CN100428068C - Thermal development apparatus - Google Patents
Thermal development apparatus Download PDFInfo
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- CN100428068C CN100428068C CNB2004100748466A CN200410074846A CN100428068C CN 100428068 C CN100428068 C CN 100428068C CN B2004100748466 A CNB2004100748466 A CN B2004100748466A CN 200410074846 A CN200410074846 A CN 200410074846A CN 100428068 C CN100428068 C CN 100428068C
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Abstract
A thermal development apparatus comprises: a photothermographic recording material feed section that contains a supply tray in the photothermographic recording material feed section, the supply tray being for containing a photothermographic recording material; an exposure section that subjects the photothermographic recording material to exposure; a first conveyance section that conveys the photothermographic recording material from the supply tray to the exposure section; a thermal development section that effects thermal development of the photothermographic recording material; a second conveyance section that conveys the photothermographic recording material from the exposure section to the thermal development section; a cassette storage section that contains a cassette, the cassette being for containing a double-sided photothermographic recording material having image forming layers on both sides of the double-sided photothermographic recording material; and a third conveyance section that conveys the double-sided photothermographic recording material from the cassette to the first conveyance section.
Description
Technical field
FIELD OF THE INVENTION
The present invention relates to the photothermal image material that is used for using dry substance is exposed to the improvement of the thermal developing apparatus of laser beam or analog.More specifically, the present invention relates to a kind of thermal developing apparatus of the two-sided photosensitive film that develops.
Background technology
The description of association area
Use accumulation of heat phosphor sheet material document image to be used for medical usage such as digital radiography system, CT, or the wet system of the image recording structure of MR (magnetic resonance) employing.In wet system, the duplicating image of photograph or record obtains by wet process on the silver halide photography photochromics.
On the contrary, up-to-date effort concentrates on and adopts dry system but not the pen recorder of wet technology.This pen recorder uses the film of photosensitive and/or temperature-sensitive photothermal image material or thermal development recording materials (below be called the photothermal image material).In the dry system pen recorder, the photothermal image material, contacts to carry out thermal development and to discharge this device in the thermal development part with heating arrangement partly to form sub-image at image exposure with laser beam irradiation (scanning).
The favourable part of this dry system is, is imaged on to finish in the time that is shorter than wet system and do not relate to the waste liq disposal concerns, and therefore the demand expection to dry system can increase.
The thermal developing apparatus of correlation technique is described below with reference to Fig. 4-8.
Fig. 4 has provided the schematic configuration diagram that correlation technique is equipped with the thermal developing apparatus 100 of imaging device 1 therein.A kind of like this device of thermal developing apparatus 100, it uses a kind of photothermal image material that need not wet photodevelopment technology, on the photothermal image material, form sub-image with the scan exposure that utilizes laser beam, carry out thermal development then, slowly cool off subsequently and be cooled to room temperature to obtain visual picture.
According to the order of photothermal image material path, the solvent of thermal developing apparatus 100 is photothermal image recording materials feeding section A, image exposure part (corresponding to imaging device 1) B, thermal development portion C, slow cool down part D and cooling segment E.Thermal developing apparatus 100 also is furnished with the transmitting device on point important between the each several part, and it is used to transmit the photothermal image material, and is furnished with the power/control section F that is used to drive/control each part.Power/control section F is furnished with CPU, can operate so various controls (exposure control, travelling speed control, and other).
Arrange thermal developing apparatus 100 like this, make: power/control section F is positioned at its bottom most portion: photothermal image recording materials feeding section A is positioned at power/control section F; With image exposure part B, the thermal development portion C, slow cool down part D and cooling segment E are positioned at temperature-sensitive photograph (thermographic) material feeding section A, and wherein image exposure part B and thermal development portion C are mutually near placing.
According to this configuration, exposure and thermal development are handled and can be carried out in the short transmission distance so that the transmission path of photothermal image material minimizes and shortens required time of section of output.In addition, the photothermal image material section can stand exposure and heat-developed step simultaneously.
Used photothermal image material can be photothermal image material or photo-thermal sensitive recording materials.The photothermal image material is a kind of photochromics with light beam (as, laser beam) record (exposure) image, and its color shows by thermal development.Simultaneously, the photo-thermal sensitive recording materials is a kind of photochromics with the light beam record image, and its color shows by thermal development, or its color shows in image recording by the heat pattern (heat) of laser beam, carries out color with optical radiation subsequently and fixes.
Photothermal image recording materials feeding section A be wherein the photothermal image material certain the time pick up and be fed to downstream image exposure part B from the supply dish of a section part and feeding section A comprise: three loading station 10a, 10b, and 10c; Three feed rollers that provide to feeding section separately are to 13a, 13b, and 13c; And delivery roll that does not provide and transmission guide piece.Particularly, the loading station 10a in being provided at three pile structures in 10b and the 10c, inserts supply dish 15a, 15b, and 15c.In the supply dish, the photothermal image material that comprises different size (as, B4 size, two legal sizes (double-legalsize) (356X432mm)) makes to be selected in can be from the dish separately contained material of the size of material and orientation.
The photothermal image material of making sheet-form usually with a folded stated number that is packaged in the bag or pack with belt (as, 100) form of section obtains.This packing is installed in separately the supply dish and in the layer separately of photothermal image recording materials feeding section A and loads.
Fig. 5 is the amplification cross-sectional view that comprises near the driven roller it, and it transfers to image exposure part B with the photothermal image material 5 that photothermal image recording materials feeding section A is supplied with.
Below describe an example of driven roller 21 in detail.Driven roller 21 is arranged to respect to sweep 31, and the latter is the border between adjacent part 29 and the sloping portion 25.Shown in Fig. 5 B, it has provided the enlarged schematic side view of the part of Fig. 5 A, driven roller 21 is preferably placed in such scope, and (180 °-straight line M Φ) contacts the periphery of driven roller 21 with interior angle to minute this guide plate wherein to pass through the sweep 31 (wherein angle change point) of guide plate 23.Note, be not particularly limited the relation between driven roller 21 diameters and guide plate 23 length.
Predetermined clearance G forms between the outer surface of driven roller 21 and guide plate 23.This clearance G preferably equals thickness " t " (t≤G≤10t) of 10 times photothermal image material 5.
In the above structure of the hop that is used for sub-direction of scanning 17, when photothermal image material 3 by the front end (leading end) of sloping portion 25 when entering, the front end of photothermal image material 3 enters the zone between guide plate 23 and the driven roller 21.In this technology because adjacent part 29 bendings of guide plate 23 and sloping portion 25 are forming predetermined angle Φ, when photothermal image material 3 when sloping portion 25 moves to adjacent part 29,3 bendings of photothermal image material.This flexing with elastic repulsion be imparted to photothermal image material 3 from one's body.As response, occur predetermined friction force between photothermal image material 3 and the driven roller 21 and transmit driving force transferring to photothermal image material 3 from driven roller 21 reliably to this elastic repulsion.Therefore, photothermal image material 3 is transmitted.
In the presence of sloping portion 26 and driven roller 22, even at photothermal image material 3 during from guide plate 23 discharging, the bending of photothermal image material 3 produces a kind of elastic repulsion, occurring predetermined friction force and photothermal image material 3 like this between photothermal image material 3 and driven roller 22 is transmitted reliably.
In addition, photothermal image material 3 is pressed on the adjacent part 29, and this has suppressed photothermal image material 3 and has trembleed from transfer surface.In other words, vertical judder is suppressed.When laser beam is irradiated on the photothermal image material 3 between the driven roller, can obtain the gratifying record that not exposure is moved.
The photothermal image material that image exposure part B transmits from photothermal image recording materials feeding section A with light beam L scanning on main scanning direction.It also loses the heat picture material uploading perpendicular to the sub-direction of scanning (that is, transmission direction) of main scanning direction, like this on the photothermal image material record required image to form sub-image.
Image exposure part B is below described.
Fig. 6 has provided image exposure part B, wherein the imaging device of 1 expression correlation technique, 2 expression semiconductor lasers and 5 expression photochromicss.Light beam 111 collimated lens 112 calibrations of sending from semiconductor laser 2 and striking subsequently on the mirror polygon 113 as the main sweep device.Light beam 111 is reflected by mirror polygon 113 on the direction shown in the arrow A and deflection and laser beam 111 is through scanning lenses 114 subsequently, and the latter generally is made of f θ lens and scanning photochromics 5 on the main scanning direction shown in the arrow X.Photochromics 5 transmits on perpendicular to direction shown in the arrow Y of main scanning direction X by the driven roller 116 as sub-scanister under predetermined speed.As mentioned above, photochromics 5 can scan on main sweep and sub-direction of scanning by light beam 111.
Simultaneously, data image signal D carries out the gradient correction process and is imported into D/A converter 121 according to the gradient table of corrections in the gradient means for correcting 120, and wherein data image signal D is converted to analog picture signal S.Picture signal S is by variable gain amplifier 122 amplifications and be input to the 3rd switch 123 subsequently.The 3rd switch 123 switches by control circuit 124 and when the 3rd switch 123 was in close stance, picture signal S was input to semiconductor laser driving circuit 125 as modulation signal.Semiconductor laser driving circuit 125 drives semiconductor laser 2 and when picture signal S was input to semiconductor laser driving circuit 125, semiconductor laser 2 was directly modulated according to picture signal S.As mentioned above, the intensity of light beam 111 is modulated according to view data D, and the image that view data D is entrained is registered as photographic latent image on photochromics 5.Then, photochromics 5 carries out thermal development technology, to obtain visual picture by sub-image.
Semiconductor laser driving circuit 125 is connected on first driving signal generator 132 and by second switch 131 by first switch 130 and is connected on second driving signal generator 133.These signal generators 132 and 133 produce the first fixing horizontal drive signal S1 and the second fixing horizontal drive signal S2 respectively, and they drive semiconductor laser 2 respectively under predetermined output.The control of the controlled circuit 124 of switch of first switch 130 and second switch 131.
Simultaneously, photochromics 5 provides a main sweep starting point detecting sensor 134 on certain position outside the effective main sweep zone of light beam 111 relatively, and it comprises optical diode or the analog that is used for detection laser beam 111.In sweep trace, provide a front-end detection sensor 135.Front-end detection sensor 135 makes the laser beam 111 that is positioned at effective main sweep zone can accept light beam.Front-end detection sensor 135 can comprise optical diode or analog.Output signal P1 and P2 that main sweep starting point detecting sensor 134 and front-end detection sensor 135 produce respectively are transfused to control circuit 124.
In the main sweep process, wherein light beam 111 strikes near the main sweep starting point detecting sensor 134, and the first fixing horizontal drive signal S1 is transfused to semiconductor laser driving circuit 125.Make semiconductor laser 2 send light beam 111 like this with the horizontal L1 of first predetermined strength.
In addition, in effective main sweep process, the second fixing horizontal drive signal S2 is transfused to semiconductor laser driving circuit 125, makes semiconductor laser 2 send light beam 111 with the horizontal L2 of second predetermined strength like this.
In addition, by making mirror polygon driving circuit 113 input mirror polygon rotation angle signal R to control circuit 124, or by other method, can be a kind of roughly realize control to the opening and closing operation of first switch 130 and second switch 131 with the synchronous mode of the main sweep of light beam 111.
When the light beam 111 of semiconductor laser 2 was accepted, main sweep starting point detecting sensor 134 produced output signal P1.Front-end detection sensor 135 produces output signal P2, as shown in Figure 6.In the main sweep process, wherein light beam 111 strikes near the main sweep starting point detecting sensor 134, and the intensity of light beam 111 is set to the first high relatively horizontal L1.Therefore, the output signal P1 that main sweep starting point detecting sensor 134 is produced when detecting light beam 111 is with waveform appearance clearly.Therefore, in control circuit 124, expression light beam 111 can produce by the waveform shaping that for example makes output signal P1 through the horizontal-drive signal Hsync of predetermined main sweep starting point.
When photochromics 5 is exposed to the position of light beam 111 by further transmission with its front end arrival, has been set the light beam 111 that enters front-end detection sensor 135 and has been blocked by the front end of photochromics 5.As a result, the pulse waveform that produces because of beam detection disappears from the output signal P2 of front end detecting sensor 135.Control circuit 124 detects the disappearance of pulse waveform.Then, in the pent effective main sweep process of second switch 131, control circuit 124 opens second switch 131 and cuts out the 3rd switch 123 therein.In effective main sweep process, picture signal S is transfused to semiconductor laser driving circuit 125 and semiconductor laser 2 sends the light beam of having modulated according to picture signal S 111, makes photochromics 5 carry out image recording like this.
In this case, according to being input to digital-to-analog converter 121 from the signal P1 of main sweep starting point detecting sensor 134 outputs, by input and the synchronous pixel clock signal of horizontal-drive signal Hsync that produces by control circuit 124, make picture signal S synchronous, carry out the timing of digital-to-analog when transforming with therefore control figure view data D to the main sweep of the incoming timing of semiconductor laser driving circuit 125 and light beam 111.
As mentioned above, when the photochromics that transmits on direction shown in the arrow Y 5 arrives that wherein its front end is exposed to the position of light beam 111, be set the light beam 111 that enters front-end detection sensor 135 and blocked by the front end of photochromics 5.As a result, response laser beam detection and the pulse waveform that produces disappears.In this technology, because the perviousness of photochromics 5 reduces by adding sensitized material, light beam 111 can be blocked reliably.
The thermal treatment that the thermal development portion C time is carried out back scan light heat picture material 5 by transmission influences thermal development.The structure of thermal development portion C makes a plurality of board heating apparatus 51a, 51b, be bent and be arranged in continuous circular arc with 51c, described a plurality of board heating apparatus series arrangement and as having the heating element of handling photothermal image material 5 required heating efficiencies in the transmission direction of photothermal image material.
More specifically, comprise board heating apparatus 51a, the thermal development portion C of 51b and 51c has structure as shown in Figure 4, wherein each board heating apparatus has recessed surface, makes photothermal image material 5 with the contact of recessed surface and the relative board heating apparatus of board heating apparatus the photothermal image material be slided.As the transmitting device of photothermal image material 5, feed roller 53 and a plurality of pressure roller 55 are provided, they are used for heat is transferred to the thermal development recording materials from every kind of board heating apparatus in addition.Pressure roller 55 contacts with the outer surface of rotating circular disk 52 and the rotation by rotating circular disk 52 is driven.As pressure roller 55, can use metallic roll, resin roll, rubber rollers, or analog.According to above-mentioned configuration, photothermal image material 5 is pressed towards board heating apparatus 51a when being transmitted, 51b, and 51c.Therefore, can prevent the bending of photothermal image material 5.The downstream end in photothermal image material 5 paths in the thermal development portion C provides the discharging roller 57 that is used to transmit the photothermal image material.
Fig. 7 is a key diagram, and the layer that has provided the photothermal image material is formed.
The composition of photothermal image material 5 at first, is described.As shown in Figure 7, the following formation of photothermal image material: be coated with the basic film that has thickness 176 μ m and form with emulsion layer Em by PET (polyethylene terephthalate) or other material with thickness 20 μ m; Further with protective seam PC coating emulsion layer Em with thickness 4 μ m.At the back side of basic film, apply back coating BC and anti-halo layer AH with gross thickness 3 μ m.The gross thickness of photothermal image material 5 is set in the scope 150-250 μ m.
The refractive index of equivalent layer is set as follows: protective seam PC 1.52, emulsion layer Em 1.54, basic film (PET) 1.66, back coating BC 1.52, anti-halo layer AH 1.52, on average about 1.5-1.7.Use has light transmission rate 50% or lower blank photothermal image material 5, wherein 30% or lower light transmission rate be preferred.
Be sidelong by the protective seam PC of photothermal image material 5 when laser beam and penetrate, laser beam is advanced forward when its light path is refracted, and arrives the interface of end back coating BC and anti-halo layer AH below air.Laser beam is reflected on the interface, and reflecting bundle is back to protective seam PC.When the laser beam of the reflecting bundle on the photothermal image material surface enters a P1 and leave distance L m between the P2 greater than the diameter of laser beam, can avoid interference problem.
Fig. 8 is board heating apparatus 51a, one of 51b and 51c: for example, and the enlarged perspective of board heating apparatus 51b.This figure shows that it covers removed heater stand.Board heating apparatus 51b comprises aluminium guide plate 51G, silicon rubber heater 51H, thermistor (not shown), heater terminal (protector) 51P and pressure roller 55.
Above twisted plate well heater is an embodiment and can is configured to comprise endless belt and separates ratchet (separation pawl) by using another formation plate well heater or heating cylinder.
The photothermal image material 5 that to send out from the thermal development portion C cools off carefully gradually not produce any wrinkle and to have curved shape at slow cool down part D.
In slow cool down part D, arrange a plurality of slow cool down rollers to 59 in the path of photothermal image material 5, to produce desirable constant curvature R.This means that photothermal image material 5 transmits with constant curvature R and is cooled to or is lower than the vitrifying point of material until it.Because curvature is deliberately given to the photothermal image material, extremely or before being lower than vitrifying point do not form unnecessary bending in the photothermal image material cooled.Do not form new crooked under vitrifying point or lower temperature: therefore, amount of bow does not change.
In addition, regulate the temperature of slow cool down roller self and the interior atmosphere of slow cool down part D.These adjustment make after starting soon state and the difference between the state after fully moving minimize.Like this, can reduce variable density.
The photothermal image material 5 of vitrifying point that is cooled to or is lower than the material among the slow cool down part D is by being transferred into cooling segment E near the roller that provides the slow cool down part D outlet to 59.
In cooling segment E, provide coldplate 61.At this, photothermal image material 5 is further cooled the temperature that can not be burnt to the operator when contacting.Then, the photothermal image material is disposed to discharge plate 16 by the discharging roller to 63.
Summary of the invention
Summary of the invention
Simultaneously, the x-ray film that is used for direct radiography comprises imaging layer that is arranged in bearing one side and the fluorescence enhancement layer that is arranged in the bearing opposite side.When being exposed to the X-ray, the fluorescence enhancement layer is sucked and sends fluorescence so that the made imaging layer exposure of photochromics forms sub-image like this.The two-sided photosensitive film that is exposed to the X-ray and forms sub-image thereon is loaded onto the thermal developing apparatus that specialized designs is used for for example strictly being stored in the two-sided photosensitive film of magazine.In thermal developing apparatus, two-sided photosensitive film is picked up from magazine and is stood thermal development, and wherein film is heated so that sub-image is processed into visual picture.
As normal result, the user (as, hospital) buy independently and use with lower device: (1) is used to expose/develop the thermal developing apparatus of the image that derives from CT or MRI and (2) with the develop two-sided photosensitive film thermal developing apparatus of two-sided photosensitive film of X-x-ray apparatus being used to of using.As mentioned above, because the user uses two kinds of different types of developing apparatuss, every kind of device not only needs to buy and standing charges, and needs installing space.
In addition, two-sided photosensitive film need be loaded into its each sheet material in the magazine.But consider the characteristic of photosensitive film, this operation can not be carried out in the place that light is arranged, and must be undertaken by skilled operating personnel in the darkroom in each case.This work extremely bothers.
Carry out if more than operate in the place of light, need film shovel loader (automatic film loading machine).But this film shovel loader costliness, and need installing space.
The present invention is used to address the above problem and an object of the present invention is to provide and a kind ofly can be used for MRI/CT and X-ray usually and need not broad installing space and relate to the photothermal image device of low expense.
In order to deal with problems, according to a first aspect of the invention, a kind of thermal developing apparatus is provided, and it comprises: comprise the photothermal image recording materials feeding section of supply dish in photothermal image recording materials feeding section, described supply dish is used to comprise the photothermal image recording materials; The exposed portion that the photothermal image recording materials are exposed; The photothermal image recording materials are sent to first hop of exposed portion from the supply dish; Carry out the heat-developed thermal development part of photothermal image recording materials; The photothermal image recording materials are sent to second hop of thermal development part from exposed portion; The magazine storage compartment that comprises magazine, described magazine are used to be included in the two-sided photothermal image recording materials that have imaging layer on the two sides of two-sided photothermal image recording materials; With the 3rd hop that two-sided photothermal image recording materials is sent to first hop from magazine.
According to a second aspect of the invention, provide a kind of thermal developing apparatus of setting forth in first aspect present invention, wherein thermal development partly comprises heating part, and the latter heats the front and back through the photothermal image recording materials of transmission path.
According to a third aspect of the invention we, provide a kind of thermal developing apparatus of setting forth in second aspect present invention, wherein heating part is the combination of the heating pressure roller of twisted plate well heater and the close twisted plate well heater of arrangement.
According to a forth aspect of the invention, provide a kind of thermal developing apparatus of setting forth in second aspect present invention, wherein heating part is the combination of the warm-up mill of heating cylinder and the close heating of arrangement drum surface.
According to a fifth aspect of the invention, a kind of thermal developing apparatus of setting forth to the fourth aspect either side in the present invention second is provided, and the transmission speed (described two-sided photothermal image recording materials from magazine) of wherein two-sided photothermal image recording materials through heating part the time is set to and is different from the speed (described photothermal image recording materials from supply coil) of photothermal image recording materials through heating part the time.
According to a sixth aspect of the invention, a kind of thermal developing apparatus of setting forth to the fourth aspect either side in the present invention second is provided, wherein, the temperature (described two-sided photothermal image recording materials from magazine) of two-sided photothermal image recording materials through heating part the time is set to and is different from the temperature (described photothermal image recording materials from supply coil) of photothermal image recording materials through heating part the time.
According to a seventh aspect of the invention, a kind of thermal developing apparatus of setting forth in first aspect present invention is provided, wherein the 3rd hop comprises photothermal image recording materials detecting sensor, and the operation of exposed portion switches to according to the output of photothermal image recording materials detecting sensor and opens or closes.
According to an eighth aspect of the invention, a kind of thermal developing apparatus of setting forth in first aspect present invention is provided, wherein, at exposed portion, the device information of thermal developing apparatus is recorded in from the photothermal image recording materials of supply dish and the two-sided photothermal image recording materials from magazine.
According to a ninth aspect of the invention, provide a kind of thermal developing apparatus of setting forth in first aspect present invention, wherein first hop and second hop operationally are sent to magazine with the photothermal image recording materials from the supply dish.
According to the tenth aspect of the invention, provide a kind of thermal developing apparatus of setting forth in first aspect present invention, wherein the two-sided photothermal image recording materials that operate in of exposed portion carry out being passivated under the heat-developed situation.
The accompanying drawing summary
Fig. 1 has provided the thermal development unit that has the magazine storage compartment in its underpart;
Fig. 2 is the skeleton view of the object lesson of thermal development unit C;
Fig. 3 has provided the thermal development unit that has the magazine storage compartment at its sidepiece;
Fig. 4 has provided and has been different from a kind of thermal development of the present invention unit;
Fig. 5 is sent to the driven roller of image exposure part and near the amplification cross-sectional view it with the photothermal image material;
Fig. 6 is the description figure of the exposure system of image exposure part;
Fig. 7 is the key diagram that the layer of display light heat picture material constitutes; With
Fig. 8 is near the enlarged perspective of board heating apparatus.
Detailed Description Of The Invention
By with reference to the accompanying drawings, will describe the present invention in detail.
[first embodiment]
Heat-development recording apparatus according to first embodiment of the invention can two-sidedly heat.Thermal developing apparatus shows in Fig. 1.In Fig. 1, the heat-development recording apparatus (image processing apparatus) of reference number 200 expression first embodiment of the invention.Heat-development recording apparatus 200 comprises: (1) be used to expose/develop thermal developing apparatus 201 of the image that derives from CT or MRI; (2) be positioned under the thermal developing apparatus 201 and its effect is the two-sided photosensitive film cassette storage compartment 210 that transmits the two-sided photosensitive film of taking a picture with the X-x-ray apparatuss to thermal developing apparatus 201.
Below explain thermal developing apparatus 201 and two-sided photosensitive film cassette storage compartment 210.Thermal developing apparatus 201 utilizes picks up the section that the supply dish 15a of a slice ground from photothermal image recording materials feeding section A of roller 13a picks up the photothermal image material, and it being added to image exposure part B downstream by the first hop X, the described first hop X is sent to image exposure part B with the photothermal image material from supply dish 15a.After exposure, thermal developing apparatus 201 makes the photothermal image material heat-treat in the thermal development portion C, described photothermal image material passes through the second hop Y from image exposure part B, subsequently at slow cool down part D gradually with its cooling with it is cooled off in cooling segment E and discharge the photothermal image material at last to discharging magazine outward.Element outside the heat extraction development portion C identical with the element of the described correlation technique of Fig. 4 is represented with identical reference number, and is omitted its repetition of explanation at this.
The thermal development portion C makes back scan light heat picture material carry out thermal development by heat-treating when transmitting.As shown in Figure 1, the thermal development portion C is provided, has wherein handled the temperature required a plurality of board heating apparatus 51a of photothermal image material 5,51b to reach as well heater, 51c arranges in the transmission direction of photothermal image material, wherein each well heater is crooked, these board heating apparatus 51a, 51b, 51c arranges and forms the continuous circular arc shape, 51x is provided as towards board heating apparatus 51a, 51b, 51c with another heating arrangement.
More specifically, the thermal development portion C comprises board heating apparatus 51a, and 51b, and 51c have structure as shown in Figure 4, and each board heating apparatus has recessed surface, and photothermal image material 5 is contacted with the recessed surface of board heating apparatus and the photothermal image material that relatively slides.As the transmitting device of photothermal image material 5, a plurality of metal pressure rollers 55 are provided, they are also as the heat removal devices from each board heating apparatus to photothermal image material 5.Metal pressure roller 55 contacts with the outer surface of rotating circular disk 52 and the rotation by rotating circular disk 52 is driven.According to above-mentioned structure, photothermal image material 5 is pressed towards board heating apparatus 51a, 51b, and 51c when transmitting.Therefore, can prevent the bending of photothermal image material 5.In addition, heating arrangement 51X is provided at rotating circular disk 52 sides of metal pressure roller 55 with adjacent metal pressure roller 55, and metal pressure roller 55 is heated by heating arrangement 51X like this.Therefore, the two sides of the photothermal image material that transmits by metal pressure roller 55 is by use board heating apparatus 51a, 51b, and 51c and metal pressure roller 55 heat and develop.
