JP2000227642A5 - Heat-developed photosensitive material and X-ray image forming unit using it - Google Patents

Description

〔式中、Ｈａｌ₁及びＨａｌ₂はハロゲン原子を表す。Ｈａｌ₁及びＨａｌ₂は同じであっても異なっていても良い。Ｘは表されるアニオン基表す。Ｒ₁はカルボニル基を部分構造として有する基を表しＲ₂及びＲ₃は窒素原子に置換可能な置換基又は水素原子を表す。Ｒ₁〜Ｒ₃は窒素原子が環内原子となる環状構造を形成するように互いに結合することはない。ｎは１又は２を表す。〕
【化２】

〔式中、Ｈａｌ₃及びＨａｌ₄はハロゲン原子を表す。Ｈａｌ₃及びＨａｌ₄は同じであっても異なっていても良い。Ｚは隣接する窒素原子とともに５〜７員環の含窒素ヘテロ環を構築するのに必要な原子群を表す。この含窒素ヘテロ環はその他の環と縮合、又は結合基により結合していてもよい。〕
【請求項２】 支持体を挟んで両側に有機銀塩、感光性ハロゲン化銀、銀イオンのための還元剤及びバインダーを有することを特徴とする請求項１に記載の熱現像感光材料。
【請求項３】 請求項１又は２に記載の熱現像感光材料の感光性ハロゲン化銀を含む層を有する面の少なくとも一方を、希土類蛍光体粒子を有するＸ線増感スクリーンの蛍光面と密着させてなることを特徴とするＸ線画像形成ユニット。
【請求項４】 請求項３に記載されたＸ線画像形成ユニットを、Ｘ線発生装置を光源として露光することにより画像を得ることを特徴とする画像記録方法。
【請求項５】 請求項３に記載のＸ線画像形成ユニットをＸ線発生装置を光源として露光後、熱現像感光材料を１００〜１７０℃に加熱することにより画像を得ることを特徴とする画像形成方法。 [Claims]
1. In a heat-developed photosensitive material having an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions and a binder on a support, the photosensitive silver halide is chemically sensitized with a chalcogen compound. A heat-developed photosensitive material, which is characterized by containing a compound represented by the following general formula 1 or 2.
[Chemical 1]

[In the formula, Hal ₁ and Hal ₂ represent halogen atoms. Hal ₁ and Hal ₂ may be the same or different. X represents the represented anion group. R ₁ represents a group having a carbonyl group as a partial structure, and R _{2 and R 3} represent a substituent or a hydrogen atom substitutable with a nitrogen atom. R _{1 to} R ₃ do not bond to each other so as to form a cyclic structure in which nitrogen atoms become intra-ring atoms. n represents 1 or 2. ]
[Chemical 2]

[In the formula, Hal ₃ and Hal ₄ represent halogen atoms. Hal ₃ and Hal ₄ may be the same or different. Z represents a group of atoms required to construct a 5- to 7-membered nitrogen-containing heterocycle with adjacent nitrogen atoms. This nitrogen-containing heterocycle may be condensed with another ring or bonded with a bonding group. ]
2. The heat-developed photosensitive material according to claim 1, further comprising an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, and a binder on both sides of the support.
3. At least one of the surfaces of the heat-developed photosensitive material according to claim 1 or 2 having a layer containing a photosensitive silver halide is in close contact with the fluorescent surface of an X-ray sensitized screen having rare earth phosphor particles. An X-ray image forming unit characterized by being made to work.
4. An image recording method characterized in that an image is obtained by exposing the X-ray image forming unit according to claim 3 using an X-ray generator as a light source.
5. An image characterized in that an image is obtained by exposing the X-ray image forming unit according to claim 3 to an X-ray generator as a light source and then heating a heat-developed photosensitive material to 100 to 170 ° C. Forming method.

[0001]
[Technical field to which the invention belongs]
The present invention relates to a radiophotographic element, and more particularly to a radiophotographic element capable of forming an image by thermal development.

Further, a reference example relates to a silver halide photosensitive material, and more particularly to a silver halide photosensitive material having an infrared photosensitive silver halide emulsion layer having low fog, high sensitivity and excellent storage stability, and a heat-developed photosensitive material.

