United States Patent (19) (11) 4,396,712 Kinoshita et al. 45) Aug. 2, 1983

54) DRY IMAGE FORMING MATERIAL organic silver salt oxidizing agent, (b) a reducing agent for silver ions, (c) a silver halide component or a silver 75 Inventors: Shozo Kinoshita; Muneaki Kimura; halide-forming component, (d) a toning agent and (e) a Tetsuo Shiga, all of Fuji, Japan lipophilic binder, characterized by the inclusion of a 73) Assignee: Asahi Kasei Kogyo Kabushiki Kaisha, specific 2-(2'-hydroxyphenyl)benzotriazole compound Osaka, Japan having bulky tert-butyl or tert-amyl groups at its ortho and para-positions relative to the hydroxyl group in a 21 Appl. No.: 268,438 layer containing the component (a). The dry image (22 Filed: May 29, 1981 forming material of the present invention has high stor (30) Foreign Application Priority Data age stability prior to use for image formation. When the dry image forming material comprises a combination of May 30, 1980 JP Japan ...... 55-71529 a silver salt oxidizing agent-containing layer comprising Jun. 20, 1980 JP Japan ...... 55-82792 the specific 2-(2'-hydroxyphenyl)benzotriazole com Jul. 10, 1980 (JP) Japan ...... 55-932.38 pound and a reducing agent-containing layer compris 51) int. Cl...... G03C 1/02 ing a high impact acrylic resin as a binder material, the 52) U.S.C...... 430/614; 430/600; material is remarkably improved in storage stability of 430/618; 430/619; 430/620 raw material in the dark or under light with wave 58) Field of Search ...... 430/614, 618, 619, 620, lengths of 450 nm or more and the stability of a latent 430/600 image, and shows minimized variation in image quality 56) References Cited with heat development conditions. When the dry image forming material comprises, as the component (a), a U.S. PATENT DOCUMENTS silver salt of long chain fatty acid having 16 or more

3,152,904 10/1967 Sorensen et al...... 430/966 carbon atoms and, as the component (c), a silver halide 3,764,329 10/1973 Lee ...... 430/.353 component including silver iodide or a silver halide 3,802,888 4/1974 Willits ...... 430/203 forming component capable of forming a silver halide 4,307,187 12/1981 Ikenoue et al...... 430/620 component including silver iodide, and further com FOREIGN PATENT DOCUMENTS prises (g) an oxidizing agent for free silver, (h) a photo 54-48537 4/1979 Japan ...... 430/614 reactive halogeno oxidizing agent and, in the layer con taining the components (a), (c), (e) and (f), (i) a specific Primary Examiner-Won H. Louie, Jr. cyanine spectral sensitizing dye, the material is of the Attorney, Agent, or Firm-Sprung, Horn, Kramer & post-activation type and spectrally sensitized without Woods sacrificing the storage stability of raw material. (57 ABSTRACT A novel dry image forming material comprising in one or more layers on a support (a) a non-photosensitive 4 Claims, No Drawings 4,396,712 1. 2 period is longer. Thus, they are poor in latent image DRY IMAGE FORMING MATERAL stability. There have been proposed post-activation type dry This invention relates to a dry image forming mate image forming materials as disclosed in U.S. Pat. Nos. rial. More particularly, the present invention relates to a 3,802,888 and 3,764,329, wherein the incorporation of a dry image forming material which is improved in stabil spectral sensitizing dye into a dry image forming mate ity during the storage thereof prior to use for image rial is mentioned. These proposed post-activation type formation (hereinafter often referred to as "storage dry image forming materials, however, are defective stability of raw material'), and which can further be either in that they are so poor in light or storage stability improved in latent image stability and image quality, 10 of raw material as to undergo marked deterioration in and which can advantageously be rendered subject to their photographic or sensitometric characteristics much less variation of image quality with heat develop when stored under lighting conditions or when exposed ment conditions which may change. to high temperatures even if stored in the dark, or in As one class of dry image forming materials on which that they are too insufficient in sensitivity to be used in a visible image can be formed by only a dry process 15 photographing. As the stability of a raw image forming involving heating, there have been proposed heat material is increased, the sensitivity of the material is apt developable dry image forming materials which essen to be decreased, whereas the stability of a raw image tially comprise a non-photosensitive organic silver salt forming material is apt to be decreased as the sensitivity of the material is increased. Therefore, none of the oxidizing agent, a reducing agent for silver ions, a cata conventional post-activation type dry image forming lytic amount of a silver halide or a silver halide-forming materials are good in both stability and sensitivity. compound, and a binder. Accordingly, there has been earnestly desired such a The dry image forming materials of the silver salt dry image forming material as can meet such require type as described above include those which are photo ments that it should not substantially undergo any dete sensitive under normal lighting conditions (hereinafter 25 rioration in image forming characteristics during stor often referred to as "already photosensitive type dry age thereof prior to use, that it should not be so much image forming material'), such as disclosed in U.S. Pat. affected in quality of an image formed thereon by the Nos. 3, 152,904 and 3,457,075, and those which are non variation in heat development conditions, that it should photosensitive under normal lighting conditions (here give, after preliminary heating and light exposure, a inafter often referred to as "postactivation type dry 30 latent image which is excellent in stability, and that it image forming material'), such as disclosed in U.S. Pat. should be spectrally sensitized but have excellent stor Nos. 3,764,329, 3,816,132, 4,113,496, and 4,173,482. The age stability of raw material. latter image forming materials can be handled under As is described in Japanese Patent Application Laid room light, provided they are not activated, and can be Open Nos. 122430/1976 and 28417/1978, a combined rendered photosensitive when they are activated, for 35 use of benzotriazole and benzenethiosulfonic acid or its example, by heating the same prior to exposure to light. sodium salt or a combined use of benzotriazole and The former image forming materials can form thereon a sulfinic acid may be effective for improving the storage visible image when subjected to imagewise exposure to stability of dry image forming materials. However, the light and subsequent heat development, whereas the incorporation of benzotriazole greatly lowers the sensi latter image forming materials can form thereon a visi tivity of the dry image forming materials, as is apparent ble image when subjected to preliminary heat activa from the results of Comparative Example 24 which will tion, imagewise exposure to light and subsequent heat be given later. Thus, repeatedly stated, it is quite natural development. that the storage stability of a raw image forming mate The dry image forming materials of the silver salt rial be increased with the sensitivity of the material type are superior in simplicity of image forming proce 45 being decreased. dures to the conventional wet process silver halide On the other hand, as is disclosed in U.S. Pat. Nos. photographic materials because they can form thereon 3,004,896 and 3,189,.615, 2-(2'-hydroxyphenyl)benzo an image by only heating without the use of any liquid triazoles can function as ultraviolet absorbers, and, chemical agents. However, they are so poor in storage hence, are known to be effective as anti-photodegrada stability of raw material as to be readily subject, during 50 tion agents for polymers. It is described in U.S. Pat. No. their storage prior to use for image formation, to deteri 3,253,921 that the use of a 2-(2'-hydroxyphenyl)benzo oration in image forming characteristics. More specifi triazole in a filter layer on the photographic emulsion cally, they, after stored, are liable to be blackened even layer of a wet process color photographic material is in the light-unexposed portions by image forming pro effective for avoiding the loss of color balance due to cedures to form an image having a dark background, 55 too strong development of blue color undesirably that is, they are prone to undergo the so-called fogging caused by the irradiation of the material with ultraviolet in image formation. Also, they are apt to become poor rays and for preventing the fading and/or discoloration in sensitivity during the course of storage thereof. Fur of a colored image formed on the material. Thus, 2-(2'- ther, since the image forming characteristics of the hydroxyphenyl)benzotriazoles have been used as the materials inherently are largely dependent on the condi 60 ultraviolet absorbers. However, no investigations have tions of heat development for visible image formation, been made on the action or function of 2-(2'-hydroxy the quality of images formed on the materials greatly phenyl)benzotriazoles as stabilizers in the dark free of varies when the heat development conditions change. ultraviolet rays or in the case of exposure to light with Furthermore, these dry image forming materials are apt wavelengths of 450 nm or more incapable of being to undergo some deterioration in capability of forming 65 absorbed by the 2-(2'-hydroxyphenyl)benzotriazoles. a visible image during the period between light expo It is an object of the present invention to provide a sure and heat development, and, hence, the quality of dry image forming material having high sensitivity and images formed thereon is poorer as the abovementioned excellent storage stability of raw material. 4,396,712 3 4. It is another object of the present invention to pro tures and high humidities but also when it is stored in a vide a dry image forming material of the above charac light room. ter, which can give a stable latent image, and which can According to a preferred embodiment of the present form an image of high quality, which is not so much invention, the dry image forming material comprises a dependent on heat development conditions. layer comprising the component (b) and, as a material of Still another object of the present invention is to the component (e), a high impact acrylic resin having an provide a practically usable post-activation type dry Izod impact strength (notched) of at least 0.4 ft.lb/in as image forming material which is spectrally sensitized measured in accordance with ASTM D 256 and pro but has high sensitivity and excellent storage stability of vided on a layer comprising at least the components (a), raw material, and which can form an image of high 10 (c), (e) and (f), whereby it is improved in latent image quality. stability and is subject to less variation of image quality With a view to developing dry image forming materi with heat development conditions. als of the character as described above, we have made When the dry image forming material according to extensive and intensive investigations to find that such the present invention comprises, as the component (a), a dry image forming materials can be obtained when a 15 silver salt of long chain fatty acid having 16 or more specific 2-(2'-hydroxyphenyl)benzotriazole having tert carbon atoms and, as the component (c), a silver halide butyl or tert-amyl groups at the 3'-and 5'-positions is component including silver iodide or a silver halide incorporated in the layer of the materials containing an forming component capable of forming a silver halide organic silver salt oxidizing agent. We have completed component including silver iodide, and further com the present invention based on such a finding. 20 prises (g) an oxidizing agent for free silver and (h) a More specifically, in accordance with the present photoreactive halogeno oxidizing agent, the image invention, there is provided a dry image forming mate rial comprising in one or more layers on a support: forming material is desirable as being of the post-activa (a) a non-photosensitive organic silver salt oxidizing tion type. The post-activation tye dry image forming 25 material of the present invention as mentioned just agent, above preferably further comprises, in the layer con (b) a reducing agent for silver ions, taining the components (a), (c), (e) and (f), (i) a cyanine (c) a silver halide component or a silver halide-form spectral sensitizing dye with a unique chemical struc ing component capable of forming a silver halide com ture, which performs without sacrificing the storage ponent by the reaction thereof with the component (a), 30 stability of raw material by virtue of the component (f), (d) a toning agent, i.e., a specific 2-(2'-hydroxyphenyl)benzotriazole, so (e) a lipophilic binder, and that the dry image forming material remains practically (f) at least one member selected from the group con useful with an increased sensitivity. sisting of those compounds represented by the follow The cyanine spectral sensitizing dye (i) consists of at ing formulae; 35 least one compound selected from those compounds represented by the following formulae: HO (tert-butyl) (I) (III) 2N. Z Z. s^ N , and 40 )-CH=(-CH=( Cl X N X R (tert-butyl) A A HO (tert-amyl) (II) SO3- SO3M 45 2N. Z Z. (IV)IV N