Fig. 2 is the skeleton view of the object lesson of thermal development unit C.In Fig. 1,51b represents to comprise aluminium guide plate 51G, silicon rubber heater 51H, thermistor (not shown), the board heating apparatus of heater terminal (protector) 51P and metal pressure roller 55.Aluminium guide plate 51G is formed recessed surface by moulding with the transmission direction along the photothermal image material.On the Width of aluminium guide plate 51G, seven metal pressure rollers 55 are placed along transmission direction with even interval.Metal pressure roller 55 is used to transmit the photothermal image material that has transmitted on recessed surface, simultaneously it is pressed to recessed surface.
Therefore, the face side of the photothermal image material that transmits by board heating apparatus 51b heated by board heating apparatus 51b and its back side by 55 heating of metal pressure roller, described metal pressure roller is heated by board heating apparatus 51X; Therefore, its both sides all are heated.
According to the invention of correlation technique, one-sided heating is carried out in the thermal development portion C.On the contrary, the invention provides two-sided heating.Therefore,, can expect that heating-up temperature should be regulated by the transmission speed of regulating the photothermal image material when photothermal image material thermal development in the thermal development portion C of in supply dish 15a, loading.
Therefore, the present invention has and can reduce the thermal development attendant advantages in used processing time.
The heating arrangement of alternatively, thermal development portion C can comprise the lip-deep a plurality of warm-up mills that the heating of heating unit cylinder wherein are provided and are positioned at the heating cylinder.In this case, by rotation heating cylinder, the photothermal image material carries out two-sided heating, transmits between heating cylinder and warm-up mill simultaneously.
Have the interior center that Halogen lamp LED or heating element are placed on the hollow cylindrical cylinder by making, the heating cylinder is a kind of firing equipment of lower cost and provides than the uniform heating more of the board heating apparatus with sheathed heater.
The object lesson of used photothermal image film comprises; For example, by Fuji Photo Film Co., the DI-ALEm.No.51151 (keeping life is in Dec, 2003) that Ltd. makes.
In addition, the thermal developing apparatus according to first embodiment of the invention comprises two-sided photosensitive film cassette.
As shown in Figure 1, heat recording device is characterised in that except supply dish 15a, two-sided photosensitive film cassette storage compartment 210 is provided at the bottom of this device.Below describe two-sided photosensitive film cassette storage compartment 210 in detail.
The two-sided photosensitive film sheet material that is formed with sub-image on its imaging layer is loaded in the magazine 211, and magazine 211 is loaded in the magazine storage compartment 210, and it is packed two-sided light-sensitive emulsion sheet in the magazine 211.Open the opening and closing lid 211a of magazine 211, and from magazine 211, pick up recording materials by picking up device such as sucker 212 (or picking up roller).
The two-sided photosensitive film of so picking up is connected on the first hop X of thermal developing apparatus 201 213 the 3rd hop Z by comprising transmission guide piece 214 and delivery roll, is transferred to the image exposure part B that is positioned at the downstream along transmission direction subsequently.But do not expose at exposed portion B because formed the two-sided photosensitive film of sub-image on it, so just through this part.Therefore, when the operator carried out the thermal development of two-sided photosensitive film in two-sided photosensitive film cassette storage compartment 210, operation panel or exposed portion off switch (not shown) must turn to closed with passivation exposed portion B.
In order to make above step robotization, recording materials detecting sensor 215 can be provided near magazine 211 outlets, when recording materials detecting sensor 215 detected two-sided photosensitive film, the exposed portion unsharp signal was sent to control section F like this, and the operation of exposed portion B stops automatically like this.Near the recording materials detecting sensor 215 of replacement magazine dismounting outlet 211, the exposing operation at exposed portion B place can be by stopping with moving up and down of sucker 212 synchronously and automatically.
In addition, discern the device information of two-sided photosensitive film can implanted its part in, the reading device that is provided in the device of this information reads the automatic like this exposing operation that stops at exposed portion B place like this.
So there are not the recording materials of exposure to be transferred into the thermal development portion C by the second hop Y through exposed portion B.Two-sided photosensitive film is transferred into the thermal development portion C, and wherein the face side of two-sided photosensitive film is described in the board heating apparatus 51b heating of Fig. 2 and its back side by 55 heating of metal pressure roller, and wherein the latter is heated by board heating apparatus 51X.
After finishing thermal development, the photothermal image material is cooled to carefully or is lower than the vitrifying point of this material and does not produce wrinkle or form curved shape at slow cool down part D, and is sent to cooling segment E subsequently.In cooling segment E, the photothermal image material further is cooled to and does not cause operator's temperature that generation is burnt when contact photothermal image material and last, and the photothermal image material is disposed to discharge plate 16.
Consider that sub-image forms on two-sided photosensitive film, optional in the exposure at exposed portion B place.But device information can be recorded on the two-sided photosensitive film at exposed portion B place.Similarly, device information can be recorded on the photosensitive film of single face (photothermal image material) of supply dish at exposed portion B place.The material of two-sided photosensitive film is below described.
[second embodiment]
Thermal developing apparatus according to second embodiment of the invention can load raw stock.
Usually, the sheet material of two-sided photosensitive film is loaded onto in the double coated film magazine, and this loading is by x-ray technology person or by using film loading bin (automatic film loading machine) to carry out.Therefore, the loading work that is used for two-sided light-sensitive emulsion sheet is loaded into two-sided photosensitive film cassette is trouble.In addition, the film loading bin is expensive and needs installing space.
Thermal developing apparatus shown in Figure 1 has the supply dish 15a that comprises the photothermal image material, and the raw stock that will be used for laser log loads wherein.As mentioned above, raw stock usually by the first hop X (delivery roll to 203 and the transmission guide piece 204) be transferred into laser log part B from the supply dish.At laser log part B, be recorded on the film based on the sub-image of view data, be sent to the thermal development portion C by the second hop Y subsequently.In the thermal development portion C, film carries out thermal development and is disposed to discharge plate 16 at last.
Second embodiment can be sent to magazine 211 with the raw stock that is arranged in supply dish 15a.
At first, empty magazine 211 is inserted into magazine storage compartment 210.Because the operator selects " automatically load " or operates a special switch (not shown) from the operation panel (not shown), the raw stock sheet material that is included among the supply dish 15a is picked up, and is sent to the first hop X (delivery roll is to 203 and transmit guide piece 204).Then, it is transmitted rearward to the 3rd hop Z (from the transmitting device of magazine 211 to first hop X (delivery roll to 213 and transmission guide piece 204)) and is loaded at last in the magazine 214 in the magazine storage compartment 210 from the first hop X.
Therefore, use this device can eliminate demand to film loading bin and manually load.The film that more than description hypothesis is used for the laser imaging device is identical with two-sided photosensitive film; If but the film that is used for the laser imaging device is different with two-sided photosensitive film, two-sided photosensitive film can be loaded among the supply dish 15a in advance, maybe can provide another supply dish 15b (in Fig. 1, only show supply dish 15a, but in fact, as with reference to shown in Figure 4, provide a plurality of supply dish 15b and the 15c that are used for the different size film, and one of supply dish is obtainable like this).
In addition, double coated film magazine 211 is comprised in the magazine storage compartment.Can open the whole lid (211a) of magazine; But it can be designed to only open its part, and this device be drawn and therefore be sent to film can from opening part like this.
[the 3rd embodiment]
Thermal developing apparatus according to third embodiment of the invention can be provided with a position of loading two-sided photosensitive film cassette.Thermal developing apparatus is shown in Fig. 3.
Fig. 1 has provided the thermal developing apparatus that has the magazine storage compartment in its underpart, but the magazine storage compartment can be provided at its sidepiece.Fig. 3 has provided an example, and wherein the magazine storage compartment is provided at the sidepiece of this device.
In Fig. 3,300 expressions relate to the thermal developing apparatus (image processing apparatus) of third embodiment of the invention.Thermal developing apparatus 300 comprises: (1) be used to expose/develop thermal development unit 301 of the image that derives from CT or MRI; (2) be positioned at two-sided photosensitive film container 310 on the sidepiece of thermal development unit 301, be used for thermotropism developing cell 301 and transmit the two-sided photosensitive film of being taken a picture by the X-x-ray apparatus.Consider that thermal development unit 301 is identical with the thermal developing apparatus 201 that accompanying drawing shows, omits its repetition of explanation at this.
Two-sided photosensitive film container 310 comprises magazine 311.Open the opening and closing lid 311a of magazine 311, and two-sided photosensitive film is picked up from magazine 311, regain from the side of thermal developing apparatus 313 by delivery roll subsequently by picking up device such as sucker 312.
The two-sided photosensitive film so regained is connected on first hop of thermal developing apparatus 301 313 the 3rd hop Z ' by comprising transmission guide piece 314 and delivery roll, is transferred to the exposed portion B that is positioned at the downstream along transmission direction subsequently.After through exposed portion B, film is sent to the thermal development portion C by the second hop Y, and wherein the two sides of two-sided photosensitive film is heated; Face side is heated by board heating apparatus 51b and the back side is heated by metal pressure roller 55, and the latter is heated by board heating apparatus 51X.Then, film is cooled to carefully in slow cool down part D or is lower than the vitrifying point of this material and does not produce wrinkle or form curved shape, be sent to cooling segment E subsequently, wherein the photothermal image material is further cooled the temperature of not burning to the operator when contacting, at last, film is disposed to discharge plate 16.
As mentioned above, the thermal developing apparatus according to the 3rd embodiment can use on highly limited position effectively.
Below be described in detail in and be used for the photothermal image material that heat-development recording apparatus of the present invention uses.In used photographic light-sensitive material, image information writes by scanning with laser beam or analog, rather than by in focal plane, exposing and document image.
Usually, these films are usually used in wet system photochromics field, and known example comprises: be used for the film that medical science is used, directly or indirectly x-ray film and mammography film or analog; The various films that are used for printed panel; The industry recording film; Or be used for the film of common photograph.Object lesson comprise the photothermal image material that uses with the double spread type X-x-ray apparatus that adopts the blue-fluorescence intensifying screen (as, referring to the open No.3229344 of Jap.P.), the photothermal image material of use silver iodide plate-like grain (as, referring to JP-A-59-142539), or be used for the photochromics of medical usage, in the latter, the two sides of bearing scribble the high-load silver chloride with (100) principal plane plate-like grain (as, JP-A-10-282606).In addition, the material that is used for double spread photothermal image material also is disclosed in other patent document.(as, referring to JP-A-2000-227642, JP-A-2001-22027, JP-A-2001-109101, JP-A-2002-90941).Although use 0.1 μ m or lower silver halide compact grained material not to have the turbidity of variation according to these known examples, these materials have been found owing to low sensitivity is not enough to actual use.Simultaneously, use 0.3 μ m or more silver halide compact grained material to be found and be not enough to actual use, because the turbidity variation that remaining silver halide caused can seriously reduce picture quality, and the printout variation.
Use the silver iodide plate-like grain as the photochromics of silver halide grain in wet development field be known (as, referring to JP-A-59-119344 and JP-A-59-119350), but be not applied to the example formerly of photothermal image material.Its reason is that these materials have low sensitivity as mentioned above, and lacks effective sensitization means.Another reason is to have more challenging technology barrier when this material is applied to thermal development.
In order to be suitable for being used as this photographic light-sensitive material, the photothermal image material require has the susceptibility of further increase, and needs the gained image to have higher levels of picture quality in turbidity or similar aspect.
It below is the useful components that satisfies the above heat developable photosensitive material that requires.
1. heat developable photosensitive material
The photothermal image material of this embodiment has imaging layer, and the latter has photothermographic silver halide, non-photosensitivity organic silver salts, reductive agent, and bonding agent on the one side at least bearing.Preferably, the photothermal image material also can have the back of the body protective seam on sealer or backing layer that is provided on the imaging layer or the opposite face that is provided at imaging layer.
Below describe the structure and the preferred composition of these layers in detail.
(minimizing in fact) because the compound of the visible absorption that photothermographic silver halide brings
In embodiments, compare the compound that after thermal development, reduces visible absorption in fact before preferably adding a kind of and thermal development.Silver iodide compound formation agent especially is preferably used as and is reduced in fact after the thermal development because the compound of the visible absorption that photothermographic silver halide brings.
(the silver iodide compound being formed the description of agent)
Silver iodide compound formation agent according to this embodiment can be used for the reaction of Lewis Acid-Base, and in this reaction, at least one nitrogen-atoms of this compound and sulphur atom give its electronics (electron donor: Lewis alkali) to the silver ion as the part atom.The stability of compound can be by progressively stability constant or general stability constant define; But silver ion is depended in this definition, and iodide ion and its silver composite form the combination of agent.In general, the high stability constant can obtain by the following method, comprising: form chelate ring in molecule, obtain chelation like this; With the Acid-Base dissociation constant that increases part.
It is undistinct as yet that the silver iodide compound forms agent working mechanism in this embodiment; But deducibility, silver iodide dissolve by the stable compound that formation comprises three kinds of components (comprising iodide ion) at least.The silver iodide compound that is used for this embodiment forms agent and has the bad dissolving silver bromide or the ability of silver chloride, but it specifically acts on silver iodide.
The silver halide compound that is used for this embodiment forms agent, and to improve the details of mechanism of image storage stability undistinct as yet.But can infer that at least a portion is used for the photothermographic silver halide of this embodiment and silver iodide compound and forms agent and react and forms compound in the thermal development process, reduces like this or the elimination lightsensitivity, this improves the storage stability under optical radiation again.Except more than, the specific characteristic that the silver halide compound forms agent is, can obtain transparent and high-quality image, because the turbidity on the film that silver halide caused also can be reduced.Turbidity on the film can be checked by the decline that the ultraviolet-visible in the measure spectrum absorption spectrum absorbs.
In embodiments, the uv-visible absorption spectra of photothermographic silver halide can be measured by transmission method or method for reflection.If because the absorption of absorption that other additive compound in the photothermal image material is brought and photothermographic silver halide is overlapping, possible countermeasure comprises the employing differential spectrum, remove other compound and its combination by using solvent.The feasible uv-visible absorption spectra that can observe photothermographic silver halide of these countermeasures.
Be used for the silver iodide compound formation agent of this embodiment and the difference of conventional silver ion compound formation agent and be that iodide ion is that the formation stabilized complex is necessary.Conventional silver ion compound forms agent and acts on the salt that comprises silver ion and dissolve them.The example of this salt comprises organic complex salt such as silver bromide, silver chloride and mountain Yu acid silver.On the contrary, the silver iodide compound that is used for this embodiment forms agent and be characterised in that it only works in the presence of silver iodide.
The specific compound that the silver iodide compound that is used for this embodiment forms agent comprises and is described in detail in Japanese patent application No.2002-367661, those of Japanese patent application No.2002-367662 and Japanese patent application No.2002-367663.In addition, the object lesson that is described in the compound of these patented claims object lesson that also can be used as the compound of this embodiment is mentioned.
In embodiments, in order to improve the storage stability of image, especially largely improve the storage stability under optical radiation, the intensity of the uv-visible absorption spectra of photothermographic silver halide after thermal development be preferably before thermal development 80% or lower, more preferably 40% or lower, especially preferred 20% or lower, most preferably 10% or lower.
The silver iodide compound that is used for this embodiment forms agent can be introduced into coating solution and so in any form, as solution, and the emulsification dispersion, or solid fine grain dispersion is introduced in the photochromics.The example of the emulsification dispersion method of knowing comprises a kind of by using oil, as dibutyl phthalate, and tricresyl phosphate, glyceryl triacetate, or phthalic acid diethyl ester, or secondary solvent, dissolve as ethyl acetate or cyclohexanone and machinery forms the method for emulsification dispersion.
(to the explanation of photothermographic silver halide)
1) halogen composition
The photothermographic silver halide that is used for this embodiment must have high agi content 40-100mol%.Be not particularly limited other component, they can be selected from silver halide such as silver chloride and silver bromide; With organic silver salts such as silver thiocyanate and silver orthophosphate; But silver chloride and silver bromide are especially preferred.The silver halide that employing has this high agi content makes to design to have excellent storage stability after developing; Especially, otherwise the preferred photothermal image material that can increase because of the obvious little turbidity that exposure causes.
In addition, consider image storage stability to optical radiation after handling, the agi content of photothermographic silver halide is preferably 70-100mol%, more preferably 80-100mol%, especially preferably 90-100mol%.
It can be uniformly that intragranular halogen composition distributes, or halogen composition can progressively or continuously change.In addition, the preferred silver halide grain that uses with core/shell structure.Preferred structure is dual to five weight structures, and it is preferred wherein having dual nuclear to the quadruple structure/shell crystal grain.Further preferably in the nuclear part, have the nuclear structure that is rich in silver iodide of high-load silver iodide, or in the shell part, have the shell structure that is rich in silver iodide of high-load silver iodide.Preferred adopt a kind of lip-deep technology that silver bromide or silver iodide is positioned at crystal grain as epitaxial part.
Be not particularly limited the β phase/γ phase ratio of the iodide compound of this embodiment.Term " β phase " is meant a kind of structure that is rich in silver iodide with sexangle wurtzite structure, is meant a kind of structure that is rich in silver iodide with cube zinc-blending structure with " γ-mutually ".Term " γ-phase content ratio " is meant the definite ratio of method that proposes by C.R.Berry referred in this.This method is used for according to the silver iodide (100) that derive from the X-ray powder diffraction, and (101), the β of (002) is with γ-peak ratio of (111) is determined γ-phase content ratio mutually.The details of this method is for example referring to Physical Review, reel number 161, No.3, P.848-851 (1967).
2) grain size
For the silver halide that is rich in silver iodide that is used for this embodiment, can select its size enough big to realize the crystal grain of high lightsensitivity.In embodiments, the average ball equivalent diameter of silver halide is preferably 0.3-5.0 μ m, more preferably, and 0.5-3.0 μ m.Term " ball equivalent diameter " expression has the diameter of the ball of the volume identical with silver halide grain referred in this.The ball equivalent diameter can followingly obtain: by the volume of observed projected area under electron microscope and THICKNESS CALCULATION crystal grain; Subsequently this volume is changed into the ball with equal volume.
3) coating weight
In general, the coating weight of its silver halide even the photothermal image material that still keeps after thermal development is restricted on a small quantity, although need the increase susceptibility.The reason of this restriction is as follows: when the coating weight increase of silver halide, the transparency of film descends, and this is unfavorable for image.But in embodiments, the film turbidity that silver halide brought because thermal development can reduce, the coating weight of silver halide can increase.In this embodiment, the coating weight of every mol non-photosensitivity organic silver salts is preferably 0.5-100mol%, more preferably 5-50mol%.
4) crystal grain formation method
The method that forms photothermographic silver halide be well known in the art and, for example, can use to be described in Research Disclosure No.17029 (in June, 1978) and U.S. patent No.3,700,458 method.Particularly, adopt a kind of method that supplies silver compound and supply halogen compound gelatin or other polymer solution to prepare photothermographic silver halide and silver halide is mixed with organic silver salts by adding.In addition, be described in the JP-A-11-119374 that paragraph is counted 0217-0224, the method for JP-A-11-352627 and JP-A-2000-347335 also is preferred.
About forming the method for silver halide plate-like grain, the preferred method that is described in JP-A-59-119350 and JP-A-59-119344 of using.
5) grain shape
Be used for silver halide grain of the present invention and preferably present plate-like shape.More specifically, according to the structure of side plane, plate-like grain comprises tabular-octahedra crystal grain, tabular-tetrakaidecahedron crystal grain and tabular-icosahedron crystal grain.Wherein, tabular-octahedra crystal grain and tabular-tetrakaidecahedron crystal grain are preferred.Term " tabular-octahedra crystal grain " is meant and has { the 0001}, { crystal grain on 1 (1) 00} plane or have { 0001}, { 1 (2) 10}, { crystal grain on 0} plane, (1) 2 (1) referred in this; Term " tabular-tetrakaidecahedron crystal grain " expression has { 0001}, { 1 (1) 00}, { crystal grain on 1 (1) 01} plane has { 0001}, { 1 (2) 10}, { (1) 2 (1) 0}, 1 (2) 11}}, { crystal grain on 1} plane, (1) 2 (1) has { 0001}, { 1 (1) 00}, the crystal grain on { 1 (1) 0 (1) } plane has { 0001}, { 1 (1) 00}, the crystal grain on { 1 (1) 0 (1) } plane, or have { 0001}, { 1 (2) 10}, { (1) 2 (a 1) 0}, { 1 (2) 1 (1) }, the crystal grain on { (1) 2 (1) (1) } plane; Term " tabular-icosahedron crystal grain " is meant to have { 0001}, { 1 (1) 00}, 1 (1) 01}, and the crystal grain on plane, 1 (1) 0 (1), or have { 0001}, { 1 (2) 10}, { (1) 2 (1) 0}, { 1 (2) 11}, { (1) 2 (1) 1}, { 1 (2) 1 (1) }, the crystal grain on { 1}2 (1) (1) } plane.Above symbol " 0001} " represent to have to be equivalent to { the crystrallographic plane group of the planar index on 0001} plane.Other plate-like grain with shape in addition to the above also is preferred.
The dodecahedron of silver iodide, the tetrakaidecahedron and octahedra crystal grain can be with reference to JP-A-2002-080120, JP-A-2003-287835, or JP-A-2003-287836 and preparing.
In the present invention, the projected area equivalent diameter that presents the silver halide of plate-like grain form preferably falls into scope 0.4-8.0 μ m, more preferably in the 0.5-3 μ m." projected area equivalent diameter " used herein is meant the diameter that has with the ring of the projected area area identical of single silver halide grain.The projected area equivalent diameter can change into the diameter of ring of the same area by the projected area (by obtaining with electron microscope observation crystal grain) with each crystal grain and determine.
The die thickness that is used for photothermographic silver halide of the present invention is preferably 0.3 μ m or lower, more preferably 0.2 μ m or lower, further preferred 0.15 μ m or lower.The aspect ratio of photothermographic silver halide is 2-100 preferably, more preferably 5-50.
The silver halide that is rich in silver iodide of this embodiment can have complicated shape.Preferably adopt as people such as R.L.JENKINS, J.ofPhoto.Sci., 28 (1980) P.164, joint crystal grain shown in Figure 1.This smooth crystal grain that provides in identical Fig. 1 also is preferred.Silver halide grain with round angle also is preferred.Be not particularly limited the planar index (Miller index) of the outer surface plane of photosensitive silver halide grains; But [100] plane of preferred big percentage shows high spectral sensitization efficient when absorption spectral sensitization dyestuff.This percentage is preferably 50% or more, and more preferably 65% or more, more preferably 80% or more.Percentage with plane of Miller index [100] can be by being described in T.Tani, J.Imaging Sci, and 29,165 (1985) method determines that this method is based on the plane dependence of the absorption of sensitizing dyestuff between [111] and [100] plane.
6) heavy metal
The photosensitive silver halide grains that is used for this embodiment can comprise the III of family of periodic table metal (having provided the I of family to the XVIII of family) or its metal composite to the XIV of family.Preferably, the VIII of periodic table family is preferably rhodium to the metal of the X of family or the central metal of metal composite, ruthenium, or iridium.These metal composites can be independent, or being used in combination with two or more compounds of same metal or different metal.Metal composite content is preferably 1X10
-9-1X10
-3Mol/mol silver.These metals and metal composite and adding method thereof are described in JP-A-7-225449, the paragraph Nos.0018-0024 of JP-A-11-65021 and the paragraph Nos.0227-0240 of JP-A-11-119374.
In embodiments, the silver halide grain that comprises six cyano group metal composite ions is preferred.The example of six cyano group metal composites comprises: [Fe (CN)
6]
4-, [Fe (CN)
6]
3-, [Ru (CN)
6]
4-, [Os (CN)
6]
4-, [Co (CN
6)]
3-, [Rh (CN)
6]
3-, [Ir (CN)
6]
3-, [Cr (CN)
6]
3-And [Re (CN)
6]
3-
Remove and to mix with water, six cyano group metal composites can by with the suitable organic solvent miscible with water (as, alcohol, ether, glycol, ketone, ester, acid amides, or analog) mixing, or add by in gelatin, mixing.
The amount of six cyano group metal composites is preferably 1X10
-8-1X10
-2Mol/mol silver, more preferably 1X10
-7-1X10
-3Mol.
The metallic atom that can be included in the silver halide grain that is used for this embodiment is (as, [Fe (CN)
6]
4-) and the method that is used for the desalination of silver halide emulsion and chemical sensitization be described in paragraph Nos.0046-0050, the paragraph Nos.0025-0031 of JP-A-11-65021 and the paragraph Nos.0242-0250 of JP-A-11-119374 of JP-A-11-84574.
7) gelatin
Various gelatin can be used as the gelatin that is included in the photosensitive halogenation silver emulsion that is used for this embodiment.In order to keep the fine dispersion of photosensitive halogenation silver emulsion in comprising the coating solution of organic silver salts, the preferred use has molecular weight 500-60,000 low molecular weight gelatine.These low molecular weight gelatines can use in the dispersion process in the crystal grain forming process or after desalinating process; But use in the preferred dispersion process after desalinating process.
8) chemical sensitization
Photothermographic silver halide in this embodiment can need not chemical sensitization in use, but preferably by at least a: chalcogen method for sensitizing, golden method for sensitizing and reduction method for sensitizing and chemical sensitization.The chalcogen method for sensitizing comprises the sulphur sensitization method, selenium method for sensitizing and tellurium method for sensitizing.
For sulphur sensitization, can use non-unsettled sulphur compound.These non-unsettled sulphur compounds are described in P.Grafkides, Chemie et Pysique Photographique (Paul Momtel, 1987, the five editions), Research Disclosure (Vol.307, No.307105) etc.
