BE889003A - DRY IMAGE FORMING MATERIAL - Google Patents

Description

       

  "Dry image forming material" The present invention relates to a dry image forming material. More particularly, it relates to a dry image formation material whose stability is better during storage, before use for image formation (hereinafter often "storage stability of the raw material"), and of which the stability of the latent image and the quality of the image can be further improved, and which can advantageously be made subject to much less variations in the quality of the image with the conditions of heat development which may switch.

  
As a class of dry imaging material where a visible image can be formed only by a dry method including heating, there have been proposed dry heat developable imaging materials which essentially contain an agent non-photosensitive organic silver salt oxidant, a silver ion reducing agent, a catalytic amount of a silver halide or a silver halide forming compound and a binder.

  
The dry image materials of the silver salt type described above include those which are photosensitive under normal lighting conditions
(hereinafter often "dry imaging material of the already photosensitive type -), such as those disclosed in

  
  <EMI ID = 1.1>

  
which are non-photosensitive under normal lighting conditions (hereinafter often "dry imaging material of the post-activation type") such as

  
  <EMI ID = 2.1>

  
4,113,496 and 4,173,482. These latter materials can be manipulated by room light, provided they are not activated and can be made photosensitive when activated, for example, by heating them before exposure to the light. Early imaging materials can form a visible image when exposed to light to <EMI ID = 3.1>

  
that the latter materials can form a visible image when subjected to preliminary heat activation, exposure to light to form an image, and subsequent heat development.

  
The dry imaging materials of the silver salt type are superior by the simplicity of the imaging processes, to the photo-

  
  <EMI ID = 4.1>

  
wet process, because they can form an image simply by heating them without using any liquid chemical agents. However, they have such poor storage stability of the raw material that they are easily subject, during storage before being used for imaging, to deterioration of the imaging characteristics. More particularly, after storage, they can be blackened even in the parts not exposed to light by the image formation processes to form an image having a dark background, i.e. they can undergo the training

  
veil during image formation. Likewise, their sensitivity may become poor during storage. Furthermore, since the imaging characteristics of the materials are inherently strongly dependent on the conditions of heat development for the formation of the visible image, the quality of the images formed on the materials varies greatly when

  
  <EMI ID = 5.1>

  
On the other hand, these dry imaging materials may suffer some deterioration in ability to form a visible image during the period between

  
  <EMI ID = 6.1>

  
and consequently, the quality of the images which are formed therein is all the worse the longer the above period. Thus, they exhibit poor stability of the latent image.

  
We have proposed dry imaging materials of the poat-activation type as is

  
  <EMI ID = 7.1>

  
the incorporation of a spectral sensitization dye into a dry imaging material is mentioned. These dry imaging materials

  
  <EMI ID = 8.1>

  
defective either because they have such poor stability

  
  <EMI ID = 9.1>

  
  <EMI ID = 10.1>

  
  <EMI ID = 11.1>

  
insufficient to use them in photography. As the stability of a raw imaging material is increased, the sensitivity of the material may decrease

  
  <EMI ID = 12.1>

  
of an image may decrease as the material's aenaibility increases. Therefore "none of the traditional dry-imaging materials of the bridge-activation type is good for both its stability and sensitivity *

  
Consequently, it is very seriously desirable to find such a dry image-forming material which can meet these needs "therefore not substantially undergoing deterioration in its characteristics.

  
  <EMI ID = 13.1>

  
its use, not being affected too much in quality of the image formed by the variation of the conditions of

  
  <EMI ID = 14.1>

  
storage stability of the raw material.

  
As described in patent applications

  
  <EMI ID = 15.1>

  
of <EMI ID = 16.1>

  
A combination of benzotriazole and tallow acid can be effective in improving the storage stability of dry imaging materials. However, the incorporation of benzotriazole greatly lowers the sensitivity of the dry imaging materials, as will be apparent from the results of Comparison Example 24 which will be given below. Thus, it can be repeated that it is quite natural that the storage stability of a raw imaging material increases while the sensitivity of the material decreases.

  
Furthermore, as revealed in the

  
  <EMI ID = 17.1>

  
hydroxyphenyl) benzotriazoles can serve as ultraviolet absorbing agents and therefore it is known

  
  <EMI ID = 18.1>

  
triazole in a filtering layer on the photographic emulsion layer of a color photographic material for wet processing is effective in preventing the loss of color balance due to the too strong development of the blue caused in an unintended manner

  
  <EMI ID = 19.1>

  
and to prevent alteration and / or discoloration of a colored image formed on the material.

  
  <EMI ID = 20.1>

  
used as ultraviolet absorbing agents. However, no research has been done on the action or function

  
  <EMI ID = 21.1>

  
  <EMI ID = 22.1>

  
  <EMI ID = 23.1>

  
  <EMI ID = 24.1>

  
Another subject of the present invention is a dry image forming material of the above character, which can give a stable latent image, and which can form a high quality image, not very dependent on the conditions of heat development. .

  
Another subject of the present invention is a

  
  <EMI ID = 25.1>

  
  <EMI ID = 26.1>

  
sensitized but having a high sensitivity and excellent storage stability of the raw material, while being able to form a high quality image.

  
In order to develop dry imaging materials of the character described above, extensive and intensive research was done to find that such materials could be obtained if a

  
  <EMI ID = 27.1>

  
tert-butyl or tert-amyl groups at positions 3′- and

  
  <EMI ID = 28.1>

  
an oxidizing agent with organic silver salt. The current

  
  <EMI ID = 29.1>

  
More particularly, according to the present invention, there is provided a dry image forming material which

  
  <EMI ID = 30.1>
(a) an oxidizing agent with non-photosensitive organic silver salt /
(b) a reducing agent for silver ions, <EMI ID = 31.1>

  
silver halide forming component capable of forming a silver halide component by its reaction with component (a),
(d) a turning agent, <EMI ID = 32.1>

  
  <EMI ID = 33.1>

  

  <EMI ID = 34.1>


  
where R indicates a hydrogen atom, an alkyl group at

  
  <EMI ID = 35.1>

  
carbon atoms, a phenyl group or a halogen atom selected from Cl, Br and I;

  
the component (t) being incorporated into a layer containing the component (a).

  
  <EMI ID = 36.1>

  
of the veil and the preservation of the sensitivity of the

  
  <EMI ID = 37.1>

  
humidities * By the way, in] The or material of

  
  <EMI ID = 38.1>

  
  <EMI ID = 39.1> a layer containing component (b) and, as a material

  
component (e), a high strength acrylic resin

  
impact having an Izod impact resistance (with notch) of at least 0.2136 J / cm when measuring according to the American standard

  
  <EMI ID = 40.1>

  
components (a), (c), (e) and (f), thereby obtaining better stability of the latent image with less variation in image quality with the conditions of heat development.

  
When the dry imaging material

  
  <EMI ID = 41.1>

  
a silver salt of a long chain fatty acid having
16 or more carbon atoms and as component (c), a

  
  <EMI ID = 42.1>

  
  <EMI ID = 43.1>

  
  <EMI ID = 44.1>

  
comprising silver iodide and further comprising (g) a free silver oxidizing agent and (h) a photoreactive halogen oxidizing agent, the imaging material is desirable as being of the post-activation type. The dry imaging material of the post-activation type according to the invention and which has just been mentioned preferably also comprises, in the layer containing the components (a), (c), (e) and F),

  
(i) a cyanine spectral sensitization dye having a unique chemical structure, which acts without sacrificing the storage stability of the raw material in

  
  <EMI ID = 45.1>

  
specific benzotrlazole, so the dry imaging material remains practically useful with increased sensitivity.

  
The cyanine spectral sensitization dye (i) consists of at least one compound chosen from the compounds represented by the formulas which follow:

  

  <EMI ID = 46.1>
 

  
where each X independently indicates a hydrogen atom, a methyl group, a chlorine atom, a phenyl group, a methoxy group or an acetamido group, Y indicates a hydrogen atom, a methyl group or an ethyl group, each Z independently indicates a selenium atom,

  
  <EMI ID = 47.1>

  
independently indicates a selenium atom or a sulfur atom, each A. independently indicates a straight or branched chain alkylene group having 2 to 4 carbon atoms, and M indicates a hydrogen atom,

  
  <EMI ID = 48.1>

  
sodium atom.

  
Those skilled in the art know that it is very difficult to apply the knowledge and technique acquired and the various additives used in the field of photographic materials with silver halide for wet process, in the field of photographic or image-forming materials for dry process, because the two types of materials are quite different by their components and the mechanism of image formation. More particularly, the dry image material of the silver salt type, which is generally heated to a temperature of at least 100 [deg.] C to effect its development, contains an oxidizing agent to the salt of organic silver and a reducing agent required for image development, and

  
a silver halide component or a silver halide forming component as a catalyst, while the silver halide photographic material for wet process does not contain a reducing agent for development. Therefore, in the case of the dry image material of the silver salt type, it is very difficult, due to the presence

  
of the reducing agent, to improve the storage stability of the raw material without sacrificing the sensitivity of the material. It should be noted in particular that the materials forming a dry image of the post-activation type,

  
d which must be capable of being displayed or stored under normal lighting conditions, substantially without undergoing any deterioration in their photographic characteristics

  
  <EMI ID = 49.1>

  
storage and imaging conditions, photographic materials for wet process

  
and even dry imaging materials of the already photosensitive type which are never exposed to light before they are used for imaging. Therefore, it is quite impossible to know,

  
  <EMI ID = 50.1>

  
dry imaging materials of the already photosensitive type may or may not be successfully used in dry imaging materials of the post-activation type. In fact, it is quite natural that such an additive cannot be used in a dry-imaging material of the post-activation type, since the incorporation of the additive in the formation material of a dry image of the poat-activation type quite often results in poor light stability or storage of the raw forming material

  
dry image.

  
  <EMI ID = 51.1>

  
compared to hydroxyl group at position 2 'could improve dry imaging material

  
comprising an oxidizing agent with a non-photosensitive organic silver salt, a reducing agent for silver ions,

  
a silver halide component or a silver halide forming component and a binder, with respect to the storage stability of the raw material in the dark without ultraviolet rays. It is also beyond what you would expect and quite surprising that these

  
  <EMI ID = 52.1> <EMI ID = 53.1>

  
are capable of improving a dry imaging material as mentioned above, with respect to the stability of the raw material which is stored at a light

  
  <EMI ID = 54.1>

  
"In the case of photographic silver halide materials for the wet process and dry imaging materials heat developable of the already photosensitive type, the spectral sensitization dyes commonly used in these Materials do not necessarily have to be stable to light irradiation and heating, as the materials are never exposed to light or heat before use for imaging.

