JP2003226439A - Wrapper for sheet-like recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wrapper for a sheet-like recording material, allowing easy detection of the recording material to run out with a suction pad and effectively suppressing the occurrence of scratches or density irregularity of the recording material stored in the lowest portion. <P>SOLUTION: The wrapper for the sheet-like recording material has at least a base bottom portion for holding the sheet-like recording material. When the sheet suction pad for the sheet-like recording material has contact with the base bottom portion, air is fed to the sheet suction pad through a cutout portion provided passing through the base bottom portion so that no existence of the sheet-like recording material on the base bottom portion can be sensed. A recessed portion being 1 mm or less in depth is provided continuously on an extension line of the cutout portion. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for containing a sheet-shaped recording material. In particular, the present invention relates to a packaging material that suppresses scratches that may occur on a sheet-shaped recording material during transportation and a change in sensitivity that occurs during storage and that can easily detect when a sheet-shaped recording material is used up by a single-wafer suction cup.

[0002]

2. Description of the Related Art When an image is recorded on a sheet-shaped recording material, an image recording device is generally used. For example, when performing image recording on a photosensitive sheet-shaped recording material, when the unexposed sheet-shaped recording material is accumulated in advance in a light-shielded accumulating unit in the image recording apparatus and image recording becomes necessary. The recording material is carried out one by one from the accumulating section and exposed and developed. Since it is necessary to reliably set a large number of sheet-shaped recording materials in the accumulating section without being exposed, the recording material loaded in the packaging material is usually attached to the accumulating section together with the packaging material.

The packaging material for loading the recording material is designed to prevent the sheet-shaped recording material from being bent or damaged and to be easily stored in the accumulating portion. Then, the sheet-shaped recording material accumulated at the time of exposure is sucked by a sheet-shaped recording material sheet-fed suction plate (hereinafter simply referred to as a suction plate),
It is designed to be carried out to the exposure section (see FIG. 7). When all the unexposed sheet-shaped recording material in the accumulating section has been carried out, a means for causing the image recording apparatus to detect that the accumulating section has become empty is necessary. Therefore, a hole is provided in advance at a portion of the packaging material base, which is in contact with the recording material to be conveyed last, that is, the recording material accumulated at the bottom is in contact with the suction cup. . When the last recording material is used up, the suction plate will suck the holes, and the suction pressure will not decrease. Therefore, the suction pressure sensor detects that the suction pressure does not decrease, and detects that the recording material has run out.

[0004]

However, when such a detecting means is used, the recording material is scratched during transportation due to the holes provided in the base of the packaging material. Further, since the air entering through the holes directly contacts the recording material, the sensitivity changes only in the portion in contact with the holes or in the vicinity thereof. Therefore, it has been required to develop a new detection means that solves these problems. Therefore, it has been required to solve these technical problems.

Therefore, according to the present invention, it is possible to easily detect that the sheet-shaped recording material has been used up, and it is possible to effectively suppress the occurrence of scratches and uneven density of the sheet-shaped recording material stored in the lowermost portion. The purpose was to provide packaging material.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have achieved the above-mentioned object by forming a notch and a recess at the base of the packaging material according to specific conditions. The present invention has been accomplished by finding that a packaging material that can meet the requirements can be obtained.

That is, the present invention is a packaging material for a sheet-shaped recording material, which comprises at least a base portion for holding a sheet-shaped recording material, and when the suction cup of the image recording apparatus is in contact with the base portion, Air can be blown into the suction plate through a notch provided so as to penetrate the base so that the absence of the sheet-shaped recording material on the base can be sensed, and the extension line of the notch can be detected. Provided is a sheet-like packaging material for a recording material, which is provided with a recess having a depth of 1 mm or less continuously. The packaging material of the present invention can be preferably used particularly as a packaging material for medical films.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the packaging material for a sheet-shaped recording material of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning including the numerical value described before and after that as a lower limit and an upper limit.

The sheet-shaped recording material packaging material of the present invention includes at least a base portion. The base portion functions as a pedestal on which the sheet-shaped recording material is placed.
The packaging material may be provided with a cover portion so as to partially cover the side portion and the upper portion of the accumulated sheet-shaped recording material.
The cover portion is formed in a region where the suction plate of the image recording device does not hinder the operation. A typical packaging material shape is illustrated in FIG. As shown in the figure, the packaging material (2) of the present invention for accommodating the sheet-shaped recording material (1) has a case-like shape including a base portion (4), side portions (5) and a cover portion (6). preferable.

On the base of the packaging material of the present invention, a sheet-shaped recording material is usually loaded with the image recording surface facing downward. The packaging material of the present invention loaded with a sheet-shaped recording material is transported in a state of being hermetically sealed with a light-shielding film (for example, an aluminum sheet or an aluminum sheet laminated with polypropylene) and set in an image recording apparatus. Therefore, the sheet-shaped recording material repeats minute movements on the base of the packaging material due to vibrations and impacts received during transportation. Particularly, the recording surface of the lowermost sheet-shaped recording material rubs against the surface of the base of the packaging material while receiving the weight of the sheet-shaped recording material accumulated on the recording surface. For this reason, if a cut portion is provided at the base of the packaging material so that the image recording apparatus can easily detect that the sheet recording material has been used up, the sheet recording is performed centering on the portion in contact with the cut portion. The material was scratched and the sensitivity was lowered, causing uneven density. The present invention is
Such a problem is solved by providing a concave portion on the extension line of the cut portion.

The notch and the recess provided in the base of the packaging material of the present invention must be continuous so that they are located on the extension lines of each other. That is, a continuous line composed of the cut portion and the concave portion is provided in the base portion in a straight line shape or a smooth curved line shape. Preferred is a mode in which the continuous line consisting of the cut portion and the recess is linear or a curved line close to a straight line, and more preferred is a mode in which the continuous line consisting of the cut portion and the recess is straight. .

More specifically, the cut portion and the recess are continuous, the cut portion, the recess, and the cut portion are continuous in this order, and the recess, the cut portion, and the recess are consecutive, and the cut portion is Any of the mode in which the concave portions and the concave portions are alternately continuous can be adopted. Preferred is an aspect including a structure in which the recess extends from both ends of the cut portion. By adopting such an aspect, it is possible to more effectively prevent scratches and a decrease in sensitivity.

The direction of the linear structure in which the cut portion and the recess are continuous is not particularly limited, but it is preferable that the linear structure is at a right angle or a direction close to a right angle with respect to the paper discharge direction. The paper discharge direction is usually the longitudinal direction of the base.

Further, a plurality of linear structures in which the cut portion and the recess are continuous may be provided. When a plurality of linear structures are provided, each linear structure may be the same or different. When a plurality of lines are provided, it is preferable that they are in parallel with each other or in a line with each other.

The cut portion referred to in the present specification means a linear cut portion that penetrates the base portion. As long as the notch portion does not suck air by the suction disc, substantially no air flows, and if the air can be sent into the suction disc during suction by the suction disc, the notch in the present specification Included in the section. The length of the cut portion is not particularly limited, but is usually 8 to 50 mm, preferably 10 to 3
It is 5 mm. In addition, the total length of the notches provided on one line is 50 times the length in the notch direction of the base.
% Or less, and more preferably 40% or less. The strength of the packaging material can be further increased by setting the length to 50% or less of the length of the base portion in the cutting direction. The cut portion can be formed by pressing a plate fitted with a cutting blade or making a cut with a knife.

The concave portion referred to in the present specification means a portion including a portion which is depressed with respect to the plane of the base portion, and the shape of the depression is not particularly limited. Therefore, the cross section of the recess may be V-shaped, U-shaped, or W-shaped, and may be composed of a flat bottom portion and slope-like gently inclined surfaces formed on the left and right sides thereof. Further, the bottom portion may not be flat and may be wavy. Furthermore, the cross section of the recess is
It may change depending on the position where the cross section is taken. That is, the cross section of the recess may be U-shaped at one end and V-shaped at the other end.

The depth of the recess is set to 1 mm or less in order to prevent the sheet-shaped recording material from being scratched and deteriorating the sensitivity. The preferable depth is 0.1 to 1 mm, more preferably 0.1 to 0.8 mm, and particularly preferably 0.1 to 0.5 mm. Further, it is preferable that the width of the concave portion be approximately the same as the width of the cut portion that is continuously provided. The width of the recess is usually 0.1 to 2 mm, preferably 0.1 to 1 mm, and more preferably 0.3 to 1 mm. The length of the recess is not particularly limited, but is usually 8 to
It is 50 mm, preferably 10 to 35 mm. The recess is
For example, it can be formed by pressing a plate in which a pressing blade is fitted.

The base of the packaging material of the present invention is preferably made of paper, plastic such as polypropylene, or a laminate thereof.

Various materials can be used as the material, and can be selected from the materials described in "New Development of Functional Packaging Materials", pages 33 and 118 to 122, published by Toray Research Center. Preferably polypropylene,
(For example, biaxially oriented polypropylene (Trefan YM-11) manufactured by Toray Industries, Inc., biaxially oriented polypropylene (OPA) manufactured by Nimura Chemical Co., Ltd.), and polyethylene (high-density polyethylene is more preferable) are mentioned.

The laminated film may be composed of a plurality of layers. Examples of the layer structure in that case include (1) a polymer, a metal-containing layer, and a polymer laminated in this order, (2) a polymer, a metal-containing layer laminated in this order, and (3) a metal vapor-deposited structure. The base can be formed by stacking these on paper. At the time of stacking, the paper is preferably subjected to surface treatment such as corona discharge in advance. In the cases (1) and (2), the polymer contacting the paper may be melted by heat and used as an adhesive with the metal-containing layer. Also, a method of pressure bonding or vacuum bonding can be used. Particularly preferred is a method in which polyethylene is extruded onto a corona-discharged paper, and a sheet obtained by vacuum-bonding a metal foil and a biaxially stretched polymer is attached.
The total film thickness of the laminated film is preferably 5 to 100 μm, and 5 to 50 μm.
μm is more preferable. In addition, the thickness of the paper itself before attaching the laminated film is preferably 250 to 450 μm,
It is preferably 400 μm or less. In addition, the pulp material is B
It is preferable to use BSP rather than KP. Among the materials of the laminated film, the thickness of the metal-containing layer is preferably 1 to 40 μm, more preferably 2 to 20 μm.

The recording material loaded in the packaging material of the present invention is a sheet-shaped recording material. The packaging material of the present invention can be preferably used particularly as a packaging material for loading a medical film. Medical images are required to be particularly finely drawn, and it is necessary to form high-quality images excellent in sharpness and graininess. Further, from the viewpoint of ease of diagnosis, cold-black images tend to be preferred. There is a risk of causing misdiagnosis if there is a scratch or partial sensitivity decrease in the medical film, but the use of the packaging material of the present invention can effectively suppress the scratches and the sensitivity decrease and thus the risk of misdiagnosis. Can be prevented.

The heat-sensitive recording material, which is one of typical sheet-shaped recording materials that can be loaded in the packaging material of the present invention, will be described below.

The heat-sensitive recording material has a heat-sensitive recording layer and a protective layer in this order on a support, and further has other layers if necessary. When an intermediate layer is provided on the heat-sensitive recording layer or as the above-mentioned other layer on the heat-sensitive recording layer, the protective layer is formed on the intermediate layer. The protective layer is formed by applying a protective layer coating liquid, the protective layer coating liquid contains at least a pigment and a binder, further, to improve the head matching, and to obtain a good coated surface, It preferably contains an emulsion of silicone oil (hereinafter, may be simply referred to as “silicone oil”) dispersed with an average particle size of 0.15 μm or less and, if necessary, other components. .

Silicone oil has an average particle size of 0.15.
The average particle size is preferably 0.10 μm or less, and the average particle size is 0.08 μm.
The following is more preferable. If the average particle size exceeds 0.15 μm, the emulsion of silicone oil is destroyed by strong stirring or ultrasonic irradiation to form huge oil droplets, which tends to cause coating failure due to cissing. In this specification, the average particle size of silicone oil is COULTER.
It refers to the value measured by N4 type submicron particle analyzer manufactured by the same company.

The average particle size of the silicone oil is 0.15μ
In order to disperse the m or less, for example, a homogenizer, a dissolver, a colloid mill, in the presence of a dispersion aid such as polyvinyl alcohol or various surfactants, preferably a nonionic surfactant or an alkylbenzene sulfonate.
A known disperser such as an ultrasonic emulsifier can be used to disperse the particles to the above-mentioned average particle size.

Usable poly (dimethylsiloxane) can be used as the silicone oil, and ether-modified silicone oil, carboxy-modified silicone oil, amino-modified silicone oil, carbinol-modified silicone oil, phenol-modified silicone oil, and Mercapto-modified silicone oil is preferred,
Ether-modified silicone oil, carboxy-modified silicone oil, and amino-modified silicone oil are more preferred. These may be used alone or in combination of two or more. These modified silicone oils
It may be modified at the side chain or at the end.

The viscosity of the silicone oil is 400 to
100,000 mPa · s is preferable, 1000-500
00 mPa · s is more preferable. The viscosity is 400 mPa
・ If it is smaller than s, when the surface of the protective layer is touched with a finger, it may become sticky and leave fingerprint marks. On the other hand, the viscosity is 10
If it exceeds 0000 mPa · s, the average particle size becomes 0.15μ.
It may be difficult to emulsify and disperse it to m or less.

The amount of the silicone oil added is preferably 1 to 15% by mass, based on the total amount of the protective layer applied, and 2-1.
0 mass% is more preferable. If the amount added is less than 1% by mass, the effect of imparting slipperiness to the head may not be obtained. On the other hand, even if the addition amount exceeds 15% by mass, not only further effects cannot be obtained, but also an adverse effect of head contamination may occur.

The pigment used in the heat-sensitive recording material is usually
Make recording with a thermal head suitable, that is,
It is used for the purpose of suppressing the occurrence of sticking and abnormal noise, but it is preferable to use an organic and / or inorganic pigment.

The pigment used in the protective layer has an average particle size, specifically, 50 measured by a laser diffraction method.
% Volume average particle size (laser diffraction particle size distribution measuring device LA7
00 (manufactured by Horiba, Ltd.), the average particle size of the pigment particles corresponding to 50% volume in the pigment. Hereinafter, it may be simply referred to as “average particle size”. ) Is 0.20
It is preferably 1.00 μm, and in particular, from the viewpoint of preventing sticking, noise and the like between the head and the heat-sensitive recording material when recording with a thermal head, the 50% volume average particle diameter is 0.1. 20-0.50 μm
Is more preferably in the range. If the 50% volume average particle size exceeds 1.00 μm, the effect of reducing wear on the thermal head is small, which is not preferable, and if it is less than 0.20 μm, the effect of pigment addition, that is,
The effect of preventing welding between the thermal head and the binder in the protective layer decreases, and as a result, the thermal head and the protective layer of the thermal recording material adhere to each other during printing, causing so-called sticking, which is not preferable. .

