JP2001201818A - Base for heat developable photosensitive material, method for producing the same and heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base for a heat developable photosensitive material superior in various physical properties, such as creep deformation, surface roughness, thermal dimensional stability, planeness and scuffing resistance, a method for producing the base and a heat developable photosensitive material. SOLUTION: An undercoat layer is formed on a polyester, film before the completion of crystal orientation by applying and drying an aqueous coating solution containing a resin having 40 deg.C or higher glass transition temperature and inorganic particles, and after stretching, heat fixation and relaxation treatment, the polyester film is heat-treated under conveyance under the conditions of a temperature Tp ( deg.C), a tension Ts (kg/cm2) and a time Tm (min) which satisfy expression (1) 6.0<=Q<=7.4 (Q=(Tp/25)+log(Tm)) and expression (2) 1.8<=(Q/Ts)<=5.0 to produce the objective base for a heat developable photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photothermographic material for plate making suitable for multi-plate printing, a support for the photothermographic material for providing the photothermographic material, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making, waste liquid caused by wet processing of an image forming material has become a problem in terms of workability. In recent years, the amount of treated waste liquid has been reduced from the viewpoint of environmental protection and space saving. It is strongly desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter and can form a high-resolution, clear black image. As this technique, for example, US Pat. No. 3,152,904,
Nos. 3,487,075 and D.I. “Dry Silver Photographic Material (D
ry SilverPhotographic Mat
erials) "(Handbook of Imag
ing Materials, Marcel Dekk
er Inc. 48, 1991) are well known. Since these photosensitive materials are usually developed at a temperature of 80 ° C. or higher, they are called photothermographic materials.

When color printing is performed using a photosensitive material for plate making, usually, a plurality of films separated for each color are used. The films are printed on the respective printing plates and printed in layers. When films separated for a plurality of colors are overlapped, if they do not overlap exactly, a phenomenon occurs in which colors are shifted when printed. Therefore, when providing a photothermographic material for printing plate making, it is an important issue how to suppress a dimensional change of the plate due to heat.

As methods for improving the heat-resistant dimensional stability of photothermographic materials, Japanese Patent Application Laid-Open Nos. 10-10676 and 10-10677 disclose a high temperature of 80 to 200 ° C. and 0.04 to 6 kg. A technique is disclosed in which heat treatment is performed while transporting the support at a low tension of / cm ² to reduce the thermal dimensional change rate due to thermal shrinkage of the support. However, even in the case of a photothermographic material support in which the thermal dimensional change rate is adjusted to be small in this manner, in the case of roll transport, since the roll is transported at high temperature and low tension, the adhesion between the softened support and the roll is reduced. It was found that the transportability was increased and the flatness and scratch resistance of the support for photothermographic material were deteriorated.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been proposed to solve the above-mentioned problems, and it is an object of the present invention to provide excellent thermal dimensional stability even under high-temperature processing by thermal development, and to further improve creep. A method for producing a support for a photothermographic material excellent in deformation, surface roughness, flatness and scratch resistance, a support for a photothermographic material obtained by the production method, and a support for the photothermographic material An object of the present invention is to provide a photothermographic material used.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on the above problems and found that a specific undercoat layer was applied before the oriented crystals were completed in the polyester film forming stage. By controlling the physical properties of the surface of the obtained photothermographic material support, heat-transfer the resulting photothermographic material support at a specific temperature, time, and tension, By performing any one of the three methods such as adjusting the width of the orientation of the support for the developing photosensitive material, or by combining at least two of the three methods, the thermal dimensional change is small, the amount of creep deformation, and the surface roughness are reduced. Well,
It is found that a support for a photothermographic material having excellent physical properties such as flatness, orientation, and scratch resistance, and a photothermographic material having excellent adhesiveness between the photosensitive layer and the support in addition to the physical properties can be obtained. It was reached.

The structure of the present invention is shown below. 1. An aqueous coating solution containing a resin having a glass transition point of 40 ° C. or more and inorganic particles is applied to the polyester film before crystal orientation is completed, dried to form an undercoat layer, and further stretched, heat-set and relaxed. A method for producing a support for a photothermographic material, wherein the stretching, heat-setting and relaxation treatments are performed, and then a temperature Tp (° C.) that simultaneously satisfies the following formulas (1) and (2): ), Tension Ts (kg / c
m ² ), a method for producing a support for a photothermographic material, wherein the support is heat-treated at a time Tm (min).

Equation (1) 6.0 ≦ Q ≦ 7.4 Equation (2) 1.8 ≦ (Q / Ts) ≦ 5.0 where Q = (Tp / 25) + log (Tm) 2. The photothermographic material according to item 1, wherein the resin having a glass transition point of 40 ° C. or higher is made of at least one selected from a polyester resin, an acrylic resin, an acryl-modified polyester resin, and a urethane resin. A method for producing a support.

3. After forming the undercoat layer on the polyester film, stretching, heat setting and relaxation treatment, slit so that the difference in the orientation angle is 1 ~ 25 °, winding on a take-up roll, 3. The method for producing a photothermographic material support according to the above item 1 or 2, wherein the heat treatment is carried out from the winding roll.

[0010] 4. 4. A support for a photothermographic material, which is manufactured by the method for manufacturing a support for a photothermographic material according to any one of the above items 1 to 3.

5. A support for a photothermographic material, comprising a biaxially stretched polyester film containing polyethylene terephthalate as a main component and having an undercoat layer, wherein the support is subjected to a heat treatment at 120 ° C. for 60 seconds. The dimensional change rate is 0.001 to 0.04%, the glass transition point of the undercoat layer is 40 ° C. or more, and the surface roughness R
A support for a photothermographic material, wherein a is 0.3 to 5.0 μm.

6. A support for a photothermographic material, comprising a biaxially stretched polyester film containing polyethylene terephthalate as a main component and having an undercoat layer, wherein the support is subjected to a heat treatment at 120 ° C. for 60 seconds. The dimensional change rate is 0.001 to 0.04%, the creep deformation is 0.3 to 0.8 μm, and the surface roughness R
A support for a photothermographic material, wherein a is 0.3 to 5.0 μm.

7. 7. The support for photothermographic material as described in 5 or 6, wherein the difference in the orientation angle in the biaxially stretched polyester film is 1 to 25 °.

8. A photothermographic material using the photothermographic material support according to any one of the above items 4 to 7.

9. 9. The photothermographic material as described in 8 above, further comprising a layer containing a hydrazine compound on the photothermographic material support.

Hereinafter, the present invention will be described in detail. [Support for Photothermographic Material] The following polyester resin is used for the production of the biaxially stretched polyester film constituting the support for the photothermographic material of the present invention (hereinafter also referred to simply as a support).

(Polyester resin) As the polyester resin, polyethylene terephthalate (PET),
It is manufactured using a resin such as polyethylene naphthalate (PEN), polycarbonate (PC), and polyarylate (PAr). Among them, preferred resins for polyester film are PET resin and PEN resin, and particularly preferred is PET resin. Incidentally, the resin constituting the biaxially stretched polyester film may be a polyester resin alone, but may be a copolymer resin of polyester and another resin monomer and a blend resin of a polyester resin and another resin. Is preferably 50% or more by mass.

The PET resin is composed of terephthalic acid and ethylene glycol, and the PEN resin is composed of naphthalenedicarboxylic acid and ethylene glycol. The polymerization is carried out by condensing these under appropriate reaction conditions in the presence of a catalyst. At this time, one or more appropriate third components may be mixed. A suitable third component may be any compound having a divalent ester-forming functional group. Examples of the dicarboxylic acid include the following.

Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
Examples thereof include diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketonedicarboxylic acid, and phenylindanedicarboxylic acid.

Examples of glycols include propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis Examples thereof include (4-hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol.

The intrinsic viscosity of the PET resin of the present invention and a film using the resin is preferably 0.5 to 0.8. Further, those having different intrinsic viscosities may be mixed and used. The method for synthesizing the PET resin of the present invention is not particularly limited, and it can be produced according to a conventionally known method for producing a PET resin. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, a dialkyl ester is first used as a dicarboxylic acid component, a transesterification reaction between the dicarboxylic acid component and a diol component is performed, and the excess A transesterification method of polymerizing by removing the diol component can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. Examples of the heat stabilizer include phosphoric acid, phosphorous acid, and ester compounds thereof. In addition, in each step of the synthesis, an anti-coloring agent, a crystal nucleating agent, a slipping agent, a stabilizer, an anti-blocking agent, an ultraviolet absorber, a viscosity regulator, a clarifying agent, an antistatic agent, a pH regulator, a dye, a pigment, etc. May be added.