Especially, can use known sulphur compound such as thiosulfate (as, sodium thiosulfate); Thiocarbamide (as, rhenocure CA, triethyl thiocarbamide, N-ethyl n '-(4-methyl-2-thiazolyl) thiocarbamide and ethyloic trimethyl thiourea); Thioamides (as, thioacetamide); Rhodanine (as, diethyl rhodanine, 5-benzal-N-ethyl rhodanine); Phosphine sulfide (as, the trimethyl phosphine sulfide); Thiohydantoin; 4-oxo-oxazolines-2-40 thione derivatives; Disulfide or polysulfide (as, dimorpholine disulfide (dimorphorinedisulfide), cystine, hexathionic acid-thioketones (hexathiocan-thione)); Polythionate; Elementary sulfur; And active gelatin.Wherein, thiosulfate, thiocarbamide and rhodanine are especially preferred.
In the selenium sensitization, can use unsettled selenium compound.Spendable unsettled selenium compound comprises and is described in JP-B-43-13489 and JP-B-44-15748, JP-A-4-25832, JP-A-4-109340, JP-A-4-271341, JP-A-5-40324, JP-A-5-11385, Japanese patent application No.4-202415, Japanese patent application No.4-330495, Japanese patent application No.4-333030, Japanese patent application No.5-4203, Japanese patent application No.5-4204, Japanese patent application No.5-106977, Japanese patent application No.5-236538, Japanese patent application No.5-241642, those among the Japanese patent application No.5-286916 etc.
Especially, can use the colloidal metal selenide; Selenourea (as, N, N-dimethyl selenourea, trifluoromethyl carbonyl-trimethyl selenourea, and acetyl group-trimethyl selenourea); The selenium acid amides (as, selenium acid amides and N, N-diethyl phenyl selenium acid amides); The selenizing phosphine (as, triphenyl selenizing phosphine and pentafluorophenyl group-triphenyl selenizing phosphine); The selenium phosphate (as, selenium tricresyl phosphate-right-tolyl ester and selenium tricresyl phosphate-just-butyl ester); Selenium ketone (as, the selenium benzophenone); Different selenium cyanate; Selenium carbonic acid; The selenium ester; With the diacyl selenide.In addition, also can use the non-unsettled selenium compound such as the selenic acid that are described in JP-B-46-4553 and JP-B-52-34492, selenium cyanic acid, selenazoles, and selenide.Especially, the selenizing phosphine, the salt of selenourea and selenium cyanic acid is preferred.
In the tellurium sensitization, use unsettled tellurium compound.Available tellurium sensitizer comprises and is described in JP-A-4-224595, JP-A-4-271341, JP-A-4-333043, JP-A-5-303157, JP-A-6-27573, JP-A-6-175258, JP-A-6-180478, JP-A-6-208186, JP-A-6-208184, JP-A-6-317867, JP-A-7-140579, JP-A-7-301879, the unsettled tellurium compound among the JP-A-7-301880 etc.
Particularly, can use the tellurium phosphine (as, butyl-diisopropyl tellurium phosphine, tributyl tellurium phosphine, three butoxy tellurium phosphines, and ethoxy-diphenyl tellurium phosphine); Diacyl (two) telluride (as, two (diphenyl amino formoxyls), two tellurides, two (N-phenyl-N-methylamino formoxyl), two tellurides, two (N-phenyl-N-methylamino formoxyl), two tellurides, two (N-phenyl-N-benzylamino formoxyl) telluride and two (ethoxy carbamyl) telluride); The tellurium urea (as, N, N '-dimethyl ethylidene tellurium urea and N, N '-diphenylethylene tellurium urea); The tellurium acid amides; Tellurium ester etc.Wherein, diacyl (two) telluride and tellurium phosphine are especially preferred.What be described in the compound of paragraph No.0030 of JP-A-11-65021 and JP-A No.5-313284 is expressed as general formula (II), (III) and compound (IV) be preferred.
Selenium sensitization and tellurium sensitization are the preferred example of chalcogen sensitization, and wherein the tellurium sensitization is preferred.
In golden sensitization, can use to be described in P.Grafkides Chemie et PysiquePhotographique (Paul Momtel, 1987, the five editions) and Research Disclosure (Vol.307, golden sensitizer No.307105).Particularly, can use gold chloride, potassium chloroaurate, golden potassium rhodanide (potassium chloroaurate), aurosulfo, Auric selenide etc.Also can use and be described in P.Grafkides, Chemie et Pysique Photographique (Paul Momtel, 1987, the 5th edition) and the metal except that gold of Research Disclosure (Vol.307, No.307,105), as platinum, other precious metal salt of palladium and iridium.
The gold sensitization can be used independently; But it preferably is used in combination with aforementioned chalcogen sensitization.The object lesson of these combinations comprises gold-sulphur sensitization (gold-add-sulphur sensitization), gold-selenium sensitization, gold-tellurium sensitization, gold-sulphur-selenium sensitization, gold-sulphur-tellurium sensitization, gold-selenium-tellurium sensitization, and gold-sulphur-selenium-tellurium sensitization.
In embodiments, chemical sensitization can be used at any time, as long as it is after crystal grain forms and before coating.After desalination these comprise constantly: (1) before spectral sensitization, (2) and spectral sensitization simultaneously, (3) after spectral sensitization and (4) just before being coated with.
The amount that is used for the chalcogen sensitizer of this embodiment can be according to used silver halide grain, chemical ripening condition etc. and change and the chalcogen sensitizer with about 10
-8-10
-1The mol/mol silver halide, preferred 10
-7-10
-2The amount of mol is used.
Similarly, the addition that is used for the golden sensitizer of this embodiment can change and generally is every mol silver halide about 10 according to various conditions
-7-10
-2Mol, preferred 10
-6-5X10
-3Mol.Condition when being not particularly limited emulsion by chemical sensitization.But pAg is 8 or lower, preferred 7.0 or lower, more preferably 6.5 or lower and especially preferred 6.0 or lower; With pAg be 1.5 or more, preferred 2.0 or more and especially preferred 2.5 or more; PH is 3-10, preferred 4-9; Fall into the about 20-95 of scope ℃ with temperature, in preferred 25-80 ℃.
In embodiments, the reduction sensitization also can be used in combination with chalcogen sensitization or golden sensitization.Particularly, the reduction sensitization preferably is used in combination with the chalcogen sensitization.The object lesson of reduction sensitizer of sensitization of being preferred for reducing comprises ascorbic acid, thiourea dioxide, and dimethylamine borane, and stannous chloride, amino imino Loprazolam, hydrazine derivate, borane compound, silane compound, and polyamine compounds.The reduction sensitizer can extremely just any stage of the preparation process before coating adds from crystal growth in photosensitive emulsion production technology.In addition, the reduction sensitization is preferably undertaken by slaking, simultaneously the pH of emulsion remain on 8 or higher and pAg remain on 4 or lower.In addition, the reduction sensitization is preferably undertaken by introduce single adding silver ion part in the crystal grain forming process.
The addition of reduction sensitizer can change and generally is every mol silver halide about 10 according to various conditions
-7-10
-1Mol, preferred, 10
-6-5X10
-2Mol.
Be used for the silver halide emulsion of this embodiment, the thiosulfonic acid compound can be by being described in EPNo.293,917 method and adding.
Photosensitive silver halide grains in this embodiment is the chemical sensitization by at least a method in golden method for sensitizing and the chalcogen method for sensitizing preferably, so the high photosensitive photothermal image material of design.9) can carry out one-electron oxidation to form the compound of its one-electron oxidation product, wherein the one-electron oxidation product can discharge one or more electronics.
Photothermal image material according to this embodiment preferably comprises a kind of one-electron oxidation that can carry out to form the compound of its one-electron oxidation product, and wherein the one-electron oxidation product can discharge one or more electronics.This compound can be by being used in combination the susceptibility that increases silver halide independently or with aforementioned various chemical sensitizers.
Being included in the photothermal image material of this embodiment and can carrying out one-electron oxidation is a kind of component of following Class1-5 with the compound that forms its one-electron oxidation product, and wherein the one-electron oxidation product can discharge one or more electronics.
(Class1)
Can carry out one-electron oxidation to form the compound of its one-electron oxidation product, wherein the one-electron oxidation product can further discharge two or more electronics and follow subsequently key dissociative reaction;
(type 2)
Can carry out one-electron oxidation to form the compound of its one-electron oxidation product, wherein the one-electron oxidation product can further discharge an electronics and follow carbon-carbon bond dissociative reaction subsequently and have the compound of two or more groups to the silver halide adsorbability in its molecule;
(type 3)
Can carry out one-electron oxidation to form the compound of its one-electron oxidation product, wherein the one-electron oxidation product can further discharge one or more electronics after through the technology of key formation subsequently;
(type 4)
Can carry out one-electron oxidation to form the compound of its one-electron oxidation product, wherein the one-electron oxidation product can further discharge one or more electronics after through ring dissociative reaction in the molecule subsequently; With
(type 5)
Be expressed as the compound of X-Y, wherein X represents to reduce group, Y represents to separate group, its one-electron oxidation produce thing that produces with the one-electron oxidation of reduction group by being expressed as X can break away from Y to produce the X group and to follow the dissociative reaction of X-Y keyed jointing subsequently and can discharge another electronics.
At Class1, in the compound of type 3-5, preferably " compound that in its molecule, has the adsorption group that acts on silver halide respectively " or " compound that in its molecule, has the part-structure of sensitizing dyestuff respectively " and more preferably " compound that in its molecule, has the adsorption group that acts on silver halide respectively ".The compound of Class1-4 is more preferably " having the nitrogen heterocyclic ring group that replaced by the two or more mercapto groups compound as adsorption group ".
The compound of the Class1 of this embodiment-4 be described in detail in JP-A-2003-114487, JP-A-2003-114486, JP-A-2003-140287, JP-A-2003-75950, JP-A-2003-114488, those of Japanese patent application No.2003-25886 and Japanese patent application No.2003-33446 are identical.The specific compound that is described in these patented claims also is the example of compound of the Class1-4 of this embodiment.The synthetic embodiment of the compound of the Class1 of this embodiment-4 is also with to be disclosed in those of these patents identical.
The object lesson of the compound of the type 5 of this embodiment is to be called the compound of " photon two electronics sensitizers " or " deprotonation electron donability sensitizer " as being described in JP-A-9-211769 (Compound P MT-1 one S-37 is described in table E and the F of number of pages 28-32), JP-A-9-211774, JP-A-11-95355 (Compound I NV 1-36), JP-T-2001-500996 (term used herein " JP-T " is meant the Japanese translation of disclosed PCT patented claim) (compound 1-74,80-87, and 92-122), U.S. Patent No. 5,747,235 and U.S. Patent No. 5,747,236, EP No.786692A1 (Compound I NV1-35), EP-A-893732A1 and U.S. Patent No. 6,054,260 and U.S. Patent No. 5,994, those of 051.
The compound of Class1-5 can use in any moment in the emulsion preparation process and in the photochromics manufacturing step.Example constantly is included in crystal grain and forms, in the desalination step, when chemical sensitization and before coating.This compound also can divide a plurality of parts to add in these step process separately.Constantly be from finishing to before the desalination step that crystal grain forms preferred the adding, when chemical sensitization (just before the beginning chemical sensitization to just after it is finished), or before coating.Preferred adding constantly is when chemical sensitization or with before the non-photosensitivity organic silver salts mixes.
The compound of Class1-5 is preferably as at water or water-soluble solvent such as methyl alcohol, ethanol, or the solution in the potpourri of these solvents adds.When compound dissolution is in water, raise along with pH or reduce and the compound that increases for its solubleness, can add this solution that its PH raises or reduces.
The compound of Class1-5 is preferred for comprising the emulsion layer of photothermographic silver halide and non-photosensitivity organic silver salts; But this compound can add protective seam or middle layer with the emulsion layer that comprises photothermographic silver halide and non-photosensitivity organic silver salts, and compound is spread in coating process.The adding of the compound of this embodiment constantly can be before or after the adding constantly of sensitizing dyestuff.Every kind of compound is preferably with 1X10
-9-5X10
-1Mol/mol silver halide, more preferably 1X10
-8-5X10
-2The amount of mol is included in the silver halide emulsion liquid layer.
10) have adsorption group and the reduction group the adsorption and oxidation reducing compound.
In embodiments, preferably introduce a kind of adsorption and oxidation reducing compound that in molecule, has adsorption group and act on the reduction group of silver halide.Preferably, adsorption compound is the compound with following formula (I) expression.
Formula (I): A-(W) n-B
[in formula (I), A is illustrated in the group (below be called adsorption group) of adsorbability on the silver halide, and W represents divalent linker, " n " be 0 or 1 and B represent to reduce group.]
The adsorption group that is expressed as the A in the formula (I) is meant that the group that directly is adsorbed onto on the silver halide or promotion are adsorbed onto the group on the silver halide.The object lesson of adsorption group comprises mercapto groups (or its salt); The thioketones group (C (=S)-); Comprise at least one and be selected from nitrogen-atoms, sulphur atom, the heterocyclic group of the atom of selenium atom and tellurium atom; Sulfide group; The disulfide group; Cation group; With the ethinyl group.
Term " mercapto groups (or its salt) " as adsorption group not only is meant mercapto groups (or its salt) itself, and preferably is meant the heterocycle that is replaced by at least one mercapto groups (or its salt), aryl, or alkyl group.At this, heterocyclic group is meant 5-to 7-unit's monocycle or condensed ring, aromatics, or non-aromatic heterocyclic.The example of heterocyclic group comprises the imidazole ring group, thiazole ring group ， oxazole cyclic group, the benzimidazole cyclic group, benzothiazole cyclic group, benzoxazole cyclic group, the triazole ring group, thiadiazoles cyclic group ， oxadiazole cyclic group, the tetrazole ring group, purine ring group, pyridine ring group, the quinoline cyclic group, isoquinoline cyclic group, pyrimidine ring group and triazine ring group.Heterocyclic group can be comprise the quaternary nitrogen atoms that can become mesoionic because of the disassociation of the mercapto groups that replaces a kind of.When mercapto groups formed salt, the example of its counter ion counterionsl gegenions comprised alkaline metal, earth alkali metal, or the kation of heavy metal (as, Li
+, Na
+, K
+, Mg
2+, Ag
+, or Zn
2+); Ammonium ion; The heterocyclic group that comprises quaternary nitrogen atoms; And phosphonium ion.
Mercapto groups as adsorption group can further be changed into the thioketones group by tautomerism.
The example that is used as the thioketones group of adsorption group also comprises linearity or ring-type thio acylamino group, ghiourea group group, thioxanthamide group and dithiocarbamate groups group.
Comprising at least one and be selected from nitrogen-atoms as adsorption group, sulphur atom, selenium atom, with the heterocyclic group of the atom of tellurium atom have can form imino group silver (＞NAg) as the nitrogen heterocyclic ring group of heterocyclic moiety structure-NH-group, or have and to be coordinated to " S-" group on the silver ion by coordination link as the heterocyclic moiety structure, " Se-" group, " Te-" group, or the heterocyclic group of "=N-" group.The former heterocyclic group can be, for example, and benzotriazole group, triazole group, indazole group, pyrazole group, tetrazol group, benzimidazole group, imidazole group, or purine group.Latter's heterocyclic group can be, for example, and thienyl group, thiazolyl group, oxazole group, benzothiazole group, benzoxazole group, thiadiazoles group, oxadiazole group, triazine group, selenazoles group, benzo selenazoles group, tellurium azoles group, or benzo tellurium azoles group.
As the example of the sulfide group of adsorption group comprise all comprise part-structure " S-" or " S-S-" group.
Cation group as adsorption group is meant the group that comprises quaternary nitrogen atoms; Particularly, comprise the group of amine groups (ammonio group), or comprise the nitrogen heterocyclic ring group of quaternary nitrogen atoms.The nitrogen heterocyclic ring group that comprises quaternary nitrogen atoms can be, for example, and any pyridinio group, quinolinio group, isoquinolinio group and imidazolio group.
Ethinyl group as adsorption group is meant-C ≡ CH group that its hydrogen atom can be substituted.
Above adsorption group can have any substituting group.
In addition, the object lesson of adsorption group is included in those that enumerate on the number of pages 4-7 of JP-A-11-95355.
The adsorption group that is expressed as the A in the structural formula (I) be preferably the nitrogen heterocyclic ring group that replaced by sulfydryl (as, 2-dimercaptothiodiazole group, 3-sulfydryl-1,2,4-triazole group, 5-mercapto-tetrazole group, 2-sulfydryl-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzothiazole group, 1,5-dimethyl-1,2,4-triazole-3-mercaptide (thiolate) group, 2,4-dimercapto mercaptopyrimidine group, 2,4-triazole group, 3,5-dimethyl sulfydryl-1,2,4-triazole group, or 2,5-dimercapto-1,3-thiazoles group), or have can form imino group silver (＞NAg) as the heterocyclic moiety structure-the nitrogen heterocyclic ring group of NH-group (as, the benzotriazole group, benzimidazole group, or indazole group), more preferably 2-mercaptobenzimidazole group, or 3,5-dimercapto-1,2,4-triazole group.
In formula (I), W represents divalent linker.Can use any divalent linker, as long as it does not have adverse effect to photographic property.For example, can use to comprise carbon atom hydrogen atom, oxygen atom, the divalent linker of nitrogen-atoms and sulphur atom.The object lesson of divalence keyed jointing group comprise alkylidene group with 1-20 carbon atom (as, methylene, ethylidene, trimethylene, tetramethylene, or hexa-methylene), alkenylene group with 2-20 carbon atom, have 6-20 carbon atom arylene group (as, phenylene or naphthylene),-CO-,-SO
2-,-O-,-S-,-NR
1-and the combination of these divalent linkers.R referred in this
1The expression hydrogen atom, alkyl group, heterocyclic group, or aromatic yl group.Expression can have any substituting group as the divalent linker of W.
In formula (I), the reduction group that is expressed as B represents to reduce the group of silver ion.The object lesson of B comprises the formoxyl group, amino group, triple bond group (comprising acetylene group or propargyl group); or by from following material, removing the residue that hydrogen atom obtains: mercapto groups, hydramine, hydroxamic acid; hydroxycarbamide, hydroxycarbamide amino, reductone (comprising the reductone derivant); aniline; phenols (comprise benzodihydropyran-6-alcohol, 2,3-dihydroxy benzo furans-5-alcohol; aminophenols; sulfonamido phenols and polyhydric phenol such as p-dihydroxy-benzene, catechol; resorcinol; benzene triol, and bis-phenol), acid hydrazide; the carbamyl hydrazine, 3-pyrazolone etc.Certainly, these groups can have any substituting group.
The oxidation potential that is expressed as the every kind of reducing compound of the B in the formula (I) can be described in " DENKIKAGAKU SOKUTEIHOU " pp.150-208 by use, GIHODO SHUPPANCo.Ltd., with " JIKKEN KAGAKU KOUZA Experimental chemical Course " the 4th edition, Chemical Society of Japan edits and writes, Vol.9, pp.282-344, Maruzen Co., the measuring method of Ltd. and measuring.For example, can use the rotating circular disk voltammetry.Particularly, sample dissolution was also passed through nitrogen 10 minutes in the solution of ratio 10%-90% (volume %) methyl alcohol and Britton-Robinson buffering agent (pH 6.5).Then, by using: as the rotating disk electrode (r.d.e) of making by vitreous carbon (RDE) of working electrode with bottom electrode; Platinum line as the electrode that contends with; With the saturated calomel electrode as reference electrode, the oxidation potential of sample is at 25 ℃, and 1000 rev/mins of sweep velocitys and 20mV/s measure down.Half wave potential (E1/2) can be determined by the gained voltammogram.
When measuring by above method, the oxidation potential that is expressed as the reducing compound of B in this embodiment is preferably approximately-0.3 to 1.0V, more preferably from about-0.1 to 0.8V with especially preferred about 0 to 0.7V.
In formula (I), the reduction group that is expressed as B is preferably by from hydramine, hydroxamic acid, and hydroxycarbamide, hydroxycarbamide amino, reductone, phenol, acid hydrazide, the carbamyl hydrazine, the 3-pyrazolone is removed hydrogen atom in waiting and the residue that obtains.
Below provide the object lesson of the reduction group that is expressed as B; But this embodiment is not limited to these.At this, the A in group and the formula (I) or the position of W keyed jointing are wherein reduced in symbol " * " expression.
The compound of the formula that is expressed as (I) of this embodiment can be introduced ballast group or be commonly used for the polymeric groups of stablizing photograph adjuvant such as coupling agent.The example of polymkeric substance comprises and being described in, as, those of JP-A-1-100530.
The compound of the formula that is expressed as (I) of this embodiment can be the compound of two-form or three-form.The molecular weight of the compound of the formula that is expressed as (I) of this embodiment preferably falls into scope 100-10, and 000, more preferably 120-1,000, more preferably in the 150-500.
In embodiments, the adsorption and oxidation reducing compound with adsorption group and the reduction group that acts on silver halide be described in detail in the identical of Japanese patent application No.2002-328531 and Japanese patent application No.2002-379884.The specific compound that is described in these patented claims also is the object lesson with adsorption group and adsorption and oxidation reducing compound of the reduction group that acts on silver halide.
The compound of this embodiment can be synthetic by the example that uses known method easily.
The compound that is expressed as formula (I) can use separately; But their preferred two or more being used in combination.When two or more compounds were used in combination, they can be added into individual layer or different layers.In addition, they can be added in every kind of compound by different adding methods.
The compound of the formula that is expressed as (I) of this embodiment preferably preferably is added into the silver halide emulsion liquid layer in preparation silver halide emulsion process.Fashionable when adding in the emulsion preparation process, this compound can any step in technology add; For example, in the crystal grain forming process, before the desalination step, in the desalination step process, before chemical maturation stage, in chemical maturation stage process, or in the process before the emulsion adjustment of finishing.This compound can repeatedly separately add in step process.This compound is preferred for emulsion layer, but this compound can be added into protective seam or middle layer with emulsion layer, and this compound is spread in coating process.
Preferred addition height depends on adding method or the above-mentioned kind that adds compound.In general, addition is 1X10
-6-1mol/mol silver halide, preferred 1X10
-5-5X10
-1Mol, more preferably 1X10
-4-1X10
-1Mol.
The compound that is expressed as formula (I) can be by being dissolved in water or water-soluble solvent such as methyl alcohol, ethanol, or in the potpourri of these solvents and add.In the time of in being dissolved in water or hydrosolvent, its pH can regulate with acid or alkali as required.Surfactant also can exist.In addition, this compound can add by being dissolved in the high boiling solvent as the emulsification dispersion.It also can be used as solid dispersions and adds.
11) sensitizing dyestuff
The sensitizing dyestuff that can be used for this embodiment can advantageously be selected from those of spectral characteristic that can be fit to exposure light source by spectral sensitization silver halide grain in the absorption on the silver halide grain and in required wavelength region may and its spectrum sensitivity.The photothermal image material of this embodiment preferably is sensitized as has spectrum sensitivity peak 600nm-900nm, or 300nm-500nm.About the description of sensitizing dyestuff and its adding method can be at the compound that is expressed as general formula (II) of the paragraph Nos.0103-0109 of JP-A-10-186572, the dyestuff that is expressed as general formula (I) of JP-A-11-119374 and the paragraph No.0106 of JP-A-11-119374, U.S. Patent No. 5,510,236, U.S. Patent No. 3,871,887 embodiment 5, be disclosed in the dyestuff of JP-A-2-96131 and JP-A-59-48753, EP No.0803764A1 (19 page 38 is walked to 20 page of 35 row), Japanese patent application No.2000-86865, Japanese patent application No.2000-102560 finds among the Japanese patent application No.2000-205399 etc.These sensitizing dyestufves can independent or two or more being used in combination.
The amount of sensitizing dyestuff can be as requested, as susceptibility or atomization and determine; But it is preferably 10
-6Silver halide in the-1mol/mol imaging layer (photosensitive layer), more preferably 10
-4-10
-1Mol.
In embodiments, super sensitizer can be used for improving spectral sensitization efficient.The example that can be used for the super sensitizer of this embodiment comprises and is described in EP No.587,338, and U.S. Patent No. 3,877,943, U.S. Patent No. 4,873,184, JP-A-5-341432, the compound of JP-A-11-109547 and J-P-A-10-111543.
12) silver halide is used in combination
Be used for the photochromics of this embodiment, can using only a kind of photosensitive halogenation silver emulsion, maybe can be used in combination two or more emulsions (for example, have different average crystal grain sizes, halogen is formed, crystalline nature, or the emulsion of chemical sensitization condition).If use a plurality of photothermographic silver halides with varying sensitivity, gradient can be controlled.Correlation technique can comprise and for example is described in JP-A-57-119341, JP-A-53-106125, JP-A-47-3929, JP-A-48-55730, JP-A-46-5187, those of JP-A-50-73627 and JP-A-57-150841.Preferably, emulsion has 0.2log E or more sensitivity difference.
13) mixing of silver halide and organic silver salts
The crystal grain of photothermographic silver halide especially preferably forms and carries out chemical sensitization under the situation that does not have the non-photosensitivity organic silver salts.This is because can not produce enough susceptibilitys sometimes by halogenating agent being added the method that forms silver halide in the organic silver salts.
The example that mixes the method for silver halide and organic silver salts comprises and utilizes high speed agitator, bowl mill, sand mill, colloidal mill, vibrating mill, or homogenizer mixes the photothermographic silver halide of preparation separately and organic silver salts and it is prepared completed photothermographic silver halide and the organic silver salts that is in preparation and will prepares organic silver salts mixes.The effect of this embodiment can obtain by above-mentioned any method
14) silver halide is mixed in the coating liquid
In embodiments, add silver halide to preferred moment of imaging layer coating solution and be 180 minutes before the coating to just before coating, preferably before being coated with 60 minutes to 10 seconds.The effect of this embodiment is not particularly limited mixed method and mixing condition, as long as can realize satisfactorily.The object lesson of mixed method is included in the jar and mixes, wherein be controlled to produce required time by flow velocity that adds and the mean residence time that is fed to the rate calculations of spreader, with for example be described in N.Harnby by using, M.F.Edwards, the static mixer of A.W.Nienow (by Koji Takahashi translation) " LiquidMixing Technology " (Nikkan Kogyo Shinbun, 1989) the 8th chapter mixes etc.