    In fact, unstable spectral sensitization dyes are widely used in materials <EMI ID = 55.1> of spectral sensitization acquired in the field of photographic materials with silver halide to proceed in the wet state and materials for forming a dry image of the type already photosensitive cannot be applied in the area of training materials

  
  <EMI ID = 56.1>

  
results * from the point of view of storage stability of raw materials.

  
For example, as revealed in the patent

  
  <EMI ID = 57.1>

  
spectral awareness in a system comprising a

  
  <EMI ID = 58.1>

  
  <EMI ID = 59.1>

  
photosensitive, can often give an image-forming material to seo of the current photosensitive typa.

  
  <EMI ID = 60.1> "does not have certain photosensitivity until it is

  
  <EMI ID = 61.1>

  
which must be able to be exposed to light before use and be heated beforehand, before

  
  <EMI ID = 62.1>

  
noticeably deterioration of its photographic characteristics and aenometric and without undergoing significant haze formation, a spectral sensitization dye, if incorporated into the material, generally degrades the stability in storage or

  
in the light of the Raw Imaging Material and makes the material more subject. the formation of a veil.

  
Almost all attempts to use, in dry imaging materials of the type to

  
  <EMI ID = 63.1>

  
such as those commonly used in materials

  
  <EMI ID = 64.1>

  
wet and imaging materials

  
  <EMI ID = 65.1>

  
failed, either because spectral sensitization dyes adversely affect the stability of the raw materials resulting from dry imaging

  
  <EMI ID = 66.1>

  
  <EMI ID = 67.1>

  
  <EMI ID = 68.1>

  
decompose or bleach in the materials of

  
  <EMI ID = 69.1>

  
spectral awareness too quickly during storage of raw materials, to allow practical use.

  
  <EMI ID = 70.1>

  
It spectral generally make the resulting materials of image formation more subject area Influences of the halo and / or the irradiation than the materials of formation

  
  <EMI ID = 71.1>

  
a high quality image with high resolution on a spectrally imaging material

  
  <EMI ID = 72.1>

  
the irradiation that is usually necessary for the imaging material. It should be noted that it is very difficult to use, in training materials

  
  <EMI ID = 73.1>

  
preventing the halo and / or irradiation used :. in silver halide photographic materials for wet processing and dry imaging materials of the type already photosensitive because, as described above, the forming materials

  
  <EMI ID = 74.1>

  
it is quite unexpected that specific 2- (2'-hydroxyphenyl) benzotriazoles, unable to absorb light

  
  <EMI ID = 75.1>

  
Incorporated in dry image formation materials of the post-activation type, may contribute to preventing the quality of the images formed on the materials) from decreasing, due to the halo and / or the acquired irradiation produced only when the imaging materials have increased spectral sensitivity to light

  
  <EMI ID = 76.1>

  
  <EMI ID = 77.1>

  
dark or light at wavelengths of

  
  <EMI ID = 78.1>

  
  <EMI ID = 79.1>

  
for example that in training materials a

  
  <EMI ID = 80.1>

  
ffi <EMI ID = 81.1> polymers can be used as a binder of a layer containing a forced reducing agent on a? layer containing an oxidizing agent with silver salt.

  
It was unexpectedly and surprisingly found that a combination of a layer containing an oxidizing agent

  
  <EMI ID = 82.1>

  
specific triazole having a unique chemical structure and a layer containing a reducing agent comprising, as binder material, a high impact acrylic resin having an Izod impact resistance (with

  
  <EMI ID = 83.1>

  
  <EMI ID = 84.1>

  
for forming a dry image having a storage stability of the raw material in the dark or in the light

  
  <EMI ID = 85.1>

  
improved, as well as the stability of a latent image and

  
  <EMI ID = 86.1>

  
according to varying conditions of heat development.

  
A detailed explanation will be given below.

  
  <EMI ID = 87.1>

  
according to the invention.

  
As the non-photosensitive organic silver salt oxidizing agent (a) to be used in the dry imaging material according to the invention, it is possible to

  
  <EMI ID = 88.1>

  
long chain, saccharin or benzotriazole. The silver salts of long chain fatty acids such as silver behenate, silver) stearate,

  
  <EMI ID = 89.1>

  
silver note. Above all, we prefer silver. Bans the or of a material forming a

  
  <EMI ID = 90.1> non-photosensitive organic silver salt oxidizing agent (a) that may be mentioned as preferred examples, silver salts of long-chain fatty acids having 16 or more carbon atoms, such as silver palmitate, silver margarate, silver stearate, silver arachidate,

  
  <EMI ID = 91.1>

  
silver, of which silver behenate is preferred. The organic silver salt oxidizing agent (a) is preferably used in an amount of about 0.1 to about

  
  <EMI ID = 92.1>

  
image forming material according to the invention.

  
As a reducing agent for silver ions to be used as component (b) of the imaging material

  
  <EMI ID = 93.1>

  
organic which has a reduction capacity so suitable that, when heated, it reduces the silver salt of non-photosensitive long chain fatty acid (a), using

  
catalyzing the free silver produced by the silver halide in the exposed portions of the dry imaging material activated to form a visible silver image. Examples of silver ion reducing agents that may be mentioned include monohydroxybenzenes such as p-phenyl-

  
  <EMI ID = 94.1>

  
phenol and 2,5-di-tert-4-methoxyphenol; polyhydroxybenzenes such as hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone and

  
  <EMI ID = 95.1>

  
4-aminonaphthol and 4-methoxynaphthol; hydroxy-

  
  <EMI ID = 96.1> <EMI ID = 97.1>

  
A suitable reducing agent can be chosen depending on the kind of organic silver salt oxidizing agent (a) used in combination with it. Phenols are preferred ... and preferably, pocket phenols where one or two sterically bulky groups are linked to the carbon atom

  
  <EMI ID = 98.1>

  
in the light and therefore their use is effective in ensuring high storage stability of the raw material, in particular in the case of the raw material.

  
  <EMI ID = 99.1>

  
As examples of such hindered phenols, there may be mentioned

  
  <EMI ID = 100.1>

  
butyl-4-methoxyphenol. These reducing agents can be used either alone or in combination. The appropriate amount of the reducing agent is usually between 0.1 and 3 moles per mole of the oxidizing agent to the organic silver salt (a).

  
Component (c) to be used in the dry imaging material according to the invention is a silver halide component or a silver halide forming component capable of forming a halide component of silver by its reaction with the oxidizing agent

  
  <EMI ID = 101.1> of silver halide, silver chloride,

  
silver bromide, silver iodide, silver bromoiodide and silver chlorobromide. They can be used alone or in combination. As is usual in the field of the production of photographic films, one or more silver halides can be formulated

  
  <EMI ID = 102.1>

  
components such as the organic silver salt oxidizing agent, into a composition for forming the coating or image-forming layer of the dry image-forming material as disclosed in the U.S. Patent.

  
  <EMI ID = 103.1>

  
one or more silver halides either in a composition for producing the image-forming coating of the dry imaging material or in the coated image-forming layer of the dry imaging material, by the reaction of a component forming a silver halide (c) with part of the oxidizing agent to the organic silver salt (a), as disclosed in the

  
  <EMI ID = 104.1>

  
silver halide (c) which is used in the last mode mentioned above. and which is a kind of halogenating agent, mention may be made of (i) hydrogen halides; (ii) metal halides; (iii) halogenated molecular species and their complexes (see

  
  <EMI ID = 105.1>

  
  <EMI ID = 106.1>

  
  <EMI ID = 107.1>

  
No. 3,764,329), (v) arylhalomethanes (see U.S. Patent

  
  <EMI ID = 108.1>

  
belonging to Group IV, V or VI of the Periodic Table and having an atomic number of 14 or more (see U.S. patent

  
  <EMI ID = 109.1>

  
organic of an element belonging to Group IV, V or VI of the Periodic Table and having an atomic number of 14 or more with either (iii) a balogenated molecular species or a complex of a halogenated molecular species, or <EMI ID = 110.1>

  
They can be used alone or in combination. As specific examples of the halogenating agent, there may be mentioned compounds respectively represented by the formulas:

  

  <EMI ID = 111.1>


  
In the above formulas, X is bromine or

  
iodine. As other specific examples of the halogenating agent, iodine, bromine, iodine bromide, a complex of triphenyl phosphite and iodine, a complex of p-dioxane and iodine, a complex of p-dioxane and

  
  <EMI ID = 112.1>

  
In these formulas, X is bromine or iodine.

  
The preferred amount of the silver halide component is between 0.001 and 0.5 mole per mole of

  
  <EMI ID = 113.1>

  
stability of raw imaging materials, a silver halide component containing silver iodide and a silver halide component capable of forming a silver halide component <EMI ID = 114.1>

  
In view of the sensitivity of the dry imaging materials, a mixture or mixed crystals of silver iodide with silver chloride or silver bromide is preferred. In the case of the imaging material

  
  <EMI ID = 115.1>

  
halogenants mentioned above in (ili) to (vii).

  
In the case of the imaging material

  
  <EMI ID = 116.1>

  
to be spectrally sensitized, it is preferable that the silver halide component (c) or the silver halide component formed from the silver halide component (c) contains silver iodide. In order for the silver iodide to have a sufficient effect in the context of the invention, it is preferable that the iodide

  
  <EMI ID = 117.1>

  
  <EMI ID = 118.1>

  
The preferable amount of silver iodide is at least

  
  <EMI ID = 119.1>

  
silver. From the sensitivity point of view of the imaging material, it is desirable that the silver halide component contain, in addition to the iodide

  
  <EMI ID = 120.1>

  
silver halide, silver bromide and / or silver chloride component, although the silver halide component may contain only silver iodide,

  
  <EMI ID = 121.1>

  
from the viewpoint of stability of the raw imaging material, it is desirable that the silver halide component contain, in addition to the silver iodide, arming bromide rather than silver chloride. Therefore, the whole silver halide component

  
  <EMI ID = 122.1>

  
In this case, the silver iodide and the silver bromide can be) prou as a mixture or

  
  <EMI ID = 123.1>

  
  <EMI ID = 124.1>

J

  
  <EMI ID = 125.1>

  
  <EMI ID = 126.1>

  
with post-activation which can be spectrally sensitized, the preferred amount of the silver halide component

  
  <EMI ID = 127.1>

  
based on the amount of the organic silver salt oxidizing agent (a). On-site preparation, such as

  
As described above, the silver halide component containing silver iodide is preferred, in which silver iodide and any other silver halide are

  
  <EMI ID = 128.1>

  
long chain (a) and the silver halide component (c). In this case also, the halogenating agents

  
  <EMI ID = 129.1>

  
Among these, those indicated in (111) and (iv) are entirely preferred when considering the stability of the

  
  <EMI ID = 130.1>

  
stability of the raw material, the preferred halogenating agents to form silver iodide are iodine and

  
  <EMI ID = 131.1>

  
iodine coma a complex of triphenyl phosphite and iodine and a complex of p-dioxane and iodine. In the case of

  
  <EMI ID = 132.1>

  
of the silver halide component.