-- s/ N )-CH=(-CH=( N R (tert-amyl) 50 i i wherein R stands for a hydrogen atom, a C1-C8 straight SO3 SO3M or branched chain alkyl group, a C1-C4 straight or branched chain alkoxyl group, a phenyl group or a W W (V) halogen atom selected from Cl, Br and I; 55 the component (f) being included in a layer containing -- )-CH=( , and the component (a). X X The dry image forming material according to the present invention, whether it is either of the post-activa SO3- SO3M tion type or of the already photosensitive type, is im 60 proved in storage stability of raw material during its storage in the dark, and especially in suppression of VI fogging in and retention of sensitivity of the material -- stored under high temperatures and/or high humidities. N )-CH=( N Furthermore, in the case of the post-activation type dry 65 image forming material according to the present inven tion, its storage stability of raw material is improved not SO3 SOM only when it is stored in the dark under high tempera 4,396,712 5 6 wherein each X independently stands for a hydrogen being stored under light with wavelengths of 450 nm or aton, a methyl group, a chlorine atom, a phenyl group, O. a methoxy group or an acetamido group, Y stands for a In the case of wet process silver halide photographic hydrogen atom, a methyl group or an ethyl group, each materials and heat-developable dry image forming ma Z independently stands for a selenium atom, a sulfur terials of the already photosensitive type, spectral sensi atom or an oxygen atom, each Windependently stands tizing dyes as commonly used in these materials are not for a selenium atom or a sulfur atom, each A indepen necessarily required to be stable to light irradiation and dently stands for a C2-C4 straight or branched chain heating since the materials are never exposed to light alkylene group, and M stands for a hydrogen atom, a and heat prior to use in image formation. In fact, unsta triethylammonium group, a pyridinium group or a so O ble spectral sensitizing dyes are widely used in the dium atom. above-mentioned materials. Therefore, it is usual that It is well known to those skilled in the art that it is the technique of spectral sensitization acquired in the very difficult to apply the knowledge and technique field of wet process silver halide photographic materials acquired and the various additives used in the field of and dry image forming materials of the already photo wet process silver halide photographic materials to the 15 sensitive type be unable to be applied to the field of field of dry process photographic or image-forming post-activation type dry image forming materials be materials, because both types of the material are quite cause it naturally tends to downgrade the resulting different in components and mechanism of image for post-activation type dry image forming materials in mation. More specifically, the dry image forming mate respect of storage stability of raw material. rial of the silver salt type, which is generally heated at For example, as is disclosed in U.S. Pat. No. a temperature of at least 100° C. for effecting the devel 3,933,507, incorporation of a spectral sensitizing dye opment thereof, comprises an organic silver salt oxidiz into a system comprising an organic silver salt oxidizing ing agent and a reducing agent required for image de agent and a reducing agent for silver ions but no photo velopment, and a silver halide component or a silver sensitive silver halide may often result in a dry image halideforming component as the catalyst, while the wet 25 forming material of the common already photosensitive process silver halide photographic material contains no type. As will be easily understood from this instance, a reducing agent for development. Therefore, in the case spectral sensitizing dye incorporated into an image of the dry image forming material of the silver salt type, forming system has a tendency to impart photosensitiv it is all the more difficult because of the presence therein ity to the system as long as it is not decomposed. Ac of the reducing agent to improve the storage stability of 30 cordingly, in the case of a post-activation type dry raw material without sacrificing the sensitivity of the image forming material which is required to be capable material. It is particularly noted that post-activation of being exposed to light prior to use and of being pre type dry image forming materials, which are required to liminarily heated prior to image-wise exposure to light be capable of being exposed to or stored under normal substantially without deterioration of its photographic lighting conditions substantially without undergoing 35 or sensitometric characteristics and not to undergo deterioration in their photograhic or sensitometric char substantial fogging, a spectral sensitizing dye, if incor acteristics, are quite different in conditions of storage porated into the material, generally downgrades drasti and image formation from the wet process photo cally the light or storage stability of the raw image graphic material and even dry image forming materials forming material and renders the material more subject of the already photosensitive type which are never 40 to fogging. exposed to light prior to use in image formation. There Almost all of the attempts to use in post-activation fore, it is quite impossible to anticipate whether or not type dry image forming materials spectral sensitizing an additive suitable for those wet process photographic dyes as commonly used in wet process silver halide materials or those dry image forming materials of the photographic materials and heat-developable dry image already photosensitive type can be used successfully in 45 forming materials of the already photosensitive type post-activation type dry image forming materials. In have failed either because the spectral sensitizing dyes fact, it is rather natural that such an additive be unable adversely affect the stability of the resulting raw post to be used in a post-activation type dry image forming activation type dry image forming materials so that they material since incorporation of the additive into the cause the resulting dry image forming materials to un post-activation type dry image forming material quite 50 dergo fogging at the step of preliminary heating prior to often results in low light or storage stability of the raw light exposure and the escalation of the fogging at the dry image forming material. step of heat development, or because the spectral sensi It has never been knon that, among such 2-(2'- tizing dyes themselves are so decomposed or bleached hydroxyphenyl)benzotriazoles as known as the ultravi in the post-activation type dry image forming materials olet absorbers, only those having bulky tert-butyl or 55 as not to exhibit any spectrally sensitizing capability tert-amyl groups at their ortho- and para- positions from the outset, or as to lose their spectrally sensitizing relative to the hydroxyl group at the 2'-position are capability too rapidly during the storage of the raw capable of improving a dry image forming material materials to be practically useful. comprising a nonphotosensitive organic silver salt oxi Furthermore, the spectral sensitizing dyes generally dizing agent, a reducing agent for silver ions, a silver 60 render the resulting image forming materials more sub halide component or a silver halide-forming component ject to the influences of halation and/or irradiation than and a binder, in respect of storage stability of raw mate those image forming materials not spectrally sensitized. rial in the dark free of ultraviolet rays. It also is beyond In order to obtain a high quality image with a high usual expectations and quite surprising that such 2-(2'- resolution on a spectrally sensitized image forming ma hydroxyphenyl)benzotriazoles as cannot absorb light 65 terial, a means for preventing halation and/or irradia with wavelengths of 450 nm or more are capable of tion is usually necessary for the image forming material. improving a dry image forming material such as men It is noted that it has been very difficult to employ in tioned above, in respect of stability of raw material post-activation type dry image forming materials such 4,396,712 8 halation- and/or irradiation-preventing means as em present invention, there is used an organic reducing ployed in wet process silver halide photographic mate agent which has such a suitable reducing ability that, rials and dry image forming materials of the already when heated, it reduces the non-photosensitive long photosensitive type, because, as described above, the chain fatty acid silver salt (a) with the aid of catalysis of post-activation type dry image forming materials are the free silver produced from silver halide in the ex required to have good stability of raw material even posed portions of the activated dry image forming ma when stored under severer conditions. Accordingly, it terial to form a visible silver image. Examples of the is quite unexpected that the specific 2-(2'-hydroxy silver ion-reducing agents include monohydroxyben phenyl)benzotriazoles incapable of absorbing light with Zenes such as p-phenylphenol, p-methoxyphenol, 2,6-di wavelengths of 450 nm or more, when incorporated 10 tert-butyl-4-methylphenol and 2,5-di-tert-4-methoxy into post-activation type dry image forming materials, phenol; polyhydroxybenzenes such as hydroquinone, can contribute to preventing the quality of images tert-butylhydroquinone, 2,6-dimethylhydroquinone, formed on the materials from lowering due to halation chlorohydroquinone and catechol; naphthols such as and/or irradiation which occurs only when the image o-naphthol, g-naphthol, 4-aminonaphthol and 4 forming materials have an increased spectral sensitivity 15 methoxynaphthol; hydroxybinaphthyls such as 1,1'- to light with long wavelengths of 450 nm or more, as dihydroxy-2,2'-binaphthyl and 4,4'-dimethoxy-1, 1'- well as to improving the storage stability of raw mate dihydroxy-2,2'-binaphthyl; phenylenediamines such as rial in the dark or under light with wavelengths of 450 p-phenylenediamine and N,N'-dimethyl-p- O Ofe. phenylenediamine; aminophenols such as N-methyl-p- It is demonstrated, for example, in Examples of U.S. 20 aminophenol and 2,4-diaminophenol; sulfonamido Pat. No. 3,589,903 that in dry image forming materials a phenols such as p-(p-toluenesulfonamido)phenol and layer comprising a polymer binder and a reducing agent 2,6-dibromo-4-(p-toluenesulfonamido)phenol; and me may be provided on a layer containing silver salt oxidiz thylenebisphenols such as 2,2'-methylenebis(4-methyl ing agent, the polymer binder being polyvinyl pyrrol 6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert idone or cellulose acetate. It is generally known that 25 butylphenol), 2,2'-methylenebis4-methyl-6-(1-methyl various polymers are usable as the binder of a reducing cyclohexyl)phenol), 1,1-bis(2-hydroxy-3,5-dimethyl agent-containing layer provided on a silver salt oxidiz phenyl)-3,5,5-trimethylhexane, 2,6-bis(2'-hydroxy-3- ing agent-containing layer. tert-butyl-5'-methylbenzyl)-4-methylphenol and 1,1- It has unexpectedly and surprisingly be found that a bis(2-hydroxy-3-tert-butyl-5-methylphenyl)pentane. A combination of a silver salt oxidizing agent-containing 30 suitable reducing agent may be chosen depending on layer comprising a specific 2-(2'-hydroxyphenyl)benzo the kind of organic silver salt oxidizing agent (a) em triazole having a unique chemical structure and a reduc ployed in combination therewith. Preferred are phe ing agent-containing layer comprising as a binder mate nols. More preferred are hindered phenols in which one rial a high impact acrylic resin having an Izod impact or two sterically bulky groups are bonded to the carbon strength (notched) of at least 0.4 ft.lb/in as measured in 35 atom or carbon atoms contiguous to the hydroxyl accordance with ASTM D 256 can give dry image group-bonded carbon atom to sterically hinder the hy forming materials remarkably improved in storage sta droxyl group. Such hindered phenols have a high stabil bility of raw material in the dark or under light with ity to light and, hence, the use thereof is effective for wavelengths of 450 nm or more and the stability of a assuring a high storage stability of raw material espe latent image as well as in suppression of variation of 40 cially in the case of the post-activation type dry image image quality according to varied heat development forming material. As examples of such hindered phe conditions. nols, there can be mentioned 2,6-di-tert-butyl-4-methyl With respect to the components of the dry image phenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), forming material of the present invention, a detailed 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,4,4- explanation will now be given as follows. 45 trimethylpentylbis(2-hydroxy-3,5-dimethylphenyl)me As the non-photosensitive organic silver salt oxidiz thane (i.e., 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5- ing agent (a) to be used in the dry image forming mate trimethylhexane), 2,6-methylenebis(2-hydroxy-3-tert rial of the present invention, there can be mentioned, for butyl-5-methylphenyl)-4-methylphenol, 2,2'- example, silver salts of long chain fatty acids, saccharin methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol or benzotriazole. Preferred are silver salts of long chain 50 and 2,5-di-tert-butyl-4-methoxyphenol. These reducing fatty aids such as silver behenate, silver stearate, silver agents may be used either alone or in combination. The palmitate, silver myristate, silver laurate, silver oleate, suitable amount of the reducing agent is usually in the silver margarate, silver arachidate, silver cerotate and range of from 0.1 to 3 moles per mol of the organic silver milissinate. Most preferred is silver behenate. In silver salt oxidizing agent (a). the case of the post-activation type dry image forming 55 The component (c) to be used in the dry image form material according to the present invention, preferred ing material of the present invention is a silver halide examples of the non-photosensitive organic silver salt component or a silver halide-forming component capa oxidizing agent (a) include silver salts of long chain ble of forming a silver halide component by the reaction fatty acids with 16 or more carbon atoms, such as, silver thereof with the organic silver salt oxidizing agent (a). palmitate, silver margarate, silver stearate, silver arachi 60 Examples of the silver halide include silver chloride, date, silver behenate, silver cerotate and silver melissi silver bromide, silver iodide, silver bromoiodide and nate, of which silver behenate is most preferred. The silver chlorobromide. They may be used either alone or organic silver salt oxidizing agent (a) is used preferably in combination. As usual in the field of photographic in an amount of about 0.1 to about 50 g/m2, more pref. film manufacture, a silver halide(s) may be formulated erably 1 to 10 g/m2 of the support area of the present 65 as the silver halide component (c), together with other image forming material. components such as the organic silver salt oxidizing As the reducing agent for silver ions to be used as the agent, into a composition for providing the image form component (b) of the dry image forming material of the ing coating or layer of the dry image forming material, 4,396,712 10 as is disclosed in U.A. Pat. No. 3, 152,904. Alternatively, component including silver iodide are preferred. From a silver halide(s) can be prepared in situ either in a com the viewpoint of sensitivity of dry image forming mate position for providing the image forming coating of the rials, a mixture or mixed crystals of silver iodide with dry image forming material or in the coated image silver chloride or silver bromide is preferred. In the case forming layer of the dry image forming material, by the of the post-activation type dry image forming material, reaction of a silver halide-forming component (c) with the halogenating agents mentioned before under (iii) to part of the organic silver salt oxidizing salt (a), as is (vii) are preferred. disclosed in U.S. Pat. No. 3,457,075. As the silver ha In the case of the post-activation type dry image lide-forming component (c) that is used in the latter forming material according to the present invention mode mentioned above and which is a kind of haloge 10 that may be spectrally sensitized, it is preferred that the nating agent, there can be mentioned (i) hydrogen ha silver halide component (c) or the silver halide compo lides; (ii) metal halides; (iii) halogen molecular species nent formed from the silver halide-forming component and complexes thereof (see U.S. Pat. No. 4,173,482), (c) include therein silver iodide. In order for the silver (iv) organic N-haloamides containing a unit of the for iodide to exert a sufficient effect for the purpose of the mula-CONX- or -SO2NX- wherein X is chlorine, 15 bromine or iodine (see U.S. Pat. No. 3,764,329), (v) present invention, it is preferable that silver iodide be arylhalomethanes (see U.S. Pat. No. 4,188,266), (vi) included in an amount of at least 30 mole % based on organic halides of elements belonging to Group IV, V the silver halide component. The more preferable or VI of the periodic table and having an atomic num amount of silver iodide is at least 50 mole % based on ber of 14 or more (see U.S. Pat. No. 4,133,496), and (vii) 20 the silver halide component. From the viewpoint of combinations of an organic compound of an element sensitivity of the image forming material, the silver belonging to Group IV, V or VI of the periodic table halide component is desired to contain, besides silver and having an atomic number of 14 or more with either iodide, at least 2 mole %, based on the silver halide (iii) a halogen molecular species or a complex of a halo component, of silver bromide and/or silver chloride, gen molecular species, or (iv) an organic N-haloamide 25 although the silver halide component may include only (see U.S. Pat. No. 4,113,496). They may be used either silver iodide, i.e. 100 mole % of silver iodide. Further alone or in combination. Specific examples of the halo more, from the viewpoint of stability of the raw image genating agent include compounds respectively repre forming material, it is desirable that the silver halide sented by the formulae: component contain, besides silver iodide, silver bromide rather than silver chloride. Therefore, the most pre ferred silver halide component consists of silver iodide and silver bromide. In this case, silver iodide and silver ( GeX2, ( bromide may be provided in the form of either a mix ture thereof or mixed crystals thereof. The molar ratio 35 of silver iodide to silver bromide may be preferably 30/70 to 98/2, more preferably 50/50 to 95/5. In the case of the post-activation type dry image forming ma terial that may be spectrally sensitized, the more pre ( Kyr. ( ()-or. ferred amount of the silver halide component including 40 silver iodide is 0.1 to 20 mole %, based on the amount of the organic silver salt oxidizing agent (a). The in situ preparation, as described before, of the silver halide component including silver iodide is preferred in which ( () is co-)-te. silver iodide and any other silver halide(s) are formed 45 by the reaction between the long chain fatty acid silver salt (a) and the silver halide-forming component (c). In O TeX2, ( SeX2 and TeX2. this case also, the preferred halogenating agents are those described before under (iii) to (vii). Of them, those \ / 2 under (iii) and (iv) are more preferred when the stability 50 of raw dry image forming materials of the post-activa In the above formulae, X is bromine or iodine. Further specific examples of the halogenating agent include tion type is taken into consideration. From the view iodine, bromine, iodine bromide, a complex of triphenyl point of sensitivity as well as stability of raw material, phosphite and iodine, a complex of p-dioxane and io the preferred halogenating agents for forming silver dine, a complex of p-dioxane and bromine, N-bromo(or 55 iodide are iodine and N-iodosuccinimide. Complexes of -iodo)phthalimide, N-bromo(or -iodo)succinimide, N iodine such as a complex of triphenyl phosphite and bromo(or -iodo)phthalazinone, N-bromo(or iodine and a complex of p-dioxane and iodine are also -iodo)acetamide, N-bromo(or -iodo)acetanilide and a preferred. In the case of N-iodosuccinimide, it is pre bromo(or -iodo)diphenylmethane. Still further specific ferred that a solution of N-iodosuccinimide in an alco examples of the halogenating agent include CoX2, 60 hol such as methanol or ethanol, which has been previ NiX2, Mgx2, Bax2, RbX, CsX, TeX2, TeX4 and AsX3. ously prepared, be incorporated into an emulsion for the In these formulae, X is bromine or iodine. desired dry image forming material. From the view The preferred amount of the silver halide component point of sensitivity as well as stability of the raw image is in the range of from 0.001 to 0.5 mole per mole of the forming material, the preferred halogenating agents for silver salt oxidizing agent (a). From the viewpoint of 65 forming silver bromide are N-bromosuccinimide, cobalt stability of raw image forming materials, a silver halide dibromide, nickel dibromide and a-bromodiphenylme component including silver iodide and a silver halide thane. The amount, in equivalents, of the halogenating forming component capable of forming a silver halide agent to be used may be equal to or more than the de 4,396,712 11 12 sired amount, in equivalents, of the silver halide compo nent. The toning agent (d) is employed in the present in HO (tert-butyl) (f1) vention for developing a black color in the image areas N of the imagewise-exposed material. Various toning 5 N agents known in the art can be employed. Examples of I)s / such toning agents include phthalazinone and phthalic N anhydride (see U.S. Pat. No. 3,080,254); 2-pyrazolin (tert-butyl) 5-ones, cyclic imides, e.g., phthalimide and N-hydrox yphthalimide, and quinazolinones (see U.S. Pat. No. 10 HO (tert-butyl) (f2) 3,846,136); mercapto compounds (see U.S. Pat. No. H3C N 3,832, 186); oxazinediones (see U.S. Pat. No. 3,951,660); 2 N N combinations of phthalic acid or phthalamic acid with s / imidazole (see U.S. Pat. No. 3,847,612); and combina N tions of phthalazine with an aromatic acid or its anhy 15 dride (see U.S. Pat. No. 4,123,282). The amount of the (tert-butyl) toning agent (d) is preferably in the range of 1 to 100 mole %, based on the organic silver salt oxidizing agent HO (tert-butyl) (f3) H3CO N (a). 2 N The lipophilic binder (e) to be used in the dry image 20 N forming material of the present invention is capable of s / dissolving in organic solvents. As the material of the N binder (e), there can be mentioned, for example, polyvi (tert-butyl) nyl butyral, polymethyl methacrylate, cellulose acetate, polyvinyl acetate, cellulose acetate propionate, cellu 25 HO (tert-butyl) (f4) lose acetate butyrate, polystyrene, polyvinyl formal and (H17C8-n 2N. high impact acrylic resins having an Izod impact N strength (notched) of at least 0.4 ft.lb/in as measured in s / accordance with ASTM D256. Preferred are polyvinyl N butyral, and high impact acrylic resins which are espe 30 (tert-butyl) cially useful in the aforementioned preferred embodi ment of the present invention. It is also preferred that HO (tert-butyl) (f5) polyvinyl butyral be used in a layer containing the com N ponents (a), (c) and (f), and that a high impact acrylic 2 N 35 N resin as mentioned above be used in a layer containing s / the component (b). These binder materials may be used C N either alone or in combination. In the case of the binder used in a layer containing the non-photosensitive or (tert-butyl) ganic silver salt oxidizing agent (a), it is preferred that HO (tert-amyl) the binder be used in such an amount that the weight 40 (f6) N ratio of the binder to the organic silver salt oxidizing 2 N. agent is in the range of from about 0.1 to about 10. N The use of the component (f) constitutes the charac s / teristic feature of the present invention, and greatly N contributes to an improvement in storage stability of the 45 (tert-amyl) raw dry image forming material according to the pres ent invention. The component (f) is at least one com HO (tert-amyl) (f7) pound selected from those compounds represented by N the formulae (I) and (II) mentioned before. Compounds 2 N N having either an alkyl group with 9 or more carbon 50 s / atoms or an alkoxy group with 5 or more carbon atoms H3CO N instead of R in the formula (I) or (II) are not usable because they have too poor a compatibility with the (tert-amyl) other components to exert a sufficient effect for the HO (tert-amyl) (f8) purpose of the present invention. In the formulae (I) and 55 H5C6 N (II), R is preferably a hydrogen atom. The compounds 2 N of the formula (I) is preferred to those of the formula N (II). In order to enable the component (f) to sufficiently s / interact with the organic silver salt oxidizing agent (a) N to provide a sufficient effect for the purpose of the 60 (tert-amyl) present invention, the compound (f) must be contained in a layer containing the component (a). The preferred HO (tert-amyl) amount of the component (f) is in the range of 1 x 10-2 N 2 N to 6x 101 mole, more preferably in the range of N 3X 10-2 to 3x 10-1 mole, per mole of organic silver salt 65 s / oxidizing agent (a). Specific examples of compounds Cl N usable as the component (f) include those represented (tert-amyl) by the following formulae. 4,396,712 13 14 -continued impact acrylic resin, there can be mentioned polyure HO (tert-butyl) (f10) thanes, styrene-butadiene copolymers, ethylene-vinyl N acetate copolymers, polyacrylates and the like. The 2 N rubber-elastic polymer is desired to have a glass transi N s / tion temperature of at most 80° C., preferably - 80 to (n-C4H9)O N 40° C., more preferably - 60° to 10° C. Polyacrylates are most preferred as the rubber-elastic polymer. The (tert-butyl) rubber-elastic polyacrylates preferably comprise at least HO (tert-butyl) (f11) 5% by weight, more preferably at least 30% by weight, 10 N of monomer units of at least one unsubstituted or substi 2 N tuted C1-C22 alkyl ester of acrylic acid, or at least 80% N s / by weight, more preferably at least 90% by weight, of Br N monomer units of at least one unsubstituted or substi tuted C7-C22 alkyl ester of methacrylic acid (the above (tert-butyl) 15 specified lower limit of amount of the monomer units of The high impact acrylic resin, which may be used as said at least one alkyl ester of methacrylic acid can be a binder material of the dry image forming material of lowered when said at least one alkyl ester of meth the present invention, and the use of which is advanta acrylic acid is used in combination with said at least one geous especially in the aforementioned preferred em alkyl ester of acrylic acid). The substituted alkyl group bodiment of the present invention, may be a blend of at that may be contained in the above-mentioned ester of least one rigid thermoplastic acrylic polymer and at acrylic acid or methacrylic acid may be one substituted least one rubber-elastic polymer, or at least one copoly with a halogen, amino, hydroxy, a C1-C4 alkoxy or a mer comprising rigidity-providing acrylic monomer di(C1-C4 alkyl)amino. Specific examples of the unsub units and rubber elasticity-providing monomer units or 25 stituted or substituted C1-C22 alkyl ester of acrylic acid a combination thereof with at least one rigid thermo include methyl acrylate, propyl acrylate, ethyl acrylate, plastic acrylic polymer and/or at least one rubber-elas n-butyl acrylate, isobutyl acrylate, 2-hydroxypropyl tic polymer. The high impact acrylic resin has an Izod acrylate, diethylaminoethyl acrylate and dimethylami impact strength (notched) of at least 0.4 ft.lb/in, usually noethyl acrylate. Specific examples of the unsubstituted 0.5 to 25 ft.lb/in, most practically 0.5 to 5 ft.lb/in, as or substituted C7-C22 alkyl ester of methacrylic acid measured in accordance with ASTM D 256. The high 30 include 2-ethylhexyl methacrylate, lauryl methacrylate, impact acrylic resin preferably contains 0.5 to 300 parts tridecyl methacrylate and stearyl methacrylate. The by weight, more preferably 5 to 200 parts by weight, of rubber-elastic polyacrylate may contain other monomer the rubber-elastic polymer and/or rubber elasticity units selected from monomer units of at least one unsub providing monomer units per 100 parts by weight of the stituted or substituted C1-C6 alkyl, C6-C10 aryl, benzyl rigid thermoplastic acrylic polymer and/or rigidity 35 or tetrahydrofurfuryl ester of methacrylic acid as men providing acrylic monomer units. tioned before, styrene monomer units, ethylvinylben The rigid thermoplastic acrylic polymer, which pref. erably has a weight average molecular weight of 5,000 zene monomer units, acrylonitrile monomer units, vinyl to 1,000,000, more preferably 10,000 to 500,000, may be acetate monomer units, acrylic acid monomer units, an acrylic homopolymer of an unsubstituted or substi 40 maleic acid or anhydride monomer units and the like. It tuted C1-C4 alkyl, cyclohexyl, C6-C10 aryl, benzyl or is preferred that the rubber-elastic polyacrylate be par tetrahydrofurfuryl ester of methacrylic acid or an tially crosslinked by incorporating thereinto up to 20% acrylic copolymer comprising monomer units of at least by weight, more preferably up to 5% by weight, of one member selected from unsubstituted or substituted monomer units of at least one crosslinkable monomer C1-C6 alkyl, C6-C10 aryl, benzyl or tetrahydrofurfuryl 45 selected from divinylbenzene, ethylene glycol diacry esters of methacrylic acid, and is desired to have a late, ethylene glycol dimethacrylate, diethylene glycol Rockwell hardness of M 75 to M 120, preferably M80 diacrylate, diethylene glycol dimethacrylate, glycerin to M 110. The acrylic copolymer may contain up to triacrylate, glycerin trimethacrylate, dipropylene gly about 10% by weight of acrylic acid and/or meth col diacrylate, dipropylene glycol dimethacrylate, bu acrylic acid monomer units. The substituted alkyl, aryl, 50 tylene glycol diacrylate, butylene glycol dimethacry benzyl or tetrahydrofurfuryl group that may be con late, diallyl maleate, trially cyanurate and the like. tained in the above-mentioned esters of methacrylic The high impact acrylic resin of the copolymer type, acid may be one substituted with a halogen, nitro, which preferably has a weight average molecular amino, hydroxy or a C1-C4 alkoxy. Specific examples of weight of 5,000 to 1,000,000, more preferably 10,000 to the ester of methacrylic acid capable of forming the 55 500,000, may comprise rigidity-providing monomer rigid thermoplastic acrylic polymer of either the homo units of at least one ester of methacrylic acid as men polymer type or the copolymer type usable in the high tioned before as being capable of forming the rigid impact acrylic resin of the blend type include methyl thermoplastic acrylic polymer of the homopolymer methacrylate, ethyl methacrylate, cyclohexyl methac type and 0.5 to 300% by weight, based on the rigidity rylate, tert-butyl methacrylate, benzyl methacrylate, 60 providing monomer units, of rubber elasticity- or flexi tetrahydrofurfuryl methacrylate, phenyl methacrylate, bility-providing monomer units of at least one member p-bromophenyl methacrylate, a-naphthyl methacrylate selected from unsubstituted or substituted C1-C22 alkyl and 6-naphthyl methacrylate. esters of acrylic acid and unsubstituted or substituted As the rubber-elastic polymer that may be suitably C7-C22 alkyl esters of methacrylic acid which are men used for blending with the rigid thermoplastic acrylic 65 tioned before as being capable of forming the rubber polymer or combining with the copolymer comprising elastic polyacrylate. rigidity-providing acrylic monomer units and rubber The high impact acrylic resin may also be one pre elasticity-providing monomer units to form the high pared by polymerizing, in the presence of at least one 4,396,712 15 6 copolymer comprising rigidity-providing monomer a complex of trivalent iron and acetylacetone and a units and flexibility-providing monomer units of the complex of trivalent iron and bipyridyl. As examples of kinds as mentioned above with respect to the high im the compounds of trivalent cobalt, there can be men pact acrylic resin of the copolymer type and/or at least tioned a complex of trivalent cobalt and acetylacetone one rubber-elastic polymer, at least one ester of meth 5 and a complex of trivalent cobalt and o-phenanthroline, acrylic acid as mentioned before as being capable of and cobaltic halides such as cobaltic iodide and cobaltic forming a rigid thermoplastic acrylic polymer of the bromide. Examples of the compounds of divalent palla homopolymer type. In this case, the high impact acrylic dium include a complex of divalent palladium and ace resin may comprise a block or graft copolymer al tylacetone, and palladium (II) halides such as palladium though there remains a possibility that the resin is a 10 (II) iodide and palladium (II) bromide. As examples of mere blend of said at least one copolymer and/or said at the sulfinic acid compound, there can be mentioned least one rubber-elastic polymer with a polymer formed n-octylsulfinic acid and p-toluenesulfinic acid. As the from said at least one ester of methacrylic acid. component (g), the compounds of divalent mercury are A monomer or monomers capable of copolymerizing most preferred. The preferred amount of the compo with an ester of methacrylic acid, which may be se 15 nent (g) is in the range of from 0.01 to 10 mole % based lected, for example, from vinyl acetate, styrene, acrylo on the organic silver salt oxidizing agent (a). nitrile, acrylic acid and maleic acid or anhydride, may It is to be noted that the component (g) may also be be used for partial replacement thereof for the ester(s) used as an anti-foggant in the case of the dry image of methacrylic acid mentioned before as being capable forming material according to the present invention of forming a rigid thermoplastic acrylic polymer. 20 The high impact acrylic resin, which may be either of which is even of the type other than the post-activation the blend type, or of the copolymer type or the combi type of material that may be spectrally sensitized. nation type thereof as described hereinbefore, is desired In the case of the post-activation type dry image to comprise at least 50 parts by weight, preferably 80 forming material according to the present invention parts by weight, of the acrylic and/or methacrylic ester 25 which is preferably spectrally sensitized, the free silver component per 100 parts by weight of the acrylic resin. oxidizing agent (g) is reduced by serving to oxidize the Here, the term "acrylic and/or methacrylic ester com free silver produced during the storage of the raw ponent' is intended to indicate all of monomer units of image forming material into the original silver halide. the acrylic and/or methacrylic ester type contained in The thus reduced free silver-oxidizing agent, in turn, is the polymer or polymers constituting the acrylic resin. 30 oxidized, under lighting conditions, by the action of the For the measurement of a weight average molecular photoreactive halogeno oxidizing agent (h), whereby it weight, there may be adopted a gel permeation chroma is effectively returned to the original state in which the tography (GPC) method using, as standard samples, component (g) has a capacity of oxidizing free silver. polystyrenes manufactured by Pressure Chemical Co., The photoreactive halogeno oxidizing agent (h) that U.S.A and as an apparatus, WATERS 200 manufac 35 may advantageously be used in combination with the tured by Japan-Waters Co., Japan. component (g) especially in the case of the post-activa Examples of the method for preparing the high im tion dry image forming material which may advanta pact acrylic resin that may be used in the dry image geously be spectrally sensitized is such a halogeno com forming material of the present invention together with pounds as can generate free radicals of halogen upon the recipe of the acrylic resin are described in U.S. Pat. 40 light exposure. Preferred examples of such a halogeno No. 3,793,402, No. 4, 180,529, No. 4,052,525 and No. compound are halogenated organic compounds having 3,681,475. bromine- and/or iodine-carbon linkages. If desired, additives of various kinds such as a lubri Whether or not a given halogen compound is suitable cant, an anti-oxidizing agent, an ultraviolet absorber and for use as the component (h) in the present invention a colorant may be added to the high impact acrylic 45 can be determined, for example, by the following pho resin. toreaction test. The oxidizing agent for free silver that may be used as 1 Mole of silver behenate suitable as the silver behen the component (g) in the post-activation type dry image ate is one which has been synthesized in a mixed solvent forming material according to the present invention, (1:5-5:1 by volume) of water and at least one water-sol which is preferably spectrally sensitized, has a capacity 50 uble or partially water-soluble alcohol having 3 to 8 of oxidizing free silver produced during the storage of carbon atoms), 450 g of polyvinylbutyral and 0.25 mole the material, thereby contributing to improving the of said given halogeno compound for use as the "photo stability of raw material. As examples of the free silver reactive halogeno oxidizing agent' are dissolved into a oxidizing agent (g), there can be mentioned compounds mixed solvent (2:1 by weight) of methyl ethyl ketone of divalent mercury (Hg), compounds of trivalent 55 and toluene, and then formed into a film according to an iron (Fe+ + +), compounds of trivalent cobalt ordinary casting method. (Co+ + F), compounds of divalent palladium (Pd* +) The film thus formed is tested with respect to the and sulfinic acid compounds. As examples of the com following two requirements. When the film satisfies pounds of divalent mercury, there can be mentioned both of the requirements, the halogeno compound (for mercuric salts of aliphatic carboxylic acids such as mer 60 use as the photoreactive oxidizing agent) employed is curic acetate and mercuric behenate; mercuric salts of suitable for the purpose of the present invention. aromatic carboxylic acids such as mercuric benzoate, Requirement 1: when the film is examined by X-ray mercuric m-methylbenzoate and mercuric acetamido diffractometry, the peak due to silver bromide benzoate; mercuric halides such as mercuric bromide (20=31.0) or the peak due to silver iodide (26=23.7) and mercuric iodide; mercuri-benzotriazole; and mer 65 should not substantially be observed the relative inten curi-phthalazinone. Preferred are mercuric acetate, sity of said peak is less than about 10 when the relative mercuric bromide and mercuric iodide. As examples of intensity of the peak due to silver behenate (20 = 12.1) the compounds of trivalent iron, there can be mentioned is defined as 100. 4,396,712 17 18 Requirement 2: subsequently, the film is irradiated with a light (0.5 mW/cm2) emitted from a black lamp in an atmosphere having a temperature of 50° C. and a S S (1) relative humidity of 80% for 2 hours, and then exam- )-CH=CH-CH=( ined by X-ray diffractometry again. The peak due to 5 silver bromide (20=31.0) or the peak due to silver s iodide (20=23.7) should be substantially observed the (CH2)3SO3 (CH2)3SO3Na relative intensity of said peak is about 10 or more when the relative intensity of the peak due to silver behenate (2) (20= 12.1") is defined as 100). 10 S S In the above test, the values of 26 are those of diffrac- )-CH=CH-CH=( tion peaks obtained by using CuKo line. In the test, as C N N C the apparatus for X-ray diffractometry is used an appa- m ratus of Rotor Unit type (RU-200 PL type) manufac- 15 (CH2)3SO3 (CH);SO.Na tured and sold by Rigaku Denki Kabushiki Kaisha, Japan. S CH3 S (3) Specific examples of halogeno compounds capable of )-CH=l-ch being used as the photoreactive halogeno oxidizing N N agent (h) include a,a,a',a'-tetrabromo-o-xylene, a,a,a'- 2O a'-tetrabromo-m-xylene, ethyl a,d,a-tribronoacetate, (CH2)3SO3 (CH2)3SO3H.N(CH5)3 a,c,d-tribromoacetophenone, o,a,a-tribromo-p- bromotoluene, 1,1,1-tribromo-2,2-diphenylethane, tet- S CH3 S (4) bromoethylcyclohexylrabromomethane, 2,2,2,-tribromoethanol, carbamate, 2,2,2-tribromoethyl- 2,2,2-tri 25 )-CH=(-CH=( Cl phenyl carbamate, 2,2,2-tribromoethyl benzoate, 2,2,2- C N N C tribromoethyl ethylcarbamate, 2-methyl-1,1,1-tri- Hso- dison bromo-2-propanol, bis(2,2,2-tribromoethoxy)- diphenylmethane, 2,2,2-tribromoethyl stearate, 2,2,2- (5) tribromoethyl-2-fuorate, bis(2,2,2-tribromoethyl) succi- 30 S Hs S nate, 2,2,2-tribromoethyl phenylsulfonate, 2,2,2-tri- )-CH=(-CH=( bromoethoxytrimethyl silane, 2,2,2-tribromo-1- N N phenylethanol, 2,2,2-tribromoethyldiphenyl phosphate, 1,2-diiodoethane and iodoform. They may be employed (CH2)3SO3 (CH2)2SO3H.N(C2H5)3 either alone or in combination. Of them, the bromo 35 compounds are preferred since they give little coloring S C2H5 S (6) andforming improved material. stability Especially to the preferred resulting are raw a,a,a',a'-tet- dry image )- CH={-CH=( O rabromo-o-xylene, a,a,a', d'-tetrabromo-m-xylene, N ethyl a,a,a-tribromoacetate, a,a,a-tribromo-p- 40 (CH2)4SO3 (CH2)4SO3H.N(C2H5)3 bromotoluene, a,c,d-tribromoacetophenone, 1,1,1-tri bromo-2,2-diphenylethane and 2,2,2-tribromoethanol. (7) Most preferred are a,a,a",o'-tetrabromo-o-xylene and Se Se o,a,a',a'-tetrabromo-m-xylene. The amount of the )-CH=CH-CH=( photoreactive halogeno oxidizing agent (h) is prefera- 45 N N i.als, based on the organic silver salt choso- Hysohn C.H.) It is desirable in the present invention to employ the photoreactive halogeno oxidizing agent (h) in even the 50 Se CH3 Se (8) spectrallypost-activation sensitized, type dryfrom image the viewpointforming material of storage not )- CH=(-CH =( DO stability of raw material. The spectral sensitizing dye (i) that may advanta- (CH2)3SO3 (CH2)3SO3H.N(C3H5)3 geously be used in the post-activation dry image form- 5 ing material according to the present invention consists (9) of at least one compound selected from those com- Se Se pounds represented by the formulae (III), (IV), (V) and )-CH=CH-CH=( (VI) mentioned before, in which A is preferably a Cl N N Cl straight chain propylene group for the purpose of the 60 present invention. The preferred amount of the compo nent (i) is 0.001 to 1 mole % based on the organic silver oxidizing agent (a). The spectral sensitizing dye (i) may S CH3 Se (10) also be, in some cases, used in the already photosensitive )-CH=l-CH=( type dry image forming material according to the pres- 65 N N ent invention. Specific examples of the spectral sensitiz ing dye compounds usable as the component (i) include (CH2)3SO3 (CH2)3SO3H.N(C2H5)3 those represented by the following formulae.