0003
[Conventional technology]
(Explanation of Conventional Techniques for the Present Invention)
Conventionally, in the fields of printing plate making and medical treatment, waste liquid associated with wet treatment of image forming materials has been a problem in terms of workability, and in recent years, there is a strong desire to reduce the amount of treatment waste liquid from the viewpoint of environmental protection and space saving. It is rare.

(Explanation of prior art for reference examples)
The silver halide photographic photosensitive material is made by using silver halide fine particles having excellent properties such as high photosensitivity, memory, and high S / N characteristics. However, since the photosensitive region of the silver halide particles is as short as the long wave end near 500 nm, spectroscopic sensitization using a dye is indispensable for exposing the silver halide particles to the longer wave side. Particularly in recent years, with the development of light sources, the importance of photosensitive materials that are sensitive to infrared laser wavelengths has increased in industrial recording materials. In addition, as an imaging recording photosensitive material, an infrared sensitive material which is excellent in recording environmental information or improving descriptive ability has been attracting attention.

0016.
[Problems to be Solved by the Invention]
Therefore,
An object of the present invention is to provide an X-ray image forming unit in combination with a heat-developed photosensitive material having high sensitivity and suppressed fog and an X-ray intensifying screen using the same.
The purpose of the reference example is to provide an infrared photosensitive silver halide emulsion having high sensitivity and low fog, a silver halide photosensitive material having an infrared photosensitive silver halide emulsion layer, and a heat-developed photosensitive material. To provide a combination of a strong color sensitizer and an infrared photosensitive dye used in the above.

1. 1. In a heat-developed photosensitive material having an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions and a binder on a support, the photosensitive silver halide is chemically sensitized with a chalcogen compound and is described below. A heat-developed photosensitive material containing a compound represented by the general formula 1 or 2.

For reference examples , the solutions are shown in 6 to 11 below.
6. A silver halide emulsion comprising a strong color sensitizer represented by the following general formula [1] and a sensitizing dye represented by the general formula [2a] or the general formula [2b].

Hereinafter, the present invention will be described in detail.

Next, a reference example will be described in detail below.

Ru specific examples of the compounds represented by one general formula (1) below.

In the reference example , the infrared photosensitive silver halide emulsion is a silver halide emulsion having sensitivity to light having a wavelength other than 400 nm to 700 nm in the visible region. The photosensitive wavelength of the silver halide emulsion is preferably 700 nm to 900 nm, more preferably 780 nm to 850 nm.

In the reference example , the infrared photosensitive silver halide emulsion is a photosensitive material that forms a black-and-white image by development, fixing, and washing, and the emulsion layer contains a coupler, a colored coupler, and a DIR compound, and is developed, bleached, fixed, and washed. It can be applied to any of a color photosensitive material that forms a color image, a heat-developed photosensitive material that is not wet-treated, and the like.

The sensitizing dye that can be advantageously used with the strong color sensitizer of the reference example has a thioether group in the dye matrix, and examples thereof include the compounds described in JP-A-9-166844 and JP-A-9-292673. The sensitizing dye represented by the general formulas [2a] and [2b] is advantageous.

Of these compounds represented by the general formulas [2a], [2b], [3] or [4], the _{groups represented by R 3} , R ₄ , R ₁₃ and R ₁₄ are cyclic alkyl groups, respectively. In the case of an alkenyl group or a heterocyclic group, an alkenyl group is particularly preferable, and a vinyl group is particularly preferable. The effect of these forward to strong color sensitization agent is preferred increases. It seems that it is preferable that the substituent here is aromatic rather than simple alkyl in order for the sensitizing dye to form stacking with the strong color sensitizer. Further, in arylthio, the substituent seems to be too large and the effect is slightly reduced, and it seems that the condition is that the substituent is not so large.

The following are typical examples of the compounds described in JP-A-9-166844 and JP-A-9-292674, and representatives of photosensitive dyes represented by the above general formulas [2a], [2b], [3] or [4]. to indicate such things.

The method for synthesizing the compound according to the reference example will be specifically described below.

