JP3913866B2 - Photothermographic material for laser exposure - Google Patents

Description

【０１２１】
《下塗り塗布液Ｂの調製》
蒸留水680mlにスチレン−ブタジエン共重合体水分散物(スチレン／ブタジエン／イタコン酸=47／50／3(重量比)、濃度30wt%)200ml、ポリスチレン微粒子(平均粒径2.5μm)0.1gを添加し、さらに蒸留水を加えて1000mlとして下塗り塗布液Ｂとした。
【０１２２】
《下塗り塗布液Ｃの調製》
イナートゼラチン10gを蒸留水500mlに溶解し、そこに特開昭61-20033号明細書記載の酸化スズ−酸化アンチモン複合物微粒子の水分散物(40wt%)40gを添加して、これに蒸留水を加えて1000mlとして下塗り塗布液Ｃとした。
【０１２３】
《下塗り支持体の作成》
下記青色染料で色味付けした厚さ175μmの２軸延伸ポリエチレンテレフタレート支持体の片面（感光面）にコロナ放電処理を施した後、上記下塗り塗布液Ａをバーコーターを用いてウエット塗布量が5cc/m²になる様に塗布して180℃で5分間乾燥した。乾燥膜厚は約0.3μmであった。
【０１２４】
次いで、この裏面(バック面)にコロナ放電処理を施した後、下塗り塗布液Ｂをバーコーターを用いてウエット塗布量が5cc/m²、乾燥膜厚が約0.3μmになる様に塗布して180℃で5分間乾燥し、更にこの上に下塗り塗布液Ｃをバーコーターを用いてウエット塗布量が3cc/m²、乾燥膜厚が約0.03μmになる様に塗布して180℃で5分間乾燥して下塗り支持体を作成した。
【０１２５】
【化２】

【０１２６】
《熱画像形成材料の調製》
下塗り支持体にバック層塗布液を647nmの光学濃度が0.7となる流量で、バック面保護層塗布液を50g/m²でStephen F. Kistler、Petert M. Schweizer著“LIQUID FILM COATING”(CHAPMAN & HALL社刊、1997年)427頁のFigure 11b.1と同様のコーターで同時重層塗布した後、バック面と反対の面に支持体側から乳剤層塗布液82cc/m²、中間層塗布液6.5cc/m²、保護層-1塗布液12.5cc/m²、保護層-2塗布液12cc/m²となるように塗布し、10℃(露点0℃以下)のチルドゾーンを通過させた後30℃40%RH風速20m/secの風で乾燥した。ただし、表１に記載のように同時重層は乳剤面４層を同時重層し、逐次塗布は乳剤層をまず塗布乾燥した後、残りの３層を同時に塗布乾燥した。保護層-2の塗布銀量は2.1g/m²であり、ポリメチルメタクリレート微粒子は7700ヶ/m²含まれている。
【０１２７】
【化３】

【０１２８】
《屈折率の測定》
バインダーの溶液(または分散液)をガラス板上に塗布して50℃で1時間乾燥して、厚さ約100μmのポリマー膜を作成した。この膜をガラス板から剥離して、アッベ屈折率計(アタゴ(株)製タイプ1T)を用いてナトリウムランプのＤ線に対する屈折率を測定した。
【０１２９】
(干渉縞の評価)
660nmの半導体レーザー(最大出力30mW)を用いて図２のθ=90°にて写真材料を露光した後、写真材料を120℃15秒間処理(現像)し、画像濃度1.0に仕上げた。木目状の干渉縞を目視評価した。
【０１３０】
干渉縞の評価は以下の通りである。
干渉縞評価
○：干渉縞発生しない。
△：干渉縞少し発生。
×：干渉縞発生。
【０１３１】
(折り曲げ脆性の評価)
作成された感光材料を3.5cm×25cmのサイズに裁断して、25℃10%RHの条件にて3時間以上調湿する。乳剤層塗布面を外側にして角度5°に設定した楔型の脆性試験器に長手方向に通し、片端をクリップで固定し、もう片端を脆性試験器の隙間を通して手で引っ張る。感光材料は引っ張るにつれて曲率が大きくなり、折れ曲がるように設定されているので、表面にひび割れが発生した位置を確認し、クリップで固定した位置からの距離を読みとる。距離が短い方が好ましい。評価の必要によっては、ひび割れた部分に粘着テープを張り付けてから剥し、ひび割れた部分の密着性を判断する。
【０１３２】
折り曲げ脆性の評価は以下の通りである。
折り曲げ脆性評価
○：ひび割れ発生せず。
△：ひび割れやや発生。
×：ひび割れ強く発生。
【０１３３】
結果を表１に示す。
【０１３４】
【表１】

【０１３５】
表１の結果から、本発明の試料が干渉縞、折り曲げ脆性いずれも優れていることがわかる。
【０１４０】
実施例２
実施例１において乳剤面保護層-2のマット剤(ポリメチルメタクリレート微粒子)の量を全く添加しないと干渉縞の発生が試料６でわずかに見られる。これはレーザー露光のθを84°にすれば消える。
【０１４１】
【発明の効果】
本発明により、干渉縞が発生せず、脆性の点で優れた熱画像形成材料が得られる。
【図面の簡単な説明】
【図１】典型的なレーザー走査露光方法を模式的に表わした説明図である。
【図２】レーザー走査露光方法におけるレーザービームと露光される感光材料との角度を模式的に表わした説明図である。
【図３】走査露光方法における１つの典型を模式的に表わした説明図である。
【符号の説明】
１：レーザー光源
２：レーザービーム
３：変調器
４：変調器駆動回路
５：画像信号出力装置
６：ビームエキスパンダ
７：シリンドリカルレンズ
８：回転多面鏡
９：ｆθレンズ
１０：シリンドリカルミラー
１１：写真感光材料
矢印Ａ：主走査方向
矢印Ｂ：副走査方向[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photographic material for laser exposure.
[0002]
[Prior art]
Conventionally, as a means for outputting image information such as MRI and X-ray CT, a method of performing exposure by scanning a photographic photosensitive material with a laser beam has been used. In recent years, semiconductor laser diodes having high output and high stability as light sources have become widespread, and have created some margin in the sensitivity of photographic photosensitive materials as output media. On the other hand, these photosensitive materials are desired to have a small amount of coated silver from the viewpoint of rapid processing and environmental protection. For this reason, in order to maintain a desired maximum optical density (Dmax), movement of finer emulsion grains has been promoted. Progressing. Furthermore, in the case of a system without a fixing process for dissolving and removing silver halide such as a heat development process, the photosensitive material is required to have no haze.
[0003]
However, such a photosensitive material having fine emulsion grains or high transparency is accompanied by generation of interference fringes resulting from reflection of laser light inside the photosensitive material. This interference fringe is described in detail in Japanese Patent Publication No. 6-10735 as “non-contact interference fringe”.
[0004]
A typical laser scanning exposure method is shown in FIGS. As shown in FIGS. 1 to 3, the laser beam 2 emitted from the laser light source 1 is modulated in accordance with the image signal by the modulator 3 via the modulator driving circuit 4 from the image signal output device 5, Through the panda 6 and the cylindrical lens 7, the light is incident on and reflected by the rotary polygon mirror 8, is incident on the cylindrical mirror 10 through the fθ lens 9, and is reflected by the reflected light to the photosensitive material 11 in the main scanning direction (arrow A) and Exposure is performed in the sub-scanning direction (arrow B).
[0005]
As shown in FIG. 2, the angle formed by the main scanning direction and the laser beam varies depending on the scanning, but is usually designed to be perpendicular to the center of the scanning. In addition, the angle θ formed by the sub-scanning direction and the laser beam shown in FIG. 3 is normally considered to deviate from the vertical direction in order to prevent the reflected laser light from the photosensitive material from returning to the inside of the laser apparatus. It is at most 1 to 2 degrees. For this reason, conventionally, an area where the incident angle of the laser beam with respect to the exposure surface of the light-sensitive material is almost perpendicular during laser scanning is always used. However, in such an exposure region where the laser incident angle is almost vertical, there is a problem that the overlapping of the reflected laser beams as described above occurs and the generation of interference fringes cannot be suppressed.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a material that eliminates laser interference fringes generated in a photosensitive material when an image is formed by laser exposure and is satisfactory in terms of brittleness.
[0007]
[Means for Solving the Problems]
The above object has been achieved by the following means.
(1) On a support, at least one photosensitive layer containing a photosensitive silver halide and a binder, and a non-photosensitive layer adjacent to at least one of the photosensitive layers (in the case of being the outermost layer) A heat-developable photosensitive material for laser exposure,
SaidAdjacent to the photosensitive layerThe non-photosensitive layer includes at least one pigment selected from metals, metal salts, organic silver salts and metal oxides, and a binder in a ratio of pigment / binder ratio of 1/1 or less,And next to itThe photosensitive layer in contactWhenA photothermographic material for laser exposure in which the difference in refractive index is from 0.10 to 0.70, and both layers are simultaneously coated and dried.
(2) The photosensitive silver halide has an average grain size of 0.01 μm or more and less than 0.1 μm, and the coated silver amount is 0.01 g / m.²0.3 g / m or more²The photothermographic material for laser exposure according to the above (1), which is the following.
(3) The photothermographic material for laser exposure according to the above (1) or (2), wherein the photosensitive layer and the coating solution for the non-photosensitive layer adjacent thereto are both aqueous coating solutions.
(4) The photothermographic material for laser exposure according to any one of (1) to (3), wherein the photosensitive layer contains a reducing agent for an organic silver salt and silver ions.