The pigment contained in the protective layer includes
It is not particularly limited, and known organic and inorganic pigments can be mentioned, but in particular, inorganic pigments such as calcium carbonate, titanium oxide, kaolin, aluminum hydroxide, amorphous silica, zinc oxide, and urea formalin. Organic pigments such as resins and epoxy resins are preferred. Among them, Kaolin,
Aluminum hydroxide and amorphous silica are more preferable. These pigments may be used alone or in combination of two or more. Among these, an inorganic pigment surface-coated with at least one selected from the group consisting of higher fatty acids, metal salts of higher fatty acids, higher alcohols, and higher fatty acid amides is particularly preferable. Examples of the higher fatty acid include stearic acid, palmitic acid, myristic acid, and lauric acid.

These pigments are, for example, dispersion aids such as sodium hexametaphosphate, partially saponified or completely saponified modified polyvinyl alcohol, polyacrylic acid copolymers, various surfactants, etc., preferably partially saponified or completely saponified. It is preferable that the saponified modified polyvinyl alcohol and the polyacrylic acid copolymer ammonium salt are used in the coexistence of a known disperser such as a dissolver, a sand mill, and a ball mill to obtain the above-mentioned average particle size. That is, it is preferable to disperse the pigment until the 50% volume average particle diameter thereof reaches a particle diameter in the range of 0.20 to 1.00 μm before use. From the viewpoint of improving the transparency of the protective layer, a completely saponified polyvinyl alcohol, a carboxy-modified polyvinyl alcohol, a silica-modified polyvinyl alcohol, or the like is preferable as the binder.

The protective layer may contain known hardeners, metallic soaps and the like. Further, in order to uniformly form a protective layer on the heat-sensitive recording layer or on the intermediate layer, it is preferable to add a surfactant to the coating liquid for forming a protective layer. Examples of the surfactant include a sulfosuccinic acid-based alkali metal salt and a fluorine-containing surfactant, and specifically, di- (2-ethylhexyl) sulfosuccinic acid, di-
(N-hexyl) sulfosuccinic acid and the like sodium salts or ammonium salts and the like.

Furthermore, wax is added to the protective layer for the purpose of reducing the wear of the recording head, and surfactants, metal oxide fine particles, inorganic electrolytes, polymer electrolytes, etc. are added for the purpose of preventing the electrification of the heat-sensitive recording material. Good. The wax preferably has a melting point in the range of 40 to 100 ° C. and a 50% volume average particle diameter of 0.7 μm or less,
It is more preferably 0.4 μm or less. If the average particle diameter exceeds 0.7 μm, the transparency of the protective layer tends to be low, and image blurring tends to occur. If the melting point is less than 40 ° C, the surface of the protective layer may become tacky, and if it exceeds 100 ° C, sticking tends to occur.

Examples of the wax having a melting point of 40 to 100 ° C. include paraffin wax; petroleum wax such as microcrystalline wax; synthetic wax such as polyethylene wax; vegetable wax such as candelilla wax, carnauba wax and rice wax; Animal waxes such as lanolin; mineral waxes such as montan wax. Among these, the melting point is 55 to 7
Paraffin wax having a temperature of 5 ° C. is particularly preferable. The amount of the wax used is 0.5 to 40% by mass of the entire protective layer.
Is preferable, and 1 to 20 mass% is more preferable. Further, these waxes may be used in combination with a 12-hydroxystearic acid derivative, a higher fatty acid amide or the like.

As a method for dispersing the wax to the above-mentioned 50% volume average particle diameter, the wax is dispersed with a known wet disperser such as a Dynomill or a sand mill in the presence of an appropriate protective colloid or a surfactant. Examples of the method include, from the viewpoint of forming fine particles, after the wax is once heated and melted, means such as high-speed stirring, ultrasonic dispersion, etc. in a solvent in which the wax is insoluble or hardly soluble at a temperature equal to or higher than this melting point. And a method of dissolving the wax in an appropriate solvent and then emulsifying it in a solvent in which the wax is insoluble or hardly soluble. At this time, an appropriate surfactant or protective colloid may be used together. The protective layer may have a single layer structure or a laminated structure of two or more layers. The dry coating amount of the protective layer is preferably 0.2 to 7 g / m ² , and 1
-4 g / m ² is more preferable.

The heat-sensitive recording layer contains at least a color-forming component and, if necessary, further contains other components. The heat-sensitive recording layer may be of any composition as long as it has excellent transparency when untreated and has a property of being colored by heating. Such a heat-sensitive recording layer is a so-called two-component type heat-sensitive recording layer containing a substantially colorless color-forming component A and a substantially colorless color-forming component B which reacts with the color-forming component A to form a color. The color-forming component A or the color-forming component B is preferably included in microcapsules. Examples of the combination of the two components forming the two-component type thermal recording layer include the following (a) to (s).

(A) A combination of an electron-donating dye precursor and an electron-accepting compound. (A) A combination of a photodegradable diazo compound and a coupler. (C) Organic metal salts such as silver behenate and silver stearate,
Combination with reducing agents such as protocatechuic acid, spiroindane, hydroquinone. (D) Combination of long-chain aliphatic salts such as ferric stearate and ferric myristate with phenols such as gallic acid and ammonium salicylate. (E) Organic acid heavy metal salts such as salts with nickel, cobalt, lead, copper, iron, mercury, silver, etc. such as acetic acid, stearic acid, palmitic acid, calcium sulfide, strontium sulfide,
Combination with alkaline earth metal sulfides such as potassium sulfide,
Alternatively, a combination of the organic acid heavy metal salt and an organic chelating agent such as s-diphenylcarbazide and diphenylcarbazone. (F) A combination of (heavy) metal sulfates such as silver sulfide, lead sulfide, mercury sulfide and sodium sulfide and sulfur compounds such as Na-tetrathionate, sodium thiosulfate and thiourea. (G) an aliphatic ferric salt such as ferric stearate;
Combination with aromatic polyhydroxy compounds such as 4-dihydroxytetraphenylmethane. (H) Organic noble metal salts such as silver oxalate and mercury oxalate,
Combination with organic polyhydroxy compounds such as polyhydroxy alcohol, glycerin and glycol. (K) A combination of a ferric iron salt such as ferric pelargonate and ferric laurate with a thiocecylcarbamide or isothiocesylcarbamide derivative. A combination of an organic acid lead salt such as (co) lead caproate, lead pelargonate, and lead behenate and a thiourea derivative such as ethylenethiourea and N-dodecylthiourea. (A) A combination of higher fatty acid heavy metal salts such as ferric stearate and copper stearate, and zinc dialkyldithiocarbamate. (C) A substance that forms an oxazine dye, such as a combination of resorcin and a nitroso compound. (S) A combination of a formazan compound with a reducing agent and / or a metal salt.

Among these, (a) a combination of an electron-donating dye precursor and an electron-accepting compound, (b) a combination of a photodecomposable diazo compound and a coupler, or (c) an organic metal salt and a reducing agent. It is preferable to use the combination of, and it is particularly preferable to use the combination of (a) or (a). Further, in the heat-sensitive recording material, an image having excellent transparency can be obtained by configuring the heat-sensitive recording layer so as to reduce the haze value calculated from (diffuse transmittance / total light transmittance) × 100 (%). You can This haze value is an index representing the transparency of the material, and is generally calculated from a total light transmission amount, a diffuse transmission light amount, and a parallel transmission light amount using a haze meter. As a method of lowering the haze value, for example, 50% of both components of the color forming components A and B contained in the thermosensitive recording layer are used.
Volume average particle size is 1.0 μm or less, preferably 0.6 μm
m or less and a binder is contained in the range of 30 to 60% by mass of the total solid content of the heat-sensitive recording layer, one of the color-forming components A and B is microencapsulated, and the other is substantially dried after coating and drying. Examples include a method of forming a continuous layer, for example, a method of using as an emulsion. It is also effective to bring the refractive index of the component used in the heat-sensitive recording layer as close as possible to a constant value.

Next, the combination (a, b, c) of the above-mentioned composition which is preferably used in the heat-sensitive recording layer will be described in detail below. First, the combination of (a) an electron donating dye precursor and an electron accepting compound will be described. The electron-donating dye precursor preferably used in the heat-sensitive recording material is
It is not particularly limited as long as it is substantially colorless, but it has a property of developing a color by donating an electron or by accepting a proton such as an acid,
It is preferably a colorless compound having a partial skeleton such as lactone, lactam, sultone, spiropyran, ester or amide, and these partial skeletons are ring-opened or cleaved when contacted with an electron accepting compound.

Examples of the electron-donating dye precursors include triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leuco auramine compounds, rhodamine lactam compounds, tris. Examples thereof include phenylmethane compounds, triazene compounds, spiropyran compounds, fluorene compounds, pyridine compounds and pyrazine compounds.

Specific examples of the phthalides include US Reissue Patent No. 23,024 and US Patent No. 3,49.
No. 1,111, No. 3,491,112, No. 3,491,116, No. 3,50
Examples thereof include the compounds described in the specification of No. 9,174. Specific examples of the fluoranes include US Pat. Nos. 3,624,107 and 3,627,787.
No. 3,641,011 and No. 3,641,011
No. 462,828, No. 3,681,390, No. 3,920,510, No. 3,95
Examples thereof include the compounds described in the specification of No. 9,571. Specific examples of the spiropyrans include compounds described in US Pat. No. 3,971,808. Examples of the pyridine-based and pyrazine-based compounds include US Pat. Nos. 3,775,424, 3,853,869 and 4,246,318.
The compounds described in the specification etc. may be mentioned. Specific examples of the fluorene compound include Japanese Patent Application No. 61-240.
The compounds described in Japanese Patent No. 989 and the like are mentioned. Among these, in particular, black-colored 2-arylamino-3-
[H, halogen, alkyl or alkoxy-6-substituted aminofluorane] is preferred.

Specifically, for example, 2-anilino-3-
Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-N-cyclohexyl-N-methylaminofluorane, 2-p-chloroanilino-3-methyl-6-dibutylaminofluorane, 2-anilino- 3-
Methyl-6-dioctylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-
Anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-
N-ethyl-N-dodecylaminofluorane, 2-anilino-3-methoxy-6-dibutylaminofluorane,
2-o-chloroanilino-6-dibutylaminofluorane, 2-p-chloroanilino-3-ethyl-6-N-ethyl-N-isoamylaminofluorane, 2-o-chloroanilino-6-p-butylanilinoflu Oran, 2-
Anilino-3-pentadecyl-6-diethylaminofluorane, 2-anilino-3-ethyl-6-dibutylaminofluorane, 2-o-toluidino-3-methyl-6-
Diisopropylaminofluorane, 2-anilino-3-
Methyl-6-N-isobutyl-N-ethylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N
-Tetrahydrofurfurylaminofluorane, 2-anilino-3-chloro-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-
Methyl-N-γ-ethoxypropylaminofluorane,
2-anilino-3-methyl-6-N-ethyl-N-γ-
Ethoxypropylaminofluorane, 2-anilino-3
-Methyl-6-N-ethyl-N-γ-propoxypropylaminofluorane and the like can be mentioned.

Examples of the electron-accepting compound that acts on the electron-donating dye precursor include phenol compounds, organic acids or metal salts thereof, and acidic substances such as oxybenzoic acid esters. For example, JP-A-61-291183. Examples thereof include the compounds described in Japanese Patent Publication No. In particular,
2,2-bis (4'-hydroxyphenyl) propane (generic name: bisphenol A), 2,2-bis (4'-
Hydroxyphenyl) pentane, 2,2-bis (4'-
Hydroxy-3 ', 5'-dichlorophenyl) propane,
1,1-bis (4'-hydroxyphenyl) cyclohexane, 2,2-bis (4'-hydroxyphenyl) hexane, 1,1-bis (4'-hydroxyphenyl) propane, 1,1-bis (4 ' -Hydroxyphenyl) butane, 1,1-bis (4'-hydroxyphenyl) pentane, 1,1-bis (4'-hydroxyphenyl) hexane, 1,1-bis (4'-hydroxyphenyl) heptane, 1, 1-bis (4'-hydroxyphenyl) octane, 1,1-bis (4'-hydroxyphenyl) -2-
Methyl-pentane, 1,1-bis (4'-hydroxyphenyl) -2-ethyl-hexane, 1,1-bis (4 '
-Hydroxyphenyl) dodecane, 1,4-bis (p-
Hydroxyphenylcumyl) benzene, 1,3-bis (p-hydroxyphenylcumyl) benzene, bis (p
-Hydroxyphenyl) sulfone, bis (3-allyl-
Bisphenols such as 4-hydroxyphenyl) sulfone and bis (p-hydroxyphenyl) acetic acid benzyl ester; 3,5-di-α-methylbenzylsalicylic acid,
3,5-di-tert-butyl salicylic acid, 3-α-
Salicylic acid derivatives such as α-dimethylbenzyl salicylic acid and 4- (β-p-methoxyphenoxyethoxy) salicylic acid; or polyvalent metal salts thereof (particularly zinc and aluminum are preferable); p-hydroxybenzoic acid benzyl ether, p- Hydroxybenzoic acid-2-ethylhexyl ester, β-resorcinic acid- (2-phenoxyethyl)
Oxybenzoic acid esters such as esters; p-phenylphenol, 3,5-diphenylphenol, cumylphenol, 4-hydroxy-4′-isopropoxy-diphenylsulfone, 4-hydroxy-4′-phenoxy-diphenylsulfone, etc. Phenols of.
Of these, bisphenols are particularly preferable from the viewpoint of obtaining good color development characteristics. Further, the electron-accepting compound is
They may be used alone or in combination of two or more.

Next, the combination of (a) the photodecomposable diazo compound and the coupler will be described. The photodecomposable diazo compound is a compound that develops a desired hue by a coupling reaction with a coupler, which is a coupling component described later, and decomposes when receiving light in a specific wavelength range before the reaction, and is no longer coupled. It is a photodecomposable diazo compound that loses its ability to develop color even when components are present. The hue in this color development system is determined by the diazo dye produced by the reaction between the diazo compound and the coupler. Therefore, the color hue can be easily changed by changing the chemical structure of the diazo compound or the coupler, and depending on the combination,
Any color hue can be obtained.

