropwise. After the completion of the dropwise addition, the solution was stirred for 2 hours at the same temperature. The crystals formed were filtered off and recrystallized from glacial acetic acid. 9 g of crystals with a melting point of 184 ^° C. were obtained in this way.

Preparation example 5 (compound 5)

14 g of 2,2'-dichlorobenzalazine were dissolved in 400 ecm of glacial acetic acid and 10 g of potassium thiocyanate were added to it. The resulting mixture was heated on a water bath as in Example 1 for 30 minutes and then cooled. The crystals formed were filtered off and recrystallized from ethyl alcohol. 9 g of crystals with a decomposition point of 226 ^° C. were obtained.

Preparation example 6 (compound 6)

104 g of hydrazine hydrochloride and 196 g of potassium thiocyanate were dissolved in 500 ecm of water and 150 ecm of glacial acetic acid were added. Then 116 g of propyl aldehyde was gradually added dropwise thereto while stirring and while cooling with ice. After the completion of the dropwise addition, stirring was continued for a further 2 hours while cooling with ice. The crystals formed were filtered off and taken out of a

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Mixed solvent recrystallized from methanol and water. 165 g of crystals with a melting point of 186 to 187 ^° C. were obtained in this way.

Preparation example 7 (compound 7)

21 g of hydrazine hydrochloride, 39 g of potassium thiocyanate and 50 ecm of glacial acetic acid were added to 200 ecm of water and stirred while cooling with ice. To this, 18 g of acetaldehyde was gradually added dropwise. After the completion of the dropwise addition, the solution was further stirred for 2 hours while cooling with ice. The crystals formed were filtered off and recrystallized from alcohol. 23 g of crystals with a melting point of 189 ^° C. were obtained in this way.

The compounds according to the invention used as blackening agents are most advantageously added in an amount of from 0.0001 to 1 mol, preferably 0.001 to 0.5 mol, to 1 mol of the silver salt of benzotriazole. The amount vari · ¹ · ated depending on the type of compound used, the various components contained in the photosensitive material, the treatment temperature door and the like, so that the above range is not limiting as such, but it will be in the operation in the above range, these factors are particularly considered in the preferred range.

It will also be apparent to those skilled in the art that mixtures of the compounds within the above general formula can be used with equal success. Palis applied, the total amount of all compounds is within the above range.

The silver salt of benzotriazole used according to the invention is a light-insensitive silver salt, which can be reduced with a reducing agent and a silver image only provides "where exposed

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tetes silver halide is present and only when heated. The absolute amount of the silver salt of the benzotriazole can vary widely, provided a picture of acceptable density for use is obtained. If the fairly wide differences of the visual Sensitivity of the average consumer should be taken into account «it is best if the silver salt des benzotriazole is present in an amount of from about 0.3 g / m to about 3 g / m, more preferably from 0.5 g / m to 2 g / m the latter value being influenced by the relatively high cost of the silver salt. If the Particle size of the silver salt of benzotriazole 0.01 micron to 5 microns, preferably 0.1 microns to 3 microns, extremely clear images are obtained. This area is but not limiting, as the desired clarity can of course vary from consumer to consumer.

As stated above, must be considered within the scope of the invention Usable reducing agents are those used which are used to reduce the silver salt of benzotriazole in Presence of exposed silver halide when heated under Formation of a silver image are suitable, can be used. As already discussed above, however, the silver salt of benzotriazole is more stable than silver behenate and is therefore difficult to reduce by heating. Therefore, even if a reducing agent for silver behenate, such as a bisphenol, is used for the silver salt of benzotriazole, the silver salt of benzotriazole is difficult to reduce due to the poor reducing property of these reducing agents.

However, it has already been found that ascorbic acid and / or derivatives thereof are effective as reducing agents for the silver salt of benzotriazole, including the Japanese See Patent Publication 22185/70. Examples for effective derivatives of ascorbic acid include mono- or dialiphatic esters of ascorbic acid, for example the Monolaurat, Monomyristat, Monopimmitat, Monostearat, Mono-

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behenat, dilaurate, dimyristate, dipaimitate, distearate and Dibehenate and the like of ascorbic acid. In general groups with 10 to 22 carbon atoms are considered aliphatic Share preferred to form the ester structure. In addition, D-araboascorbic acid is also within the scope of the invention suitable as a good reducing agent.