Sensitizing dye of Example may be used alone, it may be used in combination on a two or more kinds.

When the photosensitive dyes of the reference examples were used alone or in combination, the total amount was 1 × 10 ^-6 mol to 5 × 10 ^-3 mol, preferably 1 × 10 ^{-5 per mol of silver halide.} It is contained in the silver halide emulsion in a proportion of mol to 2.5 × 10 ^-3 mol, more preferably 4 × 10 ^-5 mol to 1 × 10 ^{-3 mol.}

When two or more kinds of photosensitive dyes are used in combination in the reference example , the photosensitive dye can be contained in the silver halide emulsion in an arbitrary ratio.

When two or more kinds of photosensitive dyes of the reference example are combined, the photosensitive dyes can be dispersed in the silver halide emulsion independently or by mixing them in advance by the following method.

The photosensitive dye of the reference example can be dispersed directly into the emulsion. In addition, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, n-propanol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. it can. Ultrasound can also be used for dissolution. Further, as a method for adding the photosensitive dye, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is obtained. A method of adding a water-insoluble dye to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and the dispersion is added to the emulsion; A method of dissolving a dye in a surfactant and adding the solution to an emulsion as described in No. 3,822,135; a compound which shifts to a long wavelength side as described in JP-A-51-74624. Method of dissolving using and adding the solution to the emulsion; a method of dissolving the dye in a substantially water-free acid and adding the solution to the emulsion as described in JP-A-50-80826. Etc. are preferably used. In addition, for addition to the emulsion, the methods described in US Pat. Nos. 2,912,343, 3,342,605, 2,996,287, 3,429,835, etc. are used. Used.

Of course can be used in combination supersensitizer other than Reference Example Reference Example, they Research Disclosure (Research Disclosure) 176 Vol 17643 (December 1978) J terms of the first page 23, IV, Alternatively, it is described in JP-A-49-25500, JP-A-43-4933, JP-A-59-19032, JP-A-59-192242, JP-A-3-15049, and JP-A-62-123454.

The silver halide emulsions of the reference examples include those used for color and black-and-white photographic photosensitive materials, and these silver halide emulsions include those used in Research Disclosure No. Those described in 308119 (hereinafter abbreviated as RD308119) can be used.

[Item] [Page of RD308119]
Iotitude composition 993 IA term manufacturing method 993 IA term and 994 E term crystal wall normal crystal 993 IA term twin crystal 993 IA term epitaxial 993 IA term halogen composition uniform 993 IB term Non-uniform 993 IB term halogen conversion 994 IC term halogen substitution 994 IC term metal-containing 994 ID term monodisperse 995 IF term solvent addition 995 IF term latent image formation position Surface 995 I -G internal 995 I-G applicable sensitive material negative 995 I-H positive (including internal fog particles) 995 I-H emulsion mixed 995 IJ desalted 995 II-A
In the reference example , the silver halide emulsion used is physically aged, chemically aged, and spectroscopically sensitized. The additives used in such a process are Research Disclosure No. 17643, No. 18716 and No. It is described in 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). The description points are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716]
Chemical sensitizer 996 III-A item 23 648
Spectral sensitizer 996 IV-AA, 23-24 648-649 H,
B, I,
C, J terms
D-term strong color sensitizer 996 IV-AE, 23-24 648-649
Item J Anti-fog agent 998 VI 24-25 649
Stabilizer 998 VI 24-25 649
Known photographic additives that can be used as reference examples are also described in the above research disclosure. The relevant descriptions are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716]
Color turbidity inhibitor 1002 VII-I item 25 650
Dye image stabilizer 1001 VII-J item 25
Whitening agent 998 V 24
UV absorber 1003 VIII-I item 25-26
XIII-C term light absorber 1003 VIII 25-26
Light scatterer 1003 VIII
Filter dye 1003 VIII 25-26
Binder 1003 IX 26 651
Antistatic agent 1006 XIII 27 650
Dural agent 1004 X 26 651
Plasticizer 1006 XII 27 650
Lubricant 1006 XII 27 650
Activator / application aid 1005 XI 26-27 650
Matte 1007 XVI
Developer (contained in sensitive material) Item 1001 XXB
Various couplers can be added to the reference example, and specific examples thereof are described in the above-mentioned research disclosure. The relevant descriptions are shown below.

