JP2003035944A - Method for thermally developing thermally developable photographic sensitive material and its thermally developable sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for thermally developing a thermally developable photographic sensitive material having good flatness after thermal development and free of a print blur fault. SOLUTION: In the method for thermally developing a thermally developable photographic sensitive material, the thermally developable photographic sensitive material which ensures 0 mm/50 cm to 4 mm/50 cm respective curvature quantities of the end parts of four sides after thermal development and undergoes -0.05 to +0.05% dimensional change under heating at 120 deg.C for 30 sec in both the longitudinal direction and width direction is thermally developed after heating at 1-15 deg.C/sec.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat developing method for a photothermographic material and a photothermographic material obtained thereby.

[0002]

2. Description of the Related Art Conventionally, a silver halide photographic light-sensitive material is wet-developed by using a developer after photographing. However, this method has the following problems and has been desired to be improved. Since development, bleaching, fixing, and drying are performed, development processing requires time. Since a plurality of tanks containing the developing solution are required, the developing machine cannot be made compact and lightweight. It requires time and labor such as replenishment of the developing solution, disposal and cleaning of the developing tank. To improve this, US Pat. No. 3,152,904,
U.S. Pat. No. 3,457,075, Japanese Patent Publication No. 43-4921
No. 4, pp. 4924, and the like, a photographic light-sensitive material using a developing method by heat at 80 to 150 ° C. (hereinafter sometimes abbreviated as heat development) is proposed.
As one example of this, a precursor of a developing agent is previously contained in the photosensitive layer, and this is decomposed by heat to obtain a developing agent,
Examples include a method of developing. In such a heat development system, the development process can be performed in a short time by only applying heat, and the developing machine can be downsized. Furthermore, it has the feature that there is no need to worry about replenishment or disposal of the developer. However, when this type of photosensitive material is used as the printing photosensitive material, image distortion or 4th plate (blue, blue,
A color shift of green, red, and black) occurred. In order to solve this, Japanese Unexamined Patent Publication No. 8-212547 discloses a technique of heat-treating a support with low tension. However, in this method, after the heat development treatment, the photothermographic material is contact-exposed to a printing plate (PS plate), and then a failure called "burning" occurs on the PS plate, and improvement is desired. It was This burn-in defect is a focus blur defect that occurs when the flatness of the photosensitive material after heat development is deteriorated and locally rises. Is 4
5 cm or more).

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method for thermal development of a photothermographic material which has good flatness after thermal development and does not cause a blurring defect, and a photothermographic material developed by the method. The purpose is to provide.

[0004]

That is, the present invention is as follows.
(1) Each warp amount at the four side edges after heat development is 0
mm / 50 cm or more and 4 mm / 50 cm or less, 120 ° C
A heat-developable photographic material having a thermal dimensional change of −0.05 or more and + 0.05% or less in the longitudinal and width directions for 30 seconds is 1 ° C.
/ Second or more and 15 ° C / second or less, and then heat-developed, followed by heat development. (2) The amount of warp at each end of four sides after heat development 0 mm / 50
cm or more and 4 mm / 50 cm or less, the thermal dimensional change at 120 ° C. for 30 seconds is −0.05 or more +0.0 in both the longitudinal and width directions.
After heat development, the heat developable photographic light sensitive material of 5% or less is -8 ° C.
/ Sec or more and -1 ° C / sec or less, the method for thermal development of a photothermographic material, (3) the amount of each warp at the edges of the four sides after thermal development is 0 mm / 50 cm or more Four
A heat-developable photographic material having a thermal dimensional change of −0.05 or more and + 0.05% or less in the longitudinal and width directions at 120 ° C. for 30 seconds at a temperature of mm / 50 cm or less and a transport tension distribution of 0 or more and 0.
A heat development method for a heat-developable photographic light-sensitive material, wherein the heat development is carried out at a temperature of 80 ° C.
Any of the above (1) to (3), wherein the temperature distribution is not less than 140 ° C and not more than 140 ° C, the temperature distribution in the width direction is not less than 0 ° C and not more than 10 ° C, and the heat development time is not less than 10 seconds and not more than 120 seconds. (5) A method of heat development for a heat-developable photographic light-sensitive material according to item 1.
The heat developing photosensitive material, the undulation of the end of the four sides after thermal development are both ^{0 mm} 2/50 cm or more 500m
characterized in that m is ^2/50 cm or less (1) -
120. The heat development method for a photothermographic material according to any one of (4), (6)
Any of the items (1) to (5) characterized in that the rate of dimensional change of water absorption after heat development at 30 ° C. is 0% / 2 hours or more and 0.025% / 2 hours or less in both the longitudinal and width directions. (7) The method of heat development for a heat-developable photographic light-sensitive material, (7) The support for the heat-developable photographic light-sensitive material is a polyethylene terephthalate film, which is one of (1) to (6). Or (8) the support for the heat-developable photographic light-sensitive material is 140
20 ° C or more and 200 ° C or less, tension 0 kg / m or more and 5 kg / m or less 20
A heat-developable method for a heat-developable photographic light-sensitive material according to any one of (1) to (7), which is a polyethylene terephthalate film heat-treated for at least 2 seconds and not more than 5 minutes; The support of the developed photographic light-sensitive material has a polyvinylidene chloride resin layer of 0.5 μm or more on each side.
It is characterized by being applied below 0 μm (1) ~
The heat development method for a photothermographic material according to any one of (8), and the heat development according to any one of (10), (1) to (9). A heat-developable photographic light-sensitive material, which is a feature of the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION A heat-developable photographic light-sensitive material after heat development (hereinafter sometimes abbreviated as a heat-developable photosensitive material or a heat-developable photosensitive material) is slit on one side with a width of 1 cm and the slit is opposite When the side edges are placed along a straight ruler, if one end of the slit is aligned with the ruler, there will be a gap between the ruler and the ruler. A value obtained by normalizing the distance between the gaps by the length of the slit side is called the warp amount. If the amount of warp is large, the outer peripheral portion of the photosensitive material becomes like an arc, and the peripheral length increases, so that deflection occurs, which causes blurring. The amount of each warp at the four side edges of the photothermographic material of the present invention is preferably 0 mm / 50 cm or more.
mm / 50 cm or less, more preferably 0 mm / 50 cm
3 mm / 50 cm or less, more preferably 0 mm /
It is 50 cm or more and 2 mm / 50 cm or less.

[0006] Thus each undulation of the end of the four sides after thermal development, either ^{0 mm} 2/50 cm or more 500 mm ²
/ 50cm or less, more preferably ^0mm 2 / 50cm
Above 400 mm ^2/50 cm or less, more preferably to below ^{0 mm} 2/50 cm or more 300 mm ^2/50 cm. The amount of waviness is a measurement of a wavy, raised portion that occurs when the heat-developable photosensitive material after heat development is placed on a flat table, and the height (m
m) and the width (mm) are multiplied, and this is added for each side, and standardized by the length of each side. By controlling the warp amount and the waviness amount as described above, the contact exposure to the PS plate can be favorably performed without causing the burning blur.

To achieve such a heat-developable photosensitive material after heat-development, it is necessary to improve the heat-developable photosensitive material and the heat-development method.
Although it is possible to obtain the effect even if there is one or only one, it is most preferable to carry out these in combination. This will be described in detail below.

Improvement of heat-developable light-sensitive material The point in improving the heat-developable light-sensitive material is to reduce dimensional change during heat development. That is, the thermal dimensional change at 120 ° C. for 30 seconds is −0.05% or more +0.05 both in the longitudinal direction (hereinafter referred to as MD) and the width direction (hereinafter referred to as TD).
% Or less, more preferably -0.03% or more and + 0.04% or less, still more preferably -0.02% or more and + 0.04% or less. The heat-developable photosensitive material is roll-fed in the heat-development machine, but since the nip force of the roll is not uniform over the entire width, the heat-developable photosensitive material is partially stretched. Such non-uniformity of the nip force is particularly remarkable at the ends of the four sides of the photothermographic material. For this reason, the ends are easily stretched and easily deformed into a wavy shape.