(5) The photothermographic material for laser exposure according to any one of (1) to (4), wherein the binder of the photosensitive layer contains a polymer latex.
(6) The photothermographic material for laser exposure according to any one of (1) to (5), wherein the binder of the non-photosensitive layer contains a water-soluble polymer.
(7) The photothermographic material for laser exposure according to any one of (1) to (6), wherein the uppermost layer on the side where the photosensitive layer is provided contains a matting agent.
(8) The matting agent has an average particle size of 1 μm or more and 10 μm or less, and 200 particles / mm on the uppermost layer on the side where the photosensitive layer is provided.²More than 10,000 pieces / mm²The photothermographic material for laser exposure according to any one of (1) to (7), which is included below.
(9) The refractive index of the photosensitive layer is 0.10 to 0.70 higher than the refractive index of the non-photosensitive layer adjacent to the photosensitive layer. The photothermographic material for laser exposure according to any one of 8).
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0009]
The photothermographic material of the present invention comprises, on a support, at least one photosensitive layer containing a photosensitive silver halide and a binder,Pigment andAnd at least one non-photosensitive layer containing a binder. The photosensitive layer may be one layer or two or more layers (preferably four layers or less). The non-photosensitive layer may be a single layer or two or more layers (preferably four layers or less).
[0010]
In the present invention, the difference in refractive index between at least one photosensitive layer and the non-photosensitive layer adjacent thereto is 0.10 or more and 0.70 or less. The difference in refractive index is preferably from 0.10 to 0.50, and more preferably from 0.10 to 0.40.
[0011]
As long as the difference in refractive index between the two layers is as described above, either layer may have a higher refractive index, but usually the photosensitive layer is preferably higher. Moreover, as long as the difference in refractive index between the two layers is as described above, the refractive index of each layer may be any, but the refractive index of the photosensitive layer is preferably 1.50 or more and 2.60 or less, 1.55 or more and 2.30 or less are more preferable, and 1.60 or more and 2.00 or less are particularly preferable. The refractive index of the non-photosensitive layer is preferably 1.40 or more and 1.90 or less, more preferably 1.45 or more and 1.80 or less, and particularly preferably 1.50 or more and 1.65 or less.
[0012]
To adjust the refractive index, the binder has a high refractive index.Quality, ieVarious metals and metal salts,Organic silverSalt, metal oxidePigment selected fromDisperse and adjustTheHowever,Such a pigmentAddition of a large amount increases the pigment / binder ratio and weakens the strength of the film such as brittleness. Specifically, the pigment / binder ratio is 1/1 or more.Underdo it. Although any known method may be used to measure the refractive index, it is preferable to measure the refractive index of the sodium lamp with respect to the D line using an Abbe refractometer. For example, a film having the same composition as the layer to be measured may be formed on a glass substrate with a thickness of about 100 μm, and the refractive index may be measured by peeling the film from the substrate.
[0013]
The photothermographic material of the present invention may contain additional materials as desired, such as toning agents, coating aids and other aids. The light-sensitive material of the present invention comprises an organic silver salt and silver halide in the first light-sensitive layer (usually a layer adjacent to the support), and some other components in the second layer or both layers. Or a two-layer construction comprising a single photosensitive layer containing all components and a non-photosensitive protective topcoat. Moreover, the structure which has a non-photosensitive intermediate | middle layer between a protective layer and multiple layers or a protective layer and a photosensitive layer is also mention | raise | lifted. The construction of a multicolor photosensitive photothermographic material may include a combination of these two layers for each color and includes all components in a single layer as described in US Pat. No. 4,708,928. Also good. In the case of multi-dye multi-color photothermographic materials, each photosensitive layer generally uses a functional or non-functional barrier layer between each photosensitive layer as described in US Pat. No. 4,460,681. By doing so, they are kept distinguished from each other. In the present invention, for one photosensitive layer, one non-photosensitive layer adjacent to it may have the above refractive index, but for all photosensitive layers, all non-photosensitive layers adjacent to it have the above-mentioned refractive index. It is preferable to have a difference in refractive index.
[0014]
The photosensitive layer and the non-photosensitive layer of the present invention are provided by simultaneous application and drying. For this reason, it is preferable that both layers are applied with an aqueous coating solution. For coating with an aqueous coating solution, there are a method of making the binder a water-soluble polymer and a method of dispersing the hydrophobic polymer with water or a mixture of water and a water-soluble solvent (to make a polymer latex). . In the present invention, the latter method is preferable for the photosensitive layer, and the former method is preferable for the non-photosensitive layer.
[0015]
The photosensitive layer of the present invention is preferably prepared by applying an aqueous coating solution and then drying it. However, the term “aqueous” as used herein means that 30 wt% or more, preferably 50 wt% or more, particularly 70 to 100 wt% of the solvent (dispersion medium) of the coating solution is water. As components other than water in the coating solution, water miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used. Specific examples of the solvent composition include the following. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 90/10, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80 / 15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent wt%.)
[0016]
The photosensitive layer of the present invention is preferably a layer containing the polymer latex described below in an amount of 50 wt% or more, more preferably 70 to 100 wt% of the total binder. Hereinafter, this photosensitive layer is referred to as “the photosensitive layer of the present invention”, and the polymer latex used for the binder is referred to as “the polymer latex of the present invention”. However, the “polymer latex” here is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, emulsion polymerized, micelle-dispersed, or partially hydrophilic in the polymer molecule and the molecular chain itself is molecular. Any of dispersed ones may be used. As for the polymer latex of the present invention, “Synthetic resin emulsion (Hiraku Okuda, Hiroshi Inagaki, published by Kobunshi Publishing (1978))”, “Application of synthetic latex (Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara) (Published by Kobunshi Publishing Co., Ltd. (1993)), “Synthetic Latex Chemistry (by Soichi Muroi, published by Kobunshi Publishing Co., Ltd. (1970))” and the like. The average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably about 5 to 1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.
[0017]
The polymer latex of the present invention may be a so-called core / shell type latex other than a normal polymer latex having a uniform structure. In this case, it may be preferable to change the glass transition temperature between the core and the shell.
[0018]
The minimum film-forming temperature (MFT) of the polymer latex of the present invention is preferably -30 to 90 ° C, more preferably about 0 to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film-forming aid, also called a plasticizer, is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex.For example, the `` Synthetic Latex Chemistry (Souichi Muroi, published by Kobunshi Publishing Co. ))"It is described in.
[0019]
Examples of the polymer species used in the polymer latex of the present invention include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. . The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is a number average molecular weight of 5,000 to 100,000, preferably about 10,000 to 100,000. When the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and when the molecular weight is too large, the film forming property is poor, which is not preferable.
[0020]
The polymer latex polymer used in the present invention preferably has an equilibrium water content at 25 ° C. and 60% RH of 0.01 wt% to 2 wt%, more preferably 0.02 wt% to 1 wt%. For the definition and measurement method of the equilibrium moisture content, for example, “Polymer Engineering Course 14, Polymer Material Testing Method (Edited by Polymer Society, Jinshokan)” can be referred to.
[0021]
The photothermographic material of the present inventionPhotosensitivitySpecific examples of the polymer latex used as the binder of the layer include the following. Latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer , Latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer, and the like. Moreover, such a polymer is also marketed and the following polymers can be utilized. For example, as an example of acrylic resin, polyester resin such as Ceviane A-4635, 46583, 4601 (made by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 821, 820, 857 (made by Nippon Zeon Co., Ltd.) FINETEX ES650, 611, 675, 850 (Dainippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical), and other polyurethane resins include HYDRAN AP10, 20, 30, 40 ( Rubber resins such as LACSTAR 7310K, 3307B, 4700H, 7132C (above Dainippon Ink and Chemicals Co., Ltd.), Nipol Lx416, 410, 438C, 2507, (Zeon Japan) Such as G351, G576 (made by Nippon Zeon Co., Ltd.), vinylidene chloride L502, L513 (made by Asahi Kasei Co., Ltd.), etc., and olefin resin as Chemipearl. S120, SA100 (Mitsui Petrochemical Co., Ltd.) Kill. These polymers may be used alone or in combination of two or more as required.
[0022]
The photosensitive layer of the present invention has a hydrophilic property such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose within the range of 50 wt% or less, more preferably 30 wt% or less of the total binder as necessary. A polymer may be added.
[0023]
The total binder amount in the photosensitive layer of the present invention is 0.2 to 30 g / m.², More preferably 1-15m²The range of is preferable. The photosensitive layer of the present invention may contain a crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like.
[0024]
The photosensitive layer coating liquid in the present invention is preferably a so-called thixotropic fluid. Thixotropy refers to the property that the viscosity decreases as the shear rate increases.
[0025]
Although any apparatus may be used for the viscosity measurement of the present invention, an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is preferably used and measured at 25 ° C.
[0026]
In the present invention, the photosensitive layer coating solution has a shear rate of 0.1 S.^-1The viscosity in is preferably 400 mPa · s or more and 100,000 mPa · s or less, and more preferably 500 mPa · s or more and 20,000 mPa · s or less. Also, shear rate 1000S^-1Is preferably from 1 mPa · s to 200 mPa · s, more preferably from 5 mPa · s to 80 mPa · s.
[0027]
Various systems that exhibit thixotropic properties are known, and are described in “Lectures / Rheology” edited by Polymer Publishing Co., “Polymer Latex” (published by Polymer Publishing Co., Ltd.) co-authored by Muroi and Morino. In order for the fluid to exhibit thixotropy, it is necessary to contain a large amount of solid fine particles. In order to enhance the thixotropy, it is effective to contain a thickening linear polymer, to increase the aspect ratio with the anisotropic shape of the contained solid fine particles, to increase the alkali viscosity, and to use a surfactant.