[Item] [Page of RD308119] [RD17643]
Yellow Coupler 1001VII-D VIIC to G Magenta Coupler 1001VII-D VIIC to G Cyan Coupler 1001VII-D VIIC to G Colored Coupler 1002VII-G VIIG DIA Coupler 1001VII-F VIIF BAR Coupler 1002VII- F term and other useful residue release 1001VII-F term coupler A Alkaline soluble coupler 1001VII-E term
The additive used in the reference example can be added by the dispersion method described in RD308119XIV or the like.

In the reference example , the support described in RD17643 page 28, RD18716 pages 647-648 and RD308119 XIX can be used. The photosensitive material of the reference example may be provided with an auxiliary layer such as the filter layer or the intermediate layer described in the above-mentioned RD308119VII-K. In addition , various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in Section VII-K of RD308119 can be adopted.

To develop the silver halide photographic photosensitive material of the reference example, for example, T.I. H. James, Theory of the Photographic Process, 4th Edition (The Theory of The Photographic Process Force Edition), pp. 291 to 334, and Journal of the American Chemical Society, Volume 3, Phenol , 100 (1951), hydroquinone, p-aminophenol, N-methyl-p-amino described in, for example, JP-A-4-15641, JP-A-4-16841, etc. Phenol, 2,4-diaminophenol, 1-phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl- 1-Phenyl-3-pyrazolidone, etc.) can be used alone or in combination, and may be developed by the usual methods described in RD17643, pages 28-29, RD18716, 615 and RD308119XIX described above. Can be done.

Further, reference example not only conventional silver halide photographic material as described above, cut with advantageously applicable to the photothermographic material.

While the present invention has been described each Example, and then will be described in detail below photothermographic material is a part of the common. In the present invention, a heat-developed photosensitive material is a constituent requirement, but as described above, a reference example is used for a normal conventional silver halide photographic photosensitive material that is developed, bleached, fixed, etc. with a liquid treatment liquid. it can implementation can have you in addition to the thermal developing light-sensitive material that can.

Can be used also for preparation of silver halide grains as described at the silver halide used in the present invention is a silver halide which can be used in the heat development system in reference example for the present invention for sensitization It is not always necessary to have all the required requirements, and even if it is sensitized or unsensitized according to the purpose of use of the heat-developed photosensitive material, it is further sensitized by another sensitization method. It may be used in combination with the above-mentioned sensitization method.

The photosensitive silver halide particles used here can also be desalted by methods known in the art such as a noodle method and a floculation method, but they may or may not be desalted.

Preferred chemical sensitization methods include the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, which are described in detail in Reference Examples as well known in the art, as well as gold compounds, platinum, palladium, and iridium. Precious metal sensitization methods such as compounds and reduction sensitization methods can also be used. The above-mentioned compounds can be used as the compounds preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, and the compounds preferably used in the noble metal sensitization method include, for example, gold chloride acid and potassium chloroauric acid. Rate, potassium auricionate, gold sulfide, gold selenide, or compounds described in US Pat. Nos. 2,448,060, UK Pat. No. 618,061 and the like can be preferably used. As a specific compound of the reduction sensitization method, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivative, borane compound, silane compound, polyamine compound and the like can be used in addition to ascorbic acid and thiourea dioxide. .. Further, the emulsion can be reduced and sensitized by aging while keeping the pH of the emulsion at 7 or more or pAg at 8.3 or less. In addition, reduction sensitization can be achieved by introducing a single addition portion of silver ions during particle formation.

