JP2000280625A - Non-silver salt thermal development image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a thermal development image recording material not generating creases when the thermal development is carried out and generating extremely small dimension change before and after the thermal development and extremely small dimension change after the thermal development with time. SOLUTION: In the constitution of a non-silver salt thermal development image recording material, the thermal development is carried out at the 80 deg.C-140 deg.C development temperature, and a substrate provided with prime coated layers, containing vinylidene chloride copolymer repeated units of at least 70 wt.% on both faces and having the 0.3 μm thickness or more (total thickness per one face), is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-silver-salt heat-developable image recording material, and more particularly to a non-silver-salt heat-developable image recording material used for photolithography, and more particularly, to image recording for scanners and imagesetters. More particularly, the present invention relates to a non-silver-salt heat-developable image recording material suitable for color photographic plate making, which is excellent in dimensional stability without causing wrinkles in a film by heat development. The present invention relates to an image recording medium utilizing a color development (or decolorization) reaction accelerated by an acid catalyst, and more particularly to a highly sensitive and storable storage system incorporating an amplification mechanism in the production of an acid and / or a dye. The present invention relates to a good image recording medium.

[0002]

2. Description of the Related Art One of the methods for exposing a photographic photosensitive material is to scan an original drawing, perform exposure on the photosensitive material based on the image signal, and form a negative image or a positive image corresponding to the image of the original drawing. 2. Description of the Related Art An image forming method using a scanner method is known. In addition, there is a demand for a scanner light-sensitive material having ultra-high contrast characteristics for a case in which the image is output from a scanner to a film and then directly printed on a printing plate without going through a turning process, or a scanner light source having a soft beam profile. Many photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image are known.
Among them, a technology for forming an image by thermal development is a system that can simplify environmental preservation and image forming means. 2. Description of the Related Art In recent years, in the field of photolithography, there has been a strong demand for reduction of processing waste liquid from the viewpoints of environmental conservation and space saving.
Therefore, attention has been focused on a technique relating to a photosensitive heat-developable material for photoengraving, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a sharp image having high resolution and sharpness. ing. These photosensitive heat-developable materials eliminate the use of solution-based processing chemicals, and can provide customers with a simpler heat-development system that does not damage the environment.

The method of forming an image by thermal development can be roughly classified into a method using a silver salt and a method not using a silver salt. Regarding the former, for example, U.S. Patent Nos. 3,152,904 and 3,457,075,
And D. Morgan and B.A. "The Silver System Treated by Heat (Thermally P
rocessed Silver Systems ”(Imaging Processes and Materials)
s and Materials) Neblette 8th edition, Sturg
e), V. Walworth, A .; Shep
p) Compilation, page 2, 1969). The problems with these systems include the problems of handling in a bright room and the recovery of silver resources, etc. due to the photosensitivity of silver. To improve these, the development of non-silver salt heat-developable recording materials has been conducted. Have been done. The main image forming methods using non-silver salt heat-developable light-sensitive materials (monosheets and waste materials) include (1) a color-forming method using an acid and a color-forming agent using thermoresponsive microcapsules, and (2) light-generating method using light. Using acid or radical,
(3) a method of causing a chemical reaction by heat to develop color. Regarding (1), although it is widely used as an output material for various printers and facsimile machines,
There is a problem that it is difficult to increase the color density in developing the material for plate making. Regarding (2), since it is exposed to weak light (photon mode), there is a problem in handling in a bright room as with the silver halide photographic material. Regarding (3),
There is a possibility that the problems described in (1) and (2) can be solved. U.S. Pat. Nos. 4,602,263 and 4,826,9
No. 76 describes the thermal decomposition of carbamate,
No. 52 discloses a dye forming reaction utilizing an intramolecular nucleophilic substitution reaction. However, these methods have low sensitivity, and there has been a problem in increasing the sensitivity. U.S. Pat. No. 5,286,612 discloses a method of increasing sensitivity by combining the techniques of (2) and (3) as a means of increasing sensitivity and inducing a color reaction using a superstrong acid generated by light as a catalyst. Nos. 5,395,736, 5,441,850, and JP-T-8-503081 and JP-8-503082. Although the sensitivity was certainly improved by this method, there was a problem of further increasing the sensitivity (as a heat development condition) and improving the photosensitivity (photon mode). Furthermore, even in these non-silver salt photothermographic materials, application to G / A films has not been substantially studied.

[0004] Conventionally, there has been a problem of dimensional stability of a support as a common problem of heat-developable photosensitive materials. Conventionally, many of these photographic materials use stretched film-formed polyester as a support, and when subjected to thermal development, there is an inconvenience that an image is deformed due to a change in thermal dimension (mainly heat shrinkage) of the support. I will. In addition, the binder of the image forming layer simultaneously undergoes dehydration shrinkage and thermal expansion during thermal development, resulting in wrinkles in the film because it differs from the thermal dimensional change behavior of the support, making the film unsuitable for color printing used in superposition. I can only get it.

As a technique for preventing such dimensional changes and wrinkles due to thermal development, various heat treatment methods have been disclosed for alleviating internal strain generated when a support is stretched and formed. JP-A-3-24936, JP-A-64-6483
3, JP-A-8-211547 and JP-A-3-9752
No. 3, JP-A-61-154829, JP-A-3-975
No. 23, JP-A-57-109946 and the like. Certainly, although the methods disclosed therein reduce the amount of thermal shrinkage of the support formed by biaxial stretching, it cannot reduce the dimensional change over time after the heat development.

[0006] For color photoengraving, Y, M, C, K
Although it is good to perform the exposure and heat development of these four plates at the same time by using four films of the plate, it is often the case that the exposure / heat development is performed with a time lag.
In such a case, since the elapsed time after the heat development processing of each film is different, the dimensions of each film do not match and often cause color shift. There is a demand for a technique for providing a photothermographic material having excellent dimensional stability in any handling state.

[0007]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to reduce the dimensional change over time after thermal development, to eliminate wrinkles during thermal development, and to further reduce thermal development. It is an object of the present invention to provide a non-silver-salt heat-developable image recording material having a small dimensional change before and after. Another object of the present invention is to provide a non-silver-salt heat-developable image recording material which gives an image excellent in photographic properties. A second object of the present invention is to provide a novel image recording medium having a high thermal sensitivity, a monosheet, a non-waste material and excellent storage stability that can be handled in a bright room, and an image recording method using the same. It is in.

[0008]

This object has been achieved by the following means. (1) The undercoat layer containing a vinylidene chloride copolymer containing at least 70% by weight of a vinylidene chloride monomer repeating unit is subjected to thermal development at a developing temperature of 80 ° C. or more and 140 ° C. or less. A heat-developable image recording material comprising a support provided with a thickness of 3 μm or more (total thickness per side). (2) On the support, from 360 nm to 900 nm by a reaction between a compound generating an acid by light or heat and an acid.
The non-silver salt heat-developable image recording material according to (1), further comprising an image forming layer containing a compound which undergoes a change in absorption between the two. (3) On the support, there is provided an image forming layer containing an organic silver salt, a reducing agent and a photosensitive silver halide, and at least one protective layer provided on the image forming, wherein the vinylidene chloride is provided. The heat according to the above (2), wherein the copolymer contains 70 to 99.9% by weight of vinylidene chloride monomer repeating units and 0.1 to 5% by weight of carboxyl group-containing vinyl monomer repeating units. Developed image recording material. (4) The heat-developable image recording material according to any one of (1) to (3), wherein the weight average molecular weight of the vinylidene chloride copolymer is 45,000 or less. (5) The heat-developable image recording material according to any one of (1) to (4), wherein the support is a biaxially stretched polyester. (6) After the support is provided with an undercoat layer containing the vinylidene chloride copolymer, the support is 130 ° C. or more and 185 ° C.
The heat-developable image recording material according to the above (5), which has been heat-treated at the following temperature. (7) The thermal dimensional change rate of the heat-treated support when heated at 120 ° C. for 30 seconds in the longitudinal (MD) direction is −
0.03% or more and 0.01% or less and horizontal (T
The heat-developable image recording material according to the above (6), which is 0% or more and 0.04% or less in the direction D). (8) The heat-developable image recording material according to any one of (3) to (7), wherein a polymer latex is used as a binder for the image forming layer and the protective layer. (9) The non-silver-salt heat-developable recording material according to (1) to (8), wherein an acid generator represented by the following general formula (1) which generates an acid by the action of heat or an acid, and a molecule formed by the action of an acid A non-silver salt heat-developable recording material according to any one of (1) to (8), comprising a compound which causes an internal or intermolecular reaction to cause a change in the absorption range of 360 to 900 nm. Formula (1) W ¹ OP ^{1 In the} formula, W ¹ represents a residue of an acid represented by W ¹ OH, and P ¹ represents a substituent which is released by the action of heat or an acid. (10) The non-silver salt heat-developable recording material according to (9), wherein the acid generator represented by the general formula (1) is a compound selected from the following general formulas (2) to (4). General formula (2)

[0009]

Embedded image

In the formula, R ¹ represents an electron-withdrawing group having a Hammett σp value of more than 0 and 1 or less. R ² represents an alkyl group. R ³ represents a group capable of leaving by the action of heat or an acid. W ¹ has the same meaning as in formula (1). General formula (3)

[0011]

