JP2002059651A - Image recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image recording medium which has high heat sensitivity and can produce a sufficient change in density even when it is used as a UV mask film for a plate making material, of which the haze, a problem as to an outward appearance, is low even when a high output laser is used and which hardly causes an abrasion or the like and is excellent in handling properties. SOLUTION: The image recording medium has on a substrate an image recording layer which contains a compound producing the change in the density in an absorption zone of 360-900 nm under the action of heat or an acid and contains no silver salt and a protective layer which has a coating amount of binder of 3 g or more per 1 m2. Particularly, the image recording layer contains further an infrared absorbing substance and/or a substance producing the acid under light or heat.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording medium having high sensitivity and good handleability utilizing a color (or decoloring) reaction by the action of heat or an acid.

[0002]

2. Description of the Related Art A heat-sensitive recording material expresses an image area and a non-image area as a temperature difference distribution, and includes a color transfer reaction between two components due to a melt transfer or sublimation transfer of a colorant, heat melting or capsule destruction, and a phase transition. Many schemes have been devised, such as changes in optical properties. This type of thermal recording medium is widely used as an output material for various printers, word processors, facsimile machines, etc. because of its advantages that a recorded image can be obtained by a dry and simple system and that it is maintenance-free. In recent years, with the progress of laser recording devices, applications to optical disks and plate making materials are being studied.

Conventionally, silver halide photographic materials requiring wet processing have been used as plate making materials. However, due to the demand for simplification of processing steps and the problem of environmental pollution caused by processing solutions, development of dry processing has been required. Desirably, several technical proposals have been made in recent years using the thermal recording method. From the viewpoint of resolution, image recording using a laser is preferable. For example, a method called dye abrasion using a high-power laser has been developed, and the recording material is disclosed in
-164755, -149063, 7-149
No. 065, the image forming apparatus is disclosed in JP-A-8-48053.
And No. 8-72400.

In this system, a recording material having a dye composition comprising an image dye, a substance having absorption in a laser wavelength range (infrared absorbing substance) and a binder is irradiated with a laser from the dye layer side. By doing so, image recording is performed. The energy provided by the laser causes a sharp local change in the imaging layer at the spot where the laser beam hits the material, thereby driving the material out of the layer. According to the above patent publication, this is not a complete physical change (e.g., melting, evaporation or sublimation), but some kind of chemical change (e.g., bond breaking), rather than partial image dye removal. It is said to be complete elimination. In such a dye ablation method, a high-power laser is indispensable in order to increase the efficiency of removing the dye at the laser exposure site, and a dust collector is required to collect the removed dye. there were.

As a method that does not require a dust collector, a description of an ablation transfer type image recording method using a laser as a heat source is disclosed in US Pat. No. 5,171,650. In this system, a dye donor sheet containing a dynamic release layer overcoated with an ablative carrier topcoat is used, and the image is transferred to another adjacently aligned receiving sheet. For this reason, there has been a problem that a sheet that has become unnecessary after image recording becomes a waste material. Also in this case, a high-output laser was indispensable to enhance the transfer efficiency. As described above, the conventional thermal recording method using laser ablation requires a high-output laser, and has a problem that dust and waste materials cannot be avoided.

On the other hand, as a thermal recording method using laser and not involving ablation, a system called "dry silver" has been developed in Japanese Patent Laid-Open No. Hei 6-1947.
No. 81, etc. In this system, laser recording is performed on a recording material containing a silver source that can be thermally reduced, a reducing agent for silver ions, and a photothermal conversion dye. This was insufficient for practical performance.

[0007] Further, as a compound which proliferates an acid by the action of an acid, K. Asahi. Ichimura, Chem. Let
t. , 551 (1995) and JP-A-8-24856.
No. 1 discloses a compound that generates an organic acid by decomposition with an acid catalyst, and the compound is formed from an acid-reactive compound comprising a combination of a photoacid generator and a substance that undergoes a structural change by the action of an acid. A polymer composition is described. However, in this document, the action of the acid generated by the photoacid generator causes a structural change such as solubilization or insolubilization in a polar solvent or an aqueous alkali solution, and is intended for a so-called photoresist.
There is no description about a recording material utilizing an absorption change.

[0008] JP-A-11-180048 and JP-A-11
No. -181031, the Ichimura (Ichimura)
An image forming method using a change in absorption by light or heat using a compound developed by the present inventors as a thermal acid generator is described. However, if the image forming method described in this patent is used as it is as a UV mask film for plate making materials, it will be caused by adhesion during transport in the mask exposure step on the PS plate (for example, between the film and transport rollers, guide plates, films). Problems such as poor conveyance and easy scratching, and problems such as poor adhesion due to adhesion to heat developing machine members (for example, conveying rollers, guide plates and heat source drums) during thermal development processing, and easy scratching there were.

In the image forming method described in JP-A-11-180048 and JP-A-11-181031, the present inventors provide a photosensitive material with a protective layer.
It has been found that the problem of poor transport and scratches, which are likely to occur during exposure of a PS plate to a mask or during thermal development, can be avoided (filed in Japanese Patent Application No. 2000-65238). However, although this technology is very effective in terms of transport characteristics and physical strength of the image surface, when a high-power laser is used to secure the necessary color density for the UV mask film used for plate making materials, the Part of the surface of the layer was thermally destroyed (so-called ablation), haze was increased, and there was a problem in appearance.

The present inventor has further improved the technology of an image forming method for forming a high-density dye image with a low haze even when irradiated with a high-power laser, and has also filed an application for the same (Japanese Patent Application No. 2000-2000). 91994, Japanese Patent Application 2000-919
95). However, even in the image forming method to which these improvements are applied, when applied to a UV mask film used in a plate making process, the level of haze is not sufficient, and handling such as abrasion is likely to occur. The problem remains.

[0011]

SUMMARY OF THE INVENTION A first object of the present invention is to provide an image recording medium having high thermal sensitivity and capable of causing a sufficient density change even when applied as a UV mask film used for a plate making material. To provide. A second object of the present invention is to provide an image recording medium which has a low haze, which is a problem in appearance even when a high-power laser is used, and has excellent handleability in which scratches and the like are less likely to occur.

[0012]

The above object of the present invention is attained by the following image recording medium. (1) At least one layer of an image recording layer containing a compound which causes a concentration change in the absorption region of 360 to 900 nm by the action of heat or acid and containing no silver salt, and at least one layer of protection on a support An image recording medium having a protective layer, wherein the coating amount of the protective layer is 3 g or more per 1 m ² .

(2) The method according to the above (1), comprising at least one kind of infrared absorbing substance, wherein a concentration change occurs in an absorption region of 360 to 900 nm by the action of heat or acid generated by laser irradiation. The image recording medium according to the above.

(3) Containing at least one infrared absorbing substance, and having a concentration change of 3.0 or more at a specific wavelength in an absorption range of 360 to 900 nm due to the action of heat or acid generated by laser irradiation. The image recording medium according to the above (1) or (2), wherein

(4) The support is a permeable support,
The haze value is not more than 20% before and after the concentration is changed in the absorption region of 360 to 900 nm due to the action of heat or acid, either of the above (1) to (3).
Item 2. The image recording medium according to Item 1.

(5) 360-9 by the action of heat or acid
(1) to (4), wherein before and after the concentration change occurs in the absorption region of 00 nm, the surface of the protective layer has a thick needle scratching strength of 30 g or more and a fine needle scratching strength of 10 g or more. 13. The image recording medium according to claim 1.

(6) An acid generator which generates an acid by the action of heat, and a compound which causes an intramolecular or intermolecular reaction by the action of the acid to cause a concentration change in an absorption region of 360 to 900 nm. Features (1) to (5)
8. The image recording medium according to any one of the above.

(7) The image recording medium as described in (6) above, wherein the acid generator is a compound represented by the following formula (I).

Formula (I)

[Formula 6]

In the general formula (I), R ¹ represents an alkyl group, an aryl group or a heterocyclic group. R ² and R ³ each independently represent an alkyl group or an aryl group, but R ² and R ³ are not simultaneously an aryl group. R ² and R ³ may combine to form a ring. (8) The image recording medium according to (7), wherein the acid generator represented by the general formula (I) is a compound represented by the following general formula (II).

Formula (II)

[Formula 7]

In the general formula (II), R ³¹ represents an alkyl group, an aryl group or a heterocyclic group. R ³² represents a substituent. R ³³ and R ³⁴ independently represent a hydrogen atom or a substituent. X ¹ represents an atomic group necessary for forming a ring. R ³² , R ³³ or R ³⁴ may combine with X ¹ to form a ring.

(9) Compounds which cause an intramolecular or intermolecular reaction by the action of an acid to cause a concentration change in the absorption range of 360 to 900 nm are compounds represented by any of the following formulas (III) to (V) The image forming method according to any one of the above (6) to (8), wherein

Formula (III)

[Formula 8]

In the general formula (III), X ² is N (R ⁵⁸ ),
Represents O or S, Y ¹ represents an atomic group necessary for forming a cyclic structure together with N—C—X ² , and A ¹ represents C (R ⁵⁹ ) or
Represents N, R ^{51 to} R ⁵⁹ represent a hydrogen atom or a substituent, and may be the same or different, and R ⁵⁴ ,
R ⁵⁵ , R ⁵⁶ and R ⁵⁷ may combine with each other to form a condensed ring, and B ¹ represents an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, an arylamino group or a heterocyclic amino group.

General formula (IV)

[Formula 9]

In the general formula (IV), Ar ¹ and Ar ²
Represents an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, and may be the same or different;
⁷¹ represents a hydrogen atom or a substituent, Y ² represents an aromatic hydrocarbon ring or a hetero ring, and X ³ represents O, S or N
(R ⁷² ), wherein R ⁷² represents a hydrogen atom or a substituent.

General formula (V)

[Formula 10]

In the general formula (V), Ar ³ and Ar ⁴
Represents an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different, and
¹ represents an aromatic hydrocarbon ring or a hetero ring, A ² represents O, S or N (R ⁷³ ), and R ⁷³ represents a hydrogen atom or a substituent.