Another group of reducing agents suitable for the invention are the 3-pyrazolidone derivatives listed. That is, effective 3-pyrazolidone derivatives include 1-phenyl-3-pyrazolidone, i-phenyl-4-methyl-3-pyra zolidon, 1-p-methylpheny1-3-pyra zolidon, 1-pheny1-5-carboxy-3-pyrazolidone, 1-pheny1-4,4-dimethy1-3-pyrazolidone, 1-Pheny1-5-carboxyäthy1-3-pyrazolidone and 1-Pheny1-5-Bethy1-3-pyrazoldione and similar connections.

The preferred ascorbic acid derivatives are the mono- or dicarboxylates of ascorbic acid and the preferred 3-pyrazolidone derivatives are those with alkyl groups with 1 to 4 carbon atoms, carboxyalkyl groups with 1 to 5 carbon atoms or substituted 1-aryl-3-pyrazoldiones.

If desired, combinations of ascorbic acid can be used and derivatives thereof, combinations of 3-pyrazolidone derivatives or combinations of ascorbic acid or derivatives thereof and 3-pyrazolidone derivatives are used.

According to the invention, the reducing agent is most conveniently used in an amount of 0.1 to 5 moles per 1 mole of silver salt of the benzotriazole added. As already stated, the silver halide used according to the invention is converted by reaction of an inorganic halide with the silver salt of the benzotriazole with conversion of part of the silver salt of benzotriazole, the silver halide is formed. For example, as in the test procedure listed above, the silver halide can only by adding a solution of the inorganic halide, for example mercury bromide and / or mercury iodide to a polymer dispersion of the silver salt of benzo

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triazoles are added. The formation of the silver halide during the reaction between a part of the silver salt of the benzotriazole and these halides results, for example, from the investigation of the change in the X-ray diffraction pattern of the system. The conditions of the reaction are not particularly critical since this reaction proceeds quite easily and the reaction is usually carried out at atmospheric pressure at mild temperatures, for example 20 to 60 ^° C. In practice, the solution of the inorganic halide is only added to the polymer dispersion of the silver salt of benzotriazole and the system is agitated for 5 minutes.

Examples of suitable inorganic halides are those of the formula M Xn, in which M is a cation, for example H ⁺ , NH ^ ⁺ or a metal, X is the group Gl ", Br" *, I ~ and η is the valence of M. Specific examples include hydrogen bromide, hydrogen iodide, ammonium bromide, ammonium;) odide, ammonium chloride, metal halides such as the chlorides, bromides or iodides of metals such as strontium, cadmium, zinc, chromium, sodium, potassium, barium, iron, cesium, lanthanum, copper, Nickel, magnesium, aluminum, antimony, cobalt, mercury, lead, beryllium, lithium, calcium, tin, gold, manganese, indium, rhodium, ruthenium, palladium, osmium, iridium, platinum, thallium, bismuth and the like.

“The inorganic halides are cheapest in in an amount of 1/1000 to 0.5 mole per 1 mole of the silver salt of the benzotriazole added. The reaction with the silver salt of benzotriazole is practically stoichiometric. Consequently 1/100 mol of an inorganic halide of suitable valence gives a yield of 1/100 mol of the silver halide .

The thermally developable photosensitive Masses of material used in practicing the invention are incorporated into a binder. All binders can be used which are at least ha Ib transparent, so that the exposure light has the thermal

3 09 8 45 / 09Θ7

mixed viable substance reached, which in the Exposure or hot conditions and which serve as good dispersing material. The appropriate ones Binders are usually hydrophobic, but hydrophilic ones can also be used. These are clear or semi-transparent and include natural substances, such as gelatin, gelatin derivatives, cellulose derivatives and the like and synthetic polymer materials such as polyvinyl compounds, Acrylamide polymers and the like. Other synthetic polymeric compounds that can be used include dispersions of the latex type, of one or more vinyl compounds. Preferred high molecular weight materials and resins include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, polyvinyl pyrrolidone, ethyl cellulose, Polystyrene, polyvinyl chloride, chlorinated rubbers, polyisobutylene, butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, Vinyl acetate-vinyl chloride-maleic acid copolymers as well as polyvinyl alcohol.