In order to produce such a heat-developable light-sensitive material having a small heat-dimensional change, the point is to reduce the heat-dimensional change of the support.
This is achieved by heat-treating the support while conveying it with low tension. The heat treatment temperature of the support is preferably 140 ° C. or higher and 200 ° C. or lower, more preferably 145 ° C. or higher and 180 ° C. or lower, and even more preferably 150 ° C. or higher and 165 ° C. or lower. The transport tension is preferably 0 kg / m or more and 5 kg / m or less, more preferably 0 kg / m or more and 4 kg / m or less, and even more preferably 0.5 kg / m or more and 3 kg / m or less. The heat treatment time is preferably 20 seconds or more and 5 minutes or less, more preferably 30 seconds or more and 3 minutes or less, and 45
More preferably, it is not less than 2 seconds and not more than 2 minutes. Such heat treatment may be carried out anywhere after the support is formed and before the photosensitive layer is coated, but more preferably, it is after the back layer is coated and before the photosensitive layer is coated.

The support is polyethylene terephthalate (P
ET), polyesters such as polyethylene naphthalate (PEN), vinyl polymers such as polycarbonate (PC), polyacrylate, syndiotactic polystyrene (SPS), and cellulose polymers such as cellulose triacetate (TAC) are heat-treated with thermoplastic resin. The polyethylene terephthalate film can be used, but PET, PEN, PC, SPS and composites (laminates, blends) of these are preferable, and PET is particularly preferable. The thickness of these supports is preferably 80 μm or more and 200 μm or less, and 95 μm
180 μm or less is more preferable, 100 μm or more 1
It is more preferably 40 μm or less.

Further, the dimensional change in water absorption after heat development at 120 ° C. for 30 seconds is preferably 0% / 2 hours or more and 0.025% / 2 hours or less, and more preferably 0% / 2 hours or more and 0.020%. / 2 hours or less, more preferably 0% / 2
The time is 0.015% / 2 hours or less. Moisture in the photosensitive layer and the support instantly evaporates with heat development, but when left at room temperature, it absorbs water again, and as a result, the heat-developable photosensitive material expands in volume and its dimensions grow with time. The rate of dimensional change in water absorption after thermal development at 120 ° C. refers to this rate of change. That is, the water absorption rate was calculated from the difference between the size immediately after heat development (after 3 minutes) and the size after a predetermined time (2 hours). If this is too large, it means that water absorption occurs rapidly, and just as the paper absorbs water and undulates, the photothermographic material is likely to undulate.

The photothermographic material having such a water absorption dimensional change rate has a polyvinylidene chloride resin layer on each side of the support, preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, Preferably 1.
This can be achieved by applying 5 μm or more and 3 μm or less. Further, it is preferable to use a copolymer of polyvinylidene chloride, and the amount of vinylidene chloride residue contained is 70 to 99.
It is preferably 9% by weight, more preferably 85 to 99% by weight, further preferably 90 to 99% by weight. Methacrylic acid and its esters, methyl methacrylic acid and its esters as copolymerization components other than vinylidene chloride,
Acrylonitrile etc. can be mentioned. The weight average molecular weight of these copolymers is preferably 5,000 or more and 100,000 or less, more preferably 8,000 or more and 80,000 or less, still more preferably 10,000 or more and 45,000 or less. The coating of the polyvinylidene chloride resin on the support may be either a method of dissolving the polyvinylidene chloride resin in an organic solvent and coating or a method of coating a water-dispersed latex, but the latter is more preferable.

Improvement of the heat development method It is more preferable to further improve the heat development method. The point here is to make uniform the transport tension in the thermal processor (to reduce the transport tension distribution). That is, the left and right edges,
The central transport tension is made uniform. The distribution of transport tension can be measured by the following method. 1) Cut the light-sensitive material into a width of a thermal developing machine and a length of 50 cm. This is divided into three equal parts in the width direction. 2) At the same time, this is inserted into the heat developing machine to perform heat developing treatment. 3) Measure the time until the sensitive material is delivered. When there is a distribution of the transport tension, the time for carrying out the sensitive material transported in a portion where the transport tension is large is short, and the time for transporting the sensitive material is long in a weak zone. Therefore, the ratio of transport time {(longest time-shortest time) / shortest time} is equal to the distribution of the ratio of transport tension (transport tension distribution), and the preferred transport tension distribution is 0 or more and 0.5 or less,
It is more preferably 0 or more and 0.2 or less, and even more preferably 0 or more and 0.1 or less.

As a result of the analysis of the present invention, it has been revealed that the transport tension distribution is generated by the following mechanism. The transport roll is composed of two or more rolls, and the photosensitive material is transported between the rolls. 1) When the transport roll is heated to the heat development temperature, it linearly expands. Both ends of the transport roll are fixed, and this elongation is
It is absorbed by the roll bending. 2) When the roll bends upward (a central portion of the roll is lifted up with respect to the sensitive material), the central conveying tension is lowered. On the other hand, when the roll bends downward (a state in which both ends of the roll are raised with respect to the photosensitive material), the conveyance tension at the end is reduced.

Therefore, the point of the present invention is to make the transport tension uniform by the following method. B) Elongation absorbers are provided at both ends of the transport roll. ・ The bearing of the roll is provided with play so that the roll can be displaced in the width direction. The amount of play is preferably 0.1 to 1 mm, more preferably 0.2 to 0.9 mm, still more preferably 0.3 to 0.8 mm. (B) Use a deforming roll so as to cancel the deformation of the roll.-When the roll is deformed to be convex upward, use a roll (crown roll) having a central diameter larger than that of both ends. A preferable convex amount (a rate of increase in the diameter of the central portion with respect to both ends of the crown roll) is 1 to 10%, more preferably 2 to 9%,
More preferably, it is 3 to 8%. -When the roll is deformed to be convex downward, use rolls (reverse crown rolls) whose both ends have a diameter larger than that of the central part. The preferable convex amount (the rate of increase in the diameter of both ends with respect to the central portion of the inverted crown roll) is 1 to 10%, more preferably 2 to 9
%, And more preferably 3 to 8%. Such transport tension distribution is likely to occur when the transport width (width of TD) is wide as is clear from the above mechanism, and the present invention is effective at a width of 30 cm or more, more effective at a width of 45 cm or more, and 55 cm. The above is more effective.

Further, it is also preferable to control the temperature rising / falling rates at the inlet and outlet of the thermal processor. That is, the rapid thermal expansion of the photothermographic material due to the rapid temperature rise and the abrupt contraction of the photothermographic material due to the abrupt temperature decrease tend to cause warping or waviness at the ends of the four sides. The rate of temperature rise at the inlet is 1 ° C / sec or more and 15 ° C / sec.
Second or less is preferable, 2 ° C./second or more and 10 ° C./second or less is more preferable, and 2 ° C./second or more and 6 ° C./second or less is further preferable. Such setting of the heating rate can be achieved by dividing the heater into the inlet portion of the thermal developing machine and increasing the temperature continuously or stepwise.

After that, thermal development is carried out, and the preferred thermal development temperature is 80 ° C. or higher and 140 ° C. or lower, more preferably 90 ° C.
℃ or more and 130 ℃ or less, more preferably 100 ℃ or more 1
It is 25 ° C or lower. At this time, especially the temperature distribution in the width direction is 0 ° C
The warpage amount and the waviness amount can be further reduced by setting the temperature to 10 ° C. or higher and more preferably 0 ° C. to 5 ° C. inclusive, and more preferably 0 ° C. to 3 ° C. inclusive. This time,
Since the temperature at both ends of the heat developing machine tends to be lower than that at the central part, the set temperature of the heater is set at the end part (1 to 20 cm, more preferably 3 to 15 cm, further preferably 5 to 10 c).
In m), it is preferably 1 ° C. or higher and 20 ° C. or lower, more preferably 2 ° C. or higher and 15 ° C. or lower, and further preferably 5 ° C. or higher and 15 ° C. or lower than the central portion. The heat development time is preferably 10 seconds or more and 120 seconds or less, more preferably 14 seconds or more and 60 seconds or less, and further preferably 18 seconds or more and 40 seconds or less. Such heat development may be performed by radiant heat from the panel heater, or may be performed by directly contacting the heater.

The temperature drop at the exit of the thermal processor after thermal development is -8 ° C.
/ Sec or more and -1 ° C / sec or less, more preferably -5 ° C / sec or more and -1.5 ° C / sec or less, further preferably -3 ° C / sec or more and -1.5 ° C / sec or less. Is. Such a temperature reduction can be carried out by surrounding the area after the outlet with a heat insulating material or by actively heating with a heater.