(to the description of organic silver salts)
The non-photosensitivity organic silver salts that is used for this embodiment is a kind of relatively stable but be heated to 80 ℃ or can form the silver salt of silver-colored image when higher in the presence of the photothermographic silver halide of exposure and reductive agent in when exposure.Organic silver salts can be can reduce the organic material in source of silver ion any comprising.This non-photosensitivity organic silver salts is described in the paragraph 0048-0049 of JP-A-10-62899, EPNo.0803764A1 (18 page 24 is walked to 19 page of 37 row), EP No.0962812Al, JP-A-11-349591, JP-A-2000-7683, be preferably the organic acid silver salt with the JP-A-2000-78711. organic silver salts, more preferably the silver salt of long chain aliphatic carboxylic acid (having 10-30 carbon atom, especially preferred 15-28 carbon atom).Preferred organic silver salts comprises mountain Yu acid silver, arachidic acid silver, silver stearate, oleic acid silver, lauric acid silver, caproic acid silver, myristic acid silver, palmitic acid silver and its potpourri.In these acylates, its mountain Yu acid silver content is that the organic acid silver salt of 50-100mol% is preferred for this embodiment.Especially preferred, mountain Yu acid silver content is 75-98mol%.
Be not particularly limited the form of the organic silver salts that can be used for this embodiment, and this form can be aciculiform, rod, tabular, or squamous.
In embodiments, the organic silver salts of squamous form is preferred.In embodiments, the squamous organic silver salts is defined as follows.When organic silver salt was observed under electron microscope, the shape of organic silver salts crystal grain was approximately rectangular parallelepiped, and its limit is prescribed as follows: minor face is " a "; The limit of intermediate length is " b "; With longest edge is " c " (" c " can equal " b ")." x " uses short value " a " to calculate with " b " is following:
x＝b/a
Like this, " x " and average " x " that calculates about 200 crystal grain is called " x (on average).When " x (on average) " satisfied " x (on average) " and be equal to or greater than 1.5 concern, this crystal grain was defined as squamous crystal grain." x (on average) " is preferably 1.5-30, more preferably 1.5-15.By the way, when " x (on average) " is 1 or more and be lower than 1.5, this crystal grain has the needle-like form.
In squamous crystal grain, value " a " can be regarded as having the thickness as the plate-like grain of the principal plane on its limit with " b " and " c ".The mean value of " a " is preferably 0.01-0.3 μ m, more preferably 0.1-0.23 μ m.The mean value of c/b preferably falls into scope 1-6, and more preferably 1-4 is more preferably in 1-3 and the especially preferred 1-2.
The grain size distribution of organic silver salts is preferably monodispersed.Term " the single dispersion " is meant referred in this, by the value (percentage) that the standard deviation of the length of minor axis is obtained divided by the length of minor axis, or value (percentage) by the standard deviation of the length of major axis is obtained divided by the length of major axis, it is preferably 100% or lower, more preferably 80% or lower and more preferably 50% or lower.The shape of organic silver salts can be determined by the image of organic silver salts dispersion under transmission electron microscope.The other method that is used for determining monodispersity is a kind of method of standard deviation of volume weighting mean diameter of definite organic silver salts.Percentage (coefficient of variation) by value that the standard deviation of volume weighting mean diameter is obtained divided by the volume weighting mean diameter is preferably 100% or lower, and more preferably 80% or lower, further more preferably 50% or lower.Measuring process comprise with laser beam irradiation to the organic silver salts that is dispersed in the solution to determine the autocorrelation function of the relative time dependence fluctuation in the scattered light, obtain grain size (volume weighting mean diameter) like this.
Known technology can be used for preparing organic silver salts and its dispersion that can be used for this embodiment.For example referring to JP-A-10-62899, EP No.0803763A1, EP No.0962812A1, JP-A-11-349591, JP-A-2000-7683, JP-A-2000-72711, JP-A-2001-163827, JP-A-2001-163889, JP-A-2001-163890, JP-A-11-203413, JP-A-2001-188313, JP-A-2001-83652, JP-A-2002-6442, JP-A-2002-31870, and JP-A-2001-107868.
In embodiments, photochromics can be by making organic silver salts aqueous dispersion and the mixing of photosensitive silver salt aqueous dispersion.The method of mixing two or more organic silver salts aqueous dispersions and two or more photosensitive silver salt aqueous dispersions is preferred for controlling photographic property.
In embodiments, can use the silver salt of aequum; But the amount in silver content is preferably 0.1-5g/m
2, more preferably 1-3g/m
2, especially preferred 1.2-2.5g/m
2
(nucleator)
Photothermal image material of the present invention preferably comprises nucleator.
" nucleator " according to the present invention is meant a kind of compound, and it can produce because of initial development can be by reacting the compound of inducing other development with product (obtaining) in developing process.It is conventional known adopting nucleator in being applicable to the superelevation contrast photochromics of printed panel.Its average gradient be 10 or higher superelevation contrast photochromics be unsuitable for as the photochromics of common photograph and especially be not suitable for the medical usage that wherein needs high diagnosis capability.In addition, because its low graininess and lack sharpness, superelevation contrast photochromics is not suitable for medical usage fully.Produce the effect that is different from correlation technique superelevation contrast photochromics fully according to nucleator of the present invention.Do not increase contrast according to nucleator of the present invention.Even being a kind of photosensitive silver halide grains number, nucleator according to the present invention compares the compound that obviously after a little while also can cause enough developments with the amount of non-photosensitivity silver halide.Its mechanism is undistinct as yet; But illustrate, when thermal development was carried out according to nucleator of the present invention by use, the number of developed silver crystal grain was greater than the photosensitive silver halide grains in the highest density region.Therefore can infer, not exist therein according to nucleator of the present invention on the point of silver halide grain and set up other development point (that is development center).
Being used for nucleator of the present invention is and those identical compounds of working as that are described in detail in Japanese patent application No.2004-136053.The object lesson that is described in the compound of this patented claim also can be used as the instantiation of the nucleator of this embodiment and mentions.
Below provide the object lesson of the compound in the above-mentioned nucleator, but nucleator is not limited thereto.
For the adding method, nucleator can arbitrary form, as solution, and the emulsification dispersion, or solid fine grained dispersion is introduced in the coating solution, enters photochromics like this.
The example of the emulsification dispersion method of knowing comprises and nucleator is dissolved in oil as dibutyl phthalate, tricresyl phosphate, decanedioic acid dioctyl ester, tri-2-ethylhexyl phosphate, or in secondary solvent such as ethyl acetate or the cyclohexanone; Subsequently by adding surfactant such as neopelex, oleoyl-N methyl taurine sodium, or two (2-ethylhexyl) sodium sulfosuccinates and machinery forms the method for emulsification dispersion.At this moment, preferably add the viscosity that polymkeric substance such as a-Methylstyrene Low-Polymer or poly-(tert-butyl acrylamide) are used to regulate the oil droplet of refractive index.
The example of solid fine grained dispersion method comprises by using bowl mill, colloidal mill, vibromill, sand mill, jet mill, roller mill, or utilize ultrasound wave that nucleator is dispersed in the suitable solvent such as water with powder type, prepare the method for solid dispersions like this.At this moment, can adopt protecting colloid (as, polyvinyl alcohol (PVA)) or surfactant (as, anionic surfactant such as triisopropyl sodium naphthalene sulfonate (potpourris of three kinds of different materials on the replacement position of isopropyl group)).When stating grinding machine in the use, use bead such as zirconia usually as dispersion medium.The Zr or the analog of wash-out from these beads can be mixed in dispersion.Elution fraction usually according to dispersion condition with 1-1, the amount of 000ppm is mixed.In fact, the Zr content of photochromics must be not more than 0.5mg/ gram silver.
Antiseptic (as, benzisothiazole ketone sodium salt) preferably be added in the aqueous dispersion body.
In order to disperse nucleator, solid fine grained dispersion method is especially preferred, and wherein nucleator falls into scope 0.01-10 μ m with its mean particle size, preferred 0.05-5 μ m, and more preferably the fine grain form in the 0.1-2 μ m adds.In the present invention, preferably use other solid dispersions, its grain size falls in the above scope simultaneously.
Nucleator of the present invention can be added into imaging layer or layer adjacent thereto; But nucleator preferably is added into imaging layer.The addition of nucleator falls into 10
-5-1mol, preferred 10
-4-5X10
-1In the mol/mol silver scope.Nucleator can independent or two or more being used in combination.
Photothermal image material of the present invention can comprise two or more imaging layers that comprise photothermographic silver halide.If comprise two or more imaging layers, nucleator can be comprised in any imaging layer.Preferably, comprise at least two imaging layers; Comprise the imaging layer of nucleator and do not contain another imaging layer of nucleator.
(reductive agent)
1) infectious development reductive agent
Photothermal image material of the present invention preferably comprises the infectious development reductive agent.
The infectious development reductive agent can be any reductive agent, as long as it can carry out infectious development.
Being preferred for infectious development reductive agent of the present invention is a kind of compound that is expressed as following general formula (R1).
General formula (R1)
In general formula (R1), R
11And R
11' expression has the second month in a season or the tertiary alkyl groups of 3-20 carbon atom independently respectively.R
12And R
12' hydrogen atom, nitrogen-atoms, oxygen atom, phosphorus atoms, or the group of sulphur atom keyed jointing are passed through in expression independently respectively.R
13Expression hydrogen atom or have the alkyl group of 1-20 carbon atom.
Being used for infectious development reductive agent of the present invention is and the identical compound that is described in detail in Japanese patent application No.2004-136052.The object lesson that is described in the compound of patented claim also can be used as the object lesson of the nucleator of this embodiment and mentions.
Below provide the object lesson that the present invention is expressed as the compound of general formula (R1); But the invention is not restricted to this.
The addition that is expressed as the reductive agent of general formula (R1) is preferably 0.01-5.0g/m
2, more preferably 0.1-3.0g/m
2The content of reductive agent is preferably every mol silver 5-50mol% on the side that imaging layer is provided therein, more preferably 10-40mol%.
The reductive agent that is expressed as general formula (R1) preferably is contained in the imaging layer.
Especially, the reductive agent that is expressed as general formula (R1) preferably is contained in the imaging layer of the silver halide emulsion that contains low lightsensitivity.
2) reductive agent
In the present invention, other reductive agent can be used in combination with the reductive agent that is expressed as general formula (R1).Can comprise that any silver ion that can reduce becomes the material (preferred, organic substance) of elemental silver with the reductive agent that the reductive agent that is expressed as general formula (R1) is used in combination.The example of reductive agent is described in paragraph Nos.0043-0045 and the EP-ANo.0803764 (P.7, p.18 34 walk to, 12 row) of JP-A-11-65021.
In embodiments, reductive agent is preferably so-called hindered phenol reductive agent or has substituent bis-phenol agent on the neighbour-position of phenolic hydroxyl group.The compound that is expressed as following general formula (R) is especially preferred.
General formula (R)
In general formula (R), R
11And R
11' expression has the alkyl group of 1-20 carbon atom independently respectively.R
12And R
12' expression can replace the substituting group group of hydrogen atom or phenyl ring independently respectively.L represents-the S-group or-CHR
13-group.R
13Expression hydrogen atom or have the alkyl group of 1-20 carbon atom.X
1And X
1' expression can replace the group of hydrogen atom or phenyl ring independently respectively.
Below describe each substituting group in detail.
1) R
11And R
11'
R
11And R
11' respectively independently expression have a 1-20 carbon atom can substituted alkyl group.Be not particularly limited the substituting group that is used for alkyl group; But preferred example comprises aromatic yl group, oh group, alkoxy base, aryloxy group, alkylthio groups; the aryl thio group, acylamino-group, sulfonamide group, sulfonyl group, phosphoryl group; carboxyl groups, carbamyl group, ester group, and halogen atom.
2) R
12And R
12', X
1And X
1'
R
12And R
12' expression can replace the group of hydrogen atom or phenyl ring independently respectively.
X
1And X
1' expression can replace the group of hydrogen atom or phenyl ring independently respectively.The preferred example of each group that can substituted benzene ring comprises alkyl group, aromatic yl group, halogen atom, alkoxy base and acylamino-group.
3)L
L represents-the S-group or-CHR
13-group.R
13Expression hydrogen atom or have the alkyl group of 1-20 carbon atom, wherein alkyl group can have substituting group.
R
13The alkyl group object lesson of non-replacement comprises methyl group, ethyl group, propyl group, butyl group, heptyl group, undecyl group, isopropyl group, 1-ethyl pentyl group group and 2,4,4-tri-methyl-amyl group.
As R
11Substituting group, the substituent example that is used for alkyl group comprises halogen atom, alkoxy base; alkylthio groups; aryloxy group, aryl thio group, acylamino-group; the sulfonamide group; the sulfonyl group, phosphoryl group, oxygen base carbonyl group; carbamyl group and sulfamoyl group.
4) preferred substituted
Preferably, R
11And R
11' be respectively the second month in a season or tertiary alkyl groups with 3-15 carbon atom.Object lesson comprises isopropyl group, isobutyl groups, tert-butyl group, uncle-pentyl group, uncle-octyl group group, cyclohexyl groups, cyclopentyl group, 1-methylcyclohexyl group and 1-methyl cyclopropyl group.More preferably, R
11And R
11' be respectively tertiary alkyl groups with 4-12 carbon atom, tert-butyl group wherein, uncle-pentyl group, or 1-methylcyclohexyl group is especially preferred and the tert-butyl group is most preferred.
Preferably, R
12And R
12' be respectively alkyl group with 1-20 carbon atom.Its object lesson comprises methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, uncle-pentyl group, cyclohexyl groups, 1-methylcyclohexyl group, benzyl group, methoxy group and methoxy ethyl group.Wherein, more preferably example is a methyl group, ethyl group, propyl group, isopropyl group and tert-butyl group.
Preferably, X
1And X
1' be respectively hydrogen atom, halogen atom, or alkyl group, wherein hydrogen atom is preferred.
L is preferably-CHR
13-group.
R
13Be preferably hydrogen atom or have the alkyl group of 1-15 carbon atom.The preferred example of alkyl group comprises methyl group, ethyl group, propyl group, isopropyl group and 2,4,4-tri-methyl-amyl group.Especially preferred, R
13Be hydrogen atom, methyl group, propyl group, or isopropyl group.
Work as R
13Be hydrogen atom, R
12And R
12' preferably have the alkyl group of 2-5 carbon atom, more preferably ethyl group or propyl group and most preferably ethyl group respectively.
Work as R
13Be uncle or secondary alkyl group with 1-8 carbon atom, R
12And R
12' methyl group preferably respectively.If have the uncle or the secondary alkyl group of 1-8 carbon atom, R
13Be more preferably methyl group, ethyl group, propyl group, or isopropyl group, more preferably methyl group, ethyl group, or propyl group.
If R
11, R
11' and R
12, R
12' be respectively methyl group, R
13Be preferably secondary alkyl group.In this case, if secondary alkyl group, R
13Be preferably isopropyl group, isobutyl groups, or 1-ethyl pentyl group group, wherein isopropyl group is preferred.
Above-mentioned reductive agent has various thermal development performance, and this depends on R
11, R
11' and R
12, R
12', and R
13Combination.The thermal development performance can be controlled by two or more reductive agents that use various mixture ratios.Therefore, preferably, two or more reductive agents are used in combination according to purposes.
Below provide the object lesson of the compound that is expressed as general formula (R) of this embodiment, but the compound of this embodiment is not limited thereto.
Especially preferred example is to be expressed as (R-1) compound to (R-20).
Reductive agent amount in embodiments is preferably 0.01-5.0g/m
2, more preferably 0.1-3.0g/m
2The side of imaging layer is provided therein, and the content of reductive agent is preferably 5-50mol%/mol and deposits thereon silver, more preferably 10-40mol%.
In embodiments, reductive agent can be added into the imaging layer that comprises organic silver salts or photothermographic silver halide, or adds layer adjacent thereto; But reductive agent preferably is introduced into imaging layer.
In embodiments, reductive agent can be introduced in the coating solution in any form.For example, it can solution, the emulsification dispersion, or the form of solid fine grain dispersion is introduced into, and the gained coating solution is introduced in the photochromics like this.
The example of the emulsification dispersion method of knowing comprises a kind of by using oil as dibutyl phthalate, and phosphate trimethylbenzene is cruel, glyceryl triacetate, or diethyl phthalate, or secondary solvent, as ethyl acetate or cyclohexanone dissolves and machinery forms the method for emulsification dispersion.
The example of solid fine grain dispersion method comprises a kind of by using bowl mill, colloidal mill, and vibromill, sand mill, jet mill, roller mill, or ultrasound wave is dispersed in reductive agent in the suitable solvent such as water, prepares the method for solid dispersions like this.Method for optimizing is to use the dispersion method of sand mill.When disperseing, can adopt protecting colloid (as, polyvinyl alcohol (PVA)) or surfactant (as, anionic surfactant such as triisopropyl sodium naphthalene sulfonate (that is, three kinds on the replacement position of isopropyl group the potpourri of different materials) mutually).Preferably, antiseptic (as, benzisothiazole ketone sodium salt) is added into water-borne dispersions.
Especially preferred is the solid fine grain dispersion method of reductive agent, and wherein reductive agent is to have average crystal grain size 0.01 μ m-10 μ m; Preferred 0.05 μ m-5 μ m; More preferably the compact grained form of 0.1 μ m-1 μ m adds.In present patent application, other solid dispersions also preferably is dispersed into the grain size that falls in the above-mentioned scope.
(description of development accelerant)
In the photothermal image material of this embodiment, the following material of preferred employing is as the sulfonamide phenolic compounds that is expressed as general formula (A) among development accelerant: JP-A-2000-267222 or the JP-A-2000-330234; The hindered phenol compound that is expressed as general formula (II) among the JP-A-2001-92075; Be expressed as the general formula (I) among JP-A-10-62895 or the JP-A-11-15116 or be expressed as the hydrazine compound of the general formula (1) among the Japanese patent application No.2001-074278; Or the phenol or the naphthol compound that are expressed as general formula (2) among the Japanese patent application No.2000-76240.The consumption of the relative reductive agent of these development accelerants is 0.1-20mol%, preferred 0.5-10mol%, more preferably 1-5mol%.Can be applicable to development accelerant is added photochromics with the similar method of the method that is used for reductive agent; But especially preferred is the method that adds with solid dispersions or emulsification dispersion form of development accelerant wherein.If development accelerant adds with the form of emulsification dispersion, preferable methods is: wherein development accelerant is with the form that is dispersed in the emulsification dispersion in the potpourri method by using secondary solvent to add, and described secondary solvent contains at room temperature to be solid and to have lower boiling high boiling solvent; Or the method that adds with the form of the so-called no oily emulsification dispersion that need not high boiling solvent of development accelerant wherein.
In embodiments, more preferably, in above-mentioned development accelerant, use a kind of hydrazine compound that is expressed as the general formula (1) among the Japanese patent application No.2001-074278, or be expressed as the phenol or the naphthol compound of the general formula (2) among the Japanese patent application No.2000-76240.
Below provide the preferred example of the development accelerant of this embodiment; But this embodiment is not limited thereto.
(to the description of hydrogen bonding compound)
In embodiments, the preferred use has and can (OH), or exist under the situation of amino group, form the non-reduced compound of the group of hydrogen bond with the amino group of reductive agent with the aromatic hydroxy group of reductive agent.
The example that can form the group of hydrogen bond comprises the phosphoryl group, sulfoxide radicals, sulfonyl group, carbonyl group, amide group, ester group, urethane groups, ureido groups, uncle's amino group and nitrogenous aromatic group.Wherein, preferably has the phosphoryl group; sulfoxide radicals; amide group (prerequisite be it does not have＞the N-H group but in the mode of＞N-Ra (wherein Ra is a substituting group of getting rid of H) by end-blocking), urethane groups (prerequisite be it does not have＞the N-H group but in the mode of＞N-Ra (wherein Ra is the substituting group except that H) by end-blocking) or ureido groups (prerequisite be it does not have＞the N-H group but in the mode of＞N-Ra (wherein Ra is the substituting group except that H) by end-blocking) compound.
Especially preferred hydrogen bonding compound is to be expressed as those of following general formula (D) in this embodiment.
General formula (D)
In general formula (D), R
21-R
23Respectively expression can substituted alkyl group independently, aromatic yl group, alkoxy base, aryloxy group, amino group, or heterocyclic group.
Work as R
21-R
23Have substituting group respectively, substituent example comprises halogen atom, alkyl group; aromatic yl group, alkoxy base, amino group; carboxyl groups, acylamino-group, alkylthio groups; the aryl thio group, sulfonamido group, acyloxy group; oxygen base carbonyl group, carbamyl group, sulfamoyl group; the sulfonyl group, phosphoryl group etc.Wherein, preferred substituted is alkyl group and aromatic yl group; As, methyl group, ethyl group, isopropyl group, tert-butyl group, uncle-octyl group group, phenyl group, 4-alkoxyl phenyl group, 4-acyloxy phenyl group etc.
Be expressed as R
21-R
23The object lesson of alkyl group comprise methyl group, ethyl group, butyl group respectively, the octyl group group, dodecyl group, isopropyl group, the tert-butyl group, uncle-pentyl group, uncle-octyl group group, cyclohexyl groups, 1-methylcyclohexyl group, benzyl group, phenethyl group and 2-phenoxy propyl group.
The example of aromatic yl group comprises phenyl group, tolyl group (cresyl group), xylyl group, naphthyl group, 4-tert-butyl phenyl group, uncle 4--octyl phenyl group, 4-anisyl group and 3,5-dichlorophenyl group.
The example of alkoxy base comprises methoxy group, ethoxy group, butoxy radicals, octyloxy group, 2-ethylhexyl oxygen base group, 3,5,5-trimethyl hexyl oxygen base group, dodecyl oxygen base group, cyclohexyl oxygen base group, 4-methylcyclohexyl oxygen base group and benzyloxy group.
The example of aryloxy group comprises the phenoxy group group, tolyl oxygen base group (cresyloxygroup), isopropyl phenoxy group group, 4-tert-butyl phenoxy group group, naphthoxy group and biphenylyloxy group.
The example of amino group comprises the dimethylamino group, diethylamino group, dibutylamino group, dioctyl amino group, N-methyl-N-hexyl amino group, dicyclohexyl amino group, diphenyl amino group and N-methyl-N-phenyl amino group.
Preferably, R
21-R
23Be respectively alkyl group, aromatic yl group, alkoxy base, or aryloxy group.About the effect of this embodiment, preferred, one or more R
21-R
23Be alkyl group or aromatic yl group and more preferably, wherein two or more are alkyl group or aromatic yl group.Consider the availability under low cost, R
21-R
23Be preferably identical group.
Below provide according to this embodiment and comprise those the object lesson of hydrogen bonding compound that is expressed as general formula (D); But this embodiment is not limited thereto.
Except that the object lesson of above-mentioned hydrogen bonding compound those comprises those that are described in Japanese patent application No.2000-192191 and Japanese patent application No.2000-194811.
Hydrogen bonding compound according to this embodiment can be as reductive agent with solution, the emulsification dispersion, or the form of solid fine grain dispersion is introduced in the coating solution, and the gained coating solution is introduced in the photochromics like this.When being in solution state, the compound of this embodiment forms bond complexes with the compound with phenolic hydroxyl group.In these combinations of reductive agent and the compound that is expressed as formula (A) some can be used as crystal attitude compound and is separated.
Especially preferably the crystal powder that will so separate uses with the form of solid fine grain dispersion, obtains stable performance like this.Alternatively, preferably use a kind of reductive agent that will be respectively powder type to mix, and, form the method for compound like this by using suitable spreading agent that the gained potpourri is dispersed in the sand muller with hydrogen bonding compound.
Relative reductive agent, the consumption that is expressed as the compound of general formula (D) is preferably 1-200mol%, more preferably 10-150mol%, most preferably 30-100mol%.
(to the description of bonding agent)
The bonding agent that is used for the layer that contains organic silver salt of this embodiment can be that any polymkeric substance and suitable bonding are transparent or semitransparent and general colourless.Its example comprises: natural resin; Polymkeric substance and multipolymer; Synthetic resin, polymkeric substance and multipolymer; And filming medium; As, gelatin, rubber, poly-(vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate-butyrate, poly-(vinyl pyrrolidone), casein, starch, poly-(acrylic acid), poly-(methyl methacrylate), poly-(vinyl chloride), poly-(methacrylic acid), styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, Styrene-Butadiene, polyvinyl acetaldehyde (as, poly-(vinyl alcohol formal), poly-(vinyl butyral)), poly-(ester), poly-(urethanes), phenoxy resin, poly-(vinylidene chloride), poly-(epoxide), poly-(carbonic ester), poly-(vinyl acetate), poly-(alkene), cellulose esters and poly-(acid amides).Bonding agent also can be by water, organic substance, or the emulsion utilization is coated with and forms.
In embodiments, the bonding agent that is used to contain the layer of organic silver salt preferably has 10-80 ℃ of glass transition temperature (Tg), especially preferred 20-70 ℃ and more preferably 23-65 ℃.
In instructions, Tg calculates by following equation:
1/Tg＝∑(Xi/Tgi)
Wherein polymkeric substance obtains by copolyreaction n kind monomeric compound (i=1 to i=n), and Xi is that the weight fraction (∑ Xi=1) and the Tgi of i monomer is the glass transition temperature (absolute temperature) of the homopolymer of i monomer; Wherein ∑ is represented the summation of i=1 to i=n.
The glass transition temperature of the homopolymer of every kind of monomer (Tgi) is worth from J.Brandrup and E.H.Immergut, " Polymer Handbook " (third edition, Wiley-Interscience (1989)).
As the polymkeric substance of bonding agent can be separately or, as required, as two or a plurality of admixture uses.Have the polymkeric substance of 20 ℃ or more glass transition temperatures and have another polymkeric substance that is lower than 20 ℃ of glass transition temperatures and can be used in combination.When two or more had the polymer blending of different Tgs, its weight average Tg preferably fell in the above-mentioned scope.