Embedded image

In the formula, R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group or an aryl group, and W ¹ represents a compound represented by the general formula (1)
Is synonymous with Formula (4) P ² -X-LC (R ⁷ ) (R ⁸ ) -OW ^{1 In the} formula, P ² represents a substituent capable of leaving by the action of heat or an acid. X is O, S, NR ⁹ (R ⁹ represents a hydrogen atom or a substitutable group), or CR ¹⁰ R ¹¹ (R ¹⁰ and R ¹¹ represent a hydrogen atom or a substitutable group, and May be different). L represents a linking group. R ⁷ and R ⁸ represent a hydrogen atom or a substitutable group, and may be the same or different. W ¹ has the same meaning as in formula (1). (11) The non-silver-salt heat-developable recording material according to any one of (1) to (8), has a partial structure having a function of generating an acid by the action of heat or an acid, and changes to an absorption region of 360 to 900 nm by the action of an acid. The non-silver salt heat-developable recording material according to any one of (1) to (8), further comprising a polymer having a resulting partial structure. (12) The polymer described in (11) is represented by the following general formula (5)
The non-silver salt heat-developable recording material according to (11), which is a polymer represented by the formula: Formula (5)-(A) _x- (B) _y- (C) _{z- wherein} A is obtained by polymerization of at least one vinyl monomer having a function of generating an acid by the action of heat or an acid. B represents a repeating unit obtained by polymerization of at least one type of vinyl monomer having a partial structure that causes a change in the absorption range of 360 to 900 nm by the action of an acid; Represents a repeating unit obtained by polymerization of at least one or more kinds of polymerizable vinyl monomers, and x, y
And z represent% by weight, and 1 ≦ x ≦ 99 and 1 ≦
It represents y ≦ 99, 0 ≦ z ≦ 98, and x + y + z = 100.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The non-silver salt heat-developable image recording material of the present invention forms an image by a heat development process, and its developing temperature is 80 ° C.
It is 140 ° C. or lower. The heating in the thermal development in this case includes not only heating for image formation, but also preliminary heating for the purpose of suppressing processing unevenness and the like.
Therefore, the development may be performed at a constant temperature, or may be multi-stage heating in which heating is performed at a constant temperature followed by heating at a higher temperature.

In such a heat-developable image recording material,
By using a support coated on both sides with an undercoat layer containing a vinylidene chloride copolymer and having a thickness of 0.3 μm or more (total thickness per one side), it is possible to prevent dimensional change with time after thermal development. it can. In addition, since it is possible to eliminate wrinkles and suppress a dimensional change due to thermal development, the dimensional change due to the lapse of time after the thermal development is extremely small. In particular, in the present invention, a biaxially stretched polyester support is preferably used. In such a support, preferably, a dimensional change due to heating of the support itself or heat treatment is performed by applying a heat treatment after providing an undercoat layer. When the polyester support thus treated is used as a support for a non-silver-salt heat-developable image recording material, the occurrence of wrinkles during thermal development of the non-silver-salt heat-developable image recording material can be suppressed. And the dimensional change before and after thermal development is reduced. Therefore, in the polyester support preferably used in the present invention, after the heat treatment, preferably after providing the undercoat layer containing vinylidene chloride,
The heat treatment is preferably performed at a temperature of 0 ° C. or more and 185 ° C. or less.

On the other hand, unlike the present invention, when only a polymer other than the vinylidene chloride copolymer (for example, a styrene-butadiene copolymer) is used for the undercoat layer covering both sides of the support, the thermal development The dimensional change due to aging cannot be suppressed. Further, even if the thickness of the undercoat layer (total thickness per one side) is less than 0.3 μm, the dimensional change over time after thermal development cannot be suppressed.

The non-silver salt heat-developable image recording material of the present invention is preferably an image comprising a light absorbing agent or a light-to-heat converting material on a polyester support coated on both sides with an undercoat layer containing a vinylidene chloride copolymer. It has a formation layer. Further, the non-silver salt heat-developable image recording material of the present invention preferably has at least one back layer on the side opposite to the image forming layer with respect to the support, and comprises an image forming layer, a protective layer, and a back layer. When having a binder of the back layer,
A hydrophobic synthetic polymer or a hydrophobic natural polymer is used.

When these polymers or vinylidene chloride copolymers are used as polymer latex, aqueous coating using a solvent (dispersion medium) containing water as a main component becomes possible, which is advantageous in terms of environment and cost, and is particularly preferable. A desired effect can be obtained even with a heat-developable image recording material obtained by applying a solution using a polymer dissolved in various organic solvents as a binder.

An undercoat layer containing a vinylidene chloride copolymer is provided on both sides of the support of the present invention. The vinylidene chloride copolymer at this time is a repeating unit of a vinylidene chloride monomer (hereinafter, also referred to as “vinylidene chloride monomer”).
At least 70% by weight. When the amount of the vinylidene chloride monomer is less than 70% by weight, sufficient moisture-proof property cannot be obtained, and the dimensional change over time after thermal development becomes large. Further, the vinylidene chloride copolymer may contain a repeating unit of a carboxyl group-containing vinyl monomer (hereinafter, also referred to as “carboxyl group-containing vinyl monomer”) as another constituent repeating unit of the vinylidene chloride monomer. preferable. Including such a constitutional repeating unit is that a polymer (polymer) is crystallized only with a vinyl chloride monomer, and it is difficult to form a uniform film when a moisture-proof layer is applied. This is because a carboxyl group-containing vinyl monomer is indispensable for stabilizing the (polymer).

The vinylidene chloride copolymer of the present invention has a content of 70%.
〜99.9% by weight, more preferably 85-99% by weight of vinylidene chloride monomer and 0.1-5% by weight, more preferably 0.2-3% by weight of a carboxyl group-containing vinyl monomer. Is a copolymer. The carboxyl group-containing vinyl monomer used in the vinylidene chloride copolymer of the present invention is a vinyl monomer having one or more carboxyl groups in a molecule, and specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, and citracone. Acids and the like can be mentioned.

The vinylidene chloride copolymer of the present invention may contain a repeating unit of a monomer copolymerizable therewith in addition to the vinylidene chloride monomer and the carboxyl group-containing monomer. Specific examples of these monomers include acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, and styrene. These monomers may be used alone or in combination of two or more.

The vinylidene chloride copolymer of the present invention has a weight average molecular weight of 45,000 or less, more preferably 10,000 to 45.
000 or less is preferred. When the molecular weight increases, the adhesion between the vinylidene chloride copolymer layer and the support layer such as polyester deteriorates. The vinylidene chloride copolymer of the present invention may be in the form dissolved in an organic solvent or in the form of an aqueous dispersion of latex, but the form of an aqueous dispersion of latex is preferred. In this case, a latex of polymer particles having a uniform structure or a latex of polymer particles having a so-called core-shell structure having different compositions in a core portion and a shell portion may be used.

The particle size and the like of the polymer particles in the latex are the same as those used for the binder of the image forming layer and the protective layer described later. The arrangement of the monomer units of the vinylidene chloride copolymer is not limited, and may be any of periodic, random, block, and the like. Specific examples of the vinylidene chloride copolymer of the present invention include the following. However, the numbers in parentheses indicate weight ratios.
The average molecular weight represents a weight average molecular weight.

V-1 Latex of vinylidene chloride: methyl acrylate: acrylic acid (90: 9: 1) (average molecular weight)
42000) V-2 Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (87:
Latex of 4: 4: 4: 1) (average molecular weight of 40,000) V-3 Latex of vinylidene chloride: methyl methacrylate: glycidyl methacrylate: methacrylic acid (90: 6: 2: 2) (average molecular weight of 38000) V-4 Vinylidene chloride : Ethyl methacrylate: 2-hydroxyethyl methacrylate: acrylic acid (90: 8:
1.5: 0.5) latex (average molecular weight 44000) V-5 core-shell type latex (core 90% by weight, shell 10% by weight) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (93:
3: 3: 0.9: 0.1) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (8
8: 3: 3: 3: 3) (Average molecular weight 38000) V-6 Core-shell type latex (70% by weight core, 30% by weight shell) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (9
2.5: 3: 3: 1: 0.5) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (90: 3: 3: 1: 3) (average molecular weight 20,000)

The vinylidene chloride copolymer may be used alone or in combination of two or more. The vinylidene chloride copolymer of the present invention has a total thickness of 0.3 μm or more, preferably 0.3 μm or more and 4 μm or less, as a total film thickness per one side of the undercoat layer containing the vinylidene chloride copolymer.

The vinylidene chloride copolymer layer as the undercoat layer is preferably provided as the first undercoat layer directly provided on the support, and is usually provided one layer on each side. May be provided in two or more layers.
When a multi-layer structure of two or more layers is used, the total amount of the vinylidene chloride copolymer may be within the range of the present invention.

As described above, since the vinylidene chloride copolymer layer is usually formed as a single layer, its thickness is preferably 0.3 μm or more and 4 μm or less in order to obtain a good coated surface. More preferably, it is in the range of 0.6 μm or more and 3 μm or less, and still more preferably in the range of 1.0 μm or more and 2 μm or less.

Such a layer may contain a crosslinking agent and a matting agent in addition to the vinylidene chloride copolymer.