The method for preparing the photosensitive layer and back layer of the heat-developable photosensitive material of the present invention will be described below. The heat-developable photosensitive material of the present invention has an image forming layer (photosensitive layer) containing an organic silver salt, a reducing agent and a photosensitive silver halide on a support, and at least one protective layer is provided on the image forming layer. It is provided. A back layer for providing antistatic property, slip property, antihalation property, matte property, scratch resistance and the like is provided on the opposite side of the photosensitive layer. If necessary, an undercoat layer may be provided between the back layer, the photosensitive layer and the support.

The photosensitive layer contains silver halide, a chemical sensitizer, an organic silver salt, a reducing agent, an ultrahigh contrast agent, a sensitizing dye, in a binder.
An antifoggant, a plasticizer, etc. are dispersed. Acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, and polyolefin resin are preferably used as the binder, and more specifically, methyl methacrylate / ethyl methacrylate / methacrylic acid. Copolymer, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene /
Acrylic acid copolymers, styrene / butadiene / acrylic acid copolymers, styrene / butadiene / divinylbenzene / methacrylic acid copolymers, methyl methacrylate / vinyl chloride / acrylic acid copolymers, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymers, and more preferred. Is styrene /
Butadiene-based polymer latex (LACSTAR3307B, Ni
pol Lx430, 435) are preferably used. The weight average molecular weight thereof is preferably 5,000 to 1,000,000, more preferably 10,000 to 100,000. Further, in the binder, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, in the range of 20% by weight or less of the total binder,
Hydrophilic polymers such as hydroxypropyl methylcellulose may be added. The amount of binder applied is 0.2-
30 g / m ^2, more preferably in the range of 1.0~15g / m ^2.

The silver halide may be any of silver chloride, silver chlorobromide and silver iodochlorobromide. The grain size of silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less, further preferably 0.02 μm.
Above 0.12 μm is preferable. The shape of the silver halide grains may be cubic, octahedral, tabular grains, spherical grains, rod-shaped grains, potato-shaped grains and the like. In the present invention, cubic grains and tabular grains are particularly preferable. The average aspect ratio when using tabular silver halide grains is preferably 100: 1 to 2: 1, more preferably 50: 1.
~ 3: 1 is good. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (Miller index) of the outer surface of the photosensitive silver halide grain is not particularly limited, but the {100} plane, which has a high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, is likely to be high. preferable. The ratio is preferably 50% or more, more preferably 65% or more, still more preferably 80% or more. Methods of forming these silver halides are well known in the art and are described, for example, in Research Disclosure, June 1978, 17th Edition.
The methods described in 029 and U.S. Pat. No. 3,700,458 can be used.

The silver halide grains preferably contain a metal or metal complex of Group VII or Group VIII (Group 7 to Group 10) of the periodic table, more preferably rhodium, rhenium, ruthenium, Osnium and iridium. These are disclosed in JP-A-7-225449 and JP-A-63-2042.
JP-A 1-285941, 2-20852, 2-20855, etc. The addition amount of these compounds is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, and particularly preferably 1 × 10 ⁻⁸ mol to 1 mol of silver halide.
It is 1 × 10 ⁻⁶ mol.

The silver halide grains include cobalt, iron, nickel, chromium, palladium, platinum, gold, thallium, copper,
A metal atom such as lead may be contained, and a hexacyano metal complex can be preferably used for a compound of cobalt, iron, chromium or ruthenium. The addition amount of these is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt, or a complex salt can be added and added at the time of preparing particles.

It is preferable that the silver halide emulsion is chemically sensitized, and a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method,
A noble metal sensitization method or the like can be used. For sulfur sensitization, sulfur compounds, thiosulfates, thioureas, thiazoles, rhodanins and the like in gelatin can be used, and the addition amount is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. As selenium sensitizers, JP-B-44-15748 and 43-1
3489, JP-A-4-25832, 4-109240, 4-324855
The compounds described in the publications can be used. Tellurium sensitizers are represented by the general formulas (II), (III) in JP-A-5-313284,
The compound represented by (IV) is preferable. The amount of selenium and tellurium sensitizers used is 10 ⁻⁸ per mol of silver halide.
It is 10 ⁻² mol. Examples of the noble metal sensitizer include gold, platinum, palladium, iridium and the like, but gold sensitization is particularly preferable, and it is 10 ^-7 to 1 mol per mol of silver halide.
10 ⁻² mol is used.

Reduction sensitization can be used in the present invention. As a specific compound for the reduction sensitization method, ascorbic acid, thiourea dioxide, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivative, borane compound, silane compound, polyamine compound and the like can be used.

The organic silver salt is any organic substance containing a source capable of reducing silver ions, and in particular, a silver salt of a long chain fatty carboxylic acid (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms) is preferable.
Further, a silver salt of a compound containing a mercapto group or a thione group and derivatives thereof can also be used. The shape of the organic silver salt is not particularly limited, but needle crystals having a short axis and a long axis are preferable. Minor axis 0.01 μm or more and 0.20 μm or less, major axis 0.
It is preferably 10 μm or more and 5.0 μm or less. For the organic silver salt, a method of preparing a solid fine particle dispersion using a dispersant is used for the purpose of obtaining fine particles without aggregation.

The method for dispersing the organic silver salt in solid fine particles is as follows:
In the presence of a dispersion aid, known means for refining (for example, balls
Mill, sand mill, jet mill, high pressure homogenizer
-) Can be dispersed. As a dispersant,
Lylic acid, acrylic acid copolymer, maleic acid copolymer,
Maleic acid monoester copolymer, acryloylmethyl
Propane sulfonic acid copolymer, carboxymethyl demp
, Carboxymethyl cellulose, alginic acid, pectic
Acid, polyvinyl alcohol, polyvinylpyrrolidone,
Hydroxypropyl cellulose, hydroxypropylme
Chill cellulose, gelatin, JP-A-52-92716, WO88 /
Anionic surfactants described in 04794, JP-A-9-1
Use by appropriately selecting the compound described in No. 79243
You can Organic silver salt has a silver content of 0.1-5 g / m^TwoIs preferred
More preferably 1 to 3 g / m ^TwoIs. halogen
The amount ratio of silver halide and organic acid silver is photosensitive to 1 mol of organic silver salt.
The silver halide content is preferably 0.01 mol or more and 0.5 mol or less, and
02 mol or more and 0.3 mol or less are more preferable, and 0.03 mol or more
It is particularly preferably 0.25 mol or less.

It is preferred to include a reducing agent for the organic silver salt, such as phenidone, hydroquinone and catechol,
A hindered phenol reducing agent is preferable, and a hindered phenol reducing agent is particularly preferable, and specific examples thereof include bisphenol and chromanol. The reducing agent is preferably contained in an amount of 5 to 50% (mol) with respect to 1 mol of silver, and 10 to 40%.
It is more preferable that the content is included in% (mol).

To improve the image quality, it is preferable to add a toning agent. Preferred color toning agents include cyclic imide, cobalt complex, mercaptan, phthalazinone, phthalazinone derivative, phthalazine and phthalazine derivative.
More preferred is phthalazinone, a phthalazinone derivative,
Phthalazine and phthalazine derivatives are preferable, and phthalazine and phthalazine derivatives are particularly preferable. The toning agent is preferably contained in an amount of 0.1 to 50% (mol) per mol of silver on the surface having the image forming layer, and 0.5 to 20% (mol).
More preferably, it is included.

In order to obtain a high contrast image, a substituted alkene derivative represented by the general formula (1), a substituted isoxazole derivative represented by the general formula (2), and a specific acetal represented by the general formula (3). Compounds and hydrazine derivatives are preferably used.

[0031]

[Chemical 1]

In the general formula (1), R ¹ , R ² and R
³ each independently represents a hydrogen atom or a substituent,
Z represents an electron-withdrawing group or a silyl group. General formula (1)
In, R ¹ and Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure. In the general formula (2), R ⁴ represents a substituent. In formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group,
It represents a heterocyclic oxy group, a heterocyclic thio group, or a heterocyclic amino group. In the general formula (3), X and Y or A and B may be bonded to each other to form a cyclic structure.

Among the compounds represented by the general formula (1), more preferred are those in which Z represents a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group, and R ¹ represents an electron withdrawing group. Or R ² or R ³ is a hydrogen atom and the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, or a heterocyclic oxy group. A compound representing a group, an alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group. More preferred is that Z and R ^{1 form a} non-aromatic 5- to 7-membered cyclic structure, and R ² or R ^{2
One of 3} is a hydrogen atom and the other is a hydroxy group
(Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group. At this time, Z which forms a non-aromatic cyclic structure together with R ¹ is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group or the like, and R ¹ is an acyl group or a carbamoyl group. , An oxycarbonyl group,
Thiocarbonyl group, sulfonyl group, imino group, imino group substituted with N atom, acylamino group, carbonylthio group and the like are preferable.