These binders are best added in a ratio of 4: 1 to 1: 4 (weight ratio to the silver salt des benzotriazole).

As useful supports in practicing the invention for the thermally developable above A wide variety of supports can be used with the treated photosensitive materials. Examples for typical carriers are cellulose nitrate films, cellulose ester films, Polyvinyl acetal films, polystyrene films, polyethylene terephthalate films, Polycarbonate films, other resinous materials, glass, paper, metal and the like.

In general, all supports can be used according to the invention, which are well connected to the thermally developable Substance adhere and which are not adversely damaged during exposure or development.

The thermally developable photosensitive devices used in practicing the invention

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Materials can have an antistatic layer or an electroconductive layer. An antihalation substance and an antihalation dye can also be incorporated in the bulk of the thermally developable photosensitive Materials can be incorporated if desired.

If desired, the thermally developable material used according to the invention can also be used Matting agents such as starch, titanium oxide, and silica the like and / or fluorescent brightening agents such as fluorescent brightening agents of the stilbene, triazine, oxazole or coumarin type or similar materials are incorporated will.

The one used in the practical execution of the invention thermally developable photosensitive layer can be placed under various coating processes Inclusion of the immersion method, the air spreading method, the curtain coating process and the extrusion coating process be drawn up using a funnel according to US Pat. No. 2,681,294 «If so desired two or more layers can be applied at the same time.

Although not particularly wise, results will be best obtained when the photosensitive layer according to the invention has a thickness of about 1 micron to about 20 microns Microns, preferably 3 microns rock 10 microns. Applying a thickness of less than 1 micron will give one insufficient strength for the element under normal handling and use of a thickness greater than 20 microns does not give better results than those obtained with a thickness of 20 microns. This range is chosen mainly in consideration of the mechanical factors and is in no way limiting on the concept of the invention.

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Optical sensitizing dyes can be used advantageously can be used to impart photosensitivity to the element in practicing the invention. For example, the element can be made optically by adding a sensitizing dye in the form of a solution in one organic solvent or sensitized as a dispersion will. Optical sensitizers that can be used are exemplified are cyanine dyes, merocyanine dyes and the same.

After imagewise exposure to a light source such as a xenon lamp, tungsten lamp, mercury lamp and the like, the latent images formed in the photosensitive layer of the thermally developable photosensitive material described above are developed merely by heating the element. Therefore, another embodiment of the invention relates to a method of developing the latent image formed in the photosensitive layer of the exposed thermally developable photosensitive material by heating at about 100 to 160 ^° C. until the desired image is developed.

A suitable development temperature is 100 to 160 ^° C. and a temperature of 110 to HO ^° C. is usually used. By lengthening or shortening the heating period, higher or lower temperatures within the above range can be used. A developed and stable image can usually be obtained within 1 second to 60 seconds.

Various means can be used as a means of supplying the necessary heat. The above Element can be brought into contact with simple heating plates and the like or can be in contact with a Heating drum can be brought or in some cases the element can be passed through a boiler room and a high frequency induction heater be subjected.

309845/0967

The following specific examples of preferred embodiments of the invention serve to further illustrate the invention in detail.

example 1

The above-mentioned dispersion A was prepared in the above-mentioned manner. The dispersion A was mixed in a ball mill for 4 hours. Afterward Dispersion A was mixed with the following ingredients to produce the following composition:

Dispersion A in a mixed amount of 40 ml \ methanol solution with a content of

5 wt. - $> mercury bromide and 8.5

Weight # mercury iodide 1 ml

Acetone solution with a content of 0.2% by weight of benzoxazolylidene thiohydantoin as sensitizing dye 1 ml

Methylcellosolve solution containing of 25 wt .- $ ascorbic acid monopalmitate 8 ml

Methylcellosolvel solution containing 1% by weight of the above-described compound 1 5 ml ,

at 50 ⁰ C, pressure 1 atm;

each solution was consecutive 5 min apart added

The mass thus obtained was coated on a polyethylene terephthalate film at 5O ⁰ C to a Haßstärke of 80 microns. The coated Piim obtained was dried at 70 ⁰ C for an hour to prepare the thermally developable photosensitive material.