  
The toning agent (d) is used in the present invention to develop a black color in the imaged sones of the material exposed for the formation here: an image.

  
Various known tackifiers can be used. Examples of these toning agents that may be mentioned include phthalazinone and phthalic anhydride (see U.S. patent

  
  <EMI ID = 133.1>

  
  <EMI ID = 134.1>

  
  <EMI ID = 135.1>

  
combinations of phthalic acid or phthalamic acid

  
  <EMI ID = 136.1>

  
combinations of phthalazine with an aromatic acid or

  
  <EMI ID = 137.1>

  
of the toning agent (d) is preferably between 1 and 100% in black, based on the oxidizing agent with organic silver salt (a).

  
The lipophilic binder (e) to be used in the material

  
  <EMI ID = 138.1>

  
capable of dissolving in organic solvents.

  
As binder material, it can be mentioned, for

  
  <EMI ID = 139.1>

  
cellulose acetate, polyvinyl acetate, cellulose acetate propionate, cellulose acetate butyrate,

  
polystyrene, polyvinyl formai and high impact strength acrylic resins

  
  <EMI ID = 140.1>

  
  <EMI ID = 141.1>

  
resistance to choo, which are particularly useful in

  
  <EMI ID = 142.1> above mentioned impact resistance be used in

  
  <EMI ID = 143.1> <EMI ID = 144.1>
(a), it is preferable that the binder is used in an amount such that the weight ratio of the binder to the oxidizing agent to the organic silver is between approximately 0.1 and approximately 10.

  
The use of component (f) constitutes the main characteristic of the present invention, and contributes greatly to the improvement of the stability at

  
  <EMI ID = 145.1>

  
according to the invention. Component (f) is at least one compound chosen from the compounds represented by the formulas (I) and (II) previously mentioned. Compounds having either an alkyl group of 9 or more carbon atoms or an alkoxy group of 5 or more carbon atoms for R in formula (I) or formula (II) are not

  
  <EMI ID = 146.1> <EMI ID = 147.1>

  
  <EMI ID = 148.1>

  
act sufficiently with the organic silver salt oxidizing agent (a) to produce a sufficient effect in the

  
  <EMI ID = 149.1>

  
contained in a layer containing component (a). The

  
  <EMI ID = 150.1>

  
  <EMI ID = 151.1>

  
  <EMI ID = 152.1>

  
organic silver (a). We can cite as examples

  
  <EMI ID = 153.1>

  
rates represented by the following formulas

J

  

  <EMI ID = 154.1>
 

  

  <EMI ID = 155.1>
 

  

  <EMI ID = 156.1>


  
The acrylic resin with high impact resistance, which can be used as binder material for dry imaging material according to the invention, and the use of which is advantageous in particular in the preferred embodiment below. mentioned above of the present invention, may be a mixture of at least one rigid thermoplastic acrylic polymer and at least one polymer having the elasticity of rubber, or at least one copolymer containing acrylic monomer units

  
giving the rigidity and units of monomer giving the elasticity of the rubber, or their combination with at least one rigid thermoplastic acrylic polymer and / or at least one polymer having the elasticity of the rubber.

  
High impact acrylic resin has Izod impact resistance (with notch) of at least

  
1 0.2136 J / cm, usually from 0.267 to 13.35 J / cm and better from 0.267 to 2.67 J / cm, measuring according to the standard

  
  <EMI ID = 157.1>

  
impact strength preferably contains 0.5 to 300 parts by weight, more preferably 5 to 200 parts by weight, of polymer having the elasticity of rubber and / or of monomer units giving elasticity of rubber, per 100 parts in weight of the rigid thermoplastic acrylic polymer and / or the acrylic monomer units giving the rigidity.

  
  <EMI ID = 158.1>

  
which preferably has a weight average molecular weight

  
  <EMI ID = 159.1>

  
be an acrylic homopolymer of an alkyl of 1 to 4 carbon atoms, cyclohexy &#65533; aryl of 6 to 10 carbon atoms, benzyl or tetrahydrofurfuryl ester unsubstituted or substituted with methacrylic acid or an acrylic copolymer comprising monomer units of at least

  
an element chosen from an alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, benzyl or tetrahydrofurfuryl ester substituted or unsubstituted / methacrylic acid, and it is desirable that it has

  
  <EMI ID = 160.1>

  
to M 110. The acrylic copolymer can contain up to

  
  <EMI ID = 161.1>

  
and / or methacrylic acid. The alkyl group,

  
substituted aryl, banzyl or tetrahydrofurfuryl which may be contained in the above-mentioned esters of methacrylic acid may be a group substituted by halogen, nitro, amino, hydroxy or alkoxy of 1 to 4 carbon atoms. Mention may be made, as specific examples, of the ester of methacrylic acid which can form the polymer.

  
  <EMI ID = 162.1>

  
or of the copolymer type usable in acrylic resin

  
  <EMI ID = 163.1>

  
methyl, ethyl methacrylate, cyclohexyl methacrylate, tert-butyl methacrylate, methacrylate <EMI ID = 164.1>

  
As a polymer having the elasticity of rubber which can advantageously be used for mixing with the rigid thermoplastic acrylic polymer or a

  
  <EMI ID = 165.1>

  
acrylic monomer giving the rigidity and units of a monomer giving the elasticity of the rubber to form the acrylic resin with high impact resistance, one can

  
  <EMI ID = 166.1>

  
butadiene, ethylene-vinyl acetate copolymers, polyacrylates and the like. It is desirable that the polymer having the elasticity of rubber have a

  
  <EMI ID = 167.1>

  
having the elasticity of rubber. Polyacrylates having the elasticity of rubber preferably comprise at least

  
  <EMI ID = 168.1>

  
  <EMI ID = 169.1>

  
carbon atoms, unsubstituted or substituted, of acrylic acid, or at least 80% by weight and better still at least 90% by weight of units of a monomer of at least one alkyl ester

  
  <EMI ID = 170.1>

  
  <EMI ID = 171.1>

  
specified amount of the monomer units of this alkyl ester of methacrylic acid can be lowered if this alkyl ester of methacrylic acid is used in combination with the alkyl ester of acrylic acid).

  
  <EMI ID = 172.1>

  
the above ester of acrylic acid or acid

  
  <EMI ID = 173.1> <EMI ID = 174.1>

  
isobutyl acrylate, 2-hydroxypropyl acrylate, diethylaminoethyl acrylate and sodium acrylate

  
  <EMI ID = 175.1>

  
that of the alkyl ester of 7 to 22 carbon atoms, unsubstituted or substituted, of methacrylic acid, 2-ethylhexyl methacrylate, lauryl methacrylate,

  
  <EMI ID = 176.1>

  
The polyacrylate having the elasticity of the rubber may contain other monomer units chosen from units of at least one alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, benzyl or tetrahydrofurfuryl ester substituted or not -substituted acid

  
  <EMI ID = 177.1>

  
  <EMI ID = 178.1>

  
vinylbenzene, acrylonitrile monomer units, vinyl acetate monomer units, acrylic acid monomer units, maleic acid or anhydride monomer units and the like. It is preferable that the polyacrylate having the elasticity of the rubber be

  
  <EMI ID = 179.1>

  
  <EMI ID = 180.1>

  
a crosslinkable monomer chosen from divinylbenzene, ethylene glycol diacrylate, dimethacrylate

  
  <EMI ID = 181.1>

  
d the rigidity of at least one ester of methacrylic acid as mentioned above and which can form the rigid thermoplastic acrylic polymer of the homo- type

  
  <EMI ID = 182.1>

  
monomer units giving rigidity, units of a monomer giving the elasticity of the rubber or the flexibility of at least one element chosen from alkyls

  
  <EMI ID = 183.1>

  
carbon of acrylic acid and substituted or unsubstituted alkyl esters of 7 to 22 carbon atoms of methacrylic acid, mentioned previously as being able to form the polyacrylate having the elasticity of rubber.

  
The high impact acrylic resin can also be a resin prepared by polymerization, in the presence of at least one copolymer comprising monomer units giving rigidity and monomer units giving flexibility of the above-mentioned kinds <EMI ID = 184.1> methacrylic as mentioned above as being able to form a thermoplastic acrylic polymer

  
  <EMI ID = 185.1>

  
high impact acrylic may include a block or graft copolymer although there remains a possibility that the resin is a simple mixture of this copolymer and / or of this polymer giving the elasticity of rubber with a polymer formed from this ester of acid. methacrylic.

  
A monomer or monomers which can copolymerize with an ester of methacrylic acid, which can

  
be chosen, for example, from vinyl acetate,

  
  <EMI ID = 186.1>

  
partially the methacrylic acid ester (s) previously mentioned as being able to form a polymer

  
  <EMI ID = 187.1>

  
The high impact acrylic resin, which can be either of the mixed type or of the copolymer type or the combination of the two as described above, should advantageously contain at least 50 parts by weight, preferably 80 parts by weight of the ester component

  
  <EMI ID = 188.1>

  
indicate all the monomer units of the acrylic and / or methacrylic ester type contained in the polymer or polymers constituting the acrylic resin.

  
For the measurement of a weight average molecular weight, a gel infiltration chromatography (GPC) method can be adopted, using, as standard samples, polystyrenes manufactured by Pressure Chemical Co., E.U.A. and as a device, WATERS 200 manufactured by Japan-Vaters Co., Japan.

  
  <EMI ID = 189.1>

  
according to the invention as well as the formula of the resin

  
  <EMI ID = 190.1>

  
4,180,529, 4,052,525 and 3,681,475.

  
Additives of various kinds, if desired

  
such as a lubricant, an antioxidant, an ultraviolet absorbing agent and a color can be

  
  <EMI ID = 191.1>

  
free silver oxidizing agent which can be used as a component: (g) in the forming material

  
  <EMI ID = 192.1>

  
during the storage of the material, in order to thus contribute

  
  <EMI ID = 193.1>

J

  
divalent palladium compounds (Fd ++) and sulfinic acid compounds. As examples of mercury compounds

  
  <EMI ID = 194.1>

  
aliphatic carboxyls such as mercuric acetate and mercuric behenate; mercuric sela of aromatic carboxylic acids such as mercuric benzoate, mercuric m-methylbenzoate and mercuric acetamidobenzoate; mercuric halides such as bromide

  
  <EMI ID = 195.1>

  
mercuric, mercuric bromide and mercuric iodide.