In the general formula (2), the substituent R ⁴ is an electron-withdrawing group or an aryl group, preferably a substituted or unsubstituted phenyl group having a total carbon number of 0 to 30, a cyano group, an alkoxycarbonyl group and carbamoyl. A group, a heterocyclic group, most preferably a cyano group, a heterocyclic group or an alkoxycarbonyl group.

Substituents represented by X and Y in the general formula (3)
Is preferably a total carbon number of 1 to 40, more preferably a total carbon number.
A group having 1 to 30 carbon atoms, more preferably a cyano group,
Alkoxycarbonyl group, carbamoyl group, alkyls
Rufonyl group, arylsulfonyl group, acyl group, acyl
Thio group, acylamino group, thiocarbonyl group, formyl
Group, imino group, imino group substituted with N atom, heterocyclic group
Or a phenyl group substituted with any electron-withdrawing group, etc.
is there. X and Y are bonded to each other to form a non-aromatic carbocycle or
Is also preferred if it forms a non-aromatic heterocycle.
Yes. The ring structure formed is preferably a 5- to 7-membered ring,
The total carbon number of 1 is preferably 1 to 40, more preferably 3 to 30.
As X and Y forming a cyclic structure, an acyl group,
Lubamoyl group, oxycarbonyl group, thiocarbonyl
Group, sulfonyl group, imino group, imino substituted with N atom
A group, an acylamino group and a carbonylthio group are preferred.
In the general formula (3), A and B are each independently an alcohol
Xy, alkylthio, alkylamino, aryl
Oxy group, arylthio group, anilino group, heterocyclic thio
Represents a group, a heterocyclic oxy group or a heterocyclic amino group,
These have 1 to 30 total carbon atoms. A and B are connected to each other
It is more preferable that the ring structure is formed to form a 5-membered structure.
A 7-membered non-aromatic heterocycle is more preferred. This place
In this case, if an example in which A and B are linked (-AB-) is given,
For example -O- (CH_Two)_Two-O-, -O- (CH_Two)_Three
-O-, -S- (CH_Two)_Two-S-, -S- (CH_Two)
_Three-S-, -S-ph-S-, -N (CH_Three)-(CH
_Two)_Two-O-, -N (CH _Three)-(CH_Two)_Two-S-,
-O- (CH_Two)_Two-S-, -O- (CH_Two)_Three-S
-, -N (CH_Three) -Ph-O-, -N (CH_Three) -P
h-S-, -N (ph)-(CH_Two)_Two-S-, etc.
It

The compounds represented by the general formulas (1) to (3) include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercaptoheterocyclic groups and triazole groups which are adsorbed on silver halide. Groups may be incorporated. The compounds represented by the general formulas (1) to (3) include an alkyl group, an aralkyl group, an alkoxy group,
Those having a ballast group incorporated therein such as a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group are more preferable.

The compounds represented by the general formulas (1) to (3) include a cationic group (a group containing a quaternary ammonio group or a nitrogen-containing hetero atom containing a quaternized nitrogen atom). A cyclic group), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, (alkyl, aryl,
Or a heterocycle) thio group, or a dissociable group capable of dissociating with a base (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.) is more preferable, and an ethyleneoxy group is particularly preferable. Alternatively, a group containing a repeating unit of a propyleneoxy group, or a group containing a (alkyl, aryl, or heterocycle) thio group is preferable. The amount of the compound represented by the general formula (1) to the general formula (3) used is 1 with respect to 1 mol of silver.
X10 ^-6 to 1 mol is preferable, and 1 x 10 ^{-5 to} 5 x 1
0 ^-1 mol is more preferable, 2 x 10 ^-5 to 2 x 10
Most preferred is ^-1 mole.

It is also preferable to use a hydrazine derivative represented by the following general formula (H) as the ultrahigh contrast agent. R ¹² -NA ¹ -NA ² - in _{^{(G 1) m1 -R 11 (}} H) ^{formula, R 12} represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group is preferably an alkyl group having 1 to 30 carbon atoms, an alkenyl group or an alkynyl group. The aromatic group is a monocyclic or condensed ring aryl group, for example, a phenyl group,
A naphthyl group may be mentioned. The heterocyclic group is a monocyclic or condensed ring, saturated or unsaturated, aromatic or non-aromatic heterocyclic group. Of these, an aryl group or an alkyl group is preferable.

Preferred as the substituent which R ¹² may have is, when R ¹² represents an aliphatic group, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamide group, Ureido group, sulfamoylamino group, imide group, thioureido group, phosphoramide group, hydroxy group, alkoxy group, aryloxy group,
Acyloxy group, acyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, carbamoyl group, carboxy group (including salts thereof), (alkyl, aryl, or heterocycle) thio group, sulfo group (including salts thereof), sulfamoyl group, halogen atom, cyano group, nitro group preferable. When R ¹² represents an aromatic group or a heterocyclic group, an alkyl group (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group. ,
Imido group, thioureido group, phosphoramide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including salts thereof), (alkyl , Aryl, or heterocycle)
Thio group, sulfo group (including salts thereof), sulfamoyl group, halogen atom, cyano group, nitro group and the like are preferable.

R¹¹Represents a hydrogen atom or a block group
You The block group is an aliphatic group (specifically, an alkyl group,
Alkenyl group, alkynyl group), aromatic group (single ring or
Is a condensed ring aryl group), a heterocyclic group, an alkoxy group,
Represents an aryloxy group, amino group or hydrazino group
You R¹¹May be substituted, and as an example of the substituent,
R ¹²Examples of the above are given. A¹, A^TwoTogether
Hydrogen atom, or one of which is a hydrogen atom and the other has 20 or more carbon atoms
Lower alkylsulfonyl group, or arylsulfonyl group
Group (preferably phenylsulfonyl group, or Hammett
Substituted so that the sum of the substituent constants of is -0.5 or more
Phenylsulfonyl group), or acyl group (preferably
The sum of benzoyl group or Hammett's substituent constants is -0.
A benzoyl group substituted to have 5 or more, or
Represents an aliphatic acyl group). m1 is 0 or 1 and m1 is
When 0, R¹¹Is an aliphatic group, aromatic group, or heterocycle
Represents a group. A¹, A^TwoIs most preferably a hydrogen atom.
G¹Is -CO-, -COCO-, -C (= S)-, -SO_Two-, -SO-, -PO
(R^Thirteen) -Group (R^ThirteenIs R¹¹Same range as defined in
R selected from¹¹May be different from. ) Or
Represents an imino methylene group.

The hydrazine derivative of the general formula (H) incorporates a group capable of adsorbing silver halide (alkylthio group, arylthio group, thiourea group, thioamide group, mercaptoheterocyclic group, triazole group, etc.). May be. R ¹¹ or R ^{12 in} the general formula (H) is a ballast group such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group or an alkylphenoxy group, or described in JP-A-1-100530. The polymer may be incorporated. General formula (H)
R ¹¹ or R ¹² is a cationic group (a group containing a quaternary ammonio group, or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom), an ethyleneoxy group or a propyleneoxy group. Includes groups containing repeating units, (alkyl, aryl, or heterocycle) thio groups, or dissociable groups that can be dissociated by bases (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.) May be. The addition amount of the hydrazine derivative that can be used in the present invention is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per 1 mol of silver, and 1 × 10 ^{6
-5 to} 5 x 10 ^-3 mol is more preferable, and 2 x 10 ^{-5 to} 5 mol
Most preferred is ^{x10 -3} mol.

Further, the present invention is for forming a super-high contrast image,
A contrast enhancing agent can be used in combination with the above-mentioned ultra contrast enhancing agent. For example, amine compounds described in U.S. Pat.No. 5,545,505, hydroxamic acids described in 5,545,507, acrylonitriles described in 5,545,507 and 5,545,507.
Hydrazine compounds described in 558,983, JP-A-9-29
Onium salts described in 7368 can be used.