Examples of the photodecomposable diazo compound preferably used in the heat-sensitive recording material include aromatic diazo compounds, specifically, aromatic diazonium salts, diazosulfonate compounds, diazoamino compounds and the like. . Examples of the aromatic diazonium salt include, but are not limited to, compounds represented by the following general formula. The aromatic diazonium salt is preferably used because it has excellent photofixability, little generation of colored stain after fixing, and stable color-developing portion. Ar-N ₂ ⁺ X ^{-In the} above formula, Ar represents a substituted or unsubstituted aromatic hydrocarbon ring group, N ₂ ⁺ represents a diazonium group, X represents
^- represents an acid anion. As the above-mentioned diazosulfonate compound, a large number have been known in recent years, which are obtained by treating each diazonium salt with sulfite,
It can be suitably used for a heat-sensitive recording material.

The diazoamino compound can be obtained by coupling the diazo group with dicyandiamide, sarcosine, methyltaurine, N-ethylanthranic acid-5-sulphonic acid, monoethanolamine, diethanolamine, guanidine and the like. Therefore, it can be suitably used as a heat-sensitive recording material. Details of these diazo compounds are described in, for example, JP-A-2-136286. On the other hand, examples of the coupler that undergoes a coupling reaction with the above-mentioned diazo compound include 2-hydroxy-3-
Besides naphthoic acid anilide, resorcin and those described in JP-A-62-146678 can be mentioned.

When a combination of a diazo compound and a coupler is used in the heat-sensitive recording layer, these coupling reactions are sensitized from the viewpoint that the reaction can be further promoted by performing them in a basic atmosphere. A basic substance may be added as an agent. Examples of the basic substance include water-insoluble or sparingly soluble basic substances and substances that generate an alkali by heating, for example, inorganic or organic ammonium salts, organic amines, amides, urea and thiourea or their derivatives, Thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines,
Nitrogen-containing compounds such as forimuazines and pyridines can be mentioned. Specific examples of these include, for example, Japanese Patent Laid-Open No.
Examples thereof include those described in JP-A 1-291183.

Next, (c) a combination of an organometallic salt and a reducing agent will be described. Specific examples of the organic metal salt include silver salts of long-chain aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachiate and silver behenate; benzotriazole silver. Salts, silver salts of organic compounds having an imino group such as benzimidazole silver salts, carbazole silver salts or phthalazinone silver salts; silver salts of sulfur-containing compounds such as s-alkylthioglycolates; aroma such as silver benzoate and silver phthalate Group carboxylic acid silver salt; Sulfonic acid silver salt such as silver ethane sulfonate; o
A silver salt of sulfinic acid such as silver toluenesulfinate; a silver salt of phosphoric acid such as silver phenylphosphate; silver barbiturate;
Mention may be made of silver saccharinate, silver salts of salicylasdoxime or any mixture thereof. Of these, long-chain aliphatic carboxylic acid silver salts are preferable, and silver behenate is more preferable. Also, behenic acid may be used with silver behenate.

As the reducing agent, there is disclosed Japanese Patent Laid-Open No. 53-102.
It can be appropriately used based on the description of JP-A No. 0, page 227, lower left column, line 14 to page 229, upper right column, line 11. Among them, mono, bis, tris or tetrakisphenols, mono or bisnaphthols, di or polyhydroxynaphthalenes, di or polyhydroxybenzenes,
Hydroxy monoethers, ascorbic acids, 3-pyrazolidones, pyrazolines, pyrazolones, reducing sugars, phenylenediamines, hydroxylamines, reductones, hydrooxamic acids, hydrazides, amidoximes, N-hydroxyurea It is preferable to use a class or the like. Among the above, aromatic organic reducing agents such as polyphenols, sulfonamide phenols or naphthols are particularly preferable.

In order to ensure sufficient transparency of the heat-sensitive recording material, (a) a combination of an electron-donating dye precursor and an electron-accepting compound, or (b) a photodecomposable diazo compound is used in the heat-sensitive recording layer. It is preferred to use a combination of In addition, it is preferable to use one of the color-forming component A and the color-forming component B in a microencapsulated form,
It is more preferable to use the electron-donating dye precursor or the photodecomposable diazo compound in the form of microcapsules.

The method for producing microcapsules will be described in detail below. There are an interfacial polymerization method, an internal polymerization method, an external polymerization method and the like for producing the microcapsules, and any method can be adopted. As described above, the thermal recording material is
It is preferable to microencapsulate the electron-donating dye precursor or the photodecomposable diazo compound, and in particular, the electron-donating dye precursor or the photodecomposable diazo compound which is the core of the capsule is dissolved in a hydrophobic organic solvent. Alternatively, the oil phase prepared by dispersion is mixed in a water phase in which a water-soluble polymer is dissolved, and after emulsification and dispersion by a means such as a homogenizer, a polymer formation reaction occurs at the oil droplet interface by heating, It is preferable to adopt an interfacial polymerization method for forming the microcapsule wall of a polymer substance.

The reactant forming the polymer substance is added inside the oil droplet and / or outside the oil droplet. Specific examples of the polymer substance include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, and styrene-acrylate copolymer. Among these, polyurethane, polyurea, polyamide, polyester,
Polycarbonate is preferable, and polyurethane and polyurea are particularly preferable.

For example, when polyurea is used as the capsule wall material, polyisocyanates such as diisocyanate, triisocyanate, tetraisocyanate and polyisocyanate prepolymer, and polyamines such as diamine, triamine and tetraamine, 2 A microcapsule wall can be easily formed by reacting the above-described amino group-containing prepolymer, piperazine or a derivative thereof, polyol or the like with the interfacial polymerization method in the aqueous phase.

Further, for example, a composite wall made of polyurea and polyamide or a composite wall made of polyurethane and polyamide is, for example, a polyisocyanate and a second substance (for example, acid chloride or polyamine, which reacts therewith to form a capsule wall). It can be prepared by mixing a polyol) with a water-soluble polymer aqueous solution (aqueous phase) or an oil medium (oil phase) to be encapsulated, emulsifying and dispersing these, and then heating. Details of the method for producing the composite wall composed of polyurea and polyamide are described in JP-A-58-66948.

As the polyisocyanate compound,
A compound having a trifunctional or higher functional isocyanate group is preferable, but a bifunctional isocyanate compound may be used in combination. Specifically, xylene diisocyanate and its hydrogenated product, hexamethylene diisocyanate, tolylene diisocyanate and its hydrogenated product, diisocyanate such as isophorone diisocyanate as a main raw material, and these dimers Alternatively, in addition to trimers (burette or isocyanurate), polyfunctional adducts of polyols such as trimethylolpropane and difunctional isocyanates such as xylylene diisocyanate, polyols such as trimethylolpropane and xylyl. Examples thereof include compounds in which a high molecular weight compound such as polyether having active hydrogen such as polyethylene oxide is introduced into an adduct with a difunctional isocyanate such as diisocyanate, and a formalin condensate of benzene isocyanate. JP 62-2
No. 12190, No. 4-26189, No. 5-317694, and No. 10-114153.
The compounds described in JP-A No. 1994-200242 are preferred. The polyisocyanate has a microcapsule average particle size of 0.3 to 12
It is preferably added so that the thickness of the capsule wall is 0.01 to 0.3 μm. The dispersed particle size is 0.
It is generally about 2 to 10 μm.

Specific examples of the polyol or / and polyamine which is added to the aqueous phase and / or the oil phase as one of the constituents of the microcapsule wall by reacting with polyisocyanate include propylene glycol, glycerin and trimethylol. Examples include propane, triethanolamine, sorbitol, hexamethylenediamine and the like. A polyurethane wall is formed when the polyol is added.
In the above reaction, it is preferable to keep the reaction temperature high or to add an appropriate polymerization catalyst from the viewpoint of accelerating the reaction rate. Polyisocyanates, polyols, reaction catalysts, and polyamines for forming a part of the wall material are well known in the literature (edited by Keiji Iwata, Polyurethane Handbook, Nikkan Kogyo Shimbun (1987)).

If necessary, a metal-containing dye, a charge control agent such as nigrosine, or any other additive substance may be added to the microcapsule wall. These additives can be contained in the wall of the capsule at the time of forming the wall or at any time. Further, a monomer such as a vinyl monomer may be graft-polymerized in order to adjust the chargeability of the capsule wall surface, if necessary.

Further, in order to make the wall of the microcapsule excellent in material permeability even in a lower temperature condition and rich in color development, it is preferable to use a plasticizer suitable for the polymer used as the wall material. The melting point of the plasticizer is preferably 50 ° C. or higher, more preferably 120 ° C. or lower. Of these, those that are solid at room temperature can be suitably selected and used. For example, when the wall material is made of polyurea or polyurethane, a hydroxy compound,
Carbamic acid ester compound, aromatic alkoxy compound, organic sulfonamide compound, aliphatic amide compound,
Aryl amide compounds and the like are preferably used.

In the preparation of the oil phase, the hydrophobic organic solvent used when the electron-donating dye precursor or the photodegradable diazo compound is dissolved to form the core of the microcapsule has a boiling point of 100 to 300. Organic solvents at ° C are preferred. Specifically, in addition to esters, dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene,
Dimethylbiphenyl, diisopropylbiphenyl, diisobutylbiphenyl, 1-methyl-1-dimethylphenyl-2-phenylmethane, 1-ethyl-1-dimethylphenyl-1-phenylmethane, 1-propyl-1-dimethylphenyl-1-phenylmethane , Triallyl methane (eg tritoluyl methane, toluyl diphenyl methane), terphenyl compounds (eg terphenyl), alkyl compounds, alkylated diphenyl ethers (eg propyl diphenyl ether), hydrogenated terphenyls (eg hexahydroterphenyl) , Diphenyl ether and the like. Among these, it is particularly preferable to use esters from the viewpoint of emulsion stability of the emulsion dispersion.

Examples of the above-mentioned esters include phosphates such as triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, cresylphenyl phosphate;
Phthalates such as dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, octyl phthalate, butylbenzyl phthalate; dioctyl tetrahydrophthalate; ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, Benzoic acid esters such as benzyl benzoate; Abietic acid esters such as ethyl abietic acid and benzyl abietic acid; Dioctyl adipate; Isodecyl succinate; Dioctyl azelate;
Oxalic acid esters such as dibutyl oxalate and dipentyl oxalate; diethyl malonate; maleic acid esters such as dimethyl maleate, diethyl maleate, dibutyl maleate; tributyl citrate; methyl sorbate, ethyl sorbate, butyl sorbate, etc. Sorbic acid ester; sebacic acid ester such as dibutyl sebacate, dioctyl sebacate; formic acid monoester and diester,
Butyric acid monoester and diester, lauric acid monoester and diester, palmitic acid monoester and diester, stearic acid monoester and diester,
Ethylene glycol esters such as oleic acid monoesters and diesters; triacetin; diethyl carbonate; diphenyl carbonate; ethylene carbonate; propylene carbonate; boric acid esters such as tributyl borate and tripentyl borate.

Of these, the use of tricresyl phosphate alone or in combination is particularly preferable because the emulsion has the best stability. It is also possible to use the above oils together or in combination with other oils.

When the electron-donating dye precursor to be encapsulated or the photodecomposable diazo compound has poor solubility in the above-mentioned hydrophobic organic solvent, a low-boiling solvent having high solubility is used in combination as an auxiliary. You can also Preferred examples of such a low boiling point solvent include ethyl acetate, isopropyl acetate, butyl acetate and methylene chloride.

When the electron-donating dye precursor or the photodecomposable diazo compound is used in the heat-sensitive recording layer of the heat-sensitive recording material, the content of the electron-donating dye precursor is 0.1-5.
Preferably ^{0g / m 2, 1.0~3.5g / m} 2 is more preferable. The content of the photodegradable diazo compound is
0.02-5.0 g / m < ² > is preferable, and 0.10-4.0 g / m < ² > is more preferable in terms of color density.

The content of the electron-donating dye precursor is 0.
If the content of the photodecomposable diazo compound is less than 1 g / m ² , or the content of the photodecomposable diazo compound is less than 0.02 g / m ² , sufficient color density may not be obtained, and the content of both may be 5 or less. If it exceeds 0.0 g / m ² , the transparency of the heat-sensitive recording layer may decrease.

On the other hand, an aqueous solution in which a water-soluble polymer is dissolved is used as a protective colloid for the aqueous phase to be used, and after the oil phase is added thereto, it is emulsified and dispersed by a means such as a homogenizer. Makes the dispersion uniform and easy and acts as a dispersion medium for stabilizing the emulsified and dispersed aqueous solution. Here, a surfactant may be added to at least one of the oil phase and the water phase in order to more uniformly emulsify and stabilize the emulsion. As the surfactant, a well-known emulsifying surfactant can be used. The amount of the surfactant added is 0.1 with respect to the mass of the oil phase.
-5% is preferable, and 0.5-2% is more preferable.

The surfactant to be contained in the aqueous phase is preferably selected from anionic or nonionic surfactants which do not cause precipitation or aggregation by acting on the protective colloid. it can. Preferred surfactants include, for example, sodium alkylbenzenesulfonate, sodium alkylsulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (for example,
And polyoxyethylene nonylphenyl ether).

The emulsification is performed by rapidly stirring the oil phase containing the above components and the aqueous phase containing the protective colloid and the surfactant.
It can be easily carried out by using a known emulsifying device such as a means used for ordinary fine particle emulsification such as ultrasonic dispersion, for example, a homogenizer, a Manton-Gory, an ultrasonic disperser, a dissolver, a Keddy mill. After the emulsification, the emulsion is preferably heated to 30 to 70 ° C. in order to accelerate the capsule wall forming reaction. Further, during the reaction, in order to prevent aggregation of the capsules, it is preferable to add water to reduce the collision probability of the capsules or to perform sufficient stirring.

A dispersion for preventing aggregation may be added again during the reaction. Generation of carbon dioxide gas is observed with the progress of the polymerization reaction, and the end of the generation can be regarded as the approximate end point of the capsule wall forming reaction. Usually, the desired microcapsules can be obtained by reacting for several hours.