(10) The image forming method according to any one of the above (1) to (9), comprising a polymer represented by the following general formula (VI). Formula (VI)-(A) _x- (B) _y- (C) _{z- In the} formula (VI), A represents a repeating unit obtained by polymerization of an acid generator monomer, and B represents an action of an acid. Represents a repeating unit obtained by polymerization of at least one type of vinyl monomer having a partial structure that causes a concentration change in an absorption range of 360 to 900 nm, and C represents at least one type of vinyl monomer copolymerizable with A and B Represents a repeating unit obtained by polymerization of
x, y and z represent mol%, and 1 ≦ x ≦ 10
0, 0 ≦ y ≦ 99, 0 ≦ z ≦ 99, x + y + z = 100
Represents

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The present invention uses 360 to 900 n by the action of heat or acid.
The present invention relates to a recording medium that contains a compound that causes a change in density in an absorption region of m and forms an image.

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 distant 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. When the image recording medium of the present invention is used for a material requiring a high resolution, such as a plate making material, a method of scanning and exposing with a laser beam is preferable. In particular, when a laser beam shaped so as to exhibit a substantially square intensity distribution in the sub-scanning direction described in Japanese Patent Application No. 11-273162 or the like is applied, resolution and image cutting are improved, and it is preferably used. be able to. Further, in order to form an image with less heat energy, the heat-sensitive recording material of the present invention can be heated in advance to an appropriate temperature.
In the present invention, after imagewise heating is performed by these methods, a temperature of 60 to 150 ° C. (preferably 60 to 12 ° C.) may be used in some cases.
In some cases, the change in image density can be increased by heating the entire surface at 0 ° C.).

When an image is formed by converting laser light into heat energy, a dye that absorbs light having the wavelength of the laser light must be present. Laser light sources include excimer laser, argon laser, helium neon laser, semiconductor laser, glass (YAG) laser, carbon dioxide laser, dye laser, etc.
Helium neon lasers, semiconductor lasers and glass lasers 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 a semiconductor laser is usually 67
The dye used in the photosensitive material for these lasers is preferably a dye having an absorption in the near infrared region described above.

As near infrared absorbing dyes, cyanine dyes,
Squarylium dyes, merocyanine dyes, oxonol dyes, phthalocyanine dyes and the like are used. Specific examples thereof include, for example, US Pat. No. 4,973,572,
No. 4,948,777 and No. 4,950,640
No. 4,950,639 and No. 4,948,77
No. 6, 4948,778, and No. 4,942,141,
Nos. 4,952,552, 5,036,040 and 4,912,083. When the image recording medium of the present invention is a so-called negative type in which laser-exposed portions develop color, it is preferable that the unexposed portions have low absorption. For example, UV
In the case of using as a mask film, an infrared absorbing dye having a small side absorption in a UV wavelength region is preferable, and specific examples thereof are described in Japanese Patent Application No. 2000-590004.

When the image recording medium of the present invention is used as an image recording medium of a photon mode system (a system in which image recording is performed by light, also referred to as an optical mode system), a compound which generates an acid by the action of light is used. Addition is essential.
In this case, a laser is selected according to 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. Known acid generators include “Organic Materials for Imaging”, edited by Organic Electronics Materials Research Group, published by Bunshin Publishing Company (1997), p. 37-
91, and the compounds described in the references described therein. Also,
Many of the photoacid generators described herein also function as thermal acid generators.

In a preferred embodiment of the present invention, an acid generator which generates an acid by the action of heat and a compound which accelerates intramolecular or intermolecular reaction by the action of an acid and causes a concentration change in an absorption range of 360 to 900 nm are used. The used image recording medium is exemplified.

As the acid generator, those which generate a strong acid by laser irradiation are preferable, and among them, those which generate a sulfonic acid are preferable. Examples of the acid generator that generates sulfonic acid include, for example, “Organic Materials for Imaging”, edited by Organic Electronics Materials Research Group, published by Bunshin Publishing Company (1.
997). Further, Japanese Unexamined Patent Publication No.
Acid generators described in JP-A-180048 and JP-A-11-181031 are also preferable compounds. Among them, a secondary alkyl ester of sulfonic acid can be preferably used. More preferably, it is represented by the general formula (I) or (II).

In the general formula (I), R ¹ is an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, dodecyl, cycloalkyl) Represents an propyl, cyclopentyl, cyclohexyl, etc.), an aryl group (eg, a phenyl group, a naphthyl group, etc.) or a heterocyclic group (eg, a furyl, thienyl, pyrimidinyl, benzothiazolyl, etc.). Among these, an alkyl group or an aryl group is preferable, and an aryl group is particularly preferable.

These groups may further have a substituent, and any substituent may be used as long as it can be substituted. As a substituent, a halogen atom (for example, fluorine,
Groups such as chlorine, bromine and iodine), alkyl groups (including cycloalkyl groups and bicycloalkyl groups, specific examples are as described above), and alkenyl groups (for example, vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopentene) -1
-Yl and the like), an alkynyl group (for example, each group such as ethynyl, propargyl and trimethylsilylethynyl), an aryl group (the specific examples are the same as described above), a heterocyclic group (the specific examples are the same as described above), and a cyano group , Hydroxyl group,
Nitro group, carboxyl group, alkoxy group (for example, methoxy, ethoxy, isopropoxy, t-butoxy, n
-Octyloxy or the like), an aryloxy group (for example, a phenoxy group, a naphthoxy group, or the like), a silyloxy group (for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, or the like), a heterocyclic oxy group (for example, pyridyl) Oxy group, 2-tetrahydropyranyloxy group, etc.), acyloxy group (for example, each group such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy), carbamoyloxy group (for example, N, N-dimethylcarbamoyloxy) , Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy, etc.), alkoxycarbonyloxy groups (for example, methoxycarbonyloxy, ethoxycarbonyloxy) t- butoxycarbonyl-oxy, n
-Octylcarbonyloxy and the like), an aryloxycarbonyloxy group (for example, a phenoxycarbonyloxy group and the like),

Amino groups (including anilino groups, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, etc.), acylamino groups (eg, acetylamino, pivaloylamino, lauroylamino, Benzoylamino, 3,4,5
-Tri-n-octyloxyphenylcarbonylamino, etc.), carbamoylamino group (for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, etc.) An alkoxycarbonylamino group (for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, etc.), an aryloxycarbonylamino group (for example, Phenoxycarbonylamino group, etc.), sulfamoylamino group (for example, sulfamoylamino, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group, etc.), Alkyl and arylsulfonylamino groups (e.g., methylsulfonylamino, butylsulfonylamino, each group such as phenylsulfonylamino),

A mercapto group, an alkylthio group (for example,
Groups such as methylthio, ethylthio, n-hexadecylthio), arylthio groups (eg, phenylthio), heterocyclic thio groups (eg, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group, etc.), and sulfamoyl Groups (eg, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl,
Groups such as N- (N′-phenylcarbamoyl) sulfamoyl), a sulfo group, an alkyl and arylsulfinyl group (eg, each group such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl), an alkyl and arylsulfonyl group (eg, methyl Sulfonyl,
Groups such as ethylsulfonyl and phenylsulfonyl),
Acyl groups (eg, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl group), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, t-) Each group such as butoxycarbonyl and n-octadecyloxycarbonyl), a carbamoyl group (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl,
Groups such as N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl, imide groups (eg, N-succinimide group, N-phthalimido group), phosphino groups (eg, dimethylphosphino group) ,
Diphenylphosphino group), a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group (for example, each group such as trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl). The substituent may be further substituted. R
Most preferably as ^a substituent an alkyl group.

Specific examples of R ¹ are shown below, but the present invention is not limited thereto.

[0043]

[Formula 11]

[0044]

[Formula 12]

[0045]

[Formula 13]

The substituents R ² and R ³ each independently represent an alkyl group or an aryl group, but R ² and R ³ are not simultaneously an aryl group. Examples of the alkyl group and the aryl group are the same as those described for R ¹ , and may further have a substituent. Preferred substituents are those described for R ¹ . At least one of R ² and R ³ may have a polymerizable unsaturated group, and a vinyl group is preferable as the polymerizable unsaturated group. R ² and R ³ may combine to form a ring. Although various examples are given as such examples, preferred forms are those represented by the general formula (VII).

[0047]

[Formula 14]

In the general formula (VII), R ¹ has the same meaning as in the general formula (I). X ⁴ represents an atomic group necessary for forming a ring together with C. X ⁴ forms a ring together with C, and the size of the ring is preferably 3 to 8, more preferably 5 or 6, and particularly preferably 6. X ⁴ is preferably a non-metallic atomic group, and more preferably —C (R ⁴ ) (R ⁵ ) —, —C (＝ Y ³ ) —, and —.
N (R ⁶ ) —, —O—, and —S—, and particularly preferably —C (R ⁴ ) (R ⁵ ) —. Here, R ⁴ , R ⁵ , and R ⁶ represent a hydrogen atom or a substituent, and preferred examples of the substituent are the same as those described as the substituent in the description of R ¹ . When a plurality of R ⁴ , R ⁵ or R ⁶ are present in the molecule, they may be the same or different, and any two or more may be combined to form a ring. good. Y ³ is ＯO, ＳS, or ＮN-R
^And R ⁶ is the same as described above. Further, the compound represented by the general formula (VII) exhibits more excellent performance by being polymerized as described later. Preferred as the monomer having a polymerizable unsaturated group therefor is a compound represented by the following formula (VIII).

[0049]

[Formula 15]

In the formula, R ¹ has the same meaning as in formula (I).
R ⁷ represents a hydrogen atom or an alkyl group, and the alkyl group may further have a substituent. Specific examples of the alkyl group and the substituent are those described in the specific examples of R ¹ .
R ⁷ is preferably a hydrogen atom or a methyl group. Hereinafter, specific examples of the compound represented by Formula (I), Formula (VII) or Formula (VIII) are shown, but the present invention is not limited thereto. Some compounds have isomers such as cis- and trans-forms, and the use of these as a mixture is also included in the present invention.

[0051]

[Formula 16]

[0052]

[Formula 17]

[0053]

[Formula 18]

[0054]

[Chemical Formula 19]

[0055]

[Formula 20]

In the general formula (II), R ³¹ has the same meaning as R ^{1 in the} general formula (I). In the general formula (II), the substituent R ³² represents a substituent, and examples of the substituent include those described as a substituent in the description of R ¹ . R ³² is preferably an alkyl group, a halogen atom or an alkoxy group, and more preferably an alkyl group. R ³³
And R ³⁴ each independently represent a hydrogen atom or a substituent, and examples of the substituent include those described as a substituent in the description of R ¹ . R ³³ and R ³⁴ are preferably a hydrogen atom, an alkyl group, a halogen atom or an alkoxy group, and more preferably a hydrogen atom or an alkyl group. Further, at least one of R ³³ and R ³⁴ is preferably a substituent.