As the sensitizing dye in the present invention, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. As examples of spectral sensitization to red light, JP-A-54-18726, JP-A-6-75322, and JP-A-7-287338 are applicable to red light sources such as He-Ne laser, red semiconductor laser and LED.
JP-B-55-39818, JP-A-62-284343, JP-A-7-
The compounds described in 287338 can be used. 750-
For a semiconductor laser light source in the wavelength range of 1400 nm,
It can be advantageously sensitized by various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes. Also, as a dye forming a J-band, US Pat.
0,236, 3,871,887, JP-A-2-96131, JP-A
No. 59-48753 can be preferably used. The amount of the sensitizing dye used in the present invention is preferably 10 ⁻⁶ to 1 mol, and more preferably 10 ⁻⁴ to 10 mol per mol of silver halide in the photosensitive layer.
^-1 mol is more preferred.

Antifoggants, stabilizers and stabilizer precursors include thiazonium salts described in US Pat. Nos. 2,131,038 and 2,694,716, azaindenes described in US Pat. 2,
728,663 mercury salts, U.S. Pat.No. 3,287,135 urazole, U.S. Pat.No. 3,235,652 sulfocatechol, U.K. Pat.No. 623,448 oximes, nitrones, nitroindazoles, U.S. Pat.
405 polyvalent metal salts, U.S. Pat. No. 3,220,839 thiuronium salts, and U.S. Pat.
, Platinum and gold salts described in U.S. Pat. No. 4,597,915 and U.S. Pat. Nos. 4,108,665 and 4,442,20.
Halogen-substituted organic compounds described in US Pat. No. 4,12
Examples thereof include triazines described in 8,557 and 4,137,079, 4,138,365 and 4,459,350, and phosphorus compounds described in US Pat. No. 4,411,985. Further, benzoic acids may be contained for the purpose of preventing fog and increasing the sensitivity. Examples of preferable structures of benzoic acids include U.S. Pat. Nos. 4,784,939 and 4,152,160.
-329865, 9-329864, 9-28
Examples thereof include compounds described in No. 1637, and it is preferable to add them to the organic silver salt-containing layer. This amount is 1 silver
The amount is preferably 1 μmol or more and 2 mol or less, and more preferably 1 mmol or more and 0.5 mol or less, per mol.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained for the purpose of suppressing or accelerating the development and controlling the development, improving the spectral sensitization efficiency, and improving the preservability before and after the development. be able to. The mercapto compound is preferably a mercapto-substituted heteroaromatic compound, and specific examples thereof include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and 2-mercapto-5.
-Methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolthiol, 2- Mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-
Mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino- 6-Hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-
Thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-
Mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole, etc. Is mentioned. The amount of these mercapto compounds used is preferably 0.0001 to 1.0 mol, and more preferably 0.001 to 0.3 mol, per mol of silver in the emulsion layer.

The imaging layer may contain polyhydric alcohols as plasticizers and lubricants (eg glycerin and diols of the type described in US Pat. No. 2,960,404), US Pat. Nos. 2,588,765 and 3,121,060. Fatty acids or esters, silicone resins described in British Patent No. 955,061 and the like can be used. In the photosensitive layer which is the image forming layer, various dyes and pigments can be used from the viewpoint of color tone improvement and prevention of irradiation, but a preferable dye is an anthraquinone dye (JP-A-5-341441,
Compounds described in JP-A-5-165147), azomethine dyes
(Compound described in JP-A-5-341441), indoaniline dye (JP-A-5-289227, JP-A-5-341441, JP-A-5-16
5147, etc.) and azo dyes (JP-A-5-34
1441) and the like). The amount of these compounds used is preferably 1 μg or more and 1 g or less per 1 m ^{2 of the} light-sensitive material.

An antihalation layer can be provided on the side remote from the light source with respect to the photosensitive layer. The antihalation layer preferably has a maximum absorption in the desired wavelength range of 0.3 or more and 2 or less, more preferably 0.5 or more and 2 or less of the exposure wavelength, and 0.001 or more in the visible region after processing. It is preferably less than 0.5, and more preferably a layer having an optical density of 0.001 or more and less than 0.3. As a single dye, JP-A-59-56458, JP-A-2-216140, JP-A-7-13295, JP-A-7-216295
-11432, U.S. Pat.No. 5,380,635, JP-A-2-68539
No. 3-24539, etc. can be used. As dyes that are decolorized by processing, JP-A-52-139136 and JP-A-53-132334
No. 56, No. 56-501480, No. 57-16060, No. 57-68831,
57-101835, 59-182436, JP-A-7-36145,
7-199409, Japanese Patent Publication No. 48-33692, No. 50-16648, Special Fairness
2-41734, U.S. Pat.Nos. 4,088,497, 4,283,487
Nos. 4,485,896 and 5,187,049 can be preferably used.

It is also preferable to provide a protective layer on the outermost layer of the photosensitive layer. As the binder for the protective layer, acrylic, styrene, acrylic / styrene, vinyl chloride and vinylidene chloride polymer latexes are preferably used. Specifically, acrylic resin-based VONCORT R3370, 428
0, Nipol Lx857, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, Nipol G576 of vinyl chloride resin, Alon D5071 of vinylidene chloride resin are preferably used. It is more preferable to add a crosslinking agent such as isocyanate into these layers. The coating amount of the protective layer is preferably 0.5 to 10 g / m ² , more preferably 1 to 7 g.
/ m ² , more preferably 1.5 to 5 g / m ² . Further, it is more preferable to add a matting agent to the protective layer. Inorganic matting agents include silicon dioxide, titanium and aluminum oxides, zinc and calcium carbonates, barium and calcium sulfates, calcium and aluminum silicates, and organic matting agents such as cellulose. Mention may be made of organic polymeric matting agents such as esters, polymethylmethacrylate, polystyrene or polydivinylbenzene and copolymers thereof. Two or more of these matting agents may be used in combination.
The average particle size of the preferred matting agent is 1 to 10 μm, and the preferred addition amount is 5 to 400 mg / m ² , and especially 10 to 200 mg.
/ M ² range.

The heat-developable image recording material (heat-developable light-sensitive material) of the present invention has an image-forming layer (light-sensitive layer) such as a light-sensitive layer containing at least one silver halide emulsion on one side of a support. It is preferably a so-called single-sided image recording material having a back layer (backing layer) on the other side. In the present invention, the back layer preferably has a maximum absorption in the desired wavelength range of 0.3 or more and 2 or less, more preferably 0.5 or more and 2 or less, and 0.001 or more in the visible region after treatment. It is preferably less than 0.5, and more preferably a layer having an optical density of 0.001 or more and less than 0.3. The examples of the antihalation dye used for the back layer are the same as those for the antihalation layer described above.

Conductive crystalline metal oxide as a charge control agent
Surface resistivity by adding fine particles or composite oxide particles
0¹²The following is also preferable. Conductive crystalline oxidation
As the fine particles of the compound or its composite oxide, the volume resistivity is 1
0⁷Ωcm or less, more preferably 10⁵Ωcm or less
Is desirable. The particle size is 0.01-0.7μ.
m, particularly preferably 0.02 to 0.5 μm.
These conductive crystalline metal oxides or complex oxides
Japanese Patent Laid-Open No. 56-14343 discloses a method for producing fine particles.
It is described in detail in the specification of Japanese Unexamined Patent Publication No. That is, the first
Improves conductivity by making fine particles of metal oxide by firing
Method of heat treatment in the presence of heteroatom, second firing
Improves conductivity when producing metal oxide fine particles
A method of coexisting heteroatoms for the purpose of
The oxygen concentration in the atmosphere when producing fine metal particles
Then, the method of introducing oxygen defects is easy. Metal atom
As an example including, for example, ZnO, Al, In, etc., TiO
_TwoFor Nb, Ta, etc., SnO_Two For S
Examples thereof include b, Nb and halogen elements. Heteroatom addition
The addition amount is preferably in the range of 0.01 to 30 mol%, but is preferably 0.
It is particularly preferably 1 to 10 mol%. Out of these
SnO with Sb added _Two Most complex metal oxide particles
preferable.

It is also preferable to add fine particles for matting the back surface. Examples of the fine particles include inorganic fine particles (silica, alumina, calcium carbonate, titania, zirconia, etc.) and organic fine particles (PMMA, PSt, and cross-linked products thereof). In the present invention, the porous matting agents described in JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4, JP-A-4-127142, page 3, upper right column, line 7 ~ Matt agent surface-modified with an alkali described on page 5, lower right column, line 4, paragraph number "000" of JP-A-6-118542
It is more preferable to use the matting agent of the organic polymer described in "5" to "0026". The preferred particle size is 0.3
μm to 10 μm, more preferably 1 μm to 8 μm
m or less, more preferably 3 μm or more and 7 μm or less. The preferred amount is 1 to 50 mg / ^{m 2,} more preferably 2~30mg / ^{m 2,} more preferably 3~15mg
/ M ² . The preferable Beck's smoothness (JIS P8119) achieved by this is 2000 seconds or less, and more preferably 10 seconds to 2000 seconds.