[0028]
The amount of photosensitive silver halide used in the present invention is 0.01 g / m.²0.3g / m or more²The following is preferable, 0.02 g / m²0.2 g / m²The following is more preferable. There are no particular limitations on the method and conditions for mixing the separately prepared photosensitive silver halide into the image forming layer coating solution as long as the effects of the present invention are sufficiently exhibited.
[0029]
The formation method of the photosensitive silver halide in the present invention is well known in the art. For example, the methods described in Research Disclosure No. 17029 of June 1978 and US Pat. No. 3,700,458 can be used. . Specific methods that can be used in the present invention include a method in which a part of silver of an organic silver salt is converted into photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin Alternatively, a method of preparing photosensitive silver halide grains by adding a silver supply compound and a halogen supply compound to another polymer solution and mixing it with an organic silver salt can be used. In the present invention, the latter method is preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.01 μm or more and less than 0.1 μm, more preferably 0.01 μm or more and 0.08 μm or less, and still more preferably. Is preferably 0.01 μm or more and 0.06 μm or less. The grain size here refers to the length of the edge of the silver halide grain when the silver halide grain is a so-called normal crystal of a cube or octahedron. Further, when the silver halide grain is a tabular grain, it means the diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other non-normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it means the diameter when considering a sphere equivalent to the volume of silver halide grains.
[0030]
Examples of the shape of the silver halide grains include cubes, octahedrons, tabular grains, spherical grains, rod-shaped grains, and potato grains. In the present invention, cubic grains and tabular grains are particularly preferred. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1. Further, grains having rounded corners of silver halide grains can be preferably used. There are no particular restrictions on the surface index (Miller index) of the outer surface of the photosensitive silver halide grains, but the {100} surface occupies a high proportion of spectral sensitization efficiency when the spectral sensitizing dye is adsorbed. preferable. The ratio is preferably 50% or more, more preferably 65% or more, and still more preferably 80% or more. The ratio of Miller index {100} plane is calculated by T.Tani; J.Imaging Sci., 29, 165 (1985) using the adsorption dependence of {111} plane and {100} plane in sensitizing dye adsorption. It can be determined by the method described. The halogen composition of the photosensitive silver halide is not particularly limited and may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, and silver iodide. In the present invention, silver bromide or silver iodobromide can be preferably used. Particularly preferred is silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to 40 mol%, more preferably from 0.1 mol% to 20 mol%. The distribution of the halogen composition in the grain may be uniform, the halogen composition may be changed stepwise, or may be continuously changed. High silver iodobromide grains can be used. In addition, silver halide grains preferably having a core / shell structure can be used. As the structure, core / shell particles having a preferably 2- to 5-fold structure, more preferably a 2- to 4-fold structure can be used.
[0031]
The photosensitive silver halide grain of the present invention preferably contains at least one metal complex selected from rhodium, rhenium, ruthenium, osnium, iridium, cobalt, mercury or iron. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 nmol to 10 mmol, and more preferably in the range of 10 nmol to 100 μmol, with respect to 1 mol of silver. As a specific metal complex structure, a metal complex having a structure described in JP-A-7-225449 can be used. For cobalt and iron compounds, hexacyano metal complexes can be preferably used. Specific examples include, but are not limited to, ferricyanate ions, ferrocyanate ions, hexacyanocobaltate ions, and the like. The phase containing the metal complex in the silver halide may be uniform, may be contained in the core part at a high concentration, or may be contained in the shell part at a high concentration, and there is no particular limitation.
[0032]
The photosensitive silver halide grains can be desalted by washing with water known in the art, such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted.
[0033]
The photosensitive silver halide grains in the present invention are preferably chemically sensitized. As a preferable chemical sensitization method, a sulfur sensitization method, a selenium sensitization method and a tellurium sensitization method can be used as is well known in the art. Further, noble metal sensitization methods such as gold compounds, platinum, palladium, iridium compounds, and reduction sensitization methods can be used. As the compound preferably used in the sulfur sensitization method, selenium sensitization method and tellurium sensitization method, known compounds can be used, but compounds described in JP-A-7-128768 and the like can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Compounds having Te bond, tellurocarboxylates, Te-organyltellurocarboxylic acid esters, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having P-Te bond, Te-containing heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium and the like can be used. As the compound preferably used in the noble metal sensitization method, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, or compounds described in US Pat. No. 2,448,060, British Patent 618,061, etc. are preferable. Can be used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, etc. may be used. it can. Further, reduction sensitization can be performed by ripening the emulsion while maintaining the pH at 7 or higher or pAg at 8.3 or lower. Further, reduction sensitization can be performed by introducing a single addition portion of silver ions during grain formation. The photosensitive layer of the present invention preferably contains an organic silver salt and a reducing agent for silver ions.
[0034]
The organic silver salt of the present invention can be used in a desired amount, but the silver amount is 0.1 to 5 g / m.²Is preferred, more preferably 1 to 3 g / m²It is.
[0035]
The organic silver salt that can be used in the present invention is relatively stable to light, but is 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. It is a silver salt that forms a silver image when heated above. The organic silver salt may be any organic material containing a source capable of reducing silver ions. Silver salts of organic acids, particularly silver salts of long-chain aliphatic carboxylic acids (having 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Preference is also given to organic or inorganic silver salt complexes in which the ligand has a complex stability constant in the range of 4.0 to 10.0. The silver supply material can preferably comprise about 5 to 70 wt% of the photosensitive layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the aliphatic carboxylic acid silver salt include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate and fumarate. Silver acid, silver tartrate, silver linoleate, silver butyrate and silver camphor, mixtures thereof, and the like.
[0036]
Silver salts of compounds containing a mercapto group or a thione group and derivatives thereof can also be used. Preferred examples of these compounds include silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, 2 Silver salt of thioglycolic acid such as silver salt of-(ethylglycolamide) benzothiazole, silver salt of S-alkylthioglycolic acid (wherein the alkyl group has 12 to 22 carbon atoms), silver salt of dithioacetic acid, etc. Silver salt of dithiocarboxylic acid, silver salt of thioamide, silver salt of 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, US Patent No. Silver salts described in US Pat. No. 4,123,274, silver salts of 1,2,4-mercaptothiazole derivatives such as silver salts of 3-amino-5-benzylthio-1,2,4-thiazole, and the like described in US Pat. 3- (3-carboxyethyl) -4- Include silver salts of thione compounds such as silver salt of chill-4-thiazoline-2-thione. Furthermore, a compound containing an imino group can also be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole, US Patent 1,2,4-triazole or silver salt of 1-H-tetrazole as described in US Pat. No. 4,220,709, and silver salts of imidazole and imidazole derivatives. For example, various silver acetylide compounds described in US Pat. Nos. 4,761,361 and 4,775,613 can also be used.
[0037]
Although there is no restriction | limiting in particular as a shape of the organic silver salt which can be used for this invention, The acicular crystal | crystallization which has a short axis and a long axis is preferable. In the present invention, the minor axis is preferably 0.01 μm to 0.20 μm, the major axis is 0.10 μm to 5.0 μm, the minor axis is 0.01 μm to 0.15 μm, and the major axis is 0.10 μm to 4.0 μm. The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion is preferably 100% or less, more preferably 80% or less, and even more preferably 50% of the value obtained by dividing the standard deviation of the lengths of the short and long axes by the short and long axes, respectively. It is as follows. The method for measuring the shape of the organic silver salt can be obtained from a transmission electron microscope image of the organic silver salt dispersion. Another method for measuring monodispersity is to obtain the standard deviation of the volume average diameter of organic silver salt, and the 100 fraction (coefficient of variation) of the value divided by the volume average diameter is preferably 100% or less. More preferably, it is 80% or less, and further preferably 50% or less. As a measurement method, for example, the organic silver salt dispersed in the liquid is irradiated with laser light, and the particle size (volume load average diameter) obtained by calculating the autocorrelation function with respect to the temporal change of the fluctuation of the scattered light is obtained. be able to.
[0038]
The organic silver salt that can be used in the present invention can be preferably desalted. There is no particular limitation on the method for performing desalting, and a known method can be used. However, it is preferable to use a known filtration method such as circular filtration, suction filtration, ultrafiltration, and floc-forming water washing by a coagulation method. it can.
[0039]
For the purpose of obtaining fine particles having a small particle size and no aggregation, the organic silver salt that can be used in the present invention is a method of forming a solid fine particle dispersion using a dispersant. The method of dispersing the organic silver salt in the form of solid fine particles is carried out in the presence of a dispersion aid by known finer means (for example, ball mill, vibration ball mill, planetary ball mill, sand mill, colloid mill, jet mill, roller mill, microfluidizer, Nanomizer, Gaurin homogenizer) can be mechanically dispersed, and a microfluidizer, Nanomizer, and Gaurin homogenizer are preferably used.
[0040]
When organic silver salt is made into solid fine particles using a dispersant, for example, polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropane sulfonic acid Synthetic anionic polymers such as copolymers, semi-synthetic anionic polymers such as carboxymethyl starch and carboxymethyl cellulose, anionic polymers such as alginic acid and pectic acid, anions described in JP-A-52-92716, WO88 / 04794, etc. Surfactants, compounds described in Japanese Patent Application No. 7-350753, or known anionic, nonionic, cationic surfactants, and other polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose Known polymers such as Alternatively, a polymer compound existing in nature such as gelatin can be appropriately selected and used.