X ¹ represents an atomic group necessary for forming a ring. The size of the ring is preferably 3 to 8,
It is more preferably 5 or 6, and particularly preferably 6. Preferably X ¹ is non-metallic atomic group, more preferably ^{-C (R 35) (R 3} 6) -, - C (= Y 4)
—, —N (R ³⁷ ) —, —O—, and —S—, and particularly preferably —C (R ³⁵ ) (R ³⁶ ) —. Where R ³⁵ , R
³⁶ and R ³⁷ represent a hydrogen atom or a substituent, and preferred examples of the substituent are the same as those described for R ¹ . When a plurality of R ³⁵ , R ³⁶ or R ³⁷ are present in the molecule, they may be the same or different, and any two or more may combine to form a ring. good. Y is = O, = S, or = N-
It represents R ^37, R ³⁷ are the same as those described above.
R ³² , R ³³ or R ³⁴ may combine with X ¹ to form a ring. Further, at least one of R ^{31 to} R ³⁴ preferably has a polymerizable unsaturated group, and a vinyl group is preferable as the polymerizable unsaturated group. In addition, the general formula (II)
Among the compounds represented by the formula, a compound represented by the following general formula (IX) is more preferred.

[0058]

[Formula 21]

[0059] In the formula, R ³¹ to R ³⁴ has the same meaning as R ³¹ to R ³⁴ shown in the general formula (II). R ³⁸ and R ⁴⁰ represent a hydrogen atom or a substituent (specific examples are the same as the substituents in the description of R ¹ ), preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R ³⁹ represents a hydrogen atom or a substituent (specific examples are those described in the description of R ¹ ), and preferably has a Hammett σm value of 0 or more, and more preferably a hydrogen atom or an acyloxy group. Further, the compound represented by the formula (IX) preferably has a polymerizable unsaturated group at any position, and a vinyl group is preferable as the polymerizable group.

Specific examples of the compounds represented by formulas (II) and (IX) are shown below, but the present invention is not limited thereto. In some compounds, cis-form and tr
Some isomers such as ans-isomers exist, but the following description does not specify the structure of the isomers, and includes the case where the isomers are used as a mixture of isomers.

[0061]

[Formula 22]

[0062]

[Formula 23]

[0063]

[Formula 24]

[0064]

[Formula 25]

[0065]

[Formula 26]

The amount of these acid generators varies depending on the type of the compound having a change in absorption, but is generally 0.001 to the compound having a change in absorption in the wavelength region of 360 to 900 nm due to the action of an acid described later. The range is preferably from 20 to 20 equivalents, particularly preferably from 0.01 to 5 equivalents.

In the present invention, a compound that changes the absorption range of 360 to 900 nm by an intramolecular or intermolecular reaction due to the action of heat or an acid is stable as long as it is stored at room temperature under neutral conditions. , A compound that undergoes an intramolecular or intermolecular reaction upon the action of heat or an acid to cause a change in absorption in the above range.

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 decolored image in the region by a Diels-Alder reaction, A compound that forms a color image (e.g., an adduct of 9,10-distyrylanthracene and maleic anhydride, an adduct of diphenylisobenzofuran and acrylamide, etc.), a conjugated system is expanded by β-hydrogen elimination, and a color image is formed in the region. Compounds to be formed (for example, 1-acetoxy-1,2-diarylethane, 1-sulfoxy-1,2-diallylethane, etc.), and a combination of an aldehyde and an active methylene compound which form a color image in the area by dehydration condensation (for example, Photographic 4) Equivalent magenta A coupler and a p-methoxycinnamaldehyde) or an amino group or a hydroxyl group substituted by a substituent whose decomposition or elimination is promoted by the action of an acid in the molecule. And the like.

In a compound in which the absorption is changed by the decomposition or elimination of the amino group by the action of an acid, the amino group is substituted by an alkoxycarbonyl group (for example, a t-butoxycarbonyl group, a cyclohexyloxycarbonyl group, (2-methyl) butoxycarbonyl group, 2- (2-phenyl) propyloxycarbonyl group, 2-chloroethoxycarbonyl group and the like, acyl group (for example, acetyl group, benzoyl group, 2-nitrobenzoyl group, 4-chlorobenzoyl group, A naphthoyl group) or a formyl group are preferred examples. In the present invention, β is preferred from the viewpoint of storage stability and heat sensitivity.
An alkoxycarbonyl group having a hydrogen atom at the position is particularly useful. Examples of such compounds are described in, for example, U.S. Pat. Nos. 4,602,263 and 4,826,976. When combined with the thermal acid generator of the present invention, higher sensitivity and storage stability can be obtained. The present invention can provide a heat-sensitive recording medium having excellent heat resistance.

As the substituent of the hydroxyl group in the compound in which the absorption is changed by the decomposition or elimination of the hydroxyl group by the action of an acid, the hydroxyl group has a hydrogen atom at the β-position.
Secondary or tertiary alkoxycarbonyl group (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) A 2- (2-methoxypropyl) group and a secondary or tertiary alkyl group having a hydrogen atom at the β-position (eg, tetrahydropyranyl, tetrahydrofuranyl, 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. Examples of compounds whose absorption is changed by decomposition of a hydroxyl group substituent are described in U.S. Pat. No. 5,243,052 and JP-A-9-25360.

Further, a basic leuco dye or the like which develops a color instantly upon contact with an acid can be used in the image forming material. Examples of such compounds include compounds described in “Organic Materials for Imaging” edited by Organic Electronics Materials Society of Japan, published by Bunshin Publishing Company (1997), and compounds described in references cited therein. No. In the present invention, 360 to 900
Compounds that cause a change in concentration in the absorption region of nm may be used alone or in combination of two or more.

Preferred compounds for use in the present invention include:
They are represented by the general formulas (III) to (V). In the leuco dye represented by the general formula (III) of the present invention, R ⁵¹
To R ⁵⁷ represent a hydrogen atom or a substituent, which may be the same or different. Examples of the substituent include the substituents represented by R ¹ in the general formula (I). In the general formula (III), R ⁵¹ and R ⁵² are preferably an alkyl group.

When R ⁵⁴ , R ⁵⁵ , R ⁵⁶ or R ⁵⁷ represents a substituent, two adjacent groups may be bonded to each other to form a condensed ring. Examples of the case of forming a condensed ring include a naphthalene ring, an anthracene ring, a benzofuran ring, a benzothiophene ring, and the like.

In the general formula (III), X ² is N (R ⁵⁸ ),
Represents O or S, R ⁵⁸ represents a hydrogen atom or a substituent,
As an example of the case where the R ⁵⁸ represents a substituent include those described above as examples of the case where R ⁵¹ to R ⁵⁷ represents a substituent. X ² is particularly preferably O.

In the general formula (III), Y ¹ represents an atomic group necessary for forming a cyclic structure together with NC—X ² , preferably an atomic group necessary for forming a 5- or 6-membered ring. It is. Examples of the constituent atoms of Y ¹ necessary for constituting the ring skeleton, a carbon atom, a nitrogen atom, a sulfur atom, and silicon atom or a phosphorus atom, chromatic these atoms is a hydrogen atom or necessary substituents When plural substitutions are possible, the respective substituents may be different or the same, and the substituents may be bonded to each other to further form a ring.

When the atom constituting Y ¹ has a substituent, examples of the substituent include ＝ O (forming a carbonyl group, a sulfonyl group and the like together with the skeleton atom of Y ¹ ), 、 S (Y
And the like are formed thiocarbonyl group with ¹ skeletal ^{atoms), = N-R 60 (} R 60 represents a hydrogen atom or a substituent.
Examples of the substituent include those described above as examples when R ^{51 to} R ⁵⁷ represent a substituent.

Y¹A preferred form of is -C (R⁶¹) (R⁶²)
Or a divalent group represented by -C (= O)-
A divalent linking group formed by linking (R
⁶¹, R⁶²Represents a hydrogen atom or a substituent, and
May also be different, R⁶¹And R⁶²Or multiple in the molecule
R exists⁶¹And R⁶²Are bonded to each other to form a ring
Well, R⁶¹, R⁶²An example of R⁵¹~ R⁵⁷Represents a substituent
Examples of such cases include those described above). these
Y among¹A preferred form of is-[C (R⁶¹) (R⁶²)]_Two−
It is. Y¹Particularly preferred forms are, for example, -CH_Two CH
_Two−, − CH_Two CH_Two CH_Two-, -CH (CH _Three) CH_Two−, −CH_TwoC
(= O)-, -C (= O) CH_Two-, -CH_Two CH_TwoC (= O)
-, -C (= O) CH_TwoCH_Two-, -CH = CH-, etc.
It is mentioned.

In the general formula (III), A ¹ represents C (R ⁵⁹ ) or N, and R ⁵⁹ represents a hydrogen atom or a substituent. R ⁵⁹
Represents a substituent, examples of the substituent include those described above as examples when R ^{51 to} R ⁵⁷ represent a substituent.
A particularly preferred form for A ¹ is CH.

B ¹ represents an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, an arylamino group or a heterocyclic amino group. Examples of these include those described above as examples where R ^{1 to} R ⁷ represent a substituent. These groups may have a substituent at a substitutable position,
Examples of the substituent include those described above as examples when R ^{51 to} R ⁵⁷ represent a substituent. These substituents may be bonded to form a condensed ring by combining two different groups each other and may form a ring with R ^59. Preferred forms for B ¹ are an aryl group or a heterocyclic group.

Among the compounds represented by the formula (III) of the present invention, a particularly preferred embodiment is the compound represented by the formula (X).