These back layers may use a hydrophilic colloid as a binder and a hydrophobic polymer as a binder. The most preferred hydrophilic polymer is gelatin. When a hydrophilic polymer is used, it is also preferable to apply a backing layer on top of the same undercoat as the photosensitive layer in order to impart stronger adhesion. As a binder for the hydrophobic polymer layer, polymethylmethacrylate,
(Meth) acrylic acid ester polymers such as ethyl acrylate, olefin polymers such as polyethylene, styrene polymers, urethane polymers, and rubber polymers such as butadiene are used. This layer is 2
It may be more than one layer. Further, a hardener may be used in the back layer. Examples of hardeners include polyisocyanates described in U.S. Pat.No. 4,281,060 and JP-A-6-208193, epoxy compounds described in U.S. Pat.No. 4,791,042, and JP-A-62-89048. The vinyl sulfone compounds described in, etc. are used.

A protective layer may be provided on the outermost layer of the back layer. The total amount of binder for the protective layer is 0.2 ~ 5.0g / m
² , more preferably in the range of 0.5 to 3.0 g / m ² . As the binder for the back layer, an acrylic-based, olefin-based, vinylidene chloride-based polymer latex is used, and specifically, acrylic resin-based Julimer ET-410, Sevian A-4635, polysol F410, and other olefin resin-based binders. Chemipearl S120, vinylidene chloride L5
02, Aron D7020 and the like are preferable.

The back layer preferably contains a fluorine-containing surfactant. The preferred fluorine-containing surfactant has a fluoroalkyl group, a fluoroalkenyl group, or a fluoroaryl group having 4 or more carbon atoms (preferably 4 or more and 15 or less), and an anionic group (sulfonic acid (salt)) as an ionic group. , Sulfuric acid (salt), carboxylic acid (salt),
Phosphoric acid (salt), cation group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt, phosphoammonium salt, ) Or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group or sorbitan residue). These fluorine-containing surfactants are disclosed in JP-A-49-10722.
U.S. Pat.No. 4,335,201
No. 4,347,308, British Patent No. 1,417,915, JP Sho
55-149938, 58-196544, British Patent No. 1,439,402
No. etc. Two or more kinds of these fluorine-containing surfactants may be mixed. The amount of the fluorine-containing surfactant used is 0.0001 to 1 g per 1 m ^{2 of the} image recording material.
However, it is more preferably 0.0002 to 0.2.
5 g, particularly preferably 0.0003 to 0.1 g.

It is more preferable to use a slipping agent in the outermost layer of the back layer. Typical examples of the lubricant are silicone-based lubricants, higher fatty acid-based lubricants, alcohol-based, acid amide-based lubricants, metal soaps, ester-based lubricants, ether-based lubricants,
There are taurine-based lubricants, etc. Specific examples of the slip agent that is preferably used include Cerosol 524 (main component carnauba wax), Polylon A, 393, H-481 (main component polyethylene wax), Hymicron G-110 (main component ethylenebisstearic acid amide), High micron G-270 (main component stearic acid amide) (above,
Chukyo Yushi Co., Ltd., etc. The amount of the slipping agent used is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, based on the amount of the binder in the additive layer.

The back layer may be a single layer or multiple layers. The thickness of each layer is preferably 0.02 to 10 μm, more preferably 0.1 to 7 μm, and the total thickness of these layers is 0 to 5 μm. Is preferred. The back layer and the undercoat layer are coated by a dip coating method, an air knife coating method,
It can be applied by a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or the like. These may be applied as a single layer or as two or more layers simultaneously. The heat-developable photosensitive material prepared in this manner is cut at the time of use, but it may be used in the form of a roll or a sheet. In each case, the preferable width (the direction orthogonal to the processing direction when passing through the thermal processor) is 4
0 cm or more and 150 cm or less, more preferably 45 cm or more 10
It is 0 cm or less, more preferably 50 cm or more and 80 cm or less.

The heat-developable image recording material of the present invention may be exposed by any method, but a laser beam is preferable as an exposure light source. The laser light according to the present invention is preferably a gas laser, a YAG laser, a dye laser, a semiconductor laser or the like. Alternatively, a semiconductor laser and a second harmonic wave generating element may be used. The heat-developable image recording material of the present invention has a low haze upon exposure and tends to cause interference fringes. As a technique for preventing the occurrence of interference fringes, Japanese Patent Laid-Open No.
Techniques for obliquely entering the laser light disclosed in 5-113548 and the like with respect to the image recording material, and methods of using the multimode laser disclosed in WO95 / 31754 and the like are known, It is preferable to use these techniques. To expose the heat-developable image recording material of the present invention, SPIE v
ol.169 Laser Printing pages 116-128 (1979), JP-A-4-51
As disclosed in 043, WO95 / 31754 and the like, it is preferable that the laser beams are exposed so as to overlap each other so that the scanning lines cannot be seen. The heat-developable image recording material of the present invention may be heat-developed by any method, but usually, the heat-developable image recording material exposed imagewise is heated and developed by the above-mentioned method.

The methods for measuring the physical properties specified in the present invention will be described below. The measuring methods (1) and (2) will be described with reference to the drawings. (1) Measurement of the amount of warp at the edges of the four sides after heat development (see FIGS. 1 and 2) After heat-development of a heat-developable photosensitive material having four sides cut into 50 cm under predetermined conditions, as shown in FIG. Then, the edges of the four sides of the photosensitive material 1 after the heat development are slit at slit positions 2 having a width of 1 cm. When the slit is made, the side 8 of the slit piece 4 loses the deflection (waviness) due to this slit, and becomes an arc shape as shown in FIG. As shown in FIG. 2, one end a of the side 8 opposite to the side 3 of the slit piece 4 is aligned with one side of the ruler 6, and a gap (distance) 5 between the other end b of the slit piece and the ruler is measured. . Similarly, align the b end with a ruler and measure the gap with the a end. The average value of these values is the amount of warp (mm / 50 cm). This is measured over 4 sides. When the sensitive material is other than 50 cm, the amount of warp (A) after slitting each side with a width of 1 cm by the above method
Is measured and corrected according to the following formula. Warp amount (mm / 50cm) = A (mm) x {50 / side length of sensitive material (c
m)}

(2) Measurement of each wavy amount at the ends of the four sides after heat development (see FIG. 3) The heat-developable photosensitive material whose four sides were cut to 50 cm was heat-developed under predetermined conditions, and after this heat-development The photosensitive material 1 is placed on a horizontal and smooth table 7 with the photosensitive layer facing upward. After 3 minutes, the amount of waviness is measured for each of the four sides as follows. The maximum height (H _i mm) of each generated wave
And the width (W _i mm) are measured using a ruler, calipers or the like. Following integrating _{H i} (mm) × _{W i} (mm) of each four sides in accordance with formula, and the waving of the end of the four sides ^(mm 2 / 50cm).

[0060]

[Equation 1]

When the sensitive material is other than 50 cm, the waviness amount (B) is measured by the above method and corrected according to the following formula. Rippling amount (mm ² / 50cm) = B (mm ² ) × {50 / side length of sensitive material (cm)}

(3) Thermal dimensional change at 120 ° C. for 30 seconds The heat-developable photosensitive material is cut out in the width direction (TD) 5 cm × longitudinal direction (MD) 25 cm to obtain a sample for MD direction. A sample for the TD direction is similarly cut out in the width direction (TD) 25 cm × longitudinal direction (MD) 5 cm. 20c after conditioning them for 12 hours at 25 ℃ and 60% RH
Make holes at intervals of m and measure the length using a pin gauge.
₁ (mm)). These are brought into contact with a heat block heated to 120 ° C. for 30 seconds and heated under no tension. After conditioning the humidity of these at 25 ° C. and 60% RH for 12 hours, the dimensions are measured using a pin gauge (this is defined as L ₂ (mm)). According to the following formula, the thermal dimension change is 120 ° C. for 30 seconds. Thermal dimensional change (%) at 120 ° C. for 30 seconds = 100 × (L ₂ −L
₁ ) / L ₁

(4) Water absorption after heat development at 120 ° C. for 30 seconds
Law change rate Heat in the width direction (TD) 5 cm x length direction (MD) 25 cm
The image sensitive material is cut out and used as a sample for MD direction. Width direction
(TD) 25cm × longitudinal direction (MD) 5cm similarly cut
A sample for the TD direction is used. Humidify them at 25 ° C and 40% RH for 12 hours,
Make holes at cm intervals and measure the length using a pin gauge.
L₀(mm)). These were developed with a thermal processor installed at 25 ° C and 75% RH.
Image (30 seconds contact with a heat block heated to 120 ℃
And heat without tension). Size (L at 3 minutes after thermal development at 25 ° C and 75% RH)_Three)When
Dimensions after 120 minutes (L ₁₂₀) With a pin gauge.
Set. Water absorption dimension change after thermal development at 120 ° C for 30 seconds according to the following formula
Ask for Water absorption dimensional change rate (%) after heat development at 120 ° C. for 30 seconds =
{100 x (L₁₂₀-L₀) / L₀}-{100 ×
(L_Three-L₀) / L₀}

[0064]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto.