The non-silver salt heat-developable image recording material of the present invention includes
Various supports can be used. Typical supports include polyesters such as polyethylene terephthalate, polyethylene naphthalate, etc., cellulose nitrate, cellulose esters, polyvinyl acetal, polycarbonate and the like. Of these, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferred in terms of strength, dimensional stability, chemical resistance and the like. The thickness of the support is preferably 90 to 180 μm as a base thickness excluding the undercoat layer.

The support used in the heat-developable image recording material of the present invention is intended to alleviate the internal strain remaining in the film during biaxial stretching and to eliminate the heat shrinkage distortion generated during heat development.
Polyester, particularly polyethylene terephthalate, which has been subjected to a heat treatment in a temperature range of 130 to 185 ° C is preferably used. Such a thermal relaxation treatment may be performed at a constant temperature within the temperature range, or may be performed while increasing the temperature.

The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web. In the case where the transfer is carried out in the form of a web, the transfer tension of the support during the heat treatment is preferably relatively low, and specifically, 7 kg /
cm ² or less, particularly preferably to 4.2 kg / cm ² or less. The lower limit of the transport tension at this time is not particularly limited, but is about 0.5 kg / cm ² .

Such a heat treatment is preferably carried out after a treatment for improving the adhesion of the image forming layer and the back layer to the support, an undercoat layer containing a vinylidene chloride copolymer, and the like are applied. .

After the heat treatment, the support 12
The heat shrinkage by heating at 0 ° C for 30 seconds is-
0.03% to + 0.01%, lateral direction (TD) is 0 to 0.
Preferably, it is 04%.

The support may be coated with an undercoat layer using SBR, polyester, gelatin or the like as a binder, if necessary, in addition to the vinylidene chloride copolymer layer. These undercoat layers may have a multilayer structure or may be provided on one side or both sides of the support. At least one of these undercoat layers can be a conductive layer. The general thickness (per layer) of the undercoat layer may be from 0.01 to 5 μm, more preferably from 0.05 to 1 μm, and the thickness as a conductive layer is from 0.01 to 1 μm, more preferably from 0.1 to 1 μm. 03-
0.8 μm, but the total thickness of the undercoat layer on one side is 0.3 μm or more.

Next, the image forming layer will be described in detail. In the present invention, a non-silver salt image forming method is used. Specific examples include an image forming method using a non-silver salt mentioned in the prior art. Preferred image forming methods are shown below, an acid generator that generates an acid by the action of heat or an acid, and an acid generator. 360-200 by intramolecular or intermolecular reaction by action
This is an image forming method using a recording medium for forming an image, which contains a compound that changes the absorption region at 900 nm. The compound represented by the general formula (1) has a function of generating an acid by the action of heat or an acid. In the acid generator represented by the general formula (1), W ¹ represents a residue of an acid (sulfonic acid, carboxylic acid, phosphoric acid, phenol, etc.) represented by W ¹ OH. W ¹ OH is preferably an acid having a pKa smaller than 3, and preferred examples thereof include arylsulfonic acid, alkylsulfonic acid, carboxylic acid having an electron-withdrawing group, arylphosphonic acid, and alkylphosphonic acid. P ¹ represents a substituent capable of leaving by the action of heat or an acid, and the acid represented by W ¹ OH is generated from the acid generator represented by W ¹ OP ¹ with the release of P ¹ . Examples of such a substituent include an alkyl group having a hydrogen atom at the β-position (eg, a tetrahydropyranyl group, a tetrahydrofuranyl group, a t-butyl group, a cyclohexyl group,
4,5-dihydro-2-methylfuran-5-yl group, 2
-Cyclohexenyl group), an alkoxycarbonyl group having a hydrogen atom at the β-position (for example, t-butoxycarbonyl group, cyclohexyloxycarbonyl group, 2- (2-methyl) butoxycarbonyl group, 2- (2-phenyl) propyloxycarbonyl group 2,2-chloroethoxycarbonyl group, etc.), silyl group (eg, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, phenyldimethylsilyl group, etc.), or these groups, or acetal, ketal, thioketal, pinacol, epoxy Substituents which release ring decomposition to trigger (for example, W ¹ O in the description of the following general formulas (2) to (4))
H-substituted group). Examples of the acid generator represented by the general formula (1) include, for example, trifluoroacetic acid (α-phenylisopropyl) ester, trifluoroacetic acid t-butyl ester, toluenesulfonic acid cyclohexyl ester, p-nitrobenzoic acid triethylsilyl ester, Tetrahydropyranyl p-nitrobenzoate, poly (4-vinyl-1-t-butoxycarbonyloxy-2-nitrobenzene), poly (cyclohexyl 4-vinylbenzenesulfonate) and the like can be mentioned. From the viewpoint of storage stability, compounds represented by formulas (2) to (4) are preferred.

In the general formula (2), R¹Is in Hammett
σ_pRepresents an electron-withdrawing group having a value greater than 0 and not more than 1.
Then R¹Preferably an acyl group (eg, acetyl,
Propanoyl, 2-methylpropanoyl, pivaloyl,
Benzoyl, naphthoyl), cyano group, alkylsulfo
Nyl group (methanesulfonyl, ethanesulfonyl, benzyl
Rusulfonyl, t-butylsulfonyl, etc.) or ant
Sulfonic acid group (such as benzenesulfonyl).
You. R¹Is more preferably an acyl group. R^TwoIs
Alkyl group (methyl, ethyl, isopropyl, octyl,
Dodecyl). R^TwoPreferably has 6 or more carbon atoms
The group below. R^ThreeRepresents a group which is released by heat or acid.
A preferred group is a secondary group having a hydrogen atom at the β-position.
Alternatively, a tertiary alkyl group (t-butyl, 1,1-dimethyl
Tylpropyl, 1,1,3,3-tetramethylbutyl,
Cyclohexyl, 2-cyclohexenyl, etc.), silyl group
(Trimethylsilyl, t-butyldimethylsilyl, etc.),
Or an alkoxymethyl group (methoxymethyl,
Luoxymethyl, tetrahydropyranyl, tetrahydro
Furanyl, 4,5-dihydro-2-methylfuran-5
And the like). R^ThreePreferably at the β-position
A secondary or tertiary alkyl group having a hydrogen atom
You. These R¹~ R^ThreeThe group represented by further has a substituent
May be. W ¹Has the same meaning as in formula (1). next
The compound represented by Formula (3) will be described. one
In the general formula (3), R^Four, R^Five, R⁶Are independently
Hydrogen atom, alkyl group (methyl, ethyl, isopropyl
, T-butyl, octyl, dodecyl, etc.)
Represents a reel group (phenyl, naphthyl, etc.). R^Four,
R^Five, R⁶May further have a substituent. R^FourAnd R^Five,
R^FourAnd R⁶Or R^FiveAnd R⁶Are linked to form a ring
You can do it. W¹Has the same meaning as in formula (1). General
Compounds represented by formulas (2) and (3) are disclosed in JP-A-8-248.
The compound can be synthesized according to the method described in No. 561.

The compound capable of releasing an acid by a completely different mechanism has at least one substituent removed by the action of heat or an acid, and the nucleophilic substitution reaction in the molecule following the removal of the substituent. And a compound which generates an acid. A preferred form is a compound represented by the general formula (4). General formula (4) P ² -X-LC (R ⁷ ) (R ⁸ ) -OW ^{1 In the} formula, P ² represents a substituent removed by the action of heat or an acid. X is O, S, NR ⁹ (R ⁹ represents a hydrogen atom or a substitutable group), or CR ¹⁰ R ¹¹ (R ¹⁰ and R ¹¹ represent a hydrogen atom or a substitutable group, and May be different). L represents a linking group. R ⁷ and R ⁸ represent a hydrogen atom or a substitutable group, and may be the same or different. W ¹ has the same meaning as in formula (2). Substituent P removed by the action of heat or acid
² is introduced into a nucleophilic group such as a hydroxyl group, a mercapto group, an amino group, or a carbon atom to prevent an intramolecular nucleophilic substitution reaction during storage or in a non-image area. Is decomposed and eliminated, so that an acid can be generated by an intramolecular nucleophilic substitution reaction. Useful substituents represented by P ² include, when introduced into an oxygen atom, an alkoxycarbonyl group (for example, t-butoxycarbonyl group, isopropyloxycarbonyl group, 1-phenylethoxycarbonyl group, 1,1-diphenylethoxy group). Carbonyl group, 2-cyclohexeneoxycarbonyl group, etc.), alkoxymethyl group (for example, methoxymethyl group,
Ethoxymethyl group, n-octyloxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, 4,5
-Dihydro-2-methylfuran-5-yl group, etc.), silyl group (for example, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, phenyldimethylsilyl group, etc.), and β
Secondary or tertiary alkyl group having a hydrogen atom at position (for example, t-butyl, 1,1-dimethylpropyl,
Preferred examples include 1,1,3,3-tetramethylbutyl, cyclohexyl, 2-cyclohexenyl, and the like. Among those introduced into a sulfur atom, an alkoxymethyl group (eg, isobutoxymethyl group, tetrahydropyranyl group, etc.), an alkoxycarbonyl group (eg, benzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, etc.), an acyl group (eg, acetyl Groups, a benzoyl group, etc.), and a benzyl group (eg, a p-methoxybenzyl group, a bis (4-methoxyphenyl) methyl group, a triphenylmethyl group, etc.) are preferred examples. Among those introduced into a nitrogen atom, alkoxycarbonyl groups (for example, t-butoxycarbonyl group, cyclohexyloxycarbonyl group, 2- (2-methyl) butoxycarbonyl group, 2- (2-phenyl) propyloxycarbonyl group, 2-chloroethoxycarbonyl Groups), an acyl group (eg, an acetyl group, a benzoyl group, a 2-nitrobenzoyl group, a 4-chlorobenzoyl group, a naphthoyl group, etc.) or a formyl group. A tertiary alkoxycarbonyl group (such as a t-butoxycarbonyl group) is preferably introduced as a carbon atom.