(Manufacture of polyester film and support) In the present invention, an unstretched polyester film is manufactured using the above polyester resin, and the unstretched polyester film is stretched. Before completion of the formation, the undercoat layer of the present invention is formed on one or both surfaces thereof, and further, orientation crystallization is completed, and then a stabilization treatment including a heat setting and a relaxation treatment is performed to obtain a support or the like. In the present invention, the support is further subjected to a heat treatment for transport under specific conditions to obtain the support of the present invention having excellent thermal dimensional stability, flatness, scratch resistance and the like.

The term "polyester film before completion of the crystal orientation" as used herein refers to an unstretched film obtained by heat-melting a polyester resin to form a film, or an unstretched film in a longitudinal direction (longitudinal direction) or a transverse direction. Uniaxially stretched film oriented in one of two directions (width direction), and further stretched and oriented at a low magnification in two directions of longitudinal and transverse directions (finally oriented by re-stretching in the longitudinal or transverse direction) Biaxially stretched film before crystallization is completed).

The method for obtaining the unstretched polyester film and the method for uniaxially stretching in the machine direction can be carried out by a conventionally known method. For example, the polyester resin as a raw material is formed into a pellet, dried with hot air or vacuum dried, melt-extruded, extruded into a film from a T-die, brought into close contact with a cooling drum by an electrostatic application method, and solidified by cooling. Obtain a stretched film. Next, the obtained unstretched film is heated in a range from the glass transition temperature (Tg) of the polyester resin to Tg + 100 ° C. through a plurality of roll groups and / or a heating device such as an infrared heater, and longitudinally stretched. . The stretching ratio is usually in the range of 2.5 to 6 times.

At this time, by making the stretching temperature have a temperature difference between the front and back of the polyester film, it is possible to make the winding harder. More specifically, the temperature can be controlled by providing a heating means such as an infrared heater on one side during the longitudinal stretching. The temperature difference during stretching is
Preferably 0 ° C to 40 ° C, more preferably 0 ° C to 20 ° C
It is. If the temperature difference is larger than 40 ° C., the polyester film cannot be stretched uniformly, and the flatness of the polyester film tends to deteriorate, which is not preferable.

Next, the polyester film uniaxially stretched in the machine direction obtained as described above is subjected to Tg to Tg + 1.
The film is stretched at a low magnification in a temperature range of 20 ° C., and usually an undercoat layer is formed before or after the low-magnification transverse stretching, and a final transverse stretching is performed to complete the oriented crystallization. The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is determined by measuring the physical properties of the obtained biaxially stretched polyester film and appropriately adjusted so as to have preferable characteristics. Subsequently, a stabilizing treatment such as a heat setting and a relaxation treatment is performed to obtain a support. Here, the heat setting is preferably performed at a temperature higher than the final transverse stretching temperature, within a temperature range of Tg + 180 ° C. or lower, and at two or more temperatures, usually for 0.5 to 300 seconds. By thermally fixing the polyester film at two or more temperatures in this manner, its thermal dimensional stability can be improved. Further, the above-mentioned relaxation treatment is also performed for the purpose of improving the thermal dimensional stability of the polyester film,
It is preferable that the heat treatment is performed in the stretching film forming process of the polyester film, in a transverse stretching tenter, or in a process from exiting the tenter to winding. The relaxation treatment is preferably performed at a treatment temperature of 80C to 200C, and more preferably at a treatment temperature of 100C to 180C.
The relaxation rate is 0.1 to 10 in both the longitudinal direction and the width direction.
%, More preferably in a range of 2 to 6%. After the above-mentioned heat fixing and relaxation treatments, the transfer heat treatment of the present invention described below is performed to obtain a support having a preferable thermal dimensional change rate, flatness, and scratch resistance.

Although the thickness of the support of the present invention is not particularly limited, it is preferable that the thickness is large in terms of the thermal dimensional change rate. When the support is used for a medical photographic light-sensitive material, the thickness is preferably 90 to 200 μm including the handleability. Preferred, especially 150 to 190 μm
It is preferred that When used for a photographic light-sensitive material for printing, transparency is required due to simultaneous printing of four plates, and it is preferably from 70 to 180 μm, particularly preferably from 100 to 140 μm.

Regarding the orientation angle of the support, the difference of the orientation angle within the width of the support is 1 before the heat treatment for transport under the specific conditions of the present invention.
It is preferable to slit so that it becomes 25 °. By setting the difference in the orientation angle in this range, the difference in tension in the width direction of the support at the time of low-tension conveyance can be reduced, and conveyability is improved. For the above reasons, the flatness and scratch resistance of the support and the uniformity of the thermal dimensional change in the support are maintained. on the other hand,
If the difference in the orientation angle of the support is greater than 25 °, the transportability will deteriorate, and the flatness and scratch resistance of the support will deteriorate, which is not preferable. Orientation angle is conventionally known X-ray diffraction, coefficient of thermal expansion,
It can be examined by measuring the mechanical properties in the vertical and horizontal directions, and using a microwave molecular orientation meter. In the present invention, a method is used in which a sample is placed between two polarizing plates, and the orientation angle is determined by measuring the intensity of light passing through the sample while rotating the sample. Since the angle is always 0 degrees at the center in the stretching longitudinal direction (hereinafter MD) and the stretching width direction (hereinafter TD), the orientation angle can be compared between different samples by utilizing this property. When the sample is rotated between the polarizing plates, the angle at which the amount of light transmitted through the sample is minimized is the orientation angle of the sample. The orientation angle is a symmetric value (+ −−) at the center in the TD direction.
(The sign is reversed). The absolute value of the orientation angle gradually increases in the width direction of the support.

(Formation of Undercoat Layer) In the formation of the undercoat layer of the present invention, it is preferable to use an aqueous coating solution composed of a resin having a Tg of 40 ° C. or higher. This is because the photothermographic material using the support composed of the undercoat layer not only can provide a support having good flatness without causing transport failure or scratching even during the low tension transport heat treatment. Is more preferable because it has excellent adhesion to the photosensitive layer during thermal development. When the Tg is lower than 40 ° C., the adhesion of the coated film to a roll increases during the heat treatment for transporting the film, which is unfavorable because of poor transport. Further, the use of a heat-developable photosensitive material is not preferred because the adhesiveness of the photosensitive layer to the support during thermal development is poor.

As the resin having a Tg of 40 ° C. or higher, polyester, acrylic-modified polyester, polyurethane, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine vinylidene resin, polyethyleneimine, polyvinyl alcohol, modified polyvinyl alcohol, gelatin and the like are preferable. . In particular, polyester, acryl-modified polyester, polyurethane, and acrylic resin are preferable from the viewpoint that adhesion to a roll is small during transfer heat treatment and transfer failure does not occur.

As the polyester resin, a copolyester having a sulfonic acid alkali base, a carboxylic acid alkali base, or the like in a molecule for imparting hydrophilicity is preferably exemplified. Specifically, terephthalic acid-isophthalic acid- (5-
Sulfoisophthalic acid sodium salt) -ethylene glycol-diethylene glycol-neopentyl glycol-based copolymer polyester is preferred.

Examples of the acryl-modified polyester include modified polymers obtained by grafting an acrylic monomer or the like to the above polyester. Specifically, terephthalic acid
Polymerization of methyl methacrylate-ethyl acrylate-ammonium acrylate-butyl acrylate (50%) in the presence of (5-sulfoisophthalic acid sodium salt) -diethylene glycol-1,4-butanediol copolymerized polyester (50%) Preferred examples include modified polymers obtained by the above.

Preferred examples of the polyurethane resin include hydrophilic polyurethanes having a sulfonic acid alkali base or a carboxylic acid amine base in the molecule. Specifically, polyethylene glycol-diphenylmethane diisocyanate-ethylenediamine, dimethylolpropionate amine-based polyurethane and the like are preferably mentioned.