Example-1 (1) Preparation of support (base) Using terephthalic acid and ethylene glycol, IV (intrinsic viscosity) = 0.66 (phenol / tetrachloroethane = 6 /) according to a conventional method. 4 (weight ratio) measured at 25 ° C) PET
Got After pelletizing this, it is dried at 130 ° C. for 4 hours, melted at 300 ° C., then extruded from a T-die and quenched.
An unstretched film having a thickness such that the film thickness after heat setting was 120 μm was produced. This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then laterally stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C and 13 ° C, respectively.
It was 0 ° C. After that, heat setting was carried out at 240 ° C. for 20 seconds, and then relaxation was carried out in the lateral direction by 4% at the same temperature. After this tenter
After slitting the chuck part, the both ends were knurled and wound at 4.8 kg / cm ² . Thus, a roll having a width of 2.4 m, a length of 3500 m and a thickness of 120 μm was obtained.

(2) Undercoat layer After coating an undercoat layer (a-1) or (a-2) of the following composition on both surfaces of the support (base), the undercoat layer (b) is applied. Was sequentially applied and dried at 180 ° C. for 4 minutes. The coating film thickness of (a-1) or (a-2) after drying has the values shown in Table 1, and the coating film thickness of (b) is 1.
It was adjusted to 0 μm. (2-1) Undercoat layer (a-1) PVdC polymer latex Core-shell type latex having 90% by weight of core part and 10% by weight of shell part Core part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93 /3/3/0.9/0.1 (wt%) Shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (wt%) Weight average molecular weight 38000 3000 parts by weight 2,4-dichloro-6-hydroxy-s-triazine 23 parts by weight Matting agent (polystyrene, average particle size 2.4 μm) 1.5 parts by weight

(2-2) Undercoat layer (a-2) SBR polymer latex styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/30 / 2.5 / 0.5 (wt%) 160 parts by weight 2,4 -Dichloro-6-hydroxy-s-triazine 4 parts by weight Matting agent (polystyrene, average particle size 2.4 μm) 3 parts by weight (2-3) Undercoat layer (b) Alkali-treated gelatin (Ca ++ content 30 ppm, jelly strength) 230g) 50mg / m ²

(3) Back layer The undercoat layer (a-1) or (a-2) and the undercoat layer
The following conductive layer and protective layer are applied on one side on which (b) is applied.
Apply sequentially and dry at 180 ° C for 4 minutes.
A PET support with a black layer / undercoat layer was prepared. (3-1) Conductive layer (Surface resistivity at 25 ° C 25% RH 10⁹ Ω)   Julimer ET-410 (manufactured by Nippon Pure Chemical Industries, Ltd.): Tg = 52 ° C. 38 mg / m^Two   SnO_Two/ Sb (9/1 weight ratio, average particle size 0.25 μm) 120 mg / m^Two   Matting agent (polymethylmethacrylate, average particle size 5 μm) 7 mg / m^Two   Denacol EX-614B (manufactured by Nagase Kasei Co., Ltd.) 13 mg / m^Two (3-2) Protective layer   Chemipearl S-120 (Mitsui Petrochemical Co., Ltd.): Tg = 77 ° C 500mg / m^Two   Snowtex-C (Nissan Chemical Co., Ltd.) 40mg / m^Two   Denacol EX-614B (manufactured by Nagase Kasei Co., Ltd.) 30 mg / m^Two

(4) Heat Treatment The PET support having the back layer / undercoat layer was heat treated while being conveyed in the heating zone at the temperature, tension and time shown in Table 1.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

(5) Image forming layer (photosensitive layer) The following image forming layer and protective layer were sequentially coated on the undercoat layer on the opposite side of the back layer and dried at 65 ° C. for 3 minutes to obtain a heat-developable image sensitive material. It was (5-1) Preparation of silver halide grains 11 g of phthalated gelatin, 30 mg of potassium bromide and 10 mg of sodium thiosulfonate were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at a temperature of 35 ° C.
159 ml of an aqueous solution containing 8.6 g and an aqueous solution containing potassium bromide at 1 mol / l were added by the controlled double jet method for 6.5 minutes while keeping the pAg at 7.7. Subsequently, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and a halogen salt aqueous solution containing 1 mol / liter of potassium bromide at pAg of 7.7 were added by the control double jet method over 30 minutes, and then 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene (1 g) was added, and the pH was further lowered to cause aggregation and sedimentation for desalting treatment. Then, 0.1 g of phenoxyethanol was added, and p
The preparation of silver bromide grains (cubic grains having an average size of 0.12 μm, a projected area diameter variation coefficient of 8% and a (100) plane ratio of 88%) was adjusted by adjusting the H5.9 and pAg to 8.2. The silver halide grains thus obtained were heated to 60 ° C., 8.5 × 10 ⁻⁴ mol of sodium thiosulfonate was added per 1 mol of silver, the mixture was aged for 120 minutes and then rapidly cooled to 40 ° C., and then 1 ×.
10 ⁻⁵ mol of dye S-1, 5 × 10 ⁻⁵ mol of 2-mercapto-5-methylbenzimidazole and 5 × 1
0 ^-5 mol of N- methyl -N '- rapidly cooled was added to {3- (mercaptomethyl tetrazolyl) phenyl} urea 30 ° C. to obtain a silver halide emulsion.

[0075]

[Chemical 2]

(5-2) Preparation of silver dispersion of organic acid Stearic acid 4.4 g, behenic acid 39.4 g, distilled water 7
While stirring 70 ml at 90 ° C, 103 ml of 1N-NaOH aqueous solution
Was added and reacted for 240 minutes, and the temperature was lowered to 75 ° C. Then, 112.5 ml of an aqueous solution of 19.2 g of silver nitrate was added over 45 seconds, the mixture was allowed to stand for 20 minutes, and the temperature was lowered to 30 ° C. Then, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtered water reached 30 μS / cm. 10 wt% of hydroxypropylmethylcellulose was added to the solid content thus obtained.
% Aqueous solution (100 g), and then water to a total weight of 270 g, which was dispersed in an automatic mortar to obtain a crude organic acid silver dispersion. This organic silver salt dispersion was used with a Nanomizer (manufactured by Nanomizer Co., Ltd.) to obtain a pressure of 1000 at the time of collision.
It was dispersed at kg / cm ³ to obtain an organic acid silver dispersion. The organic acid silver particles contained in the thus obtained organic acid silver dispersion have an average short diameter of 0.1.
The particles were acicular particles having a diameter of 04 μm, an average major axis of 0.8 μm and a coefficient of variation of 30%. (5-3) Preparation of reducing agent dispersion 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,
To 100 g of 5-trimethylhexane and 50 g of hydroxypropyl cellulose, 850 g of water was added and mixed well to obtain a slurry. Zirconia beads 84 with an average diameter of 0.5 mm
0 g was prepared and put in a vessel together with the slurry, and dispersed by a disperser (1/4 G sand grinder mill: manufactured by AIMEX Co., Ltd.) for 5 hours to obtain a reducing agent dispersion.