When an electron-donating dye precursor or a photodecomposable diazo compound is encapsulated as a core substance, the electron-accepting compound or coupler used is, for example, a water-soluble polymer and an organic base, or another color-developing agent. It can be used by solid-dispersing it with a means such as a sand mill together with an auxiliary agent or the like, but after dissolving it in a high boiling organic solvent which is hardly soluble or insoluble in water in advance, it is mixed with a surfactant and / or a water-soluble polymer. It is more preferable to use it as an emulsified dispersion prepared by mixing with a polymer aqueous solution (aqueous phase) contained as a protective colloid and emulsifying with a homogenizer or the like. In this case, a low boiling point solvent may be used as a dissolution aid, if necessary. Further, the coupler and the organic base can be emulsified and dispersed separately, or can be mixed and then dissolved in a high-boiling point organic solvent to be emulsified and dispersed. A preferable emulsified dispersed particle diameter is 1 μm or less.

The high-boiling organic solvent used in this case is
For example, it can be appropriately selected from the high boiling point oils described in JP-A-2-141279. Among them, it is preferable to use esters from the viewpoint of emulsion stability of the emulsion dispersion, and tricresyl phosphate is particularly preferable. The above oils can be used together or with other oils.

The water-soluble polymer contained as the protective colloid can be appropriately selected from known anionic polymers, nonionic polymers and amphoteric polymers, and water at the temperature at which emulsification is attempted. A water-soluble polymer having a solubility of 5% or more in water is preferable, and specific examples thereof include polyvinyl alcohol or its modified product, polyacrylic acid amide or its derivative, ethylene-vinyl acetate copolymer, and styrene-maleic anhydride copolymer. Combined, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer,
Examples include cellulose derivatives such as carboxymethyl cellulose and methyl cellulose, casein, gelatin, starch derivatives, arabic gum, sodium alginate and the like. Among these, polyvinyl alcohol, gelatin, and cellulose derivatives are particularly preferable.

Further, the mixing ratio of the oil phase to the water phase (oil phase mass / water phase mass) is preferably 0.02 to 0.6, and is preferably 0.
1 to 0.4 is more preferable. When the mixing ratio is less than 0.02, the amount of the aqueous phase is too large to be diluted and the production suitability is poor. On the other hand, when the mixing ratio is more than 0.6, the viscosity of the liquid is increased to the contrary. It is not preferable because it causes inconvenience in handling and decreases the stability of the coating solution.

When an electron-accepting compound is used in the heat-sensitive recording material, the amount of the electron-accepting compound is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 30 parts by mass with respect to 1 part by mass of the electron-donating dye precursor. 10 parts by mass is more preferable. When a coupler is used in the heat-sensitive recording material, the coupler is used in an amount of 0.1 to 30 with respect to 1 part by mass of the diazo compound.
Parts by mass are preferred.

The heat-sensitive recording layer coating liquid can be prepared, for example, by mixing the microcapsule liquid prepared as described above and the emulsified dispersion. Here, the water-soluble polymer used as a protective colloid in the preparation of the microcapsule liquid, and the water-soluble polymer used as a protective colloid in the preparation of the emulsion dispersion are used as a binder in the thermosensitive recording layer. Function. Further, a binder may be added and mixed separately from these protective colloids to prepare a coating liquid for the heat-sensitive recording layer. The binder to be added is generally a water-soluble binder, and polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer Examples thereof include coalesce, isobutylene-maleic salicylic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein, gelatin and the like. In addition, a water resistant agent may be added to these binders for the purpose of imparting water resistance, or an emulsion of a hydrophobic polymer, specifically, a styrene-butadiene rubber latex or an acrylic resin emulsion may be added.

When the above-mentioned coating liquid for heat-sensitive recording layer is coated on the support, known coating means used for water-based or organic solvent-based coating liquid are used. In this case, the coating liquid for heat-sensitive recording layer can be used safely and safely. In order to maintain the strength of the coating film while applying it uniformly, in the heat-sensitive recording material, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, starches, gelatin, polyvinyl alcohol,
Carboxy-modified polyvinyl alcohol, polyacrylamide, polystyrene or its copolymer, polyester or its copolymer, polyethylene or its copolymer, epoxy resin, acrylate resin or its copolymer, methacrylate resin or its copolymer Polyurethane resin, polyamide resin, polyvinyl butyral resin, etc. can be used.

Other components that can be used in the heat-sensitive recording layer will be described below. The other components are appropriately selected depending on the intended purpose without any limitation, and examples thereof include known heat-fusible substances, ultraviolet absorbers, and antioxidants.

The heat-fusible substance can be contained in the heat-sensitive recording layer for the purpose of improving the thermal response. Examples of the heat-fusible substance include aromatic ethers, thioethers,
Examples thereof include esters, aliphatic amides and ureides. Examples of these are disclosed in JP-A-58-57989 and JP-A-58-87.
094, 61-58789, 62-10968.
No. 1, No. 62-132674, No. 63-151478.
No. 63-233591, JP-A-2-184489.
No. 2,215,585.

Suitable examples of the UV absorber include benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, cyanoacrylate UV absorbers, oxalic acid anilide UV absorbers, and the like. To be Examples of these are disclosed in JP-A-4
No. 7-10537, No. 58-111942, No. 58-
212844, 59-945, 59-46
646, 59-109055, 63-5354.
No. 4, Japanese Patent Publication No. 36-10466, No. 42-26187
No. 48-30492, 48-31255, 48-41572, 48-54965, 50-.
No. 10726, U.S. Pat. No. 2,719,086
Nos. 3,707,375 and 3,754,919
No. 4,220,711, and the like.

As the antioxidant, a hindered amine-based antioxidant, a hindered phenol-based antioxidant,
Suitable examples include aniline-based antioxidants and quinoline-based antioxidants. Examples of these are disclosed in JP-A-59-15509.
No. 0, No. 60-107383, No. 60-107384
No. 61-137770, No. 61-139481
No. 61-160287, and the like.

The coating amount of the other components is 0.
05-1.0 g / m ² is preferable, 0.1-0.4
g / m ² is more preferable. The other ingredients are
It may be added inside the microcapsules or outside the microcapsules.

The heat-sensitive recording layer has the energy required to obtain the saturated transmission density (D _T-max ) in order to suppress the density unevenness caused by a slight difference in heat conduction of the thermal head and obtain a high quality image. It is preferable that the heat-sensitive recording layer has a wide amount range, that is, a wide dynamic range. The heat-sensitive recording material has the heat-sensitive recording layer as described above, and is 90 to 150 mJ / mm.
It is preferable that the heat-sensitive recording layer has a characteristic that the transmission density _DT 3.0 can be obtained with the amount of heat energy in the range of ² .

The heat-sensitive recording layer is coated so that the dry coating amount after coating and drying is 1 to 25 g / m ² .
And it is preferable that the thickness of the layer is applied to be 1 to 25 μm.

A transparent support is preferably used as the heat-sensitive recording material in order to obtain a transparent heat-sensitive recording material. Examples of the transparent support include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose triacetate films, synthetic polymer films such as polyolefin films such as polypropylene and polyethylene, and these may be used alone or in combination. be able to. The thickness of the synthetic polymer film is 2
5-250 μm is preferable, and 50-200 μm is more preferable.

The above-mentioned synthetic polymer film may be colored in any hue. As a method of coloring a polymer film, a method of kneading a dye into a resin to form a film before forming a resin film, preparing a coating solution in which the dye is dissolved in an appropriate solvent, and preparing a colorless transparent resin Known coating methods such as a gravure coating method, a roller coating method, a wire coating method and the like can be mentioned. Above all, it is preferable that a polyester resin such as polyethylene terephthalate or polyethylene naphthalate in which a blue dye is kneaded is formed into a film and subjected to heat treatment, stretching treatment and antistatic treatment.

Particularly, when a transparent heat-sensitive recording material is observed from the side of the support on a Schaukasten, the Schaukasten light passing through the transparent non-image portion may cause an illusion to make an image difficult to see. In order to avoid this, as the transparent support, A (x = 0.2805, y = 0.30 on the chromaticity coordinate defined by the method described in JIS-Z8701) is used.
05), B (x = 0.2820, y = 0.2970),
C (x = 0.2885, y = 0.3015), D (x =
It is particularly preferable to use a blue-colored synthetic polymer film in a rectangular area formed by four points (0.2870, y = 0.340).

The thermosensitive recording material comprises an intermediate layer, an undercoat layer, an ultraviolet filter layer, and other layers on the support, as other layers.
A light antireflection layer or the like can be provided.

The intermediate layer is preferably formed on the thermosensitive recording layer. The intermediate layer is provided to prevent mixing of the layers and to shield gases (oxygen etc.) harmful to image storability. The binder to be used is not particularly limited, and polyvinyl alcohol, gelatin, polyvinylpyrrolidone, cellulose derivative and the like can be used depending on the system. Further, various surfactants may be added to impart coating suitability. Further, in order to further enhance the gas barrier property, the inorganic fine particles such as mica are added to the binder in an amount of 2 to
You may add 20 mass%, More preferably, 5-10 mass%.

In the heat-sensitive recording material, for the purpose of preventing the heat-sensitive recording layer from peeling off from the support, an undercoat is applied on the support before applying the heat-sensitive recording layer containing microcapsules or the like or the antireflection layer. Layers can be provided. As the undercoat layer, an acrylic acid ester copolymer, polyvinylidene chloride, SBR, aqueous polyester or the like can be used, and the layer thickness is preferably 0.05 to 0.5 μm.

When the heat-sensitive recording layer is coated on the undercoat layer, the water contained in the coating solution for the heat-sensitive recording layer may swell the undercoat layer, which may deteriorate the image recorded on the heat-sensitive recording layer. Glutaraldehyde, 2, for the undercoat layer
It is preferable to harden the film using a dialdehyde such as 3-dihydroxy-1,4-dioxane and a hardening agent such as boric acid. The amount of these hardeners added is in the range of 0.2 to 3.0% by mass according to the mass of the undercoat material, and can be appropriately added according to the desired degree of curing.

An ultraviolet filter layer may be provided on the back side of the support opposite to the coated surface of the thermosensitive recording layer for the purpose of preventing fading of the image. The UV filter layer contains a benzotriazole-based, benzophenone-based, hindered amine-based UV absorber or the like.

On the back side of the support opposite to the coated surface of the heat-sensitive recording layer, the average particle size is 1 to 20 μm, preferably 1 to 10
A light reflection preventing layer containing fine particles of μm may be provided.
By coating this light reflection preventing layer, the glossiness measured at an incident light angle of 20 ° is preferably 50% or less, and 30%.
The following is more preferable. Examples of the fine particles contained in the light antireflection layer include fine particles of barley, wheat, corn, rice, starch and the like obtained from beans, cellulose fiber, polystyrene resin, epoxy resin, polyurethane resin, urea formalin resin, poly ( (Meth) acrylate resin, polymethyl (meth) acrylate resin, copolymer resin such as vinyl chloride or vinyl acetate, fine particles of synthetic polymer such as polyolefin, calcium carbonate, titanium oxide,
Examples thereof include fine particles of inorganic substances such as kaolin, smectite clay, aluminum hydroxide, silica and zinc oxide. These may be used alone or in combination of two or more. Further, from the viewpoint of improving the transparency of the heat-sensitive recording material, it is preferably a fine particle substance having a refractive index of 1.45 to 1.75.

The heat-sensitive recording material can be preferably manufactured by the manufacturing method described below, but the manufacturing method is not limited to this, and can be manufactured by other manufacturing methods. The heat-sensitive recording material has an excellent head-matching property and a good coating surface without coating failure because the protective layer coating liquid contains an emulsion of silicone oil dispersed in an average particle size of 0.15 μm or less. In particular, it is preferably used in fields requiring high image quality such as medical recording media.

The method for producing the heat-sensitive recording material will be described below. The heat-sensitive recording material is produced by coating a support with a heat-sensitive recording layer-forming coating solution to form a heat-sensitive recording layer, and coating the heat-sensitive recording layer with a protective layer containing at least a pigment and a binder. A liquid is applied to form a protective layer and, if necessary, other layers are formed. here,
The heat-sensitive recording layer and the protective layer may be formed at the same time, and in that case, the heat-sensitive recording layer and the protective layer-forming coating solution are coated on the support at the same time to form the heat-sensitive recording layer. The recording layer and the protective layer can be simultaneously formed on the recording layer.

In the method for producing a heat-sensitive recording material, the coating liquid for forming the protective layer contains an emulsion of silicone oil dispersed preferably with an average particle size of 0.15 μm or less. The emulsion does not break due to the shearing force when passing through the plate or the ultrasonic defoaming machine, and thus giant oil droplets are not formed to cause cissing-like coating failure, and the manufacturing stability is excellent.

As the support used here, the support described above for the heat-sensitive recording material can be used. The coating liquid for forming the thermosensitive recording layer may be the coating liquid for forming the thermosensitive recording layer described above, and the coating liquid for forming the protective layer may also be used for the protective layer containing the pigment and the binder described above. A coating liquid can be used. Examples of the other layer include other layers such as the intermediate layer and the undercoat layer described above. In the method for producing a heat-sensitive recording material, on the support, in order to sequentially form an undercoat layer, a heat-sensitive recording layer, an intermediate layer, a protective layer, a blade coating method, an air knife coating method, a gravure coating method, a roll coating coating method, Known coating methods such as a spray coating method, a dip coating method and a bar coating method are used. According to the above manufacturing method, the thermal recording material described above can be manufactured.

Next, a heat-developable image recording material which is another typical sheet recording material which can be loaded in the packaging material of the present invention will be described. The heat-developable image recording material has a constitution containing on one surface of a support at least one non-photosensitive organic silver salt, a reducing agent for silver ions and a binder. The organic silver salt and the binder are contained in the image forming layer, and the image forming layer preferably further contains a reducing agent for silver ions of the organic silver salt. Further, the heat-developable image recording material preferably has a photosensitive layer containing a photosensitive silver halide and a binder. Most preferably, the image forming layer contains a photosensitive silver halide and functions as a photosensitive layer. In such a heat-developable image recording material, the image-forming layer, particularly preferably the photosensitive image-forming layer, can be water-based coated using a coating liquid in which 30% by mass of the environmentally preferable solvent is water. And is preferable for obtaining good photographic performance 2
A polymer having an equilibrium water content of 2% by mass or less at 5 ° C. and a relative humidity of 60% is preferably used as a main binder. In the following description, a photothermographic material containing a photosensitive silver halide in the image forming layer will be described as an example. The photothermographic material is preferably a monosheet type (a type capable of forming an image on the photothermographic material without using another sheet such as an image receiving material). It is particularly effective in a photothermographic material for red to infrared exposure.