In the intramolecular nucleophilic substitution reaction following the removal of these substituents, a form in which a 5- to 10-membered ring is formed is preferred, and a 5- or 6-membered ring is particularly preferred. The linking group L is preferably selected so as to form a ring of these sizes.

The acid generator of the present invention may form a polymer by linking a plurality of polymerizable groups introduced at substitutable positions. When applied to an image recording medium utilizing the fact that the hue changes due to the action of an acid described below, the coatability is imparted without using a separate binder by forming a polymer, so that the image recording layer can be used. This is advantageous for thinning. The molecular weight of the polymer is 1000-1
It is preferably in the range of 000000, particularly preferably in the range of 2000 to 500,000.
In this case, it may be a homopolymer or a copolymer with another monomer. When the compound of the present invention is used as a polymer, the number of carbon atoms may exceed the definition of carbon number described in the above description. Hereinafter, specific examples of the compounds represented by formulas (1) to (4) of the present invention are shown, but the present invention is not limited thereto.

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

The amount of these acid generators varies depending on the type of the compound having a change in absorption, but is generally preferably in the range of 0.001 to 20 equivalents, particularly preferably, with respect to the compound having a change in absorption. Is the case of 0.01 to 5 equivalents.

In the present invention, a compound that changes the absorption band at 360 to 900 nm by an intramolecular or intermolecular reaction caused by the action of an acid is stable as long as it is stored under neutral to basic conditions. When the acid acts, the activation energy of the intramolecular or intermolecular reaction decreases,
It is a compound that easily undergoes a reaction by heating to cause a change in absorption in the above range. At this time, the heating temperature for forming an image is 80 to 140 ° C.,
Preferably it is 80-120 degreeC. The compound having such an absorption change may be a single compound or may be composed of two or more components. For example, a compound (for example, 9,10-distyrylanthracene and maleic anhydride, tetraphenylcyclopentadiene and an acrylate ester) that forms a decolorized image in the area by a Diels-Alder reaction, Compounds that form color images (eg, 9,
Compounds (eg, adducts of 10-distyrylanthracene and maleic anhydride, adducts of diphenylisobenzofuran and acrylamide), and compounds which form a color image in the region by expanding the conjugated system by β-hydrogen elimination (eg, 1-acetoxy-1,2) -Diarylethane, 1-sulfoxy1,
2-dialylethane, etc.), a combination of an aldehyde and an active methylene compound which forms a color image in the area by dehydration condensation (for example, 4 equivalents of photographic magenta coupler and p-methoxycinnamaldehyde) or decomposed by the action of an acid. Compounds which have an amino group or a hydroxyl group substituted by a substituent which promotes elimination in a molecule, and whose absorption in the above-mentioned absorption region is changed by removal of the substituent, are exemplified. A basic leuco dye or the like which develops color instantly upon contact with an acid can also be used in the image forming medium. However, such a compound acts as a base and uses microcapsules to inhibit the acid growth process. It is necessary to keep it separate from the acid generator and the acid multiplying agent by coating or applying it to another layer.

In the present invention, a compound whose absorption is changed by the decomposition or elimination of a substituent of an amino group or a hydroxyl group by the action of an acid is particularly useful. Examples of such a substituent of the amino group include an alkoxycarbonyl group (for example, t-butoxycarbonyl group, cyclohexyloxycarbonyl group, 2- (2-methyl) butoxycarbonyl group, 2- (2-phenyl) propyloxycarbonyl group, 2-chloro Preferred examples include an ethoxycarbonyl group), an acyl group (eg, an acetyl group, a benzoyl group, a 2-nitrobenzoyl group, a 4-chlorobenzoyl group, and a naphthoyl group), and a formyl group. From the viewpoint of heat sensitivity, an alkoxycarbonyl group having a hydrogen atom at the β-position is particularly useful. Such compounds include, for example, U.S. Pat.
Nos. 602,263, 4,826,976, etc., which provide a heat-sensitive recording material having higher sensitivity and excellent storage stability when combined with the thermal acid generator and the acid multiplying agent of the present invention. be able to. Examples of the substituent of the hydroxyl group which is decomposed or eliminated by the action of an acid include a secondary or tertiary alkoxycarbonyl group having a hydrogen atom at the β-position (for example, t-butoxycarbonyl group, isopropyloxycarbonyl group, 1-phenylethoxycarbonyl group) ,
1,1 diphenylethoxycarbonyl group, 2-cyclohexeneoxycarbonyl group, etc.), silyl group (for example, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, phenyldimethylsilyl group, etc.), Alkoxymethyl group (for example, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-phenoxyethyl group, 2- (2-methoxypropyl) group, etc.) and secondary or tertiary alkyl group having a hydrogen atom at the β-position (For example, tetrahydropyranyl group, tetrahydrofuranyl group, 4,5-dihydro-2
-Methylfuran-5-yl group, t-butyl group, 2-cyclohexenyl group and the like) are preferred examples,
In the present invention, a secondary or tertiary compound having a hydrogen atom at the β position is particularly preferred.
Grade alkoxycarbonyl groups are preferred. No. 5,243,052 or JP-A-9-2536 discloses compounds whose absorption is changed by decomposition of a hydroxyl group substituent.
There is a description example in No. 0 and the like. Below 360-action by the action of acid
Specific examples of the compound that causes a change in the absorption region at 900 nm are shown, but the present invention is not limited to these.

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

The image recording medium of the present invention is generally 360 to 900 by the action of the acid generator, acid multiplying agent and acid.
It is prepared by applying a composition that changes the absorption range in nm on a support. At this time, a binder is usually coexisted, unless one of these is a polymer or an amorphous having good coatability. When the binder does not need to be used, there is an advantage that the film thickness can be easily reduced and a sharp image can be obtained. When a binder is used, gelatin, casein, starches, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, a water-soluble binder such as ethylene-maleic anhydride copolymer, and polyvinyl butyral, triacetyl cellulose, polystyrene, acrylic Any water-insoluble binder such as a methyl acid-butadiene copolymer and an acrylonitrile-butadiene copolymer can be used. Further, in the present invention, a compound in which color is changed or decolored by the action of an acid to change the hue and an acid generator are made into a copolymer, so that an acid is generated in the immediate vicinity of the compound in which the hue changes. High sensitivity can be expected. In addition, by controlling the diffusion of molecules by polymerization, there is a possibility that the cut-off and preservation of images can be improved. These characteristics are particularly preferable for applications requiring high image quality, such as graphic arts films. A preferred form of such a compound is represented by the general formula (5). The general formula (5) will be described. In the general formula (5), A represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer having a function of generating an acid by the action of heat or an acid. As the compound having such a function, the compounds represented by the aforementioned general formulas (1) to (1)
It can be obtained by introducing a polymerizable group into any part of the compound represented by (4). When the polymer having a thermal acid generating function of the present invention is applied to a laser heat mode type image recording medium, it is useful without adding an acid generator separately. Specific examples of the vinyl monomer forming A in the general formula (5) are shown below, but the invention is not limited thereto. These compounds can be synthesized in the same manner as in the method described in JP-A-8-248561.

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

In the general formula (5), B represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer having a partial structure in which the absorption range from 360 to 900 nm is changed by the action of an acid. Compounds that cause an absorption change by the action of an acid are as described above,
In the above structure, a polymerizable group is introduced at a substitutable position. Specific examples are shown below, but the present invention is not limited to these.

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

C in the general formula (5) represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer capable of forming a copolymer with A and B, and represents a polarity, a glass transition temperature and the like. The storage stability, the color-forming activity and the like can be controlled by adjusting. Such vinyl monomers may be used in combination of two or more. Preferred examples include acrylate, methacrylate, acrylamide, styrene, vinyl ether and the like. Specific examples of the monomer forming C are shown below, but the present invention is not limited thereto.

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

In the general formula (5), x, y and z represent weight% of each composition. x, y and z are respectively 1 ≦ x ≦ 99,
1 ≦ y ≦ 99, 0 ≦ z ≦ 99, and x + y + z = 100
It is. It is preferable that the relation of 0.01y <x ≦ 10y be satisfied, and particularly preferable that the relation of 0.1y ≦ x ≦ 5y be satisfied. z is preferably 0 ≦ z ≦ 50.

The molecular weight of the polymer represented by the general formula (5) is preferably in the range of 1,000 to 1,000,000, particularly preferably in the range of 2,000 to 500,000. The polymer may be in any form such as a random copolymer, an alternating copolymer and a block copolymer, but a random copolymer which is easily synthesized is generally used.

The monomers forming A, B, C in the polymer represented by the general formula (5) and x, y, z
Are shown, but the present invention is not limited to these.