(5-4) Preparation of Organic Polyhalide Dispersion To 50 g of tribromomethylphenyl sulfone and 10 g of hydroxypropylmethyl cellulose, 940 g of water was added and mixed well to form a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 nm, put them in a vessel together with the slurry, and disperse them for 5 hours with a disperser (1 / 4G sand grinder mill: manufactured by AIMEX Co., Ltd.) to obtain an organic polyhalide dispersion. Obtained. (5-5) Preparation of coating liquid for image forming layer 100 g of the organic acid silver dispersion obtained above and 20 of reducing agent dispersion
g, organic polyhalide dispersion 15 g, LACSTA
R3307B (manufactured by Dainippon Ink and Chemicals, Inc .; SBR latex; Tg 13 ° C.) 49 wt% 40 g, MP-203 (Kuraray Co., Ltd .; polyvinyl alcohol) 10 wt% aqueous solution 20 g, silver halide emulsion 20 g, hydrazine compound (general) Compound of formula (H)) 8 ml of 1 wt% methanol solution,
Further, 100 g of water was added and mixed well to prepare an image forming layer coating solution. This coating solution was applied such that the coating silver amount was 1.5 g / m ² and the solid content of the polymer latex was 5.7 g / m ² .

(6) Protective Layer (6-1) Preparation of Protective Layer Coating Solution The following coating solution was applied onto the above-mentioned photosensitive layer so that the solid content of the polymer latex was 2 g / m ² . 40 wt% polymer latex (methyl methacrylate / styrene /
2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / methacrylic acid = 59/9/26 /
5/1 copolymer; Tg 47 ° C.) 500 g, H ₂ O
262 g was added, and as a film forming aid, 14 g of benzyl alcohol, the following compound-22.5 g, and Cerosol 524.
(Chukyo Yushi Co., Ltd.) 3.6 g, the following compound-312
g, the following compound-4 1 g, the following compound-5 2 g, the following compound-6 7.5 g, and an average particle size of 3 as a matting agent.
3.4 g of polymethylmethacrylate fine particles of μm were sequentially added, and further H ₂ O was added to make 1000 g to prepare a coating solution having a viscosity of 5 cp (25 ° C.) and pH = 3.4 (25 ° C.).

[0079]

[Chemical 3]

(7) Thermal development / contact exposure / evaluation of photosensitive material The obtained thermal developable photosensitive material was subjected to 12
The thermal dimension change at 0 ° C. for 30 seconds and the water absorption dimension change rate after thermal development at 120 ° C. for 30 seconds were obtained. Further, a photothermographic material prepared by the above method was exposed with a 10% flat screen image to obtain 50 cm × 5.
After cutting to 0 cm, heat development was performed under the conditions shown in Tables 2-4. The heat-developable photosensitive material was heated from room temperature to a constant temperature under each condition described in Tables 2 to 4 at each level, and the constant temperature part 3 was used.
After 0 seconds, the temperature was lowered from the constant temperature to room temperature. After heat development, the amounts of warpage and waviness on the four sides were measured by the above-mentioned methods and are shown in Tables 2-4. Then, the PS plate was contact-exposed with a contact exposure printer. The PS plate was developed according to a standard method, and the area of the part where the halftone image was sticking (where the halftone dots were crushed and continuous) was visually measured, and the results are shown in Tables 2 and 4. Point defect rate).

As can be seen from the results of Comparative Example 1 in Tables 1 and 2, the support was not provided with a polyvinylidene chloride layer as an undercoat layer on both sides, and heat treatment was conducted under the heat treatment conditions other than those specified in the present invention. When a heat-developable photosensitive material whose thermal dimensional change and water absorption dimensional change rate are not within the range specified in the present invention is subjected to thermal development under conditions other than the thermal development conditions specified in the present invention, the amount of warpage after heat development and waviness As the amount increases and a high halftone dot defect rate is exhibited, a burning blurring failure occurs, which is not preferable. On the other hand, as shown in the inventions 1 to 8, when the photothermographic material defined in the invention is heat-developed by the heat development method defined in the invention, both the warp amount and the waviness amount after the heat development are small, and It can be seen that the point defect rate becomes low and the burning blurring failure does not occur. In addition, in the photothermographic material shown in the present invention-2 which does not have polyvinylidene chloride in the undercoat layer, in the present invention-7 in which the thermal dimensional change does not fall within the range specified in the present invention without the heat treatment specified in the present invention. When heat development was carried out using the heat-developable photosensitive material shown below, and as shown in Invention-8, the heat development was carried out by a heat development method in which the temperature rising condition and the temperature lowering condition were out of the ranges specified in the present invention. In this case, in comparison with the case where the photothermographic material specified in the present invention is heat-developed by the heat development method specified in the present invention, the warp amount and the waviness amount are slightly larger on some sides, but the comparison is made. Compared with Example-1, there is no problem in the halftone dot defect rate and no burning blurring failure occurs. Further, as shown in Inventions 9 to 16, when the thermal development is carried out by making the transport tension uniform by setting the range of the transport tension distribution defined in the present invention, both the warp amount and the waviness amount after the heat development are caused. , Smaller, low dot defect rate,
It turns out to be preferable.

[0082]

The method for developing a heat-developable photographic light-sensitive material of the present invention is an excellent method not only for ordinary use but also for printing, and the light-sensitive material after heat-development image formation has good flatness. Therefore, it has an excellent effect that a burning blurring failure does not occur.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing the positions of slits for measuring the warp and the warp amount of four sides in the present invention.

FIG. 2 is an explanatory diagram showing a method for measuring the amount of warpage in the present invention.

FIG. 3 is a schematic view showing the wavy state of the four sides of the present invention by the end surface of the photosensitive material.

[Explanation of symbols]

1 Photosensitive material after heat development 2 Slit position 3, 8 sides 4 Slit piece 5 Gap when aligned at a end 6 Ruler 7 Horizontal table a, b One end of side 8 H _i Maximum height of a certain wavy i generated H _{i + 1} generated there waving i + 1 of the maximum height _{H i + 2} generated is waving i + 2 of the maximum height _{W i} generated is waving width _{W i + 1} generated there waving i + 1 of the width _{W i + 2} generated is waving i + 2 of the width of the i

Claims (10)

[Claims] 1. The amount of each warp at the edges of the four sides after heat development is 0 mm / 50 cm or more and 4 mm / 50 cm or less,
Thermal dimensional change at 120 ° C for 30 seconds in both longitudinal and width directions
A method for thermal development of a photothermographic material, which comprises heat-developing a photothermographic material of 0.05 or more and 0.05% or less at a temperature of 1 ° C./sec or more and 15 ° C./sec or less and then performing thermal development. . 2. The amount of each warp at the end portions of the four sides after heat development is 0 mm / 50 cm or more and 4 mm / 50 cm or less,
Thermal dimensional change at 120 ° C for 30 seconds in both longitudinal and width directions
A method for thermal development of a photothermographic material, comprising: decreasing the temperature of the photothermographic material, which is 0.05% or more and 0.05% or less, at −8 ° C./sec or more and −1 ° C./sec or less after thermal development. . 3. The amount of each warp at the end portions of the four sides after heat development is 0 mm / 50 cm or more and 4 mm / 50 cm or less,
Thermal dimensional change at 120 ° C for 30 seconds in both longitudinal and width directions
A heat development method for a heat development photographic light-sensitive material, which comprises subjecting a heat development photographic light-sensitive material of 0.05 or more to 0.05% or less to heat development with a transport tension distribution of 0 or more and 0.5 or less. 4. The heat development is carried out at a temperature of 80.degree.
The temperature distribution in the width direction is 0 ° C. or more and 10 ° C. or less, and the heat development time is 10 seconds or more and 120 seconds or less. 4. Photothermographic method of photothermographic material. 5. The heat-developable photographic light-sensitive material has a wavy amount of 0 mm ² / 50c at each end of four sides after heat development.
heat development process of photothermographic material according to any one of claims 1 to 4, characterized in that m or more and 500 mm ^2/50 cm or less. 6. The photothermographic material is 120 ° C. 3
The rate of dimensional change of water absorption after 0 second heat development is 0% / 2 hours or more and 0.025% / 2 hours or less in both the longitudinal and width directions. Method of heat development of photographic light-sensitive material. 7. The method of thermal development for a photothermographic material according to claim 1, wherein the support for the photothermographic material is a polyethylene terephthalate film. 8. The support of the photothermographic material is 1
A polyethylene terephthalate film heat-treated at a temperature of 40 ° C to 200 ° C and a tension of 0 kg / m to 5 kg / m for 20 seconds to 5 minutes.
The heat development method for a photothermographic material according to any one of 1. 9. The support of the photothermographic material is coated with a layer of polyvinylidene chloride resin on both sides of 0.5 μm or more and 10 μm or less, respectively. 2. A method of heat development for a heat-developable photographic light-sensitive material as described in item 1. 10. A heat-developable photographic light-sensitive material, which is heat-developed by the method according to any one of claims 1 to 9.