Then, the material obtained was at 7 / olframlieht (.10 lux) for 2 minutes through a transparent negative original with varying graduation exposed and heated while seconds by layering between metal plates, which were heated to 130 ⁰ C. As a result, a black colored positive image with a graduation corresponding to that of the original was obtained.

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A comparative element was made in the same way as prepared above, but omitting compound 1, and exposed and processed in the same manner. That the image obtained was yellowish-brown in tone and showed only an extremely low image density.

Separately, an element was prepared in the same manner, but using phthalazinone in place of the compound 1 was used in the same amount, which element was then exposed and treated as above. That image obtained had a brown tone and showed only a low one. Image density.

Furthermore, an element as above was used of 3-mercapto-4-phenyl-1,2,4-triazole as a tinting agent according to Japanese patent publications 18416/70, 12700/70 and 26582/69 were used in place of compound 1 in the same amount, followed by exposure as above and has been processed. The image obtained was brown in tone, if somewhat blackish, and showed one low image density.

Furthermore, an element was made using 1,3-diphenylguanidine as a tinting agent disclosed in Japanese Patent Publication 12700/70 in place of the compound 1 prepared and exposed in the same amount and processed as above. The image obtained showed a good image density while being blackish-brown in tone.

This results from the above test values the following: phthalazinone, which is effective for silver behenate is ineffective for the silver salt of the benzotriazole system and the toning agents according to the invention give far better black-colored images than they do with the usual ones Tinting agents are obtained, for example 3-mercapto-4-phenyl-1,2,4-triazole, 1,3-diphenylguanidine and the like, which are effective for the silver salt of the benzotriazole system are.

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Example 2

The Yerfahren according to Example 1 was repeated, however the compound 2 was used instead of the compound 1 in the same amount. A good picture with black color like in Example 1 was obtained.

Example 3

The procedure of Example 1 was repeated, however the compound 3 was used instead of the compound 1 in the same amount. It turned out to be a good picture with black paint as obtained in example 1.

Example 4

The procedures described in Example 1 were repeated, however, Compound 5 was used in place of Compound 1 in the same amount. It turned out to be a good picture obtained with black color as in Example 1.

Example 5

The procedure described in Example 1 was repeated, however, the compound 6 was used instead of the compound 1 in the same amount. It turned out to be a good picture obtained with black color as in Example 1.

Example 6

The following ingredients were mixed to prepare a mass ι

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Dispersion A 40 ml

Methanol solution containing 6% by weight of zinc "bromide" and 9 wt .- $ zinc joaid 1 ml

Chloroform solution with a content of 0.2 wt .- ^ Benzoxazolylidenrhodanin as sensitizing dye 1 ml

Methylcellosolve solution with a content of 25 wt .- ^ 1-phenyl-3-pyrazolidone 8 ml

Methyl cellosolve solution with

a content of 3 wt .- #

of compound 4 0.5 ml

atmj at 5O ⁰ C, pressure 1

each solution was added as in Example 1 at 5 minute intervals

The mass thereby obtained was coated on a polyethylene terephthalate film as a support at 5O ⁰ C to a wet thickness of 80 microns. The coated film was dried at 7O ⁰ C for 1 hour to produce a thermally developable light-sensitive material dried "This material was then exposed to a xenon flash lamp for 10 ~ ^ seconds (10 Lux) through a transparent negative original with varying graduation. The material was then heated for 30 seconds by stratification between metal plates, which were heated to 13O ⁰ C. As a result, a positive image of black color with a graduation corresponding to that of the original was obtained.

Example 7

The procedure according to Example 6 was repeated, however the compound 7 used instead of the compound 4 in the same amount. It became a picture with black color like obtained in Example 6.