[0081]

[Formula 27]

In the general formula (X), R ^{51 to} R ⁵⁷ have the same meaning as in the general formula (III), and D ¹ represents an aryl group or a heterocyclic group. Examples of the aryl group or heterocyclic group represented by D ¹ include those described above in the example of the case where R ⁵¹ to R ⁵⁷ represents a substituent. General formula (II
I) or (a compound represented by X), the was introduced into the substitutable position of R ⁵¹ to R ⁶² polymerizable group (acryl group,
It may be a polymer formed by linking a plurality of methacryl groups and 4-vinylphenyl groups. Hereinafter, specific examples of the compound represented by formula (III) or (X) useful in the present invention are shown, but the present invention is not limited thereto. These compounds are described in JP-A-51-34885 and JP-A-51-34885.
-44127, according to the method described in each publication such as 56-149489, for example, an aldehyde group of an aromatic or heterocyclic aldehyde compound, a nitroso group of a nitroso compound and an active methyl group at the 2-position of the indolenine nucleus Alternatively, it can be synthesized by a dehydration condensation reaction with a methylene group. In the following polymer materials of the present invention, the value represented by n or m represents the mole percentage of the polymer composition.

[0083]

[Formula 28]

[0084]

[Formula 29]

[0085]

[Formula 30]

[0086]

[Formula 31]

[0087]

[Formula 32]

[0088]

[Formula 33]

[0089]

Embedded image

[0090]

[Formula 35]

[0091]

Embedded image

In the leuco dye represented by formula (IV) of the present invention, R ⁷¹ represents a hydrogen atom or a substituent. Examples of the substituent include the substituents described above as the substituent in the description of R ^{1 in} the general formula (I). Preferred substituents include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy, and an amino group. (Including an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group or a silyl group, particularly preferably an alkyl group or an aryl group ,
A heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group. Among the above substituents, those having a hydrogen atom may be removed, and further substituted with the above group.

In the general formula (IV), Ar ¹ and Ar ²
Represents an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different. Aryl groups include phenyl and naphthyl groups; heterocyclic groups include furyl, thienyl, pyrimidyl, and benzothiazolyl; and alkenyl groups include vinyl, allyl, prenyl, geranyl, oleyl, and 2-cyclopentene-1. Examples of each group such as -yl and the alkynyl group include groups such as ethynyl, propargyl and trimethylsilylethynyl. Further, these groups may further have a substituent at a substitutable position, and examples of the substituent include those described above as examples when R71 represents a substituent.

Ar¹And Ar^TwoHas multiple substituents
In these cases, these may be combined with each other to form a condensed ring.
Ar¹And Ar^TwoMay be linked to form a ring
No. Ar ¹Substituents introduced into each other or Ar^TwoIntroduced in
Where the substituted substituents combine with each other to form a fused ring
Examples of the case include a julolidine ring, a naphthalene ring,
Toracene ring, Benzofuran ring, Benzothiophene ring, etc.
Ar¹And Ar^TwoLink to form a ring
Examples of such a case include a 9H-xanthene ring,
Chiru 9,10-dihydroacridine ring, 9H-thioki
Santen ring, 1-alkyl-4H-chromeno [2,3-
C] pyrazole ring, 11H-benzo [b] thieno [2,
3-b] Chromene ring, 6-alkyl-5-oxo-5,
6-dihydro-12H-chromeno [2,3-C] isoki
Norin ring, 4H-chromene ring, 2H-chromene ring or
And a fluorene ring.

Ar ¹ and Ar ² are preferably an aryl group or a heterocyclic group. In a particularly preferred case, at least one of Ar ¹ and Ar ² is an electron-donating aryl group (for example, p-dimethyl Aminophenyl group, p-julolidyl group, p-methoxyphenyl group, etc.) or 1,2,3,4-tetrahydroquinoline-6
-Yl group, 3,3-dimethylindoline-5-yl group,
3,4-methylenedioxyphenyl group, 1,2-dimethyl-5-benzimidazolyl group, 10-ethylphenoxazin-3-yl group, 9-ethylcarbazol-3-yl group, dibenzofuran-3-yl group, dibenzo Thiophen-3-yl group, quinolin-8-yl group, 1,2-dimethylindol-3-yl group, ethylindazol-3
-Yl group, benzo [b] -furan-3-yl group, benzo [b] -thiophen-3-yl group, 1-ethylpyrrol-3-yl group, 3-furyl group, 3-thienyl group, 2- In the case of a heterocyclic group selected from a thiazolyl group, a 2-benzoxazolyl group, a 2-pyridyl group or a 4-quinolyl group, or at least one of Ar ¹ and Ar ² has an electron-donating group as a substituent, This is the case where Ar ¹ and Ar ² are linked to form the above fused ring.

Y ² represents an aromatic hydrocarbon ring (for example, benzene ring, naphthalene ring, anthracene ring, etc.) or a hetero ring (for example, pyridine ring, pyrimidine ring, indole ring, furan ring, thiazine ring, etc.). The substitutable position of the ring may be substituted by a substituent, and examples thereof include those described as examples when R ¹ represents a substituent. A preferred form of Y ² is an aromatic hydrocarbon ring, particularly preferably a benzene ring.

X ³ represents O, S or N (R ⁷² );
⁷² represents a hydrogen atom or a substituent, and examples of the case where R ⁷² represents a substituent include those described as examples when R ⁷¹ represents a substituent. X ³ is preferably O or S.

Compounds represented by the general formula (IV) and the general formula (V) described below can be obtained by introducing a polymerizable group (such as an acryl group, a methacryl group, or a 4-vinylphenyl group) introduced into a substitutable position. May be a polymer formed by connecting a plurality of groups. In this case, the molecular weight of the polymer is preferably in the range of 1,000 to 1,000,000, particularly preferably 2,000 to 30.
This is the case in the range of 10,000. In this case, it may be a homopolymer or a copolymer with another monomer.

The compound represented by the general formula (IV) can be used, for example, in the form of an acid halide or a triarylmethane derivative having an amino group at the ortho position, which is synthesized from Michlerhydrols and arylamines. It can be synthesized by reacting isocyanates and the like and then oxidizing with an oxidizing agent such as lead dioxide, manganese dioxide or chloranil.
These are described in detail in gazettes such as No. 697, No. 61-17573, and No. 63-251278.

Specific examples of the compound represented by formula (IV) useful in the present invention are shown below, but the present invention is not limited to these. Hereinafter, in the polymer material of the present invention, the value represented by n or m indicates the mole percentage of the polymer composition.

[0101]

[Formula 37]

[0102]

[Formula 38]

[0103]

[Formula 39]

[0104]

[Formula 40]

[0105]

[Formula 41]

[0106]

[Formula 42]

[0107]

[Formula 43]

[0108]

[Formula 44]

[0109]

[Formula 45]

[0110]

[Formula 46]

[0111]

[Formula 47]

[0112]

[Formula 48]

[0113]

[Formula 49]

[0114]

[Formula 50]

[0115]

[Formula 51]

Next, the general formula (V) will be described. Ar ³
And Ar ⁴ represent an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different, and are the same as those of the above-mentioned general formula (IV).
Represent the same meanings as ¹ and Ar ^2.

Z ¹ represents an aromatic hydrocarbon ring or a hetero ring, which has the same meaning as Y ² in the aforementioned general formula (IV). A ² represents O, S or N (R ⁷³ );
⁷³ represents a hydrogen atom or a substituent, and examples of the case where R ⁷³ represents a substituent include those described as examples when R ⁷¹ represents a substituent. A preferred example of A ² is S.
The compound represented by formula (V) of the present invention is disclosed in JP-A-58-170.
It can be synthesized by the method described in No. 36. Hereinafter, specific examples of the compound represented by formula (V) useful in the present invention will be shown, but the present invention is not limited thereto.

[0118]

[Formula 52]

[0119]

[Formula 53]

[0120]

[Formula 54]

[0121]

[Formula 55]

[0122]

[Formula 56]

[0123]

[Formula 57]

The image forming material of the present invention is generally prepared by coating a support with a compound capable of changing the wavelength range from 360 to 900 nm by the action of the acid generator and the acid. At this time, when any of these is a polymer,
Or, unless it is amorphous with good coatability,
Usually, a binder coexists. 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, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, ethylene-
Water-soluble binders such as maleic anhydride copolymers, and polyvinyl butyral, triacetyl cellulose,
Any of water-insoluble binders such as polystyrene, methyl acrylate-butadiene copolymer, and acrylonitrile-butadiene copolymer can be used.

On the other hand, by the action of an acid generator or an acid, 3
When one or both of the compounds (including copolymerization) that change in the wavelength range of 60 to 900 nm are polymers, it is not particularly necessary to add a binder. In that case, high sensitivity can be expected in the sense that an acid is generated very near the compound whose hue changes. 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 as such a compound is represented by the general formula (VI).

The formula (VI) will be described. In the general formula (VI), A represents a repeating unit obtained by polymerization of an acid generator monomer. Preferable examples are compounds represented by the general formulas (I), (II), or (VII) to (IX). And those having a polymerizable unsaturated group. Specific examples thereof are represented by the general formulas (I), (II), or (VI
Among the compound examples I) to (IX), those having a polymerizable unsaturated group correspond.

In the general formula (VI), B represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer having a partial structure which causes a change in concentration in the absorption range of 360 to 900 nm due to the action of an acid. Is a compound having a polymerizable unsaturated group among the compounds represented by formulas (III) to (V) and (X). Specific examples thereof include those having a polymerizable unsaturated group among the compound examples of the general formulas (III) to (V) and (X). B may be a single type of repeating unit derived from a single compound or a combination of two or more types. Further, B, which is a coloring site in the polymer, may be used in combination with another coloring agent separately added to the image recording layer.

In the general formula (VI), C represents A and B
At least one capable of forming a copolymer with
Represents a repeating unit obtained by polymerization of two or more kinds of vinyl monomers, and can control storage stability, color-forming activity, and the like by adjusting polarity, glass transition temperature, and the like. 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.

[0129]

[Formula 58]

[0130]

[Formula 59]

[0131]

Embedded image

[0132]

Embedded image

In the general formula (VI), x, y, and z represent mol% of each composition. x, y, z are each 1 ≦ x ≦ 10
0, 0 ≦ y ≦ 99, 0 ≦ z ≦ 99, and x + y + z = 1
00. The molecular weight of the polymer represented by the general formula (VI) is preferably in the range of 1,000 to 1,000,000, and particularly preferably in the range of 2,000 to 500,000. The polymer may be in any form such as a homopolymer, a random copolymer, an alternating copolymer, and a block copolymer, but a homopolymer and a random copolymer which are synthetically easy are generally used. . Preferred combinations of monomers forming A, B, and C and x, y, and z in the polymer represented by the general formula (VI) are shown below, but the invention is not limited thereto.