The photothermographic material has a photosensitive layer containing a photosensitive silver halide (catalytically active amount of photocatalyst) and a reducing agent and a non-photosensitive layer. The photosensitive layer further comprises a binder (generally a synthetic polymer), an organic silver salt (a reducible silver source).
And preferably contains a reducing agent. Further, it is preferable to contain a hydrazine compound (super-high contrast agent) and a color tone adjusting agent (control the color tone of silver). The photothermographic material may be provided with a plurality of photosensitive layers. For example, a high-sensitivity photosensitive layer and a low-sensitivity photosensitive layer can be provided in the photothermographic material for the purpose of adjusting gradation. Regarding the order of arrangement of the high-sensitivity photosensitive layer and the low-sensitivity photosensitive layer, the low-sensitivity photosensitive layer may be arranged below (support side) or the high-sensitivity photosensitive layer may be arranged below. The non-photosensitive layer may be provided as another functional layer such as a surface protective layer in addition to the dye-containing layer, that is, the filter layer or the antihalation layer.

As the support for the photothermographic material, paper, polyethylene-coated paper, polypropylene-coated paper, parchment, cloth, metal (eg, aluminum, copper, magnesium, zinc) sheet or thin film, glass, Glass and plastic films coated with metals (eg chromium alloys, steel, silver, gold, platinum) are used. Preferably, it is a transparent plastic film, and examples of plastics used for the support include polyalkyl methacrylate (eg, polymethyl methacrylate), polyester (eg, polyethylene terephthalate: PET), polyvinyl acetal, polyamide (eg, nylon) and Cellulose esters (eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate) are included. The support preferably has a thickness of 90 to 190 μm, more preferably 150 to 185 μm.

The support may be coated with a polymer. Examples of polymers include polyvinylidene chloride, acrylic acid-based polymers (eg, polyacrylonitrile, methyl acrylate) polymers of unsaturated dicarboxylic acids (eg, itaconic acid, acrylic acid), carboxymethyl cellulose and polyacrylamides. Copolymers may be used. Instead of coating with a polymer, a subbing layer containing a polymer may be provided.

Examples of organic silver salts used in the photothermographic material include silver salts of fatty acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid) and carboxyalkylthioureas (eg, 1 -(3-
Carboxypropyl) thiourea, silver salt of 1- (3-carboxypropyl) -3,3-dimethylthiourea), polymer reaction product of aldehyde (eg formaldehyde, acetaldehyde, butyraldehyde) and hydroxy-substituted aromatic carboxylic acid Silver complex, an aromatic carboxylic acid (for example, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), a thioene compound (for example, 3- (2-carboxyethyl)- Four
-Hydroxymethyl-4-thiazolin-2-thioene,
3-carboxymethyl-4-thiazoline-2-thioene) silver salt or silver complex, nitric acid (eg imidazole, pyrazole, urazole, 1,2,4-thiazole, 1H-tetrazole, 3-amino-5-benzylthio) -1,2,4-triazole, benzotriazole)
And silver complexes of saccharin, silver salts of saccharin, silver salts of 5-chlorosalicylaldoxime and silver salts of mercaptides. Most preferred is silver behenate. The organic silver salt is preferably used in a silver amount of 0.05 to 3 g / m ² , and more preferably 0.3 to ² g / m ² .

The photothermographic material contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt may be any substance (preferably organic substance) that reduces silver ions to metallic silver. Such reducing agents are disclosed in JP-A No. 11-65021, paragraphs 0043 to 0045, and European Patent Publication No. 0803.
No. 764, page 7, line 34 to page 18, page 1
It is described in two lines. Among them, particularly bisphenol reducing agents (for example, 1,1-bis (2-hydroxy-3,
5-dimethylphenyl) -3,5,5-trimethylhexane) is preferred. The amount of reducing agent added is 0.01 to 5.0.
g / m ² is preferable, and 0.1 to 3.0 g / m ²
It is more preferable that the content is 5 to 50% by mole, and further preferably 10 to 40% by mole based on 1 mole of silver on the surface having the image forming layer. The reducing agent is preferably contained in the image forming layer.

The reducing agent may be added to the photothermographic material by being added to the coating solution by any method such as a solution form, an emulsion dispersion form and a solid fine particle dispersion form. Well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion A method of producing the same can be given. As the solid fine particle dispersion method, a powder of a reducing agent is dispersed in a suitable solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves to prepare a solid dispersion. There is a method. At that time, a protective colloid (eg, polyvinyl alcohol) or a surfactant (eg, anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three different isopropyl group substitution positions) or the like) may be used. Good. The water dispersion may contain a preservative (for example, benzoisothiazolinone sodium salt).

The photosensitive silver halide used in the photothermographic material is not particularly limited in halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver iodochlorobromide are used. You can The distribution of the halogen composition in the grain may be uniform, the halogen composition may be changed stepwise, or the halogen composition may be continuously changed. Further, silver halide grains having a core / shell structure can be preferably used. A preferable structure is a 2- to 5-layer structure, and more preferably a 2- to 4-layer structure core / shell particles can be used. Further, a technique of localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used. Methods of forming light sensitive silver halide are well known in the art and are described, for example, in Research Disclosure, June 1978, No. 17029.
The method described in US Pat. No. 3,700,458 can be used, but specifically, the addition of a silver-providing compound and a halogen-providing compound into a gelatin or other polymer solution. Is used to prepare a photosensitive silver halide and then mixed with an organic silver salt.

The grain size of the photosensitive silver halide is preferably small in order to suppress white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm or less.
To 0.15 μm, more preferably 0.02 to 0.12 μm
m is good. The grain size as used herein means the volume of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal, or when it is not a normal crystal, such as a spherical grain or a rod-shaped grain. It means the diameter when considering an equivalent sphere, and when the silver halide grains are tabular grains, it means the diameter when converted into a circular image having the same area as the projected area of the main surface.

The shape of the silver halide grains is cubic,
Examples thereof include octahedra, tabular grains, spherical grains, rod-shaped grains and potato-shaped grains, and cubic grains are particularly preferable. Grains with 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 high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, may be high. preferable. The ratio is preferably 50% or more, more preferably 65% or more, still more preferably 80% or more. The ratio of Miller index {100} plane is {1 in the adsorption of sensitizing dye.
T.Ta using the adsorption dependence of the 11} and {100} planes
ni; J.Imaging Sci., 29, 165 (1985).

The photosensitive silver halide grains contain a metal or metal complex of Group 8 to Group 10 of the Periodic Table (showing Groups 1 to 18). The metal of Group 8 to 10 of the periodic table or the central metal of the metal complex is preferably rhodium, rhenium, ruthenium, osmium or iridium. One of these metal complexes may be used, or two or more of the same metal complex and different metal complexes may be used in combination. The preferred content is 1 × 10 ^-9 mol to 1 × 10 1 mol of silver.
A range of ^-3 mol is preferred. Regarding these metal complexes, JP-A No. 11-65021, paragraph numbers 0018 to 00
24.

Among them, it is preferable to include an iridium compound in the silver halide grains. Examples of the iridium compound include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium, pentachloronitrosyliridium, and the like. These iridium compounds are used by dissolving them in water or a suitable solvent, and are generally used for stabilizing the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid,
A method of adding bromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide. The addition amount of these iridium compounds is 1 × 10 ⁻⁸ mol to 1 × per mol of silver halide.
The range of 10 ⁻³ mol is preferable, and 1 × 10 ⁻⁷ mol to 5 × 1.
The range of 0 ^-4 mol is more preferable.

Metal atoms which can be contained in silver halide grains used in the photothermographic material (for example, [Fe
(CN) ₆ ] ^4- ), desalting method, and chemical sensitization method, paragraph Nos. 0046 to 005 of JP-A No. 11-84574.
0, JP-A-11-65021, paragraph number 0025 to
0031. The photosensitive silver halide emulsion in the photothermographic material may be of one kind or two or more kinds (for example, different average grain sizes, different halogen compositions, different crystal habits, chemical sensitization conditions). Different ones) may be used together. Gradation can be adjusted by using a plurality of photosensitive silver halides having different sensitivities. Japanese Patent Application Laid-Open No. 57-1193
No. 41, No. 53-106125, No. 47-3.
929 publication, 48-55730 publication, 46-5.
No. 187, No. 50-73627, No. 57-1.
No. 50841 is cited. Regarding the difference in sensitivity, it is preferable that each emulsion has a difference of 0.2 log E or more.

The addition amount of the photosensitive silver halide is 0.03 to 0.03 in terms of the coated silver amount per 1 m ^{2 of the} photothermographic material.
It is preferably 0.6 g / m ² , and 0.05 to 0.
It is more preferably 4 g / m ² , and 0.1 to 0.
It is most preferably 4 g / m ² , 0.01 to 0.5 mol of photosensitive silver halide is preferable, and 0.02 to 0.3 mol is more preferable, relative to 1 mol of organic silver salt.
0.03 to 0.25 mol is particularly preferable. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide grains and organic silver salt are mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, a homogenizer. And the like, or a method of mixing the photosensitive silver halide prepared at any timing during the preparation of the organic silver salt to prepare the organic silver salt, but there is no particular limitation.

The time of addition of silver halide to the coating liquid for the image forming layer is preferably 180 minutes before coating, and preferably 60 minutes before 10 seconds before coating, but there is no particular limitation. Specific mixing methods include a method of mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid fed to the coater is set to a desired time, N. Harnby, MFEdwa
rds, AW Nienow, translated by Koji Takahashi, "Liquid Mixing Technology" (published by Nikkan Kogyo Shimbun, 1989), Chapter 8 and the like.

When the organic silver salt-containing layer is formed by coating with a coating solution in which 30% by mass or more of the solvent is water and drying, the binder of the organic silver salt-containing layer is further added with an aqueous solvent (water. It is preferable that the polymer latex is soluble or dispersible in a (solvent), and particularly comprises a polymer latex having an equilibrium water content of 2% by mass or less at 25 ° C. and 60% relative humidity. The most preferable form is prepared so that the ionic conductivity is 2.5 mS / cm or less, and such a preparation method includes a method of purifying using a separation functional membrane after polymer synthesis. The aqueous solvent in which the polymer is soluble or dispersible as used herein is water or a mixture of water and 70% by mass or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide. It should be noted that the term “aqueous solvent” is used here even in the case of a system in which the polymer is not thermodynamically dissolved and exists in a so-called dispersed state.

"Equilibrium water content at 25 ° C. and 60% relative humidity" means the mass W1 of the polymer in humidity controlled equilibrium in the atmosphere of 25 ° C. and 60% relative humidity, and the polymer in an absolutely dry state at 25 ° C. It can be expressed as follows using the mass W0 of

[Equation 1] For the definition and measurement method of water content, for example, Polymer Engineering Course 14, Polymer Material Testing Method (Polymer Society of Japan, Jijijinkan)
Can be used as a reference. 25 of binder polymer
The equilibrium water content at a temperature of 60 ° C. and a relative humidity of 60% is preferably 2% by mass or less, more preferably 0.01 to
The amount is preferably 1.5% by mass, more preferably 0.02 to 1% by mass.

Particularly preferred are polymers dispersible in an aqueous solvent. Examples of the dispersed state include a latex in which fine particles of a solid polymer are dispersed, a state in which polymer molecules are dispersed in a molecular state or in the form of micelles, and both are preferable. In a preferred embodiment, acrylic resin, polyester resin, rubber resin (for example, SB
Hydrophobic polymers such as R resin), polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinylidene chloride resin, and polyolefin resin can be preferably used. The polymer may be a linear polymer, a branched polymer or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more kinds of monomers are polymerized. In the case of a copolymer, even a random copolymer,
It may be a block copolymer. The number average molecular weight of the polymer is 5,000 to 1,000,000, preferably 10
000-200000 is preferable. If the molecular weight is too small, the mechanical strength of the emulsion layer is insufficient, and if it is too large, the film formability is poor and it is not preferred.

The "aqueous solvent" means 30% by mass of the composition.
The above is a dispersion medium containing water. As the dispersion state, those which are emulsified and dispersed, those which are micelle dispersed, those in which a polymer having a hydrophilic site in the molecule is dispersed in the molecular state, and the like.
Any may be used, but latex is particularly preferred among these. The following may be mentioned as specific examples of the preferred polymer latex. In the following, the raw material monomers are used, and the numerical values in parentheses are mass% and the molecular weights are number average molecular weights. P-1; -MMA (70) -EA (27) -MAA (3)
-Latex (Mw 37,000) P-2; -MMA (70) -2EHA (20) -St
Latex of (5) -AA (5)-(Mw 40000) P-3; -St (50) -Bu
Latex of (47) -MAA (3)-(molecular weight 45000) P-4; -St (68) -B
u (29) -AA (3)-latex (Mw 60000) P-5; -St (70) -B
u (27) -IA (3)-latex (Mw 120000) P-6; -St (75)-
Bu (24) -AA (1) -latex (Mw 108000) P-7; -St (60)
-Bu (35) -DVB (3) -MAA (2) -latex (Molecular weight 150000) P-
8; -St (70) -Bu (25) -DVB (2) -AA (3) -latex (molecular weight 2
80000) P-9; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5) -latex (Molecular weight 80000) P-10; -VDC (85) -MMA ( 5) -EA (5) -MA
Latex of A (5)-(molecular weight 67000) P-11; -Et (90) -MAA (10)
-Latex (Mw 12000) P-12; -St (70) -2EHA (27) -AA
Latex of (3) (Molecular weight 130000) P-13; -MMA (63) -EA (35)
-Latex of AA (2) (molecular weight 33000) The abbreviations for the above structures represent the following monomers. MMA; methyl methacrylate, EA; ethyl acrylate, MAA; methacrylic acid, 2EHA; 2 ethylhexyl acrylate, St;
Styrene, Bu; Butadiene, AA; Acrylic acid, DV
B: divinylbenzene, VC: vinyl chloride, AN: acrylonitrile, VDC: vinylidene chloride, Et: ethylene, IA: itaconic acid.