[0041]
Dispersing aid is generally mixed with organic silver salt powder or wet cake organic silver salt before dispersion, and sent to the disperser as a slurry. It is good also as an organic silver salt powder or a wet cake by heat-treating and the process by a solvent. The pH may be controlled with an appropriate pH adjusting agent before or during dispersion.
[0042]
In addition to mechanical dispersion, it may be coarsely dispersed in a solvent by controlling the pH, and then finely divided by changing the pH in the presence of a dispersion aid. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the formation of fine particles.
[0043]
The prepared dispersion is stored with stirring for the purpose of suppressing sedimentation of fine particles during storage, or stored in a highly viscous state (for example, in a gelatinized state using gelatin) with a hydrophilic colloid. You can also In addition, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.
[0044]
The reducing agent for the organic silver salt of the present invention may be any substance, preferably an organic substance, that reduces silver ions to metallic silver. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 5 to 50% by mole, more preferably 10 to 40% by mole, based on 1 mole of silver on the surface having the photosensitive layer. The reducing agent may be a so-called precursor that is derivatized so as to have an effective function only during development.
[0045]
In photothermographic materials using organic silver salts, a wide range of reducing agents are disclosed in JP-A-46-6074, 47-1238, 47-33621, 49-46427, 49-115540, 50-14334, 50-36110, 50-147711, 51-32632, 51-1023721, 51-32324, 51-51933, 52-84727, 55 -108654, 56-146133, 57-82828, 57-82829, JP-A-6-3793, U.S. Patent 3,667,9586, 3,679,426, 3,751,252, 3,751,255, 3,761,270 No. 3,782,949, No. 3,839,048, No. 3,928,686, No. 5,464,738, German Patent No. 2321328, European Patent No. 692732, and the like. For example, amide oximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2-bis (hydroxymethyl) propionyl- Combinations of aliphatic carboxylic acid aryl hydrazides such as β-phenylhydrazine and ascorbic acid and ascorbic acid; combinations of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (eg hydroquinone and bis (ethoxyethyl) ) Such as combinations of hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine); such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-arininhydroxamic acid Hydroxamic acid; Combination of azine and sulfonamidophenol (for example, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); Ethyl-α-cyano-2-methylphenylacetate, ethyl-α-cyanophenylacetate Α-cyanophenylacetic acid derivatives such as: 2,2-dihydroxy-1,1-binaphthyl, 6,6-dibromo-2,2-dihydroxy-1,1-binaphthyl and bis (2-hydroxy-1-naphthyl) methane A combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative (such as 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone); 5-pyrazolones such as 1-phenyl-5-pyrazolone; dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and Reductones as exemplified by hydrodihydropiperidone hexose reductone; sulfonamide phenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and 2-phenylindan-1, 3-diones, etc .; 2,2-dimethyl-7-t-butyl-6-hydroxychromans and other chromanes; 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridines and other 1,4- Dihydropyridines; bisphenols (eg bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis ( 2-t-butyl-6-methylphenol), 1,1, -bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5- Dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid Conductors (e.g., palmitate 1-ascorbyl stearate, etc. Ascorbyl); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidones and certain indane-1,3-dione; chromanol (tocopherol), and the like. Particularly preferred reducing agents are bisphenol and chromanol.
[0046]
The reducing agent of the present invention may be added by any method such as a solution, a powder, or a solid fine particle dispersion. The solid fine particle dispersion is performed by a known refinement means (for example, a ball mill, a vibrating ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, a microfluidizer, a nanomizer, and a Gaurin homogenizer). A dispersion aid may be used when dispersing the solid fine particles.
[0047]
The photosensitive silver halide in the present invention is preferably spectrally sensitized with a sensitizing dye.
[0048]
Any sensitizing dye of the present invention may be used as long as it can spectrally sensitize the silver halide grains in a desired wavelength region when adsorbed on the silver halide grains. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a hoholor cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, or the like can be used. Useful sensitizing dyes used in the present invention are, for example, documents described or cited in RESEARCH DISCLOSURE Item 17643IV-A (December 1978, p.23), Item1831X (August 1979, p.437) It is described in. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light sources of various laser imagers, scanners, image setters and plate-making cameras can be advantageously selected.
[0049]
As an example of spectral sensitization to red light, a so-called red light source such as a He-Ne laser, a red semiconductor laser, or an LED is disclosed in Japanese Patent Application Laid-Open No. 54-18726. Compounds, compounds of I-1 to I-35 described in JP-A-6-75322, compounds of I-1 to I-34 described in JP-A-7-287338, dyes described in JP-B-55-39818 1 to 20, compounds of I-1 to I-37 described in JP-A-62-284343 and compounds of I-1 to I-34 described in JP-A-7-287338 are advantageously selected.
[0050]
For semiconductor laser light sources in the 750-1400 nm wavelength range, a variety of known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes can be spectrally sensitized. it can. Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nucleus, oxazoline nucleus, pyrroline nucleus, pyridine nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus and imidazole nucleus. Useful merocyanine dyes are preferably acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus in addition to the above basic nucleus. Including. Of the above-mentioned cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, U.S. Pat.Nos. -194781 and 6-301141 may be appropriately selected from known dyes.
[0051]
Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, JP-A Nos. 62-58239, 3-138638, 3-138642, and 4- No. 255840, No. 5-72659, No. 5-72661, No. 6-222491, No. 2-230506, No. 6-258757, No. 6-317868, No. 6-324425, and No. 7- 500926, a dye described in U.S. Pat.No. 5,541,054), a dye having a carboxylic acid group (for example, dyes described in JP-A-3-163440, 6-301141, U.S. Pat.No. 5,441,899), a merocyanine dye, Multinuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329, 49-105524, 51-127719, 52-80829, 54-61517, 59-214846, 60-6750) No. 63-159841, JP-A-6-35109, JP-A-6-59381, JP7-65537, JP7-65537, JP-T55-50111, British Patent 1,467,638, US Patent 5,281,515 Dyes described in 1).
[0052]
Further, as dyes forming J-band, dyes described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887, JP-A-2-96131 and JP-A-59-48753 are disclosed, which are preferable in the present invention. Can be used.
[0053]
These sensitizing dyes may be used alone or in combination of two or more. A combination of sensitizing dyes is often used for the purpose of supersensitization. Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (issued December 1978), page 23, Section J, or JP-B 49-25500. No. 43-4933, JP-A-59-19032, 59-192242 and the like.
[0054]
Two or more sensitizing dyes used in the present invention may be used in combination. In order to add sensitizing dyes to silver halide emulsions, they can be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3 -Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion.
[0055]
Further, as disclosed in US Pat. No. 3,469,987, etc., the dye is dissolved in a volatile organic solvent, this solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to the emulsion. Method, as disclosed in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22091, etc., a dye is dissolved in an acid, and this solution is added to an emulsion, or an acid or a base is added. A method of adding it into an emulsion as an aqueous solution, as disclosed in U.S. Pat.Nos. 3,822,135, 4,006,025, etc. A method of adding, as disclosed in JP-A-53-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, Using red-shifting compounds as disclosed in 51-74624 Dissolving a dye, the solution can also be used a method of adding to the emulsion. In addition, ultrasonic waves can be used for the solution.
[0056]
The time when the sensitizing dye used in the present invention is added to the silver halide emulsion of the present invention may be during any step of emulsion preparation that has been found useful. For example, as disclosed in the specifications of U.S. Pat.Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, JP-A-58-184142, 60-196749, etc., a silver halide grain forming step Or / and the time before desalting, during the desilvering step and / or after desalting to before the start of chemical ripening, as disclosed in the specification of JP-A-58-113920, etc. The emulsion may be added at any time just before or during the process, after chemical ripening and before the emulsion is coated before the coating. Further, as disclosed in the specifications of U.S. Pat.No. 4,225,666, JP-A-58-7629, etc., the same compound is used alone or in combination with a compound having a different structure, for example, during the particle formation step and the chemical ripening step. It may be added separately during or after completion of chemical ripening, or before or during chemical ripening or after completion of the process, etc., and the type of compound and combination of compounds added separately may be changed. May be added.
[0057]
The amount of the sensitizing dye used in the present invention may be a desired amount in accordance with the performance such as sensitivity and fog, but is 10 per mol of silver halide in the photosensitive layer.^-6~ 1 mole is preferred, 10^-Four~Ten^-1Mole is more preferred.
[0058]
Inclusion of an additive known as a “toning agent” that improves the image may increase the optical density. The toning agent may also be advantageous in forming a black silver image. The toning agent is preferably contained in an amount of 0.1 to 50% mol, more preferably 0.5 to 20% mol per mol of silver, on the surface having the image forming layer. The toning agent may be a so-called precursor that is derivatized so as to have an effective function only during development.