  
As examples of the trivalent iron compounds, one can

  
  <EMI ID = 196.1>

  
and a complex of trivalent iron and bipyridyl. As examples of the trivalent cobalt compounds, there may be mentioned a complex of trivalent cobalt and acetylacetone and a complex of trivalent cobalt and o-phenanthrolina, and cobalt halides such as cobalt iodide and cobalt bromide. Examples of divalent palladium compounds include a complex of divalent palladium and acetylacetone, and palladium (II) halides such as palladium iodide
(II) and palladium bromide (II). As examples of

  
compounds of tallow acid "we can mention the acid

  
  <EMI ID = 197.1>

  
component (g), divalent mercury compounds are used. The preferred amount of component (g) is

  
  <EMI ID = 198.1>

  
the oxidizing agent with organic silver salt (a).

  
Note that component (g) can also

  
  <EMI ID = 199.1>

  
for forming a dry image according to the present invention, which is even of the type other than the post-activation type which can be spectrally sensitized.

  
In the case of the imaging material

  
dry type post-activation according to the invention which is preferably spectrally sensitized, the oxidizing agent free silver (g) is reduced by serving. oxidize the free silver produced during storage of the raw material forming an original silver halide image.

  
The oxidizing agent thus reduced free silver is in turn oxidized under lighting conditions, by the action of

  
  <EMI ID = 200.1>

  
effectively returned to its original state where component (g) has the capacity to oxidize free silver. The photoreactive halogen-oxidizing agent (h) which can advantageously be used in combination with the component (g) in particular in the case of the dry imaging material

  
of the post-activation type which can advantageously be spectrally sensitized is a halogen compound which can produce halogen free radicals upon exposure to light. As preferred examples of such a halogen compound, mention may be made of halogenated organic compounds having bromine-and / or iodine-carbon bonds.

  
It can be determined, for example by the following photoreaction test, whether or not a given halogen compound is suitable as component (h) in the present invention.

  
One mole of silver behenate is dissolved [as silver behenate is appropriate a behenate synthesized in a mixed solvent (1: 5-5: 1 by volume) of water and at least one alcohol soluble or partially soluble in

  
  <EMI ID = 201.1>

  
polyvinyl butyral and 0.25 mole of the halogen compound given for use as a "photoreactive halogen-oxidizing agent in a mixed solvent (2: 1 by weight) of methyl ethyl ketone and toluene, and then formed into a film according to a process ordinary casting.

  
The film thus formed is examined with respect to the following two conditions. When the film satisfies the two conditions, the halo compound (to be used as a photoreactive oxidizing agent) used is suitable in the context of the invention.

  
Condition 1: when the film is examined by .1 <EMI ID = 202.1>

  
relative of this peak is less than about 10 when the relative intensity of the peak due to silver behenate

  
  <EMI ID = 203.1>

  
Condition 2: subsequently, the film is irradiated with light (0.5 mV / cm) emitted from a black lamp in an atmosphere at a temperature of 50 ° C. and a

  
  <EMI ID = 204.1>

  
re-examine by X-ray diffractometry. We must appreciably observe the crest due to silver bromide

  
  <EMI ID = 205.1>

  
[the relative intensity of this peak is of the order of 10 or more when the relative intensity of the peak due to

  
  <EMI ID = 206.1>

  
  <EMI ID = 207.1>

  
  <EMI ID = 208.1>

  
  <EMI ID = 209.1>

  
X-ray diffractometry, we use a Rotor Unit type device (type RU-200 PL) manufactured and sold by

  
  <EMI ID = 210.1>

  
Mention may be made, as specific examples, of halogen compounds which can be used as an agent.

  
  <EMI ID = 211.1> <EMI ID = 212.1>

  
They can be used either alone or in combination. Among them, bromo compounds are preferred since they give little coloration and improve the stability of the raw material resulting from the formation of a dry image. We prefer

  
  <EMI ID = 213.1>

  
the photoreactive halogen-oxidizing agent (h) is preferably

  
  <EMI ID = 214.1>

  
with organic silver salt (a).

  
It is desirable in the present invention to employ the photoreactive halogen-oxidizing agent (h) even in the dry imaging material of the post-activation type which is not spectrally sensitized, from the viewpoint of stability to storage of raw material.

  
The spectral sensitization dye (i) which can advantageously be used in the material of

  
  <EMI ID = 215.1>

  
according to the invention consists of at least one compound chosen from those represented by the formulas (III), (IV). (V) and (VI) mentioned above, where A is preferably a straight chain propylene group in the context of the present invention. The preferred quantity of the component (i)

  
  <EMI ID = 216.1>

  
oxidizer with organic silver salt (a). The dye of

  
  <EMI ID = 217.1>

  
case, be used in the dry imaging material of the type already photosensitive according to the present invention. Mention may be made, as specific examples, of coloring spectral sensitization compounds which can be used

  
  <EMI ID = 218.1>

  

  <EMI ID = 219.1>
 

  

  <EMI ID = 220.1>
 

  

  <EMI ID = 221.1>
 

  

  <EMI ID = 222.1>
 

  

  <EMI ID = 223.1>
 

  

  <EMI ID = 224.1>
 

  

  <EMI ID = 225.1>
 

  

  <EMI ID = 226.1>
 

  

  <EMI ID = 227.1>
 

  

  <EMI ID = 228.1>
 

  

  <EMI ID = 229.1>
 

  

  <EMI ID = 230.1>


  
If desired, 9 a *

  
  <EMI ID = 231.1>
  <EMI ID = 232.1>
  <EMI ID = 233.1>

  
straight or branched chain alkyl of 1 to 10 carbon atoms, an alkoxyl group of 1 to 4 carbon atoms, an aralkyl group selected from benzyl groups

  
  <EMI ID = 234.1>

  
methoxy or halogen, hydroxyl group, cyano group, carboxyl group, alkoxy carbonyl group of 2 to 5 carbon atoms, nitro group, amino group or carbamoyl group, and D is hydrogen , a hydroxyl group or an amino group; and 3-pyrazoline-5-one compounds as disclosed in the patent

  
  <EMI ID = 235.1>

  
following :

  

  <EMI ID = 236.1>


  
  <EMI ID = 237.1>

  
straight or branched chain of 1 to carbon atoms, an unsubstituted or substituted phenyl group or a cycloalkyl group of 3 to 8 unsubstituted carbon atoms or

  
  <EMI ID = 238.1>

  
branched from 1 to 5 carbon atoms, a phenyl group

  
  <EMI ID = 239.1>

  
unsubstituted or substituted or a cycloalkyl group of 3 to 8 carbon atoms unsubstituted or substituted and

  
  <EMI ID = 240.1>

  
represents a hydrogen atom, a straight or branched chain alkyl group of 1 to 5 carbon atoms, an unsubstituted or substituted phenyl group or an unsubstituted or substituted phenylalkyl group having a straight or branched chain alkyl moiety having from 1 to 5 carbon atoms. It can be used either alone or in combination

  
  <EMI ID = 241.1>

  
based on the organic silver salt oxidizing agent
(at). Mention may be made, as specific examples of 3-pyrazoline-5-one compounds, of 2-phenyl-3-pyrazoline-5-one, <EMI ID = 242.1>

  
pyrazoline-5-one, 2-o-tolyl-3-methyl-4-ethyl-3pyrazoline-5-one, 2-cyclohexyl-3-pyrazoline-5-one,

  
  <EMI ID = 243.1>

  
The preferred method for preparing the dry imaging material according to the invention will be described by way of example as follows. An organic silver salt oxidizing agent is dispersed in a solution of a polymer to form a binder by means of a ball mill, a homogenizer, a mixer, a sand mill or the like. To the resulting dispersion, the other essential components and possibly various additives are added. The composition thus obtained is applied to a support such as plastic film, glass plate, paper or metal plate, and then dried to prepare a dry imaging material.

   As the plastic film, there may be mentioned a polyethylene film, a cellulose acetate film, a polyethylene terephthalate film, a polyamide film, a polypropylene film and the like. The dry thickness of the coating as a layer for forming

  
  <EMI ID = 244.1>

  
The essential components of the imaging material according to the invention can be applied either in one layer as described above or in two or more separate adjacent layers Rais. For the protection of the layer forming an image which can be developed by heat and so on, an upper layer or above can be provided. The material for the top layer <EMI ID = 245.1> as mentioned above. In the case of the post-activation type dry imaging material, the preparation, application to a support and subsequent drying of one or more compositions containing the essential components can be carried out even in a room lit, but preferably at a temperature of 50 ° C or less.

  
When the sheet material thus prepared is

  
of the already photosensitive type, it can form a visible image there when it is subjected to an exposure for forming an image to light and to a development with heat which is usually undertaken at a temperature of the order of 90 to 150 'C for about 1 to 30 seconds.

  
When the sheet material is of the postactivation type, it does not lose its ability to form an image even if it is stored under normal lighting conditions and it can be handled in a lighted room. When a given area of this sheet material is heated in the dark, that area is made photosensitive. This preliminary heating is preferably carried out at a temperature of the order of 90 to approximately

  
  <EMI ID = 246.1>

  
the heating time can be shortened proportionally. When the area made photosensitive by heating is exposed to light to form an image and is then

  
  <EMI ID = 247.1>

  
1 It is preferable that heat development be

  
  <EMI ID = 248.1>

  
150 * C. The duration of heating in the preliminary heating or heat development stage can be controlled between about 1 and about 30 seconds. When preliminary heating to make the material photosensitive and heat development are undertaken

  
  <EMI ID = 249.1>

  
the heat is generally equal to or greater than the time for the preliminary heating. In the image-forming material according to the invention, a visible isiage can be selectively recorded on a given area, and

  
  <EMI ID = 250.1>

  
entry to another area as necessary. Furthermore, the image forming material according to the invention makes it possible to form an image by even photographing a colored manuscript.

  
The examples which follow illustrate the present invention in more detail but must in no case limit the scope thereof. In the following examples and comparison examples, the relative sensitivity, the

  
  <EMI ID = 251.1>

  
Dry imaging techniques are evaluated as follows.

  
The sensitivity of a dry imaging material is defined as being the inverse of the amount of exposure light it takes to

  
  <EMI ID = 252.1>

  
the minimum optical density (O.D. min) of the dry imaging material. Relative sensitivity (R.S.) is given here in terms of the proportion of the sensitivity of the dry imaging material to the sensitivity of a given imaging material. dry whose relative sensitivity is defined

  
as being 100.