Examples of the acrylic resin include methyl methacrylate-ethyl acrylate-ammonium acrylate-acrylamide copolymer, methacrylamide-butyl acrylate-sodium acrylate-methyl methacrylate-N-methylol acrylamide copolymer and the like. Preferred are mentioned. Acrylic resin can be manufactured as acrylic emulsion, aqueous acrylic solution, acrylic dispersion, etc.
Also available.

The above resins are used as one kind or as a mixture of two or more kinds. In addition, a crosslinkable resin such as an amino resin, a phenol resin, an epoxy resin, and a polyisocyanate, and other resins can be used together with these resins.

In the present invention, the aqueous coating solution may be used by adding a required amount of a surfactant such as an anionic surfactant, a cationic surfactant, or a nonionic surfactant. As these surfactants, the surface tension of the coating solution is 5
0 dyne / cm or less, preferably 40 dyne / c
m or less, and those which promote wetting to the polyester film are preferable.For example, polyalkylene oxide, polyoxyethylene alkyl phenyl ether, polyoxyethylene-fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl Sulfate, alkyl sulfonate, alkyl sulfosuccinate, quaternary ammonium chloride salt,
Alkylamine hydrochloride and the like can be mentioned. In addition, an antistatic agent, an ultraviolet absorber, a pigment, a lubricant, an antiblocking agent, a dispersant, and the like can be added.

In the present invention, a support having an undercoat layer containing the above-mentioned resin is used, and the creep deformation degree of the support surface is set to 0.3 to 0.8 μm, so that the heat treatment during low tension transfer heat treatment is performed. As a result, it was found that a support having good flatness was obtained without causing conveyance failure or abrasion.

(Measurement of the degree of creep deformation) The degree of creep deformation specified in the present invention is a micro hardness tester MZ manufactured by Akashi Co., Ltd.
It is determined from the difference in the amount of creep deformation (μm) of the support when measured under the following conditions using T-3. FIG. 1 is a diagram showing a change in the amount of creep deformation of the support during the measurement. In the figure, the measured degree of creep deformation of the support indicates the difference (h ₂ −h ₁ ) in the amount of creep deformation.

Indenter type: Vickers Load: 3 g Load speed: 3 gf / sec Load time: 1 second Hold time (t _{1 to} t ₂ ): 30 seconds Load removal time (t _{2 to} t ₃ ): 1 second Manufacturing method: The lower surface of the support sample is placed on the upper side, and a silicon wafer is brought into close contact with this with a trace amount of moisture.

In FIG. 1, horizontal axis: time axis (t seconds) vertical axis: deformation amount (indentation depth) (hμm) t _{0 to} t ₁ : time for gradually increasing the load at a constant speed (load speed) h ₀ to h _1: change in deformation amount of film when gradually increasing the load at a constant speed a: a point stop an increase in load (t _1, h _1), point was switched to the constant force t _0: measurement Initial (0 second) h ₀ : Initial measurement (0 μm) t ₁ : Time at which the increased load is switched to the constant load h ₁ : Deformation amount when the increased load is switched to the constant load B: Point at which the unloading is performed (t ₂ , H ₂ ) t ₂ : time when constant load is switched to unloading h ₂ : deformation amount when constant load is switched to unloading t _{1 to} t ₂ : time during which constant load is maintained (holding time) h ₁ to h _2: deformation amount increases further be left constant load C: a point reduced deformation amount becomes substantially constant (t _3, h _{3) 3:} Time change in the amount to de-load is almost certain to be to exit the measurement h _3: the amount of change was almost certain to de-load t ₂ ~t _3: the as-de-load time h ₂ ~h _3: The amount of change that decreases after unloading t _{2 to} t ₃ : time during which no load is applied (load removal time) In the indentation test used in the present invention, three deformation amounts (elastic deformation amount) , Plastic deformation, creep deformation), the elasticity and plastic deformation processes can be measured simultaneously. This makes it possible to obtain mechanical strength (surface physical property value) that cannot be obtained with the conventional hardness value, in particular, elastic and viscous properties of the material.

In the present invention, attention was paid to the amount of creep deformation among the three amounts of deformation, and the relationship between flatness and abrasion resistance during low-tension heat treatment was investigated. By setting the creep deformation degree obtained from the difference in deformation amount (h ₁ -h ₂ ) to 0.3 to 0.8 μm, the flatness and abrasion resistance do not deteriorate even if a force is applied to the support surface during heat treatment. I understood. It is presumed that this phenomenon did not cause conveyance failure due to creep during the heat treatment of the support surface, and as a result, both heat-resistant dimensional stability and flatness could be achieved.

The undercoat layer of the present invention preferably uses an aqueous coating solution containing inorganic particles. When inorganic particles are not contained, the adhesion of the coated film to the roll during the heat treatment for transport increases, causing poor transport and deteriorating flatness, and applying the photosensitive layer and backing layer to heat development. Poor adhesion when used as photosensitive material.

The inorganic particles include inorganic substances such as silica, alumina, barium sulfate, calcium carbonate, titania, tin oxide, indium oxide, and talc. The shape of these inorganic particles is not particularly limited, and may be needle-like, spherical, plate-like, or crushed. A preferred size is 0.1 to 15 μm, more preferably 0.2 to 15 μm.
10 to 10 μm, and more preferably 0.3 to 7 μm.
The addition amount of the particles sided 1 m ² per 0.1 to 50 mg, more preferably 0.2～30Mg, more preferably 0.
3-20 mg. In the present invention, the surface roughness (Ra) can be adjusted to a range of 0.3 to 5.0 μm by containing the inorganic particles. It has been found that in this range, poor conveyance does not occur during the low tension heat treatment, and the flatness does not deteriorate. Further, by setting the surface roughness (Ra) to 0.5 to 3.0 μm, the effect is further improved. By setting the surface roughness (Ra) within the range of the present invention, the friction between the transport roll and the thermoplastic film-based support of the present invention can be effectively reduced. If the ratio is below the range of the present invention, the flatness tends to decrease. If the ratio exceeds the range, the added fine particles are peeled off to cause roll contamination, which is not preferable.

The solid concentration of the aqueous coating solution for forming the undercoat layer of the present invention is usually 50% by mass or less,
% By mass or less is more preferable. The coating amount is 0.5 to 50 g per 1 m ² of the running polyester film,
30 g is preferred. As a coating method, any known coating method can be applied. For example, kiss coat method, reverse coat method, die coat method, reverse kiss coat method, offset gravure coat method, Meyer bar coat method, roll brush method, spray coat method, air knife coat method, impregnation method, curtain coat method, etc., alone or in combination It is good to apply. After applying and drying the aqueous coating solution on the polyester film which has been subjected to the longitudinal stretching and, if necessary, the low-strength transverse stretching, crystal orientation is completed by performing final transverse stretching, and then stabilizing treatment including heat fixing and relaxation treatment. Is carried out, and the specific transfer heat treatment of the present invention is performed to obtain the target support of the present invention. In addition, in order to perform the conveyance heat treatment of the present invention, as described above, the support is slit so that the difference in the crystal orientation of the base is 1 to 25 °, and the slit support is wound on a take-up roll. Thereafter, it is preferable to carry out the transfer heat treatment of the present invention from a take-up roll, whereby a support having further excellent thermal dimensional stability and surface properties can be obtained.

(Transportation heat treatment) In the transfer heat treatment of the support of the present invention, the support is treated in a temperature range of from Tg to the melting point in the range of 0.01 to 3 ° C.
It is preferable to perform heat treatment while transporting under a tension of 0 kg / cm ² . In particular, the temperature Tp (° C.) and the tension Ts during the heat treatment
(Kg / cm ² ), and the transfer heat treatment must be performed under such a condition that the time Tm (min) satisfies the expressions (1) and (2) at the same time. By carrying out in this range, the object of the present invention is to provide a photothermographic material for printing plate making which has excellent dimensional stability even at high temperatures, excellent color reproducibility and processability, and a support for the photothermographic material constituting the same. Body can be provided. If the above formulas (1) and (2) are not satisfied, haze is generated and flatness is deteriorated, which is not preferable.