[0134]

【table 1】

The synthesis of the polymer used in the present invention can be carried out by various polymerization methods, for example, solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Also,
Examples of the method for initiating polymerization include 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” It is described in pp. 124-154 published in 1972.

Of 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 needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, and the like. Polymerization can be performed at various temperatures, but usually the polymerization is carried out in the range of 30 to 100 ° C. In the present invention, it is preferable to carry out the polymerization in a temperature range of 30 to 90 ° C.

Examples of the radical initiator used in the polymerization include 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] is particularly preferred. The amount of the polymerization initiator used can be adjusted according to the polymerizability of the monomer and the required molecular weight of the polymer, but is preferably in the range of 0.01 to 5.0 mol% based on the monomer.

In the synthesis of the polymer represented by the general formula (VI), monomers for forming A, B and C are mixed and put into a reaction vessel first, and an initiator may be added. The polymerization may be performed through a process of dropping the monomer into the polymerization solvent.

The polymer represented by the general formula (VI) 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 polymer having a function of 360 to 900 nm by the action of an acid.
It is a polymer having a partial structure that causes a change in the wavelength range. As such a polymer, a polymer of a single monomer having both functions can be used, but the structure represented by the general formula (VI) is generally used from a synthetic viewpoint. The image forming material of the present invention generally has the general formula (VI)
It is prepared by coating a polymer represented by the formula (1) on a support.
When the polymer of the present invention also has a function of generating an acid by heat, the absorption alone changes due to the action of heat alone, so that when the polymer is used as a heat-sensitive material, the sensitivity and the sharpness of the image are excellent. I have. In the polymer of the present invention represented by the general formula (VI), there is no need to use a so-called binder, so that the film thickness can be reduced, a sharp image can be obtained, and abrasion hardly occurs. There is. However, when the polymer represented by the general formula (VI) is used, a binder may be used together if necessary, and specific examples thereof include those described above.

The binder used for the image recording layer and the protective layer in the present invention is generally colorless and is not particularly limited as long as it is a medium capable of forming a transparent or translucent film. Examples thereof include gelatin, casein, starches, and hydroxyethyl cellulose. Water-soluble binders such as carboxymethylcellulose, polyvinyl alcohol, polyacrylamide, ethylene-maleic anhydride copolymer, and polyvinyl butyral, triacetyl cellulose, cellulose acetate butyrate, polyesters, polycarbonates, polyvinyl esters (polyvinyl acetate, etc.), Polystyrene, polyvinyl chloride, acrylate and methacrylate polymers or copolymers (eg, methyl methacrylate-hydroxymethyl methacrylate) Polymers, methyl acrylate - butadiene copolymer, polymethyl methacrylate, poly t
-Butyl methacrylate, acrylonitrile-butadiene copolymer, etc.).

Among these binders, a water-insoluble binder is preferably used. The water-insoluble binder may be formed into a film from an organic solvent, or may be formed into a film in the form of an aqueous dispersion. The water dispersion referred to herein is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. Examples of these include "Synthetic Resin Emulsions (edited by Tadashi Okuda and Hiroshi Inagaki, published by The Society for Polymer Science (197
8))), `` Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka,
Edited by Souichi Suzuki and Keiji Kasahara, published by the Society for Polymer Publishing (199
3)) "," Polymer Latex Chemistry (by Soichi Muroi, published by Kobunshi Kankokai (1970)) "and the like. The average particle size of the dispersed particles is preferably in the range of 1 to 50,000 nm, more preferably about 5 to 1000 nm. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a wide particle size distribution or a monodispersed particle size distribution.

The polymer used in the image recording layer and the protective layer has a weight average molecular weight of 1,000 to 1,000.
000, preferably about 20,000 to 500,000. Further, the polymer may be used alone, or may be used by blending two or more kinds as necessary.

In some cases, cracking of the image recording medium under low humidity can be improved by adjusting the Tg of the polymer used for the image recording layer and the protective layer. Although cracking under low humidity can be improved by lowering the Tg of the polymer, the adhesion of the image recording medium may be problematic if the Tg is too low, so that there is an optimum value for the Tg of the polymer. Although the Tg of the preferred polymer depends on the low molecular weight compound used in combination, it is generally 15 ° C to 120 ° C, more preferably 20 ° C to 80 ° C.

The occurrence of cracking is remarkable under low humidity. Generally, when the image recording medium is rolled into a tube at 25 ° C. and a relative humidity of 10% RH, the cracking is evaluated by the radius of curvature at which cracking starts to occur. In many cases, a preferable value according to this evaluation method is 0 to 50 mm. The radius of curvature is 0 mm
This means that cracks do not occur even under severe bending stress under given conditions.

The protective layer of the image recording medium of the present invention may be provided in two or more layers as necessary. The total binder amount of the protective layer is 3.0 to 50.0 g / m ² , more preferably.
5.0-30.0 g / m ² , more preferably 7.0-2
A range of 0.0 g / m ² is preferred.

In the image recording medium of the present invention, haze can be reduced and abrasion resistance can be improved by setting the binder amount of the protective layer to the above-mentioned amount. The haze is represented by the degree of diffusion of a light beam incident on an image recording medium, and its value is expressed as a percentage of the ratio between the amount of diffuse transmitted light and the total amount of transmitted light. To measure haze, use a haze measuring device MODEL 100 manufactured by NIPPON DENSHOKU Co., Ltd.
1DP was used. The preferred haze value in the present invention is
The aperture of the incident light is 0 to 20% under 10 mm, more preferably 0 to 15%, particularly preferably 0 to 15%.
10%.

The image recording medium of the present invention can be applied to various image recording applications, but is preferably used as a UV mask film in the plate making process in the field of printing plate making. In this case, handling requires abrasion resistance. As an evaluation scale of abrasion resistance, a scratch strength is usually used, and this is also used in the present specification. The thick needle scratching strength referred to in the present invention means that the surface of the protective layer is scratched using a sapphire needle having a cone apex angle of 90 degrees and a tip diameter of 0.1 mm, and the scar of the image recording layer is continuously visually observed. It means the load (g) when it was recognized. Similarly, the fine needle scratching strength referred to in the present invention is such that the cone apex angle is
It means the load (g) when the surface of the protective layer is scratched with a diamond needle having a diameter of 90 mm at the tip of 0.01 mm and the image recording layer is visually observed continuously.

The preferable scratching strength of the present invention is 30 to 700 g and 10 to 300 g, respectively, for a thick needle and a fine needle, and more preferably 50 to 500 g and 15 to 200 g.
Particularly preferably, it is 70 to 300 g and 20 to 100 g.

When the image recording medium of the present invention is applied to a UV mask film used in a plate making process, a large change in image density in the UV wavelength region is required. As the image recording medium for this purpose, a medium having a large change in density due to light irradiation is preferable.
0, more preferably 3.5 to 15.0, particularly preferably 4.0 to 10.0.

In the image recording medium of the present invention, a back layer may be provided on the back surface of the support in addition to the protective layer, and a single layer or a plurality of layers of pigment or resin may be provided between the image recording layer and the support. May be provided. The back layer or undercoat layer adjacent to the support preferably contains a metal oxide to reduce dust adhesion,
It is preferable that at least one of the back layer and the undercoat layer (provided on both surfaces of the support) be conductive. The metal oxide used here is described in JP-A-61-2.
Those described in JP-A-0033 and JP-A-6-82504 are particularly preferred.

The amount of the conductive metal oxide to be used is preferably 0.05 to ²⁰ g, more preferably 0.1 to 10 g, per m ^{2 of} the image recording material. The surface resistivity of the metal oxide-containing layer is 10 ¹² Ω or less, preferably 10 ¹¹ Ω or less in an atmosphere of 25 ° C. and 25% RH. Thereby, good antistatic properties can be obtained. The lower limit of the surface resistivity at this time is not particularly limited, but is usually about 10 ⁷ Ω.

Each layer can be crosslinked for the purpose of improving abrasion resistance and the like. As the crosslinking method, a conventionally known method can be used, but as a method that does not affect the image forming reaction, Japanese Patent Application No. 2000-65209 is disclosed.
The method described in (1) can be preferably used.

The image recording medium of the present invention is preferably produced by coating a coating solution for an image recording layer and a coating solution for a protective layer on a support. Examples of the application method include curtain coating, roll coating, dip coating, spin coating, print coating, spray coating, slide coating, blade coating, and slot coating. When all the image recording layers of the present invention are low molecular compounds, a vapor deposition method can also be used. In the present invention, continuous coating is preferred, and thus curtain coating, slot coating, roll coating and slide coating are mentioned as preferred coating methods.

The image recording layer coating solution of the present invention comprises an acid generator,
It is prepared by dissolving or dispersing a desired compound, such as a compound or a binder, which changes the concentration in the absorption region of 300 to 900 nm in a coating solvent. As the coating solvent, either an aqueous solvent or an organic solvent can be preferably selected. The aqueous solvent here may be either water alone or a mixture of water-miscible organic solvent and water. The compounds used in the image recording layer of the present invention are often insoluble in water, and organic solvents are preferably used as coating solvents except when they are used as aqueous dispersions. Examples of the organic solvent include ethyl acetate, methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane,
Various organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, methylene chloride, chloroform and dichloroethane can be used alone or as a mixture of two or more.

The coating solution for the protective layer of the present invention is prepared by dissolving or dispersing a desired compound such as a binder, a matting agent and a sliding agent in a coating solvent. As a coating solvent for the protective layer coating solution, any of an aqueous solvent and an organic solvent can be used. However, when the compound that changes the concentration in the absorption region of 360 to 900 nm used in the image recording medium of the present invention is a low molecular compound, When low molecular compounds such as infrared absorbing dyes are used in the image recording layer, if the low molecular compounds have high solubility in the protective layer coating solution, they diffuse into the protective layer, resulting in a decrease in the sensitivity of the image recording medium. There is a need to be careful. In this case, it is preferable that a solvent having low solubility for the low-molecular compound is selected as the coating solution for the protective layer. Low molecular compounds such as low molecular compounds and infrared absorbing dyes that cause a change in concentration in the absorption region of 360 to 900 nm used in the image recording medium of the present invention are mostly poorly water-soluble compounds, and as a protective layer coating solution in this case, Preferably, an aqueous solvent or an alcohol solvent is used. The term "aqueous solvent" as used herein means either water alone or a mixture of a water-miscible organic solvent and water. The alcohol-based solvent refers to an alcohol alone such as methanol, ethanol, 1-propanol, 2-propanol, or 1-butanol. It represents a mixture of one or more alcohols or a mixture with another organic solvent.