  
The sensitivity conservation is given here in terms of the proportion of the sensitivity of the dry imaging material subjected to a <EMI ID = 253.1>

  
of the corresponding imaging material to

  
  <EMI ID = 254.1>

  
photographic characteristic curve of an aged material, as being an optical density (O.D.) obtained by the quantity of exposure light * 0.4 interior,

  
  <EMI ID = 255.1>

  
  <EMI ID = 256.1>

  
  <EMI ID = 257.1>

  
The sharper the image and therefore the better its quality, the lower the value of

  
  <EMI ID = 258.1>

  
  <EMI ID = 259.1>

  
ethyl ketone (mixture weight ratio - 1: 2), we have

  
  <EMI ID = 260.1>

  
  <EMI ID = 261.1>

  
homogeneous sion of silver behenate.

  
A silver behenate emulsion having the formula

  
  <EMI ID = 262.1>

  
  <EMI ID = 263.1>

  
  <EMI ID = 264.1>

  
first layer of coating. A solution containing a

  
  <EMI ID = 265.1>

  
was uniformly applied as a second coating layer on the first coating layer, at a 75 p orifice, and dried with air heated to 80 [deg.] C for 5 minutes to obtain a material for forming a dry image of type already photosensitive

  
  <EMI ID = 266.1>

  
  <EMI ID = 267.1>

  
dry imaging was performed in the dark.

  
  <EMI ID = 268.1>

  

  <EMI ID = 269.1>


  
  <EMI ID = 270.1>
  <EMI ID = 271.1>
 a comparison dry imaging material was prepared in substantially the same manner

  
  <EMI ID = 272.1>

  
  <EMI ID = 273.1>

  
A piece of each dry imaging material was exposed in a dark room for 1/8

  
  <EMI ID = 274.1>

  
very close to the material, to the light emitted by a 500 watt Toshiba Photoreflector lamp (trade name of a tungsten lamp manufactured by Tokyo Shibaura Electric Company Ltd, Japan), and then was heated for 4 seconds on a hot plate maintained at 120 [deg.] C in a dark room to carry out heat development.

  
Another piece of each material forming a

  
  <EMI ID = 275.1>

  
  <EMI ID = 276.1>

  
at the same image formation as that described above.

  
The optical densities of the imaged materials respectively derived from the materials before and after having subjected them to the accelerated deterioration test were measured. The results evaluated in terms of veil formation, relative sensitivity and conservation of sensitivity

  
  <EMI ID = 277.1>

  
seed lignification), and where the standard material with a relative sensitivity of 100 is that of the example of

  
  <EMI ID = 278.1>
  <EMI ID = 279.1>
  <EMI ID = 280.1>
 The comparison compounds (C1) to (C5) used here are mentioned below.

  

  <EMI ID = 281.1>
 

  
As is apparent from the results indicated

  
  <EMI ID = 282.1>

  
triazole (f1), (f2), (f6) and (f7) used in the materials for forming a dry image according to the invention, are

  
far superior, by their effect of improving the stability on storage, to the compounds (C1) to (C5) used in the materials for forming a dry comparison image.

  
A dry imaging material was prepared in substantially the same manner as in each of the

  
  <EMI ID = 283.1>

  
using 11 mg of silver bromide previously prepared instead of 12 mg of tetraethylammonium bromide. For each dry imaging material, the results evaluated in terms of haze formation, relative sensitivity and sensitivity retention were substantially the same as those obtained for the material.

  
  <EMI ID = 284.1>

  
corresponding comparison example.

Examples 5 to 7 and comparison examples 7 to 10.

  
A homogeneous suspension of silver laurate was prepared in the same way as for the preparation of the suspension of silver behenate of Examples 1 to 4 and Comparative Examples 1 to 6.

  
A dry imaging material of the already photosensitive type was prepared in substantially the same manner as in Examples 1 to 4 but using the formulas

  
  <EMI ID = 285.1>

  
  <EMI ID = 286.1>

  

  <EMI ID = 287.1>
 

  
  <EMI ID = 288.1>

  

  <EMI ID = 289.1>


  
  <EMI ID = 290.1>

  

  <EMI ID = 291.1>


  
A comparison dry imaging material was prepared in substantially the same manner as described above but omitting the use of the 2- (2'-hydroxyphenyl) benzotriazole compound or using a comparison compound shown in Table 2 instead of

  
  <EMI ID = 292.1>

  
One piece of each dry imaging material was subjected to the same imaging as in Examples 1 to 4 and Comparison Examples 1 to 6. Another piece of the imaging material was sec was subjected to the same accelerated deterioration test as in Examples 1 to 4 and Comparison Examples 1 to 6, and was subjected to the same imaging as in Examples 1 to 4 and Comparison Examples 1 to 6 .

  
Relative sensitivity, haze formation and

  
the preservation of the sensitivity of the dry image forming material was examined, and appeared to be as indicated in Table 2, where the standard material having a relative sensitivity of 100 is that of the example of comparison 7.

  
/
  <EMI ID = 293.1>
  <EMI ID = 294.1>
   <EMI ID = 295.1>

  
are mentioned below:

  

  <EMI ID = 296.1>


  
As is apparent from the results of the table

  
  <EMI ID = 297.1>

  
  <EMI ID = 298.1>

  
dry storage of raw imaging materials.

  
  <EMI ID = 299.1>

  
A silver behenate emulsion having the formula CE] Indicated below, where the suspension of silver behenate had been prepared in the same manner as in

  
  <EMI ID = 300.1> .suspension of silver behenate "appearing below <EMI ID = 301.1>

  
  <EMI ID = 302.1>

  
of silver was evenly applied on film

  
  <EMI ID = 303.1>

  
  <EMI ID = 304.1>

  
first layer of coating.

  
A composition contained a reducing agent having the

  
  <EMI ID = 305.1> room temperature (about 20 [deg.] C) for 5 hours to obtain a dry imaging material of the post-activation type having a total thickness of

  
  <EMI ID = 306.1>

  
dry imaging material was undertaken in a lighted room.

  
  <EMI ID = 307.1>

  

  <EMI ID = 308.1>


  
  <EMI ID = 309.1>

  
comparison was prepared in much the same way as described above, but omitting the use

  
  <EMI ID = 310.1>

  
second through a film forming a mask in very close contact with the material, to the light emitted from <EMI ID = 311.1>

  
exposed was then heated for 5 seconds on a hot plate kept at around 120 [deg.] C in a dark room to carry out the development with heat.

  
Another piece of each dry imaging material was subjected to the same accelerated deterioration test (heat and humidity acceleration) as in Examples 1 to 4 and Comparison Examples 1 to 6, with then the same image formation as that described above.

  
In order to examine the light stability of the raw material, another piece of each dry imaging material was subjected to an accelerated deterioration test (light fadeometer acceleration)

  
at 40 [deg.] C for 2 hours under a light of 200,000 lux

  
using an FX-1 fadeometer (trade name of a xenon lamp fadeometer manufactured by Suga Shikenki K.K. Japan) with then the same imaging as

  
  <EMI ID = 312.1>

  
  <EMI ID = 313.1>

  
of the FX-1 fadeometer and filtered by a VY-45 filter
(trade name of a color filter, manufactured and sold by Tokyo Shi baura Electric Company Ltd, Japan),

  
  <EMI ID = 314.1>

  
  <EMI ID = 315.1>

  
  <EMI ID = 316.1>

  
the one described above.

  
The relative sensitivity, the formation of the haze and the conservation of the sensitivity of each material have

  
  <EMI ID = 317.1>

  
  <EMI ID = 318.1>

  
relative of 100 is that of comparison example 11.

  

  <EMI ID = 319.1>


  

  <EMI ID = 320.1>
 

  

  <EMI ID = 321.1>


  

  <EMI ID = 322.1>
 

  
  <EMI ID = 323.1>

  
used here, which are the known ultraviolet absorbing agents, are mentioned below. The comparison compound (C5) is also the known ultraviolet absorbing agent.

  

  <EMI ID = 324.1>


  
As is apparent from reading the results

  
from Table 3, the 2- (2'-hydroxyphenyl) benzotriazole compounds (f4), (f6) and (f9) having tert-butyl or tert-amyl groups at the 3 'and 5' positions are very effective in improving the stability of the dry dry imaging materials during storage, either under heat and humidity or under lighting conditions, compared to known ultraviolet absorbing agents.

  
The fact that the 2- (2'-hydroxyphenyl) benzotriazole compounds (f4), (f6) and (f9) are capable of absorbing only light having wavelengths less than 400 nm may indicate that l The improvement in the light stability of the raw material obtained in the present invention cannot be attributed to the function of component (f) as an ultraviolet absorbing agent.

  
Examples 11 to 1 &#65533; and comparison examples 16 to 23.

  
A post-activation type dry imaging material was prepared in substantially the same manner as in Examples 8-10 and Comparison Examples

  
  <EMI ID = 325.1>

  
  <EMI ID = 326.1>

  

  <EMI ID = 327.1>


  
Formula Le]

  

  <EMI ID = 328.1>


  
A dry imaging material of the comparison post-activation type was prepared in substantially the same manner as described above but in

  
  <EMI ID = 329.1>

  
benzotriazole or using a comparison compound

  
v <EMI ID = 330.1>

  
Relative sensitivity, haze formation and

  
the preservation of the sensitivity of each dry imaging material was examined in the same manner as in Examples 8-10 and Comparison Examples
11 to 15 and have been found to be as illustrated in table 4, where the standard material having a relative sensitivity of 100 is that of comparison example 16.

  
/
  <EMI ID = 331.1>
  <EMI ID = 332.1>
 
  <EMI ID = 333.1>
  <EMI ID = 334.1>
 The comparison compound (C11) used here is mentioned below:

  

  <EMI ID = 335.1>


  
As is apparent from the results in Table 4, the use of the 2- (2'-hydroxy-

  
  <EMI ID = 336.1>

  
tert-butyl or tert-amyl groups at positions 3'- and 5 is very effective in improving the stability of dry imaging materials during storage either under heat and humidity or under conditions lighting. Improvement of the light stability of the raw materials obtained by incorporating one

  
  <EMI ID = 337.1>

  
which can only absorb light with wavelengths less than 400 nm.

  
Comparison example 24.

  
Dry imaging material was prepared in substantially the same manner as in Examples 1 to 4

  
  <EMI ID = 338.1>

  
  <EMI ID = 339.1>

  
The material thus obtained. been subjected to the same image formation as in examples 1 to 4 and comparison examples 1 to 6, The material could not form an image because it had

  
  <EMI ID = 340.1>

  
so that in examples 1 to 4 malt using the .0 <EMI ID = 341.1>

  
Thread formula

  

  <EMI ID = 342.1>


  
  <EMI ID = 343.1>

  

  <EMI ID = 344.1>


  
Comparison dry image-forming material was prepared substantially in the marl as described above but omitting the use of the

  
  <EMI ID = 345.1>

  
  <EMI ID = 346.1>

  
Another piece of each material forming a

  
  <EMI ID = 347.1>

  
  <EMI ID = 348.1>

  
  <EMI ID = 349.1>

  
  <EMI ID = 350.1>

  
  <EMI ID = 351.1>

  

  <EMI ID = 352.1>


  

  <EMI ID = 353.1>
 

  

  <EMI ID = 354.1>


  

  <EMI ID = 355.1>
 

  
The acrylic resin (AR-e) was a mixture of polymethyl methacrylate and 40% by weight, based on polymethyl methacrylate, of a partially crosslinked copolymer and having the elasticity of the rubber obtained by emulsion polymerization catalyzed with potassium persulfate, in water at 65 [deg.] C for 2 hours, of a

  
  <EMI ID = 356.1>

  
  <EMI ID = 357.1>

  
by weight of methyl methacrylate and 20% by weight of n-butyl acrylate.