[0085]

[Table 1]

The polymer of the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization,
It can be carried out by emulsion polymerization. The method of initiating polymerization includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and the method of initiating the polymerization are described in, for example, T. Tsuruta, “Polymer Synthesis Method” Revised Edition (Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masayoshi Kinoshita, “Experimental Method of Polymer Synthesis” Published in 1972,
It is described on pages 124-154.

Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferred. Solvents used in the solution polymerization method include, for example, ethyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, Various organic solvents such as methylene chloride, chloroform and dichloroethane may be used alone or as a mixture of two or more thereof, or may be used as a mixed solvent with water.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, and the like.
Polymerization is carried out in the range of 0 ° C. In the present invention, it is preferable to carry out the polymerization at a temperature in the range of 30 to 90 ° C. because the monomer forming the site A in the general formula (5) may decompose at a high temperature.

As the radical initiator used in the polymerization, for example, 2,2′-azobisisobutyronitrile,
Such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, and 4,4'-azobis (4-cyanopentanoic acid) Preferred are azo-based initiators and peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, and potassium persulfate (for example, redox initiators may be used in combination with sodium bisulfite). In the present invention, the initiator (for example, 2,2'-azobis (2,4-dimethylvaleronitrile)) or 2,2'-azobis (4-methoxy-2,
4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (3,4,5,6-tetrahydropropane)
Dihydrochloride] and the like are particularly preferred.

The amount of the polymerization initiator to be used can be adjusted according to the polymerizability of the monomer and the required molecular weight of the polymer, but is in the range of 0.01 to 5.0 mol% based on the monomer. Is preferred. In the synthesis of the polymer of the present invention, the monomers forming A, B and C are mixed and first put into a reaction vessel, and then an initiator may be charged, or a process of dropping these monomers into a polymerization solvent. The polymerization may be carried out via

The polymer represented by the general formula (5) of the present invention has a partial structure having a function of generating an acid by the action of heat or an acid, and a partial structure having a change in the absorption region of 360 to 900 nm by the action of an acid. It is a polymer having both Such a polymer may be a polymer of a single monomer having both functions, but the structure represented by the general formula (5) is generally used from a synthetic viewpoint. The image recording medium of the present invention is generally produced by coating a polymer represented by the general formula (5) on a support. When the polymer of the present invention also has a function of generating an acid by heat, the absorption region changes only by the action of heat alone, so that when used as a heat-sensitive recording material, the sensitivity and the sharpness of the image are excellent. ing. Further, since the image recording medium of the present invention does not require the use of a so-called binder, the thickness can be reduced, a sharp image can be obtained, and abrasion does not easily occur. However, when using the polymer represented by the general formula (5), if necessary, a binder may be used in combination, and specific examples thereof include those described above.

In the present invention, a small amount of a base is added for the purpose of enhancing the storage stability of the image recording medium, and a compound capable of generating an acid by the action of light or heat is separately added for the purpose of enhancing the sensitivity. Various additives such as a pigment, an antioxidant, and an anti-sticking agent can be added according to the requirements. Further, an overcoat layer may be provided to protect the image recording layer. The undercoat layer may contain a pigment.

When a base is added, an organic base is preferable. For example, a guanidine derivative (for example, 1,3-diphenylguanidine, 1,3-dimethylguanidine, 1,3-
Dibutylguanidine, 1-benzylguanidine, 1,
1,3,3-tetramethylguanidine, etc.), aniline derivatives (eg, aniline, pt-butylaniline, N,
N′-dimethylaniline, N, N′-dibutylaniline, triphenylamine, etc.), alkylamine derivatives (eg, tributylamine, octylamine, laurylamine, benzylamine, dibenzylamine, etc.), and heterocyclic compounds (eg, N , N'-Dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-
Undecene, triphenylimidazole, lutidine, 2
-Picoline) is a preferred example. These bases are 1 to 10 with respect to the composition represented by A in the general formula (1).
It is preferable to add 50 mol%, particularly preferably 5 to 20 mol%.

When the image recording medium of the present invention is used as a photon mode type image recording medium, it is necessary to add a compound which generates an acid by the action of light. On the other hand, when used as a heat mode image recording medium,
If the acid generator represented by A in the general formulas (1) to (4) or (5) has a function of generating an acid by the action of heat, a thermal acid generator is separately added. Although it is not necessary, a thermal acid generator may be added separately for the purpose of increasing the sensitivity. When the acid generator represented by A in the general formulas (1) to (4) or (5) does not have a function of generating an acid by the action of heat, a thermal acid generator is separately added. It is necessary to do. When a plurality of acid generators are used in combination as described above, the general formulas (1) to (4) of the present invention are used.
A plurality of acid generators contained in (4) may be used in combination. The compounds represented by the general formulas (1) to (4) of the present invention may be used in combination with a known acid generator. Examples of known acid generators include compounds described in “Organic Materials for Imaging” edited by Organic Electronics Materials Research Society, published by Bunshin Publishing Company (1997), pp. 37-91, and references cited therein. And the like. Also,
Many of the photoacid generators described herein also function as thermal acid generators.

When a pigment is added, examples include diatomaceous earth, talc, kaolin, calcined kaolin, titanium oxide, silicon oxide, magnesium carbonate, calcium carbonate, aluminum hydroxide, and urea-formalin resin.

Other additives include ultraviolet absorbers such as benzophenone type and benzotriazole type, head wear and sticking preventives comprising higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin, paraffin oxide, polyethylene, Waxes, such as polyethylene oxide and caster wax, are mentioned, and can be added as needed.

In the image recording medium of the present invention, as a heating method as an image forming means, a method of contacting with a heated block or plate, a method of contacting with a heat roller or a heat drum, a halogen lamp or an infrared or infrared There are a method of irradiating an infrared lamp heater, a method of imagewise heating with a thermal head of a thermal printer, and a method of irradiating a laser beam. The image recording medium of the present invention is used for plate making materials,
In the case where a high resolution is required, a method of scanning and exposing with a laser beam is preferable. In order to form an image with less heat energy, the heat-sensitive recording material of the present invention can be heated to an appropriate temperature in advance.
In the present invention, after imagewise heating by these methods, 60
The image can be amplified by heating the entire surface at a temperature of １５０150 ° C. (preferably 60 to 120 ° C.). That is, in the polymer of the present invention, the site A is first decomposed by heating to generate an acid, and the action of the acid causes a change in absorption of B. This reaction proceeds within a very short time due to laser light irradiation, but the image can be amplified by post-heating.

When an image is formed by irradiating a laser beam, a dye that absorbs light having the wavelength of the laser beam must be present in order to convert the laser beam into heat energy. Excimer laser, argon laser, helium neon laser, semiconductor laser, glass (YAG) laser, carbon dioxide laser,
Although there is a dye laser and the like, a helium neon laser, a semiconductor laser and a glass laser are laser light sources useful in the present invention. Among them, a semiconductor laser is particularly useful because the device is small and inexpensive. The oscillation wavelength of the semiconductor laser is usually 670 to 830 nm, and a dye having absorption in the near infrared is used. As the near-infrared absorbing dye, a cyanine dye, a squarylium dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye, and the like are used. Specific examples thereof include, for example, U.S. Pat. Nos. 4,973,572, 4,948,777, 4,950,640, and 4,950,639.
Nos. 4,948,776 and 4948,778, 4,942,141, 4,952,552, 5,036,040 and 4,912,083.
And the like.

When a compound that generates an acid by light is used, a laser is selected as a means for forming a latent image in accordance with the absorption characteristics of the photoacid generator. At this time, various dyes may be added for the purpose of spectral sensitization, but in that case, it is necessary to select a laser according to the absorption wavelength of the dye.

FIG. 1 shows an example of the configuration of a heat developing machine used for the heat development of the heat-developable image recording material of the present invention. FIG.
Is a side view of the heat developing machine. An endless belt 4 for conveyance suspended by a plurality of feed rollers 3 is pressed against a peripheral surface of a cylindrical heat drum 2 containing a halogen lamp 1 as a heat source of a heating means therein, and the endless belt 4 and the heat drum The heat-developable image recording material 5 is conveyed by being sandwiched therebetween. While being transported, the heat-developable image recording material 5 is heated to a development temperature, and is subjected to heat development. In this case, the orientation of the lamp is optimized, and the temperature control in the width direction is performed accurately.

Near the outlet 6 from which the heat-developed image recording material 5 is sent out between the heat drum 2 and the endless belt 4, the heat-developed image recording material 5 released from the curvature of the peripheral surface of the heat drum 2 is formed into a flat K shape. A straightening guide plate 7 for straightening is provided. In the vicinity of the correction guide plate 7, the ambient temperature is adjusted so that the temperature of the heat-developable image recording material 5 does not become lower than a predetermined temperature.

Downstream of the outlet 6, the heat-developable image recording material 5
And a pair of flat guide plates 9 for guiding the heat-developable image recording material 5 in a state of being maintained in a flat state are provided adjacent to the roller pair 8 downstream thereof, Further downstream, another pair of feed rollers 10 is provided adjacent to the flat guide plate 9. The flat guide plate 9 has a length sufficient to cool the heat-developable image recording material 5 while the heat-developable image recording material 5 is being conveyed therebetween. That is, the heat-developable image recording material 5
Is cooled to 30 ° C. or less. As this cooling means, a cooling fan 11 is provided.

Although the above has been described with reference to the illustrated examples, the invention is not limited thereto, and the heat developing machine used in the present invention may have various structures.