In embodiments, utilize its solvent to comprise the coating solution of 30wt% or more water if contain the layer of organic silver salt by coating and dry formation, in addition, if it is solvable or dispersible in aqueous solvent (hydrosolvent) containing the bonding agent of the layer of organic silver salt, especially when bonding agent be 2% quality or lower polymer emulsion when forming by its equilibrium moisture content under 25 ℃ and 60%RH, performance is enhanced.
In the most preferred embodiment, the layer that contains organic silver salt is made with ionic conductivity 2.5mS/cm or lower.This preparation method's example is included in polymkeric substance and uses the separation function film to carry out refinement treatment after synthetic.
Term " wherein polymkeric substance is soluble or dispersible aqueous solvent " is meant water at this, or the potpourri of water and 70% quality or lower water miscibility organic solvent.
The water miscibility representative examples of organic comprises alcoholic solvent such as methyl alcohol, ethanol, and propyl alcohol; Cellosolve solvent such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Ethyl acetate; And dimethyl formamide.
Term " equilibrium moisture content under 25 ℃ and 60%RH " can be following be represented in the weight W 0 of stove dry state 25 ℃ under according to polymkeric substance weight W 1 and polymkeric substance under 25 ℃ and 60%RH atmosphere in wetting balance:
Equilibrium moisture content under 25 ℃ and 60%RH=[(W1-W0)/and W0] X100 (% quality)
About the definition and the measuring method of moisture, can be for example with reference to " Kobunshi Kogaku Koza14, Kobunshi Zairyo Shiken Hou, " (editor Kobunshi Gakkai, Chijin Shokan).
In embodiments, the equilibrium moisture content of binder polymer under 25 ℃ and 60%RH is preferably 2% quality or lower, more preferably 0.01-1.5% quality, more preferably 0.02-1% quality.
In embodiments, bonding agent especially preferably can be dispersed in the polymkeric substance in the aqueous solvent.The state that the fine grain that the example of dispersed comprises the soluble hydrophobic polymer of water wherein disperses with the latex form and wherein polymer molecule be dispersed into the molecule attitude or by forming the state that micella disperses; This two states all is preferred.
Discrete particles preferably has the about 1-50 of mean particle size, 000nm, 5-1 more preferably from about, 000nm.Being not particularly limited the particle size distribution of discrete particles, can be wide particle size distribution or monodisperse particles size distribution.
In embodiments, the embodiment preferred that can be dispersed in the polymkeric substance in the aqueous solvent comprises hydrophobic polymer such as acrylate copolymer, poly-(ester), rubber (as, the SBR resin), poly-(urethanes), poly-(vinyl chloride), poly-(vinyl acetate), poly-(vinylidene chloride) and poly-(alkene).These polymkeric substance can be linear polymers, branched polymer, or cross-linked polymer.They also can be the so-called equal multipolymers that wherein single monomer is aggregated, or the multipolymer that is aggregated of two or more monomers wherein.Multipolymer can be random copolymers or segmented copolymer.
The number-average molecular weight of these polymkeric substance is 5,000-1, and 000,000, preferred 10,000-200,000.Having the polymkeric substance of small-molecular weight too provides not enough emulsion layer resistance to vibration, and the polymkeric substance of macromolecule provides bad deposition properties and is not preferred therefore and have too.
The preferred example of polymer emulsion comprises following, and wherein latex is represented with initial monomers, and the % quality is represented with molecular weight with parenthetic numeric representation and number-average molecular weight.If the use polyfunctional monomer forms cross-linked structure; Therefore, the notion of molecular weight can not be applied to this.This latex is represented as " crosslinked ", and ignores its molecular weight.Tg represents glass transition temperature.
P-1:-MM (70)-EA (27)-MAA (3)-latex (molecular weight 37,000; 61 ℃ of Tg)
P-2:-MMA (70)-2EHA (20)-St (5)-AA (5)-latex (molecular weight 40,000; 59 ℃ of Tg)
P-3:-St (50)-Bu (47)-MAA (3)-latex is (crosslinked; Tg-17 ℃)
P-4:-St (68)-Bu (29)-AA (3)-latex is (crosslinked; 17 ℃ of Tg)
P-5:-St (71)-Bu (26)-AA (3)-latex is (crosslinked; 24 ℃ of Tg)
P-6:-St (70)-Bu (27)-IA (3)-latex (crosslinked)
P-7:-St (75)-Bu (24)-AA (1)-latex is (crosslinked; 29 ℃ of Tg)
P-8:-St (60)-Bu (35)-DVB-(3)-MAA (2)-latex (crosslinked)
P-9:-St (70)-Bu (25)-DVB-(2)-AA (3)-latex (crosslinked)
P-10:-VC (50)-MMA (20)-EA (20)-AN (5)-AA (5)-latex (molecular weight 80,000)
P-11:-VDC (85)-MMA (5)-EA (5)-MAA (5)-latex (molecular weight 67,000)
P-12:-Et (90)-MAA (10)-latex (molecular weight 12,000)
P-13:-St (70)-2EHA (27)-AA (3)-latex (molecular weight 130,000; 43 ℃ of Tg)
P-14:-MMA (63)-EA (35)-AA (2)-latex (molecular weight 33,000; 47 ℃ of Tg)
P-15:-St (70.5)-Bu (26.5)-AA (3)-latex is (crosslinked; 23 ℃ of Tg)
P-16:-St (69.5)-Bu (27.5)-AA (3) latex is (crosslinked; 20.5 ℃ of Tg)
P-17;-St (61.3)-isoprene (35.5)-AA (3)-latex is (crosslinked; 17 ℃ of Tg)
P-18;-St (67)-isoprene (28)-Bu (2)-AA (3)-latex is (crosslinked; 27 ℃ of Tg)
Following monomer: MMA represented in the abbreviation that is used for above structure; Methyl methacrylate, EA; Ethyl acrylate, MAA; Methacrylic acid, 2EHA; 2-EHA, St; Styrene, Bu; Butadiene, AA; Acrylic acid, DVB; Divinylbenzene, VC; Vinyl chloride, AN; Vinyl cyanide, VDC; Vinylidene chloride, Et; Ethene, and IA; Itaconic acid.
Above polymer emulsion is also commercially available, wherein can adopt following polymkeric substance.The example of acrylate copolymer comprises CEBIAN A-4635,4718 and 4601 (all being made by Dicel Chemical Industry Co.Ltd.) and Nipol Lx 811,814,821,820 and 857 (all being made by Nippon Zeon Co.).The example of poly-(ester) polymkeric substance comprises FINETEX ES 650,611,675 and 850 (all by Dainippon Ink Chemical Co., making) and WD-size and WMS (all by EastmanChemical Co., making).The example of poly-(urethanes) comprises HYDRAN AP 10,20,30 and 40 (all by Dai Nippon Ink Chemical C0., making).The example of rubber comprises LACSTAR 7310K, 3307B, 4700H, and 7132C (all by Dainippon Ink ChemicalCo., making) and Nipol Lx 416,410,438C and 2507 (all being made by Nippon Zeon Co.).The example of poly-(vinyl chloride) comprises G 351 and G576 (all being made by Nippon Zeon Co.).The example of poly-(vinylidene chloride) comprises L 502 and L513 (all by Asahi Kasei Industry Co.).The example of poly-(alkene) comprises CHEMIPAL S120, and SA100 (all being made by Mitsui Petrochemical Co.).
These polymer emulsions can be separately or, as required, use as its two or more potpourri.
Be used for the special preferably Styrene-Butadiene of polymer emulsion of this embodiment or the latex of styrene-isoprene multipolymer.In Styrene-Butadiene, the weight ratio of styrene monomer unit and butadiene monomer unit preferably falls into scope 40: 60-95: in 5.In addition, styrene monomer unit and butadiene monomer unit preferably account for the 60-99% quality of multipolymer.The preferred range of molecular weight is with above-mentioned identical.
The summation of styrene and butadiene is used for polymer emulsion of the present invention and preferably comprises the 1-6% quality, more preferably the acrylic or methacrylic acid of 2-5% quality relatively.
Be used for polymer emulsion of the present invention and preferably comprise acrylic acid.The preferred range of content of monomer is with above-mentioned identical.Copolymer ratios in the styrene-isoprene multipolymer etc. are identical with the situation of Styrene-Butadiene.
The example that is preferred for the Styrene-Butadiene latex of this embodiment comprises above-mentioned P-3 to P-9 and P-15 and commercially available those as LACSTAR-3307B, 7132C and Nipol Lx416.The example of styrene-isoprene multipolymer comprises aforementioned P-17 and P-18.
The layer that contains organic silver salt of the photothermal image material of this embodiment can comprise, as required, and hydrophilic polymer such as gelatin, polyvinyl alcohol (PVA), methylcellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.
The addition of these hydrophilic polymers is preferably 30% quality of total amount of the bonding agent that is introduced into the layer that contains organic silver salt or lower, more preferably 20% quality or lower.
The layer that contains organic silver salt of this embodiment (that is imaging layer) is preferably by using polymer emulsion to form as bonding agent.The total amount of the bonding agent of this layer and the weight ratio of organic silver salts are preferably 1/10-10/1, more preferably 1/5-4/1.
The layer that contains organic silver salt is copied into the photosensitive layer (emulsion layer) that comprises photothermographic silver halide usually.In this case, the total amount of the bonding agent of this layer and the weight ratio of silver halide preferably fall into scope 400-5, more preferably in the 200-10.
The total amount of the bonding agent of the imaging layer in this embodiment is 0.2-30g/m
2, preferred 1-15g/m
2Be used for crosslinked crosslinking chemical, be used to improve the surfactant of coating performance, or analog can be added in the imaging layer of this embodiment.
In embodiments, the solvent that is used for the coating solution of organic silver salt layer is preferably (" solvent " comprises dispersion medium for simplicity, referred in this) aqueous solvent of the water that comprises at least 30% part by weight.Solvent outside dewatering can be selected from water miscibility organic solvent such as methyl alcohol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethyl formamide, and ethyl acetate arbitrarily.The liquid water content of solvent is preferably 50% quality or more, more preferably 70% quality or more.
Preferred solvent compositions (the supposition ratio is a weight ratio) comprises water 100, water/methyl alcohol=90/10, water/methyl alcohol=70/30, water/methyl alcohol/dimethyl formamide=80/15/5, water/methyl alcohol/ethyl cellosolve=85/10/5, and water/methanol/isopropanol=85/10/5.
(to the description of antifoggant)
In embodiments, preferably include compound as the following general formula of being expressed as of antifoggant (H).
General formula (H): Q-(Y) n-C (Z
1) (Z
2) X
In general formula (H), Q represents alkyl group, aromatic yl group, or heterocyclic group; Y represents divalent linker; N is 0 or 1; Z
1And Z
2Represent halogen atom respectively; Represent hydrogen atom or electron-accepting group with X.
Q represents preferably to be had the phenyl group on the occasion of the electron-accepting group replacement of Hammett substituent constant op.The Hammett substituent constant for example is described in Journal of Medicinal Chemistry, 1207-1216, Vol.16, No.11, (1973).
The example of this electron-accepting group comprises halogen atom (fluorine (σ p:0.06); chlorine (σ p:0.23); bromine (σ p:0.23); iodine (σ p:0.18)); trihalomethyl group group (trisbromomethyl ((σ p:0.29); trichloromethyl ((σ p:0.33), trifluoromethyl ((σ p:0.54)), cyano group ((σ p:0.66); nitryl group ((σ p:0.78); aliphatic series-aryl or heterocycle sulfonyl group (as, mesyl ((σ p:0.72)), aliphatic series-aryl or heterocyclic acyl group (as; acetyl group ((σ p:0.50); benzoyl ((σ p:0.43)), alkynyl group (as, C ≡ CH (σ p:0.23)); aliphatic series-aryl or heterocyclic oxy group carbonyl group (as; methoxycarbonyl (σ p:0.45), phenyloxycarbonyl (σ p:0.44)), carbamyl group (σ p:0.36); sulfamoyl group (σ p:0.57); sulfoxide radicals, heterocyclic group and phosphoryl group.
σ p value preferably falls into scope 0.2-2.0, more preferably in the scope 0.4-1.
The preferred example of electron-accepting group comprises the carbamyl group, alkoxycarbonyl groups, alkyl sulphonyl group, alkyl phosphoryl group, carboxylic group, alkyl or aryl carbonyl group and alkyl phosphoryl group.Wherein, the carbamyl group, alkoxycarbonyl groups, alkyl sulphonyl group and alkyl phosphoryl group are especially preferred and the carbamyl group is most preferred.
X is preferably electron-accepting group, more preferably halogen atom, aliphatic series-aryl or heterocycle sulfonyl group; aliphatic series-aryl or heterocyclic acyl group, aliphatic series-aryl or heterocyclic oxy group carbonyl group, carbamyl group; or sulfamoyl group and especially preferred halogen atom.
In halogen atom, chlorine, bromine and iodine are preferred, and wherein chlorine and bromine are preferred and bromine is especially preferred.
Y preferably represents-C (=O)-,-SO-, or-SO
2-, more preferably-C (=O)-or-SO
2-and especially preferably-SO
2-." n " is 0 or 1, preferred 1.
Below provide the object lesson of the compound that is expressed as general formula (H) of this embodiment, but this embodiment is not limited thereto.
The consumption that is expressed as the compound of general formula (H) is preferably 10 of non-photosensitivity organic silver salts in every mol imaging layer
-4-0.8mol, more preferably 10
-3-0.1mol, further more preferably 5X10
-3-0.05mol.
Especially when use comprised the silver halide emulsion of high-load silver iodide according to this embodiment, the addition that is expressed as the compound of general formula (H) was the key factor that is used to obtain gratifying antifogging action.Therefore, use 5X10
-3This compound of-0.03mol is most preferred.
In embodiments, the object lesson of the compound that is expressed as general formula (H) being introduced the method for photochromics can find in the described method of relevant introducing reductive agent so far.
The fusing point that is expressed as the compound of general formula (H) is preferably 200 ℃ or lower, more preferably 170 ℃ or lower.
Organic poly-halid other example that is used for this embodiment comprises those of the paragraph Nos.0111 that is disclosed in JP-A-11-65021 and 0112.Be expressed as the organohalogen compound of formula (P) among the especially preferred JP-A-11-87297 of being, be expressed as the organic polyhalogen compound of general formula (II) among the JP-A-10-339934 and be described in the organic polyhalogen compound of Japanese patent application No.11-205330.
(other antifoggant)
Other example of antifoggant comprises mercury (II) salt of the paragraph No.0113 that is described in JP-A-11-65021, be described in the benzoic acid of the paragraph No.0114 of JP-A-11-65021, be described in the salicyl acid derivative of JP-A-2000-206642, the formalin scavenger compounds of the formula that is expressed as (S) of JP-A-2000-221634, triaizine compounds according to the claim 9 of JP-A-11-352624, the compound that is expressed as general formula (III) of JP-A-6-11791, with 4-hydroxyl-6-methyl isophthalic acid, 3,3a, 7-four benzazoles.
The antifoggant that can be used for this embodiment, the example of stabilizing agent and stabiliser precursor comprise the paragraph No.0070 that is described in JP-A-10-62899 and EP No.0803764A1 (20 pages, 57 walk to 21 pages, 7 the row) those and be described in JP-A-9-281637 and the compound of JP-A-9-329864.
In order to prevent atomizing, the photothermal image material of this embodiment can comprise diazo salt.The example of diazo salt comprises the compound of the formula that is expressed as (XI) of JP-A-59-193447, is described in the compound of the formula that is expressed as (II) of the compound of JP-A-55-12581 and JP-A-60-153039.Diazo salt can be added into any part of photochromics.But it preferably is added into the lip-deep layer with photosensitive layer, more preferably adds the layer that contains organic silver salt.
Diazo salt can adding in any stage in preparation coating solution process.Contain in adding under the situation of layer of organic silver salt, azo can add from preparation organic silver salts to any stage for preparing coating solution.Wherein, preferably after the preparation organic silver salts and before just being coated with, add.Diazo salt can comprise powder, and any form of solution and fine grain dispersion adds.Diazo salt also can comprise other adjuvant such as sensitizing dyestuff, reductive agent, or the form of the mixed solution of color toner adds.
In embodiments, diazo salt can any amount add; But preferably it is with 1X10
-6-2mol/mol silver, more preferably 1X10
-3The amount of-0.5mol adds.
(other adjuvant)
1) sulfydryl, disulfide, and thione compounds
In embodiments, can add sulfhydryl compound, di-sulphide compounds and thione compounds improve spectral sensitization efficient, or improve the storge quality before and after developing with by suppressing or increase to develop to control development.The example of these compounds comprises those of the paragraph Nos.0067-0069 that is described in JP-A-10-62899, the compound of its object lesson of conduct among the compound that is expressed as general formula (I) of JP-A-10-186572 and the paragraph Nos.0033-0052 of JP-A-10-186572, (36-56 is capable for EPNo.0803764A1,20 pages) and Japanese patent application No.11-273670 in compound.Wherein, the heteroaromatics of sulfydryl replacement is most preferred.
2) color toner
In the photothermal image material of this embodiment, the adding of toner is preferred.The example of color toner comprises the paragraph Nos.0054-0055 that is described in JP-A-10-62899, EPNo.0803764A1 (21 pages, 23-48 is capable), those of JP-A-2000-356317 and Japanese patent application No.2000-187298.Especially preferred is 2, and 3-benzodiazine ketone (2,3-phthalazone, 2,3-phthalazinone derivatives and its slaine; As, 4-(1-naphthyl) 2,3-phthalazone, 6-chlorine 2,3-phthalazone, 5,7-dimethoxy 2,3-phthalazone and 2,3-dihydro-1,4-2,3-benzodiazine diketone); 2,3-phthalazone and phthalic acid (as, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, phthalic acid two ammoniums, sodium phthalate, phthalic acid potassium, and tetrachlorophthalic tetrachlorophthalic anhydrid) combination; 2, and 3-benzodiazine class (2,3-benzodiazine, 2,3-naphthyridine derivative and its slaine; As, 4-(1-naphthyl) 2,3-benzodiazine, 6-isopropyl 2,3-benzodiazine, 6-tert-butyl 2,3-benzodiazine, 6-chlorine 2,3-benzodiazine, 5,7-dimethoxy 2,3-benzodiazine and 2,3-dihydro 2,3-benzodiazine).When being used in combination with the silver halide that is rich in silver iodide, 2, the combination of 3-benzodiazine class and phthalic acid is especially preferred.
2, the amount of 3-benzodiazine class is the 0.01-0.3mol/mol organic silver salts, preferred 0.02-0.2mol, especially preferred 0.02-0.1mol.Above-mentioned addition is the key factor that is used to develop and quickens, and this problem is relevant with the silver halide that is rich in silver iodide.Therefore, when selecting suitable amount, gratifying developing performance and low atomizing all can realize.
3) plastifier and lubricant
Can be used for the plastifier of photothermal image material of this embodiment and the paragraph No.0117 that lubricant is described in JP-A-11-65021.Lubricant is described in the paragraph Nos.0061-0064 of JP-A-11-84573 and the paragraph Nos.0049-0062 of JP-A-11-106881.
4) dyestuff, pigment
In embodiments, photosensitive layer can comprise various dyestuffs or pigment (as, CI. pigment blue 60, CI. alizarol saphirol 64, CI. pigment blue 15:, generate interference fringe when being suppressed at laser explosure and prevent irradiation 6) to improve tone.Can be to its detailed description at WO-98-36322, find among JP-A-10-268465 and the JP-A-11-338098 etc.
5) superelevation contrast promoter
In order to form the superelevation contrast image that is applicable to printed panel, superelevation contrast promoter preferably is added into imaging layer.To superelevation contrast promoter, the description of its adding method and addition can be in the paragraph No.0118 of JP-A-11-223898 and paragraph Nos.0136-0193 to being expressed as formula (H), (1)-(3), (A) and the description of compound (B); With in JP-A-11-91652, find in the description to the compound (specific compound: chemicals No.21 is to chemicals No.24) that is expressed as formula (III)-(V).Can in the paragraph No.0102 of JP-A-11-65021 and paragraph Nos.0194-0195, find the description of superelevation contrast promoter at JP-A-11-223898.
If formic acid or formic ether be as strong Alevaire, preferably with the 5mmol of every mol silver or lower, preferred 1mmol or lower amount are introduced into that face of the film that has the imaging layer that comprises photothermographic silver halide on it to this reagent.
If the photothermal image material of this embodiment comprises that the superelevation contrast provides agent, this reagent preferably with the acid that obtains by the phosphorus pentoxide hydration, or its salt is used in combination.The acid that obtains by the phosphorus pentoxide hydration and the example of its salt comprise metaphosphoric acid (with its salt), pyrophosphoric acid (with its salt), orthophosphoric acid (with its salt), triphosphoric acid (with its salt), four phosphoric acid (with its salt), and hexa metaphosphoric acid (with its salt).Wherein, especially preferred is orthophosphoric acid (with its salt) and hexa metaphosphoric acid (with its salt).What specifically mention as salt is sodium orthophosphate, dihydro sodium orthophosphate, sodium hexametaphosphate, Hexamethylphosphoric acid triamide etc.
Acid or aequum (that is every m, of its salt that obtains by the phosphorus pentoxide hydration
2The coating weight of photochromics) can add according to susceptibility and atomizing; But this amount is preferably 0.1-500mg/m
2, more preferably 0.5-100mg/m
2
(preparation of coating solution and coating)
In embodiments, the temperature that is used for the coating solution preparation of imaging layer is preferably 30-65 ℃, more preferably 35 ℃ or more and be lower than 60 ℃ and especially preferred 35-55 ℃.After adding polymer emulsion, the imaging layer coating solution preferably remains under 30-65 ℃.
2. layer is formed and other component
Except photosensitive layer, the photothermal image material in this embodiment can have one or more non-photosensitivity layers.The non-photosensitivity layer can be arranged according to layer and be divided into the sealer that (a) is provided at (on that face away from bearing) on the imaging layer; (b) between a plurality of imaging layers or the middle layer between imaging layer and the protective seam; (c) undercoat between imaging layer and bearing is provided at backing layer on relative that face with imaging layer with (d).
Also can be used as above layer (a) or (b) provide as the layer of optical filter.Anti-halo layer can be used as layer (c) or (d) provides on photochromics.
1) sealer
The photothermal image material of this embodiment can have sealer and be used to prevent that imaging layer from adhering to.Sealer can be a single or multiple lift.Description to sealer can and be found in Japanese patent application No.2000-171936 at the paragraph Nos.0119-0120 of JP-A-11-65021.
In embodiments, gelatin is preferably used as the bonding agent of sealer; But also preferred the employing separately or the polyvinyl alcohol (PVA) (PVA) that is used in combination with gelatin.The example of operable gel comprise the inertia gelatin (as, " Nitta gelatin 750 ") and the phthalic ester gelatin (as, " Nitta gelatin 801 ").
The example of PVA comprises those of the paragraph Nos.0009-0020 that is described in JP-A-2000-171936, with its preferred example comprise fully saponified product " PVA-105; " partly-hydrolysed product " PVA-205 " and " PVA-335; " with modified polyethylene alcohol " MP-203 " (ProductName, Kuraray Co., Ltd.)
Coating weight (the every m of polyvinyl alcohol (PVA) in protective seam (every layer)
2Bearing) 0.3-4.0g/m preferably
2, more preferably 0.3-2.0g/m
2
Coating weight (the every m of total binder (comprising water-soluble polymers and latex polymer) in sealer
2Bearing) is preferably 0.3-5.0g/m
2, more preferably 0.3-2.0g/m
2
2) anti-halo layer
The photothermal image material of this embodiment can provide anti-halo layer on facing to the face with respect to the light source of photosensitive layer.Description to anti-halo layer can be at the paragraph Nos.0123-0124 of JP-A-11-65021 with at JP-A-11-223898, JP-A-9-230531, JP-A-10-36695, JP-A-10-104779, JP-A-11-231457, JP-A-11-352625 finds among the JP-A-11-352626 etc.
Anti-halo layer is included in the antihalation that has absorption under the exposure wavelength.If exposure wavelength falls into region of ultra-red, can use infrared-absorbing dye, and in this case, the dyestuff that does not have to absorb in visibility region is preferred.
If halation prevents that at the dyestuff that visibility region has absorption preferably, the color of dyestuff does not keep basically by employing after imaging.For this reason, the preferred device that is used to decolour by heat-developed heat and especially preferably heat can be decoloured dyestuff and the alkali precursor of adopting adds the non-photosensitivity layer to produce the function as anti-halo layer.These technical descriptions are in JP-A-11-231457 etc.
The amount of dyestuff of can decolouring is determined according to the purpose of application of dye.In general, can the decolour consumption of dyestuff makes the optical density (OD) (absorptance) when measuring under required wavelength surpass 0.1.Preferably, optical density (OD) falls in the scope 0.2-2.In order to realize this optical density (OD), the amount of dyestuff generally is about 0.001-1g/m
2
By the decolouring of dyestuff, the optical density (OD) that obtains after thermal development can reduce to 0.1 or lower.Two or more dyestuffs that can decolour can be in conjunction with being used for heat can decolour recording materials or photothermal image material.And two or more alkali precursors also can be used in combination.
Can decolour in the heat decoloring technology of dyestuff and alkali precursor using this heat, consider heat decoloring ability etc., preferred (for example the use as the material that is disclosed in JP-A-11-352626, diphenyl sulfone, 4-chlorphenyl (phenyl) sulfones etc.), it can reduce by 3 ℃ of the fusing points of alkali precursor or more when mixing with alkaline precursor.
3) backing layer
The backing layer that can be used for this embodiment is described in the paragraph Nos.0128-0130 of JP-A-11-65021.
In embodiments, the colorant that has absorption peak at the 300-450nm place can be transferred or time dependence changes and adds for the silver color of improving image.The example of this colorant comprises and is described in JP-A-62-210458, JP-A-63-104046, JP-A-63-103235, JP-A-63-208846, JP-A-63-306436, JP-A-63-314535, those of JP-A-01-61745 and Japanese patent application No.11-276751.The addition of this colorant is 0.1-1g/m normally
2Preferably, colorant is introduced into relative with the photosensitive layer backing layer that is positioned on the bearing.