  
The acrylic resin (AR-c) was a 2: 1 mixture

  
by weight of the above-mentioned acrylic resin (AR-a) and of polymethyl methacrylate.

  
As is apparent from the results of Tables 5 and 6, the dry imaging materials according to a preferred embodiment of the invention, which comprise a first coating layer containing a silver salt oxidizing agent organic containing any of

  
  <EMI ID = 358.1>

  
(f6) and (f7), and a second coating layer containing a reducing agent which contains, as binder, an acrylic resin with high impact resistance chosen from acrylic resins (AR-a), (AR-b) and ( AR-c), are greater

  
  <EMI ID = 359.1>

  
before deterioration, and by the storage stability of the raw material evaluated in terms of the degree of formation of the

  
  <EMI ID = 360.1>

  
dry imaging materials according to the present invention comprising a first coating layer containing an organic silver salt oxidizing agent containing one of the 2- (2'-hydroxyphenyl) benzotriazole (f1) compounds, ( f2) and (f6), and a second coating layer containing a reducing agent containing, like Liant, a polymer other than acrylic resin with high resistance to. shock. However, these latter materials were superior, in the same respects as those mentioned above, to dry imaging materials

  
sheet comprising a first coating layer containing an oxidizing agent with an organic silver salt not containing a 2- (2'-hydroxyphenyl) benzotriazole compound and not containing a comparison compound
(C1) to (C5) or containing only one, and a second coating layer containing a reducing agent containing, as binder, an acrylic resin with high impact resistance

  
  <EMI ID = 361.1>

  
(AR-c) or a polymer of another kind.

  
Examples 30 to 35 and comparison examples 36 to 37.

  
A homogeneous suspension of silver laurate was

  
  <EMI ID = 362.1>

  
silver behenate suspension from Examples 1 to 4 and Comparison Examples 1 to 6.

  
A dry imaging material of the already photosensitive type was prepared in substantially the same manner as in Examples 1 to 4 but using the formulas

  
  <EMI ID = 363.1>

  
  <EMI ID = 364.1>

  
  <EMI ID = 365.1>

  

  <EMI ID = 366.1>


  
  <EMI ID = 367.1>

  

  <EMI ID = 368.1>
 

  

  <EMI ID = 369.1>


  
A comparison dry imaging material was prepared in substantially the same manner as described above, but omitting the use of the 2- (2'-hydroxyphenyl) benzotriazole compound.

  
A piece of each dry imaging material was subjected to the same imaging as in Examples 1 to 4 and Comparison Examples 1 to 6.

  
Another piece of each dry imaging material was subjected to the same accelerated deterioration test or examples 15 to 29 and comparison examples 25 to 35, and was subjected to the same imaging

  
  <EMI ID = 370.1>

  
Dry imaging before and after deterioration were examined, and are as shown in Table 7.

  

  <EMI ID = 371.1>


  

  <EMI ID = 372.1>
 

  
  <EMI ID = 373.1>

  
obtained by subjecting a mixture of 90 parts by weight of n-butyl acrylate, 10 parts by weight of methyl methacrylate and 0.6 parts by weight of cyanurate

  
from triallyl to catalyzed emulsion polymerization

  
  <EMI ID = 374.1>

  
hours under a nitrogen atmosphere to prepare a latex

  
  <EMI ID = 375.1>

  
crosslinked and subsequently subjecting to a mixture of 30.3 parts by weight of the crosslinked acrylic elastomer latex, 6 parts by weight of acrylonitrile, 12 parts by weight of styrene, 12 parts by weight of methyl methacrylate and 0.3 parts by weight of ethylene glycol dimethacrylate to a per-catalyzed emulsion polymerization

  
  <EMI ID = 376.1>

  
As is apparent from the results in Table 7, the dry imaging materials according to a preferred embodiment of the invention, which comprise a first coating layer containing an oxidizing agent containing organic silver salt one of the compounds

  
  <EMI ID = 377.1>

  
and a second coating layer containing a reducing agent containing the acrylic resin. high impact resistance (AR-d) as a binder, are superior in quality

  
  <EMI ID = 378.1> dry imaging materials according to the present invention, comprising a first coating layer containing an oxidizing agent with organic silver salt containing one of 2- (2'-hydroxyphenyl) compotes ) benzo-

  
  <EMI ID = 379.1> comparison dry image forming materials comprising a first coating layer containing an agent, organic silver salt oxidant not containing

  
  <EMI ID = 380.1>

  
second coating layer containing a reducing agent containing, as a binder, acrylic resin (AR-d) or

  
polymethyl methacrylate.

  
Examples 36 to 41 and comparison examples 38 to 43.

  
A dry-type imaging material of the type

  
post-activation was prepared in much the same way as in Examples 8 to 10 but using the formulas

  
  <EMI ID = 381.1>

  
respectively.

  
Will formulate

  

  <EMI ID = 382.1>


  
  <EMI ID = 383.1>

  

  <EMI ID = 384.1>


  
  <EMI ID = 385.1> a comparison compound Indicated in table 8 instead of

  
  <EMI ID = 386.1>

  
A piece of each dry imaging material was subjected to the same imaging as in Examples 8-10 and Comparison Examples 11-15.

  
Another piece of each dry imaging material was subjected to the same accelerated deterioration test (heat and humidity acceleration) as in Examples 15 to 29 and Comparison Examples 25 to 35,

  
  <EMI ID = 387.1>

  
to 10 and comparison examples 11 to 15.

  
In order to examine the light stability of the raw material, another piece of each dry imaging material was subjected to an accelerated deterioration test (filtered light acceleration) carried out in

  
  <EMI ID = 388.1>

  
for 2 hours, the material in the light emitted from the FX-1 fadeometer and filtered by the VY-45 filter, does not

  
  <EMI ID = 389.1>

  
or more to pass. The material thus deteriorated was subjected to the same image formation as in Examples 8 to 10 and Comparison Examples 11 to 15.

  
  <EMI ID = 390.1>

  
images have been measured, and are as shown in Table 8.

  

  <EMI ID = 391.1>


  

  <EMI ID = 392.1>
 

  

  <EMI ID = 393.1>


  

  <EMI ID = 394.1>
 

  
Acrylic resin (AR-e) was a polymer

  
obtained by subjecting a mixture of 61.5 parts by weight of n-butyl acrylate, 13.5 parts by weight of styrene and 0.4 parts by weight of butylene glycol diacrylate to an emulsion polymerization catalyzed with

  
  <EMI ID = 395.1>

  
to prepare a copolymer, by polymerizing at 70 [deg.] C for one hour, 25 parts by weight of methyl methacrylate in the presence of this copolymer in order to prepare a rubbery elastomer and subsequently subjecting a dispersion

  
in a mixture of monomers composed of 96% by weight of

  
  <EMI ID = 396.1>

  
  <EMI ID = 397.1>

  
1 hour .

  
The comparison compound (C12) used here is mentioned below.

  

  <EMI ID = 398.1>


  
As is apparent from the results of the table

  
  <EMI ID = 399.1>

  
of the invention, comprising a first coating layer containing an organic silver salt oxidizing agent containing one of the compounds of

  
  <EMI ID = 400.1>

  
  <EMI ID = 401.1>

  
containing high impact strength acrylic resin (AR-e) as a binder, were superior in quality

  
  <EMI ID = 402.1>

  
deterioration and the storage stability of the raw material evaluated in terms of the degree of haze formation

  
  <EMI ID = 403.1> heat and humidity or acceleration in filtered light), imaging materials

  
dry according to the invention, comprising a first coating layer containing an organic silver salt oxidizing agent containing one of the 2- (2'-hydroxyphenyl) compounds -

  
  <EMI ID = 404.1>

  
coating containing a reducing agent containing cellulose acetate as a binding agent. However, the latter materials were superior, on the same points as those mentioned above, to the comparison dry imaging materials comprising a first coating layer containing an oxidizing agent to the silver salt

  
  <EMI ID = 405.1>

  
phenyl) benzotriazole and no comparison compound

  
  <EMI ID = 406.1>

  
coating layer containing a reducing agent containing,

  
  <EMI ID = 407.1>

  
absorb only light with wavelengths

  
  <EMI ID = 408.1>

  
  <EMI ID = 409.1>

  
in the present invention is not to be attributed to the function of the compound (f) as an ultraviolet absorbing agent.

  
  <EMI ID = 410.1>

  
An already photosensitive dry imaging material was prepared in substantially the same manner

  
  <EMI ID = 411.1>

  
  <EMI ID = 412.1>

  
respectively .

  
  <EMI ID = 413.1>

  

  <EMI ID = 414.1>
 

  

  <EMI ID = 415.1>


  
  <EMI ID = 416.1>

  

  <EMI ID = 417.1>


  
A comparison dry imaging material was prepared in substantially the same manner as described above but omitting the use of the compound

  
  <EMI ID = 418.1>

  
tion of the image as in Examples 1 to 4 and Comparison Examples 1 to 6 but by modifying the development temperatures as indicated in Table 9.

  
  <EMI ID = 419.1>

  
imaged materials have been examined, and are as shown in Table 9, where the standard material having a relative sensitivity of 100 when developed

  
  <EMI ID = 420.1>

  

  <EMI ID = 421.1>


  

  <EMI ID = 422.1>
 

  

  <EMI ID = 423.1>


  

  <EMI ID = 424.1>
 

  
As is apparent from the results in Table 9,

  
  <EMI ID = 425.1>

  
  <EMI ID = 426.1>

  
high impact acrylic resin (AR-a) or
(AR-d) gave imaging materials

  
dry undergoing smaller variations in sensitivity

  
  <EMI ID = 427.1>

  
compared to dry imaging materials that do not contain 2-

  
  <EMI ID = 428.1>

  
Examples 44 and 45 and comparison examples 43 to 51.