(Transport Heat Treatment Means) The transfer heat treatment time of the present invention can be controlled by changing the transfer speed of the support or changing the length of the heat treatment zone. If the heat treatment time is too short, the thermal dimensional stability of the support decreases. Further, when the time is 60 minutes or more, the flatness and transparency of the support are deteriorated, and the support is not suitable as the support of the present invention. The transport tension during the heat treatment is desirably as low as possible in order to minimize the effect of the heat treatment of the support, that is, the dimensional change during the subsequent heat treatment (thermal development) without hindering the progress of thermal contraction. However, when the transport tension is too small, the flatness of the support is deteriorated due to a partial difference in thermal shrinkage of the support during the heat treatment, and fine scratches are generated due to friction with the transport rolls. Therefore, the transport tension is preferably 0.01 to 30 kg / cm ² .
It is more preferably 6.0 to 20 kg / cm ² , and still more preferably 4.0 to 10 kg / cm ² . The transport tension of the present invention is obtained by dividing the force applied to the support by the cross-sectional area (width × thickness) of the support.

The change in the transfer tension during the transfer heat treatment of the present invention may be changed oscillatingly, stepwise, or inclinedly. The method is preferably a stepwise and gradient changing method, and more preferably a gradient changing method. Adjustment of the tension of the transfer heat treatment can be easily achieved by adjusting the torque of the winding roll and / or the feeding roll. It can also be achieved by installing a dancer roll in the process and adjusting the load applied thereto. When the tension is changed during heat treatment and / or cooling after heat treatment, before and after these steps and / or
Alternatively, a desired tension state can be produced by installing dancer rolls in the process and adjusting their loads. In order to change the transport tension in a vibrational manner, it is effective to reduce the distance between the heat treatment rolls.

In the transfer heat treatment of the present invention, the method is not particularly limited. For example, a transfer method in which both ends of the support are gripped with pins or clips, roll transfer by a plurality of roll groups, or blowing air onto the support. A method in which the support is continuously conveyed by air conveyance or the like, and heated air is blown onto one or both surfaces of the support from multiple slits, a method using radiant heat from an infrared heater, etc., a plurality of heated rolls And a method of performing heat treatment alone or in combination of a plurality of methods.

The support subjected to the transfer heat treatment of the present invention comprises:
Attention must be paid to the fact that if the support is heated at a temperature of 100 ° C. or more for 30 seconds or more, the effect is reduced. Therefore, the heat treatment of the present invention is preferably performed after the undercoat layer is applied to the support and dried, and before the photographic photosensitive layer is applied. Specifically, after applying and drying the undercoat layer, it may be performed while being kept flat continuously, or, after winding once, installing necessary transport equipment and heating equipment. The re-transport processing may be performed.
Furthermore, after applying and drying various functional layers such as a backing layer, a conductive layer, a slippery layer, and a magnetic recording layer, the same treatment as described above may be performed.

The support which has been transported and heat-treated as described above is cooled from near Tg to room temperature and wound up. In order to maintain the flatness of the support, the cooling at this time is preferably performed at a rate of at least −5 ° C./sec or more to lower the temperature to room temperature over Tg. The support that has been heat-treated in this manner and cooled to room temperature and wound up before being sent to the next process should be wound around a core as large as possible so that it will not easily form a curl. Is preferably 200 mm or more, more preferably 300 mm or more, and still more preferably 400 mm or more.

In the support subjected to such a heat treatment for transfer, the absolute value of the thermal dimensional change at 120 ° C. for 60 seconds in any direction in the film forming width direction is 0.001 to 0.04 in the MD direction.
%, Preferably in the range of 0.001 to 0.04% in the TD direction. The same applies to the case where the photothermographic material is used. The difference between the absolute values of the thermal dimensional change at both ends at 120 ° C. for 60 seconds is 0.02% or less in both the MD and TD directions.
More preferably, it is 0.01% or less. In particular, when it is intended for use as a printed photographic light-sensitive material, the allowable range of the dimensional deviation with respect to the reference length (610 mm) is 75 μm or less, more preferably 50 μm or less, and particularly preferably 30 μm or less in both the MD and TD directions. is there.

[Photothermographic Material] The details of the photothermographic material are described in, for example, US Pat. No. 3,152,904.
No. 3,457,075, and D.C. "Dry Silver Photographic" by Morgan
Material) "and D.M. Morgan
n) and B. Shelly's "ThermalProceed Silver System"
ssed SilverSystems) "(Imaging Processes and Materials (Ima
ging Processes and Materi
als) Neblette Eighth Edition, Sturge (Stu
rge), V.R. Walworth,
A. Shepp Editing, Page 2, 1969
Year).

(Organic Silver Salt) In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid and a heteroorganic acid containing a reducible silver ion source, especially a long chain (10 to 3)
A nitrogen-containing heterocyclic ring having an aliphatic carboxylic acid having 0 (preferably 15 to 25 carbon atoms) is preferred. The ligand is
Organic or inorganic silver salt complexes having a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are described in Research Disclosure (hereinafter also referred to as RD) Nos. 17029 and 29996, and include: salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid). Carboxyalkylthiourea salts of silver (eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); aldehydes Silver complex of a polymer reaction product of a hydroxy-substituted aromatic carboxylic acid with
Aldehydes (formaldehyde, acetaldehyde,
Butyraldehyde), hydroxy-substituted acids (for example,
Salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thiones (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline) -2-thione, and 3-carboxymethyl-4-thiazoline-2-thione), imidazole, pyrazole, urazole, 1,
Complexes or salts of nitrogen acids with silver selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptides, a preferred silver source is silver behenate. The organic silver salt preferably has a silver content of 3
g / m ² or less. More preferably, 2 g / m ²
It is as follows.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver.
The controlled double jet method as described in JP-A No. 3 is preferably used.

(Silver halide grains) The silver halide grains in the present invention are added so as to function as an optical sensor. In order to suppress white turbidity after image formation and obtain good image quality, the average particle size is preferably small, and the average particle size is 0.1 μm or less, more preferably 0.01 μm to 0.1 μm, and particularly preferably 0.1 μm to 0.1 μm. 03 μm to 0.
08 μm is preferred. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. The particles are more preferably 30% or less, particularly preferably 0.1% or more and 20% or less.

Monodispersity (%) = (standard deviation of particle size) /
(Average value of grain size) × 100 In the present invention, the silver halide grains have an average grain size of 0.1.
μm or less and more preferably monodisperse particles,
By setting the content in this range, the image granularity is also improved. There is no particular limitation on the shape of the silver halide grains, but it is preferable that the proportion occupied by the Miller index [100] plane is high,
This ratio is 50% or more, further 70% or more, especially 80%
It is preferable that it is above. The ratio of the Miller index [100] plane is [111] plane and [10] in the adsorption of the sensitizing dye.
0] utilizing the adsorption dependency on the surface. Tani, J .; I
imaging Sci. , 29, 165 (1985).

Another preferred form of silver halide grains is tabular grains. The term "tabular grains" as used herein refers to those having an aspect ratio = r / h of 3 or more, where the square root of the projected area is r μm and the vertical thickness is h μm. Among them, the aspect ratio is preferably in the range of 3 to 50. Further, the particle size is preferably 0.1 μm or less, and more preferably 0.01 to 0.08 μm. These are U.S. Pat. No. 5,264,337,
No. 5,314,798, 5,320,958, etc., and the target tabular grains can be easily obtained. In the present invention, when these tabular grains are used, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used.
Any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. The silver halide grains may be added to the image forming layer by any method, wherein the silver halide grains are arranged so as to be close to a reducible silver source. Further, the silver halide grains may be prepared by converting a part or all of silver in the organic acid silver by the reaction between the organic acid silver and the halogen ion to the silver halide grains, or the silver halide grains may be prepared. It may be prepared in advance and added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, silver halide grains are preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide grains used in the present invention preferably contain ions or complex ions of metals belonging to Groups 6 to 10 of the periodic table. Examples of the above metals include W, Fe, Co, Ni, Cu, Ru, and R.
h, Pd, Re, Os, Ir, Pt, and Au are preferred,
Above all, when used for a photosensitive material for printing plate making, Rh, R
It is preferable to be selected from e, Ru, Ir, and Os.

These metals can be introduced into the silver halide grains in the form of a complex. In the present invention, the transition metal complex is
A six-coordinate complex represented by the following general formula is preferred.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0, 1-, 2-, or 3-.
Or 4-. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different. Particularly preferred specific examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), and osmium (Os).