4) matting agent
In embodiments, matting agent is preferably on the sealer and on backing layer, and purpose is to improve transmission.Description to matting agent can be found in the paragraph Nos.0126-0127 of JP-A-11-65021.
With every m
2The coated weight meter of photochromics, the amount of matting agent is preferably 1-400mg/m
2And more preferably 5-300mg/m
2.
The lip-deep dullness of emulsion can be any value, only otherwise starlike failure occurs; But preferred, in the Beck smoothness, dullness is 30-2,000 second, and more preferably 40-1,500 seconds.The Beck smoothness can be easily according to Japanese Industrial Standards (JIS) P8119, and " Paper and board-Determination ofsmoothness by Beck method " and TAPPI standard method T479 measure.
In embodiments, in the Beck smoothness, the dullness of backing layer is preferred 10-1,200 seconds, and more preferably 20-800 second and more preferably 40-500 second.
In embodiments, matting agent preferably is introduced into the outmost surface layer, is used as the layer of outmost surface layer, or the layer of close outer surface layer, or preferably is introduced into the layer as the so-called protection layer.
5) polymer emulsion
In embodiments, polymer emulsion can be added into sealer or backing layer.
Can be to the description of polymer emulsion " Synthetic Resin Emulsion " (edit and publish 1978 by Kobunshi Kankokai) by Taira Okuda and Hiroshi Inagaki; " Application ofSyntehic Latex " (by Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki and KeishiKasahara edit and are published 1993 by Kobunshi Kankokai); Find in " Chemistry of SyntheticLatex " (edit and publish 1970 by Kobunshi Kankokai) by Soichi Muroi.The object lesson of polymer emulsion comprises the latex copolymer of methyl methacrylate (33.5% quality)/ethyl acrylate (50% quality)/methacrylic acid (16.5% quality), the latex polymer of methyl methacrylate (47.5% quality)/butadiene (47.5% quality)/itaconic acid (5% quality), the latex copolymer of ethyl acrylate/methacrylic acid, the latex copolymer of methyl methacrylate (58.9% quality)/2-EHA (25.4% quality)/styrene (8.6% quality)/methacrylic acid 2-hydroxyethyl ester (5.1% quality)/acrylic acid (2.0% quality), and the latex copolymer of cruel (5.0% the quality)/acrylic acid (2.0% quality) of methyl methacrylate (64.0% quality)/styrene (9.0% quality)/butyl acrylate (20.0% quality)/methacrylic acid 2-hydroxyethyl.
The amount of polymer emulsion is preferably the 10-90% quality and the especially preferred 20-80% quality of the total binder (comprising water-soluble polymers and latex polymer) of sealer or backing layer.
6) laminar surface pH
Before thermal development, the pH of the laminar surface of the photothermal image material of this embodiment is preferably 7.0 or lower, and more preferably 6.6 or lower.Be not particularly limited its lower limit, but lower limit approximately is 3.Most preferred pH is 4-6.2.
Preferably, non-volatile acid such as organic acid (as, phthalic acid derivatives) or sulfuric acid, or volatile alkali such as ammonia are used for the lip-deep pH of regulating course to reduce the pH on the laminar surface.Ammonia is because be volatile and can be removed before application step or thermal development and be particularly preferred on laminar surface obtaining low pH.Ammonia and non-volatile alkali such as NaOH, potassium hydroxide, or being used in combination of lithium hydroxide also is preferred.The method of measuring the pH on the laminar surface is described in the paragraph No.0123 of Japanese patent application No.11-87297.
7) rigidizer
In embodiments, rigidizer can be respectively applied for photosensitive layer, protective seam, and backing layer.
Description to preferred rigidizer comprises: be described in " The Theory of the PhotographicProcess " (by T.H.James write (with by Macmillan Publishing Co., Inc publishes, the 4th edition, pp.77-87,1977) the whole bag of tricks in those.Except chrome alum chromalum, 2,4-two chloro-6-hydroxyls-s-triazine sodium salt, N, N-ethylidene-two (vinyl sulfo group acetamide) or N, N-propylidene two (vinyl sulfo group acetamide), the preferred use is described in 78 pages the polyvalent metal ion that ibid; Be described in U.S. Patent No. 4,281,060 and the polyisocyanate of JP-A-6-208193; Be described in U.S. Patent No. 4,791,042 epoxy compound; With the vinyl sulfone-alkali cpd that is described in JP-A-62-89048.
Rigidizer adds with the solution form.The time that this solution is added the coating solution that is used for protective seam be before the coating 180 minutes to the coating just in time, before the preferred coating 60 minutes to 10 seconds.Be not particularly limited mixed method and mixing condition, as long as the effect of this embodiment shows satisfactorily.
The object lesson of mixed method comprises the method that silver halide and solution are mixed in the jar of the required mean residence time of design generation (being calculated by the feed rate that adds fashionable flow velocity and relative spreader), or as being described in N.Harnby, F.Edwards, and A.W.Nienow (by Koji Takahashi translation), " Ekitai Kongo Gijutsu ", the method for the use static mixer of the chapters and sections 8 of Nikkan Kogyo Shinbun (1989).
8) surfactant
The surfactant that can be used for this embodiment is described in the paragraph No.0132 of JP-A-11-65021.
In this embodiment, preferably use fluorine surfactant.The object lesson of fluorine surfactant comprises and is described in JP-A-10-197985, the compound of JP-A-2000-19680 and JP-A-2000-214554.The polymkeric substance fluorine surfactant that is described in JP-A-9-281636 also is preferred.In embodiments, the especially preferred fluorine surfactant that is described in JP-A-2000-206560 that uses.
9) antistatic agent
In embodiments, can provide the metal oxide that comprises various known kinds or the antistatic layer of conducting polymer.Antistatic layer can be used as undercoat, back of the body sealer etc.It also can be provided independently.For antistatic layer, adaptable technology comprises the paragraph No.0135 that is described in JP-A-11-65021, JP-A-56-143430, JP-A-56-143431, JP-A-58-62646, JP-A-56-120519, the paragraph Nos.0040-0051 of JP-A-11-84573, U.S. Patent No. 5,575,957 and those of the paragraph Nos.0078-0084 of JP-A-11-223898.
10) bearing
Transparent bearing is preferably polyester, especially preferred polyethylene terephthalate, in temperature range 130-185 ℃, heat-treat on it in residue with in the biaxial stretch-formed process film of relaxing and twist, eliminate the thermal shrinkage distortion that in the thermal development process, produces like this.
The anastomose that PEN (PEN) was preferably used as and sent ultraviolet light closes the bearing of the photothermal image material of use, but bearing is not limited thereto.Especially preferred PEN type is to gather 2, the 6-(ethylene naphthalate).Poly-2 according to this embodiment, 6-(ethylene naphthalate) are represented basically by 2, those that 6-(ethylene naphthalate) unit is formed.That is, poly-2, the 6-(ethylene naphthalate) not only comprises the poly-2 of non-copolymerization in this embodiment, the 6-(ethylene naphthalate), and comprise its 5% or lower by other multipolymer of other component modification and with other mixture of polymers and composition.
Poly-2, the 6-(ethylene naphthalate) can pass through naphthalene-2, and 6-dicarboxylic acid or its functional derivatives and ethylene glycol or its functional derivatives be polymerization and synthesizing under proper reaction conditions in the presence of catalyzer.But according to poly-2 of this embodiment, the 6-(ethylene naphthalate) can be included in finish poly-2, before the polyreaction of 6-(ethylene naphthalate) to wherein adding one or more suitable the 3rd compositions (modifier) to form those of multipolymer or mixed polyester.The 3rd suitable composition comprises having the compound that divalence becomes ester group; As, oxalic acid; Hexane diacid; Phthalic acid; Terephthalic acids; Naphthalene-2, the 7-dicarboxylic acid; Succinate; Dicarboxylic acid such as diphenyl ether dicarboxylic acid or its lower alkyl esters; Right-p-methoxybenzoic acid; Oxygen yl carboxylic acid such as right-oxygen base oxethyl benzoic acid or its lower alkyl esters; Or divalent alcohol compound such as propylene glycol or trimethylene glycol.Poly-2, the multipolymer that 6-(ethylene naphthalate) or its are derived can be that its terminal hydroxy groups and/or carboxylic group functionalised compound such as benzoic acid, benzoyl benzoic acid, benzil base p-methoxybenzoic acid, or those of methoxyl poly alkylene glycol end-blocking.In addition, it can by very small amount of trifunctional or four senses become ester compounds such as glycerine or pentaerythrite in the scope that can obtain linear in fact multipolymer modification those one of.
When the photothermal image material is used for medical usage, transparent bearing can by blue dyes (as, be described in the dyestuff-1 of the embodiment of JP-A-8-240877) painted maybe can be uncoloured.
The object lesson of bearing is described in the paragraph No.0134 of JP-A-11-65021.
On bearing, advantageous applications primary coat technology, for example be described in the water-soluble polyester of .JP-A-11-84574, be described in the Styrene-Butadiene of JP-A-10-186565, or be described in the vinylidene chloride copolymer of the paragraph Nos.0063-0080 of JP-A-2000-39684 and JP-A-11-106881.
11) other adjuvant
The photothermal image material can further comprise antioxidant, stabilizing agent, plastifier, ultraviolet absorber, and coating additive.Also can add the solvent that is described in JP-A-11-65021 paragraph No.0133.These various adjuvants are added into photosensitive layer or non-photosensitivity layer.Can be to its detailed description at WO-98-36322, EP-ANo.803764A1, JP-A-10-186567 finds among the JP-A-10-18568 etc.
12) coating process
In embodiments, the photothermal image material can be coated with by any means.More specifically, can use various types of coatings operation, comprise extrusion coated, the slide coating, the curtain coating, dip coated, the cutter coating, flow coating and use are described in U.S. Patent No. 2,681,294 the sort of hopper extrusion coated.The preferred use is described in Stephen F.Kistler and Peter M.Shweizer, " LIQID FILM COATING ", pp.399-536 (Chapman﹠amp; Hall, 1997) extrusion coated or slide coating and most preferably use the slide coating.
Be used for slide coating the slide spreader shape an example Figure 11 b.1 ibid 427 pages provide.If desired, two or more layer can utilize and be described in the pp.399-536 that ibid, U.S. Patent No. 2,761, and 791 and BrP No.837,095 method applies simultaneously.
According to this embodiment, the coating solution that is used to contain the layer of organic silver salt is preferably so-called thixotropic fluid.For this technology, can be with reference to JP-A-11-52509.
According to this embodiment, the coating solution of layer that is used to contain organic silver salt is at shear rate 0.1 S
-1Viscosity under 1 is preferably 400-100,000mPas, more preferably 500-20,000mPas.
In addition, at shear rate 1000 S
-1Under viscosity be preferably 1-200mPas and more preferably 5-80mpas.
13) wrappage
For the photographic property in the preservation process before suppressing to use changes or prevent the tendency that material production is crooked or reel when storing under the roller attitude, the photothermal image material of this embodiment preferably uses the wrappage with hypoxemia transmitance and/or moisture transmitance to pack with air tight manner.Oxygen permeability under 25 ℃ is preferably 50ml/atm/m
2It or lower, more preferably 10ml/atm/m
2It or lower and more preferably 1.0ml/atm/m
2It or lower.The water transmitance is preferably 10g/atm/m
2It or lower, more preferably 5g/atm/m
2It or lower and further more preferably 1g/atm/m
2It or lower.Object lesson with wrappage of hypoxemia transmitance and/or water transmitance comprises those that are described in JP-A-8-254793 and JP-A-2000-206653.
14) other applicable technology
The example of technology that can be used for the photothermal image material of this embodiment comprises and is described in EPNo.803764A1, EP No.883022A1, WO-98-36322, JP-A-56-62648, JP-A-58-62644, JP-A-9-43766, JP-A-9-281637, JP-A-9-297367, JP-A-9-304869, JP-A-9-311405, JP-A-9-329865, JP-A-10-10669, JP-A-10-62899, JP-A-10-69023, JP-A-10-186568, JP-A-10-90823, JP-A-10-171063, JP-A-10-186565, JP-A-10-186567, JP-A-10-186569, JP-A-10-186570, JP-A-10-186571, JP-A-10-186572, JP-A-10-197974, JP-A-10-197982, JP-A-10-197983, JP-A-10-197985, JP-A-10-197986, JP-A-10-197987, JP-A-10-207001, JP-A-10-207004, JP-A-10-221807, JP-A-10-282601, JP-A-10-288823, JP-A-10-288824, JP-A-10-307365, JP-A-10-312038, JP-A-10-339934, JP-A-11-7100, JP-A-11-15105, JP-A-11-24200, JP-A-11-24201, JP-A-11-30832, JP-A-11-84574, JP-A-11-65021, JP-A-11-109547, JP-A-11-125880, JP-A-11-129629, JP-A-11-133536, JP-A-11-133537, JP-A-11-133538, JP-A-11-133539, JP-A-11-133542, JP-A-11-133543, JP-A-11-223898, JP-A-11-352627, JP-A-11-305377, JP-A-11-305378, JP-A-11-305384, JP-A-11-305380, JP-A-11-316435, JP-A-11-327076, JP-A-11-338096, JP-A-11-338098, JP-A-11-338099, JP-A-11-343420, JP-A-2000-187298, JP-A-2001-200414, JP-A-2001-234635, JP-A-2002-20699, JP-A-2001-275471, JP-A-2001-275461, JP-A-2000-313204, JP-A-2001-292844, JP-A-2000-324888, those of JP-A-2001-293864 and JP-A-2001-348546.
15) colour imaging
In the structure of polychromatic light heat picture material, can provide two-layer combination for every kind of color.Alternatively, all components can be included in the individual layer, for example are described in U.S. Patent No. 4,708,928 described individual layers.
Under the situation of polychromatic light heat picture material, corresponding emulsion layer keeps being separated from each other by functions of use or NOT-function isolation layer, for example is described in U.S. Patent No. 4,460,681.
3. formation method
3-1. exposure
According to the photothermal image material of this embodiment can be imaging layer " single side " on the bearing one side only wherein, or wherein imaging layer is provided at " double-side type " on the bearing two sides.
(two-sided photothermal image material)
The photothermal image material of this embodiment can be preferred for utilizing the X-ray to strengthen the formation method of net (X-rayintensifying screen).
This formation method preferably adopts its susceptibility to need exposure dose 1X10
-6-1X10
-3Wattsec/m
2, preferred 6X10
-6-6X10
-4Wattsec/m
2The photothermal image material, strengthen identical wavelength of the main smooth emission peak of net and the monochromatic light of half-breadth 15 ± 5nm when the photothermal image material is exposed to have with radiation like this; Carry out thermal development; During imaging layer on that face relative with plane of exposure, offer image and add 0.5 image density with least density with removal.
May further comprise the steps by the formation method that uses the photothermal image material to be used to form image:
(a) the photothermal image material being placed on a pair of X-ray strengthens between the net to obtain the step of imaging combination;
(b) object is placed on step between this combination and the X-ray generator;
(c) with its energy level be the step of X-ray irradiation to the object of 25-125kVp;
(d) step of extraction photothermal image material from this combination; With
(e) step of the photothermal image material that heating is extracted in 90-180 ℃.
According to this embodiment, the photographic silver halide material preferred for preparation that is used in combination makes to have following family curve by progressively being exposed to the X-ray with the relative family curve that defines of image that thermal development obtains in rectangular coordinate, and wherein said rectangular coordinate has optical density (OD) (D) and the exposure dose (log E) that equates mutually on the unit length of coordinate axis.Particularly, the definition of this family curve makes that adding average gamma (γ) that the point of upper density 0.1 and point that least density (Dmin) adds upper density 0.5 determine by least density (Dmin) falls in the scope 0.5-0.9 and make that adding the average gamma (g) that the point of upper density 1.2 and point that least density (Dmin) adds upper density 1.6 determine by least density (Dmin) falls in the scope 3.2-4.0.When having this characteristic photothermal image material when being used for the radiography system of this embodiment, can obtain a kind ofly having in middle density area that very long shank divides and the radiography image of the superiority characteristic of high gamma.The favourable part of this photographic property is, strengthened in density regions, as relate to low X-ray penetrability and main shade the mediastinum district describe performance.Even under the situation of the lung district image that relates to the high x-ray penetrability, obtain to have the observability of increase and the density of favourable contrast.
Have this preferred characteristic photothermal image material and can utilize for example such method to make easily, wherein every bread of imaging layer contains two or more silver halide emulsion liquid layers with different susceptibilitys.Especially preferred, form imaging layer by using in upper strata high sensitive emulsion with in the emulsion of lower floor's low sensitivity and high-contrast.Comprise two-layer this imaging layer if use, the susceptibility of one deck is 1.5-to 20-times of another layer, and is preferred, and 2-to 15-doubly.The ratio of amount of emulsion that is used for every layer is by the difference decision of the emulsion that is applied on susceptibility and covering power.In general, the consumption of high sensitive emulsion reduces along with the increase of sensitivity difference.For example, if a kind of emulsion to be another emulsion responsive 2 times and its covering power much at one, in the amount of silver, the ratio of high sensitive emulsion and low sensitivity emulsion falls into scope 1: 20-1: in 5 so.
As the technology that is used for reducing intersection (being used for two-sided photochromics) and anti-corona (being used for the single face photochromics), can use the dyestuff and the mordant that are described in JP-A-2-68539 (1 of hurdle, 13 pages of lower-lefts walks to 9 row on hurdle, 14 pages of lower-lefts).
The fluorescence of below describing in detail according to this embodiment strengthens net (radiation enhancing net).Radiation strengthens net and is made up of bearing and the phosphor layer that forms on its one side basically.Phosphor layer is to comprise the layer that is dispersed in the phosphor in the bonding agent.In addition, protective clear layer generally is provided at the surface (that face relative with bearing) of phosphor layer upward to protect phosphor layer not to be subjected to chemical modification or physical influence.
The object lesson of the preferred phosphor in this embodiment comprises following: tungstate-type phosphor (as, CaWO
4, MgWO
4, CaWO
4: Pb), the rare earth metal oxygen base sulfide-type phosphor of terbium-activation [as, Y
2O
2S:Tb, Gd
2O
2S:Tb, La
2O
2S:Tb, (Y, Gd)
2O
2S:Tb, (Y, Gd)
2O
2S:Tb, Tm], the rare earth element phosphate-type phosphor of terbium-activation (as, YPO
4: Tb, GdPo
4: Tb, LaPo
4: Tb), the rare earth element oxygen base halogenide-type phosphor of terbium-activation [as, LaOBr:Tb, LaOBr:Tb, Tm, LaOCl:Tb, LaOCl:Tb, Tm, LaOBr:Tb, GdOBr:Tb, GdOCl:Tb], the rare earth element oxygen base halogenide-type phosphor of thulium-activation [as, LaOBr:Tm, LaOCl:Tm], barium sulphate-type phosphor [as, BaSO
4: Pb, BaSO
4: Eu
2+, (Ba, Sr) SO
4: Eu
2+], the alkali earth metal phosphate of divalent europium-activation-type phosphor [as, (Ba
2PO
4)
2: Eu
2+, (BaPO
4)
2: Eu
2+]], the alkaline-earth halide of divalent europium-activation-type phosphor [as, BaFCl:Eu
2+, BaFBr:Eu
2+, BaFCl:Eu
2+, Tb, BaFBr:Eu
2+, Tb, BaF
2BaClKCl:Eu
2+, (Ba, Mg) F
2BaClKCl:Eu
2+], iodide-type phosphor (as, CsI:Na, CsI:Tl, NaI, KI:T1), the sulfide type phosphor [as, ZnS:Ag (Zn, Cd) S:Ag, (Zn, Cd) S:Cu, (Zn, Cd) S:Cu, Al], phosphoric acid hafnium-type phosphor (as, HfP
2O
7: Cu), and YTaO
4Various activators on it, have been added as those of luminescent center.But the phosphor that is used for this embodiment is not limited thereto, and can use any phosphor, as long as it has the light emission in visible or near ultraviolet region when irradiation.
Be preferred for radiofluorescence of the present invention strengthen net luminous make 50% or more light have the wavelength that falls in the scope 350-420nm.Especially, the phosphor that is included in the radiofluorescence enhancing net is preferably the phosphor that divalence Eu-activates, more preferably the barium halide phosphor of divalence Eu-activation.Light emission wavelength zone is preferably 360-420nm, more preferably 370-420nm.In addition, the fluorescence net more preferably sends 70% or more light and further preferred 85% or more in this zone.
Luminous ratio is calculated as follows.Emission spectrum is by being taken under the equal intervals in the light emission wavelength on the transverse axis of antilogarithm, and the photon number of sending on Z-axis and determining.The value that area by 350-420nm place among the figure that will so obtain obtains divided by the area of whole emission spectrum is defined in has photoemissive ratio among the wavelength region may 350-420nm.When light is launched and uses photothermal image material of the present invention under these wavelength, can realize high lightsensitivity.
The most of light that sent by phosphor fall in the above-mentioned wavelength region may.Therefore, luminous half-band width is preferably narrow.Half-band width is preferably 1-70nm, more preferably 5-50nm, further preferred 10-40nm.
Be not particularly limited and be used for phosphor of the present invention, as long as obtain above-mentioned light emission.But it is that divalence Eu is to realize the phosphor as the improved Eu-activation of purpose lightsensitivity of the present invention that phosphor is preferably its light launching centre.
Below provide the object lesson of this phosphor, but the invention is not restricted to this:
BaFCl:Eu, BaFBr:Eu, BaFI:Eu and its halogen composition, BaSO
4: Eu, SrFBr:Eu, SrFCl:Eu, SrFI:Eu, (Sr, Ba) Al
2Si
2O
8: Eu, SrB
4O
7F:Eu, SrMgP
2O
7: Eu, Sr
3(PO
4)
2: Eu, Sr
4P
2O
7: Eu etc.
Preferred phosphor is the barium halide phosphor that is expressed as the divalence Eu-activation of formula M X1X2:Eu, and wherein Ba is the key component of M; But can preferably comprise a spot of other compound such as Mg, Ca, and Sr.X1 and X2 represent and can be selected from F arbitrarily, Cl, the halide atoms of Br and I.X1 is preferably fluorine.X2 can be selected from Cl, Br, and I, and can preferably use the potpourri of more than one these halogen composition.Further preferred, X is Br.Relative Ba, the content ratio that is used as the Eu of light launching centre is preferably 10
-7To 0.1.More preferably, content range is 10
-4-0.05.Also can preferably mix a spot of other compound.Most preferred phosphor comprises BaFCl:Eu, BaFBr:Eu, and BaFBrl-XIX:EU.
＜fluorescence strengthens net 〉
Fluorescence strengthens the network optimization choosing by bearing, the undercoat that on bearing, provides, and phosphor layer and sealer are formed.
Phosphor layer can followingly form: dispersion is by making the particle dispersion of aforementioned phosphor in comprising the organic solvent of adhesive resin; Subsequently, dispersion is applied directly on the bearing (under the situation that undercoat such as reflection layer are provided, is administered on the undercoat); The dispersion of using with drying.Also can adopt following alternative approach: the phosphor sheet material forms with the dry dispersion of being used by using above-mentioned dispersion on the temporary support of preparation separately; Subsequently, the phosphor sheet material is peeled off from temporary support; With by using bonding agent that the phosphor sheet material is provided on bearing.
Be not particularly limited the grain size of phosphor particles, it falls into the about 1-15 μ of scope m usually, preferably falls in the about 2-10 μ of the scope m.The volume filling ratio of the phosphor particles in the phosphor layer is preferably higher and fall into scope 60-85% usually, and preferred 65-80% is in the especially preferred 68-75%.(ratio of phosphor particles in phosphor layer be 80% quality or higher normally, preferred 90% quality or higher, especially preferred 95% quality or higher).Various known reference file descriptors be used to form adhesive resin, organic solvent and the various adjuvant that can adopt arbitrarily of phosphor layer.The thickness of phosphor layer can be set ideally according to the target susceptibility degree; But the thickness of the net on the front preferably falls in the scope 70-150 μ m and the thickness of the net on the back side preferably falls in the scope 80-400 μ m.Notice that the X-radiation absorption ratio of phosphor layer is by the coating weight decision of phosphor particles.
Phosphor layer can be by individual layer, or two or more layers of composition and preferably by the 1-3 layer, and more preferably one or two-layer composition.For example, comprise various grain sizes and relative narrow particle size distribution phosphor particles the layer can be by lamination.In this case, can adopt to arrange to make this layer the closer to bearing, the grain size of this layer is more little.Especially preferred, the surface protection aspect scribbles big phosphor particles and seating plane scribbles little phosphor particles.Little phosphor particles preferably has big or small 0.5-2.0 μ m and big phosphor particles preferably has big or small 10-30 μ m.Alternatively, phosphor layer can form by the phosphor particles that mixes the variable grain size, maybe can be phosphor layer, for example be described in JP-A-55-33560 (3 of 3 pages of left hurdles walk to 39 row on 4 pages left hurdle) with gradient particle size distribution of phosphor particles.The coefficient of variation of the particle size distribution of phosphor falls in the scope 30-50% usually; But its coefficient of variation be 30% or lower single phosphor dispersed particle also can preferably use.
Attempted obtaining relating to the preferred sharpness of light emission wavelength by dry phosphor layer.But being preferably designed to, layer uses drying as few as possible.The absorption length of phosphor layer is preferably 100 μ m or longer, more preferably 1,000 μ m or longer.
Scattering length is preferably designed to 0.1-100 μ m, more preferably 1-100 μ m.Scattering length and absorption length can be calculated by the expression formula derived from the Kubeluka-Munk theory, will be described following.