[0059]
In photothermographic materials using organic silver salts, a wide range of color toning agents are disclosed in JP-A-46-6077, 47-10282, 49-5019, 49-5020, 49-91215, 49-91215, 50-2524, 50-32927, 50-67132, 50-67641, 50-114217, 51-3223, 51-27923, 52- 14788, 52-99813, 53-1020, 53-76020, 54-156524, 54-156525, 61-183642, JP 4-56848, JP-B 49- Nos. 10727, 54-20333, US Pat. Nos. 3,080,254, 3,446,648, 3,782,941, 4,123,282, 4,510,236, British Patent 1380795, Belgian Patent 841910, and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as: naphthalimide (eg, N-hydroxy-1,8-naphthalimide); cobalt complex (eg, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4 Mercaptans, exemplified by 2-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryl Dicarboximide (eg, (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); Click of pyrazole, isothiuronium derivatives and certain photobleaching agents (e.g., N, N^,-Hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole) ); And 3-ethyl-5 [(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivatives or metal salts, or 4 Derivatives such as-(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (eg phthalic acid) , 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); phthalazine, phthalazine derivatives or metal salts, or 4- (1-naphthyl) phthalazine, 6-chlorophthalazi , Derivatives of 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine; phthalazine and phthalic acid derivatives such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride A quinazolinedione, benzoxazine or naphthoxazine derivative; a rhodium complex which functions not only as a color modifier but also as a source of halide ions for in situ silver halide formation, such as ammonium hexachlororhodium (III), Rhodium bromide, rhodium nitrate and potassium hexachlororhodium (III), etc .; inorganic peroxides and persulfates, such as ammonium peroxide disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione, 8-Methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione Which benzoxazine-2,4-diones; pyrimidines and asymmetric-triazines (eg 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg 3,4 6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6-dimercapto-1H, 4H-2 , 3a, 5,6a-tetraazapentalene).
[0060]
The toning agent of the present invention may be added by any method such as a solution, a powder, or a solid fine particle dispersion. The solid fine particle dispersion is performed by a known finer means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). A dispersion aid may be used when dispersing the solid fine particles.
[0061]
The silver halide emulsions and / or organic silver salts in the present invention are further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and against reduced sensitivity during inventory storage. Can be stabilized. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium salts described in U.S. Patent Nos. 2,131,038 and 2,694,716, U.S. Patent Nos. 2,886,437 and 2,444,605. Azaindene described in U.S. Pat.No. 2,728,663, mercury salt described in U.S. Pat.No. 3,287,135, sulfocatechol described in U.S. Pat.No. 3,235,652, oxime described in British Patent No. 623,448, nitrone, nitro Indazole, polyvalent metal salts described in U.S. Pat.No. 2,839,405, thiuonium salts described in U.S. Pat.No. 3,220,839, and palladium, platinum and gold salts described in U.S. Pat.Nos. 2,566,263 and 2,597,915, U.S. Pat. Halogen-substituted organic compounds described in US Pat. Nos. 4,108,665 and 4,442,202, U.S. Pat.Nos. 4,128,557 and 4,137,079, 4,138,365 and And triazine described in U.S. Pat. No. 4,459,350, and phosphorus compounds described in U.S. Pat. No. 4,411,985.
[0062]
Antifoggants preferably used in the present invention are organic halides, such as JP-A-50-119624, 50-120328, 51-121332, 54-58022, 56-70543, 56-99335, 59-90842, 61-129642, 62-129845, JP-A-6-208191, 7-5621, 7-2781, 8-15809, US Examples thereof include compounds disclosed in Japanese Patent Nos. 5340712, 5369000, and 5464737.
[0063]
The antifoggant of the present invention may be added by any method such as a solution, powder or solid fine particle dispersion. The solid fine particle dispersion is performed by a known finer means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). A dispersion aid may be used when dispersing the solid fine particles.
[0064]
Although not necessary to practice the present invention, it may be advantageous to add mercury (II) salts to the emulsion layers as antifoggants. Preferred mercury (II) salts for this purpose are mercury acetate and mercury bromide. The addition amount of mercury used in the present invention is preferably in the range of 1 nmol to 1 mmol, more preferably 10 nmol to 100 μmol, per mol of applied silver.
[0065]
The photothermographic material in the invention may contain benzoic acids for the purpose of increasing sensitivity and preventing fog. The benzoic acid derivatives of the present invention may be any benzoic acid derivative. Examples of preferred structures include U.S. Pat. Nos. 4,784,939, 4,152,160, Japanese Patent Application Nos. 8-512242, 8-151241, and 8-98051. And the compounds described in the above. The benzoic acids of the present invention may be added to any part of the light-sensitive material, but the addition layer is preferably added to the layer having the photosensitive layer, and more preferably added to the organic silver salt-containing layer. . The benzoic acid of the present invention may be added at any step of preparing the coating solution, and when added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be used. It is preferable that the salt is prepared and immediately before coating. As a method for adding the benzoic acid of the present invention, any method such as powder, solution, fine particle dispersion and the like may be used. Moreover, you may add as a solution mixed with other additives, such as a sensitizing dye, a reducing agent, and a color toning agent. The addition amount of the benzoic acid of the present invention may be any amount, but it is preferably 1 μmol or more and 2 mol or less, more preferably 1 mmol or more and 0.5 mol or less per 1 mol of silver.
[0066]
In the present invention, a mercapto compound, a disulfide compound, and a thione compound can be contained in order to suppress or promote development and control development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. .
[0067]
When a mercapto compound is used in the present invention, any structure may be used, but those represented by Ar-SM and Ar-S-S-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (e.g., Br and Cl), hydroxy, amino, carboxy, alkyl (e.g., having one or more carbon atoms, preferably 1 to 4 carbon atoms) and alkoxy ( For example, it may have one selected from a substituent group consisting of one or more carbon atoms, preferably one having 1 to 4 carbon atoms. Mercapto-substituted heteroaromatic compounds include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2, 2'-dithiobis- (benzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercapto Quinoline, 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6 -Hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydrido Rosi-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, Examples include 2-mercapto-4-phenyloxazole, but the present invention is not limited to these.
[0068]
The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of silver in the emulsion layer, and more preferably 0.01 to 0.3 mol per mol of silver.
[0069]
In the photosensitive layer in the present invention, a polyhydric alcohol (for example, glycerin and diol of the type described in US Pat. No. 2,960,404) as a plasticizer and a lubricant, described in US Pat. Nos. 2,588,765 and 3,121,060 are used. Fatty acids or esters, silicone resins described in British Patent No. 955,061 and the like can be used.
[0070]
In the present invention, an ultrahigh contrast agent can be used to form an ultrahigh contrast image. For example, U.S. Patent Nos. 5,464,738, 5,496,695, 6,512,411, 5,536,622, Japanese Patent Application Nos. 7-228627, 8-215822, 8-130842, 8-148113, 8-156378 Hydrazine derivatives described in JP-A-8-148111 and 8-148116, compounds having a quaternary nitrogen atom described in Japanese Patent Application No. 8-83566, and acrylonitrile compounds described in US Pat. No. 5,545,515. Can be used. Specific examples of the compound include compounds 1 to 10 of the aforementioned US Pat. No. 5,464,738, H-1 to H-28 of 5,496,695, I-1 to I-86 of Japanese Patent Application No. 8-215822, and 8- 130842 H-1 to H-62, 8-148113 1-1 to 1-21, 8-148111 1-50, 8-148116 1-40, 8-83566 P-1 to P-26 and T-1 to T-18, CN-1 to CN-13 of US Pat. No. 5,545,515, and the like.
[0071]
Further, in the present invention, in order to form a super high contrast image, a high contrast accelerator can be used in combination with the super high contrast agent. For example, amine compounds described in U.S. Pat.No. 5,545,505, specifically, AM-1 to AM-5, hydroxamic acids described in 5,545,507, specifically HA-1 to HA-11, and 5,545,507 Described acrylonitriles, specifically CN-1 to CN-13, hydrazine compounds described in US Pat. No. 5,558,983, specifically CA-1 to CA-6, and ones described in Japanese Patent Application No. 8-132836 Salt, specifically A-1 to A-42, B-1 to B-27, C-1 to C-14, and the like can be used.
[0072]
The synthesis method, the addition method, the addition amount, and the like of these super-high contrast agents and high-contrast accelerators can be performed as described in the respective cited patents.
[0073]
In the image forming material of the present invention, it is necessary to provide a surface protective layer for the purpose of preventing adhesion of the image forming layer. These protective layers are located on the side farther than the image forming layer with respect to the support, and may be composed of two or more layers.
[0074]
At least one of the protective layers of the present invention is preferably 50% by weight or more, particularly 70% by weight or more of the binder as a binder, and particularly preferably 50% by weight or more, particularly 70% by weight or more of the outermost layer binder.
[0075]
Any adhesion preventing material may be used as the surface protective layer of the present invention. Examples of anti-adhesion materials include wax, silica particles, styrene-containing elastomeric block copolymers (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate, and these There is a mixture. Moreover, you may add surfactant etc. for coating property improvement.
[0076]
A hardening agent is used for the protective layer of the present invention. Without a hardener, the water resistance is lost, and stickiness and dissolution due to water droplets occur, which significantly impairs handling as an image forming material.
[0077]
Examples of the hardener of the present invention include the methods described in TH-James “THE THEORY OF THE PHOTOGRAPHIC PROCESS FOURTH EDITION” (published by Macmillan Publishing Co., Inc., 1977), pages 77 to 87. Polyvalent metal ions as described on page 78, polyisocyanates such as US Pat. No. 4,281,060, JP-A-6-208193, epoxy compounds such as US Pat. No. 4,791,042, vinyl sulfone compounds such as JP-A 62-89048 In particular, polyvalent metal ions such as chromium ions and aluminum ions are preferably used, and any amount may be used as long as the desired purpose is achieved, but the image forming layer of the support is preferable. 1 μmol or more and 1 mmol or less, more preferably 5 μmol or more and 200 μmol or less, per 1 g of gelatin with respect to the total amount of gelatin on the side having the above.