The polymer latexes described above are commercially available, and the following polymers can be used. Examples of acrylic resins include Sebian A-4635,46
583, 4601 (all manufactured by Daicel Chemical Industries, Ltd.),
Nipol Lx811, 814, 821, 820, 8
Examples of polyester resins such as 57 (all manufactured by Nippon Zeon Co., Ltd.) include FINETEX ES650 and 61.
1,675,850 (above Dainippon Ink and Chemicals, Inc.)
), WD-size, WMS (all manufactured by Eastman Chemical Co., Ltd.), and HYD as an example of the polyurethane resin.
Examples of the rubber resin such as RAN AP10, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) include LA.
CSTAR 7310K, 3307B, 4700H, 7
132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipo
Examples of vinyl chloride resins such as Lx416, 410, 438C, and 2507 (all manufactured by Nippon Zeon Co., Ltd.) are G351, G576 (all manufactured by Nippon Zeon Co., Ltd.), and vinylidene chloride resin is L502. , L5
Examples of the olefin resin such as 13 (all manufactured by Asahi Kasei Co., Ltd.) include Chemipearl S120 and SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.). These polymer latexes may be used alone, or may be used by blending two or more kinds as required.

As the polymer latex, a latex of styrene-butadiene copolymer is particularly preferable. The mass ratio of the styrene monomer unit and the butadiene monomer unit in the styrene-butadiene copolymer is 40:
It is preferably 60 to 95: 5. The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 60 to 99% by mass. The preferred molecular weight range is the same as above. Preferable styrene-butadiene copolymer latexes are the above-mentioned P-3 to P-8 and commercially available LACSTA.
R-3307B, 7132C, Nipol Lx416
Etc.

If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose may be added to the organic silver salt-containing layer of the photothermographic material. The addition amount of these hydrophilic polymers is preferably 30% by mass or less, more preferably 20% by mass or less based on the total amount of binders in the organic silver salt-containing layer. The organic silver salt-containing layer (that is, the image forming layer) is preferably formed using a polymer latex. The amount of the binder in the organic silver salt-containing layer is preferably such that the total binder / organic silver salt mass ratio is 1/10 to 10/1, more preferably 1/5 to 4/1. Further, such an organic silver salt-containing layer is usually
It is also a photosensitive layer (emulsion layer) containing a photosensitive silver halide which is a photosensitive silver salt, and in such a case, the total binder / silver halide mass ratio is 400 to 5, more preferably 200 to A range of 10 is preferred. The total amount of binder in the image forming layer of the photothermographic material is 0.2 to 30 g / m ² ,
The range of 1 to 15 g / m ² is more preferable. A cross-linking agent for cross-linking, a surfactant for improving coatability, and the like may be added to the image forming layer.

The solvent of the coating solution for the organic silver salt-containing layer of the photothermographic material (here, for simplicity, the solvent and the dispersion medium are collectively referred to as the solvent) is an aqueous solvent containing 30% by mass or more of water.
As a component other than water, any water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide or ethyl acetate may be used. The water content of the solvent of the coating liquid is preferably 50% by mass or more, more preferably 70% by mass or more. To give an example of a preferable solvent composition,
Other than water, water / methyl alcohol = 90/10, water / methyl alcohol = 70/30, water / methyl alcohol / dimethylformamide = 80/15/5, water / methyl alcohol / ethyl cellosolve = 85/10/5, Water / methyl alcohol / isopropyl alcohol = 85/10 /
There are 5 etc. (numerical value is% by mass).

The sensitizing dye applicable to the photothermographic material is capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and has a spectrum suitable for the spectral characteristics of the exposure light source. Sensitizing sensitizing dyes can be advantageously selected. Regarding the sensitizing dye and addition method,
Paragraph Nos. 0103 to 0 of JP-A No. 11-65021
109, Japanese Patent Application Laid-Open No. 10-186572.
Compounds represented by I), European Patent Publication No. 0803764
See page 19, line 38 to page 20, line 35 of the publication. In the present invention, the sensitizing dye is added to the silver halide emulsion preferably after the desalting step and before coating, more preferably after the desalting step and before the start of chemical ripening.

Antifoggants, stabilizers and stabilizer precursors which can be used in the photothermographic material.
Paragraph No. 0070 of 899 Publication, European Patent Publication No. 08
The patents described on page 20, line 57 to page 21, line 7 of Japanese Patent No. 03764 can be mentioned. Further, the antifoggants preferably used in the photothermographic material are organic halides, which are disclosed in JP-A-11-6.
Those disclosed in the patents described in paragraph Nos. 0111 to 0112 of Japanese Patent No. 5021 are cited. In particular, JP-A-1
Organic polyhalogen compounds represented by the general formula (II) of 0-339934 (specifically, tribromomethylnaphthyl sulfone, tribromomethylphenyl sulfone,
Tribromomethyl (4- (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone and the like is preferable.

Examples of the method for incorporating the antifoggant into the photothermographic material include the methods described in the method for incorporating the reducing agent, and the organic polyhalogen compound is also preferably added in the form of solid fine particle dispersion. Other antifoggants include mercury (II) salts described in paragraph No. 0113 of JP-A No. 11-65021 and paragraph No. 0114 of the same publication.
Benzoic acids of. An azolium salt may be used in the photothermographic material for the purpose of preventing fog. As the azolium salt, compounds represented by formula (XI) described in JP-A-59-193447, JP-B-55-1
No. 2581, JP-A-60-15303
Examples thereof include compounds represented by the general formula (II) described in JP-B-9. The azolium salt may be added to any part of the photothermographic material, but as an addition layer, it is preferably added to the layer having the photosensitive layer, and more preferably to the organic silver salt-containing layer. The azolium salt may be added at any step in the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, it may be at any step from the preparation of the organic silver salt to the preparation of the coating solution, but after the preparation of the organic silver salt. Therefore, immediately before coating is preferable. The azolium salt may be added by any method such as powder, solution and fine particle dispersion. Also, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a toning agent. The amount of the azolium salt added may be any amount, but it is 1 per mol of silver.
× 10 ⁻⁶ mol to 2 mol is preferable, and 1 × 10 ⁻³ mol to
0.5 mol is more preferable.

A mercapto compound, a disulfide compound or a thione compound may be contained in order to suppress or accelerate the development to control the development, to improve the spectral sensitization efficiency, or to improve the storage stability before and after the development,
Paragraph numbers 0067 to 0 of JP-A-10-62899
069, compounds represented by the general formula (I) in JP-A-10-186572 and specific examples thereof are described in paragraphs 0033 to 0052 and European Patent Publication No. 0803764, page 20, lines 36 to 56. ing.
Of these, mercapto-substituted heteroaromatic compounds are preferable.

A color tone agent is preferably added to the photothermographic material. Regarding the color toning agent, JP-A-10-6289
Paragraph Nos. 0054-0055 of Japanese Patent Publication No. 9 and European Patent Publication No. 0803764, page 21, lines 23-48, and particularly phthalazinone, a phthalazinone derivative or a metal salt, or 4- (1-naphthyl). Derivatives such as phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (eg phthalic acid, 4-methylphthalic acid, 4-
(Such as nitrophthalic acid and tetrachlorophthalic anhydride)
A combination of phthalazines (phthalazine, a phthalazine derivative or a metal salt, or 4- (1-naphthyl) phthalazine, 6-isopropylphthalazine, 6-t-butylflatazine, 6-chlorophthalazine, 5,7-dimethoxy. Phthalazine and derivatives such as 2,3-dihydrophthalazine); a combination of phthalazines and a phthalic acid derivative (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) is preferable, A combination of phthalazines and a phthalic acid derivative is particularly preferable.

Regarding the plasticizer and lubricant which can be used in the photosensitive layer of the photothermographic material, JP-A-11-65 is known.
No. 021 Publication, paragraph 0117, for super-high contrast agents for forming super-high contrast images, paragraph No. 0118,
General formula (III) described in Japanese Patent Application No. 11-91652.
To (V) compounds (specific compounds: chemical formula 21 to chemical formula 24),
The contrast enhancer is described in paragraph No. 0102 of JP-A No. 11-65021.

The photothermographic material may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer. The surface protective layer is described in paragraph Nos. 0119 to 0120 of JP-A No. 11-65021. Gelatin is preferred as the binder for the surface protective layer, but it is also preferred to use polyvinyl alcohol (PVA). As PVA, completely saponified PVA-105 [polyvinyl alcohol (PVA) content 94.0 mass% or more, saponification degree 98.5 ± 0.5 mol%, sodium acetate content 1.5]
Mass% or less, volatile content 5.0 mass% or less, viscosity (4 mass%, 20 ° C.) 5.6 ± 0.4 mPa · s], partially saponified PVA-205 [PVA content 94.0 mass%, Saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0% by mass, volatile content 5.0% by mass, viscosity (4% by mass,
20 ° C.) 5.0 ± 0.4 mPa · s], modified polyvinyl alcohol MP-102, MP-202, MP-20
3, R-1130, R-2105 (above, Kuraray Co., Ltd.
Product name) etc. Protective layer (per layer)
Polyvinyl alcohol coating amount (per 1 m ^{2 of} support)
Is preferably 0.3 to 4.0 g / m ^{2, and} 0.3 to 4.0
2.0 g / m ² is more preferable.

The preparation temperature of the coating liquid for the image forming layer is 30 to 65.
C is good, more preferable temperature is 35 ° C or higher and lower than 60 ° C, and more preferable temperature is 35 to 55 ° C. The temperature of the coating liquid for the image forming layer immediately after the addition of the polymer latex is preferably maintained at 30 to 65 ° C. Further, it is preferable that the reducing agent and the organic silver salt are mixed before the addition of the polymer latex. The organic silver salt-containing fluid or the thermal image forming layer coating solution is preferably a so-called thixotropic fluid. The thixotropic property means a property that the viscosity decreases as the shear rate increases. Although any device may be used for the viscosity measurement, an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is preferably used and the viscosity is measured at 25 ° C. Here, the organic silver salt-containing fluid or the thermal image forming layer coating solution has a shear rate of 0.1 S.
The viscosity at ^-1 is preferably 400 to 100,000 mPa · s, and more preferably 500 to 20,000 mP.
a · s. Further, at a shear rate of 1000 S ^−1, it is preferably ¹ to 200 mPa · s, and more preferably 5
˜80 mPa · s.

Various systems exhibiting thixotropy are known, and “Course / Rheology” edited by Polymer Publishing Society, Muroi,
Morino co-authored in "Polymer Latex" (published by Polymer Publishing Association). It is necessary that the fluid contains a large amount of solid fine particles in order to exhibit thixotropic properties.
Further, in order to enhance thixotropy, it is effective to add a thickening linear polymer, to increase the aspect ratio in the anisotropic solid particles contained therein, to increase the alkali viscosity, and to use a surfactant.

The heat-developable photographic emulsion is composed of one or more layers on a support. The one-layer construction must contain organic silver salts, silver halides, developers and binders, and optionally additional materials such as toning agents, coating aids and other auxiliaries. The two-layer construction comprises an organic silver salt and a silver halide in the first emulsion layer (usually the layer adjacent to the support) and some other ingredients in the second layer or both layers. I won't. However, a bilayer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The composition of the multicolor photosensitive photothermographic material may include a combination of these two layers for each color,
It may also include all components in a single layer as described in US Pat. No. 4,708,928. In the case of multi-dye multicolor light-sensitive photothermographic materials, each emulsion layer generally contains a functional or non-functional layer between each light-sensitive layer as described in U.S. Pat. No. 4,460,681. The use of functional barrier layers keeps them distinct from each other.

Various dyes and pigments can be used in the photosensitive layer from the viewpoints of improving color tone, preventing interference fringes during laser exposure, and preventing irradiation. These are described in detail in International Publication WO98 / 36322. Preferred dyes and pigments used in the photosensitive layer are anthraquinone dyes, azomethine dyes, indoaniline dyes, azo dyes, anthraquinone-based indanthrone pigments (such as CI Pigment Blue 60), phthalocyanine pigments.
(Copper phthalocyanine such as CI Pigment Blue 15, CI Pi
gment Blue 16 and other metal-free phthalocyanines), dyed lake pigment-based triarylcarbonyl pigments, indigo, inorganic pigments (ultra-blue, cobalt blue, etc.). As a method for adding these dyes and pigments, any method such as solution, emulsion, solid fine particle dispersion, and a state of being mordanted with a polymer mordant may be used. The amount of these compounds used is determined depending on the desired absorption amount, but it is generally preferable to use in the range of 1 μg to 1 g per 1 m ^{2 of the} photothermographic material.

The antihalation layer can be provided on the side farther from the light source than the photosensitive layer. The antihalation layer is described in paragraph Nos. 0123 to 0124 of JP-A No. 11-65021. It is preferable to add a decolorizing dye and a base precursor to the non-photosensitive layer of the photothermographic material so that the non-photosensitive layer functions as a filter layer or an antihalation layer. Photothermographic materials generally have a non-photosensitive layer in addition to the photosensitive layer.
The non-photosensitive layer is (1) a protective layer provided on the photosensitive layer (the side farther than the support) from the arrangement, (2) between a plurality of photosensitive layers or between the photosensitive layer and the protective layer. Can be classified into an intermediate layer provided in (3), (3) an undercoat layer provided between the photosensitive layer and the support, and (4) a back layer provided on the opposite side of the photosensitive layer. The filter layer is provided on the photothermographic material as the layer (1) or (2). The antihalation layer is provided on the photothermographic material as the layer (3) or (4).

The decolorizing dye and the base precursor are preferably added to the same non-photosensitive layer. However, it may be separately added to two adjacent non-photosensitive layers. Also, a barrier layer may be provided between the two non-photosensitive layers. As a method of adding the decolorizable dye to the non-photosensitive layer, a method of adding a solution, an emulsion, a solid fine particle dispersion or a polymer-impregnated material to a coating liquid for the non-photosensitive layer can be adopted. Further, a dye may be added to the non-photosensitive layer by using a polymer mordant. The method of adding these is the same as the method of adding a dye to a general photothermographic material. Latex used for polymer impregnation is described in US Pat. No. 4,199,363.
Specification, West German Patent Publication Nos. 25141274, 2541230, and European Patent Publication 029104.
And Japanese Patent Publication No. 53-41091. An emulsification method of adding a dye to a solution in which a polymer is dissolved is described in International Publication WO88 / 00723.

The addition amount of the decolorizing dye is determined depending on the use of the dye. Generally, it is used in such an amount that the optical density (absorbance) measured at a target wavelength exceeds 0.1. The optical density is preferably 0.2 to 2. The amount of dye used to obtain such an optical density is generally 0.00
It is about 1 to 1 g / m ² , and particularly preferably 0.01
It is about 0.2 g / m ² . By decoloring the dye in this way, the optical density can be lowered to 0.1 or less. Two or more kinds of decolorizable dyes may be used together in the thermally decolorizable recording material or the photothermographic material. Similarly, two or more kinds of base precursors may be used in combination. The photothermographic material is preferably a so-called single-sided photosensitive material having a photosensitive layer containing at least one layer of a silver halide emulsion on one side of a support and a back layer on the other side.