Used bearing can be selected from those that are used for known radiation enhancing net ideally according to purpose.For example, the preferred polymer film that comprises Chinese white such as titania or black pigment such as carbon black that adopts.Undercoat can (provide on the surface of that face of phosphor layer) on the surface of bearing therein as the reflection layer that comprises light reflecting material.The reflection layer that is disclosed in JP-A-2001-124898 also is preferred.Especially, preferably use the reflection layer of the employing yttria of the first and the 4th embodiment that is described in JP-A-2001-124898.About preferred reflection layer, referring to the description among the JP-A-2001-124898 (15 of the right hurdle of third part walks to 23 row on tetrameric right hurdle).
Sealer preferably is provided on the surface of phosphor layer.The scattering length of measuring under the main smooth emission wavelength of phosphor preferably falls into scope 5-80 μ m, and more preferably 10-70 μ m is in the especially preferred 10-60 μ n.Term " scattering length " is meant light straight mean distance that advances before scattering referred in this; Wherein scattering length is short more, and light is scattered more.Absorption length-it represents the average free distance that light wherein advanced-be arbitrarily before being absorbed.But consider the susceptibility of net, sealer is absorbing light not preferably, because this causes lightsensitivity to descend.But the mode of scattering deficiency by way of compensation, sealer can have quite low receptivity.Absorption length is preferably 800 μ m or longer, especially preferred 1,200 μ m or longer.Light scattering length and light absorption length can be calculated by using the value that records according to following steps by the expression formula derived from the Kubeluka-Munk theory.
At first, obtain the film sample that three or more has composition identical with the target sealer and different thickness.Then, measure corresponding sample thickness (μ m) and diffuse transmittance coefficient (%).Diffuse transmission factor can utilize the spectrophotometric determination with integrating sphere.In the present invention, measurement has 150 by use
Uatomatic recording spectrophotometer (the U-3210 type of integrating sphere (150-0901); Make by HITACHI Ltd.) carry out.In measurement, wavelength must be corresponding to the main smooth emission peak wavelength that comprises the phosphor in the phosphor layer that provides the target sealer thereon.Subsequently, film thickness that will obtain in above measurement (μ m) and diffuse transmittance (%) substitution are derived from the following equation (A) of Kubeluka-Munk theory.Equation (A) can be released by the equation 5.1.12-5.1.15 that is described in " Keikotai Handbook " (403 pages, Ohm publication, 1987) under the boundary condition that provides diffuse transmittance T (%) easily.
T/100=4 β/[(1+ β)
2Exp (α d)-(1-β)
2Exp (α d)] ... (equation A),
Wherein T represents diffuse transmittance coefficient (%), and " d " represents film thickness (μ m), and α and β are respectively by following equation definition:
α=[K (K+2S)]
1/2And
β＝[K/(K+2S)]
1/2。
The T that records of three or more film (diffuse transmittance coefficient: %) with " d " (film thickness:, determine to satisfy the K of equation (A) and the value of S like this μ m) by the above equation of substitution (A).Scattering length (μ m) is by the 1/S definition, and absorption length (μ m) is defined by 1/K.
The sealer preferred configuration makes optical scatter be included in the resin material with dispersing mode.The optical index of optical scatter normally 1.6 or higher, preferred 1.9 or higher.The grain size of optical scatter falls in the scope 0.1-1.0 μ m usually.The example of this optical scatter comprises aluminium oxide, magnesium oxide, zinc paste, zinc sulphide, titanium dioxide, niobium oxide, barium sulphide, ceruse, monox, polymethylmethacrylate, the fine grained of styrene and melamine.
Be not particularly limited the resin material that is used to form sealer; But preferably adopt polyethylene terephthalate, PEN, polyamide, aromatic poly amide, fluorocarbon resin, polyester etc.Sealer can followingly form: dispersion is made by the aforementioned lights scattering particles are dispersed in the organic solvent solution that comprises resin material (adhesive resin); Subsequently, dispersion is applied directly to (alternatively, by any auxiliary layer) on the phosphor layer; With the dispersion drying that will be used to obtain sealer.Alternatively, the protective seam sheet material that forms separately can be provided on the phosphor layer by the intervention of bonding agent.The thickness of sealer falls into scope 2-12 μ m usually, in the preferred 3.5-10 μ m.
To be used to prepare radiation strengthen the preferable production process of net and be used for this material be described in detail in JP-A-9-21899 (47 of 6 pages left hurdle walks to 5 row on 8 pages left hurdle), and JP-A-6-347598 (17 of 2 pages right hurdle walks to 33 row on 3 pages left hurdle) and (42 of 3 pages left hurdle walks to 4 pages 22 the going of left hurdle).
The fluorescence that is used for this embodiment strengthens the network optimization choosing and has implanted the phosphor with gradient crystalline granular texture.Especially preferred, the surface of protective seam scribbles big crystal grain and seating plane scribbles small-size grains.The preferred size of little crystal grain is that the preferred size of 0.5-2.0 μ m and big crystal grain is 10-30 μ m.
(machine glazing heat picture material)
Be preferably used as the photochromics of breast X-radiography especially according to the machine glazing heat picture material of this embodiment.
The photothermal image material that is designed for above purposes is even more important, and the image with suitable contrast range is provided like this.
For the preferred ingredients requirement of the used photochromics of breast X-radiography, can be with reference to JP-A-5-45807, JP-A-10-62881, the description among JP-A-10-54900 and the JP-A-11-109564.
(with combining of Ultraluminescence net)
Use the formation method of photothermal image material to comprise in this embodiment by using the preferable methods that forms image with the phosphor in combination that has its main peak at 400nm or lower part.Preferred method be by with at 380nm or lowlyer have its main peak and use when phosphor in combination and form true picture.Two-sided photochromics or single face material all can be used as assembly.The net that is described in JP-A-6-11804 and WO-93-01521 can be used as the net that has its main glow peak at 400nm or lower part; But this net is not limited thereto.Reduce the technology of intersecting (being used for two-sided photochromics) and being used for anti-corona (being used for the single face photochromics) as being used for, can use the technology that is described in JP-8-78307.The dyestuff that is described in Japanese patent application No.2000-320809 is especially preferred uv absorption dyestuff.
3-2. thermal development
The photothermal image material of this embodiment can develop by any method, and the temperature of the photothermal image material by raising into image exposure that in general develops is carried out.Development temperature is preferably 80-250 ℃, more preferably 100-140 ℃.
Development time is preferably 1-60 second, more preferably 5-30 second and especially preferred 5-20 second.
Except the thermal development system according to this embodiment, the board heating apparatus method also can be used as the thermal development system.In relating to the thermal development system of using the plate heating systems, the method that is disclosed in JP-A-11-133572 is preferred.Particularly, in used thermal developing apparatus, the photothermal image material that sub-image is arranged that forms on it partly contacts in thermal development with heating unit, obtains visual picture like this.Thermal developing apparatus comprises board heating apparatus and a plurality of pressure roller as heating unit, and the latter arranges along a surface of board heating apparatus and towards board heating apparatus, makes thermal development be undertaken by making photothermal image material process between pressure roller and board heating apparatus.Board heating apparatus is divided into 2-6 and preferably reduces 1-10 ℃ or in its vicinity in fact as the temperature of the part of heating period and end portion.
This method is described in JP-A-54-30032 in addition, can be removed to outside this system comprising moisture in the photothermal image material and organic solvent, and can prevent that the bearing of photothermal image material from promptly heating and being out of shape.
3-3. system
As the medical laser imager of being furnished with exposing unit and thermal development unit, can mention the dried imager of FM-DPL type Fuji medical science.The details of this system is described in Fuji Medical Review, No.8, and pp39-55, and can adopt its technology.In addition, the photothermal image material of this embodiment can be used as the photothermal image material of laser imaging device in " AD network ", and this is a kind of network system that meets dicom standard that is proposed by the Fuji medical system.
4. the purposes of this embodiment
Form monochrome silver image and therefore be preferably used as according to the photothermal image material of this embodiment and be used for medical diagnosis, industry is taken a picture, printing, and the photothermal image material of COM (computing machine is exported little film).
Photothermal image material described so far is described in detail by embodiment; But the photothermal image material is not limited thereto.
Embodiment
[embodiment]
1.PET the preparation of bearing and undercoat
1-1. formation film
By terephthalic acid (TPA) and ethylene glycol, make have intrinsic viscosity IV 0.66 PET of (as in phenol/tetrachloroethane=6/4 (weight), measuring down) according to common mode at 25 ℃.With gained PET granulation, drying is 4 hours under 130 ℃, is coloured to blueness with blue mold (1,4-two-(2,6-diethylbenzene amido anthraquinone)), extrudes from the T-mold and cooling fast, and film is not like this stretched.
The gained film is gone up by using roller to be stretched to 3.3 times under different rotational speeies at MD (machine direction), goes up by using stenter to be stretched to 4.5 times at CD (laterally) subsequently.Being used for the temperature that MD stretches and CD stretches is respectively 110 ℃ and 130 ℃.Then, film is 240 ℃ of following heat fixations 20 seconds, with on the CD under identical temperature lax 4%.Then, after discharging the chuck of stenter, the edge of film is all by annular knurl, and with film at pressure 4kg/cm
2Under roll, obtain having the roller film of thickness 175 μ m like this.
1-2. surface corona is handled
By using solid-state corona discharge system, model 6KVA (being made by Pillar Technologies) carries out corona treatment with two surfaces of bearing under room temperature and speed 20m/min.According to the electric current that reads from this system this moment and the value of voltage, bearing is found at 0.375kVAmin/m
2The following processing.Handling frequency is 9.6kHz, and the gap between electrode and the dielectric roller is 1.6 μ m.
1-3. the preparation of primary coat bearing
(1) is used for the preparation of the coating solution of undercoat
Fill a prescription (1) (being used for the undercoat on the photosensitive aspect):
SnO
2/ SbO (SnO
2: SbO=9: 1 (quality); Mean particle size: 17% quality dispersion: 84g 0.5 μ m)
Pesuresin A-520 is (by TAKAMATSU OIL ﹠amp; FAT Co., Ltd makes) 30% quality solution: 46.8g
VYLONAL MD-1200 (making): 10.4g by TOYOBO.Co.Ltd.
Polyethyleneglycol nonylplenyl ether (average oxirane number=8.5) 1mol% solution: 11.0g
MP-1000 (PMMA polymer fine particles; By Soken Chemical ﹠amp; EngineeringCo., Ltd makes; Average particulate diameter: 0.4 μ m): 0.91g
Distilled water: 847ml
At biaxial stretch-formed polyethylene terephthalate bearing (thickness: after Corona discharge Treatment is carried out according to above-mentioned same way as in two surfaces 175 μ m), the coating solution of undercoat (prescription (1)) is administered on its one side by using wire bar, and subsequently 180 ℃ down dry 5 minutes so that wet coated weight 6.6ml/m to be provided
2(each surface).Then, another side is carried out identical processing, prepare the primary coat bearing like this.
2. the preparation of coating material
1) silver halide emulsion
(preparation of silver halide emulsion A)
In 1421ml distilled water, add 4.3ml 1% quality liquor kalii iodide, further add the sulfuric acid that 3.5ml has concentration 0.5mol/L subsequently, 36.5g (phthalized) gelatin of O-phthalic acidifying, with 160ml 2,5% quality methanol solution of 2 '-(ethylene sulfo-(ethylenediethio)) diethanol.Gained solution under agitation is heated to 75 ℃ of fluid temperatures in stainless reaction vessel, and will be wherein be distilled the solution A that water is diluted to the 22.22g silver nitrate of 218ml and all under constant flow rate, in 16 minutes, add wherein, and will wherein be distilled the solution B that water is diluted to the 36.6g potassium iodide of 366ml and when pAg remains on 10.2, add by controlled double-jet aeration method.Subsequently, add the aqueous hydrogen peroxide solution of 10ml3.5% quality, and add the benzimidazole aqueous solution of 10.8ml 10% quality in addition.In addition, wherein be distilled solution C adding in 80 minutes under constant rate of speed that water is diluted to the 51.86g silver nitrate of 508.2ml.Simultaneously, wherein being distilled the solution D that water is diluted to the 63.9g potassium iodide of 639ml adds when pAg remains on 10.2 by controlled pair of gunite.From begin to add solution C and D through 10 minutes after, add six chloro-iridic acids (III) potassium to obtain concentration 1X10
-4Mol/mol silver.In addition, finish add solution C after during through 5 seconds, the aqueous solution that adds six cyano group ferric acid (II) potassium is with acquisition concentration 3X10
-4Mol/mol silver.Then, regulate pH to 3.8 and after stopping stirring, this solution is stood precipitation/desalination/water wash step with 0.5mol/L sulfuric acid.In addition, regulate pH to 5.9, prepare silver halide dispersions like this with pAg 11.0 with 1mol/L NaOH.
Silver halide emulsion A is made up of pure agi grains, wherein has projected area 0.93 μ m mean diameter, the coefficient of variation of 17.7% area diameter projected, the plate-like grain of average thickness 0.057 μ m and average aspect ratio 16.3 account for the total projection area 80% or more.The equivalent bulb diameter is 0.42 μ m.The X-ray powder diffraction the analysis showed that, 30% or more silver iodide be present in the γ phase structure.
" preparation of silver halide emulsion B "
With 1mol as above (preparation of silver halide emulsion A) preparation plate-like grain silver iodide emulsion be placed in the reaction vessel.At 38 ℃ of pAg that measure down is 10.2.Subsequently, 0.5mol/L KBr solution and 0.5mol/LAgNO
3Solution was adding in 20 minutes under 10 ml/min, like this 10mol% silver bromide solution basically epitaxial deposition on AgI main body emulsion.In operating process, pAg remains on 10.2.Then, regulate pH to 3.8, and after stopping stirring, solution precipitates/desalination/water wash step with 0.5mol/L sulfuric acid.In addition, with 1mol/L NaOH pH regulator to 5.9, prepare silver halide dispersions like this with pAg11.0.
Silver halide dispersions under agitation remain on 38 ℃ down in, to wherein adding 1 of 5ml 0.34% quality, the methanol solution of 2-benzisothiazole-3-ketone and after 40 minutes, potpourri is heated to 47 ℃.During through 20 minutes, the methanol solution of sodium benzenethiosulfonate is with 7.6X10 after heating
-5The amount of/mol silver adds.After 5 minutes, the methanol solution of tellurium sensitizer C is with 2.9X10
-5The amount of mol/mol silver adds, subsequent ripening 91 minutes.Then, add the N of 1.3ml 0.8% quality, N '-dihydroxy-N "-methanol solution of diethyl melamine and after 4 minutes, the methanol solution of 5-methyl-2-mercaptobenzimidazole is with 4.8X10
-3The amount of mol/mol silver, 1-phenyl-2-heptyl-5-sulfydryl-1,3, the methanol solution of 4-triazole is with 5.4X10
-3The amount of mol/mol silver, and the aqueous solution of 1-(3-methyl urea groups phenyl)-5-mercapto-tetrazole is with 8.5X10
-3The amount of mol/mol silver adds wherein, prepares silver halide emulsion B like this.
The preparation of＜＜silver halide emulsion C〉〉
The liquor kalii iodide that adds 8ml 10% quality in 1421ml distilled water further adds the methanol solution of 2,2 '-(ethylene sulfo-) diethanol of the gelatin of 4.6g O-phthalic acidifying and 160ml 5% quality subsequently.Gained solution under agitation is heated to 75 ℃ of fluid temperatures in stainless reaction vessel, with will be wherein be distilled the solution A that water is diluted to the 22.7g silver nitrate of 223ml and all in 15 minutes and 22 seconds, add wherein under the constant flow rate, and incite somebody to action and wherein be distilled the solution B that water is diluted to the 36.6g potassium iodide of 366ml and when pAg remains on 9.96, add by controlled pair of gunite.Subsequently, the aqueous hydrogen peroxide solution of adding 10ml 3.5% quality and the further aqueous solution of the benzimidazole of adding 0.8ml10% quality.In addition, wherein be distilled solution C adding in 80 minutes under constant rate of speed that water is diluted to the 53.1g silver nitrate of 520.2ml.Simultaneously, wherein being distilled the solution D that water is diluted to the 63.9g potassium iodide of 639ml adds when pAg remains on 9.96 by controlled pair of gunite.After beginning to add solution C and D, during through 10 minutes, add six chloro-iridic acids (III) potassium immediately to obtain concentration 1X10
-4Mol/mol silver.In addition, when 5 seconds of finishing after adding solution C, six cyano group ferric acid (II) aqueous solutions of potassium are with 3X10
-4The amount of mol/mol silver adds.Subsequently, regulate pH to 3.8 and stop stirring with 0.5mol/L sulfuric acid.Solution is stood precipitation/desalination/water wash step.In addition, regulate pH to 5.9, prepare silver halide dispersions like this with pAg 11.0 with 1mol/L NaOH.
The main body crystal grain that so obtains is pure silver iodide emulsion, wherein have averaging projection's area diameter 1.36 μ m, the coefficient of variation of 17.7% averaging projection's area diameter, the plate-like grain of average thickness 0.113 μ m and average aspect ratio 12.0 account for the total projection area 80% or more.The equivalent bulb diameter is 0.68 μ m.The X-ray powder diffraction the analysis showed that, 15% or more silver halide present the γ phase structure.
The preparation of＜silver halide emulsion D 〉
The above-mentioned AgI main body of 1mol crystal grain is put into reaction vessel.At 40 ℃ of pAg that measure down is 9.1.Subsequently, every liter of halogen solution that comprises 0.088mol KBr and 0.038mol NaCl, and 0.125mol/LAgNO
3Solution added in 31 minutes under 28.7ml/ minute, have so silver-colored total amount 10mol% the bromine silver chloride basically epitaxial deposition on 6 angle points of AgI main body emulsion.In operating process, pAg remains on 7.13.
Then, regulate pH to 3.8, and stop to stir with 0.5mol/L sulfuric acid.This solution is stood precipitation/desalination/water wash step.In addition, regulate pH to 5.9, prepare silver halide dispersions like this with pAg 11.0 with 1mol/L NaOH.
The average halogen that is administered to the epitaxial part that obtains on the field emission type analytical electron microscope by the ultrathin section with the epitaxial part of silver halide grain is composed as follows: bromine 80mol%, chlorine 17mol% and iodine 3mol%.
In under silver halide dispersions stirs and remains on 38 ℃, add 1 of 5ml 0.34% quality, the methanol solution of 2-benzisothiazole-3-ketone.After 40 minutes, potpourri is heated to 60 ℃.20 minutes the time, the methanol solution of sodium benzenethiosulfonate is with 7.6X10 after temperature reaches 60 ℃
-5The amount of/mol silver adds.After 5 minutes, the methanol solution of tellurium sensitizer C is with 2.9X10
-5The amount of mol/mol silver adds, aging 91 minutes subsequently.Subsequently, add the N of 1.3ml 0.8% quality, N '-dihydroxy-N ", N "-methanol solution of diethyl melamine, and after 4 minutes, the methanol solution of 5-methyl-2-mercaptobenzimidazole is with 4.8X10
-3The amount of mol/mol silver, with 1-phenyl-2-heptyl-5-sulfydryl-1,3, the methanol solution of 4-triazole is with 5.4X10
-3The amount of mol/mol silver, and the aqueous solution of 1-(3-methyl urea groups phenyl)-5-mercapto-tetrazole is with 8.5X10
-3The amount of mol/mol silver adds together, prepares the silver halide emulsion D with extension key like this.
" preparation of the emulsion mixture that is used to be coated with "
Silver halide emulsion B and silver halide emulsion D dissolve at ratio 5 to 1 (with silver-colored molar ratio computing).To the benzothiazole iodide solution that wherein adds 1% quality to obtain concentration 7X10
-3Mol/mol silver.
In addition, adding can be carried out the compound 1,2 and 3 of one-electron oxidation, forms its one-electron oxidation product like this, and wherein the one-electron oxidation product can discharge one or more electronics, to obtain corresponding concentration 2X10
-3Mol/mol silver.
In addition, adding has the compound of adsorption group and reduction group 1,2 and 3 to obtain corresponding concentration 8X10
-3Mol/mol silver.
In addition, in the silver of every liter of emulsion mixture that is used to be coated with, add entry to obtain final silver halide content 15.6g.
2) preparation of aliphatic acid silver dispersions
The preparation of＜recrystallization mountain Yu acid 〉
Double centner mountain Yu acid (ProductName: Edenor C22-85R: by Henkel Corp. make) and 1, the 200kg isopropyl alcohol mixes, and dissolves down and is cooled to 30 ℃ at 50 ℃ after filtering by 10 μ m filtrators, carries out recrystallization like this.The cooldown rate that is used for recrystallization is controlled to 30 ℃/hr.Gained crystal grain is handled by centrifugal filtration, washs by toppling over the 100kg isopropyl alcohol, and subsequent drying.Esterified and when standing GC-FID and measuring when gained crystal grain, find that the content of mountain Yu acid is 96% quality and finds that other tetracosanoic acid content is 2%, find that arachidic acid content is 2% and find that content of erucic acid is 0.001%.
The preparation of＜aliphatic acid silver dispersions 〉
The Yu acid of 88kg recrystallization mountain, 442L distilled water, the aqueous solution of 49.2L 5mol/L concentration hydrogen sodium oxide molybdena and uncle 120L-butanols mixes, and stirs 1 hour with induced reaction down at 75 ℃ subsequently, and the solution of sodium behenate B is provided like this.Individually, the preparation 206.2L 40.4kg silver nitrate (pH 4.0) aqueous solution and remain under 10 ℃.The reaction vessel that comprises 635L distilled water and uncle 30L-butanols remains under 30 ℃, and the sodium behenate solution that will all measure and all the silver nitrate aqueous solutions of amount under fully stirring in that adding is wherein in the time in the time and 90 minutes of 93 minutes and 15 seconds respectively under the constant rate of speed.In this technology, only add in a 11-of silver nitrate aqueous solution after beginning to add silver nitrate aqueous solution minute.Then, begin to add sodium behenate solution and only sodium behenate solution adding in 14 minutes 15 seconds after finishing the adding silver nitrate aqueous solution.In this step process, the control external temperature is 30 ℃ with the internal temperature that keeps reaction vessel.Pipeline in the reinforced system of sodium behenate solution is by keeping warm at two-tube outer loop hot water, and the outlet fluid temperature with the feed introduction end is adjusted to 75 ℃ like this.Simultaneously, the pipeline in the reinforced system of silver nitrate aqueous solution is by keeping warm at two-tube outer loop chilled water.The axisymmetric arrangement of the relative stirring of the adding point of sodium behenate solution and silver nitrate aqueous solution.These are put, and also arrangement is feasible on such height avoids contacting with reaction solution.
After finishing the adding sodium behenate solution, potpourri was under agitation placed under this temperature 20 minutes.Subsequently reaction mixture was heated to 35 ℃ in 30 minutes, subsequent ripening 210 minutes.After finishing slaking, filter out solids content by centrifugal filtration immediately and wash with water and reach 30 μ S/cm until the conductance that leaches thing.Like this, obtain the aliphatic acid silver salt.The gained solids content does not have drying, but stores as wet cake.
Analyze the shape of the silver-colored crystal grain of mountain Yu acid that so obtains by the little photograph of electronics.Crystal grain is the crystal with following average-size: a=0.21 μ m, b=0.4 μ m and c=0.4 μ m have the average aspect ratio 2.1 and the average ball equivalent coefficient of variation 11% (a, b and c defined in the past) in this instructions.
In the wet cake that is equivalent to the 260kg solid, add the 19.3kg polyvinyl alcohol (PVA) (ProductName: PVA-217) and water to reach 1000kg altogether, and the gained potpourri formed slurry and carry out preliminary scatter operation with line mixer (model PM-10: by Mizuho Kogyou Kabushiki Kaisha manufacturing) by using the dissolver blade.
Then, the preliminary material solution that disperses is at decollator (ProductName; Micro-Fluidzer M-610: made and had a Z type chamber that interacts by Microfluidex International Corpoartion) pressure is adjusted to 1,150kg/cm
2In time, handle three times, obtains mountain Yu acid silver dispersions like this.In cooling down operation, provide the circular heat exchanger that sprays in the front and back in interaction chamber.Therefore, by regulating the temperature of cooling medium, dispersion temperature is set to 18 ℃.
3) preparation of reductive agent dispersion
" preparation of reductive agent-1 dispersion "
10kg water is added 10kg reductive agent-1 (1,1-two (2-hydroxyl-3,5-3,5-dimethylphenyl)-3,5,5-trimethyl cyclohexane) and 16kg 10% quality modified polyethylene alcohol (Poval MP203; Make by Kuraray company limited) solution, and the gained potpourri fully stirred to obtain slurry.The gained slurry transmits by membrane pump and has in filling and disperses in the horizontal sand mill (UVM-2: by Aimex, Ltd. makes) of the zirconia bead of 0.5mm mean diameter and handled therein 3 hours.Then, adding 0.2g benzisothiazole ketone sodium salt and water makes the concentration of reductive agent become 25% quality.Dispersion heated 5 hours down at 60 ℃, obtained reductive agent-1 dispersion like this.The particle that is included in the reductive agent in the reductive agent dispersion that so obtains has 0.40 μ m median diameter and 1.4 μ m or lower the largest particles diameter.Gained reductive agent dispersion is filtered to remove foreign matter such as dust by the polypropylene filter with 3.0 μ m bore dias, stores subsequently.
4) preparation of the compound dispersion of formation hydrogen bond
" forming the preparation of compound-1 dispersion of hydrogen bond "
10kg water is added 10kg form the compound-1 (three (4-tert-butyl phenyl) phosphine oxide) of hydrogen bond and the solution of 16kg 10%mol quality modified polyethylene alcohol (Poval MP203: make), and the gained potpourri is fully stirred to obtain slurry by Kuraray company limited.The gained slurry transmits by membrane pump and has in filling and disperses in the horizontal sand mill (UVM-2: by Aimex, Ltd. makes) of the zirconia bead of 0.5mm mean diameter and handled therein 4 hours.Then, adding 0.2g benzisothiazole ketone sodium salt and water makes the compound concentrations that forms hydrogen bond become 25% quality.Dispersions obtained 40 ℃ of following heating 1 hour, heat 1 hour compound-1 dispersion down at 80 ℃ subsequently to obtain forming hydrogen bond.The particle that is included in the compound of the formation hydrogen bond in the compound dispersion of the formation hydrogen bond that so obtains has 0.45 μ m median diameter and 1.3 μ m or lower the largest particles diameter.Gained forms the compound dispersion of hydrogen bond and filters to remove foreign matter such as dust by the polypropylene filter with 3.0 μ m bore dias, stores subsequently.