[0078]
The hardening agent is added as a solution, and the addition time of the solution into the protective layer coating solution needs to be added from 30 minutes before the application, preferably from 10 minutes to 10 seconds before the application. The mixing conditions are not particularly limited as long as the effects of the present invention are sufficiently exhibited. As a specific mixing method, a method of mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid fed to the coater becomes a desired time, or by N. Harnby, MFEdwards, AWNienow, There is a method using a static mixer or the like described in Chapter 8 etc. of Koji Takahashi's "Liquid Mixing Technology" (published by Nikkan Kogyo Shimbun, 1989).
[0079]
In the image forming layer or the protective layer of the image forming layer in the present invention, a light absorbing substance and a filter dye as described in U.S. Pat.Nos. 3,253,921, 2,274,782, 2,527,583 and 2,956,879 are used. Can be used in photographic elements including. For example, a dye can be mordanted as described in US Pat. No. 3,282,699. The amount of filter dye used is preferably an absorbance at an exposure wavelength of 0.1 to 3, particularly preferably 0.2 to 1.5.
[0080]
The image-forming layer of the image-forming layer or emulsion layer in the present invention contains a matting agent such as starch, titanium dioxide, zinc oxide, silica, and beads of the type described in US Pat. Nos. 2,992,101 and 2,701,245. Polymer beads and the like can be contained.
[0081]
Various dyes and pigments can be used for the photosensitive layer of the present invention from the viewpoint of improving the color tone and preventing irradiation. Any dyes and pigments may be used for the photosensitive layer of the present invention, for example, there are pigments and dyes described in the color index, specifically pyrazoloazole dyes, anthraquinone dyes, azo dyes, azomethine dyes, oxonol dyes, Examples thereof include carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes, indophenol dyes, organic pigments such as phthalocyanine, and inorganic pigments. Preferred dyes used in the present invention include anthraquinone dyes (for example, compounds 1 to 9 described in JP-A-5-341441, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147), Azomethine dyes (such as compounds 17 to 47 described in JP-A-5-341441), indoaniline dyes (for example, compounds 11 to 19 described in JP-A-5-289227, compound 47 described in JP-A-5-341441, JP-A-5 And compounds 2-10 to 11 described in JP-A-165147) and azo dyes (compounds 10 to 16 described in JP-A-5-341441). As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, or a state mordanted in a polymer mordant may be used. The amount of these compounds used is determined by the desired amount of absorption, but generally 1m²It is preferably used in the range of 1 μg or more and 1 g or less.
[0082]
In the present invention, the antihalation layer can be provided on the side far from the light source with respect to the photosensitive layer. The antihalation layer preferably has a maximum absorption in a desired wavelength range of 0.3 or more and 2 or less, more preferably an absorption of an exposure wavelength of 0.5 or more and 2 or less, and an absorption in the visible region after processing of 0.001 or more It is preferably less than 0.5, more preferably a layer having an optical density of 0.001 or more and less than 0.3.
[0083]
When an antihalation dye is used in the present invention, the dye has a desired absorption in the wavelength range, and after the treatment, the absorption in the visible region is sufficiently small, and any desired absorbance spectrum shape of the antihalation layer can be obtained. It may be a compound. For example, the following is disclosed, but the present invention is not limited to this. As a single dye, JP-A-59-56458, JP-A-2-216140, JP-A-7-13295, JP-A-111432, U.S. Pat.No. 5,380,635, JP-A-2-68539, page 13, lower left column From line 1 to page 14, lower left column, line 9, line 3-24539, page 14, lower left column to page 16, lower right column, the compounds described in Japanese Patent Application Laid-Open No. 52-139136, 53-132334, 56-501480, 57-16060, 57-68831, 57-101835, 59-182436, JP-A-7-36145, 7 -199409, JP-B-48-33692, JP-B-50-16648, JP-B-2-41734, US Patents 4,088,497, 4,283,487, 4,548,896, and 5,187,049.
[0084]
The photothermographic material of the present invention is a so-called single-sided photosensitive material having a photosensitive layer containing at least one silver halide emulsion on one side of a support and a back layer on the other side. It is preferable.
[0085]
In the present invention, the single-sided photosensitive material may be added with a matting agent in the back layer, the uppermost layer on the photosensitive layer side, etc. for improving the transportability. When the uppermost layer is matted, the generation of interference fringes is more effectively prevented. The matting agent is generally fine particles of an organic or inorganic compound that is insoluble in water. Any matting agent can be used.For example, organic matting agents described in U.S. Pat.Nos. 1,939,213, 2,701,245, 2,322,037, 3,262,782, 3,539,344, 3,767,448, etc. Those well known in the art such as the inorganic matting agents described in the respective specifications such as 1,260,772, 2,192,241, 3,257,206, 3,370,951, 3,523,022, and 3,769,020 can be used. For example, specific examples of organic compounds that can be used as matting agents include water-dispersible vinyl polymers such as polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, polystyrene. , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc. Examples of cellulose derivatives include methylcellulose, cellulose acetate, cellulose acetate propionate, etc. Examples of starch derivatives include carboxy starch, carboxynitrophenyl Preferably used for starch, urea-formaldehyde-starch reactants, gelatin hardened with known hardeners and hardened gelatin into cocapsulated hardened microcapsules Can be. As examples of the inorganic compound, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, diatomaceous earth, and the like can be preferably used. The above matting agents can be used by mixing different kinds of substances as required. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In the practice of the present invention, it is preferable to use one having a particle size of 1 μm to 10 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze and surface gloss of the light-sensitive material, the particle size, shape, and particle size distribution can be brought into a state as required by preparing the matting agent or mixing a plurality of matting agents. preferable.
[0086]
In the present invention, the matte degree of the back layer is preferably Beck smoothness of 250 seconds or less and 10 seconds or more, more preferably 180 seconds or less and 50 seconds or more.
[0087]
In the present invention, when the matting agent is contained in the outermost surface layer on the photosensitive layer side of the photosensitive material, the layer functioning as the outermost surface layer, or a layer close to the outer surface, it is preferable in that the generation of interference fringes is reduced. . Moreover, it is also preferable to contain in the layer which acts as what is called a protective layer. The amount of matting agent added is 200 to 10,000 / mm.²More preferably, 300 to 8000 / mm²It is preferable that
[0088]
In the present invention, a suitable binder for the non-photosensitive intermediate layer, the non-photosensitive protective layer and the back layer is transparent or translucent and generally colorless, and is a natural polymer synthetic resin, polymer and copolymer, or other medium for forming a film, for example, : Gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride) ), Poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (e.g. poly (vinyl formal) and poly (vinyl butyral) )), Poly (esters), poly (urethanes), phenoxy Fat, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and polyamides. The binder may be formed from water or an organic solvent or emulsion.
[0089]
As the non-photosensitive intermediate layer and the non-photosensitive protective layer adjacent to the photosensitive layer, those containing 50 wt% or more, particularly 70 to 100 wt% of a water-soluble polymer are preferable, and as the intermediate layer, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl A non-protein water-soluble polymer such as butyral is preferable, and the protective layer is preferably a water-soluble polymer, and particularly preferably gelatin.
[0090]
In the present invention, the back layer preferably has a maximum absorption of 0.3 or more and 2 or less in a desired wavelength range, more preferably 0.5 or more and 2 or less, and an absorption in the visible region after processing of 0.001 or more. It is preferably less than 0.5, more preferably a layer having an optical density of 0.001 or more and less than 0.3. Examples of the antihalation dye used for the back layer are the same as those of the antihalation layer described above.
[0091]
Backside resistive heating layers such as those shown in U.S. Pat. Nos. 4,460,681 and 4,374,921 can also be used in photosensitive photothermographic image systems.
[0092]
A hardener may be used for each layer such as the photosensitive layer, protective layer, and back layer of the present invention. Examples of hardeners are THJames' “THE THEORY OF THE PHOTOGRAPHIC PROCESS FOURTH EDITION” (published by Macmillan Publishing Co., Inc., published in 1977). Preferably used are polyvalent metal ions, polyisocyanates such as US Pat. No. 4,281,060 and JP-A-6-208193, epoxy compounds such as US Pat. No. 4,791,042, and vinyl sulfone compounds such as JP-A 62-89048. It is done.
[0093]
In each layer of the present invention, a surfactant may be used for the purpose of improving coating properties and charging. As an example of the surfactant, any nonionic, anionic, cationic, or fluorine-based one can be used as appropriate. Specifically, sodium dodecylbenzenesulfonate, sodium p-tert-octylphenoxyethoxyethylsulfonate, di (2-ethyl) hexylsulfosuccinate sodium salt, sodium lauryl sulfate, saponin, nonylphenoxypolyethoxyethanol, JP Fluoropolymer surfactants described in JP-A-62-170950, U.S. Pat.No. 5,380,644, etc., fluorinated surfactants described in JP-A-60-244945, JP-A-63-188135, etc., U.S. Pat. And the like, and polyalkylene oxides and anionic surfactants described in JP-A-6-301140.
[0094]
Examples of the solvent used in the present invention include New Edition Solvent Pocket Book (Ohm, published in 1994), but the present invention is not limited thereto. The boiling point of the solvent used in the present invention is preferably 40 ° C. or higher and 180 ° C. or lower.
[0095]
Examples of the solvent of the present invention include hexane, cyclohexane, toluene, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, 1,1,1-trichloroethane, tetrahydrofuran, triethylamine, thiophene, trifluoroethanol, perfluoropentane, Xylene, n-butanol, phenol, methyl isobutyl ketone, cyclohexanone, butyl acetate, diethyl carbonate, chlorobenzene, dibutyl ether, anisole, ethylene glycol diethyl ether, N, N-dimethylformamide, morpholine, propane sultone, perfluorotributylamine, water Etc.