4,396,712 23 24 -continued sensitizer. Among chemical sensitizers which improve 45 the sensitivity of the dry image forming material of the Se Se (45) present invention, those liable to spoil greatly the stor age stability of the dry image forming material prior to -- )-CH=( CH3O N CH3 the use thereof are not preferred. As chemical sensitiz (CH2)3SO3 ers which substantially improve the sensitivity of but (CH2)3SO3H not substantially spoil the storage stability of the dry image forming material of the present invention, there 4. can be mentioned, for example, amide compounds as S SH: S (46) O disclosed in Japanese patent application, Laid-Open -- )-CH=(-CH=( Specification No. 7914/1976, e.g., 1-methyl-2-pyrroli done; quinoline compounds as disclosed in Deutsche (CH2)3SO3 (CH2)3SO3H Offenlegungsschrift No. 2,845,187 and represented by the following general formula: 15 Se pHs S (47)4. R4 R5 r )-CH=(-CH=( N N R3 N-R6 (CH2)3SO3 (CH2)3SO3H es R2 N D 48 Se SH: Se (48) R -- )-CH=(-CH=( wherein R1, R2, R3, R4 R5 and Ré, each indepen N 25 dently, is a hydrogen atom, an aryl group selected from (CH2)3SO3 (CH2)3SO3H phenyl and naphthyl groups unsubstituted or substi 49 tuted with methyl, methoxy or halogen, a C1-C10 S S (49) straight or branched chain alkyl group, a C1-C4 alkoxyl group, an aralkyl group selected from benzyl and phen -- )-CH=CH-CH=( 30 ethyl groups unsubstituted or substituted with methyl, N N methoxy or halogen, a hydroxyl group, a cyano group, (H): (H): a carboxyl group, a C2-C5 alkoxycarbonyl group, a nitro group, an amino group or a carbamoyl group, and sh-so- H-son D is a hydrogen atom, a hydroxyl group or an amino CH3 CH3 35 group; and 3-pyrazolin-5-one compounds as disclosed in Se Se (50)50 Deutshe Offenlegungsschrift No. 2,934,751 and repre sented by the following formula: r )-CH=CH-CH=( 40 (H): (H): sh-so- sh-soh CH3 CH3 45 S fH, S (51)5