The typical synthesis examples of the compounds of the present invention are shown below. (Synthesis Example 1) Synthesis of S- (20)

[0105]

Embedded image

1,4-butanediol (1-1) (5
g) was dissolved in THF (50 ml) and potassium-t-butoxide (6.23 g) was added. Further, di-t-butyl dicarbonate (1-2) was added to this solution at room temperature.
(12.1 g) was added and the mixture was stirred for 2 hours. The obtained solution was added to 100 ml of water, and 200 ml of ethyl acetate was further added.
Was added to extract an organic layer. Further, the organic layer was washed twice with water, dried over magnesium sulfate, and concentrated.
Purification was performed by silica gel column chromatography to obtain 3 g of (1-3) as an oily compound. ¹ H-NMR (CDCl ₃ ) δ (ppm); 1.49 (s, 9H), 1.70 (m,
4H), 1.96 (br, 1H), 3.66 (t, 2
H), 4.10 (t, 2H) Next, (1-3) (2 g) was dissolved in 10 ml of methylene chloride, and triethylamine (1.57 ml), 0.28 g of 4-dimethylaminopyridine, and toluenesulfonyl chloride 2 .16 g was added and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into 10 ml of water, and the organic layer was extracted. Further, the organic layer was washed twice with water, dried over magnesium sulfate, and concentrated. Purification was performed by silica gel column chromatography to obtain 1.5 g of Exemplified Compound S- (20) as a colorless and transparent oily compound. ¹ H-NMR (CDC
l ₃ ): δ (ppm); 1.48 (s, 9H), 1.7
1 (m, 4H), 2.48 (s, 3H), 4.00
(T, 2H), 4.05 (t, 2H), 7.34 (d,
2H), 7.80 (d, 2H)

(Synthesis Example 2) Synthesis of A- (28)

[0108]

Embedded image

(2-1) (9.01 g) was placed in tetrahydrofuran (50 ml), and an oil dispersion of sodium hydride (4 g, content 60%) was added thereto. After stirring for 1 hour, (2-2) (15.66 g) was added and stirred for 3 hours. Then, ethyl acetate (70 ml) and water (5
0 ml) and the aqueous layer was separated. Further, the reaction solution was washed with water, and the organic layer was dried over anhydrous sodium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 (volume ratio)) to obtain 9.5 g of (2-3). Then (2
-3) (6.3 g) was dissolved in methylene chloride (50 ml), and (2-4) (5.17 g) and (2-5) (6.08) were dissolved.
g) was added and stirred for 5 hours. Hexane is added there,
As it was, the mixture was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/5 (volume ratio)) to obtain Exemplified Compound A- (28) (6.2 g, yield 5).
5%). ¹ H NMR (CDCl ₃ ): δ (ppm); 1.65 (4
H), 3.55 (2H), 4.1 (2H), 4.6 (2
H), 4.75 (2H), 5.5 (1H), 5.9 (1
H), 6.8 (1H), 7.35 (5H), 7.6 (2
H), 7.9 (2H). (Synthesis Example 3) Synthesis of S- (22)

[0110]

Embedded image

(3-1) (15.07 g) was placed in tetrahydrofuran (70 ml), and an oil dispersion of sodium hydride (4 g, content 60%) was added thereto. After stirring for 1 hour, (3-2) (15.66 g) was added and 3
Stirred for hours. Thereafter, ethyl acetate (70 ml) and water (50 ml) were added, and the aqueous layer was separated. Further, the reaction solution was washed with water, and the organic layer was dried over anhydrous sodium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/5 (volume ratio)) to obtain 8.4 g of (3-3). Next, (3-3) (2.04 g) was dissolved in methylene chloride,
(3-4) (2.6 g) and (3-5) (1.91 g) were added, and the mixture was stirred for 5 hours. Hexane was added thereto, and the mixture was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/10 (volume ratio)) to obtain Exemplified Compound S- (22) (2.3 g, yield 63).
%). ¹ H NMR (CDCl 3): δ (ppm); -0.1
(6H), 0.95 (9H), 1.6 (4H), 2.5
(3H), 3.6 (2H), 4.1 (2H), 7.4
(2H), 7.8 (2H).

(Synthesis Example 4) Synthesis of LD- (16) To 4.5 g of quinoline-N-oxide monohydrate was added 4.16 g of acetic anhydride, and the mixture was stirred at room temperature for 1 hour, whereby the system became homogeneous. To this solution was added 5 g of 3-phenylisoxazolone suspended in 10 ml of chloroform, and the mixture was stirred at room temperature for 3 hours. The reaction solution was washed with water, dried over magnesium sulfate, and concentrated. The obtained oil was purified by silica gel column chromatography (developing solvent; n-hexane / ethyl acetate = 1/1), and then methanol was added to obtain 1.75 g of a lemon yellow dye (melting point: 223 to 224). ° C, λmax = 423 nm (ε
= 16200) (in ethyl acetate). ). Next, 1 g of the obtained dye was dissolved in 10 ml of THF, and 139 mg of an oil dispersion of sodium hydride (content 60%) was added. Further, 6.2 g of di-tert-butyl-dicarbonate was added, and the mixture was heated under reflux for 30 minutes. Ethyl acetate was added to the reaction solution, and the mixture was washed with water and the organic layer was extracted. The extract was dried over magnesium sulfate and concentrated. The obtained oil was subjected to silica gel column chromatography (developing solvent; n-hexane / ethyl acetate = 1 /
Purification in 1) gave 450 mg of LD- (16) as colorless crystals (mp 137-138 ° C, λma).
x = 335 nm (ε = 14800) (in ethyl acetate)). The structure was identified by NMR and mass spectrometry.

(Synthesis Example 5) Synthesis of LD- (20) 0.3 g of the dye obtained as a synthesis intermediate of Synthesis Example 4 was
It was dissolved in 3 ml of HF, and 41.6 mg of an oil dispersion of sodium hydride (60% content) was added. Further, 0.2 ml of chloromethyloctyl ether was added, and the mixture was stirred at room temperature for 3 hours. . Ethyl acetate was added to the reaction solution, and the mixture was washed with water and the organic layer was extracted. The extract was dried over magnesium sulfate and concentrated. The resulting oil was purified by silica gel column chromatography (developing solvent; n-hexane / ethyl acetate = 3/1) to find that LD- (20) was 25 as a colorless oil.
0 mg was obtained (λmax = 340 nm (ε = 1280
0) (in ethyl acetate)). The structure was identified by ¹ H NMR and mass spectroscopy.

(Synthesis Example 6) Synthesis of P- (2) 1) Synthesis of A- (1) 2 synthesized according to the method described in JP-A-8-248561.
-Methyl-2- (2-hydroxymethyl) acetoacetic acid t
-Butyl ester 18 g, triethylamine 19.8
g and 2 g of 4-dimethylaminopyridine were dissolved in 90 ml of methylene chloride. Further, 18 g of paravinylbenzenesulfonyl chloride (synthesized by allowing thionyl chloride to act on sodium paravinylbenzenesulfonate) was added to the solution, followed by stirring at room temperature for 4 hours.
100 ml of water was added to the reaction solution to extract an organic layer, which was further washed twice with 100 ml of water. After drying the organic layer over magnesium sulfate, hydroquinone monomethyl ether 2m
g was added and the mixture was concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography (eluent: n-hexane /
Purification by ethyl acetate = 3/1) gave 17.7 g (yield 54.1%) of colorless and transparent oil A- (1).
I got The resulting structure was analyzed by mass spectrometry, elemental analysis and ¹ H
It was identified by NMR. Mass spectrometry: M ⁺ = 367 Elemental analysis: calc. C: 58.68% H: 6.57% S:
8.70% found C: 58.69% H: 6.59% S:
8.71% ¹ H-NMR (CDCl ₃ ): δ (ppm): 1.40
(S, 3H), 1.42 (s, 9H), 2.15 (s,
3H), 4.30 (ABq, 2H), 5.50 (d, 1
H), 5.93 (d, 1H), 6.78 (dd, 1
H), 7.58 (d, 2H), 7.85 (d, 2H)
2) Synthesis of B- (22) 4- (2-methacryloyloxyethyl) -2- (2H
-Benzotriazol-2-yl) phenol (manufactured by Otsuka Chemical Co., Ltd.) and 5 ml of nitrobenzene in THF
The resultant was dissolved in 300 ml, and 7.4 g of an oil dispersion of sodium hydride (content 60%) was added under cooling with water. Further, 104 g of chloromethyloctyl ether was added to this solution, and the mixture was stirred at room temperature for 3 hours. Thereafter, 500 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed with water and dried over magnesium sulfate. After the organic layer was concentrated under reduced pressure, silica gel column chromatography (eluent: hexane /
The residue was purified with ethyl acetate = 9/1) and crystallized from hexane to give B- (22) as white crystals.
8 g (yield 53%) was obtained. The structure was identified by mass spectrometry, elemental analysis and ¹ H-NMR. 3) Synthesis of P- (2) 16.6 g of A- (1) and 20.9 of B- (22)
5 g was dissolved in 40 ml of toluene, a solution of 225 mg of 2,2′-azobisisobutyronitrile in toluene (6 ml) was added thereto, and the mixture was heated and stirred at 75 ° C. for 3 hours.
A solution of 225 mg of 2'-azobisisobutyronitrile in toluene (6 ml) was added, and the mixture was heated and stirred at 75 ° C for 3 hours. The reaction solution was cooled to room temperature, added to 500 ml of MeOH, and the precipitated white polymer was isolated to obtain 34.8 g of a polymer (P- (2)) having a molecular weight of 75,000.
(93% yield) was obtained. ¹ HNMR confirmed that the copolymer was a copolymer of A- (1) and B- (1). Further, it was confirmed by elemental analysis that x: y = 50: 50.