[0096]
The photographic emulsion for heat development in the present invention can be coated on various supports. Typical supports are polyester film, primed polyester film, poly (ethylene terephthalate) film, polyethylene naphthalate film, cellulose nitrate film, cellulose ester film, poly (vinyl acetal) film, polycarbonate film and related or resinous Including materials, as well as glass, paper, metal and the like. Coated with flexible substrates, in particular partially acetylated or baryta and / or α-olefin polymers, in particular polymers of α-olefins having 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers A coated paper support is typically used. The support may be transparent or opaque, but is preferably transparent.
[0097]
The light-sensitive material in the present invention is an antistatic or conductive layer, for example, a soluble salt (for example, chloride, nitrate, etc.), a vapor-deposited metal layer, an ionic polymer as described in US Pat. Nos. 2,861,056 and 3,206,312 or It may have a layer containing an insoluble inorganic salt as described in US Pat. No. 3,428,451.
[0098]
As a method for obtaining a color image using the heat-developable photosensitive material in the present invention, there is a method described in JP-A-7-13295, page 10, left column, line 43 to 11, left column, line 40. Examples of color dye image stabilizers include British Patent 1,326,889, U.S. Patent 3,432,300, 3,698,909, 3,574,627, 3,573,050, 3,764,337, and 4,042,394. Yes.
[0099]
In the photothermographic material of the invention, the photosensitive layer and the non-photosensitive layer adjacent thereto are simultaneously applied and dried. Any method may be used. Specifically, various coating operations are used, including extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, or extrusion coating using a hopper of the type described in U.S. Pat. Stephen F. Kistler, Petert M. Schweizer “LIQUID FILM COATING” (CHAPMAN & HALL, 1997) pages 399 to 536, preferably used for extrusion coating or slide coating, particularly preferably used for slide coating It is done. An example of the shape of the slide coater used for slide coating is shown in Figure 11b.1 on page 427 of the same book. In addition, the method described in pages 399 to 536 of the same book, the method described in US Pat. No. 2,761,791 and British Patent No. 837,095 are also included.
[0100]
Additional layers in the photothermographic material of the present invention, such as a dye-receiving layer for receiving a moving dye image, an opacifying layer when reflective printing is desired, a protective topcoat layer, and a primer known in the photothermographic art Layers can be included. The light-sensitive material of the present invention can preferably form an image with only one light-sensitive material, and it is preferable that a functional layer necessary for image formation such as an image receiving layer does not become another light-sensitive material.
[0101]
The photosensitive material of the present invention may be developed by any method, but is usually developed by raising the temperature of the photosensitive material exposed imagewise. The preferred development temperature is 80 to 250 ° C, more preferably 100 to 140 ° C. The development time is preferably 1 to 180 seconds, and more preferably 10 to 90 seconds.
[0102]
As the laser beam according to the present invention, a gas laser, a YAG laser, a dye laser, a semiconductor laser and the like are preferable. A semiconductor laser and a second harmonic generation element can also be used.
[0103]
The present invention may be combined with interference fringe generation prevention technology just in case. As the technique, there are known a technique for obliquely entering a laser beam disclosed in Japanese Patent Laid-Open No. 5-113548 and the like, and a method using a multimode laser disclosed in WO95 / 31754. These techniques can be used.
[0104]
For exposing the photosensitive material of the present invention, as disclosed in SPIE vol. 169 Laser Printing, pages 116-128 (1979), JP-A-4-51043, WO95 / 31754, etc. It is preferable that the scanning line is not visible.
[0105]
【Example】
Hereinafter, the present invention will be described in more detail with specific practical examples of the present invention.
[0106]
Example 1 <<Organic silverPreparation of salt dispersion >> After stirring 7 g of stearic acid, 4 g of arachidic acid, 36 g of behenic acid, and 850 ml of distilled water at 93 ° C. while adding 187 ml of 1N-NaOH aqueous solution and reacting for 120 minutes, 65 ml of 1N nitric acid was added The temperature was lowered to 50 ° C. Next, 125 ml of an aqueous solution of 21 g of silver nitrate was added over 100 seconds while stirring more vigorously, and left as it was for 20 minutes. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the filtrate had a conductivity of 30 μS / cm. After adding 100 g of PVA205 (Kuraray Co., Ltd. polyvinyl alcohol) 10 wt% aqueous solution to the solid content thus obtained, and further adding water to a total weight of 270 g, coarse dispersion in an automatic mortarOrganic silverA coarse salt dispersion was obtained. thisOrganic silverUsing a nanomizer (manufactured by Nanomizer Co., Ltd.) with a coarse salt dispersion, the pressure at the time of collision is 1000 kg / cm^ThreeDistributed withOrganic silverA salt dispersion was obtained. Thus obtainedOrganic silverIncluded in salt dispersionOrganic silverThe salt particles were needle-like particles having an average minor axis of 0.04 μm, an average major axis of 0.9 μm, and a coefficient of variation of 35%.
[0107]
<< Preparation of reducing agent dispersion >>
To 100 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 50 g of hydroxypropylcellulose, 850 g of water was added and mixed well to obtain a slurry. 840 g of zirconia beads having an average diameter of 0.5 mm were prepared and placed in a vessel together with the slurry, and dispersed for 5 hours with a disperser (1/4 G sand grinder mill: manufactured by Imex Co., Ltd.) to obtain a reducing agent dispersion.
[0108]
<< Preparation of organic polyhalide dispersion >>
940 g of water was added to 50 g of tribromomethylphenylsulfone and 10 g of hydroxypropylcellulose, and mixed well to obtain a slurry. 840 g of zirconia beads having an average diameter of 0.5 mm were prepared, put in a vessel together with the slurry, and dispersed for 5 hours with a disperser (1/4 G sand grinder mill: manufactured by IMEX Co., Ltd.) to obtain an organic polyhalide dispersion. .
[0109]
<< Preparation of silver halide grains >>
Dissolve 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water and adjust the pH to 5.0 at 35 ° C., then add 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 0.9 g of ammonium nitrate, An aqueous solution containing a molar ratio of: 8 was added over 10 minutes by the control double jet method while maintaining pAg of 7.7. Next, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and 2 g of ammonium nitrate and an aqueous solution containing 10 μmol / liter of dipotassium hexachloroiridate and 1 mol / liter of potassium bromide at pAg7.7 for 30 minutes by the control double jet method. Then, 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the pH was further lowered to cause aggregation and sedimentation, followed by desalting. Thereafter, 0.1 g of phenoxyethanol was added, adjusted to pH 5.9, pAg 8.2, and silver iodobromide grains (iodine content core 8 mol%, average 2 mol%, average grain size 0.05 μm, projected area variation coefficient 8%, ( 100) Preparation of cubic particles having an area ratio of 85% was completed.
[0110]
The silver halide grains thus obtained were heated to 60 ° C. and 85 μmol of sodium thiosulfate and 11 μmol, 15 μmol of 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide per mol of silver. Tellurium compound, 3 μmol of chloroauric acid, 270 μmol of thiocyanic acid, ripen for 120 minutes, rapidly cool to 40 ° C., add 100 μmol of dye, 500 μmol of 2-mercapto-5-methylbenzimidazole A silver halide emulsion was obtained by rapid cooling to 0 ° C.
[0111]
<Preparation of emulsion layer coating solution>Organic silver1500 g of salt dispersion, 130 cc of 20 wt% aqueous solution of PVA205, 37 cc of 10 wt% aqueous solution of phthalazine, 220 g of reducing agent dispersion, 61 g of the above organic polyhalide dispersion, Luxstar 3307B (manufactured by Dainippon Ink & Chemicals, Inc .; SBR Latex) 1000 g and the above halogenated emulsion 120 g were mixed to prepare an emulsion layer coating solution. The silver coating amount of silver halide is 0.1 g / m²It was.
[0112]
<Preparation of emulsion surface intermediate layer coating solution> Dissolve 100 g of MP203 (Kuraray Co., Ltd., modified polyvinyl alcohol) in 900 cc of water, and then add 2 cc of a 5 wt% aqueous solution of sodium di (2-ethylhexyl) sulfosuccinate. did. Furthermore, the refractive index shown in Table 1 is obtained.Organic silverSalt dispersion was added.
[0113]
<Preparation of emulsion surface protective layer-1 coating solution>
145 g of inert gelatin dissolved in 1110 cc of warm water, 400 g of 20 wt% polyethyl acrylate latex, 57 cc of 1N-sulfuric acid, 10 cc of 5 wt% aqueous sodium salt of di (2-ethylhexyl) sulfosuccinate, 10 wt% methanol of phthalic acid 280 cc of a solution was added to obtain a protective layer coating solution.
[0114]
<Preparation of emulsion surface protective layer-2 coating solution>
100g gelatin dispersion containing 12wt% polymethyl methacrylate fine particles (average particle size size 2.5μm) in 129g inert gelatin dissolved in 1650cc warm water, 1N-sulfuric acid 65cc, sulfosuccinic acid di (2-ethylhexyl) ester The solution 1 was added with 20 cc of a 5 wt% aqueous solution of sodium salt and mixed so that the 2 wt% aqueous solution (hardener) of potassium chromium (III) sulfate 12 hydrate had a flow rate ratio of 0.3. Prepared.