It is preferable to add a matting agent to the photothermographic material in order to improve transportability, and the matting agent is described in JP-A No. 11-65021, paragraph No. 0126-.
0127. The matting agent is preferably 1 to 4 when the coating amount per 1 m ^{2 of the} photothermographic material is shown.
The amount is 00 mg / m ² , more preferably 5 to 300 mg / m ² . The matteness of the emulsion surface may be any value as long as the stardust failure does not occur, but the Beck smoothness is 30 seconds or more 20
00 seconds or less is preferable, and 40 seconds or more and 1500 seconds or less is particularly preferable. As the matte degree of the back layer, Beck's smoothness is preferably 1200 seconds or less and 10 seconds or more, 800 seconds or less and 20 seconds or more, and more preferably 500 seconds or less and 40 seconds or more. The matting agent is preferably contained in the outermost surface layer of the photothermographic material, a layer functioning as the outermost surface layer, or a layer close to the outer surface, and may be contained in a layer acting as a so-called protective layer. preferable.
Regarding the back layer applicable to the photothermographic material, paragraph Nos. 0128 to JP-A No. 11-65021 are disclosed.
0130.

A hardener may be used in each layer such as the photosensitive layer, the protective layer and the back layer. TH James as an example of a hardener
By "THE THEORY OF THE PHOTOGRAPHIC PROCESS FOURTH E
DITION "(published by Macmillan Publishing Co., Inc., 1977). Each method is described on pages 77 to 87.
Polyvalent metal ions described in pages, US Pat. No. 4,281,
No. 060, JP-A-6-208193, and other polyisocyanates, US Pat. No. 4,791,042.
Epoxy compounds such as those disclosed in JP-A-62-890
Vinyl sulfone compounds such as JP-A No. 48 are preferably used.

The hardener is added as a solution, and the time of adding this solution to the protective layer coating solution is from 180 minutes before to just before coating, preferably from 60 minutes before to 10 seconds before coating. There are no particular restrictions on the mixing conditions. As a specific mixing method, a method of mixing in a tank in which the average residence time calculated from the addition flow rate and the amount sent to the coater is a desired time, N. Harnby, MF Edwards, AWN
There is a method of using the static mixer described in Chapter 8 of “Liquid Mixing Technology” translated by Koji Takahashi (published by Nikkan Kogyo Shimbun, 1989) by ienow.

For the surfactant, see JP-A-11-65.
No. 021 publication, paragraph number 0132, a solvent, the same publication paragraph number 0133, a support, the same publication paragraph number 0134, an antistatic or conductive layer, the same publication paragraph number 0135, and a method for obtaining a color image, the same. Japanese Patent Publication No. 0136. The transparent support may be colored with a blue dye (for example, Dye-1 described in Examples of JP-A-8-240877) or may be uncolored. Regarding the undercoating technique of the support, JP-A-11-
No. 84574, No. 10-186565, and the like. Further, the antistatic layer or the undercoat is disclosed in JP-A-56-143430 and JP-A-56-1434.
31 gazette, the same 58-62646 gazette, the same 56-12.
It is also possible to apply the technology of Japanese Patent No. 0519.

The photothermographic material is preferably a monosheet type (a type capable of forming an image on the photothermographic material without using another sheet such as an image receiving material). The photothermographic material may further contain an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber or a coating aid.
Various additives are added to either the photosensitive layer or the non-photosensitive layer. International publication WO98 / 36
No. 322, European Patent Publication No. 803764, JP-A Nos. 10-186567 and 10-18568, and the like can be referred to.

The photosensitive layer preferably further contains a super-high contrast agent, which may be further contained in the non-photosensitive layer. When the photothermographic material is used in the field of printing photographs, it is important to reproduce continuous tone images and line images by halftone dots. By using a super-high contrast agent, the reproducibility of halftone images and line images can be improved. As the ultra-high contrast agent, hydrazine compounds, quaternary ammonium compounds or acrylonitrile compounds (US Pat. No. 5,545,5
No. 15 description) is used. Hydrazine compounds are particularly preferred ultrahigh contrast agents.

The hydrazine compound is hydrazine (H ₂ N
—NH ₂ ) and compounds in which at least one of its hydrogen atoms has been replaced. The substituent is an aliphatic group, an aromatic group or a heterocyclic group directly bonded to the nitrogen atom of hydrazine, or an aliphatic group, an aromatic group or a heterocyclic group bonded to the nitrogen atom of hydrazine via a linking group. . Examples of linking groups include -CO
-, - CS -, - SO 2 -, - POR- (R is an aliphatic group, an aromatic group or a heterocyclic group), - CNH- and combinations thereof. For hydrazine compounds, see US Pat. Nos. 5,464,738 and 5,49.
6,695, 5,512,411, 5,5
Nos. 36,622, Japanese Patent Publication No. 6-77138,
6-93082, JP-A-6-230497, 6
-289520, 6-313951, 7-56.
No. 10, No. 7-77783, and No. 7-104426.

The hydrazine compound can be dissolved in a suitable organic solvent and added to the coating solution for the photosensitive layer. Examples of organic solvents include alcohols (eg methanol, ethanol, propanol, fluorinated alcohols), ketones (eg acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide and methylcellosolve. Also, hydrazine compounds are oily (auxiliary)
A solution dissolved in a solvent may be emulsified in the coating liquid. Examples of oily (auxiliary) solvents include dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, diethyl phthalate, ethyl acetate and cyclohexanone. Further, a solid dispersion of the hydrazine compound may be added to the coating solution. The dispersion of the hydrazine compound is
It can be carried out using a known disperser such as a ball mill, colloid mill, manton goring, microfluidizer or ultrasonic disperser.

The addition amount of the ultra-high contrast agent is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and 1 × 10 ⁻⁵ to 5 × 10 ⁻³ with respect to 1 mol of silver halide. It is more preferably a molar amount, and most preferably 2 × 10 ⁻⁵ to 5 × 10 ⁻³ mol. In addition to the ultra-high contrast agent, a high-contrast accelerator may be used. Examples of the contrast enhancing agent include amine compounds (described in US Pat. No. 5,545,505) and hydroxamic acid (US Pat. No. 5,545,507).
Specification), acrylonitriles (US Pat. No. 5,
No. 545,507) and hydrazine compounds (described in US Pat. No. 5,558,983).

The photothermographic material may be applied by any method. Specifically, various coatings including extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. A coating operation was used, Stephen F. Kistl
er, Petert M. Schweizer "LIQUID FILM COATING" (CHA
PMAN & HALL, 1997) Extrusion coating described in pages 399 to 536 or slide coating is preferably used, and slide coating is particularly preferably used. For an example of the shape of the slide coater used for slide coating, refer to F on page 427 of the same book.
igure 11b. In 1. Also, if desired, the method described on pages 399 to 536 of the same document, US Pat.
Two or more layers can be coated simultaneously by the methods described in 1,791 and GB 837,095.

Techniques that can be used for the photothermographic material include European Patent Publication Nos. 80376 and 88.
3022, International Publication WO98 / 36322, JP-A-56-62648, and JP-A-58-6264.
No. 4, JP-A-9-281637 and JP-A-9-29736.
7, gazette 9-304869 gazette, and 9-3114 gazette.
No. 05, No. 9-329865, No. 10-10.
No. 669, No. 10-62899, No. 10-6.
9023, 10-186568, and 10
-90823, 10-171063, 10-186565, 10-186567, 10-186569 to 10-18657.
No. 2, gazette 10-197974, gazette 10-19.
No. 7982, No. 10-197983, No. 10
-197985 gazette-the same 10-197987 gazette,
No. 10-207001, No. 10-207004, No. 10-221807, No. 10-2826.
No. 01, No. 10-288823, No. 10-2
88824, 10-307365, 1
No. 0-312038, No. 10-339934, No. 11-7100, No. 11-15105, No. 11-24200, No. 11-24201, No. 11-30832, No. 11 -84574
No. 11-65021 and No. 11-1258.
No. 80, No. 11-129629, No. 11-1.
No. 33536 to No. 11-133539, No. 1
No. 1-133542 and No. 11-133543 are also cited.

The photothermographic material may be developed by any method, but it is usually developed by raising the temperature of the imagewise exposed photothermographic material. The preferred developing temperature is 80 to 250 ° C., more preferably 100 to 14
It is 0 ° C. The developing time is preferably 1 to 180 seconds, more preferably 10 to 90 seconds, and particularly preferably 10 to 40 seconds. A plate heater method is preferable as the heat development method. The heat development method using a plate heater method is described in Japanese Patent Application No. 9-229684 and JP-A No. 11-1.
The method described in Japanese Patent No. 33572 is preferable, which is a heat developing apparatus for obtaining a visible image by bringing a photothermographic material having a latent image into contact with a heating means in a heat developing section, wherein the heating means is a plate heater. A plurality of pressing rollers are arranged opposite to each other along one surface of the plate heater, and the photothermographic material is passed between the pressing roller and the plate heater to perform thermal development. Is a heat developing device. It is preferable to divide the plate heater into 2 to 6 stages and lower the temperature of the tip portion by about 1 to 10 ° C. Such a method is disclosed in JP-A-54-3003.
No. 2 publication, it is possible to exclude water and organic solvent contained in the photothermographic material from the outside of the system,
Further, it is possible to suppress the change in the shape of the support of the photothermographic material due to the rapid heating of the photothermographic material.

The photothermographic material may be exposed by any method, but a laser beam is preferable as an exposure light source. As the laser light, gas laser (Ar ⁺ , He-Ne), YAG laser, dye laser, semiconductor laser and the like are preferable. Alternatively, a semiconductor laser and a second harmonic wave generating element may be used. Preferred is a gas of red to infrared emission or a semiconductor laser. As a laser beam, a single mode laser can be used, but JP-A-11-65021
The technique described in Japanese Patent Publication No. 0140 may be used. The laser output is preferably 1 mW or more, more preferably 10 mW or more, still more preferably 40 mW or more. At that time, a plurality of lasers may be combined. The laser beam diameter is 30-200μ at 1 / e ² spot size of Gaussian beam.
It can be about m. Fuji Medical Dry Laser Imager FM-DPL can be mentioned as a laser imager provided with an exposure part and a heat development part.

The photothermographic material forms a black and white image by a silver image and is used as a photothermographic material for medical diagnosis, a photothermographic material for industrial photography, a photothermographic material for printing, and a photothermographic material for COM. It is preferably used. In these uses, based on the formed black-and-white image, a duplicate image is formed on a duplication film MI-Dup manufactured by Fuji Photo Film Co., Ltd. for medical diagnosis, and a Fuji Photo Film Co., Ltd. is used for printing. ) Film for return DO-175,
It goes without saying that it can be used as a mask for forming an image on PDO-100 or an offset printing plate.

[0148]

EXAMPLES The features of the present invention will be described more specifically below with reference to examples and comparative examples. Materials shown in the following examples,
The usage amount, ratio, processing content, processing procedure, etc. can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

<Production of Sheet-Shaped Recording Material> [Preparation of Coating Liquid for Protective Layer] (Preparation of Pigment Dispersion Liquid for Protective Layer) 110 g of water was treated with stearic acid-treated aluminum hydroxide as a pigment (trade name: Hydilite H42S, Showa Denko KK) 30g added 3
After stirring for a while, a dispersion aid (trade name: Poise 53
2A, manufactured by Kao Corporation) 0.2 g, 10 mass% polyvinyl alcohol aqueous solution (trade name: PVA105, manufactured by Kuraray Co., Ltd.) 30 g, 10 mass% dodecylbenzenesulfonic acid sodium salt aqueous solution 1.0 g, and dispersed by a sand mill Then, a pigment dispersion liquid for a protective layer having an average particle diameter of 0.30 μm was obtained. The “average particle diameter” is 0, which is obtained by dispersing the pigment used in the presence of a dispersion aid and adding water to the pigment dispersion immediately after the dispersion.
The test liquid diluted to 5% by mass was poured into warm water at 40 ° C to adjust the light transmittance to 75 ± 1.0%, and then 3
Using the average particle size of pigment particles corresponding to 50% volume of all pigments, which was sonicated for 0 seconds and measured by a laser diffraction particle size distribution measuring device (trade name: LA700, manufactured by Horiba Ltd.), All of the "average particle diameters" described are average particle diameters measured by the same method.

(Preparation of Emulsion Dispersion of Wax Fine Particles) 20.0 g of solid paraffin wax (manufactured by Kanto Kagaku Co., Ltd.) having a melting point of 68 to 70 ° C. was added to a polyoxyethylene stearyl ether surfactant (trade name: Kao Emulgen 320).
5.0 g of P, manufactured by Kao Corporation) was added, and the mixture was heated to 75 ° C. and melt-mixed. This was added to 60 g of a 5% by mass polyvinyl alcohol aqueous solution (trade name: PVA205C, manufactured by Kuraray Co., Ltd.) at 75 ° C., and an ace homogenizer (manufactured by Nippon Seiki Co., Ltd.) was used, and the average particle size was 0.7 μm at a rotation speed of 15000 rpm. Emulsification was performed so that During the emulsification, warm water having a temperature of 85 ° C. was flowed around the homogenizer to keep the temperature so that the emulsification was always performed at a temperature of 75 ° C. or higher. After completion of the emulsification, 8.3 g of warm water was added, and then the liquid temperature was gradually lowered and cooled to room temperature to obtain a wax fine particle emulsion dispersion of 30% by mass.

(Preparation of coating liquid for protective layer) To 20 g of water, 6
Mass% polyvinyl alcohol aqueous solution (trade name: PVA1
24C, manufactured by Kuraray Co., Ltd., 90 g, 20.5 mass% zinc stearate dispersion (trade name: F155, manufactured by Chukyo Yushi Co., Ltd.) 0.5 g, 1.0% boric acid aqueous solution 25 g, the above 30 mass% 3.0 g of wax fine particle emulsion dispersion, 150 g of the above pigment dispersion for protective layer, 30% by mass aqueous dispersion of silicone oil (polydimethylsiloxane, trade name: BY)
22-840, manufactured by Toray Dow Corning Co., Ltd., average particle diameter: 0.04 μm, viscosity: 2000 mPa · s) 5.0
g, 10% by weight of 2.0% sodium dodecylbenzenesulfonic acid sodium salt aqueous solution, 2 of the compound represented by the following formula (1)
15 g of a mass% aqueous solution and 1.0 g of a 40 mass% glyoxal aqueous solution were mixed to obtain a coating liquid for protective layer.