-- )-CH=(-CH=( wherein R7 is a hydrogen atom, a C1-C5 straight or N N branched chain alkyl group, an unsubstituted or substi (CH2)3SO3 (CH2)4SO3H 50 tuted phenyl group or an unsubstituted or substituted C3-C8 cycloalkyl group, R8 is a C1-C5 straight or Se SH: Se (52)52 branched chain alkyl group, an unsubstituted or substi tuted phenyl group or an unsubstituted or substituted -- )-CH=(-CH=( C3-C8 cycloalkyl group, and R9 and R10 are the same or 55 different and each represents a hydrogen atom, a C1-C5 (CH2)2SO3 (CH2)3SO3Na straight or branched chain alkyl group, an unsubstituted or substituted phenyl group or an unsubstituted or sub Se Se (53)53 stituted phenylalkyl group having a C1-C5 straight or branched chain alkyl moiety. They may be used either r )-CH=CH-CH=( 60 alone or in combination preferably in an amount of 5 to 50 mole %, based on the organic silver salt oxidizing N agent (a). Specific examples of 3-pyrazolin-5-one com (H): (CH2)3SO3Na pounds include 2-phenyl-3-pyrazolin-5-one, 1-(p-iodo H-so phenyl)-2,3-dimethyl-3-pyrazolin-5-one, 2,3,4-triphe CH3 65 nyl-3-pyrazolin-5-one, 1-phenyl-2,3-dimethyl-3-pyrazo lin-5-one, 1,3-diethyl-2-phenyl-3-pyrazolin-5-one, 2,3- If desired, the dry image forming material of the dimethyl-1-ethyl-4-isopropyl-3-pyrazolin-5-one, 2-o- present invention may further comprise a chemical tolyl-3-methyl-4-ethyl-3-pyrazolin-5-one, 2-cyclohexyl 4,396,712 25 26 3-pyrazolin-5-one, 2-methyl-1,3-diphenyl-3-pyrazolin In the following Examples and Comparative Exam 5-one and 1-cyclohexyl-2,3-dimethyl-3-pyrazolin-5-one. ples, the relative sensitivity, retention of sensitivity and The preferred method of preparing the dry image O.D.04 of dry image forming material are evaluated as forming material of this invention is described by way follows. of example as follows. An organic silver salt oxidizing The sensitivity of dry image forming material is de agent is dispersed in a binder-forming polymer solution fined to be expressed by the reciprocal of amount of by means of a ball mill, a homogenizer, a mixer, a sand exposure light required for giving an optical density mill or the like. To the resulting dispersion are added (O.D.) 0.6 higher than the minimum optical density the other essential components and optionally various (O.D. min) of dry image forming material. Relative additives. The composition thus obtained is applied 10 sensitivity (R.S.) is given herein in terms of a proportion onto a support such as a plastic film, a glass plate, a of the sensitivity of dry image forming material relative paper or a metal plate, followed by drying, to prepare a to the sensitivity of a given dry image forming material dry image forming material. As the plastic film, there whose relative sensitivity is defined as 100. can be mentioned a polyethylene film, a cellulose ace The retention of sensitivity is given herein in terms of tate film, a polyethylene terephthalate film, a polyamide 15 a proportion of sensitivity of dry image forming mate film, a polypropylene film and the like. The dry thick rial subjected to an accelerated deterioration test rela ness of the coating as the image forming layer may be 1 tive to sensitivity of the corresponding dry image form to 100, preferably 3 to 20. The essential components ing material not subjected to the accelerated deteriora of the image forming material of the present invention tion test. may be applied either in one layer as described above, 20 The O.D.0.4 is defined, in the photographic character or in two or more separate but contiguous layers. For istic curve of an imaged material, to be an optical den the purposes of the protection of the heat-developable sity (O.D.) obtained by the amount of exposure light 0.4 image forming layer and so on, a top coat may be pro lower, in terms of logarithmic value, than that required vided. The material for the top coat may be chosen for giving an optical density of 1.0. The O.D.0.4 is a from among the binder materials as mentioned herein 25 yardstick of the sharpness of an image. The sharper the before. In the case of the post-activation type dry image image and, hence, the higher the quality of the image, forming material, the preparation, application to a sup the lower the O.D.04. port and subsequent drying of a composition(s) contain EXAMPLES 1. TO 4 AND COMPARATIVE ing the essential components may be carried out even in EXAMPLES 1 TO 6 a light room, but preferably at a temperature of 50° C. 30 To 20 g of a mixed solvent of toluene and methyl or less. ethyl ketone (mixing weight ratio = 1:2) was added 3 g When the sheet materialso prepared is of the already of silver behenate, and the mixture was ball-milled for photosensitive type, the material can form thereon a about 18 hours to obtain a homogeneous silver behenate visible image when subjected to imagewise exposure to 35 suspension. light and heat development which is usually conducted A silver behenate emulsion having a recipe A as at a temperature of about 90° to 150° C. for about 1 to 30 shown below were prepared and uniformly applied seconds. onto a 100-thick polyethylene terephthalate film at an When the sheet material is of the post-activation type, orifice of 100, and dried by air heated at 80° C. for 5 the material does not lose an image forming capacity 40 minutes to form a first coating layer. A reducing agent even if stored under normal lighting conditions and it containing solution having a recipe B) as shown below can be handled in a light room. When a given area of was uniformly applied as a second coating layer onto this sheet material is heated in the dark, this area is the first coating layer at an orifice of 75u, and dried by rendered photosensitive. This preliminary heating is air heated at 80° C. for 5 minutes to obtain an already preferably carried out at a temperature of about 90° to 45 about 130 C. As the heating temperature is elevated, photosensitive type dry image forming material having the heating time may be proportionally shortened. a total coating layer thickness of about 12. The prepa When the area rendered photosensitive by heating is ration of the dry image forming material was carried exposed imagewise to light and then heat-developed, a out in the dark. visible image is obtained. It is preferred that the heat 50 development be carried out at a temperature of about 90° to about 150° C. The heating time at the step of Silver behenate suspension 1.5g either preliminary heating or heat development may be 10 Weight % solution of polyvinyl 2.0 g butyral in methyl ethyl ketone controlled within the range of from about 1 to about 30 Tetraethylammonium bromide 12 mg seconds. When the preliminary heating for rendering 55 Solution of 10 mg of mercuric 0.15 cc the material photosensitive and the heat development acetate in 3 cc of ethanol are conducted at the same temperature, the time for the 1-Methyl-2-pyrrolidone 30 mg heat development is generally equal to or longer than 2-(2'-Hydroxyphenyl)benzotriazole 35 mg compound(s) as indicated in Table 1 the time for the preliminary heating. In the image form (according to the present invention) ing material of this invention, a visible image can be 60 Recipe B recorded selectively on a given area, and updated infor Cellulose acetate 6.3.g mation may be additionally recorded on other area 2,2'-Methylenebis(4-methyl-6-tert- 3.5g butylphenol) according to need. Furthermore, the image forming Phthalazinone 0.9 g material of this invention can form thereon an image by Acetone 83g photographing even a colored manuscript. 65 The following Examples illustrate the present inven tion in more detail but should not be construed as limit A comparative dry image forming material was pre ing the scope of the invention. pared in substantially the same manner as described 4,396,712 27 28 above except that the use of the 2-(2'-hydroxyphenyl)- benzotriazole compound was omitted, or that a compar -continued ative compound as indicated in Table 1 was used instead HO (C4) of the 2-(2'-hydroxyphenyl)benzotriazole compound. N A piece of each dry image forming material was, in a 5 2 N dark room, exposed for second through a mask film / N closely contacted with the material to light emitted NN from a 500-watt Toshiba Photoreflector Lamp (trade name of a tungsten lamp manufactured by Tokyo (iso-C8H17) Shibaura Electric Company Ltd., Japan), and then 10 heated for 4 seconds on a hot plate maintained at 120° C. HO CH3 (C5) N in a dark room to effect heat development. 212 N. Another piece of each dry image forming material N was subjected to an accelerated deterioration test which was carried out by allowing the material to stand in a 15 s/ dark room at 50 C. and at a relative humidity of 80% CH3 for 3 days. The deteriorated material was subjected to the same image formation as described above. As is apparent from the results shown in Table B 1, The optical densities of the imaged materials respec the 2-(2'-hydroxyphenyl)benzotriazole compounds (f1), tively derived from the materials before and after sub- 20 (f2), (f6) and (f7) used in the dry image forming materi jected to the accelerated deterioration test were mea als according to the present invention are by far supe sured. The results evaluated in terms of fogging, rela rior in storage stability-improving effect to the com tive sensitivity and retention of sensitivity are shown in pounds (C1) to (C5) used in the comparative dry image Table 1, in which (f1), (f2), (f6) and (f7) indicate the forming materials. aforementioned 2-(2'-hydroxyphenyl)benzotriazole 25 A dry image forming material was prepared in sub compounds listed under such numbers (such indications stantially the same manner as in each of Examples 1 to used hereinafter have the same meanings), and in which 4 and Comparative Examples 1 to 6 except that 11 mg of the standard material with a relative sensitivity of 100 is silver bromide previously prepared was used instead of of Comparative Example 1. 12 mg of tetraethylammonium bromide. With respect to TABLE 1. Before Accelerated After Accelerated 2-(2'-Hydroxyphenyl)- Deterioration Deterioration benzotriazole Compound Fogging Relative Fogging Retention of Run No. or Comparative Compound (O.D. min) Sensitivity (O.D. min) Sensitivity (%) Example i (f1) 0.07 96 O. 12 92 Example 2 (f2) 0.07 91 O.13 88 Example 3 (f6) 0.07 92 0.14 89 Example 4 (f3) -- (f7).5/5 by weight 0.07 90 0.15 87 Comparative Example 1 Ole 0.07 100 0.72 - Comparative Example 2 (C1) 0.10 0.1 O.89 - Comparative Example 3 (C2) 0.09 0.1 0.37 --- Comparative Example 4 (C3) 0.07 46 0.62 30 Comparative Example 5 (C4) 0.07 58 0.58 35 Comparative Example 6 (C5) 0.07 66 0.51 39 The comparative compounds (C1) to (C5) used herein are mentioned below. each dry image forming material, the results evaluated H (C1) in terms of fogging, relative sensitivity and retention of N sensitivity were substantially the same as those obtained H5C2 S- C2H5 55 with respect to the dry image forming material pre pared in the corresponding Example or Comparative N N Example. N (C2) N EXAMPLES 5 TO 7 AND COMPARATIVE N 60 EXAMPLES 7 TO 10 / N A homogeneous silver laurate suspension was pre H pared in the same manner as in the preparation of the silver behenate suspension in Examples 1 to 4 and Com HO (C3) parative Examples 1 to 6. P An already photosensitive 65 type dry image forming material was prepared in 2N substantially the same manner as in Examples 1 to 4 N except that recipes (C and D) were employed instead s/ of the recipes A and B), respectively. 4,396,712 29 30 -continued Recipe Cl HO CH3 (C7) Silver laurate suspension 1.5g a N 10 Weight 2 solution of polyvinyl 2.0 g N butyral in methyl ethyl ketone 5 N Calcium bromide 12 mg s^ Solution of 10 mg of mercuric 0.15 cc bromide in 3 cc of methanol 1-Methyl-2-pyrrolidone 30 mg As is apparent from the results shown in Table 2, the 2-(2'-Hydroxyphenyl)benzotriazole 35 mg 2-(2'-hydroxyphenyl)benzotriazole compounds (f3), (f5) (accordingcompound asto indicatedthe present in invention)Table 2 10 d (f8) are very eeffective ective forOr iImproving ing thee ststorage Recipe D) stability of raw dry image forming materials. State 8. EXAMPLES 8 TO O AND COMPARATIVE 1,1-Bis(2-hydroxy-3-tert-butyl- 3.5g EXAMPLES 11 TO 15 isyphenylpentane 83 g ' A silver behenate emulsion having a recipe E as shown below, in which the silver behenate suspension A comparative dry imagea- forming material was pre- wasand Comparativeprepared in the Examples same manner 1 to 6 as(the in "silverExamples behenate 1 to 4 pared in substantially the same manner, as described 20 suspension' appearing hereinafter was the same as pre above except that the use of the 2-(2 -hydroxyphenyl)- pared in Examples 1 to 4 and Comparative Examples 1 benzotriazole compound was omitted, or that a compart to 6), was prepared at room temperature (about 20° C). ative compound as indicated in Table 2 was used instead The silver behenate emulsion was uniformly applied of the 2-(2 -hydroxyphenyl)benzotriazole compound. onto a 100u-thick polyethylene terephthelate film at an A piece of each dry image forming material was 25 orifice of 100, and air-dried at room temperature subjected to the same image formation as in Examples 1 (about 20 C.) for 2 hours to form a first coating layer. to 4 and Comparative Examples 1 to 6. Another piece of A reducing agent-containing composition having a rec each dry image forming material was subjected to the ipe (F) as shown below was uniformly applied as a same accelerated deterioration test as in Examples 1 to second coating layer onto the first coating layer at an 4 and Comparative Examples 1 to 6, are subjected to the 30 orifice of 75u, and air-dried at room temperature (about same image formation as in Examples 1 to 4 and Com- 20 C.) for 5 hours to obtain a post-activation type dry parative Examples 1 to 6. a image forming material having a total coating layer The relative sensitivity, fogging and retention of sen- thickness of about 12u. The preparation of the dry sitivity of the dry image forming material were exam image forming material was conducted in a light room. ined, and were found to be as shown in Table 2, in which the standard material with a relative sensitivity 35 of 100 is of Comparative Example 7. TABLE 2. Before Accelerated After Accelerated 2-(2'-Hydroxyphenyl)- Deterioration Deterioration benzotriazole Compound Fogging Relative Fogging Retention of Run No. or Comparative Compound (O.D. min) Sensitivity (O.D. min) Sensitivity (%) Example 5 (f3) 0.07 92 0.12 89 Example 6 (f5) 0.07 94 0.13 90 Example 7 (f8) 0.07 89 0.6 85 Comparative Example 7 One 0.07 100 0.8 o Comparative Example 8 (C5) 0.07 70 0.41 30 Comparative Example 9 (C6) 0.07 73 0.38 28 Comparative w Example 10 (C7) 0.07 77 O.30 49