Specific examples of the transition metal coordination complex are shown below. 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^4- 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^{2 -} 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: _{[Os (NS) Cl 4 (TeCN} ) ] ^{2 -} 23: [Ru (NS) C _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^2- of these metals One kind of ion or complex ion may be used, or two or more kinds of the same kind of metal and different kinds of metal may be used in combination. The content of these metal ions or complex ions is generally 1 × 10 ⁻⁹ per mol of silver halide.
~ 1 × 10 ^-2 mol is suitable, preferably 1 × 10 ^-8 mol.
１1 × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation.
In the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added to the silver halide grains as described in JP-A-63-29603 and JP-A-2-3062.
No. 36, No. 3-167545, No. 4-76534,
As described in JP-A-6-110146, JP-A-5-273683 and the like, the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during particle formation, or a silver salt solution and a halide solution are mixed simultaneously. A method of preparing silver halide grains by a method of simultaneous mixing of three liquids, adding a required amount of an aqueous solution of a metal compound to a reaction vessel during grain formation, or adding a third solution at the time of silver halide preparation. There is a method in which another silver halide grain doped with metal ions or complex ions in advance is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution of a metal compound and NaCl dissolved in a water-soluble halide solution is preferable. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

(Reducing Agent) Examples of the reducing agent contained in the coating solution of the present invention include generally known reducing agents, such as phenols, polyphenols having two or more phenol groups, naphthols and bisphenols. Naphthols, polyhydroxybenzenes having two or more hydroxyl groups, polyhydroxynaphthalenes having two or more hydroxyl groups, ascorbic acids, 3-pyrazolidones, pyrazolin-5-ones, pyrazolines, phenylenediamines, hydroxyl There are amines, hydroquinone monoethers, hydroxamic acids, hydrazides, amide oximes, N-hydroxyureas, and the like. More specifically, for example, U.S. Patent Nos. 3,615,533 and 3,679, No. 426, No. 3,672,904, No. 3,751, 25 Nos., The No. 3,782,949,
Nos. 3,801,321 and 3,794,488
No. 3,893,863, No. 3,887,37
No. 6, No. 3,770,448, No. 3,819,3
No. 82, No. 3,773, 512, No. 3, 839,
No. 048, No. 3,887,378, No. 4,00
9,039, 4,021,240, British Patent 1,486,148 or Belgian Patent 786.
086, etc. and JP-A-50-36143,
No. 50-36110, No. 50-116023, No. 5
Nos. 0-99719, 50-140113, 51-
No. 51933, No. 51-23721, No. 52-847
There are reducing agents specifically exemplified in each publication such as No. 27 or JP-B-51-35851, and the present invention can be appropriately selected from such known reducing agents and used.

Among the above reducing agents, when an aliphatic silver carboxylate is used as the organic silver salt, preferred reducing agents include polyphenols in which two or more phenol groups are linked by an alkylene group or sulfur. In particular, an alkyl group (eg, methyl group, ethyl group, propyl group, t-butyl group, cyclohexyl group, etc.) or an acyl group (eg, acetyl group, propionyl group, etc.) is provided at at least one of the positions adjacent to the hydroxy substitution position of the phenol group. Are polyphenols in which two or more of the phenol groups substituted by an alkylene group or sulfur, for example, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
5-trimethylhexane, 1,1-bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane,
1,1-bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2-hydroxy-3-tert-butyl-5-methylphenyl-2'-hydroxy-5'-methylphenylmethane, 6,6'-benzylidene-bis (2,4-di-t-butylphenol), 6,6'-benzylidene-bis (2-t-butyl-4-methylphenol), 6,6'-benzylidene-bis ( 2,4-dimethylphenol), 1,1-bis (2-hydroxy-
3,5-dimethylphenyl) -2-methylpropane,
1,1,5,5-tetrakis (2-hydroxy-3,5
-Dimethylphenyl) -2,4-ethylpentane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5
-Di-t-butylphenyl) propane and the like, and U.S. Pat. Nos. 3,589,903 and 4,021,249 or British Patent No. 1,486,148 and JP-A-51-148. Nos. 51933, 50-36110, 50-116023, 52-84727 and JP-B-51-35727, and polyphenol compounds described in U.S. Pat. No. 3,672,904. Bisnaphthols such as 2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl,
6,6'-dinitro-2,2'-dihydroxy-1,
1'-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, 4,4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl and the like, and U.S. Pat.
Sulphonamidophenols or sulphonamidonaphthols as described in U.S. Pat.
For example, 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-
Examples thereof include 4-benzenesulfonamidophenol and 4-benzenesulfonamidonaphthol.

The amount of the reducing agent contained in the coating solution in the present invention varies depending on the type of the organic silver salt and the reducing agent, and other additives.
5 to 10 mol, preferably 0.1 to 3 mol is suitable. Further, within this range, two or more of the above-mentioned reducing agents may be used in combination. In the present invention, it may be preferable to add and mix the reducing agent to the photosensitive solution immediately before coating and apply the reduced solution because the photographic performance fluctuation due to the stagnation time of the photosensitive solution is small.

(High contrast agent) The photothermographic material of the present invention preferably contains a hydrazine derivative as a high contrast agent. As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0067]

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In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group which may have a substituent.
B ₀ represents a blocking group, and A ₁ and A ₂ each represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. Here, G ₀ is -CO-
Group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )
— Group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D
₁ ) represents a group, G ₁ represents a mere bond, an —O— group, —S—
Group or -N (D ₁₎ - represents a group, D ₁ is an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, for example, a benzene ring or a naphthalene ring, and a heterocyclic ring represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring, and, -G ₀ -D ₀ group odor represented by A _0, G ₀ represents -CO-
Group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )
— Group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D
₁ )-represents a group. G ₁ is a mere bond, -O- group, -S-
Group or -N (D ₁₎ - represents a group, D ₁ is an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
It represents an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ includes a hydrogen atom, an alkyl group, an alkoxy group, an amino group, and the like. Aromatic groups A _0, heterocyclic group or -G ₀ -D ₀ group may have a substituent. Particularly preferred as A ₀ is an aryl group or -G ₀ -D ₀ group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, a photographically inert alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, Examples thereof include a phenoxy group and an alkylphenoxy group, and the total number of carbon atoms in the substituent is preferably 8 or more.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439, for example.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — represents a group. Preferred G ₀ is -CO-
Group, -COCO- group, G ₁ is a mere bond,
—O—, —S— or —N (D ₁ ) —, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D ₁ are present in the molecule If so, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or an oxalyl group (Such as an ethoxalyl group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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Other hydrazine derivatives which can be preferably used include compounds H-1 to H-20 described in US Pat. No. 5,545,505, columns 11 to 20.
-29, compounds 1 to 12 described in U.S. Pat. No. 5,464,738, column 9 to column 11. These hydrazine derivatives can be synthesized by a known method. The hydrazine derivative-added layer is a photosensitive layer containing a silver halide emulsion and / or a layer adjacent to the photosensitive layer. Further, the amount added is the particle size of the silver halide grains, the halogen composition,
The extent of chemical sensitization, although the optimum amount is not uniform such as type of inhibitor per mole of silver halide 10 ^-6 mol to 10
^The preferred range is about ^-1 mol, particularly 10 ^-5 mol to 10 ^-2 mol.

(High contrast accelerator) The photothermographic material of the present invention includes a hydroxylamine compound, an alkanolamine compound and an ammonium phthalate compound described in US Pat. No. 5,545,505, and US Pat. Fifth
No. 545,507, the hydroxamic acid compound described in U.S. Pat. No. 5,558,983.
-Acyl-hydrazine compounds, U.S. Pat. No. 5,545,545
High-contrast compounds such as acrylonitrilo compounds described in US Pat. No. 515, hydrogen atom donor compounds such as benzhydrol, diphenylphosphine, dialkylpiperidine and alkyl-β-ketoester described in US Pat. No. 5,937,449. It is preferable to add a chemical accelerator. Among them, a quaternary onium compound represented by the following general formula (P) and an amino compound represented by the general formula [Na] are preferably used. Hereinafter, 4 represented by the general formula (P)
The onium compound will be described.

[0083]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Note that R _{1 to} R ₄ may be connected to each other to form a ring.