Synthesis Example 7 Synthesis of P- (16) 2 g of A- (1) and 1.52 g of B- (14) were dissolved in 5 ml of benzene, and 2,2′-azobis (2,4-
(Dimethylvaleronitrile) (20.2 mg) was added and the mixture was stirred at 60 ° C for 10 hours. When the reaction solution was added to 30 ml of methanol, a white amorphous was obtained. After removing the supernatant by decantation, the polymer was dissolved in a small amount of methylene chloride, added to methanol, and reprecipitated.
After removing the supernatant and drying, a polymer having a molecular weight of 3800 and a molecular weight distribution of Mw / Mn = 3.2 (P- (16))
Was obtained (yield 6.25%). ¹ H NMR
It was confirmed that the copolymer was a copolymer of A- (1) and B- (14). Further, elemental analysis confirmed that x: y was 67:33. The melting point was 120 to 123 ° C, and the thermal decomposition temperature was 145 to 148 ° C. (Synthesis Example 8) Synthesis of P- (11)

[0116]

Embedded image

The compound was synthesized in the same manner as in Synthesis Example 4 (8-
After hydrolyzing 1) under ice-cooling, a leuco dye monomer (B- (18)) was obtained by condensing with 2-hydroxyethyl methacrylate using 2-chloro-1-methylpyridinium iodide as a condensing agent. Acid generator monomer (A-
P- (11) was obtained by copolymerizing 1) and B- (18) with AIBN as an initiator (molecular weight 53,000,
Thermal decomposition onset temperature 140.7 ° C).

[0118]

The present invention will be specifically described below with reference to examples. Example-1 (1) Preparation of support (base) IV (intrinsic viscosity) = 0.66 (phenol / tetrachloroethane = 6/4 (weight) using terephthalic acid and ethylene glycol according to a conventional method. PET) (measured at 25 ° C. in the ratio). This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled.
An unstretched film having a thickness of 120 μm after heat setting was prepared.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then transversely stretched 4.5 times using a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the horizontal direction at the same temperature. 3. After slitting the chuck portion of the tenter, knurling is performed on both ends.
The film was wound at 8 kg / cm ² . In this way, the width 2.4 m,
A roll having a length of 3500 m and a thickness of 120 μm was obtained.

(2) Undercoat layer (a-1) Polymer latex V-5 A core-shell type latex having a core of 90% by weight and a shell of 10% by weight. Core vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acryl Acid = 93/3/3 / 0.9 / 0.1 (% by weight) Shell part Vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (% by weight) weight Average molecular weight 38000 Solid content 3.0 g / m ² 2,4-Dichloro-6-hydroxy-s-triazine 3 mg / m ² Matting agent (polystyrene, average particle size 2.4 μm) 1.5 mg / m ² Undercoat layer (a -2) Polymer latex styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/3 /2.5/0.5 (wt%) solid content 160 mg / m ² 2,4-dichloro-6-hydroxy -s- triazine 4 mg / m ² Matting agent (polystyrene, mean particle size 2.4 [mu] m) 3 mg / m ² Undercoat layer (b) Alkali-treated gelatin (Ca ++ content 30 ppm, jelly strength 230 g) 50 mg / m ²

(3) Conductive layer (Surface resistivity at 25 ° C. and 25% RH: 10 9 Ω) Julimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.): Tg = 52 ° C. 38 mg / m ² SnO ₂ / Sb (9 / 1 weight ratio, average particle size 0.25 μm) 120 mg / m ² matting agent (polymethyl methacrylate, average particle size 5 μm) 7 mg / m ² Denacol EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.) 13 mg / m ²

(4) Protective layer (back surface) Chemipearl S-120 (manufactured by Mitsui Petrochemical Co., Ltd.): Tg = 77 ° C. 500 mg / m ² Snowtex-C (manufactured by Nissan Chemical Co., Ltd.) 40 mg / m ² Denacol EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.) 30 mg / m ²

(5) Preparation of Support I An undercoat layer (a-1) and an undercoat layer (b) were sequentially applied to both surfaces of the support (base) and dried at 180 ° C. for 4 minutes. Next, the undercoat layer (a-1) and the undercoat layer (b) are applied, and a conductive layer and a protective layer are sequentially applied to one side of the undercoat layer,
Each was dried at 180 ° C. for 4 minutes to prepare a PET support I having a back layer / undercoat layer. Undercoat layer (a-
The dry thickness (one side) of 1) was 2.0 μm.

(6) Preparation of Support II Similarly, an undercoat layer (a-
2) and the undercoat layer (b) are sequentially applied, and
After drying at 4 ° C. for 4 minutes, a conductive layer and a protective layer were sequentially applied to one side and dried at 180 ° C. for 4 minutes, respectively, to prepare a PET support II having a back layer / undercoat layer. The dry thickness (one side) of the undercoat layer (a-2) was 2.0 μm.

(7) Heat treatment for transportation (7-1) Heat treatment Table 2 shows PET supports I and II having a back layer / undercoat layer.
A heat treatment zone having a total length of 200 m set at the temperature and tension described in 3 was conveyed at a conveyance speed of 20 m / min. (7-2) Post heat treatment After the heat treatment, post heat treatment was performed at the temperature and tension shown in Table 23, and the film was wound. The winding tension at this time is 10
kg / cm ² .

Thus, the supports shown in Table 2 were obtained.
Table 2 also shows the dimensional change rate of these supports by heating at 120 ° C. for 30 seconds and the presence or absence of beveling. The dimensional change rate was obtained in the same manner as the dimensional change rate associated with the heat development processing described later, and the veins were visually observed.

[0127]

[Table 2]

Next, the following image forming layer and protective layer were sequentially coated on the undercoat layer, and each was dried at 65 ° C. for 3 minutes to obtain a sample of a heat-developable image recording material shown in Table 3.

(8) Image forming layer (Preparation of coating solution for image forming layer) P- (2) and an IR dye were dissolved in chloroform and applied to the following thickness. P- (2) 2 mmol / m ² IR dye 113 mg / m ²

(9) Protective layer A (Preparation of coating solution for protective layer) 40% by weight of polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / methacrylic acid = 59/9/26/5) 262 g of H ₂ O was added to 500 g of a copolymer (Tg 47 ° C.), 14 g of benzyl alcohol, the following compound -22.5 g, and Cellsol 524 (manufactured by Chukyo Yushi Co., Ltd.) 3.6 g as a film-forming aid. The following compound-312 g, the following compound-4 1 g, the following compound-52 g, the following compound-6
7.5 g, 3.4 g of polymethyl methacrylate fine particles having an average particle size of 3 μm as a matting agent were sequentially added, and H ₂ O was further added to 1000 g, and the viscosity was 5 cp (25
° C) and a coating solution having a pH of 3.4 (25 ° C).

This coating solution was applied such that the solid content of the polymer latex was 2 g / m ² .

[0132]

Embedded image

The samples thus obtained were measured for the occurrence of wrinkles after thermal development, the rate of dimensional change due to heat development, and the rate of dimensional change over time after heat development by the methods described below. . Table 3 shows the results.

Note that Tg in the above is determined by differential scanning calorimetry (DSC). The Beck smoothness of each sample was 1500 seconds on the emulsion surface and 350 seconds on the back surface.

1) Test Method for Generation of Wrinkles after Thermal Development Using the thermal developing machine shown in FIG.
The sample (size 60 cm × 75 cm) was subjected to heat development processing under each of the developing conditions of 5, 120 ° C. and a development time of 10, 20, and 30 seconds, and the processed sample was visually inspected for wrinkles (wrinkles). Observed. When no wrinkles were observed under any of the developing conditions, the image was evaluated as “absent”. When wrinkles were observed under any of the developing conditions, “existent” was evaluated.

In the drum type heat developing machine shown in FIG. 1, the light distribution of the lamp was optimized and the temperature accuracy in the width direction was set at ± 1 ° C. Further, the ambient temperature was adjusted so that the temperature of the heat-developable image recording material did not become 90 ° C. or less near the correction guide plate 7.

2) Measurement method of dimensional change rate due to thermal development processing Two holes having a diameter of 8 mm were formed at intervals of 200 mm on a sample (size 5 cm × 25 cm) before exposure to light on the entire surface.
The distance between the two holes was accurately measured using a pin gauge with a precision of / 1000 mm. The dimension at this time is defined as X (unit: mm). Then, using the heat developing machine shown in FIG.
After the heat development processing under the developing condition of second, the dimensions 120 minutes later were measured with a pin gauge. The dimension at this time is Y (unit: m
m). The dimensional change rate (%) = [(Y−X) / 200] × 100.

3) Measurement method of dimensional change rate with time after thermal development processing Two holes having a diameter of 8 mm were made at intervals of 200 mm on a sample (size 5 cm × 25 cm) before exposure to light on the entire surface. After performing a heat development process at 120 ° C. for 30 seconds using the heat development machine shown in FIG. 1, the dimensions 3 minutes later were measured using a pin gauge with 1/1000 mm precision. The dimension at this time is X1
(Unit: mm). Then, the size Y1 (unit: mm) after a lapse of 240 minutes was measured.