Recipe E Silver behenate suspension 1.5g 55 10 Weight % solution of polyvinyl butyral in methyl ethyl ketone 2.0 g Solution of 100 mg of mercuric acetate in 3 cc of ethanol 0.5 cc

The comparative compounds (C6) and (C7) used Ehy--CCSC Epacetate ringng herein are mentioned below. 60 Solution of 100 mg of cobalt bromide in 1 cc of nethanol 0.5 cc HO (n-C4H9) 2-(2'-Hydroxyphenyl)benzotriozole compound as indicated in Table 3 2 N (according to the present invention) 35 mg Quinoline 30 mg N 65 Recipe IF SN Cellulose acetate 6.3.g Phthalazinone 0.9 g (phenyl) 2,2'-Methylenebis(4-ethyl 6-tert-butylphenol) 3.5g 4,396,712 31 32 are mentioned below. The comparative compound (C5) -continued is also the known ultraviolet absorber. Acetone 83 g (C8) A comparative dry image forming material was pre pared in substantially the same manner as described CO OCH3 above except that the use of the 2-(2'-hydroxyphenyl)- benzotriazole compound was omitted, or that a compar ative compound as indicated in Table 3 was used instead HO of the 2-(2'-hydroxyphenyl)benzotriazole compound. 10 A piece of each dry image forming material was, in a (C9) dark room, heat-activated at 100° C. for 5 seconds, and COO exposed for second through a mask film closely con tacted with the material to light emitted from the 500 watt Toshiba Photoreflector Lamp. The exposed mate 15 HO rial was then heated for 5 seconds on a hot plate main tained at about 120° C. in a dark room to effect heat HO (C10) N development. 2 N Another piece of each dry image forming material N was subjected to the same accelerated deterioration test 20 s / (heat- and humidity-acceleration) as in Examples 1 to 4 N and Comparative Examples 1 to 6, followed by the same CH3 image formation as described above. In order to examine the light stability of raw material, As is apparent from the results shown in Table 3, the still another piece of each dry image forming material 25 2-(2'-hydroxyphenyl)benzotriazole compounds (fA), (f6) was subjected to an accelerated deterioration test (fade and (fS) having tert-butyl or tert-amyl groups at the 3'- ometer light-accleration) which was carried out at 40 and 5'-positions are very effective for improving the C. for 2 hours under a light of 200,000 luxes by using a stability of raw dry image forming materials during fadeometer FX-1 (trade name of a xenon lamp fadeome storage thereof either under heat and humidity or under ter manufactured by Suga Shikenki K. K., Japan), fol 30 lighting conditions as compared with the known ultra lowed by the same image formation as described above. violet absorbers. Still another piece of each image forming material The fact that the 2-(2'-hydroxyphenyl)benzotriazole was subjected to an accelerated deterioration test (fil compounds (f4), (f6) and (f)) are capable of absorbing tered light-acceleration) which was carried out by ex only light having wavelengths of less than 400 nm will posing, at 40 C. for 2 hours, the material to light emit 35 indicate that the improvement in light stability of raw ted from the fadeometer FX-1 and filtered through a material achieved in the present invention should not be VY-45 filter (trade name of a color filter manufactured attributed to the function of the component (f) as the and sold by Tokyo Shibaura Electric Company Ltd., ultraviolet absorber. Japan), which permits only light with wavelengths of 450 nm or more to pass therethrough. The material thus 40 EXAMPLES 11 TO 14 AND COMPARATIVE deteriorated was subjected to the same image formation EXAMPLES 16 TO 23 as described above. A post-activation type dry image forming material The relative sensitivity, fogging and retention of sen was prepared in substantially the same manner as in sitivity of each dry image forming material were exam Examples 8 to 10 and Comparative Examples 11 to 15 ined, and were found to be as shown in Table 3, in 45 except that recipes G) and H) as shown below were which the standard material with a relatively sensitivity employed instead of the recipes E and F, respec of 100 is of Comparative Example 11. tively. TABLE 3 Before Accelerated After Accelerated Deterioration 2-(2'-Hydroxyphenyl)- Deterioration Heat and Humidity Fadeometer Light Filtered Light benzotriazole Com- Relative Retention Retention Retention pound or Com- Fogging Sensi- Fogging of Sensi- Fogging of Sensi- Fogging of Sensi Run No. parative Compound (O.D. min) tivity (O.D. min) tivity (%) (O.D. min) tivity (%) (O.D. min) tivity (%) Example 8 (fA) 0.07 94 0.16 84 0.15 96 0.4 95 Example 9 (f6) 0.07 90 0.14 82 0.14 93 0.13 94 Exampie 10 (f9) 0.07 93 0.15 85 0.4 91 0.14 93 Comparative Example 11 One 0.07 100 0.33 55 0.39 58 0.34 63 Comparative Example 12 (C8) 0.07 63 0.98 .23 - 19 - Comparative Example 13 (C9) 0.07 58 1.04 1.31 - 1.25 - Comparative Example 14 (C10) 0.07 77 0.51 42 0.45 37 0.39 40 Comparative Example 15 (C5) 0.07 80 0.37 53 0.34 43 0.33 49 The comparative compounds (C8), (C9) and (C10) used herein, which are the known ultraviolet absorbers, 4,396,712 33 34

Recipe G N (C11) Silver behenate suspension 1.5 g W-OH 10 Weight % solution of polyvinyl butyral in methyl ethyl ketone 2.0 g 5 N Solution of 100 mg of mercuric acetate in 3 cc of ethanol 0.15 cc s Solution of 100 mg of nickel As is apparent from the results shown in Table 4, the Side in 1 cc of methanol 0.1; CC use of the 2-(2'-hydroxyphenyl)benzotriazole com TriphenylphosphiteOce 3 mgng O pounds (fi), (f2), (f) and (7) having tert-butyl or tertawa 1-Phenyl-2,3-dimethyl-3-pyrazolin- amyl groups at the 3'- and 5'-positions are very effective 5-one 30 mg for improving the stability of raw dry image forming aga'a'Tetrabromoto-xylene 25 mg materials during storage thereof either under heat and 2-(2'-Hydroxyphenyl)benzotriazole humidity or under lighting conditions. The improve (accordingcompound asto indicatedthe present in invention)Table 4 35 mg is ment in light stability of raw material achievedp by the Recipe IH inclusion of one of the compounds (f1), (f2), (f6) and (f7) Polymethyl methacrylate 6.3 g evidently should not be attributed to the ultraviolet ashinebisci-ethyl-6-ter- 5 rays-absorbing function of the compounds (fi), (f2), (f6) E.thalazinone 0.93.5 g and (f7) capable of absorbing only light having wave Acetone 83 g lengths of less than 400 nm. COMPARATIVE EXAMPLE 24 A comparative post-activation type dry image form A dry image forming material was prepared in sub ing material was prepared in substantially the same stantially the same manner as in Examples 1 to 4 and manner as described above except that the use of the Comparative Examples 1 to 6 except that, instead of the 2-(2-hydroxyphenyl)benzotriazole compound was 25 2-(2'-hydroxyphenyl)benzotriazole compound, 35 mg omitted, or that a comparative compound as indicated in Table 4 was used instead of the 2-(2'-hydroxyphenyl)- of benzotriazole and 0.1 ml of a 0.2 weight % solution of benzotriazole compound. sodium benzenethiosulfonate in methanol were used. The relatively sensitivity, fogging and retention of The material so obtained was subjected to the same sensitivity of each dry image forming material were 30 image formation as in Examples 1 to 4 and Comparative examined in the same manner as in Examples 8 to 10 and Examples 1 to 6. The material could not form an image Comparative Examples 11 to 15, and were found to be because it was too poor in sensitivity. as shown in Table 4, in which the standard material EXAMPLES 15 TO 29 AND COMPARATIVE with a relative sensitivity of 100 is of Comparative Ex- EXAMPLES 25 TO 35 ample 16. 35 An already photosensitive- type dry image forming TABLE 4 After Accelerated Deterioration Before Accelerated Fadeometer Light Filtered Light 2-(2'-Hydroxyphenyl)- Deterioration Heat and Humidity Retention Retention benzotriazole Com- Relative Retention of Sensi- of Sensi pound or Com- Fogging Sensi- Fogging of Sensi- Fogging tivity Fogging tivity Run No. parative Compound (O.D. min) tivity (O.D. min) tivity (%) (O.D. min) (%) (O.D. min) (%) Example 11 (f1) 0.07 95 0.14 83 0.14 94 0.14 95 Example 12 (f2) 0.07 90 0.5 80 0.14 92 0.14 94 Example 13 (f6) 0.07 91 0.15 80 0.15 93 0.15 94 Example 14 (f7) 0.07 88 0.17 78 0.16 90 0.16 91 Comparative Example 16 O 0.07 100 0.41 58 0.36 63 0.34 64 Comparative Example 17 (C1) 0.10 0.08 0.79 MMM 0.87 -- 0.85 M Comparative Example 18 (C2) 0.09 0.05 0.32 www- 0.59 0.55 w Comparative Example 19 (C3) 0.07 39 0.58 43 0.52 37 0.49 40 Comparative Example 20 (C4) 0.07 43 0.5 46 0.40 4. 0.38 43 Comparative Example 21 (C5) 0.07 52 0.40 55 0.37 46 0.32 50 Comparative Example 22 (C7) 0.07 66 0.37 62 0.3 60 0.29 62 Comparative Example 23 (C11) 0.07 0.1 0.45 m 0.43 Mww. 0.40 m

material was prepared in substantially the same manner as in Examples 1 to 4 except that recipes I and Jas shown below were employed instead of the recipes. A 65 and B), respectively. The comparative compound (C11) used herein is mentioned below. Recipe II 4,396,712 35 36 A piece of each dry image forming material was -continued subjected to the same image formation as in Examples 1 Silver15 Weight behemate % solution suspension of polyvinyl 1.5 g to 4 and Comparative- Examples 1 to 6. butyral in methyl ethyl ketone 1.3 g Another piece of each dry image forming material Tetraethylammonium bromide 12 mg 5 was subjected to an accelerated deterioration test which Solution of 10 mg of mercuric acetate was carried out by allowing the material to stand in a E. cc of ethanol 0.5 cc dark room at 40° C. and at a relative humidity of 80% 2-(2'-Hydroxyphenyl)benzotriazole-Methyl-2-pyrrolidone 30 mg for 30 days, followed by the same imageo formation- as in compound as shown in Table 5 35 mg Examples 1 to 4 and Comparative Examples 1 to 6. (according to the present invention) 10 The O.D. min and O.D.04 of the image materials Recipe IJ were measured, and were found to be as shown in Ta 2,2'-Methylenebis(4-methyl-6-tert- bles 5 and 6 butylphenol) 3.5 g TABLE 5 2-(2'Hydroxyphenyl)- Before Accelerated. After Accelerated benzotriazole Deterioration Deterioration Run No. Compound Binder Resin O.D. min O.D.04 O.D. min O.D.04 Example 15 (f1) (AR-a) 0.07 0.8 0.9 O.29 Example 16 (f1) (AR-b) 0.07 0.8 0.19 0.29 Example 17 (f1) (AR-c) 0.07 0.20 0.20 0.31 Example 18 (f2) (AR-a) 0.07 0.20 O.20 0.30 Example 19 (f2) (AR-b) 0.07 0.21 0.20 0.31 Example 20 (f2) (AR-c) 0.07 0.22 0.21 0.32 Example 21 (f6) (AR-a) 0.07 0.18 0.19 0.31 Example 22 (f6) (AR-b) 0.07 0.18 0.20 0.32 Example 23 (f6) (AR-c) 0.07 0.20 0.2 0.32 Example 24 (f7) (AR-a) 0.07 0.20 0.22 0.33 Example 25 (f7) (AR-b) 0.07 0.20 0.22 0.33 Example 26 (f7) (AR-c) 0.07 0.21 0.22 0.33 Example 27 (f1) cellulose 0.07 0.25 0.26 0.44 acetate Example 28 (f2) polymethyl 0.07 0.27 0.26 0.45 methacrylate Example 29 (f6) polystyrene 0.07 0.25 0.28 0.46

TABLE 6 Before Accelerated After Accelerated Deterioration Deterioration Run No. Comparative Compound Binder Resin O.D. min O.D.0.4 O.D. min O.D.04 Comparative cellulose Example 25 (CI) acetate 0.10 0.34 0.91 - Comparative cellulose Example 26 (C2) acetate 0.09 0.30 0.43 0.73 Comparative cellulose Example 27 (C3) acetate 0.07 0.28 0.71 0.98 Comparative cellulose Example 28 (C4) acetate 0.07 0.28 0.60 0.90 Comparative cellulose Example 29 (C5) acetate 0.07 0.30 O.S4. 0.85 Comparative Example 30 Ole (AR-a) 0.07 0.25 0.30 0.50 Comparative Example 31 e (AR-b) 0.07 0.25 0.30 0.51 Comparative Example 32 O (AR-c) 0.07 0.26 0.31 0.55 Comparative cellulose Example 33 OE acetate 0.07 0.30 0.83 Comparative polymethyl Example 34 ce methacrylate 0.07 0.30 0.46 0.79 Comparative Example 35 Oe polystyrene 0.07 0.30 0.43 0.76