In the general formula (P), substituents represented by R _{1 to} R ₄ include alkyl groups (methyl group, ethyl group,
Propyl group, butyl group, hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (Piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), amino group and the like.

The ring which may be formed by connecting R _{1 to} R ₄ to each other includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are a hydroxyl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group. As R, R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferable. X ^- include anions represented by halogen ions, sulfate ion, nitrate ion, acetate ion,
Examples include inorganic and organic anions such as p-toluenesulfonic acid ion. More preferably, the following general formula (P
a), compounds represented by (Pb) and (Pc), and compounds represented by the following general formula [T].
a), (Pb) and (Pc) will be described.

[0088]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, an aryloxy group, an amide group, and sulfamoyl. Group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group.
Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include 5
And 6-membered rings (rings such as pyridine, imidazole, thiozole, oxazole, pyrazine and pyrimidine), and a more preferred example is a pyridine ring. B _p represents a divalent linking group, and m represents 0 or 1.
Examples of the divalent linking group include an alkylene group, an arylene group,
Alkenylene _{group, -SO 2 -, - SO -} , - O -, - S
—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group. R ¹ , R ² and R ⁵ each represent an alkyl group having 1 to 20 carbon atoms. Further, R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group. X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

Hereinafter, the general formula [T] will be described.

[0092]

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The substituents R ₅ , R ₆ and R ₇ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T]
Is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property. Hammett's sigma value at the phenyl group has been described in many literatures, for example, Journal of Medical Chemistry (Journalof).
Medical Chemistry) Volume 20, 30
4, page 1977. Hansch (C. Hansc)
h) and the like, and a particularly preferable group having a negative sigma value is, for example, a methyl group (σP = −
.Sigma.P value of 0.17 or less, ethyl group (-0.1
5), cyclopropyl group (-0.21), n-propyl group (-0.13), iso-propyl group (-0.1
5), cyclobutyl group (-0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n
-Pentyl group (-0.15), cyclohexyl group (-
0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27), ethoxy group (-0.24) ,
Propoxy group (-0.25), butoxy group (-0.3
2), a pentoxy group (-0.34) and the like, all of which are useful as substituents of the compound of the general formula [T]. n represents 1 or 2, and as the anion represented by X _T ^n- , for example, a chloride ion, a bromide ion, a halide ion such as an iodide ion, an acid radical of an inorganic acid such as nitric acid, sulfuric acid, and perchloric acid; Acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically lower alkylbenzene sulfonic acid anions such as p-toluene sulfonic acid anion and higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion , Higher alkyl sulfate anions such as lauryl sulfate anion, borate-based anions such as tetraphenylboron,
Examples thereof include dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anion, higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid root such as polyacrylate anion.

The following formulas (P), (Pa) and (Pb)
Specific examples of the quaternary onium compound included in (Pc) and (Pc) are shown below, but are not limited thereto.

[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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Further, specific examples of the quaternary onium compound included in the general formula [T] are shown below, but are not limited thereto.

[0105]

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews 55 p. 33
The method described in 5-483 can be referred to. The addition amount of these quaternary onium compounds is 1 per mole of silver halide.
× 10 ^-8 to about 1 mol, preferably 1 × 10 ^-7 to 1 × 1
0 ^-1 mol. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

Next, the general formula [Na] which is an amine compound will be described.

[0108]

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In the general formula [Na], R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, a substituted aryl group or a saturated or unsaturated group. Represents a saturated heterocycle. R ₁₁ , R ₁₂ and R ₁₃ may form a ring. Particularly preferred are aliphatic tertiary amine compounds.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. Molecular weight 100 or more compounds are preferred in order to have a diffusion-resistant, still more preferably a molecular weight of 300 or more, include those having the same meaning as non-diffusible group in A ₀ in the general formula (H).
Further, preferred adsorbing groups include a heterocyclic ring, a mercapto group,
Examples include a thioether group, a thione group, and a thiourea group.

[0110] More preferred contrast enhancement accelerators than those represented by the general formula [Na] are those represented by the following general formula [Na].
2].

[0111]

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In the general formula [Na2], R ¹ , R ² , R
³ and R ⁴ are each a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group,
Represents a substituted alkynyl group, an aryl group, a substituted aryl group or a saturated or unsaturated heterocyclic ring. These can be linked to each other to form a ring. Also, R ¹ and R ² , R
³ and R ⁴ are not hydrogen atoms at the same time. X is S, S
represents an e or Te atom. L ¹ and L ² each represent a divalent linking group. Specific examples include the following groups, combinations thereof, and groups having an appropriate substituent (eg, an alkylene group, an alkenylene group, an arylene group, an acylamino group, a sulfonamide group, and the like).

-CH _2- , -CH = CH-, -C ₂ H
₄ -, _{pyridinediyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an alkyl group or an aryl group), - O -, - S
-, - (CO) -, - (SO 2) -, - CH = N-.

Further, the linking group represented by L ¹ or L ² preferably contains at least one or more of the following structures in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ )
HCH ₂ O] -, - [OC (CH ₃₎ HCH ₂ O] -, -
[OCH ₂ C (OH) HCH _2] -.

In the following, a compound represented by the general formula [Na] or [Na2]
Specific examples of the hardening accelerator represented by are given below.

[0117]

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[0118]

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[0119]

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[0120]

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The above quaternary onium compounds and amino compounds may be used alone or in combination of two or more. It may be added to any of the constituent layers of the photothermographic material, but is preferably added to at least one of the constituent layers on the side having the photosensitive layer, and further to the photosensitive layer and / or its adjacent layer.

(Binder) Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and may be any of natural polymers and synthetic resins, polymers and copolymers, other media for forming films, For example: gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (methyl methacrylic acid) Vinyl), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl) Butyral ), Poly (esters),
There are poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). Although it may be hydrophilic or hydrophobic, in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after thermal development. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, and cellulose acetate butyrate are particularly preferably used. Further, a hydrophobic binder and a hydrophilic binder may be used in combination.

In the present invention, the binder amount of the photosensitive layer is preferably 1.5 to 10 g / m ² in order to increase the speed of thermal development. More preferably, 1.7 to 8 g /
m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

(Mat Agent) In the present invention, a mat agent is preferably contained on the photosensitive layer side, and a mat agent is provided on the surface of the photothermographic material in order to prevent damage to the image after heat development. It is preferable that the matting agent is contained in a mass ratio of 0.5 to 30% with respect to all binders on the photosensitive layer side. When a non-photosensitive layer is provided on the opposite side of the photosensitive layer with respect to the support, at least one non-photosensitive layer on the non-photosensitive layer side is provided.
The layer preferably contains a matting agent, and a matting agent is preferably provided on the surface of the photothermographic material in order to prevent slippage and fingerprint adhesion of the photothermographic material. It is preferable to contain 0.5 to 40% by mass of all binders in the layer on the side. The shape of the matting agent may be either a fixed shape or an irregular shape, but is preferably a fixed shape, and a spherical shape is preferably used.

(Protective Layer) In order to protect the surface of the photothermographic material and prevent abrasion, a non-photosensitive layer may be provided outside the photosensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers. Usually, a polymer having a softening point higher than that of the binder polymer constituting the photosensitive layer is used to prevent abrasion, phase deformation, and the like. For example, cellulose acetate and cellulose acetate butyrate serve this purpose.

(Other Layers) The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer.
In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer on the opposite side, a so-called backing layer, may be formed. Dyes or pigments may be included. These non-photosensitive layers preferably contain the binder or matting agent described above, and may further contain a sliding agent such as a polysiloxane compound, wax or liquid paraffin. Further, in the photothermographic material of the present invention, various surfactants are used as a coating aid. Among them, a fluorine-based surfactant is preferably used for improving charging characteristics and preventing spot-like coating failure. The photosensitive layer may have a plurality of layers, and the sensitivity may be a high-sensitivity photosensitive layer / a low-sensitivity photosensitive layer or a low-sensitivity photosensitive layer / a high-sensitivity photosensitive layer for adjusting the gradation.

(Tone) The photothermographic material of the present invention includes:
It is preferred to add a toning agent, and examples of suitable toning agents are disclosed in RD 17029.

(Inhibitors) The photothermographic material of the present invention may contain mercapto in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve preservability before and after development. Compounds, disulfide compounds, and thione compounds can be contained.