  
A dry-type imaging material of the type

  
to post-activation was prepared in substantially the same way as in Examples 8 to 10 but using the formula

  
  <EMI ID = 429.1>

  
42 and 43 (the binder resin being as indicated in

  
  <EMI ID = 430.1>

  
  <EMI ID = 431.1>

  

  <EMI ID = 432.1>


  
Five pieces of each dry imaging material were subjected to substantially the same imaging as in Examples 15-29 and Comparison Examples
25 to 35 but by heating the material beforehand to 100 [deg.] C for 5 seconds and with development temperatures varying as indicated in table 10

  
  <EMI ID = 433.1>

  
  <EMI ID = 434.1>

  
imaged materials have been examined, and are as shown in Table 10, where the standard material having a relative sensitivity of 100 during development

  
at 125 [deg.] C for 4 seconds is that of Example 44.

  

  <EMI ID = 435.1>


  

  <EMI ID = 436.1>
 

  

  <EMI ID = 437.1>


  

  <EMI ID = 438.1>
 

  
  <EMI ID = 439.1>

  
10. combinations of 2- (2'-hydroxyphenyl) benzotriazole
(f6) (according to the invention) with the resin with high impact resistance (AR-a) or (AR-d) give materials forming a dry image undergoing smaller variations in

  
  <EMI ID = 440.1>

  
development heat that training materials

  
  <EMI ID = 441.1>

  
composed of 2- (2'-hydroxyphenyl) benzotriazole.

  
Examples 46 to 51 and Comparison Examples 49 to 52, A post-activation type dry imaging material was prepared in substantially the same manner.

  
  <EMI ID = 442.1>

  
  <EMI ID = 443.1>

  
  <EMI ID = 444.1>

  
  <EMI ID = 445.1>

  

  <EMI ID = 446.1>


  
Pomule
  <EMI ID = 447.1>
   <EMI ID = 448.1>

  
In order to examine the stability of the latent image, four pieces of each dry imaging material, after being subjected to the same heat activation and light exposure as in Examples 8-10 and comparison examples 11 to 15, were left in a dark room for 0.5, 1, 5 and 10 hours, respectively, and then developed for 5 seconds on a hot plate maintained at 125 [deg.] C.

  
The relative sensitivity and latent image stability of the dry imaging material were examined, and are as shown in Table 11 where the standard material having relative sensitivity

  
of 100 is that of comparison example 52 and where

  
the stability of the latent image is expressed as corresponding to the conservation of the sensitivity when the

  
  <EMI ID = 449.1>

  
given time is considered an accelerated deterioration test.

  

  <EMI ID = 450.1>


  

  <EMI ID = 451.1>
 

  
  <EMI ID = 452.1>

  
  <EMI ID = 453.1>

  
on polymethyl methacrylate, of Tufprene A (trade name of a styrene block copolymer-

  
  <EMI ID = 454.1>

  
Japan).

  
The acrylic resin (AR-g) was a mixture of

  
  <EMI ID = 455.1>

  
on polymethyl methacrylate, of a partially crosslinked copolymer having the elasticity of the rubber obtained

  
by emulsion polymerization catalyzed with persulfate

  
  <EMI ID = 456.1>

  
  <EMI ID = 457.1>

  
  <EMI ID = 458.1>

  
resides acrylic & high impact resistance (AR-a),
(AR-f) or (AR-g) giving dry imaging materials having higher latent image stability than dry imaging materials

  
  <EMI ID = 459.1>

  
  <EMI ID = 460.1>

  
prepared in much the same way as in each

  
  <EMI ID = 461.1>

  
  <EMI ID = 462.1>

  
  <EMI ID = 463.1>

  
each dry imaging material, advanced results in terms of relative sensitivity and stability

  
of the latent image substantially spreading the same as those obtained for the image-forming material prepared in the corresponding example or comparison example.

  
  <EMI ID = 464.1>

  
  <EMI ID = 465.1> <EMI ID = 466.1>

  
  <EMI ID = 467.1>

  
in the first coating layer was in the order of

  
  <EMI ID = 468.1>

  
Formula &#65533;

  

  <EMI ID = 469.1>


  
  <EMI ID = 470.1>

  

  <EMI ID = 471.1>


  
A comparison dry imaging material was prepared in substantially the same manner as described above but omitting the use

  
  <EMI ID = 472.1>

  
using a comparison compound shown in Table 13 instead of the 2- (2'-hydroxyphenyl) benzotriazole compound.

  
A piece of each dry imaging material was previously heated on a plate

  
  <EMI ID = 473.1> a dark room. Then, the material was exposed for 1 second through a plateau stepped at 21 rungs

  
  <EMI ID = 474.1>

  
to the light emitted from a tungsten lamp having a color temperature of 3200 [deg.] K. and filtered through a yellow color filter Y-50 (trade name of a color filter manufactured and sold by Tokyo Shibaura Electric Company Ltd., Japan). The exposed material was then heated on a hot plate held at about 125 [deg.] C for 4 seconds in a dark room to perform heat development.

  
Another piece of each dry imaging material was subjected to an accelerated deterioration test (heat and humidity acceleration) performed leaving the material in the dark at 45 [deg.] C and at a relative humidity of 80% for 10 days.

  
The deteriorated material was subjected to the same imaging as that described above.

  
The optical densities of the imaged materials respectively derived from the materials before and after the accelerated deterioration test were measured. Results evaluated in terms of relative sensitivity, formation of the veil
(O.D. min) and conservation of the sensitivity are indicated in Tables 12 and 13, where the coloring compounds (1), (4),

  
  <EMI ID = 475.1>

  
above mentioned spectral sensitization indicated under these numbers (such indications used hitherto having the same meanings), and where the standard material having a relative sensitivity of 100 is that of Example 52.

  

  <EMI ID = 476.1>


  

  <EMI ID = 477.1>
 

  

  <EMI ID = 478.1>


  

  <EMI ID = 479.1>
 

  

  <EMI ID = 480.1>


  

  <EMI ID = 481.1>
 

  
The coloring compounds (D-a) to (D-e) used here are mentioned below:

  

  <EMI ID = 482.1>


  
  <EMI ID = 483.1>
  <EMI ID = 484.1>
   <EMI ID = 485.1>

  
of Tables 12 and 13, the combinations of the compound of

  
  <EMI ID = 486.1>

  
(according to the invention), with the coloring compound (1), (4),

  
(5). (18) or (28) provide dry imaging materials having higher spectral sensitivity and greater storage stability of the raw material

  
(in terms of haze formation and sensitivity retention) than the comparison dry imaging materials containing no 2- (2'-hydroxyphenyl) benzotriazole compound and no

  
  <EMI ID = 487.1>

  
Examples 67 to 70 and comparison examples 69 to 79.

  
A dry-type imaging material of the type

  
post-activation was prepared in much the same way as in Examples 8 to 10 but using the formulas

  
  <EMI ID = 488.1>

  
  <EMI ID = 489.1>

  
  <EMI ID = 490.1>

  

  <EMI ID = 491.1>


  
e 1 &#65533;

  

  <EMI ID = 492.1>
 

  

  <EMI ID = 493.1>


  
  <EMI ID = 494.1>

  
comparison has been prepared substantially in the marl as described above but omitting the use

  
  <EMI ID = 495.1>

  
One piece of each dry imaging material was subjected to the same imaging as

  
  <EMI ID = 496.1>

  
Another piece of each dry imaging material was subjected to the same accelerated deterioration test (heat and humidity acceleration) as in Examples 52 to 66 and Comparison Examples 53 to

  
  <EMI ID = 497.1>

  
52 to 66 and comparison examples 53 to 68.

  
The relative sensitivity, the formation of the voue and the conservation of the sensitivity of each material of

  
  <EMI ID = 498.1>

  
so that in examples 52 to 66 and comparison examples
53 to 66, and are as indicated in Table 14 where the standard material having a relative sensitivity of 100 is that of Example 67.

  

  <EMI ID = 499.1>


  

  <EMI ID = 500.1>
 

  

  <EMI ID = 501.1>


  

  <EMI ID = 502.1>
 

  
The coloring compounds (D-f) and (D-g) used here are mentioned below:

  

  <EMI ID = 503.1>


  
As is apparent from the results of the table
14, the combinations of the compound of 2- (2 * -hydroxyphenyl) benzotriazole (f6) (according to the present invention) with the

  
  <EMI ID = 504.1>

  
dry imaging materials having spectral sensitivity and storage stability of the raw material (in terms of haze formation and conservation of sensitivity) stronger than imaging materials comparison dry containing no 2- (2'-hydroxyphenyl) benzotriazole compound or comparison compound (C12).

  
Examples 71 to 78 and comparison examples 69 to 79.

  
20 g of a mixed solvent of toluene and methyl

  
  <EMI ID = 505.1>

  
add 3.5 g of silver stearate, and the mixture was ball-milled for about 18 hours to obtain a homogeneous suspension of silver stearate.

  
A dry-type imaging material of the type

  
post-activation was prepared in much the same way as in Examples 8 to 10 but using the formulas

  
  <EMI ID = 506.1>

  
  <EMI ID = 507.1>

  
  <EMI ID = 508.1>

  

  <EMI ID = 509.1>


  
FormulaLyl

  

  <EMI ID = 510.1>


  
A comparison dry imaging material was prepared in substantially the same manner as described above but omitting the use

  
  <EMI ID = 511.1>

  
using the comparison compound shown in Table 15 instead of the 2- (2'-hydroxyphenyl) benzotriazole compound.

  
A piece of each dry imaging material was subjected to substantially the same imaging as in Examples 52 to 66 and Comparison Examples 53 to 68 but by performing the exposure to light for 8 seconds using light at one wavelength

  
of 480 nm emitted by a monochromator.

  
i Another piece of each dry imaging material was subjected to the same accelerated deterioration test (heat and humidity acceleration)

  
  <EMI ID = 512.1>

  
68, with then the same image formation as that described above.

  
In order to examine the light stability of the raw material, another piece of each imaging material was subjected to an accelerated deterioration test.
(acceleration in filtered light) performed by exposing,

  
  <EMI ID = 513.1>

  
an FX-1 fadeometer and filtered by a VY-45 filter
(trade name of a color filter manufactured and sold by Tokyo Shibaura Electric Company Ltd., Japan), only allowing light at wavelengths

  
of 450 nm or more to pass. The material thus deteriorated <EMI ID = 514.1>

  
conservation of the sensitivity of each material of

  
  <EMI ID = 515.1>

  
as indicated in Table 15 where the standard material having a relative sensitivity of 100 is that of Example 71.