The acrylic resin (AR-a) was a blend of polymethyl methacrylate and 40% by weight, based on the poly Phthalazinone 0.9 g methyl methacrylate, of a rubber-elastic, partially Methyl ethyl ketone 83 g 60 crosslinked copolymer obtained by the potassium per Binder resin as indicated in Table 5 6.3 g sulfate-catalyzed emulsion polymerization, in water at 65° C. for 2 hours, of a mixture of 90% by weight of A comparative dry image forming material was pre methyl acrylate and 10% by weight of 55% divinylben pared in substantially the same manner as described zene (a mixture of 55% by weight of divinylbenzene above except that the use of the 2-(2'-hydroxyphenyl)- 65 and 45% by weight of ethylvinylbenzene). benzotriazole compound was omitted, or that a compar The acrylic resin (AR-b) was a copolymer of 80% by ative compound as indicated in Table 1 was used instead weight of methyl methacrylate and 20% by weight of of the 2-(2'-hydroxyphenyl)benzotriazole compound. n-butyl acrylate. 4,396,712 37 38 The acrylic resin (AR-c) was a 2:1 by weight blend of -continued the acrylic resin (AR-a) mentioned above and poly Calcium bromide 12 mg methyl methacrylate. Barium iodide 8 Ing As is apparent from the results shown in Table 5 and Solution of 10 mg of mercuric bromide 6, the dry image forming materials according to a pre in 3 cc of methanol 0.15 cc 1-Methyl-2-pyrrollidone 30 mg ferred embodiment of the present invention, which 2-(2'Hydroxyphenyl)benzotriazole comprised an organic silver salt oxidizing agent-con compound as indicated in Table 7 35 mg taining first coating layer containing one of the 2-(2'- (according to the present invention) hydroxyphenyl)benzotriazole compounds (f1), (f2), (f6) Recipe L) and (f7), and a reducing agent-containing second coat O 1, 1'-Bis(2-hydroxy-3-tert-butyl ing layer containing, as the binder, a high impact acrylic 5-methylphenyl)pentane 3.5 g Phthalazinone 0.9 g resin selected from the acrylic resins (AR-a), (AR-b) Methyl ethyl ketone 83 g and (AR-c), were superior, in image quality evaluated Binder resin as indicated in Table 7 6.3 g in terms of value of O.D.04 before deterioration, and in storage stability of raw material evaluated in terms of 15 degree of fogging and value of O.D.04 after deteriora A comparative dry image forming material was pre tion, to the dry image forming materials according to pared in substantially the same manner as described the present invention, which comprised an organic sil above except that the use of the 2-(2'-hydroxyphenyl)- ver salt oxidizing agent-containing first coating layer benzotriazole compound was omitted. containing one of the 2-(2'-hydroxyphenyl)benzo A piece of each dry image forming material was triazole compounds (fi), (f2) and (f6), and a reducing subjected to the same image formation as in Examples 1 agent-containing second coating layer containing, as the to 4 and Comparative Examples 1 to 6. binder, a polymer other than the high impact acrylic Another piece of each dry image forming material resin. The latter materials, however, were superior, in was subjected to the same accelerated deterioration test the same respects as mentioned above, to the compara 25 as in Examples 15 to 29 and Comparative Examples 25 tive dry image forming materials comprising an organic to 35, and subjected to the same image formation as in silver salt oxidizing agent-containing first coating layer Examples 1 to 4 and Comparative Examples 1 to 6. containing no 2-(2'-hydroxyphenyl)benzotriazole com The O.D. min and O.D.04 of the dry image forming pound and none or one of the comparative compounds material before and after deterioration were examined, (C1) to (C5), and a reducing agent-containing second and were found to be as shown in Table 7. TABLE 7 Before After 2-(2'-Hydroxyphenyl)- Accelerated Accelerated benzotriazole Deterioration Deterioration Run No. Compound Binder Resin O.D. min O.D.04 O.D. min O.D.04 Example 30 (f3) (AR-d) 0.07 0.2 0.10 0.23 Example 31 (f5) (AR-d) 0.07 0.20 0.10 0.23 Example 32 (f8) (AR-d) 0.07 0.21 0.10 0.23 Example 33 (f3) polymethyl 0.07 0.26 0.19 0.44 methacrylate Example 34 (f5) polymethyl 0.07 0.26 0.19 0.45 methacrylate Example 35 (f8) polymethyl 0.07 0.25 0.20 0.46 methacrylate Comparative Example 36 Ole (AR-d) 0.07 0.25 0.30 0.55 Comparative polymethyl Example 37 Ole methacrylate 0.07 0.29 0.48 0.80 The acrylic resin (AR-d) was a polymer latex ob coating layer containing, as the binder, a high impact tained by subjecting a mixture of 90 parts by weight of acrylic resin selected from the acrylic resins (AR-a), 50 n-butyl acrylate, 10 parts by weight of methyl methac (AR-b) and (AR-c) or a polymer of the other kind. rylate and 0.6 part by weight of triallyl cyanurate to potassium persulfate-catalyzed emulsion polymeriza EXAMPLES 30 TO 35 AND COMPARATIVE tion in water at 70° C. for 2 hours under an atmosphere EXAMPLES 36 TO 37 of nitrogen to prepare a latex (solids content: about 33% A homogeneous silver laurate suspension was pre 55 by weight) of a crosslinked acrylic elastomer and subse pared in the same manner as in the preparation of the quently subjecting a mixture of 30.3 parts by weight of silver behenate suspension in Examples l to 4 and Com the crosslinked acrylic elastomer latex, 6 parts by parative Examples 1 to 6. weight of acrylonitrile, 12 parts by weight of styrene, 12 An already photosensitive type dry image forming parts by weight of methyl methacrylate and 0.3 part by material was prepared in substantially the same manner 60 weight of ethylene glycol dimethacrylate to potassium as in Examples 1 to 4 except that recipes K) and L) as persulfate-catalyzed emulsion polymerization at 70° C. shown below were used instead of the recipes A) and for 2 hours. B), respectively. As is apparent from the results shown in Table 7, the dry image forming materials according to a preferred Recipe (K 65 embodiment of the present invention, which comprised Silver laurate suspension 1.5 g. an organic silver salt oxidizing agent-containing first 15 Weight % solution of polyvinyl coating layer containing one of the 2-(2'-hydroxy butyral in methyl ethyl ketone 1.3 g phenyl)benzotriazole compounds (f3), (f5) and (f8), and 4,396,712 39 a reducing agent-containing second coating layer con 40 taining the high impact acrylic resin (AR-d) as the -continued Methyl ethyl ketone 83 g binder, were superior, in image quality evaluated in Binder resin as indicated in terms of value of O.D.04 before deterioration, and in Table 8 6.3.g storage stability of raw material evaluated in terms of 5 degree of fogging and value of O.D.04 after deteriora tion, to the dry image forming materials according to A comparative dry image forming material was pre the present invention, which comprised an organic sil pared in substantially the same manner as described ver salt oxidizing agent-containing first coating layer above except that the use of the 2-(2'-hydroxyphenyl)- containing one of the 2-(2"hydroxyphenyl)-benzo to benzotriazole compound was omitted, or that a compar triazole compounds (f3), (fS) and (f8), and a reducing ative compound as indicated in Table 8 was used instead agent-containing second coating layer containing poly of the 2-(2'-hydroxyphenyl)benzotriazole compound. methyl methacrylate as the binder. The latter materials, A piece of each dry image forming material was however, were superior, in storage stability of raw subjected to the same image formation as in Examples 8 material evaluated as described above, to the compara is to 10 and Comparative Examples 11 to 15. tive dry image forming materials comprising an organic Another piece of each dry image forming material silver salt oxidizing agent-containing first coating layer was subjected to the same accelerated deterioration test containing no 2-(2'-hydroxyphenyl)benzotriazole com (heat- and humidity-acceleration) as in Examples 15 to pound, and a reducing agent-containing second coating 29 and Comparative Examples 25 to 35, followed by the layer containing, as the binder, the acrylic resin (AR-d) same image formation as in Examples 8 to 10 and Com or polymethyl methacrylate. parative Examples 11 to 15. In order to examine the light stability of raw material, EXAMPLES 36 TO 41 AND COMPARATIVE still another piece of each dry image forming material EXAMPLES 38 TO 43 was subjected to an accelerated deterioration test (fil A post-activation type dry image forming material as tered light-acceleration) which was carried out by ex was prepared in substantially the same manner as in posing, at 40 C. at a relative humidity of 30% for 2 Examples 8 to 10 except that recipes IM) and N as hours, the material to light emitted from the fadeometer shown below were used instead of the recipes IE) and FX-1 and filtered through the VY-45 filter, which per F, respectively. mits only light with wavelengths of 450 nm or more to o pass therethrough. The material thus deteriorated was subject to the same image formation as in Examples 8 to Recipe M 10 and Comparative Examples 11 to 15. Silver behenate suspension 1.5g The O.D. min and O.D.0.4 of the image materials 15 Weight of solution of polyvinyl butyral in methyl ethyl ketone 1.3g were measured, and were found to be as shown in Table Solution of 100 mg of mercuric 8. TABLE 8 Before 2-(2'-Hydroxyphenyl) Accelerated After Accelerated Deterioration benzotriazole Compound Deterioration Heat and Humidity Filtered Light Run No. or Comparative Compound Binder resin O.D. min O.D.04 O.D. min O.D.04 O.D. min O.D.04 Example 36 (f4) (AR-e) 0.07 0.21 0.11 0.22 0.10 0.22 Example 37 (f6) (AR-e) 0.07 0.19 0.10 0.20 0.09 0.20 Example 38 (f9) (AR-e) 0.07 0.22 0.12 0.23 0.11 0.23 Example 39 (f4) cellulose acetate 0.07 0.25 0.19 0.44 0.18 0.43 Example 40 (f6) cellulose acetate 0.07 0.25 0.18 0.30 0.17 0.29 Example 41 (f)) cellulose acetate 0.07 0.26 0.20 0.32 0.19 0.31 Comparative Example 38 none (AR-e) 0.07 0.26 0.22 0.54 0.19 0.41 Comparative Example 39 Oe cellulose acetate 0.07 0.31 0.89 0.67 - Comparative Example 40 (C8) (AR-e) 0.07 0.30 0.97 -- 1.01 - Comparative Example 41 (C9) (AR-e) 0.07 0.3 1.23 -- 1.15 - Comparative Example 42 (C10) (AR-e) 0.07 0.30 0.67 0.97 0.55 0.75 Comparative Example 43 (C12) (AR-e) 0.07 0.29 0.43 0.73 0.40 0.6

acetate in 3 cc of than CC The acrylic resin (AR-e) was a polymer obtained by sailbonebromotoluene 12 . subjecting a mixture of 61.5 parts by weight of n-butyl Solution of 100 mg of cobaltic 60 acrylate, 13.5 parts by weight of styrene and 0.4 parts by bromide in 1 cc of methanol 0.15 cc weight of butylene glycol diacrylate to potassium per EYEE sulfate-catalyzed emulsion polymerization in water at compound as indicated in Table 70° C. for 30 minutes to prepare a copolymer, polymer Quinoline(according to the present invention) 3035 mg izing at 70°o C. for 1 hour 25 parts by weight of methyl Recipe IN 65 methacrylate in the presence of said copolymer to pre 2,2'-Methylenbis(4-methyl-6-tert- pare a rubbery elastomer and subsequently subjecting a butylphenol) 3.5g 4% by weight dispersion of said rubbery elastomer Phthalazinone 0.9 g dispersed in a monomer mixture composed of 96% by 4,396,712 41 42 weight of methyl methacrylate and 4% by weight of material achieved in the present invention should not be ethyl acetate to free-radical polymerization at 80° C. for attributed to the function of the component (f) as the 1 hour. ultraviolet absorber. The comparative compound (C12) used herein is mentioned below. 5 EXAMPLES 42 AND 43 AND COMPARATIVE EXAMPLES 44 TO 47 HO CH3 (C12) An already photosensitive dry image forming mate N rial was prepared in substantially the same manner as in 2 N Examples 1 to 4 except that recipes (O) and P as N 10 shown below were used instead of the recipes A and s/ B), respectively. (tert-amyl) Recipe O) As is apparent from the results shown in Table 8, the 15 Silver behenate suspension 1.5g dry image forming materials according to a preferred 15 Weight % solution of polyvinyl embodiment of the present invention,o whichhich compriseised butyralSilver bromide in methyl ethyl ketone 1.311 mgg an organic silver salt oxidizing agent-containing first Solution of 10 mg of mercuric coating layer containing one of the 2-(2'-hydroxy- acetate in 3 cc of methanol 0.15 cc phenyl)benzotriazoleduci t-containing compounds second (f4), coating (f6) and layer (f)), con- and 20 2-(2'-Hydroxyphenyl)benzotriazoleE. -- 30 mg a re. R E. 9. li A. y h compound (fi) 35 mg taining the high impact acrylic resin (AR-e) as t le Recipe P binder, were superior, in image quality evaluated in 2,4,4'-Trimethylpenthylbis(2-hydroxy-- Recipe (Pl terms of value of O.D.04 before deterioration, and in 3,5-dimethylphenyl)methane 2.8g storage stability of raw material evaluated in terms of 25 Phthalazinone 0.9 g degree of fogging and value of O.D.04 after deteriora- Methyl ethyl ketone 83 g tion (either heat- and humidity-acceleration or filtered presin as indicated in 6.3 light-acceleration), to the dry image forming materials 38 according to the prevent invention, which comprised an organic silver salt oxidizing agent-containing first 30 A comparative dry image forming material was pre coating layer containing one of the 2-(2'-hydroxy- pared in substantially the same manner as described phenyl)benzotriazole compound (f4), (f6) and (f9), and a above except that the use of the 2-(2-hydroxyphenyl)- reducing agent-containing second coating layer con- benzotriazole compound was omitted. taining cellulose acetate as the binder. The latter materi- Five pieces of each dry image forming material were als, however, were superior, in the same respects as 35 each subjected to substantially the same image format mentioned above, to the comparative dry image form- tion as in Examples 1 to 4 and Comparative Examples 1 ing materials comprising an organic silver salt oxidizing to 6 except that the development temperature were agent-containing first coating layer containing no 2-(2- varied as shown in Table 9. hydroxyphenyl)benzotriazole compound and none or The relative sensitivity and O.D.04 of the imaged one of the comparative compounds (C8), (C9), (C10) 40 materials Were examined, and were found to be 2S and (C12), and a reducing agent-containing second shown in Table 9, in which the standard material with a coating layer containing, as the binder, the acrylic resin relative sensitivity of 100 when developed at 125° C. for (AR-e) or cellulose acetate. 4 seconds is of Example 42. TABLE 9 2-(2'- Development Temperature (C) Hydroxy- 115° C. 120 C. 125 C. 130 C. 135° C. phenyl)ben- Relative Relative Relative Relative Relative zotriazole Binder Sensi- Sensi- Sensi- Sensi- Sensi Run No. Compound Resin tivity O.D.04 tivity O.D.0.4 tivity O.D.0.4 tivity O.D.0.4 tivity O.D.04 Example 42 (f1) (AR-a) 90 0.26 90 0.20 100 0.20 150 0.23 250 0.33 Example 43 (f) (AR-d) 89 0.26 92 0.20 101 0.20 150 0.23 253 0.33 Compara tive Exam ple 44 none (AR-a) 71 0.34 90 0.25 100 0.30 203 0.35 351 0.49 Compara tive Exam ple 45 e (AR-d) 7 0.34 92 0.25 0. 0.30 200 0.35 349 0.49 Compara- Oe cellulose 2 0.41 40 0.3 ' 7 0.35 98 0.43 401 0.58 tive Exam- acetate ple 46 Compara- none poly- 60 0.4 91 0.31 21 0.34 200 0.42 350 0.53 tive Exam- methyl ple 47 meth acrylate

The fact that the 2-(2'-hydroxyphenyl)benzotriazole 65 compounds (fA), (f6) and (f)) are capable of absorbing As is apparent from the results shown in Table 9, the only light having wavelengths of less than 400 nm will combinations of the 2-(2'-hydroxyphenyl)benzotriazole indicate that the improvement in light stability of raw compound (f1) (according to the present invention) 4,396,712 43 44 with the high impact acrylic resin (AR-a) or (AR-d) provided the dry image forming materials which were EXAMPLES 46 TO 51 AND COMPARATIVE subject to smaller variations in sensitivity and O.D.04 EXAMPLES 49 TO 52 with heat development conditions than the comparative A post-activation type dry image forming material dry image forming materials containing no 2-(2- 5 was prepared in substantially the same manner as in hydroxyphenyl)benzotriazole compound. Examples 8 to 10 except that recipes (R) and S) as EXAMPLES 44 AND 45 AND COMPARATIVE shownF), respectively below were usedd insteadinste offth the recipes- (E) and EXAMPLES 48 TO 51 s A post-activation type dry image forming material 10 was prepared in substantially the same manner as in - Recipe (R) Examples 8 to 10 except that recipe Q as shown below Silver15 Weight behenate % solution suspension of polyvinyl 1.5 g and the recipe P as used Examples 42 to 43 (the butyral in methyl ethyl ketone 1.3 g binder resin was as indicated in Table 10) were used Solution of 100 mg of mercuric acetate instead of the recipes E and F), respectively. 15 in 3 cc of ethanol 0.15 cc Solution of 100 mg of nickel bromide in 1 cc of methanol 0.15 cc Iodine 8 mg Recipe (Q) Triphenyl phosphite 3 mg Silver behenate suspension 1.5 g. 1-Phenyl-2,3-dimethyl-3- 15 Weight % solution of polyvinyl 20 pyrazolin-5-one 30 mg butyral in methyl ethyl ketone 1.3 g o,a,a',a'-Tetrabromo-o-xylene 25 mg Solution of 100 mg of mercuric acetate 2-(2'-Hydroxyphenyl)benzotriazole in 3 cc of ethanoi 0.15 cc compound as indicated in Table 11 35 mg N-Iodosuccinimide 17 mg (according to the present invention) Diphenylbromomethane 4 mg Recipe IS Quinolinegto Tetrabromo-m-xylene 30 mg is 2,2'-Methylenebis(4-ethyl-6-tert-butylphenol) 3.5 g 2-(2'-Hydroxyphenyl)benzotriazole Phthalazinone 0.9 g compound (f6) 35 mg Methyl ethyl ketone 83.0 g Binder resin as indicated in Fiveo pieces of each dry image forming material were Table 1 6.3 g each subjected to substantially the same image forma- 30 o tion as in Examples 15 to 29 and Comparative Examples A piece of each dry image forming material was 25 to 35 except that the material was preliminarily subjected to the same image formation as in Examples 8 heated at 100°C. for 5 seconds and that the develop- to 10 and Comparative Examples 11 to 15. ment temperatures were varied as shown in Table 10. In order to examine the stability of latent image, four The relative sensitivity and O.D.04 of the imaged 35 pieces of each dry image forming material, after sub materials were examined, and were found to be as jected to the same heat-activation and light exposure as shown in Table 10, in which the standard material with in Examples 8 to 10 and Comparative Examples 11 to 15 a relative sensitivity of 100 when developed at 125 C. were allowed to stand in a dark room for 0.5, 1, 5 and 10 for 4 seconds is of Example 44. hours, respectively, and then heat-developed for 5 sec TABLE 10 Development Temperature ('C) 120° C. 25° C. 130° C. 135° C. 2-(2'-Hydroxy- 15° C. Rela- Rela- Rela- Rela phenyl)benzo- Relative tive tive tive tive triazole Binder Sensi- Sensi- Sensi- Sensi- Sensi Run No. Compound Resin tivity O.D.0.4 tivity O.D.0.4 tivity O.D.0.4 tivity O.D.0.4 tivity O.D.04 Example 44 (f6) (AR-a) 91 0.26 90 0.20 100 0.2O 149 0.23 249 0.33 Example 45 (f6) (AR-d) 90 0.26 9i 0.20 101 0.20 150 0.23 252 0.33 Comparative Example 48 Ione (AR-a) 7 0.35 91 0.25 100 0.31 2O2 0.35 350 0.49 Comparative Example 49 Ote (AR-d) 70 0.35 92 0.25 O1 0.30 200 0.35 350 0.49 Comparative cellulose Example 50 Ole acetate 20 0.41 41 0.31 70 0.35 200 0.43 400 0.59 Comparative polymethyl Example 51 Ole methacrylate 61 0.40 91 0.31 122 0.35 20 0.4 352 0.53 onds on a hot plate maintained at 125 C. As is apparent from the results shown in Table 10, the 60 The relative sensitivity and latent image stability of combinations of the 2-(2'-hydroxyphenyl)benzotriazole the dry image forming material were examined, and (f6) (according to the present invention) with the high were found to be as shown in Table 11, in which the impact acrylic resin (AR-a) or (AR-d) provided the dry standard material with a relative sensitivity of 100 is of image forming materials which were subject to smaller Comparative Example 52, and in which the latent image variations in sensitivity and O.D.04 with heat develop 65 stability is expressed as corresponding to retention of ment conditions than the comparative dry image form sensitivity when the standing of the material in the dark ing materials containing no 2-(2'-hydroxyphenyl)benzo room for a given time is regarded as an accelerated triazole compound. deterioration test. 4,396,712 45 46 TABLE 11 2-(2'-Hydroxyphenyl) Binder Relative Latent Image Stability (%) Run No. benzotriazole Compound Resin Sensitivity 0.5 hour 1 hour 5 hours 10 hours Example 46 (fi) (AR-a) 85 100 100 100 92 Example 47 (f1) (AR-f) 86 100 100 100 90 Example 48 (f1) (AR-g) 85 100 100 100 89 Example 49 (f6) (AR-a) 85 100 100 100 90 Example 50 (f6) (AR-f) 85 00 100 00 90 Example 51 (f6) (AR-g) 85 100 100 100 90 Comparative Example 49 Oil (AR-a) 85 70 61 50 40 Comparative Example 50 none (AR-f) 85 72 62 49 41 Comparative Example 51 Ole (AR-g) 85 72 60 51 40 Comparative polymethyl Example 52 Ole methacrylate 100 51 35 20 10