In addition, if necessary, an antifoggant and the like can be contained. The above various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers.
The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. These additives and the other additives described above are described in RD 17029 (pp. 9-1 of June 1978).
The compounds described in 5) can be preferably used.

[0130]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto. The methods for measuring and evaluating the orientation angle and each characteristic value described in the examples are as follows.

[Thermal Dimensional Change (Heat Shrinkage)] As a measurement sample, the widthwise central portion of the support or the photothermographic material of Table 2 subjected to the heat treatment under the transfer heat treatment conditions of Table 1 was 150 mm.
(Longitudinal direction) × 150 mm (width direction) was used. After conditioning these samples for one day under the conditions of 23 ° C. and 55% RH, scribe lines at 100 mm intervals were drawn in the longitudinal direction on the upper side (the side on which the undercoat layer or the photosensitive layer is provided) and heated to 120 ° C. It was pressed against a hot plate (EC-1200 manufactured by Inuchi Seieido Co., Ltd.) for 60 seconds, and after adjusting the humidity for 1 day under the conditions of 23 ° C. and 55% RH, the interval between the scored lines was measured. The measurement is performed vertically and horizontally,
The difference between the intervals between the scored lines before and after the heat treatment is calculated and expressed as a percentage of the interval before the heat treatment, and the longitudinal thermal dimensional change rate (MD
(%)) And the transverse thermal dimensional change (TD (%)). In addition, the measurement was performed every five sheets, and the average value thereof was used as the measured value.

[Flatness] As a measurement sample, a sample obtained by cutting out the central part in the width direction of the support subjected to the heat treatment for conveyance shown in Table 1 to 500 mm (longitudinal direction) × 500 mm (width direction) was used. This sample was conditioned for one day under the conditions of 23 ° C. and 55% RH, and then placed on a horizontal table (undercoat layer side up).
It was placed and the height (mm) of the support raised from the table was measured with a caliper. The highest height among them was used as a measure of flatness.

[Scratchability] As a measurement sample, a sample obtained by cutting out the central part in the width direction of the support subjected to the transfer heat treatment shown in Table 1 to 20 mm (longitudinal direction) × 20 mm (width direction) was used. After the sample was conditioned for one day under the conditions of 23 ° C. and 55% RH, the number of scratches on the undercoat layer side was evaluated using a polarizing microscope.

[Surface Roughness] As a measurement sample, a sample obtained by cutting out the center part in the width direction of the support subjected to the transfer heat treatment shown in Table 1 to 20 mm (longitudinal direction) × 20 mm (width direction) was used. This sample was conditioned for one day under the conditions of 23 ° C. and 55% RH, and then three-dimensional surface roughness meter RS-plus manufactured by WYKO Co.
Was used to measure the surface roughness Ra (μm) on the undercoat layer side of each support at a magnification of 40 times.

[Adhesion] The center of the photothermographic material of Table 2 in the width direction as a measurement sample was measured to be 100 mm (longitudinal direction) × 1.
What was cut out to 00 mm (width direction) was used. Using a razor, the surface of the surface of the sample on which the photosensitive layer was coated was scratched 6 times each at 4 mm intervals in the vertical and horizontal directions.
I made 25 squares. However, the scratch was made at a depth reaching the surface of the support from the photosensitive layer. A mylar tape having a width of 25 mm was stuck thereon and sufficiently pressed. Five minutes after the pressure bonding, the Mylar tape was rapidly pulled at a peeling angle of 180 ° and peeled from the sample. This is defined as raw (before treatment) adhesiveness. At this time, the number of cells where the photosensitive layer was peeled off from the sample was counted and classified as follows. A is practically acceptable
And B.

(Evaluation Criteria) A: 0 squares of peeling B; 1 to 5 squares of peeling C; 6 to 9 squares of peeling D: 10 squares or more The same evaluation was performed for the sample thus obtained. This was defined as the adhesion after the treatment.

[Creep Deformation (μm)] The principle of the measuring method has been described above, but will be described more specifically below.

As a measurement sample, a sample cut into a support of 10 mm (longitudinal direction) × 10 mm (width direction) was used. Using a silicon wafer wetted with water in close contact with the undercoat layer side of this sample, a load of 3 g was applied to the indenter of the hardness meter MZT-3 placed thereon for 1 second over this time. the creep deformation amount of the support h ₁ (μm)
Then, the amount of creep deformation h ₂ (μm) when the pressurization was continued for 30 seconds while applying the load of 3 g described above was measured, and the difference (h ₂ −h ₁ ) in the amount of creep deformation was determined according to the present invention. Of the sample was determined.

[Orientation Angle (°)] A sample cut out from a support of 50 mm (longitudinal direction) × 50 mm (width direction) was used as a measurement sample. This sample was sandwiched between two polarizing plates of a polarizing plate measuring apparatus, and the rotation angle at which the transmitted light was minimized while rotating the measurement sample was determined. Also,
The orientation angle difference in the width direction indicates the difference between the maximum orientation angle and the minimum orientation angle in the sample.

[Preparation of Support] PET was prepared as follows.
A resin was obtained.

(Preparation of PET resin) To 100 parts by mass of dimethyl terephthalate and 65 parts by mass of ethylene glycol, 0.05 parts by mass of magnesium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. To the obtained product, 0.05 parts by mass of antimony trioxide and 0.03 parts by mass of trimethyl phosphate were added. Then, the temperature was gradually raised and reduced to 280 ° C. and 0.5 mmH.
g of PET (polyethylene terephthalate) resin having an intrinsic viscosity of 0.70.

Using the PET resin obtained as described above, a PET film was obtained in the following manner.
A support was prepared by providing an undercoat layer on the film.

(Formation of PET Film and Undercoat Layer) PE
The pelletized T resin was vacuum-dried at 150 ° C. for 8 hours, melted and extruded at 285 ° C. from a T-die in a layered form, adhered to a 30 ° C. cooling drum while applying static electricity, cooled and solidified, and then cooled. A stretched film was obtained. This unstretched film was stretched 3.3 times in the machine direction at 80 ° C. using a roll-type longitudinal stretching machine. Table 1 shows the obtained uniaxially stretched film.
An aqueous coating solution (solid content: 4% by mass) composed of the resin and inorganic particles (composition ratio 9: 1) shown in (1) was applied to one surface by a kiss coat method so as to have a WET film thickness of 2 g / m ^2. A finished film was obtained. Subsequently, the obtained undercoated film is stretched by a tenter-type transverse stretching machine at 50% of the total transverse stretching ratio at a first stretching zone of 90 ° C, and further at a second stretching zone of 100 ° C at a total transverse stretching ratio of 3. The film was stretched three times. Next, a pre-heat treatment was performed at 70 ° C. for 2 seconds, followed by heat setting at 150 ° C. in the first fixing zone for 5 seconds and heat setting at 220 ° C. in the second fixing zone for 15 seconds. Next, the film is subjected to a 5% relaxation treatment in the transverse (width) direction at 160 ° C., and after leaving the tenter-type transverse stretching machine, is subjected to a relaxation treatment in the longitudinal (longitudinal) direction at 140 ° C. by utilizing the peripheral speed difference of the driving roll. After cooling to room temperature over 60 seconds, eight types of supports were obtained. The obtained support was released from the clip, slit so as to have the orientation angle difference shown in Table 1, and wound up to obtain eight kinds of slit-supported supports 1 to 8 having a thickness of 125 μm shown in Table 1. The Tg of these supports was 79 ° C.

(Heat transfer heat treatment of support) The transfer speed was adjusted so that the eight heat treatment zones having a total length of 200 m set to the temperature and tension shown in Table 1 were set to the time shown in Table 1 on the eight kinds of slitted supports. Then, the substrate is subjected to a heat treatment for transport, and further cooled to room temperature at a rate of 10 ° C./min, and then wound up. , Flatness and abrasion were evaluated, and the results are shown in Table 1.

[0145]

[Table 1]

When the supports of Examples in Table 1 were heat-treated under the pull-down conditions of Table 1 and the heat treatment conditions of Table 1, the thermal dimensional change was small, the flatness, the amount of creep deformation, the surface roughness, and the abrasion resistance were low. All of them are excellent, but it is understood that the support of the comparative example is inferior in any of those properties and is poor in practicality.