  

  <EMI ID = 516.1>


  

  <EMI ID = 517.1>
 

  

  <EMI ID = 518.1>


  

  <EMI ID = 519.1>
 

  

  <EMI ID = 520.1>


  

  <EMI ID = 521.1>
 

  
The coloring compounds (D-h), (D-i) and (D-j) used here are mentioned below:

  

  <EMI ID = 522.1>


  
The comparison compound (C13) used here is mentioned below:

  

  <EMI ID = 523.1>
 

  
As is apparent from the results of the table
15, combinations of the 2- (2'-hydroxyphenyl) compound &#65533;

  
  <EMI ID = 524.1>

  
coloring compound (38), (39), (40) or (43) give dry imaging materials having greater stability to light or to storage of the raw material (in terms of the formation of haze and sensitivity retention) as comparison dry imaging materials containing no 2- (2 '-hydroxyphenyl) benzotria zole compound and none or any of the

  
  <EMI ID = 525.1>

  
benzotriazole (f3) and (f9) as well as the comparison compounds (C8), (C9) and (C13) are unable to absorb

  
  <EMI ID = 526.1>

  
may indicate that the improvement in light stability of the raw material obtained in the present invention cannot be attributed to the function of the component
(f) as an ultraviolet absorbing agent.

  
  <EMI ID = 527.1>

  
A post-activation type dry imaging material was prepared in substantially the same manner as in Examples 8-10 but using the

  
  <EMI ID = 528.1>

  
  <EMI ID = 529.1>

  
respectively.

  
  <EMI ID = 530.1>

  

  <EMI ID = 531.1>


  
A comparison dry imaging material was prepared in substantially the same manner as described above, but omitting the use of the 2- (2'-hydroxyphenyl) benzotriazole compound.

  
The relative sensitivity, the formation of the haze and the conservation of the sensitivity of each dry image-forming material examined in the same way as in Examples 71 to 78 and comparison examples.
69 to 79 except that image formation has been performed

  
  <EMI ID = 532.1>

  
and comparison examples 53 to 68, and were found to be as in Table 16, where the standard material having a relative sensitivity of 100 is that of Example 79.

J

  

  <EMI ID = 533.1>


  

  <EMI ID = 534.1>
 

  

  <EMI ID = 535.1>


  

  <EMI ID = 536.1>
 

  

  <EMI ID = 537.1>


  

  <EMI ID = 538.1>
 

  
  <EMI ID = 539.1>

  
  <EMI ID = 540.1>

  

  <EMI ID = 541.1>


  
Cassa it appeared. reading the results!

  
  <EMI ID = 542.1> a photograph of a resolution test diagram

  
  <EMI ID = 543.1>

  
The material was then heat developed on a hot plate maintained at about 125 [deg.] C for 4 seconds.

  
Minimum optical density (O.D. min) between lines

  
  <EMI ID = 544.1>

  
Sakura PDM-5 meter (trade name of a

  
  <EMI ID = 545.1>

  
  <EMI ID = 546.1>

  
of an imaging material be lower

  
  <EMI ID = 547.1>

  
due to water or irradiation, which leads to a good quality image.

  
The results are shown in Table 17.

TABLE 17

  

  <EMI ID = 548.1>


  
As is apparent from the results of the table

  
  <EMI ID = 549.1>

  
  <EMI ID = 550.1>

  
(according to the invention) with the coloring compound (2), (3),

  
(13), (20), (21), (29) or (48) give materials

  
dry imaging less subject to halo and irradiation influences, producing high quality images with high resolution and low O.D. value even in narrow areas between imaged lines.

  
  <EMI ID = 551.1>

  
A dry-type imaging material of the <EMI ID = 552.1>

  
  <EMI ID = 553.1>

  
  <EMI ID = 554.1>

  

  <EMI ID = 555.1>


  
  <EMI ID = 556.1>

  

  <EMI ID = 557.1>


  
A comparison dry imaging material was prepared in substantially the same manner as described above, but omitting the use of the 2- (2 * -hydroxphenyl) benzotriazole or using a comparison compound as shown in Table 18 in place of the 2- (2-hydroxyphenyl) compound -

  
  <EMI ID = 558.1>

  
For each imaging material to

  
1 <EMI ID = 559.1>

  
was measured in the same way as described in

  
  <EMI ID = 560.1>

  
The results are shown in Table 18.

  
Table 18
  <EMI ID = 561.1>
 As is apparent from the results of the table

  
  <EMI ID = 562.1>

  
  <EMI ID = 563.1>

  
with the dye compound (1), (3), (4), (8), (10),

  
  <EMI ID = 564.1>

  
  <EMI ID = 565.1>

  
halo and irradiation, producing high quality images with high resolution and low O.D. min value, marl in narrow areas between pictorial lines.

Example 98

  
A dry-type imaging material of the type

  
  <EMI ID = 566.1>

  
so as in Example 79 but using 5 mg of palladium (II) acetylacetonate and 5 mg of cobalt (III) acetylaoetonate instead of the methanol solution

  
  <EMI ID = 567.1>

  
  <EMI ID = 568.1>

  
stability of the raw material in the same way as in the example
79 were substantially more marl than those obtained in Example 79.

  
Izod impact resistance (with notch) of high impact acrylic resins used here

  
  <EMI ID = 569.1>

  
  <EMI ID = 570.1>

  
  <EMI ID = 571.1>

  

  <EMI ID = 572.1>


  
  <EMI ID = 573.1> <EMI ID = 574.1>

  
to the described embodiments which have not been given

  
  <EMI ID = 575.1>

  
the means constituting technical equivalents of the means described and their combinations if these are executed according to the spirit and implemented in the context of protection as claimed.

J

  



    

Claims (1)

CLAIMS <EMI ID = 576.1> characterized in that it comprises, in one or more layers on a support (a) an oxidizing agent with a non-photosensitive organic silver salt, (b) a silver ion reducing agent (c) a silver halide component or a silver halide forming component capable of forming a silver halide component by its reaction with said component (at), (d) a turning agent, <EMI ID = 577.1>  <EMI ID = 578.1> consisting of compounds represented by the formulas which <EMI ID = 579.1>  <EMI ID = 580.1>  <EMI ID = 581.1>  <EMI ID = 582.1> <EMI ID = 583.1> containing component (a). 2. Material according to claim 1, characterized  <EMI ID = 584.1> a hydrogen atom. 3. Material according to any one of the claims  <EMI ID = 585.1> care a statement of formula (I), 4. Material according to any one of the preceding claims, characterized in that the amount of  <EMI ID = 586.1>  <EMI ID = 587.1> 5. Material according to any one of the preceding claims, characterized in that the aforementioned component (b) is contained in a layer formed on the layer containing the components (a), (c), (e) and (f) and in that  <EMI ID = 588.1>  <EMI ID = 589.1>  <EMI ID = 590.1> (with notch) of at least 0.213 J / cm by measuring according to  <EMI ID = 591.1> 6. Material according to claim 5, characterized in and that the acrylic resin with high impact strength mentioned above is a mixture of at least one acrylic polymer  <EMI ID = 592.1> rubber or a combination with at least one polymer  <EMI ID = 593.1> polymer having the elasticity of rubber. 7. Material according to claim 6, characterized in  <EMI ID = 594.1>  <EMI ID = 595.1> in the group) consisting of alkyl of 1 to 4 atoms of  <EMI ID = 596.1> substituted with methacrylic acid and 0.5 to 300% by weight,  <EMI ID = 597.1> of units of a monomer giving the elasticity of the rubber of at least one element chosen from alkyl esters from 1 to 22 unsubstituted or substituted carbon atoms of acrylic acid and alkyl esters of 7 to 22 unsubstituted or substituted carbon atoms of methacrylic acid. 8. Material according to any one of claims 5 to 7, characterized in that the strong acrylic resin  <EMI ID = 598.1> at least one element chosen from an alkyl of 1 to 4 carbon atoms, cyclohexyl, aryl of 6 to 10 carbon atoms, benzyl or tetrahydrofurfuryl ester unsubstituted or substituted of methacrylic acid in the presence of at least one polymer having l elasticity of rubber and / or at least one copolymer comprising units of a monomer giving the stiffness of at least one  <EMI ID = 599.1> cyclohexyl, aryl of 6 to 10 carbon atoms, benzyl or tetrahydrofurfuryl esters unsubstituted or substituted of methacrylic acid and units of a monomer giving the elasticity of the rubber of at least one element chosen from alkyl esters of 1 to 22 atoms unsubstituted or substituted carbon of acrylic acid, and alkyl esters of 7 to 22 unsubstituted or substituted carbon atoms of methacrylic acid. 9. Material according to any one of the preceding claims, of the post-activation type which can be active. heat, characterized in that component (a) supra is a silver salt of a chain fatty acid long having 16 or more carbon atoms and the component (c) above is a silver halide component comprising silver iodide or a silver halide forming component capable of forming a silver halide component comprising silver iodide, and what it also includes (g) an oxidizing agent for free silver, (h) an agent <EMI ID = 600.1>  <EMI ID = 601.1> a spectral sensitization dye consisting of  <EMI ID = 602.1> compounds represented by the following formulas  <EMI ID = 603.1>  where each X independently indicates a hydrogen atom, a methyl group, a chlorine atom, a phenyl group, a methoxy group or an acetamido group, Y indicates a hydrogen atom, a methyl group or an ethyl group, each Z independently indicates a selenium atom,  <EMI ID = 604.1> independently a selenium atom or a sulfur atom,  <EMI ID = 605.1> straight or branched chain of 2 to 4 carbon atoms, M indicates a hydrogen atom, a triethylammonium group,  <EMI ID = 606.1> 10. Material according to claim 9, characterized in that in the formulas (III), (IV), (V) and (VI) above, each X is independently a hydrogen atom or a chlorine atom, Y is an atom hydrogen or a methyl group, each Z is independently a selenium atom or a sulfur atom, A is a chain propylene group  <EMI ID = 607.1> ammonium. 11. Material according to claim 9, characterized in that the aforementioned component (i) comprises a compound represented by the following formula  <EMI ID = 608.1>  <EMI ID = 609.1> in that the aforementioned component (i) comprises a compound represented by the following formula:  <EMI ID = 610.1>   <EMI ID = 611.1> in that the aforementioned component (1) comprises a compound represented by the following formula:  <EMI ID = 612.1> 14. Material according to claim 9, characterized in that the aforementioned component (i) comprises a composa represented by the formula below:  <EMI ID = 613.1> 15. Material according to claim 9, characterized in that the abovementioned compound (i) comprises a compound represented by the following formula:  <EMI ID = 614.1> 16. Material according to claim 9, characterized  <EMI ID = 615.1> represented by the following formula:  <EMI ID = 616.1>  <EMI ID = 617.1> in that the aforementioned compound (1) comprises a compound represented by the following formula  <EMI ID = 618.1>  <EMI ID = 619.1> 9 or 10, characterized in that the quantity of the component (i) above is between 0.001 and 1 mol% based on component (a). 19. Material in substance as described.