-continued The acrylic resin (AR-f) was a blend of polymethyl Quinoline 30 mg methacrylate and 40% by weight, based on the poly- 20 Solution of 10 mg of dye compound methyl methacrylate, of Tufprene A (trade name of a as indicated in Table 12 in 10 cc styrene-butadienew block copolymer manufactured by g-(2'-Hydroxyphenyl)benzotriazole methanol 0.1 cc Asahi Kasei Kogyo Kabushiki Kaisha, Japan). compound as indicated in Table 12 The acrylic resin (AR-g) was a blend of polymethyl (according to the present invention) 35 mg methacrylate and 40% by weight, based on the poly- 25 Recipe EU methyl methacrylate, of a rubber-elastic, partially- Cellulose acetate 6.3.g crosslinked copolymer obtained by the potassium per- it inity sulfate-catalyzed emulsion polymerization, in water at methylphenol p 3.2g 60° C. for 2 hours, of a mixture of 90% by weight of Acetone 83.0 g methyl acrylate and 10% by weight of dipropylene 30 Phthalazinone 1.2g glycol dimethacrylate. As is apparent from the results shown in Table 11, the A comparative dry image forming material was pre combinations of the 2-(2-hydroxyphenyl)benzotriazole pared in substantially the same manner as described compound (f1) or (f6) (according to the present inven above except that the use of the 2-(2-hydroxyphenyl)- tion) with the high impact acrylic resin (AR-a), (AR-t) 35 benzotriazole compound was omitted, or that a compar or (AR-g) provided the dry image forming materials ative compound as indicated in Table 13 was used in having a higher latent Image stability than those of the stead of the 2-(2'-hydroxyphenyl)benzotriazole com dry image forming materials containing no 2-(2'- pound. hydroxyphenyl)benzotriazole compound. A piece of each dry image forming material was A dry image forming material was prepared in Sub- 40 preliminarily heated on a hot plate maintained at about stantially the same manner as in each of Examples 46 to 100° C. for 3 seconds in a dark room. Then, the material 51 and Comparative Examples 49 to 52 except that 3 mg was exposed for 1 second through a 21-step steptablet of cobalt dibromide was used instead of the methanol (manufactured and sold by Eastman Kodak Co., Ltd., solution of nickel bromide. With respect to each dry U.S.A.) to light emitted from a tungsten lamp having a image forming material, the results evaluated in terms of 45 color temperature of 3,200 K. and filtered through a relative sensitivity and latent image stability were sub yellow color filter Y-50 (trade name of a color filter stantially the same as those obtained with respect to the manufactured and sold by Tokyo Shibaura Electric dry image forming material prepared in the correspond Company Ltd., Japan). The exposed material was then ing Example or Comparative Example. heated on a hot plate maintained at about 125 C. for 4 50 seconds in the dark room to effect heat development. EXAMPLES 52 TO 66 AND COMPARATIVE Another piece of each dry image forming material EXAMPLES 53 TO 68 was subjected to an accelerated deterioration test (heat A post-activation type dry image forming material and humidity-acceleration) which was carried out by was prepared in substantially the same manner as in allowing the material to stand in the dark at 45 C. and Examples 8 to 10 except that recipes T and U) as 55 at a relative humidity of 80% for 10 days. The deterio shown below were used instead of the recipes (E) and rated material was subjected to the same image forma F), respectively. The amount of silver behenate con tion as described above. tained in the first coating layer was about 4 g/m2 of the The optical densities of the imaged materials respec layer. tively derived from the materials before and after sub 60 jected to the accelerated deterioration test were mea Recipe IT sured. The results evaluated in terms of relative sensitiv Silver behenate suspension 1.5g ity, fogging (O.D. min) and retention of sensitivity are 15 Weight % solution of polyvinyl shown in Tables 12 and 13, in which the dye com butyral in methyl ethyl ketone 1.3 g pounds (1), (4), (5), (18) and (28) indicate the aforemen Solution of 100 mg of mercuric 65 tioned spectral sensitizing dye compounds listed under iodide in 9 cc of acetone 0.5 cc Bis-p-methoxyphenyltellurium diiodide 28 mg such numbers (such indications used hereinafter have Bis-p-methoxyphenyltellurium dibromide 14 mg the same meanings), and in which the standard material o,a,a,a'-Tetrabromo-o-xylene 30 mg with a relative sensitivity of 100 is of Example 52. 4,396,712 47 48 TABLE 12 Before Accelerated After Accelerated Deterioration Deterioration Dye 2-(2'-Hydroxyphenyl)- Relative Fogging Retention of Fogging Run No. Compound benzotriazole Compound Sensitivity (O.D. min) Sensitivity (%) (O.D. min) Example 52 (1) (f) 100 0.09 77 0.2 Example 53 (1) (f2) 99 0.09 78 0.12 Example 54 (1) (f7) 100 0.09 80 0.12 Example 55 (4) (f1) 40 0.09 69 0.11 Example 56 (4) (f2) 400 0.09 68 0.11 Example 57 (4) (f7) 398 0.09 68 0.1 Example 58 (5) (f1) 82 0.09 59 0.2 Example 59 (5) (f2) 80 0.09 58 0.12 Example 60 (5) (f7) 80 0.09 58 0.12 Example 61 (18) (f1) 30 0.09 95 0.10 Example 62 (18) (f2) 201 0.09 95 0.0 Example 63 (18) (f7) 200 0.09 94 0.10 Example 64 (28) (f1) 252 0.09 6 0.11 Example 65 (28) (f2) 249 0.09 60 0.1 Example 66 (28) (f7) 250 0.09 60 0.11

TABLE 13 Before Accelerated After Accelerated Deterioration Deterioration Dye Relative Fogging Retention of Fogging Run No. Compound Comparative Compound Sensitivity (O.D. min) Sensitivity (%) (O.D. min) Comparative Example 53 Oe none O 0.08 O 0.21 Comparative Example 54 (D-a) OC 12 0.51 O 0.65 Comparative Example 55 (D-b) One 8 0.32 O 0.64 Comparative Example 56 (D-c) none 14 0.64 O 0.65 Comparative Example 57 (D-d) Oe 15 0.52 O 0.81 Comparative Example 58 (D-e) Ole 7 0.21 O 0.83 Comparative Example 59 (1) One 100 0.09 35 0.37 Comparative Example 60 (4) One 402 0.09 36 0.29 Comparative Example 61 (5) One 81 0.09 30 0.38 Comparative Example 62 (18) One 30 0.09 45 0.31 Comparative Example 63 (28) none 251 0.09 31 0.30 Comparative Example 64 (1) (C1) 73 0.14 O 0.65 Comparative Example 65 (1) (C2) 73 0.11 0. 0.61 Comparative Example 66 (1) (C3) 84 0.09 11 0.35 Comparative Example 67 (1) (C4) 92 0.09 12 0.36 Comparative Example 68 (1) (C5) 93 0.09 0.36 The dye compounds (D-a) to (D-e) used herein are mentioned below. 55 O D-a S 1- N-C2H5 (D-a) X CH f O ss -continued N CH3 60 C2H5 S S S (D-c) (D-b) N >-en-air Nya h A 'S 65 3 O C2H5 S 3-Allyl-5-3-ethyl-(2-naphthoxazolidine)-ethylidene 1-phenyl-2-thiohydantoin C N >- arch ()- N(CH3)2 4,396,712 49 50 -continued -continued I (D-e) N-Iodosuccinimide 63 ng NaO O 2O Cobalt dibromide 3 mg a l-Methyl-2-pyrrolidone 20 mg Solution of 10 mg of dye compound as a indicated in Table 14 in 10 cc of C methanol 0.2 cc 2-(2'-Hydroxyphenyl)benzotriazole C COONa compound (f6) 35 mg O Recipe IW Cl Cl Cellulose acetate 6.3 g 2,4,4'-trimethylpenthylbis(2- Cl hydroxy-3,5-dimethylphenyl)methane 2.8g Phthalazinone 1.2g As is apparent from the results shown in Tables 12 Acetone 83.0 g and 13, the combinations of the 2-(2'-hydroxyphenyl)- 15 benzotriazole compound (f1), (f2) or (f7) (according to A comparative dry image forming material was pre the present invention) with the dye compound (1), (4), pared in substantially the same manner as described (5), (18) or (28) provided the dry image forming materi above except that the use of the 2-(2-hydroxyphenyl)- als having higher spectral sensitivity and storage stabil benzotriazole compound was omitted, or that the com ity of raw material (evaluated in terms of fogging and 20 parative compound (C12) was used instead of the 2-(2'- retention of sensitivity) than those of the comparative hydroxyphenyl)benzotriazole compound. dry image forming materials containing no 2-(2- A piece of each dry image forming material was hydroxyphenyl)-benzotriazole compound and none or subjected to the same image formation as in Examples one of the comparative compounds (C1) to (C5). 52 to 66 and Comparative Examples 53 to 68. 25 Another piece of each dry image forming material EXAMPLES 67 TO 70 AND COMPARATIVE was subjected to the same accelerated deterioration test EXAMPLES 69 TO 79 (heat-and humidity-acceleration) as in Examples 52 to A post-activation type dry image forming material 66 and Comparative Examples 53 to 68, followed by the was prepared in substantially the same manner as in same image formation as in Examples 52 to 66 and Com Examples 8 to 10 except that recipes IV) and IW as 30 parative Examples 53 to 68. shown below were used instead of the recipes E and The relative sensitivity, fogging and retention of sen F), respectively. sitivity of each dry image forming material were exam ined in the same manner as in Examples 52 to 66 and Comparative Examples 53 to 68, and were found to be Recipe IV 35 as shown in Table 14, in which the standard material Silver behenate suspension .5g with a relative sensitivity of 100 is of Example 67. TABLE 14 Before Accelerated After Accelerated 2-(2-Hydroxyphenyl)- Deterioration Deterioration Dye benzotriazole Compound Relative Fogging Retention of Fogging Run No. Compound or Comparative Compound Sensitivity (O.D. min) Sensitivity (%) (O.D. min) Example 67 (22) (f6) 00 0.09 57 0.13 Example 68 (23) (f6) 65 0.09 62 0.13 Example 69 (25) (f6) 23 0.09 71 0.2 Example 70 (37) (f6) 132 0.09 52 0.13 Comparative Example 69 Oe ce O 0.08 O 0.27 Comparative Example 70 (22) Oile 100 0.09 O 0.61 Comparative Example 71 (23) ce 67 0.09 6 0.30 Comparative Example 72 (25) lie 122 0.09 13 0.38 Comparative Example 73 (37) One 129 0.09 5 0.26 Comparative Example 74 (22) (C12) 7 0.09 O 0.31 Comparative Example 75 (23) (C12) 47 0.09 O 0.31 Comparative Example 76 (25) (C12) 81 0.09 O 0.30 Comparative Example 77 (37) (C12) 92 0.09 O 0.31 Comparative Example 78 (D-f) e O 0.35 O 0.43 Comparative Example 79 (D-g) te 27 0.35 O 0.38

15 Weight 7% solution of polyvinyl butyral in methyl ethyl ketone 1.3g inSolution 9 cc of of E. 100 mg of mercuric iodide 0.5 cc The dye compounds (D-f) and (D-g) used hereino are 2,2,2-Tribromoethanol 45 mg mentioned below. 4,396,712 51 52 -continued O SH: On 1 (D-f) indicated in Table 5 in Occ of methanol 0.2 cc 2-(2'-Hydroxyphenyl)benzotriazole -- X-CH=(H-CH={ 5 compound as indicated in Table 15 35 mg (according to the present invention) C2H5 C2H5 1-Phenyl-2,3-dimethyl-3-pyrazolin 5-one 30 mg O O (D-g) Polymethyl methacrylate 6.3 g CHCH-CH O 2,2'-Methylenebis(4-ethyl-6-tert -H X- =x butylphenol) 3.5 g CH3 N N CH3 Phthalazinone 1.2 g (CH3)3SO3 C2H5 Methyl ethyl ketone 83.0 g As is apparent from the results shown in Table 14, the 15 A comparative dry image forming material was pre combinations of the 2-(2'-hydroxyphenyl)benzotriazole pared in substantially the same manner as described compound (f6) (according to the present invention) above except that the use of the 2-(2'-hydroxyphenyl)- with the dye compound (22), (23), (25) or (37) provided benzotriazole compound was omitted, or that a compar the dry image forming materials having higher spectral ative compound as indicated in Table 15 was used in sensitivity and storage stability of raw material (evalu stead of the 2-(2'-hydroxyphenyl)benzotriazole com ated in terms of fogging and retention of sensitivity) pound. than those of the comparative dry image forming mate A piece of each dry image forming material was rials containing no 2-(2-hydroxyphenyl)benzotriazole subjected to substantially the same image formation as compound or the comparative compound (C12). in Examples 52 to 66 and Comparative Examples 53 to 25 68 except that the light exposure was carried out for 8 EXAMPLES 71 TO 78 AND COMPARATIVE seconds by using a light with a wavelength of 480 nm EXAMPLES 69 TO 79 emitted from a monochrometer. To 20 g of a mixed solvent of toluene and methyl Another piece of each dry image forming material ethyl ketone (mixing weight ratio = 1:2) was added 3.5g was subjected to the same accelerated deterioration test of silver stearate, and the mixture was ball-milled for 30 (heat-and humidity-acreleration) as in Examples 52 to about 18 hours to obtain a homogeneous silver stearate 66 and Comparative Examples 53 to 68, followed by the suspension. same image formation as described above. A post-activation type dry image forming material In order to examine the light stability of raw material, was prepared in substantially the same manner as in still another piece of each image forming material was Examples 8 to 10 except that recipes X and Y as 35 subjected to an accelerated deterioration test (filtered shown below were used instead of the recipes E and light-acceleration) which was carried out by exposing, F, respectively. at 40 C. for 2 hours, the material to light emitted from the fadeometer FX-1 and filtered through a VY-45 filter (trade name of a color filter manufactured and sold by Recipe IX 40 Tokyo Shibaura Electric Company Ltd., Japan), which Silver stearate suspension 1.5 g 15 Weight % solution of polyvinyl permits only light with wavelengths of 450 nm or more butyral in methyl ethyl ketone 1.3 g to pass therethrough. The material thus deteriorated Iodine 8 mg was subjected to the same image formation as described Triphenyl phosphite 4 mg above. Nickel dibromide 4 mg Solution of 100 mg of mercuric 45 The relative sensitivity, fogging and retention of sen acetate in 3 cc of methanoi 0.5 cc sitivity of each dry image forming material were exam a,a,a',a'-Tetrabromo-m-xylene 30 mg ined, and were found to be as shown in Table 15, in Solution of 10 mg of dye compound as which the standard material with a relative sensitivity of 100 is of Example 71.