[Preparation of Photothermographic Material] (Preparation of Silver Halide Emulsion A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, and the temperature was adjusted to 35 ° C. and the pH to 3.0. Later, silver nitrate 74
g of an aqueous solution containing 370 ml of sodium chloride, potassium bromide, potassium iodide and [Ir (NO) Cl ₅ ] salt in a molar ratio of (60/38/2) at 1 × 10 ⁻⁶ per mol of silver.
370 ml of an aqueous solution containing 1.times.10.sup.- ⁶ moles per mole of silver and a rhodium chloride salt was added by a controlled double jet method while maintaining a pAg of 7.7. Then 4
By adding -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, adjusting the pH to 8 with NaOH, and adjusting the pAg to 6.5, reduction sensitization was performed, and the average particle size was 0.06 μm. Cubic silver iodobromide grains having a monodispersity of 10%, a variation coefficient of the projected diameter area of 8%, and a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting, and then 0.1 g of phenoxyethanol was added.
H5.9 and pAg were adjusted to 7.5 to obtain silver halide emulsion A.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion) 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with sodium hydroxide solution.
147 ml of a silver nitrate solution of M was added over 7 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, water was removed, washed six times with water and removed, and then dried to obtain a preform emulsion.

(Preparation of Photosensitive Emulsion) The preform emulsion was divided into halves, and a solution of polyvinyl butyral (average molecular weight: 3000) in methyl ethyl ketone (17w) was prepared.
t%) 544 g and toluene 107 g were gradually added and mixed, and then a medium disperser using a 0.5 mm size ZrO ₂ bead mill at 4000 psi at 30 ° C. and 10 ° C.
Minutes of dispersion. Five types of supports used in Table 1 (Comparative Supports 1, 4 and Example Supports 5, 7, 8)
Then, the following layers were simultaneously coated on both sides at a drying temperature of 80 ° C. to prepare five types of photothermographic materials (comparative photothermographic materials 1, 2 and Example photothermographic materials 3, 4, 5). did. Each of the photothermographic materials was formed into a roll having a width of 590 mm, and was packed in a light room. The dimensional change rates of the obtained five types of photothermographic materials (the photothermographic materials using the supports of Comparative Examples 1 and 4 and the photothermographic materials using the supports of Examples 5, 7, and 8) and The adhesiveness before the treatment and the adhesiveness after the treatment were measured, and the results are shown in Table 2.

(Coating on Back Side) A liquid having the following composition was applied to the back side of the support 1.

Cellulose acetate butyrate (10% methyl ethyl ketone solution) 15 ml / m ² Dye-A 7 mg / m ² Dye-B 7 mg / m ² Matting agent: Monodispersity 15% Average particle size 8 μm Monodisperse silica 90 mg / m ² _{C 8 F 17 (CH 2 CH} 2 O) 12 C 8 F 17 50mg / m 2 C 9 F 17 -C 6 H 4 -SO 3 Na 10mg / m 2

[0153]

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(Coating on Photosensitive Layer Side) Photosensitive Layer 1: A solution having the following composition was coated on the upper side of Support 1 (photosensitive layer side) so that the coated silver amount was 2.1 g / m ² .

The photosensitive emulsion 240 g The following sensitizing dye (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Oxidizing agent (10% methanol solution) 1.2 ml 2,4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml) Hydrazine derivative H-26 0.4 g Hardening accelerator P-51 0.3 g Phthalazine 0.6 g 4-Methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g Calcium carbonate having an average particle size of 3 μm 0.1 g 1, 1-bis (2-hydroxy-3,5-dimethylphenyi ) -2 - methylpropane (20% methanol solution) 20.5 ml isocyanate compound (Mobay Corp., Desmodur N3300) 0.5 g

[0156]

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Surface protective layer: A solution having the following composition was applied simultaneously on the photosensitive layer. Acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² methanol 7 ml / m ² phthalazine 250 mg / m ² Matting agent: monodisperse degree of 10% average particle size 4μm monodisperse silica 5 mg / m ² CH ₂ = CHSO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH = CH ₂ 35 mg / m ² Fluorosurfactant C ₁₂ F ₂₅ (CH ₂ CH ₂ O) ₁₀ C ₁₂ F ₂₅ 10 mg / m ² C ₈ F _{17 -C 6 H 4 -SO 3 Na} 10mg / m 2

[0158]

[Table 2]

From Table 2, it can be seen that the photothermographic material using the support of the present invention has a small dimensional change during heat treatment and has good thermal stability and adhesiveness.

[0160]

As demonstrated by the examples, the support for a photothermographic material of the present invention is excellent in various physical properties such as creep deformation, surface roughness, thermal dimensional stability, flatness, and scratch resistance. In addition, the photothermographic material using the photothermographic material support has effects such as excellent adhesive properties of the photosensitive layer to the support in addition to the excellent physical properties.

[Brief description of the drawings]

FIG. 1 is a diagram showing a change in a creep deformation amount of a support.

[Explanation of symbols]

A The point at which the increase in the load was stopped (t ₁ , h ₁ ), the point at which the load was switched to the constant load t ₀ Initial measurement (0 sec) h _{0 The} initial measurement (0 μm) t _{1 The time at which the} increased load was switched to the constant load h ₁ in that the increased load is the amount of deformation B de load when switched to a constant load _{(t 2, h 2) t} 2 deformation at the time of switching the time h ₂ constant load switching the constant load de load de-loading Amount C The point at which the reduced amount of deformation becomes substantially constant (t ₃ , h ₃ ) t ₃ Time at which the change amount becomes almost constant after unloading and the measurement ends h ₃ Change amount at which the unloading becomes almost constant

Claims (9)

[Claims] 1. A polyester fiber before completion of crystal orientation.
Resin and glass having a glass transition point of 40 ° C or higher on film
Apply an aqueous coating solution containing particles and dry to form an undercoat layer
And then stretched, heat-set and relaxed to produce
A method for producing a support for a photothermographic material, comprising:
After applying heat setting and relaxation treatment, the following formula (1) and formula
Temperature Tp (° C.) and tension Ts (k) that simultaneously satisfy (2)
g / cm ^Two), Heat-treating at time Tm (min)
A method for producing a support for a photothermographic material, comprising: Equation (1) 6.0 ≦ Q ≦ 7.4 Equation (2) 1.8 ≦ (Q / Ts) ≦ 5.0 where Q = (Tp / 25) + log (Tm) 2. The resin having a glass transition point of at least 40 ° C. selected from a polyester resin, an acrylic resin, an acryl-modified polyester resin and a urethane resin.
The method for producing a support for photothermographic materials according to claim 1, wherein the support is composed of a seed. 3. After forming, stretching, heat-setting and relaxing the undercoat layer on the polyester film, slit the film so that the difference in the orientation angle is 1 to 25 °, and apply the film to a winding roll. The method for producing a support for a photothermographic material according to claim 1, wherein the support is subjected to a heat treatment for transporting the film from the winding roll. 4. A support for a photothermographic material produced by the method for producing a support for a photothermographic material according to claim 1. 5. A support for a photothermographic material, comprising a biaxially stretched polyester film containing polyethylene terephthalate as a main component and having an undercoat layer, wherein the support is subjected to a heat treatment at 120 ° C. for 60 seconds. The thermal dimensional change rate at the time of performing is 0.001 to 0.04%, the glass transition point of the undercoat layer is 40 ° C. or more, and the surface roughness Ra
Is 0.3 to 5.0 [mu] m. 6. A support for a photothermographic material comprising a biaxially stretched polyester film containing polyethylene terephthalate as a main component and having an undercoat layer, wherein the support is subjected to a heat treatment at 120 ° C. for 60 seconds. The thermal dimensional change rate at the time of performing is 0.001 to 0.04%, the creep deformation is 0.3 to 0.8 μm, and the surface roughness Ra is
Is 0.3 to 5.0 [mu] m. 7. The photothermographic material support according to claim 5, wherein the difference in the orientation angle in the biaxially stretched polyester film is 1 to 25 °. 8. A photothermographic material using the photothermographic material support according to claim 4. Description: 9. The photothermographic material according to claim 8, further comprising a layer containing a hydrazine compound on the photothermographic material support.