5) preparation of development accelerant dispersion and shade of color controlling agent dispersion
" preparation of development accelerant-1 dispersion "
10kg water is added the solution of 10kg development accelerant-1 and 20kg10%mol quality modified polyethylene alcohol (Poval MP203: made by Kuraray company limited), and the gained potpourri is fully stirred to obtain slurry.The gained slurry transmits by membrane pump and has in filling and disperses in the horizontal sand mill (UVM-2: by Aimex, Ltd. makes) of the zirconia bead of 0.5mm mean diameter and handled therein 3 hours and 30 minutes.Then, add 0.2g benzisothiazole ketone sodium salt and water and make that the concentration of development accelerant is 20% quality, obtains development accelerant-1 dispersion like this.The particle that is included in the development accelerant in the development accelerant dispersion that so obtains has 0.48 μ m median diameter and 1.4 μ m or lower the largest particles diameter.Gained development accelerant dispersion is filtered to remove foreign matter such as dust by the polypropylene filter with 3.0 μ m bore dias, stores subsequently.
The dispersion of development accelerant 2 and shade of color controlling agent-1 obtains according to being similar to the mode that is used for development accelerant-1, obtains 20% quality dispersion and 15% quality dispersion so respectively.
6) preparation of polydentate compound dispersion
" preparation of organic polyhalogen compound-1 dispersion "
With 10kg organic polyhalogen compound-1 (bromoform sulfonyl-benzene); 10kg 20% quality modified polyethylene alcohol solution (Poval MP203: make) by Kuraray company limited; 0.4kg 20% quality triisopropyl sodium naphthalene sulfonate aqueous solution and 14kg hydration also and are fully stirred to obtain slurry.The gained slurry transmits by membrane pump and has in filling and disperses in the horizontal sand mill (UVM-2: by Aimex, Ltd. makes) of the zirconia bead of 0.5mm mean diameter and handled therein 5 hours.Then, add 0.2g benzisothiazole ketone sodium salt and water and make the concentration of organic polyhalogen compound become 30% quality, obtain organic polyhalogen compound-1 dispersion like this.The particle that is included in the organic polyhalogen compound in the polydentate compound dispersion that so obtains has 0.41 μ m median diameter and 2.0 μ m or lower the largest particles diameter.Gained organic polyhalogen compound dispersion is filtered to remove foreign matter such as dust by the polypropylene filter with 10.0 μ m bore dias, stores subsequently.
" preparation of organic polyhalogen compound-2 dispersion "
With 10kg organic polyhalogen compound-2 (N-butyl-3-bromoform sulfonyl benzo acid amides); 20kg10% quality modified polyethylene alcohol solution (Poval MP203: made by Kuraray company limited) and 0.4kg 20% quality triisopropyl sodium naphthalene sulfonate aqueous solution merge and fully stir to obtain slurry.The gained slurry transmits by membrane pump and has in filling and disperses in the horizontal sand mill (UVM-2: by Aimex, Ltd. makes) of the zirconia bead of 0.5mm mean diameter and handled therein 5 hours.Then, adding 0.2g benzisothiazole ketone sodium salt and water makes the concentration of organic polyhalogen compound become 30% quality.Dispersion heated 5 hours down at 40 ℃, obtained organic polyhalogen compound-2 dispersion like this.The particle that is included in the organic polyhalogen compound in the polydentate compound dispersion that so obtains has 0.40 μ m median diameter and 1.3 μ m or lower the largest particles diameter.Gained organic polyhalogen compound dispersion is filtered to remove foreign matter such as dust by the polypropylene filter with 3.0 μ m bore dias, stores subsequently.
7) the silver iodide compound forms the preparation of agent
8kg modified polyethylene alcohol " MP203 " is added 174.57kg water, the 6-isopropyl 2 that adds the triisopropyl sodium naphthalene sulfonate aqueous solution and the 14.28kg 70%mol quality of 3.15kg 20%mol quality subsequently, 3-benzodiazine aqueous solution, the silver iodide compound that obtains 5% quality like this forms the solution of immunomodulator compounds.
8) preparation of sulfhydryl compound
(preparation of sulfhydryl compound)
" preparation of sulfhydryl compound-1 aqueous solution "
(1-(3-sulfo group phenyl)-5-mercapto-tetrazole sodium salt) is dissolved in the 993g water with 7g sulfhydryl compound-1, to prepare 0.7% quality aqueous solution.
" preparation of sulfhydryl compound-2 aqueous solution "
(1-(3-methyl uride)-5-mercapto-tetrazole sodium salt) is dissolved in the 980g water with 20g sulfhydryl compound-2, prepares 2.0% quality aqueous solution.
9-1) the preparation of SBR latex solution
SBR latex solution (Tp-1) is prepared as follows.
In the polymerization container of gaseous monomer reactor (TAS-2J model: make), add 287g distilled water, 7.73g surfactant (Pionin A-43-S: by Takemotooil ﹠amp by Taiatu Techno Corp.; Fat Co., Ltd. makes), 14.06ml 1 mol/L sodium hydrate aqueous solution, 0.15g sodium ethylene diamine tetracetate, 255g styrene, 11.25g acrylic acid, with uncle 3.0g-lauryl mercaptan, subsequently reactor is sealed with air tight manner, and potpourri is stirred under 200rpm.After finding time by vacuum pump and repeating with nitrogen wash several times,, internal temperature is risen to 60 ℃ simultaneously with the 108.75g 1,3-butadiene reactor of packing into.The 1.875g ammonium persulfate solution that is dissolved in the 50ml water is added potpourri, and continuous stirring is 5 hours simultaneously.Internal temperature further rises to 90 ℃, stirs simultaneously 3 hours.After finishing reaction, will reduce to the internal temperature room temperature, regulate pH to 8.4 with 1mol/L LiOH solution subsequently.Then, solution filters to remove foreign matter by the polypropylene filter with 1.0 μ m bore dias, stores subsequently, obtains 774.7g SBR latex TP-1 like this.Measure halogen ion concentration by chromatography of ions, the concentration that shows chloride ion is 3ppm.The concentration of sequestrant measures by high-speed liquid chromatography and the result is 145ppm.
Latex has the 90nm average particulate diameter, 17 ℃ of Tg, solid concentration 44% quality, equilibrium moisture content 0.6% quality under 25 ℃ and 60%RH, ionic conductivity 4.80mS/cm (ionic conductivity uses the diagometer CM-30S that is made by Toa Denpa Kogyo Co. to measure down at 25 ℃).
9-2) the preparation of isoprene rubber latex solution
Isoprene rubber latex solution (TP-2) is prepared as follows.
In the polymerization container of gaseous monomer reactor (TAS-2J model: make), add 1 by Taiatu Techno Corp., 500g distilled water, and with water 90 ℃ of down heating 3 hours, like this passivating coating is administered on the stainless surface of element of polymerization container or stainless stirrer.In the polymerization container that stands above processing, add wherein nitrogen 1 hour distilled water of bubbling of 582.28g, 9.49g surfactant (Pionin A-43-S: by Takemoto oil ﹠amp; Fat Co., Ltd. make), 19.56g 1mol/L sodium hydrate aqueous solution, 0.20g sodium ethylene diamine tetracetate, 314.99g styrene, 190.87g isoprene, 10.43g acrylic acid, with uncle 2.09g-lauryl mercaptan, subsequently reactor is sealed with air tight manner, and potpourri is stirred under 225rpm.The solution that the 2.61g ammonium persulfate is dissolved in the 40ml water adds potpourri, and continuous stirring is 6 hours simultaneously.The measurement of solids content is confirmed, the monomer of this moment-to the conversion ratio of-polymkeric substance be 90%.At this moment, add 5.22 acrylic acid solutions that are dissolved in the 46.98g water, add 10g water subsequently and further add the 1.30g ammonium persulfate solution that is dissolved in the 50.7ml water.After finishing adding, potpourri is heated to 90 ℃, stirs subsequently 3 hours.After finishing reaction, internal temperature is reduced to room temperature, regulate pH to 8.4 with 1mol/LLiOH solution subsequently.Then, solution filters to remove foreign matter by the polypropylene filter with 1.0 μ m bore dias, stores subsequently, obtains 1 like this, 248g isoprene rubber latex TP-1.Measure halogen ion concentration by chromatography of ions, the concentration that shows chlorion is 3ppm.The concentration of sequestrant measures by high-speed liquid chromatography and the result is 142ppm.
Latex has the 113nm average particulate diameter, 15 ℃ of Tg, solid concentration 41.3% quality, equilibrium moisture content 0.4% quality under 25 ℃ and 60%RH and ionic conductivity 5.23mS/cm (ionic conductivity uses the diagometer CM-30S that is made by Toa Denpa Kogyo Co. to measure down at 25 ℃).
10) preparation of nucleator dispersion
Be used as adding 2.5g polyvinyl alcohol (PVA) (PVA-217: make) and 87.5g water among the compound N o.SH-7 of nucleator to 10g, and the gained potpourri is fully mixed, and placed 3 hours as slurry by Kuraray company limited.Subsequently, the zirconia bead of gained slurry and 240g 0.5mm diameter is put into container together and disperseing machine (1/4G sand muller: made by AIMEX Corp.) to disperse 10 hours, is prepared the solid fine grained dispersion of nucleator like this.The grain size of 80% quality particle falls in the scope 0.1 μ m-1.0 μ m and mean particle size is 0.5 μ m.
1-3-2. the preparation of coating solution
1) is used for the preparation of the coating solution of emulsion layer (photosensitive layer)-1
To as above the preparation 1, order adds organic polyhalogen compound-1 dispersion in the potpourri of 000g aliphatic acid silver dispersions and 276ml water, organic polyhalogen compound-2 dispersion, 2,3-naphthyridine compounds-1 solution, SBR latex (TP-1) solution, isoprene rubber latex (TP-2) solution, reductive agent-1 dispersion, the nucleator dispersion, form compound-1 dispersion of hydrogen bond, development accelerant-1 dispersion, development accelerant-2 dispersion, development accelerant-3 dispersion, shade of color controlling agent-1 dispersion, and sulfhydryl compound-2 aqueous solution add the silver iodide compound subsequently and form agent.Just before coating, add the concentration (with silver amount) of silver halide potpourri emulsion, and the gained potpourri is fully stirred in acquisition 0.22mol/mol aliphatic acid silver.The gained coating solution that is used for emulsion layer is delivered to the coating mold and is used for coating by former state.
When using the Brookfield viscometer of being made by Tokyo Keiki Kogyo K.K. to measure, the viscosity of coating solution under 40 ℃ that is used for emulsion layer is 25[mPas] (the No.1 rotor, 60rpm).
25 ℃ of viscosity of using down the coating solution that RFS fields spectrometers (being made by Rheometrics Far East K.K.) measure in shear rate 0.1,1,10,100 and 1,000[1/sec] under be respectively 242,65,48,26, and 20[mPas].
The content of zirconium in coating solution is 0.52mg/g silver.
2) preparation of the lip-deep middle layer of emulsion coating solution
To 1,000g PVAC polyvinylalcohol-205 (making) and 4 by Kuraray Corp., add 27ml 5% quality dioctylis sulfosuccinas natricus (making) aqueous solution in the potpourri of the methyl methacrylate of 200ml 19% quality/styrene/acrylic butyl ester/hydroxyethyl-methacrylate/acrylic copolymer (copolyreaction ratio (quality)=64/9/20/5/2) latex solution by American Cyanamid Company, 135ml20% quality phthalic acid two aqueous ammoniums, and water, with preparation altogether 10,000g, by adding NaOH, obtain the middle layer coating solution so simultaneously with pH regulator to 7.5.The gained coating solution is at 9.1ml/m
2Under be sent to the coating mold.
40 ℃ following use coating composition viscosity that Brookfield viscometer measures as 58mPas (the No.1 rotor, 60rpm).
3) be used for the preparation of the coating solution of first protective seam
64 gram inertia gelatin are dissolved in the water, to wherein adding 112g 19.0% quality methyl methacrylate/styrene/acrylic butyl ester/hydroxyethyl meth acrylate/acrylic copolymer (copolyreaction ratio (quality) 64/9/20/5/2) latex solution, the methanol solution of 30ml 15% quality phthalic acid, the aqueous solution of 23ml10% quality 4-methylphthalic acid, 28ml 0.5mol/L concentration sulfuric acid, the aqueous solution of 5ml 5% quality dioctylis sulfosuccinas natricus (making) by American Cyanamid Company, 0.5g phenoxetol, 0.1g benzisothiazole ketone, and water, with preparation summation 750g, obtain coating solution like this.By using static mixer, just before coating, coating solution is mixed with 26ml 4% quality chrome alum chromalum, and at 18.6ml/m
2Under deliver to the coating mold.
40 ℃ of following viscosity of using the coating composition that Brookfield viscometer measures as 20mPas (the No.1 rotor, 60rpm).
4) be used for the preparation of the coating solution of second protective seam
80 gram inertia gelatin are dissolved in the water; to wherein adding 102g 27.5% quality methyl methacrylate/styrene/acrylic butyl ester/hydroxyethyl meth acrylate/acrylic copolymer (copolyreaction ratio (quality)=64/9/20/5/2) latex solution; 5.4ml the fluorinated surfactant of 2% quality (F-1) solution; 5.4ml the fluorinated surfactant of 2% quality (F-2) solution; the 5% quality dioctylis sulfosuccinas natricus of 23ml (making) aqueous solution by American Cyanamid Company; 4g fine grained (average particulate diameter: 0.7 μ m; volume weighting is evenly distributed: polymethylmethacrylate 30%); 21g fine grained (average particulate diameter: 3.6 μ m; volume weighting is evenly distributed: polymethylmethacrylate 60%); 1.6g 4-methylphthalic acid; 4.8g phthalic acid; 44ml 0.5mol/L concentration sulfuric acid; 10mg benzisothiazole ketone; and water; to prepare 650g altogether; further add 445ml subsequently and comprise 0.67% quality O-phthalic aqueous acid; and just before coating, mix by the use static mixer subsequently, prepare the coating solution of protective seam like this.Coating solution is at 8.3ml/m
2Under be sent to the coating mold.
The viscosity of the coating composition of 40 ℃ of following Shi Yongshi cloth viscometer determinings be 19mPas (the No.1 rotor, 60rpm).
1-4. the preparation of photothermal image material-1
On the two sides of bearing, imaging layer, the middle layer, first surface protective seam and second surface protective seam are prepared photothermal image material sample 1-7 like this by being coated with simultaneously according to the order that provides from the undercoat surface with the coating of slip bead.In above step process, with the adjustment to 31 in imaging layer and middle layer ℃, the adjustment to 37 of the adjustment to 36 of first surface protective seam ℃ and second surface protective seam ℃.With the aliphatic series silver of each face bearing and the summation meter of silver halide, the amount of the coating silver of bearing one side is 0.861g/m
2Summation meter with silver-colored silver halide in the aliphatic series of two sides bearing; That is, the summation of whole imaging layer, amount are 1.72g/m
2
Total coated weight (the g/m of every kind of compound of each surface imaging layer
2) as follows:
Aliphatic series silver (is benchmark with silver): 0.686
Polydentate compound-1:0.028
Polydentate compound-2:0.094
The silver iodide compound forms agent: 0.46
SBR latex: 5.20
SBR latex (TP-1): 2.09
Isoprene rubber latex (TP-2): 3.13
Reductive agent: 0.46
Nucleator-1:0.036
Form the compound-1:0.15 of hydrogen bond
Development accelerant-1:0.005
Development accelerant-2:0.035
Shade of color controlling agent-1:0.002
Sulfhydryl compound-1:0.001
Sulfhydryl compound-2:0.003
Silver halide (is benchmark with Ag): 0.175
Be used to be coated with dry condition as follows.Bearing utilized ion wind to remove static before coating.Be coated under the speed 160m/min and carry out.The coating of every kind of sample and drying condition are regulated to obtain the most stable surface condition in following scope.
-the gap that will be coated with between mold end and the bearing is set at 0.10-0.30mm;
-pressure of relief chamber is set at is lower than atmospheric pressure 196-882Pa;
-in cooling zone subsequently, film cools off under 10-20 ℃ of dry-bulb temperature with wind;
-film the time not have to contact and with the dry wind drying with 23-45 ℃ of dry-bulb temperature and 15-21 ℃ of wet-bulb temperature in transmission;
-after drying, with the regulation and control of the moisture of film 40-60%RH and 25 ℃;
-subsequently, the heating film make the film surface temperature become 70-90 ℃ and the heating after, the film surface is cooled to 25 ℃.
The photothermal image material of so making has 250 seconds dullness in the Beck smoothness.In addition, measurement shows that the pH of the laminar surface on the photosensitive layer is 6.0.
Below provide the chemical constitution of the compound of the embodiment that is used for this embodiment.
Tellurium sensitizer C
Can carry out the compound 1 of one-electron oxidation to form its one-electron oxidation product, wherein the one-electron oxidation product can discharge one or more electronics
Can carry out the compound 2 of one-electron oxidation to form its one-electron oxidation product, wherein the one-electron oxidation product can discharge one or more electronics
Can carry out the compound 3 of one-electron oxidation to form its one-electron oxidation product, wherein the one-electron oxidation product can discharge one or more electronics
(reductive agent-1)
(forming the compound-1 of hydrogen bond)
(polydentate compound-1)
(polydentate compound-2)
(sulfhydryl compound-1)
(sulfhydryl compound-2)
(the silver iodide compound forms agent)
(development accelerant-1)
(development accelerant-2)
(shade of color controlling agent-1)
(assessment of photographic property)
The gained sample is cut into the hemisection size, under 25 ℃ and 50%RH environment, wrapped up and at room temperature store 2 weeks with following wrappage.After storing, sample carries out following assessment.
(wrappage)
PET (10 μ m)/PE (12 μ m)/aluminium foil (9 μ m)/Ny (15 μ m)/the have tygon (50 μ m) of 3% carbon content, oxygen permeability: 0.02mL/atmm
225 ℃ of skies, moisture transmitance: 0.10g/atmm
225 ℃ of skies
The double spread photochromics that following assessment is so made.
Specimen holder is strengthened between two sheet materials of net A at fluorescence described below, produce the combination that is used for imaging like this.For the X-ray system DRX-3724HD (being made by TOSHIBA company) that has tungsten target by use carries out X-ray sensitometry, this combination was stood x-ray radiation 0.05 second.Electromotive force 80kVp is applied to the X-ray that sends on the device roughly is equivalent to the 7cm thickness of human body through an absorption water optical filter by the three-phase pulse generator.The X-ray that so obtains is as light source.Use step-length " log E=0.15 " to utilize distance method progressively to expose by changing X-x ray exposure x amount.After exposure, utilize thermal developing apparatus of the present invention that this material is stood thermal development and handle.The image optical density meter assessment that so obtains.
＜fluorescence strengthens the preparation of net A 〉
(1) preparation undercoat
According to the same way as of the embodiment 4 of JP-A-2001-124898, its thickness is that 50 μ m and gone up at the thick polyethylene terephthalate of 250 μ m-(that is bearing) by the reflection layer that the alumina powder is made form after drying.
(2) preparation of phosphor sheet material
The coating solution that is used to form phosphor layer with viscosity 25PS (under 25 ℃) passes through 250g BaFbr:Eu phosphor (mean particle size: 3.5 μ m); 8g polyurethane binder resin (PandexT5265M is made by DAINIPPON INK AND CHEMICAL Inc.); 2g epoxy adhesive resin (Epikote 1001, and by Japan Epoxy Resins Co., Ltd. makes); Add in the methyl ethyl ketone with 0.5g isocyanate compound (Colonate HX, by NIPPON POLYURETHANE INDUSTRY Co., Ltd makes) and utilize propeller mixer to mix and make.Coating solution is administered on the temporary support (on it polyethylene terephthalate sheet material of silicon-coating releasing agent) in advance and dry to form phosphor layer.Phosphor layer is peeled off from temporary support, obtained the phosphor sheet material like this.
(3) phosphor sheet material fixing on reflection layer
Be placed on the phosphor sheet material of as above preparation on the bearing that has the reflection layer that in above technology (1), has prepared and utilize calender roll at pressure 400kgw/cm
280 ℃ of compactings down, like this phosphor layer is fixed on the reflection layer down.The thickness of gained phosphor layer is that 125 μ m and the volume filling ratio of phosphor particles in phosphor layer are 68%.
(4) preparation of sealer
Polyester binder is administered on the one side of the thick polyethylene terephthalate of 6 μ m-, sealer is provided on the phosphor layer in the lamination mode like this.Therefore, the fluorescence that is formed by bearing strengthens net A, reflection layer, and phosphor layer and sealer obtain as mentioned above.
(5) characteristics of luminescence
Fig. 4 has provided the optical emission spectroscopy that the fluorescence that uses x-ray radiation to measure strengthens net A under 40kVp.Fluorescence strengthens net A and is presented at the narrow half-band width light emission that the 390nm place has its peak.
Simultaneously, be used for the conventional photochromics RX-U (by Fuji Photo Film Co., Ltd. makes) of wet developing method by using X-ray rule mesh HI-SCREEN B3 (light emission peak wavelength: 425nm; CaWO
4As phosphor) (by Fuji Photo Film Co., Ltd. two sheet materials manufacturing) expose under the condition identical with the above, and subsequently by using automatic processor CEPROS M2 (by Fuji Photo Film Co., Ltd. makes) to handle 45 seconds with handling solution C E-D1.
To compare and discovery has similar preferred performance by using according to the photothermal image material of this embodiment with by the photographic property that uses those images that obtain that wet developing method obtains.
As mentioned above, according to above structure, the thermal development unit except the exposure and the development of CT film are carried out in original use in individual unit also can carry out the thermal development of two-sided photosensitive film.Therefore, it can eliminate purchasing of the developing apparatus that is exclusively used in two-sided photosensitive film, and required installing space.In addition, this thermal developing apparatus can also load film and need not those of skill in the art and load raw stock.
Required each of foreign priority and the whole disclosure of all foreign patent applications to incorporate the present invention as a reference fully in this application at this.
Claims (5)
1. thermal developing apparatus, it comprises:
Comprise the photothermal image recording materials feeding section of supply dish in photothermal image recording materials feeding section, described supply dish is used to comprise the photothermal image recording materials;
Exposed portion, it exposes described photothermal image recording materials;
First hop, it is sent to described exposed portion with described photothermal image recording materials from described supply dish;
The thermal development part, it carries out the thermal development of described photothermal image recording materials;
Second hop, it is sent to described thermal development part with described photothermal image recording materials from described exposed portion;
The magazine storage compartment that comprises magazine, described magazine are used to be included in the two-sided photothermal image recording materials that have imaging layer on the two sides of two-sided photothermal image recording materials; With
The 3rd hop, it is sent to described first hop with described two-sided photothermal image recording materials from described magazine, wherein said the 3rd hop comprises photothermal image recording materials detecting sensor, and the operation of exposed portion switches to according to the output of described photothermal image recording materials detecting sensor and opens or closes;
And carry out under the heat-developed situation the exposed portion passivation at two-sided photothermal image recording materials.
2. according to the thermal developing apparatus of claim 1, wherein said thermal development partly comprises heating part, and its heating is through the front and back of the photothermal image recording materials of transmission path.
3. according to the thermal developing apparatus of claim 2, wherein said heating part is the combination of the heating pressure roller of twisted plate well heater and the close twisted plate well heater of arrangement.
4. according to the thermal developing apparatus of claim 2, wherein said heating part is the heating cylinder and arranges close combination of heating the warm-up mill of drum surface.
5. according to the thermal developing apparatus of claim 1, wherein, at exposed portion, the device information of thermal developing apparatus is recorded in from the photothermal image recording materials of supply dish and on the two-sided photothermal image recording materials from magazine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003307808 | 2003-08-29 | ||
| JP2003307808 | 2003-08-29 | ||
| JP2003-307808 | 2003-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1591225A CN1591225A (en) | 2005-03-09 |
| CN100428068C true CN100428068C (en) | 2008-10-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100748466A Expired - Fee Related CN100428068C (en) | 2003-08-29 | 2004-08-30 | Thermal development apparatus |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000356829A (en) * | 1999-06-15 | 2000-12-26 | Fuji Photo Film Co Ltd | Image forming method for heat developable photosensitive material |
| US20020135661A1 (en) * | 2001-03-22 | 2002-09-26 | Fuji Photo Film Co., Ltd | Heat development apparatus |
| US20020186294A1 (en) * | 2001-06-06 | 2002-12-12 | Fuji Photo Film Co., Ltd. | Image forming device |
| JP2003075973A (en) * | 2001-09-06 | 2003-03-12 | Konica Corp | Thermal developing device and method for controlling device therefor |
| US20030118926A1 (en) * | 2001-12-26 | 2003-06-26 | Konica Corporation | Image forming apparatus and method |
-
2004
- 2004-08-30 CN CNB2004100748466A patent/CN100428068C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000356829A (en) * | 1999-06-15 | 2000-12-26 | Fuji Photo Film Co Ltd | Image forming method for heat developable photosensitive material |
| US20020135661A1 (en) * | 2001-03-22 | 2002-09-26 | Fuji Photo Film Co., Ltd | Heat development apparatus |
| US20020186294A1 (en) * | 2001-06-06 | 2002-12-12 | Fuji Photo Film Co., Ltd. | Image forming device |
| JP2003075973A (en) * | 2001-09-06 | 2003-03-12 | Konica Corp | Thermal developing device and method for controlling device therefor |
| US20030118926A1 (en) * | 2001-12-26 | 2003-06-26 | Konica Corporation | Image forming apparatus and method |
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| Publication number | Publication date |
|---|---|
| CN1591225A (en) | 2005-03-09 |
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