In photothermographic materials definitive to the onset bright, organic silver salts are reducible silver source, a silver salt of an organic acid and hetero organic acid containing a reducible silver ion source, particularly long chain (10 to 30, An aliphatic carboxylic acid having a carbon atom number of 15 to 25) and a nitrogen-containing heterocycle are preferable. Organic or inorganic silver salt complexes in which the ligand has a total stability constant for silver ions from 4.0 to 10.0 are also useful. Examples of suitable silver salts are described in RD17029 and 29963 and include: Silver salts of organic acids (eg, gallic acid, oxalic acid, bechenic acid, arachidic acid, stearic acid, palmitic acid, laurin). Silver salts such as acids); silver carboxyalkyl thiourea salts (eg, silver salts such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); with aldehydes Silver complexes of polymer reaction products with hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butylaldehyde, etc.)) and hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5) , 5-Silver complex of polymer reaction product with thiodisalicylic acid); silver salts or complexes of thiones (eg, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazolin-2-thione, And 3-carboxymethyl-4-thiazolin-2-thione silver complex or silver salt); imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2 , A complex or salt of silver with a nitroylic acid selected from 4-triazole and benzotriazole; silver salts such as saccharin, 5-chlorosalitylaldoxime; and silver salts of mercaptides. Of these, particularly preferred silver sources are silver behenate, silver arachidic acid, and silver stearate.

[0287]
【Example】
Example [Preparation of photographic support]
Both sides of a 175 μm-thick PET film having a concentration of 0.170 (Dencitometer PDA-65 manufactured by Konica Co., Ltd.) colored in blue were subjected to a corona discharge treatment ^{of 8 w / m 2 minutes.}

Reference example 1
<Preparation of emulsion C>
While controlling 60 ° C. pAg = 8.0 and pH = 2.0, a potassium bromide aqueous solution and a silver nitrate aqueous solution were added to a 0.5% gelatin aqueous solution by a double jet method, and a monodisperse cube having an average particle size of 0.1 μm was added. A crystallite emulsion was obtained.

(Chemical sensitization and spectral sensitization)
While stirring the emulsion C at 50 ° C., the strong color sensitizers of the comparative and reference examples shown in Table 3 were dissolved in 5 ml of methanol in the amount shown in Table 3 and added, and after 10 minutes, the sensitizing dye was also added to Table 3. The amount shown in (1) was dissolved in 15 ml of methanol and added. After another 10 minutes, 5 ml of 1% ammonium thiocyanate, 1.2 ml of 0.2% chloroauric acid, 7 ml of 0.25% sodium thiosulfate and 0.4% acetate of triphenylphosphine serenide per mol of silver 3 ml of ethyl solution was added and chemically sensitized for the optimum time for maximum sensitivity. Then, 60 ml of a 1% aqueous solution of 4-hydroxy-6-methyl-1,3,3a,7-tetrazyneden was added.

From Table 4, it can be seen that the sample according to the reference example clearly has low fog and high sensitivity. In addition, the reference example sample had good storage stability and showed satisfactory results even after 6 months of natural standing.

Reference example 2
<Preparation of PET (polyethylene terephthalate) under-pulled photographic support>
A commercially available biaxially stretched heat-fixed 175 μm-thick blue-colored PET film ^{is subjected to corona discharge treatment of 8 w / m 2} · min on both sides, and the following undercoat coating solution a-1 is applied to one surface to a dry film thickness. It is applied to 0.8 μm and dried to form the undercoat layer A-1, and the following antistatic processed undercoat coating liquid b-1 is applied to the opposite surface so that the dry film thickness is 0.8 μm. It was set and dried to obtain an antistatic processed undercoat layer B-1.

As is clear from Table 6, the heat-developed silver halide photographic photosensitive material of the reference example is excellent in both fog and relative sensitivity, and the sensitivity and fog change after the forced deterioration treatment are small, and the raw film can be stored over time. It was good.

Reference example 3
The photosensitive layer coating liquid was changed as follows. Others are the same as in Reference Example 1, and the heat-developed photosensitive material sample No. 10 to 15 were prepared.

○ Almost no residual color × Large residual color is not possible As is clear from Table 8, the heat-developed photosensitive material of the reference example has excellent fog and relative sensitivity, no residual color, and the sensitivity after forced deterioration treatment. There was little variation in fog, and the shelf life of the raw film over time was good.

[0370]
【Effect of the invention】
According to the present invention, a high-quality radiographic image can be obtained by a simple process by providing a heat-developed photosensitive material having high sensitivity and suppression of fog and an X-ray image forming unit using the same and combined with an X-ray intensifying screen. ..