After Accelerated Deterioration 2-(2'-Hydroxyphenyl)- Before Accelerated Filtered Light benzotriazole Con Deterioration Heat and Humidity Retention Dye pound or Comparative Relative Fogging Retention of Fogging of Sensi- Fogging Run No. Compound Compound Sensitivity (O.D. min) Sensitivity (%) (O.E. min) tivity (%) (O.D. min) Example 71 (38) (f3) 100 0.09 7 0.12 62 0. Example 72 (39) (f3) 2O 0.09 62 O. 12 55 0. Example 73 (40) (f3) 200 0.09 75 0.1 TO O. Example 74 (43) (f3) 76 0.09 57 0.1 52 0.1 Example 75 (38) (fg) 102 0.09 71 0.2 6 0.11 Example 76 (39) (F9) 203 0.09 62 0.2 54 0.1 Example 77 (40) (f9) 200 0.09 75 O. 70 0.1 Example 78 (43) (F9) 76 0.09 58 O. 12 52 0. Comparative Example 69 de Oe O 0.08 O 0.25 O O. Comparative Example 70 (38) ce 102 0.09 35 0.30 28 0.18 Comparative Example 71 (39) de 201 0.09 30 0.34 20 0.18 Comparative 53 4,396,712 54

.. - . W . . . -continued ------...... -Hammmammadma-am-e--After Accelerated Deterioration 2-(2'-Hydroxyphenyl)- Before Accelerated Filtered Light benzotriazole Com- Deterioration, Heat and Humidity Retention - - - - - Dye. . poind or Comparative Relative Fogging Retention of Fogging of Sensi- Fogging Run No. Compound Compound Sensitivity (O.D. min) Sensitivity (%) (O.D. min) tivity (%) (O.D. min) Example 72 (40) One 200 0.09 40 0.30 40 0.18 Comparative Example 73 (43) One 174 0.09 31 0.35 25 0.18 Comparative Example 74 (D-h) One 0 0.08 O 0.30 0 0.30 Comparative Example 75 (D-i) One O 0.09 O 0.29 O 0.30 Comparative Example 76 (D-j) Ole 29 0.09 O 0.22 21 0.23 Comparative Example 77 (38) (C8) 80 0.09 O 1.19 0. 0.73 Comparative Example 78 (39) (C9) 69 0.09 O 1.02 O 0.62 Comparative Example 79 (43) (C13) 92 0.09 35 0.48 30 0.16

The dye compounds (D-h), (D-1) and (D-j) used compounds (C8), (C9) and (C13) are incapable of ab herein are mentioned below. sorbing light having wavelengths of 450 nm or more 25 will indicate that the improvement in light stability of (D-h) raw material achieved in the present invention should not be attributed to the function of the component (f) as O-alk O the ultraviolent absorber. 30 EXAMPLES 79 TO 87 AND COMPARATIVE EXAMPLES 80 TO 92 (D-i) A post-activation type dry image forming material was prepared in substantially the same manner as in Examples 8 to 10 except that recipe Z as shown below O) kDO 35 and the recipe Y as used in Examples 71 to 78 were used instead of the recipes (E) and F), respectivity.

• . . . . se ...... ses - Recipe (Z) 40 Silver behenate suspension 1.5g X-CH={ 15 Weight % solution of polyvinyl . . ; 1 NN . N butyral in methyl ethyl ketone 1.3g Iodine 8 mg Triphenyl phosphite 4 mg Diphenylbronomethane 4 mg The comparative compound (C13) used herein is 45 Solution of 100 mg of mercuric acetate in 3 cc of methanol 0.15cc mentioned below. a,a,a',a'-Tetrabromo-o-xylene 30 mg Solution of 10 mg of dye compound

...... HO CH3 (C13) as shown in Table 16 in 10 cc of methanol 0.2 cc 2-(2'-Hydroxyphenyl)benzotriazole 50 compound as indicated in Table 16 (according to the present invention) 35 mg 1-Phenyl-2,3-dimethyl-3-pyrazolin 5-one 30 mg (tert-butyl) As is apparent from the results shown in Table 15, the 55 A comparative dry image forming material was pre combinations of the 2-(2'-hydroxyphenyl)benzon pared in substantially the same manner as described triazole compound (f3) or (f)) (according to the present above except that the use of the 2-(2'-hydroxyphenyl)- invention) with the dye compound (38), (39), (40) or benzotriazole compound was omitted. (43) provided the dry image forming materials having The relative sensitivity, fogging and retention of sen higher light or storage stability of raw material (evalu 60 sitivity of each dry image forming material were exam ated in terms of fogging and retention of sensitivity) ined in the same manner as in Examples 71 to 78 and than those of the comparative dry image forming mate Comparative Examples 69 to 79 except that the image rials containing no 2-(2'-hydroxyphenyl)benzotriazole formation was carried out in substantially the same compound and none or one of the comparative com manner as in Examples 52 to 66 and Comparative Ex pounds (C8), (C9) and (C13). . . 65 amples 53 to 68, and were found to be as shown in Table The fact that the 2-(2'-hydroxyphenyl)benzotriazole 16, in which the standard material with a relative sensi compounds (f3) and (f)) as well as the comparative tivity of 100 is of Example 79. 4,396,712 55 56 TABLE 16 Before Accelerated After Accelerated Deterioration Deterioration Heat and Humidity - - Filtered Light - 2-(2'-Hydroxyphenyl)- Relative Retention Retention Dye benzotriazole Sensi- Fogging of Sensi- Fogging of Sensi- Fogging Run No. Compound Compound tivity (O.D. min) tivity (%) (O.D. min) tivity (%) (O.D. min) Example 79 (2) (f) 100 0.09 75 0.12 70 0.1 Example 80 (3) (f3) 201 0.09 96 0,12 90 0.11 Example 81 (7) (f1) 280 0.09 90 0,12 90 0.1 Example 82 (8) (f1) 300 0.09 98 0.12 95 0,1 Example 83 (13) (f5) 82 0.0 60 0.3 50 0.12. Example 84 (20) (f6) 80 0,10 59 0.13 52 0.12 Example 85 (21) (f8) 80 0.10 58 0.13 5 0,12 Example 86 (29) (f10) 251 0.09 60 0.13 54 0.12 Example 87 (48) (fl. 1) 202 0.09 96 0.12 93 0.11 Comparative Example 80 none Othe O 0.08 O 0.20 O 0.11 Comparative Example 81 (2) Ole 102 0.09 40 0.37 35 0.27 Comparative Example 82 (3) One 203 0.09 43 0.33 40 0.18 Comparative Example 83 (7) noe 280 0.09 41 0.26 35 0.7 Comparative Example 84 (8) O 300 0.09 45 0.25 45 0.16 Comparative Example 85 (13) Oe 72 0.32 29 0.35 25 0.25 Comparative Example 86 (20) Othe 70 0.30 30 0.35 22 0.27 Comparative Example 87 (21) One 71 0.30 31 0.37 25 0.26 Comparative Example 88 (29) Ole 253 0.09 43 0.30 41 0.16 Comparative Example 89 (48) Othe 201 0.09 45 0.30 42 0.17 Comparative Example 90 (D-k) Ole 53 0.22 12 0.27 1 0.24 Comparative Example 91 (D-1) none O 0.32 O 0.32 O 0.30 Comparative Example 92 (D-m) One 0 0.31 O 0.33 O 0.30 The dye compounds (D-k), (D-1) and (D-m) used herein are mentioned below. taining no 2-(2'-hydroxyphenyl)benzotriazole com 40 pound. A piece of each of the dry image forming materials Se fH, Se (D-k)D-k prepared in Examples 79 and 80, and 83 to 87, and Com parative Example 82 was heat-activated on a hot plate -- X-CH=(-CH={ maintained at about 100 C. in the dark for 3 seconds, N 45 and then put into a 35 mm still camera, followed by (CH2)3SO3 C2H5 taking a photograph of an NBS resolution test chart of 100 lines/mm (NBS; National Bureau of Standards). D-l The material was then heat-developed on a hot plate CHEC-CH maintained at about 125 C. for 4 seconds. The mini OC.X-CH=(-CH={ SH: Se (D-l) SO mum optical density (O.D..min) between the photo N I N graphed lines were measured by using a Sakura Micro C2H5 C2H5 densitometer PDM-5 (trade name of a microdensitome ter manufactured by Konishiroku Photo Ind. Co. Ltd., Se th Se (D-m)D Japan). In general, that the O.D.min of an image form 55 ing material is lower proves that the material is less X-CH=(-CH={ subject to the influences of halation or irradiation, lead ing to a high quality image. (CH2)3COO (CH2)3COOH The results are shown in Table 17. TABLE 17 As is apparent from the results shown in Table 16, the O.D.rnin between Lines combinations of the 2-(2'-hydroxyphenyl)benzotriazole Example No. (100 lines/mm) compound (f1), (f3), (fS), (f6), (f8), (f10) or (fl 1) (ac Example 79 0.26 cording to the present invention) with the dye com Example 80 0.26 pound (2), (3), (7), (8), (13), (20), (21), (29) or (48) pro Example 83. 0.27 65 Example 84 0.24 vided the dry image forming materials having higher Example 85 0.24 light or storage stability of raw material (evaluated in Example 86 0.25 terms of fogging and retention of sensitivity) than those Example 87 0.25 of the comparative dry image forming materials con Comparative 4,396,712. 57 58 TABLE 17-continued TABLE 18-continued O.D..min between Lines 2-(2'-Hydroxyphenyl)- Example No. Dye benzotriazole Com- O.D..min be (100 lines/mm) Com- pound or Comparative tween Lines Example 82 0.58 5 Run No. pound Compound (100 lines/mm) Example 93 (25) (f4) 0.26 Example 94 (28) (f5) 0.26 As is apparent from the results shown in Table 17, the Example 95 (29) (f8) 0.27 combinations of the 2-(2'-hydroxyphenyl)benzotriazole Example 96 (40) (9) 0.27 compound (f1), (f3), (fS), (f6), (f8), (f10) or (fill) (ac Example 97 (43) (f1) 0.27 cording to the present invention) with the dye com 10 Comparative Example 93 (1) One 0.57 pound (2), (3), (13), (20), (21), (29) or (48) provided the Comparative dry image forming materials which were less subject to Example 94 (4) none 0,62 the influences of halation and irradiation, producing Comparative high quality images with a high resolution and a low Example 95 (10) One 0.60 15 Comparative O.D..min even in narrow areas between imaged lines. Example 96 (25) O 0.57 Comparative EXAMPLES 88 TO 97 AND COMPARATIVE Example 97 (29) Oe 0.60 EXAMPLES 93 TO 102 Comparative Example 98 (1) (C2) 0.62 A post-activation type dry image forming materials Comparative was prepared in substantially the same: manner as in 20 Example 99 (4) (C3) 0.60 Examples 8 to 10 except that recipes a and A) as Comparative shown below were used instead of the recipes E and Example 100 (10) (C8) 0.58 Comparative (F), respectively. Example 101 (25) (C9) 0.56 25 Comparative Recipe Ial Example 102 none Oe 0.18 Silver behenate suspension 1.5g 15 Weight % solution of polyvinyl 1.3 g As is apparent from the results shown in Table 18, the butyral in methyl ethyl ketone Solution of 100 mg of mercuric acetate 0.5 cc combinations of the 2-(2'-hydroxyphenyl)benzotriazole in 3 cc of methanol 30 compound (f1), (f2), (f3), (f4), (f5), (f8) or (fS) with the Iodine 8 mg dye compound (1), (3), (4), (8), (10), (25), (28), (29), (40) Triphenyl phosphite 4 mg or (43) provided the dry image forming materials which Diphenylbromomethane 4 mg 1-Phenyl-2,3-dimethyl-3- 30 mg were less subject to the influences of halation and irradi pyrazolin-5-one ation, producing high quality images with a high resolu a,a,a",a'-Tetrabromo-o-xylene 35 mg 35 tion and a low O.D..min even in narrow areas between Solution of 10 mg of dye compound as 0.1 cc imaged lines. indicated in Table 18 in 10 cc of methanol 2-(2'-Hydroxyphenyl)benzotriazole 35 mg EXAMPLE 98 compound as indicated in Table 18 (according to the present A post-activation type dry image forming material invention) was prepared in substantially the same manner as in Recipe B Example 79 except that 5 mg of palladium (II) acetylac Acrylic resin (AR-a) 6.3.g 2,2'-Methylenebis(4-ethyl-6 3.5g etonate and 5 mg of cobalt (III) acetylacetonate were tert-butylphenol) used instead of the methanol solution of mercuric ace Phthalazinone 1.2g tate and that 20 mg of iodine was used instead of 8 mg Methyl ethyl ketone 83.0 g 45 of the same. The results evaluated with respect to stabil ity of the raw material in the same manner as in Exam A comparative dry image forming material was pre ple 79 were substantially the same as those obtained in pared in substantially the same manner as described Example 79. above except that the use of the 2-(2'-hydroxyphenyl)- The Izod impact strengths (notched) of the high im benzotriazole compound was omitted, or that a compar 50 pact acrylic resins used herein were examined in accor ative compound as indicated in Table 18 was used in dance with ASTM D 256 and found to be as shown in stead of the 2-(2'-hydroxyphenyl)benzotriazole com Table 19. pound. TABLE 19 With respect to each dry image forming material, the 55 High Impact Acrylic Izod Impact Strength (Notched) O.D.min between the photographed lines were mea Resin (ft. Ib/in) sured in the same manner as described in Example 79 to Acrylic Resin (AR-a) 0.93 87 and Comparative Examples 80 to 92. The results are Acrylic Resin (AR-b) 0.95 Acrylic Resin (AR-c) 0.70 shown in Table 18. Acrylic Resin (AR-d) 0.87 TABLE 18 Acrylic Resin (AR-e) 0.52 Acrylic Resin (AR-?) 0.42 2-(2'-Hydroxyphenyl)- Acrylic Resin (AR-g) 55 Dye benzotriazole Com- O.D..min be Com- pound or Comparative tween Lines Run No. pound Compound (100 lines/mm) The Izod impact strength (notched) of the poly Example 88 (1) (f3) 0.25 65 methyl methacrylate used herein was 0.30. Example 89 (3) (f4) 0.24 What is claimed is: Example 90 (4) (f5) 0.26 Example 91 (8) (f) 0.24 1. A dry image forming material comprising in one or Example 92 (10) (f2) 0.25 more layers on a support: 4,396,712 59 60 -continued (a) a non-photosensitive organic silver salt oxidizing HO (tert-amyl) (II) agent, a'sN (b) a reducing agent for silver ions, N (c) a silver halide component of a silver halide-form s/ ing component capable of forming a silver halide R (tert-amyl) component by the reaction thereof with the com wherein R stands for a hydrogen atom, a C1-C8 ponent (a), 10 straight or branched chain alkyl group, a C1-C4 straight or branched chain alkoxyl group, a phenyl (d) a toning agent, group or a halogen atom selected from Cl, Brand (e) a lipophilic binder, and I; the component (f) being included in a layer containing (f) at least one member selected from the group con 15 the component (a) and being present in an amount suffi sisting of those compounds represented by the cient to improve the storage stability. 2. A dry image forming material as claimed in claim following formulae; 1, wherein, in the formulae () and (II), R is a hydrogen aton. 20 3. A dry image forming material as claimed in claim HO (tert-butyl) (I) 1 or 2, wherein the component (f) comprises at least one compound of the formula (I). , and 4. A dry image forming material as claimed in claims 1 or 2, wherein the amount of the component (f) is in the 25 range of from 1 x 10-2 to 6x 10-mole per mole of the (tert-butyl) component (a). k k k x:

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