[Preparation of Coating Liquid for Thermal Recording Layer] Each liquid of the microcapsule coating liquid and the color developer emulsion dispersion was prepared as follows. (Preparation of microcapsule coating solution) As a color former, 19 g of a compound represented by the following formula (2), 4.2 g of a compound represented by the following formula (3), and a compound represented by the following formula (4) 7. 4 g, 0.6 g of the compound represented by the following formula (5), 1.9 g of the compound represented by the following formula (6), and 0.8 g of the compound represented by the following formula (7) were added to 36 g of ethyl acetate. The mixture was heated to 70 ° C, dissolved, and then cooled to 35 ° C. To this, 0.8 g of n-butanol, capsule wall material (trade name: Takenate D127N, manufactured by Takeda Pharmaceutical Co., Ltd.) 2
6.4 g was added and the temperature was kept at 35 ° C. for 40 minutes.

This solution was added to 26 g of water to prepare an 8% by mass aqueous polyvinyl alcohol solution (trade name: PVA217E,
After adding 75 g of Kuraray Co., Ltd. to the mixed aqueous phase,
An ace homogenizer (manufactured by Nippon Seiki Co., Ltd.) was used to perform emulsification at a rotation speed of 10,000 rpm for 5 minutes. After adding 140 g of water and 1.0 g of tetraethylenepentamine to the obtained emulsion, the encapsulation reaction was carried out at 60 ° C. for 3 hours to prepare a microcapsule coating solution having an average particle size of 0.7 μm.

(Preparation of Emulsion of Developer) As a developer, 3.4 g of the compound represented by the following formula (8), 8.3 g of the compound represented by the following formula (9), and the following formula (10) 8.3 g of the compound represented by the formula (4), 5.8 g of the compound represented by the formula (11) below, and compound 3.9 represented by the formula (12) below.
g, and 3.5 g of the compound represented by the following formula (13) were added to 15 g of ethyl acetate together with 0.8 g of tricresyl phosphate and 0.4 g of diethyl maleate, and the mixture was heated to 70 ° C. and dissolved. This solution was used as a 15 mass% polyvinyl alcohol aqueous solution (trade name: PVA205C, manufactured by Co., Ltd.).
(Manufactured by Kuraray) 40 g, 2.0 g by mass of 9% aqueous solution of sodium dodecylbenzenesulfonate and 9.0 g of a 2% by mass aqueous solution of a compound represented by the following formula (14) were added to the mixed aqueous phase, and then the ace homogenizer (Nippon Seiki Co., Ltd.)
Average particle size of 0.7 at 10000 rpm
It was emulsified to have a thickness of μm to obtain a color developer emulsified dispersion.

(Preparation of coating liquid for heat-sensitive recording layer) 14.2 The coating liquid for microcapsules (concentration of solid content: 27% by mass) 14.2
g, the color developer emulsified dispersion (solid concentration 21% by mass) 8
5 g and 50% by mass of the compound represented by the following formula (15)
0.4 g of the aqueous solution was mixed to prepare a coating liquid for heat-sensitive recording layer.

[Preparation of coating liquid for intermediate layer] 15% by mass aqueous gelatin solution (trade name: # 750GEL, manufactured by Nitta) 14
0 g, 3 g of 10% by weight sodium dodecylbenzenesulfonate as a surfactant, 7 g of 5% by weight sodium polystyrene sulfonate (molecular weight 760,000, manufactured by Sankyo Chemical Co., Ltd.) for viscosity adjustment, and 21 g of 2.5% by weight mica dispersion. 140
It was dissolved in g of water to prepare a coating liquid for the intermediate layer.

[Preparation of Coating Liquid for Ultraviolet Filter Layer] (Preparation of Microcapsule Liquid for Ultraviolet Filter Layer) 1.58 g of a compound represented by the following formula (16) and the following formula (1)
7.30 g of the compound represented by 7), 5.20 g of the compound represented by the following formula (18), 1.40 g of the compound represented by the following formula (19), and compound 7 represented by the following formula (20). ．
30 g was added to 8.2 g of ethyl acetate, heated to 70 ° C., dissolved, and then cooled to 35 ° C. To this, 0.9 g of capsule wall material (trade name: Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd.), 0.3 g of capsule wall material (trade name: Burnock D750, manufactured by Dainippon Ink and Co., Ltd.) were added,
The temperature was kept at 35 ° C for 5 minutes. 15% by mass of this solution
Polyvinyl alcohol aqueous solution (trade name: PVA20
(5) (produced by Kuraray Co., Ltd.) and 10% by mass of dodecylbenzenesulfonic acid sodium salt aqueous solution (8.0 g) were added to the mixed water phase, and then an ace homogenizer (produced by Nippon Seiki Co., Ltd.) was used to rotate at 15,000 rpm. For 15 minutes to obtain an emulsion having an average particle size of 0.25 μm. After further adding 60 g of water and 0.15 g of tetraethylenepentamine to the obtained emulsion, an encapsulation reaction is performed at 40 ° C. for 3 hours to prepare a microcapsule solution for an ultraviolet filter layer having an average particle size of 0.25 μm. did.

(Preparation of coating solution for UV filter layer) 42.31 g of water containing 10% by mass of silanol-modified polyvinyl alcohol (trade name: R2105, manufactured by Kuraray Co., Ltd.) 4
In a solution mixed with 0.0 g, the above-mentioned microcapsule liquid for ultraviolet filter layer (solid content concentration 24.2%) 1
3.5 g was added, and 17 g of a 50 mass% aqueous solution of a compound represented by the following formula (21) and 20 mass% colloidal silica (trade name: Snowtex O, Nissan Chemical Co., Ltd.)
65 g was mixed to prepare a coating liquid for ultraviolet filter layer.

[Preparation of coating liquid for light reflection preventing layer] 50 g of water
Rice starch with an average particle size of 5 μm (Matsuya Chemical Co., Ltd.)
0.1 g) and thoroughly dispersed, and then 2.5 g of a 2% by mass aqueous solution of di (2-ethyl) hexyl sulfosuccinate, and a 2% by mass aqueous solution of a compound represented by the following formula (22): 1.5
g, and 17 g of 20 mass% colloidal silica (trade name: Snowtex O, Nissan Kagaku Co., Ltd.) were mixed to prepare a coating solution for a light antireflection layer.

[Preparation of transparent support] The thickness is 175 μm, and in the chromaticity coordinate defined by the method described in JIS-Z8701, x = 0.850, y = 0.299.
Blue colored polyethylene terephthalate (P
ET) film was coated on one surface with SBR latex so that the dry coating amount was 0.3 g / m ² . On top of this, a 5 mass% gelatin aqueous solution (Nitta gelatin # 810)
200 g, gelatin dispersion of 5 μm particle size 2 μm polymethylmethacrylate resin particles (polymethylmethacrylate resin content 10% by mass) 0.5 g, 3% by mass 1,
2-benzothiazolin-3-one aqueous solution 1.0 g and 2
A solution obtained by mixing 10 g of a mass% aqueous solution of di (2-ethyl) hexyl sulphosuccinate in an amount of 0.1 g / m ² was applied on a dry basis.
Was applied. Further, the other surface was also coated in the same manner to form an undercoat layer on both surfaces of the support.

[Preparation of Thermosensitive Recording Material] On one surface of the support coated with the double-sided undercoat layer, the coating solution for the ultraviolet filter layer was applied so that the dry coating amount was 1.8 g / m ^2. After drying, an ultraviolet filter layer was formed. Furthermore, the coating solution for the light antireflection layer was applied on the ultraviolet filter layer so that the dry coating amount was 2.2 g / m ² .
After drying, a light reflection preventing layer was formed on the ultraviolet filter layer.

Next, the coating solution for the heat-sensitive recording layer was dried on the surface of the support opposite to the surface coated with the ultraviolet filter layer and the antireflection layer to give a dry coating amount of 16.5 g / m ² . After coating and drying, a thermosensitive recording layer was applied. The heat-sensitive recording layer, the intermediate layer coating liquid, and the protective layer coating solution successively, dry coating amount applied so that the 1.0 g / m ^2, and 2.5 g / m ² respectively, dry Thus, the intermediate layer and the protective layer were formed to obtain the transparent heat-sensitive recording material of the present invention.

[0163]

[Chemical 1]

[0164]

[Chemical 2]

[0165]

[Chemical 3]

<Manufacture of packaging material> Eight titanium oxide-containing white polypropylene sheets (thickness: 550 μm) were cut into the shape shown in the developed view of FIG. Example 1 on each of the eight bases
5 and Comparative Examples 1 to 3, the notch and the recess were formed so as to have different patterns. 4 to 5 are enlarged views of the vicinity of the tip of the base of Examples 1 to 5 and Comparative Examples 1 to 3.
6 shows. 4 to 6, the solid line indicates the cut portion, the broken line indicates the concave portion, and + indicates the installation point at the center of the suction plate. The notch was formed by pressing a wood board fitted with a cutting blade, and the recess was formed by pressing a wood board fitted with a pressing blade. The length of the notch, the depth of the recess, and the distance between the notches or the recess when a plurality of notches and / or recesses are formed in parallel are as shown in Table 1. Each polypropylene sheet was processed into a case shape, and Example 1
5 and Comparative Examples 1 to 3 were used as sheet-shaped recording material packaging materials.

<Storage of Recording Material> The sheet-shaped recording materials produced above were accumulated and stored in each of the produced sheet-shaped recording material packaging materials. At this time, the sheet-shaped recording material was housed with the recording surface facing the base of the packaging material. Furthermore, the entire packaging material (2) accommodating the sheet-shaped recording material (1) is laminated with a polyethylene / aluminum / polyester laminated film (3) as shown in FIG.
The package was sealed as shown in.

<Test> (Evaluation of Scratches) The hermetically sealed package shown in FIG. 3 was placed with the image recording surface facing downward, and the amplitude was 1 cm in each of the X-axis, Y-axis, and Z-axis directions, and a reciprocating 12-minute cycle. Frequency 0 to 50Hz
One reciprocating vibration was carried out under the condition of changing the interval. Then, the image was recorded in a medical dry imager (DRYPIX1000CR, manufactured by Fuji Photo Film Co., Ltd.) under the condition of a density of 1.2. With respect to the lowermost sheet-like recording material stored so as to be in contact with the base of the packaging material, the feeling of increase or decrease in scratches in the portion in contact with the cut portion was observed, and evaluated according to the following three grades. ○ No blemishes were found △ Scratches were found but there was no problem in practical use × Scratches were found and there was no problem in practical use

(Evaluation of uneven density) Each of the hermetically-sealed packaging materials was stored at 40 ° C. for 10 days, and then a medical dry imager (DRYPIX1 manufactured by Fuji Photo Film Co., Ltd.) was used.
000CR) and recorded an image under the condition of a density of 1.2. With respect to the lowermost sheet-like recording material stored so as to contact the base of the packaging material, the image density α of the portion in contact with the cut portion and the image density β of the other portion were measured. Based on the measurement results, the recording density reduction rate of the portion in contact with the cut portion was obtained by the following formula. The recording density reduction rate is preferably 10% or less.

[0170]

[Equation 2]

(Empty detection test) Each packaging material was medical dry imager (Fuji Photo Film Co., Ltd., DRYPI).
X1000) and evaluated whether or not empty detection by the suction cup was possible. In the suction cup, a in FIG. 7 is 70 mm,
b is 15 mm, and the center part is + in FIGS.
It is located in. The empty detection test was performed 10 times for each packaging material, and the number of times that empty detection was possible was recorded.

<Results> The results of the above tests are summarized in Table 1.

[0173]

[Table 1]

The above results show that the packaging materials of Examples 1 to 5 satisfying the conditions of the present invention are excellent in empty detection, and moreover, scratches and uneven density are unlikely to occur on the lowermost sheet-shaped recording material. Is shown. In addition, when a strong stress was applied, the packaging material of Example 5 showed a tendency to be slightly bent at the notch, but the packaging materials of Examples 1 to 4 had sufficient strength against strong stress. I was prepared.

[0175]

EFFECTS OF THE INVENTION By using the sheet-like recording material packaging material of the present invention, it is possible to easily detect that the recording material has been used up, and it is effective to prevent scratches and uneven density of the recording material stored at the bottom. Can be suppressed.

[Brief description of drawings]

FIG. 1 is a perspective view showing a specific configuration example of a packaging material of the present invention containing a sheet-shaped recording material.

FIG. 2 is a development view of packaging materials used in Examples and Comparative Examples.

FIG. 3 is a cross-sectional view showing a state in which a packaging material containing a sheet-shaped recording material is sealed with a laminated film.

FIG. 4 is a diagram showing a pattern of a cut portion and a concave portion formed in the base portion of the packaging material.

FIG. 5 is a diagram showing a pattern of a cut portion and a concave portion formed in the base portion of the packaging material.

FIG. 6 is a diagram showing a pattern of cut portions and recesses formed in the base portion of the packaging material.

FIG. 7 is a view showing a suction plate.

FIG. 8 is a diagram showing discharge of a sheet-shaped recording material by a suction disk.

[Explanation of symbols]

1 Sheet-shaped recording material 2 Sheet-like packaging material for recording material 4 base 5 sides 6 Cover 7 suction cup 11 Support 12 Rubber suction board 13 Intake pipe

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03C 3/00 G03C 3/00 510X 570X 570 571E 571 B65H 3/08 310A // B65H 3/08 310 B41M 5 / 18 ZF term (reference) 2H026 AA07 EE05 GG00 GG10 3F048 AA01 AB06 BA02 CB03 CB12 DA01 DC20 3F343 FA09 FB01 FC17 JB02 KB03 MA03 MA10 MA23 MB10 MC13 MC28

Claims (2)

[Claims] 1. A packaging material for a sheet-shaped recording material, comprising at least a base portion for holding a sheet-shaped recording material, on which a sheet-shaped recording material sheet-feeding suction plate of an image recording device is in contact. At this time, it is possible to send air into the single-wafer suction disk through a notch provided so as to penetrate the base so as to detect the absence of the sheet-shaped recording material on the base. A sheet-shaped recording material packaging material, characterized in that a recess having a depth of 1 mm or less is continuously provided on an extension line of the section. 2. The packaging material for a sheet-shaped recording material according to claim 1, wherein the sheet-shaped recording material is a medical film.