[0115]
<Back layer coating solution>
Solid base N, N^,, N^,,, N^,,,-10g salt of tetraethylguanidine and 4-carboxysulfonyl-phenylsulfone molar ratio 1: 2 with 10g PVA205 (Kuraray Co., Ltd. polyvinyl alcohol), 88g water and 1 / 16G sand grinder mill (Imex Co., Ltd.) Dispersion gave a base solution.
[0116]
An organic solvent phase in which 2.1 g of basic dye precursor, acidic substance 7.9 g, dye 0.1 g, and ethyl acetate 10 g are mixed and dissolved is mixed in an aqueous phase composed of 10 g of PVA205 (polyvinyl alcohol manufactured by Kuraray Co., Ltd.) and 80 g of water, It was emulsified and dispersed at room temperature to obtain a dye solution (average particle size 2.5 μm).
[0117]
The back surface coating solution was obtained by mixing 39 g of the base solution thus obtained, 26 g of the dye solution, and 36 g of a 10 wt% aqueous solution of PVA205 (polyvinyl alcohol manufactured by Kuraray Co., Ltd.).
[0118]
<Back surface protective layer coating solution>
Gelatin 20g, polymethylmethacrylate (average particle size 7μm) 0.6g, sodium dodecylbenzenesulfonate 0.4g, X-22-2809 (Shin-Etsu Silicone Co., Ltd. silicone compound) 1g was dissolved in 480g of water and a back surface protective layer was applied. A liquid was obtained.
[0119]
<< Preparation of undercoat coating liquid A >>
Polyester copolymer aqueous dispersion Pesresin A-515GB (30%, manufactured by Takamatsu Yushi Co., Ltd.) 200ml, polystyrene fine particles (average particle size 0.2μm) 50g, surfactant A (1wt%) 20ml was added to this Distilled water was added to make 1000 ml of the undercoat coating solution A.
[0120]
[Chemical 1]

[0121]
<< Preparation of undercoat coating liquid B >>
Add styrene-butadiene copolymer aqueous dispersion (styrene / butadiene / itaconic acid = 47/50/3 (weight ratio), concentration 30 wt%) 200 ml, polystyrene fine particles (average particle size 2.5 μm) 0.1 g to distilled water 680 ml. Further, distilled water was added to make 1000 ml of the undercoat coating solution B.
[0122]
<< Preparation of undercoat coating liquid C >>
Dissolve 10 g of inert gelatin in 500 ml of distilled water, and add 40 g of an aqueous dispersion (40 wt%) of tin oxide-antimony oxide composite fine particles described in JP-A-61-20033, to which distilled water is added. Was added to make 1000 ml of the undercoat coating solution C.
[0123]
<< Creation of undercoat support >>
One side (photosensitive surface) of a 175 μm thick biaxially stretched polyethylene terephthalate support tinted with the following blue dye is subjected to corona discharge treatment, and then the undercoat coating solution A is applied at a wet coating amount of 5 cc / s using a bar coater. m²And then dried at 180 ° C. for 5 minutes. The dry film thickness was about 0.3 μm.
[0124]
Next, this back surface (back surface) was subjected to corona discharge treatment, and then the undercoat coating liquid B was applied at a wet coating amount of 5 cc / m using a bar coater.²Then, apply to a dry film thickness of about 0.3 μm, dry at 180 ° C. for 5 minutes, and then apply the undercoat coating liquid C on this using a bar coater to a wet coating amount of 3 cc / m.²Then, it was applied so that the dry film thickness was about 0.03 μm and dried at 180 ° C. for 5 minutes to prepare an undercoat support.
[0125]
[Chemical 2]

[0126]
<Preparation of thermal image forming material>
The back layer coating solution is applied to the undercoat support at a flow rate such that the optical density at 647 nm is 0.7, and the back surface protective layer coating solution is 50 g / m²At the same time as coating the same coater as Figure 11b.1 on page 427 of “LIQUID FILM COATING” (CHAPMAN & HALL, 1997) by Stephen F. Kistler and Petert M. Schweizer Emulsion layer coating solution from the support side 82cc / m²Intermediate layer coating solution 6.5cc / m², Protective layer-1 coating solution 12.5cc / m², Protective layer-2 coating solution 12cc / m²After passing through a chilled zone at 10 ° C. (dew point of 0 ° C. or less), it was dried at 30 ° C. and 40% RH wind speed of 20 m / sec. However, as described in Table 1, the simultaneous multi-layer was formed by simultaneously superimposing the four emulsion layers, and in the sequential coating, the emulsion layer was first coated and dried, and then the remaining three layers were simultaneously coated and dried. The coating silver amount of protective layer-2 is 2.1 g / m²The polymethyl methacrylate fine particles are 7700 / m²include.
[0127]
[Chemical Formula 3]

[0128]
<Measurement of refractive index>
The binder solution (or dispersion) was applied on a glass plate and dried at 50 ° C. for 1 hour to form a polymer film having a thickness of about 100 μm. This film was peeled from the glass plate, and the refractive index of the sodium lamp with respect to the D line was measured using an Abbe refractometer (Type 1T, manufactured by Atago Co., Ltd.).
[0129]
(Evaluation of interference fringes)
The photographic material was exposed at θ = 90 ° in FIG. 2 using a 660 nm semiconductor laser (maximum output 30 mW), and then processed (developed) at 120 ° C. for 15 seconds to obtain an image density of 1.0. The wood-like interference fringes were visually evaluated.
[0130]
The evaluation of interference fringes is as follows.
Interference fringe evaluation
○: No interference fringes occur.
Δ: Some interference fringes are generated.
X: Generation of interference fringes.
[0131]
(Evaluation of bending brittleness)
The prepared photosensitive material is cut into a size of 3.5 cm × 25 cm, and is conditioned for 3 hours or more at 25 ° C. and 10% RH. Pass through the wedge-shaped brittleness tester set at an angle of 5 ° with the emulsion layer coating surface on the outside, fix one end with a clip, and pull the other end manually through the gap of the brittleness tester. Since the photosensitive material is set to bend and bend as it is pulled, the position where the crack has occurred on the surface is confirmed, and the distance from the position fixed with the clip is read. A shorter distance is preferred. Depending on the need for evaluation, adhesive tape is applied to the cracked part and then peeled off to determine the adhesion of the cracked part.
[0132]
The evaluation of bending brittleness is as follows.
Bending brittleness evaluation
○: No cracking occurred.
Δ: Slightly cracked.
X: Strongly cracked.
[0133]
The results are shown in Table 1.
[0134]
[Table 1]

[0135]
From the results in Table 1, it can be seen that the sample of the present invention is excellent in both interference fringes and bending brittleness.
[0140]
Example2
In Example 1, the generation of interference fringes is slightly observed in Sample 6 when the amount of the matting agent (polymethyl methacrylate fine particles) of emulsion surface protective layer-2 is not added at all. This disappears when θ of the laser exposure is set to 84 °.
[0141]
【The invention's effect】
According to the present invention, an interference fringe does not occur, and a thermal image forming material excellent in brittleness can be obtained.
[Brief description of the drawings]
FIG. 1 is an explanatory view schematically showing a typical laser scanning exposure method.
FIG. 2 is an explanatory view schematically showing an angle between a laser beam and a photosensitive material to be exposed in a laser scanning exposure method.
FIG. 3 is an explanatory view schematically showing one typical example in the scanning exposure method.
[Explanation of symbols]
1: Laser light source
2: Laser beam
3: Modulator
4: Modulator drive circuit
5: Image signal output device
6: Beam expander
7: Cylindrical lens
8: Rotating polygon mirror
9: fθ lens
10: Cylindrical mirror
11: Photosensitive material
Arrow A: main scanning direction
Arrow B: Sub-scanning direction

Claims (9)

On the support, at least one photosensitive layer containing a photosensitive silver halide and a binder, and a non-photosensitive layer (except for the outermost layer) adjacent to at least one of the photosensitive layers; A photothermographic material for laser exposure having
The non-photosensitive layer adjacent to the photosensitive layer is composed of at least one pigment selected from metals, metal salts, organic silver salts, and metal oxides and a binder at a pigment / binder ratio of 1/1 or less. And a photothermographic material for laser exposure, wherein the difference in refractive index between the adjacent photosensitive layers is 0.10 or more and 0.70 or less, and both layers are simultaneously applied and dried. . ^2. The laser exposure according to claim 1, wherein the photosensitive silver halide has an average grain size of 0.01 μm or more and less than 0.1 μm and an applied silver amount of 0.01 g / m ² or more and 0.3 g / m ² or less. Photothermographic material. 3. The photothermographic material for laser exposure according to claim 1, wherein the photosensitive layer and the coating solution for the non-photosensitive layer adjacent thereto are both aqueous coating solutions. The photothermographic material for laser exposure according to claim 1, wherein the photosensitive layer contains a reducing agent for organic silver salt and silver ions. The photothermographic material for laser exposure according to any one of claims 1 to 4, wherein the binder of the photosensitive layer contains a polymer latex. The photothermographic material for laser exposure according to any one of claims 1 to 5, wherein the binder of the non-photosensitive layer contains a water-soluble polymer. The photothermographic material for laser exposure according to claim 1, wherein the uppermost layer on the side where the photosensitive layer is provided contains a matting agent. The matting agent has an average particle size of 1 µm or more and 10 µm or less, and is contained in the uppermost layer on the side where the photosensitive layer is provided in an amount of 200 pcs / mm ² or more and 10000 pcs / mm ² or less. This photothermographic material for laser exposure. The refractive index of the photosensitive layer is 0.10 or more and 0.70 or less higher than the refractive index of the non-photosensitive layer adjacent to the photosensitive layer. Photothermographic material for laser exposure.

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