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Example 8

The following ingredients were mixed together to make the mass:

Dispersion A

40 ml

Methanol solution with a content of 5 wt .- ^ mercury bromide 1 ml

Acetone solution with a content of 0.2 wt .- $ benzoxazolylidene thiohydantoin as sensitizing dye 1 ml

Methyl cellosolve solution at a level of 25% by weight Ascorbic acid monomyristate 8 ml

Methyl cellosolve solution with

a content of 5 wt .- ^ of compound 2 1 ml

atmj at 5O ⁰ C, pressure 1

each solution was 5 minutes apart as in Example 1 admitted

The mass thus obtained was coated on a Polyäthylenterephthalatfilmträger "at 5O ⁰ C to a wet thickness of 80 microns The resulting coated Piim was dried at 7O ⁰ C for 20 minutes Then, the following ingredients were mixed to prepare a composition..:

Vinyl chloride-vinyl acetate copolymer (Weight ratio 85:15)

Tetrahydrofuran

15 g
100 ml

The resulting composition was coated to a wet thickness of 60 microns on top of the above Piim at 50 ⁰ C, then at 7O ⁰ C for 1 hour dried.

The thermally developable photosensitive material thus prepared is more preferable as a second original as compared with a photosensitive material having no overcoat layer due to the increase in transparency the applied layer.

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This material was then exposed to a tungsten lamp (contact pressure at 10 000 lux) for 30 seconds through a transparent negative original with varying graduation, then for 20 seconds by layering between metal plates, which were heated to 120 ⁰ C, heated. A positive image with black color and grading corresponding to that of the original was obtained.

In comparison to the pail of the omission of the topcoat layer, the percentage transmittance of the parallel light in the non-image areas was determined by means of a 3 DIM. GOlTIO PHOTOMETER, MODEL JSG-21 of JYONAN SEISAKIJSHO LTD. increased to 78 # from 75 fi obtained in the pail of the omission of the overcoat layer. Further, as compared with the omission of the overcoat layer, the maximum transmission image density was increased by 1.3 times.

Example 9

The procedures given in Example 8 were repeated, but using a mixture of 2 g of ascorbic acid monostearate and 0.2 g of 1-phenyl-3-pyrazolidone instead of ascorbic acid monostearate as the reducing agent. It was obtained as an image with black Pärbung in Example 8, and by heating at 120 ⁰ C for 10 seconds, the same maximum image density obtained in Example 8. FIG.

Example 10

The procedure of Example 8 was repeated, but the following dispersion B was used instead of dispersion A.
Preparation of dispersion B:

The following constituents were ground in the ball mill for 4 hours at about 25 ^° C. under atmospheric pressure:

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A'thy! Cellulose 6 g

Benzotriazole 4g silver salt Isopropyl alcohol 40 ml

A picture with black color became as in example 9 received.

Example 11

The following ingredients were mixed to make the mass:

Dispersion A

40 ml

Methanol solution with a content of 5 wt .- ^ ammonium bromide 1 ml

Acetone solution with a Content of 0.2% by weight of benzoxazolylidene thiohydantoin as a sensitizing dye 1 ml

MethyIc ellos olvelous ung with a content of 25 wt .- # ascorbic acid monopalmitate 8 ml

Methyl cellosolve solution with a content of 1 wt .- $

at 50 ⁰ C,
Pressure 1 atm

each solution was 5 minutes apart as in Example 1 added

the connection 3

0.3 ml

Acetone dispersion with a content of 15 wt .- $ zinc oxide 4 ml

The mass thus obtained was applied to a photographic base paper at 5O ⁰ C to a wet thickness of 100 microns. The coated material was dried at 5O ⁰ C for 30 minutes. The thermally developable photosensitive material thus obtained was exposed to tungsten light (contact pressure at 10,000 lux) for 30 seconds through a transparent negative original with varying graduation. The material was then layered between Meta11-

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plates, which ^{were heated to 110 0} C, heated. An image of black color was obtained.

In the foregoing, the invention has been described on the basis of preferred embodiments without being limited thereto is.