Further, the coating solution for the image recording layer and the protective layer of the present invention may contain a surfactant or the like for improving coating properties. In addition, various known techniques for heat-sensitive recording materials can be used.

In the present invention, when the image recording medium is transported,
A matting agent can be used for the purpose of improving the adhesive resistance during winding and storage after winding. By using a matting agent, it is possible to adjust the surface smoothness of the image recording medium, and the surface smoothness may be defined by Beck smoothness. Beck smoothness is measured according to Japanese Industrial Standards (J
IS) P8119 “Smoothness test method for paper and paperboard using Beck tester” and the tester and test method specified in TAPPI Standard Method T479.

At least one of the surface having the image recording layer of the image recording medium of the present invention and the surface of the outermost layer opposite to the surface,
Preferably both Beck smoothness are between 0 and 4000 seconds, more preferably between 0 and 2000 seconds.

The Beck smoothness of the surface of the image recording medium having the image recording layer and the surface of the outermost layer opposite to the surface can be adjusted by variously changing the average particle size and the amount of the matting agent to be added. The matting agent used in the present invention may be any solid fine particles which do not adversely affect the properties of the image forming medium. Examples of inorganic matting agents include silicon dioxide, oxides of titanium and aluminum, carbonates of zinc and calcium, sulfates of barium and calcium, and silicates of calcium and aluminum. Examples include matting agents for organic polymers such as esters, polymethyl methacrylate, polystyrene or polydivinylbenzene and copolymers thereof. The matting agent is preferably contained in the protective layer which is the outermost layer farthest from the support on the surface having the image forming layer, and is preferably contained in the back layer which is not the outermost layer on the opposite side.

The preferred average particle size of the matting agent in the present invention is in the range of 1 to 20 μm. In the present invention, the preferable addition amount of the matting agent is 5 to 400 mg / m 2, particularly 10 to 400 mg / m 2.
２００200 mg / m2.

In the present invention, the porous matting agent described on page 2, lower left column, line 8 to page 3, upper right column, line 4 of JP-A-3-109542, the page 3, upper right column of JP-A-4-127142 is disclosed. A matting agent surface-modified with an alkali described in line 7 to page 5, lower right column, line 4, paragraph number "0005" of JP-A-6-118542
More preferably, an organic polymer matting agent described in "0026" is used.

In addition, two or more of these matting agents may be used in combination. For example, a combination of an inorganic matting agent and an organic matting agent, a combination of a porous matting agent and a non-porous matting agent, a combination of an amorphous matting agent and a spherical matting agent, mats having different average particle sizes. (For example, a matting agent having an average particle diameter of 1.5 μm or more and a matting agent having an average particle diameter of 1 μm or less described in JP-A-6-118542).

In the present invention, a so-called monodisperse matting agent having a narrow particle size distribution can be preferably used. Such a monodisperse matting agent has a low content of fine particles having little effect of improving the adhesion resistance and coarse particles causing a problem such as a decrease in image density, and is advantageous for achieving both adhesion resistance and transparency. Examples of preferred monodisperse matting agents that can be used in the present invention include Research Disclosure No. 21617, no. 216
(1982), Japanese Patent Publication No. 5-59924, UK Patent 81
No. 35262, JP-A-61-230141, EP 610,522, EP 618,490, JP-A-8-278587 and the like.

In the present invention, it is preferable that a slip agent is contained in the surface having the image recording layer and / or the outermost surface layer opposite to the surface.

The slip agent in the present invention is not particularly limited, and any compound may be used as long as it reduces the friction coefficient of the surface of the object when it is present on the surface of the object as compared with the case where it is not present.

Representative examples of the slip agent used in the present invention include, for example, US Pat. No. 3,042,522 and British Patent No. 9
No. 55,061, U.S. Pat.Nos. 3,080,317, 4,004,927,
No. 4,047,958, No. 3,489,567, British Patent No. 1,143,
No. 118, and other silicone-based slip agents described in U.S. Pat.Nos. 2,454,043, 2,732,305, and 2,976,148
No. 3,206,311; German Patent No. 1,284,295;
Higher fatty acid-based, alcohol-based, and acid amide-based slip agents described in each publication such as 284,294, UK Patent No. 1,263,722
No. 3,933,516, metal soaps described in publications such as U.S. Pat.No. 3,933,516, U.S. Pat.Nos. 2,588,765, 3,121,060, and ester-based and ether-based slip agents described in each publication such as British Patent 1,198,387, U.S. Pat. No. 3,502,473 and No. 3,042,222.

Specific examples of preferably used slip agents include Cellolsol 524 (main component carnauba wax), Polylon A-393, H-481 (main component polyethylene wax), and Himicron G-110 (main component ethylene bisstearic acid). Amide), High Micron G-270
(Main component stearic acid amide) (all manufactured by Chukyo Yushi Co., Ltd.). Further, higher fatty acids and derivatives thereof, and higher alcohols and derivatives thereof are also preferable. Specifically, compounds described in JP-A-8-272039 can be preferably used.

The amount of the slipping agent is not particularly limited, but may be from 1 to 5
00 mg / m ² , more preferably 10 to 30 mg / m ^2.
0 mg / m ² .

In the present invention, a plasticizer can be added to the surface having the image recording layer and / or the opposite surface, if necessary.

The plasticizer that can be used in the present invention is not particularly limited as long as it can lower the embrittlement temperature of the film of the layer to which the plasticizer has been added. Is a high-boiling organic solvent having a temperature of 190 ° C. or higher. Such compounds include carboxylic esters, phosphoric esters, carboxylic amides, ethers, phenols, alcohols, substituted hydrocarbons, and the like.
(Souichi Muroi, published by Kobunshi Kankokai (1970)) and the like can also be preferably used.

Specific examples of the plasticizer preferably used include di-n-butyl phthalate, diisooctyl phthalate, dicyclohexyl phthalate, dimethoxyethyl phthalate, di-n-butyl adipate and tri-n-citrate.
Butyl, di-n-butyl sebacate, tricyclohexyl phosphate, tricresyl phosphate, tri-n-butyl phosphate, triisooctyl phosphate, N, N-diethylcaprylic amide, N, N-dimethylpalmitic amide , N
-Butyl- (m-pentadecyl) phenyl ether, ethyl- (2,4-di-tert-butyl) phenyl ether, 2,5-di-tert-amylphenol, triethylene glycol di-2-ethyl butyrate, CS-
12 (manufactured by Chisso Corporation) and the like.

The amount of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the amount of the binder in the additive layer.

In the present invention, a small amount of a base may be added for the purpose of enhancing the storage stability of the image recording medium, or a compound capable of generating an acid by the action of light or heat may be 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. In addition, various known techniques for heat-sensitive recording materials can be used.

When a base is added, an organic base is preferable, and 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 (for example, aniline, pt-butylaniline,
N, N′-dimethylaniline, N, N′-dibutylaniline, triphenylamine, etc.), alkylamine derivatives (eg, tributylamine, octylamine, laurylamine, benzylamine, dibenzylamine, etc.),
And heterocyclic compounds (for example, N, N'-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0]-
7-undecene, triphenylimidazole, lutidine, 2-picoline, etc.) are preferred examples. These bases are used in an amount of 1 to 50 mol% with respect to the acid generation.
It is preferred to add, particularly preferably 5 to 20 mo
1% is added.

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 an ultraviolet absorber containing a benzophenone structure, a benzotriazole structure and the like in the molecule, a head wear and sticking inhibitor comprising a metal salt of a higher fatty acid such as zinc stearate and calcium stearate, paraffin, oxidizing agent and the like. Examples include waxes such as paraffin, polyethylene, polyethylene oxide, and caster wax, and these can be added as necessary.

As the support used in the image recording medium of the present invention, paper such as high quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, polyethylene, polypropylene, polyethylene terephthalate, polyethylene
Examples thereof include polymer films such as 2,6-naphthylenedicarboxylate, polyarylene, polyimide, polycarbonate, and triacetylcellulose, glass, metal foil, and nonwoven fabric. When the image recording medium of the present invention is used for a transmission type image, for example, a film for OHP or a film for plate making, a transparent support is used. For a plate making film, a support having a small coefficient of thermal expansion and good dimensional stability and having no absorption in the photosensitive region of the PS plate is selected. As such a support, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferable from the viewpoint of strength, dimensional stability, chemical resistance and the like. The thickness of the support is not particularly limited, but when used as a UV mask film for a plate making material,
80 to 180 μm is preferred.

The support used in the image recording medium of the present invention is
In order to alleviate the internal strain remaining in the film at the time of biaxial stretching and eliminate the heat shrinkage strain, heat treatment can be performed at a temperature in the range of 130 to 210 ° C. as necessary. In this case, polyester, especially polyethylene terephthalate is preferably used. Such a thermal relaxation treatment may be performed at a constant temperature within the above temperature range, or may be performed while raising 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 7 kg / cm 2 or less, particularly preferably 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 / cm2.

Such heat treatment is preferably performed after a treatment for improving the adhesiveness of the image forming layer and the back layer to the support, for example, after providing an undercoat layer.

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 subjected to a surface treatment for providing good adhesion to the constituent layers of the image recording layer, or may be provided with an undercoat layer. Surface treatment methods include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. The undercoat layer is not particularly limited, but may be SB.
An undercoat layer using R, vinylidene chloride, polyester, gelatin or the like as a binder can be preferably used. The undercoat layer may have a multi-layer 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 of the undercoat layer is 0.01 to 5 μm, more preferably 0.1 to 5 μm.
The conductive layer may have a thickness of 0.01 to 1 μm, more preferably 0.03 to 0.8 μm.
m.