This series of measurements was performed in an atmosphere of 25 ° C. and 75% RH and in an atmosphere of 25 ° C. and 20% RH.

Dimensional change rate (%) = [(Y1-X1) / 2
00] × 100.

[0141]

[Table 3]

As is clear from Table 3, the sample of the present invention has a small dimensional change over time after the heat development. The above sample uses a biaxially stretched PET support, and by performing heat treatment, it is possible to eliminate the occurrence of wrinkles during heat development and to reduce the dimensional change due to heat development. Therefore, it can be seen that the use of the heat-treated support does not cause any wrinkles during the heat development, and the dimensional change accompanying the heat development and the dimensional change over time after the heat development are extremely small. In particular, it can be seen that good results are obtained when a support subjected to a heat treatment according to preferable conditions is used.

The samples coated with the following compounds (i) to (v) in place of P- (2) as the image forming layer were evaluated using the supports I-2 and II-2 in Table 2. As a result, in all the samples, the use of the support of the present invention showed a remarkable improvement in wrinkling and dimensional change. (Image forming layer coated material) (i) P- (11) (coating amount of x portion is 2 mmol / m ² ) (ii) P- (16) (coating amount of x portion is 2 mmol / m ² ) (iii) S- (1) (2 mmol / m ² ) LD- (16) (2 mmol / m ² ) Polystyrene (0.85 g / m ² ) (iv) S- (20) (2 mmol / m ² ) LD- (16) (2 mmol / m ² ) polystyrene (0.85 g / m ² ) (v) S- (1) (2 mmol / m ² ) LD- (7) (2 mmol / m ² ) polystyrene (0.85 g / m ² ) ( In each case, 113 mg / m ^{2 of the} IR dye was applied.
Polystyrene is Wako Pure Chemical's polystyrene beads (diameter;
(About 3.2 mm) was used. )

Example-2 The thickness (one side) of the vinylidene chloride copolymer layer of the undercoat layer (a-1) of Example-1 was 0.1 μm, 0.3 μm, 0.1 μm, 0.3 μm, 0.1 μm, 0.3 μm and 0.1 μm, respectively.
PE changed to 5μm, 1μm, 2μm, 3μm, 4μm
A T support was prepared, and then a backing layer was applied in the same manner as in Example 1, and then a transfer heat treatment was performed under the same conditions as for Support No. I-2 shown in Table 2.

Next, on the side opposite to the back layer, an image forming layer and a protective layer were applied in the same manner as in Example 1 to obtain Samples 21 to 27 shown in Table 4.

The samples were evaluated for wrinkles during thermal development, dimensional changes due to thermal development, and dimensional changes over time after thermal development, as in Example 1. Table 4 shows the results.

The coating surface state of the vinylidene chloride copolymer layer was evaluated as follows, and is shown in Table 4 by ○, Δ, and ×.

4) Evaluation of coating surface state ：: No coating unevenness, repelling, etc. were observed visually. Δ: coating unevenness, cissing, etc., to the extent that they can be visually identified or not. X: coating unevenness, cissing, etc. can be clearly recognized visually.

[0149]

[Table 4]

As is clear from Table 4, the sample of the present invention is free from wrinkles during heat development and has good dimensional change due to heat development and little dimensional change over time after heat development. I understand.

[0151]

According to the present invention, a dimensional change with time after thermal development can be reduced. In addition, it is possible to eliminate wrinkles during thermal development and dimensional changes before and after thermal development. In particular, in the case of a polyester support, a support coated on both sides with an undercoat layer having a predetermined thickness of vinylidene chloride copolymer,
When a predetermined preferable heat treatment is performed, a heat-developable image recording material is obtained in which the dimensional change before and after thermal development and the dimensional change over time after thermal development are extremely small.

[Brief description of the drawings]

FIG. 1 is a side view showing a configuration example of a heat developing machine used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 halogen lamp 2 heat drum 3 feed roller 4 endless belt 5 heat-developed image recording material 6 outlet 7 guide plate 8 feed roller pair 9 flat guide plate 10 feed roller pair 11 cooling fan

Continued on the front page F term (reference) 2H026 BB48 EE05 FF11 FF15 2H123 AD00 AD01 AD12 AD26 AE00 AE01 AE07 BA00 BA38 BA45 BA49 EA01 FA12

Claims (12)

[Claims] 1. An undercoat layer containing a vinylidene chloride copolymer containing at least 70% by weight of a vinylidene chloride monomer repeating unit on both sides under heat development at a developing temperature of 80 ° C. or more and 140 ° C. or less. A non-silver salt heat-developable image recording material comprising a support provided with a thickness of 0.3 μm or more (total thickness per one side). 2. The reaction of a compound generating an acid by light or heat with an acid on the support, from 360 nm to 9 nm.
2. The non-silver-salt heat-developable image recording material according to claim 1, further comprising an image-forming layer containing a compound which undergoes an absorption change between 00 nm. 3. The method according to claim 1, wherein the reaction between the acid and a compound capable of generating an acid by light or heat with the acid causes the support to have a wavelength of 360 nm to 9 nm.
An image-forming layer containing a compound which causes an absorption change between 00 nm and at least one protective layer provided on the image-forming layer, wherein the vinylidene chloride copolymer has a molecular weight of 70 nm.
3. The non-silver-salt heat-developable image recording material according to claim 2, comprising 〜99.9% by weight of a repeating unit of a vinylidene chloride monomer and 0.1 to 5% by weight of a repeating unit of a carboxyl group-containing vinyl monomer. . 4. The non-silver salt thermally developed image recording material according to claim 1, wherein the weight average molecular weight of the vinylidene chloride copolymer is 45,000 or less. 5. The non-silver heat-developable image recording material according to claim 1, wherein said support is a biaxially stretched polyester. 6. The method according to claim 1, wherein the support is provided with an undercoat layer containing the vinylidene chloride copolymer.
The non-silver salt heat-developable image recording material according to claim 5, which has been subjected to a heat treatment at a temperature of 85 ° C or lower. 7. The thermal dimensional change of the heat-treated support when heated at 120 ° C. for 30 seconds is from −0.03% to 0.01% in the machine direction (MD), and 7. It is 0% or more and 0.04% or less in the (TD) direction.
Non-silver heat-developable image recording material. 8. The non-silver salt thermally developed image recording material according to claim 3, wherein a polymer latex is used as a binder for the image forming layer and the protective layer. 9. The non-silver-salt heat-developable recording material according to claim 1, wherein the acid generator represented by the following general formula (1) generates an acid by the action of heat or an acid, and a molecule formed by the action of an acid. 9. A non-silver salt heat-developable recording material according to claim 1, further comprising a compound which causes an internal or intermolecular reaction to cause a change in an absorption range of 360 to 900 nm. Formula (1) W ¹ OP ^{1 In the} formula, W ¹ represents a residue of an acid represented by W ¹ OH, and P ¹ represents a substituent which is released by the action of heat or an acid. 10. The non-silver salt thermal development recording according to claim 9, wherein the acid generator represented by the general formula (1) is a compound selected from the following general formulas (2) to (4). material. General formula (2) In the formula, R ¹ represents an electron-withdrawing group having a Hammett σ _p value of more than 0 and 1 or less. R ² represents an alkyl group. R ³ represents a group capable of leaving by the action of heat or an acid. W ¹ has the same meaning as in formula (1). General formula (3) In the formula, R ⁴ , R ⁵ , and R ⁶ represent a hydrogen atom, an alkyl group, or an aryl group, and W ¹ has the same meaning as in formula (1). Formula (4) P ² -X-LC (R ⁷ ) (R ⁸ ) -OW ^{1 In the} formula, P ² represents a substituent capable of leaving by the action of heat or an acid. X is O, S, NR ⁹ (R ⁹ represents a hydrogen atom or a substitutable group), or CR ¹⁰ R ¹¹ (R ¹⁰ and R ¹¹ represent a hydrogen atom or a substitutable group, and May be different). L represents a linking group. R ⁷ and R ⁸ represent a hydrogen atom or a substitutable group, and may be the same or different. W ¹ has the same meaning as in formula (1). 11. The non-silver salt heat-developable recording material according to claim 1, wherein the partial structure having a function of generating an acid by the action of heat or an acid, and 360 to 900 n by the action of an acid.
9. The heat-developable non-silver salt recording material according to claim 1, further comprising a polymer having a partial structure causing a change in an absorption range of m. 12. The non-silver salt heat-developable recording material according to claim 11, wherein the polymer according to claim 11 is a polymer represented by the following general formula (5). Formula (5)-(A) _x- (B) _y- (C) _{z- wherein} A is obtained by polymerization of at least one vinyl monomer having a function of generating an acid by the action of heat or an acid. B represents a repeating unit obtained by polymerization of at least one type of vinyl monomer having a partial structure that causes a change in the absorption range of 360 to 900 nm by the action of an acid; Represents a repeating unit obtained by polymerization of at least one or more kinds of polymerizable vinyl monomers, and x, y
And z represent% by weight, and 1 ≦ x ≦ 99 and 1 ≦
It represents y ≦ 99, 0 ≦ z ≦ 98, and x + y + z = 100.