309845/0967

Claims (1)

. Pat entans check 1. Thermally developable photosensitive material, consisting of a support with a thereon Layer of 1) the silver salt of benzotriazole, 2) one obtained by reacting an inorganic halide silver halide formed with the silver salt of benzotriazole, 3) one of the compounds ascorbic acid, its derivatives and / or 3-pyrazolidone derivatives as reducing agents, 4) a binder and 5) one or more compounds according to the general formula • R ¹ ^ R ² N N C SH HS— C · Ή Ή 1 \ 2 Ό "D Xt Xt wherein R- and Rp are a hydrogen atom, an alkyl group or mean a substituted or unsubstituted phenyl group. 2. Thermally developable photosensitive element according to claim 1, characterized in that the The compound according to the invention is present in an amount of from 0.001 to 1 mole per mole of the silver salt of the benzotriazole. 3 · thermally developable photosensitive element according to claim 2, characterized in that the Silver salt of benzotriazole in an amount of about 0.3 up to about 3 g / m 2. ν 30984570967 4. Thermally developable photosensitive element according to claim 3, characterized in that the Reducing agent is present in an amount of 0.1 to 5 mol per mol of the silver salt of the benzotriazole and the silver halide is present in an amount of 1/1000 to 0.5 mole per mole of the silver salt of the benzotriazole. 5 · Thermally developable photosensitive element according to Claims 1 to 4, characterized in that the binder is present in a ratio of 4: 1 to 1: 4 (weight ratio to parts of the silver salt of benzotriazole). 5. Thermally developable photosensitive Element according to claims 1 to 5, characterized in that in the compound according to the invention R ^ and Rg are hydrogen a torn, an alkyl group with 1 to 4 carbon atoms, represent a phenyl group or a halogen-substituted phenyl group. 7. Thermally developable photosensitive element according to Claims 1 to 6, characterized in that the inorganic halide has the formula MX _n , in which M is a hydrogen atom, an ammonium group or a metal, X is a chloride, bromide or iodide and η is the valence of M. . 8. Thermally developable photosensitive element according to claim 7 »characterized in that M a Hydrogen atom, an ammonium group, mercury, osmium, calcium, tin, gold, manganese, gallium, indium, rhodium, ruthenium, Palladium, iridium, platinum, thallium or bismuth means 9. Thermally developable photosensitive element according to claim 1 to 8, characterized in that the reducing agent made from ascorbic acid or the monolaurate, monomyristate, monopalmitate, monostearate, monobehenate, dilaurate, Dimyristate, dipalmitate, distearate or dibehenate of ascorbic acid., 1-phenyl-3-pyrazolidone, i-phenyl-4-methyl- 3098A5 / 0967 3-pyrazolidone, i-p-methylphenyl-3-pyrazolidone, 1-phenyl-5-carboxy-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, i-phenyl-S-carboxyethyl-S-pyrazolidone or 1-phenyl-5-methyl-3-pyrazolidone consists. 10.! Thermally developable photosensitive element according to claims 1 to 9 _? characterized in that the connection consists of one of the following connections 1-7:
Connection 1: 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetrahydro zapentalen (mp. 188 ⁰ C) Connection 2: 3 »6-Dimercapto-1,1,4» 4-tetramethy 1-2, 3a, 5, 6a-tetra zapentalen (pp. 178 ⁰ C) N N-C SH HS C N N CH 30 9 845/0967 Connection 3: 1,4-diethyl-1,4 ~ dimethyl-3,6-dimercapto-2,3a, 5,6a-tetrazapentalen (pp. 191 ⁰ C) CH ₃ C ₂ H HS C C SH Il · CH ₃ ^ C ₂ H ₅ Connection 4: 1,4-Dibuty1-3 , 6-dimercapto-1H, 4H-2, 3a, 5,6a-tetra zapentalen SH HS -N Connection 5: 1,4-di (o-chlorophenyl) -3,6-dimercapto-1H, 4H-2,3a, 5,6a-tetraza pentalen · (Pp. 226 ⁰ C () dec.) H, HS C 30 9 8 45/0967 Connection 6: 1,4-diethy1-3,6-dimercapto-1H, 4H-2, 3a, 5, 6a-tetra zapentalen (M.p. 187 "C) 2 5 N C SH HS C W HC ₂ H ₅ Connection 7: 1,4 ~ dimethyl-3 »6-dimercapto-IH, 4H-2, 3a, 5, 6a-f etra zapentalen (mp. 189 ⁰ C) • _NN —.— c: ~ -SH HS-C N ^ J H CH 11. Thermally developable photosensitive Element according to Claims 1 to 10, characterized in that the silver salt of benzotriazole has a particle size from 0.01 microns to 5 microns. 30 98 45/09 67