The method for synthesizing the compound of the present invention is shown below.
The present invention is not limited to these. (Synthesis Example 1) Synthesis of Exemplified Compound (A-1)

[0184]

[Formula 62]

1b (100 mmol) was dissolved in N, N-dimethylacetamide (50 ml) and the reactor was cooled to 7 ° C. There, 1a (100 mmol) was added dropwise over 10 minutes, and the mixture was reacted for 6 hours. Ethyl acetate (200m
1) and water (200 ml) were added and stirred, and then the aqueous layer was separated. Further, the organic layer was washed with 1 mol / l hydrochloric acid aqueous solution (100 m
Washed 3 times with 1), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1 /
Purification was performed in 1) to obtain 1c in a yield of 61%. Then 1d
(50 mmol) was dissolved in pyridine (30 ml) and cooled to 7 ° C. 1c (50 mmol) was added thereto, and the mixture was stirred for 8 hours. Then, after adding water (3 ml) and stirring for 30 minutes,
Ethyl acetate (100 ml) and water (200 ml) were added and stirred, and the aqueous layer was separated. The organic layer was further washed three times with 1 mol / l aqueous hydrochloric acid (100 ml), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1).
/ 4 → 1/1), and the exemplary compound (A-1) is purified by ci.
A mixture of the s-isomer and the trans-isomer was obtained in a yield of 72%. Also
The cis form and the trans form can be separated by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1/1). The temperature was 192 ° C and the trans form was 184 ° C.

(Synthesis Example 2) Synthesis of Exemplified Compound (A-2)

[0187]

[Formula 63]

2a (100 mmol) was converted to pyridine (40 m
1) and cooled the reactor to 7 ° C. There 2b
(100 mmol) was added dropwise over 10 minutes, and then reacted for 2 hours, and then reacted at room temperature for another 5 hours. afterwards,
After adding water (4 ml) and stirring for 30 minutes, ethyl acetate (1 ml) was added.
(50 ml) and water (200 ml) were added and stirred, and the aqueous layer was separated. Further, the organic layer was washed with 1 mol / l hydrochloric acid aqueous solution (100 m
Washed 3 times with 1), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / chloroform = 1/8 → 1).
/ 1) to give 2c in a 76% yield.

Next, 2c (50 mmol) was dissolved in N, N-dimethylacetamide (60 ml), and the reactor was cooled to 7 ° C. Thereto, 2d (50 mmol) was added dropwise over 10 minutes, and then reacted at room temperature for 8 hours. Ethyl acetate (20
0 ml) and water (200 ml) were added and stirred, and then the aqueous layer was separated. Further, the organic layer was washed with 1 mol / l hydrochloric acid aqueous solution (100
ml), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1 /
The compound (A-2) was purified with cis form and trans
Obtained in 78% yield as a mixture of products. Tran of the compound
The decomposition temperature of the s-isomer was 189 ° C.

(Synthesis Example 3) Synthesis of Exemplified Compound (A-3) The compound was synthesized by the same reaction as that of Exemplified Compound (A-2) to obtain a mixture of a cis form and a trans form. The decomposition temperature of the mixture is 1
It was 81 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound (A-22) The compound was synthesized by the same reaction as that of Exemplified Compound (A-2), and was obtained as a mixture of a cis form and a trans form. The decomposition temperature of cis is 1
The decomposition temperature of the trans isomer was 173 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound (A-13) The compound was synthesized by the same reaction as that of Exemplified Compound (A-2) to obtain a mixture of a cis form and a trans form. The decomposition temperature of the mixture was measured, but no clean decomposition peak was obtained.

Synthesis Example 6 Synthesis of Exemplified Compound (A-29)

[0194]

Embedded image

29a (100 mmol) was converted to pyridine (50 m
1) and cooled the reactor to 7 ° C. There 29
b (100 mmol) was added over 10 minutes, and further reacted at room temperature for 6 hours. Then, water (3 ml) was added and the mixture was stirred for 30 minutes, and then ethyl acetate (100 ml) and water (200 m
l) was added and stirred, and the aqueous layer was separated. 1mo organic layer
The extract was washed three times with 1 / l aqueous hydrochloric acid (100 ml), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate /
Hexane = 1/5) to give the exemplified compound (A-2
9) was obtained as a mixture of isomers in 78% yield. Its decomposition temperature was 145 ° C.

(Synthesis Example 7) Synthesis of Exemplified Compound (A-35) Exemplified Compound (A-35) was synthesized by the same reaction as that of Exemplified Compound (A-29). The decomposition temperature of the compound is 14
2 ° C.

(Synthesis Example 8) Synthesis of Exemplified Compound (P-1) Exemplified Compound (A-1) (50 mmol) was added to toluene (22 m
1) and heated to 40 ° C. under a nitrogen atmosphere. A solution of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (0.125 g) in methyl ethyl ketone (3 ml) was added thereto and reacted for 2 hours. A solution of 4-methoxy-2,4-dimethylvaleronitrile) (0.125 g) in methyl ethyl ketone (3 ml) was added. After reacting for 2 hours, the reaction mixture was poured into hexane (1200 ml), and the precipitate was collected by filtration and dried to give Exemplified Compound (P-1).
Obtained in 9% yield. The weight average molecular weight was 85,000 and the decomposition temperature was 172 ° C.

(Synthesis Example 9) Synthesis of Exemplified Compound (P-2) The compound was synthesized by the same reaction as that of Exemplified Compound (P-1). The weight average molecular weight was 120,000 and the decomposition temperature was 187 ° C.

(Synthesis Example 10) Synthesis of Exemplified Compound (P-3) The compound was synthesized by the same reaction as that of Exemplified Compound (P-1). The weight average molecular weight was 100,000, and the decomposition temperature was 174 ° C.

Synthesis Example 11 Synthesis of Exemplified Compound (P-6) A-2 (7.5 mmol) and B-41 (2.5 mmol) were prepared by dissolving toluene (4.4 ml), methyl ethyl ketone (2 ml),
Dissolve in methylene chloride (4 ml) and place in a nitrogen atmosphere
Heated to ° C. There, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (0.025
g) in methyl ethyl ketone (0.6 ml), and reacted for 2 hours, followed by 2,2′-azobis (4-
Methoxy-2,4-dimethylvaleronitrile) (0.0
A solution of 25 g) in methyl ethyl ketone (0.6 ml) and methylene chloride (2 ml) were added. After reacting for 2 hours,
The reaction solution was poured into hexane (400 ml), and the precipitate was collected by filtration and dried to give Exemplified Compound (P-6) at a yield of 53%. The weight average molecular weight was 45,000.

[0201]

The following examples illustrate the usefulness of the compounds of the present invention in more detail, but the present invention is not limited thereto. <Preparation of Image Recording Layer Coating Solutions (G-1 and G-2)> Image recording layer coating solutions (G-1 and G-2) having the compositions shown in Table 2 were prepared. The crosslinking agent was Takenate D110N manufactured by Takeda Pharmaceutical Company Limited.
(75% ethyl acetate solution), and a surfactant used was Megafac F176PF (fluoropolymer) manufactured by Dainippon Ink and Chemicals, Ltd. as a 2-propanol solution having a solid content of 3% by mass. In addition, IR-1 was used as an infrared absorbing dye.

[0202]

[Formula 65]

[0203]

[Table 2]

<Preparation of Coating Solution for Protective Layer (PC-1 to 3)>
Protective layer coating solutions (PC-1 to 3) having the compositions shown in Table 3 were prepared. After adding the matting agent and the slipping agent, PC-1 and PC-2 were dispersed with a high-speed homogenizer, and stirring was continued with a stirrer until just before coating. Matting agent is Soken Chemical
SX-1101 (average particle diameter: 11 μm) manufactured by Chisso Corporation was used as a plasticizer. The surfactant used was Megafac F176PF (fluoropolymer) manufactured by Dainippon Ink and Chemicals, Inc. as a 2-propanol solution having a solid content concentration of 3%, and the following slip agent A was used as a slip agent having a solid content concentration of 5%. Used as a 2-propanol dispersion.

[0205]

[Formula 66]

[0206]

[Formula 67]

[0207]

[Table 3]

<Preparation of Comparative Protective Layer Coating Solution (PC-4 to 6)> The protective layer coating solution described in the example of Japanese Patent Application No. 2000-91994 and the protective layer coating solution PC-Example described in the example of Japanese Patent Application No. 2000-65238. 5 was prepared according to the method described. These were used as comparative protective layer coating solutions PC-4 and PC-5, respectively. (Preparation of PC-4: Japanese Patent Application No. 2000-91994) An aqueous solution containing 4% by weight of Kuraray Povar PVA-110 manufactured by Kuraray Co., Ltd. and 0.1% by weight of Emarex 710 manufactured by Nippon Emulsion Co., Ltd. was prepared and protected. The coating was performed so that the solid content of the layer was 1.0 g / m2.

(Preparation of PC-5: Japanese Patent Application No. 2000-652)
38) After dissolving the following materials in a mixed solvent of isopropanol / methyl ethyl ketone (70/30 (vol%)), a matting agent and a slipping agent were added, and the mixture was dispersed with a high-speed homogenizer. I got The matting agent is Sycilia 431 manufactured by Fuji Silysia Chemical (synthetic silica: average particle diameter 2.5 μm), the slip agent is Cellosol 524 (main component: carnauba wax) manufactured by Chukyo Yushi, and the coating aid is Megafac F176P manufactured by Dainippon Ink and Chemicals. (Fluoropolymer), plasticizer is CS-12 manufactured by Chisso Corporation
It was used.

PC-5 binder (ethyl methacrylate / 2-hydroxyethyl methacrylate (6/4 mass ratio) copolymer) 1.5 g / m ² matting agent 60 mg / m ² slipping agent 0.2 g / m ² coating aid 6.9 mg / m ² plasticizer 0.3 g / m ²

(Preparation of PC-6: Japanese Patent Application No. 2000-652)
38) After preparing the following materials as an aqueous dispersion, the mixture was stirred for 30 minutes to obtain a protective layer coating liquid (PC-6). The latex is AS563A manufactured by Daicel Chemical Industries, Ltd. The fluorine-containing surfactant is Megafac F1 manufactured by Dainippon Ink and Chemicals, Inc.
20, matting agent used was SX-713 manufactured by Soken Chemical Co., Ltd .; slip agent used was Cellosol 524 (main component: carnauba wax) manufactured by Chukyo Yushi; polyvinyl alcohol was Kuraray Poval PVA-235 manufactured by Kuraray Co., Ltd.

PC-6 latex 2.5 g / m ² matting agent 60 mg / m ² slipping agent 0.2 g / m ² fluorinated surfactant 6.9 mg / m ² polyvinyl alcohol 0.3 g / m ²

<Preparation of Image Recording Media 1-4> The image recording layer coating solutions (G-1 and G-2) prepared above were coated on a 100 μm-thick biaxially stretched PET so as to have the coating amount shown in Table 2. It was applied by a slot coating method. This is 30
After drying at 30 ° C. for 30 minutes, the coating solution for protective layer prepared above (PC
-1 to 2) were applied to the image recording layer in the combination shown in Table 4 by the same slot coating method so as to have the coating amount shown in Table 3, and dried at 40 ° C. for 30 minutes. 4 was obtained.

<Preparation of Image Recording Media 5-6> The image recording layer coating liquids (G-1 and G-2) prepared above were coated on a 100 μm-thick biaxially stretched PET so as to have the coating amounts shown in Table 2. It was applied by a slot coating method. This is 30
After drying at 30 ° C. for 30 minutes, the coating solution for protective layer prepared above (PC
-3) was applied as a first protective layer on each image recording layer by a slot coating method so as to have the coating amount shown in Table 3. After drying at 40 ° C. for 30 minutes, a protective layer coating solution (PC-2) was further applied as a second protective layer on the first protective layer by a slot coating method so as to have an application amount shown in Table 3; It dried at 30 degreeC for 30 minutes. These were designated as image recording media 5 and 6.

<Preparation of Image Recording Media 7 and 8> The image recording layer coating solutions (G-1 and G-2) prepared above were coated on a 100 μm-thick biaxially stretched PET so that the coating amounts shown in Table 2 were obtained. It was applied by a slot coating method. This is 30
After drying at 30 ° C. for 30 minutes, the coating solution for protective layer prepared above (PC
-2) was applied on the image recording layer in a combination shown in Table 4 by a slot coating method so as to have a binder coating amount shown in Table 4, and then dried at 40 ° C. for 30 minutes to perform image recording. Mediums 7 and 8 were obtained.

<Preparation of Comparative Image Recording Media 9 to 11> The image recording layer coating solution (G-1) prepared above was slotted onto a 100 μm-thick biaxially stretched PET so as to have the coating amount shown in Table 2. It was applied by a coating method. This is 30
After drying at 30 ° C. for 30 minutes, the coating amount of the comparative protective layer (PC-4 to 6) prepared above was applied to the image recording layer in the combination shown in Table 4 on the image recording layer by the slot coating method. And dried at 40 ° C. for 30 minutes to obtain comparative image recording media 9 to 11.

[0219]

[Table 4]

<Image recording method> Semiconductor laser (Spectr
a Diode Labs No.SDL-2430, wavelength range: 800-830
nm) were combined to give an output of 140 mW to provide an image writing laser. Using this laser, the beam system was 20 μm, and the laser energy density on the sample was 5
It was set to 50 mJ / cm ² . Scanning exposure was performed on the produced image recording medium from the protective layer side under the above laser exposure conditions.

<Measurement of Color Density> The image recording media 1 to 11 were exposed to a laser, and the color densities at 410 nm and 600 nm were measured. The concentration was measured with a UV-2500PC manufactured by Shimadzu Corporation. Table 4 shows the results together with the absorption density of the unexposed portion.

<Conditions for evaluating storage stability> Image recording media 1 to 11
Of each sample was allowed to stand at 45 ° C. and a relative humidity of 40% RH for 3 days, and the change in the fog density of each sample at 410 nm (measured at the same wavelength as the color density measurement) was examined. Table 4 shows the results.

<Haze evaluation conditions> Image recording media 1 to 11
Laser exposure on
NIPPON DENSHOKU Co., Ltd. haze measuring device MODEL 1001DP
Was used to measure the haze. Table 4 shows the obtained results. The haze value indicates the ratio of the amount of diffuse transmitted light to the total amount of transmitted light in percentage.

<Scratch Strength Evaluation Conditions> Image Recording Media 1
8 was exposed to a laser, and the scratch strength was measured together with the unexposed sample. Using a surface property measuring instrument Type-HEIDON14 (manufactured by Shinto Kagaku Co., Ltd.) as a device, a thick needle (a sapphire needle with a cone apex angle of 90 ° and a tip diameter of 0.1 mm) and a fine needle (a cone apex angle of 90 ° with a tip of 90 °) Diameter 0.01
Table 4 shows the results of the scratching strength performed using a
Shown in In addition, the value of the scratching strength was determined by a scratching speed of 10 m.
While moving at a speed of m / sec, the load on the needle was continuously changed (thick needle: 0 to 200 g, fine needle: 0 to 50 g) to scratch the surface of the protective layer, and the scar of the image recording layer was continuously visually observed. The load (g) when it was recognized as a value is shown. The details of the measurement method conformed to ANSI SAE J1847.

As is clear from Table 4, all the image recording media of the present invention have low densities in the unexposed areas, have excellent storage stability, and have high coloring densities. Further, comparative samples 9 to 11
Although the haze and the scratching strength were both at an insufficient level, the image recording media of the present invention all showed a sufficient level of the haze value and the scratching strength, and the usefulness of the present invention was apparent.

[0224]

According to the present invention, it is possible to obtain an image recording medium having a low density of unexposed portions, excellent storage stability and a high coloring density, and a low haze generation level even by high-power laser exposure. An image recording medium having excellent scratch resistance can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41M 5/18 108 5/26 S (72) Inventor Atsuhiro Okawa 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. In-house F term (reference) 2H026 AA07 AA24 BB02 BB24 BB48 DD02 DD31 EE05 FF01 FF11 GG10 2H111 HA14 HA23 HA35

Claims (10)

[Claims] Claims: 1. An image recording layer containing at least one layer of a compound which causes a change in concentration in the absorption range of 360 to 900 nm by the action of heat or an acid and containing no silver salt, and at least one layer on a support. An image recording medium comprising: a protective layer having a coating amount of 3 g per 1 m ^2.
An image recording medium characterized by the above. 2. The method according to claim 1, wherein the composition contains at least one kind of infrared absorbing substance, and changes the concentration in the absorption range of 360 to 900 nm by the action of heat or acid generated by laser irradiation. The image recording medium described in the above. 3. A concentration change of not less than 3.0 at a specific wavelength in an absorption region of 360 to 900 nm due to the action of heat or acid generated by laser irradiation light, containing at least one kind of infrared absorbing substance. The image recording medium according to claim 1, wherein: 4. The support is a permeable support, and has a haze value of not more than 20% before and after the concentration is changed in the absorption region of 360 to 900 nm by the action of heat or acid. The image recording medium according to claim 1. 5. 360 to 900 by the action of heat or acid.
The scratch strength of the thick needle on the surface of the protective layer is 30 g or more, and the scratch strength of the fine needle is 10 g or more before and after the concentration change occurs in the absorption region of nm.
8. The image recording medium according to any one of the above. 6. An acid generator which generates an acid by the action of heat and a compound which causes an intramolecular or intermolecular reaction by the action of an acid to cause a concentration change in an absorption region of 360 to 900 nm. The image recording medium according to claim 1. 7. The image recording medium according to claim 6, wherein the acid generator is a compound represented by the following general formula (I). General formula (I) (In the formula, R ¹ represents an alkyl group, represents a respectively .R ² and R ³ represents an aryl group or a heterocyclic group independently represents an alkyl group or aryl group, R ² and R ³ is an aryl group at the same time R ² and R ³ may combine to form a ring.) 8. An acid generator represented by the general formula (I):
Characterized by being a compound represented by the general formula (II)
The image recording medium according to claim 7. General formula (II)(Where R³¹ Is an alkyl group, an aryl group or
Represents a ring group. R³²Represents a substituent. R³³And R
³⁴Each independently represents a hydrogen atom or a substituent.
X¹Represents an atomic group necessary for forming a ring. R³²,
R³³Or R ³⁴Is X¹May be combined with to form a ring
No. ) 9. A compound which causes an intramolecular or intermolecular reaction by the action of an acid to cause a concentration change in an absorption region of 360 to 900 nm, is represented by at least one of the following general formulas (III) to (V): The image forming method according to any one of claims 6 to 8, wherein the compound is a compound to be formed. General formula (III) (Wherein X ² represents N (R ⁵⁸ ), O or S, and Y ¹ represents N-
With C-X ² represents an atomic group necessary for forming a cyclic structure, A ¹ represents C (R ⁵⁹⁾ or N, R ⁵¹ to R ⁵⁹ represents a hydrogen atom or a substituent, were respectively the same R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ may combine with each other to form a condensed ring, and B ¹ represents an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, an aryl group. Represents an amino group or a heterocyclic amino group. ) General formula (IV) (Wherein, Ar ¹ and Ar ² are an aryl group, a heterocyclic group,
Represents an alkenyl group or an alkynyl group, which may be the same or different, R ⁷¹ represents a hydrogen atom or a substituent, Y ² represents an aromatic hydrocarbon ring or a hetero ring, and X ³ represents O, S Or N (R ⁷² ), wherein R ⁷² represents a hydrogen atom or a substituent. ) General formula (V) (Wherein, Ar ³ and Ar ⁴ represent an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different, and Z ¹ represents an aromatic hydrocarbon ring or a heterocyclic ring; A ² is O, S or N (R ⁷³ )
And R ⁷³ represents a hydrogen atom or a substituent. ) 10. The image forming method according to claim 1, further comprising a polymer represented by the following general formula (VI). Formula (VI)-(A) _x- (B) _y- (C) _z- (wherein A represents a repeating unit obtained by polymerization of an acid generator monomer, and B represents 360 to 360 due to the action of an acid. 9
Represents a repeating unit obtained by the polymerization of at least one or more vinyl monomers having a partial structure that causes a change in concentration in the absorption region of 00 nm, and C represents a polymer obtained by polymerization of at least one or more vinyl monomers copolymerizable with A and B. Represents the obtained repeating unit. x, y and z represent mol%, and 1 ≦ x ≦ 100 and 0 ≦ y ≦ 9, respectively.
9, represents 0 ≦ z ≦ 99, x + y + z = 100. )