JP2001042513A - Image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a negative type image recording material capable of directly making a printing plate from digital data using IR laser, having high sensitivity to laser light and excellent in storage stability and the adhesion of a recording layer. SOLUTION: A 1st layer which is hydrophilic and becomes hydrophobic under light or heat and a 2nd layer containing a compound which generates an acid under light or heat and a compound which is crosslinked by the generated acid and lowering its alkali solubility by crosslinking are successively disposed on a substrate to obtain the objective image recording material. An IR absorber is preferably contained in the 1st layer and/or the 2nd layer from the viewpoint of the enhancement of sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plate material for lithographic printing, an image recording material which can be used as a color proof, a photoresist and a color filter. The present invention relates to a negative type image recording material which can be used as a lithographic printing plate precursor capable of performing plate making, so-called direct plate making.

[0002]

2. Description of the Related Art In recent years, as a recording light source for a system for making a plate directly from digital data of a computer, a wavelength of 760 has been used.
Solid-state lasers and semiconductor lasers that emit infrared light of nm to 1200 nm have attracted attention because high-output and small-sized ones can be easily obtained. However, many photosensitive recording materials that are practically useful have a photosensitive wavelength in the visible light range of 760 nm or less, and therefore cannot record images with these infrared lasers. Therefore, a material that can be recorded by an infrared laser is desired.

[0003] As such an image recording material recordable by an infrared laser, an onium salt, a phenol resin and a spectrophotometer described in US Pat. No. 4,708,925 (hereinafter referred to as US where appropriate). There is a recording material comprising a sensitizer. However, this image recording material is a positive type utilizing the effect of suppressing dissolution in a developer, which is exhibited by an onium salt and a phenol resin, and is not a negative type as in the present invention. On the other hand, a negative-type image recording material has, for example, a substance that absorbs light and generates heat, an alkali-soluble resin, and 4 to 8 benzene nuclei in a molecule described in JP-A-8-276558. There are recording materials made of specific phenol derivatives. However, this image recording material can achieve high printing durability when sufficiently heated, but has a relatively low reactivity, so that the sensitivity at the time of laser exposure is insufficient. Various attempts have been made to increase the sensitivity of these recording materials, but in general, means for improving the sensitivity are as follows.
There was a tendency for the storage stability of the recording material to decrease. Further, such an image recording material has a low acid generation efficiency in the vicinity of the support, has insufficient adhesion of the recording layer, and has a problem in terms of printing durability.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to make a plate directly from digital data of a computer or the like by recording using a solid-state laser and a semiconductor laser emitting infrared rays. To provide a negative-type image recording material having high sensitivity, high storage stability, and good recording layer adhesion.

[0005]

Means for Solving the Problems The present inventor paid attention to the layer structure of a negative type image recording material, and as a result of intensive studies, arranged a layer in which the exposed layer can undergo acid crosslinking by light or heat. It has been found that the above problem can be solved by disposing a layer having a polarity change from hydrophilic to hydrophobic between the support and the layer. That is, the image recording material of the present invention comprises, on a support, a first layer (hereinafter, appropriately referred to as a “polar conversion layer”) that converts the polarity from hydrophilic to hydrophobic by light or heat, and A layer containing a compound that generates an acid and a compound that is cross-linked by the generated acid, and a layer whose alkali solubility is reduced by the cross-linking (hereinafter, appropriately referred to as an acid cross-linked layer),
It is characterized by being provided sequentially. Here, it is preferable that at least one of the acid cross-linked layer and the polarity conversion layer contains an infrared absorber from the viewpoint of improving sensitivity.

Although the mechanism of action of the present invention is not clear, by providing an acid cross-linking layer on the exposed or heated surface, a cross-linked structure can be efficiently formed by the heat of the exposure / heating section, and the sensitivity is further improved. Then, the alkali solubility is rapidly reduced, an image portion having high development resistance is formed, and in the lower layer,
A polarity conversion layer is provided, and the exposed / heated portion changes its hydrophobicity, effectively preventing the developer from penetrating between the image portion where the surface crosslinked structure is formed and the support. By doing so, the adhesion of the recording layer is improved, and the storage stability and printing durability of the obtained lithographic printing plate are improved. On the other hand, in the unexposed / unheated portion, the polarity conversion layer maintains the conventional hydrophilic property, and thus is quickly removed by the developer together with the non-image portion of the alkali-soluble heat-crosslinked layer. Therefore, the difference in developing property between the two becomes large, and ON / OFF of the image portion / non-image portion becomes clear. For this reason, it is considered that an image recording material excellent in not only sensitivity and image clearness but also adhesion of the recording layer and printing durability can be obtained.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The image recording material of the present invention is obtained by sequentially providing at least two layers of a polarity conversion layer and an acid-crosslinking layer on a support, and if these layers are provided in this order, As long as the effect is not impaired, a layer provided with a known layer such as a protective layer, a back coat layer, or an intermediate layer may be provided. Less than,
Each constituent layer will be described sequentially.

[Polarity Conversion Layer] The polarity conversion layer provided on the acid-crosslinked layer has the property of converting the polarity from hydrophilic to hydrophobic by light or heat as described above. As a material constituting such a polarity conversion layer, a material having a functional group such as a carboxylate or a carbonate which is released from the layer-forming polymer itself by heating is exemplified. In the present invention, as a material which can be used for the polarity conversion layer, a photosensitive composition using a polymer containing an N-phenylglycine derivative described in JP-A-2-238002, European Patent (EP) 467,177. Polymer obtained from the compound having a carboxyl group described in JP-A-6-31
No. 7899, a cationic polymer having an ammonium side group, a polymer having a carboxyl group causing a decarboxylation reaction upon exposure described in JP-A-64-32255, and a p-polymer described in JP-A-8-27287. -Construction of a photosensitive layer using a diazonium salt of phenylenediamine and a diazo resin, construction of an image forming material using microcapsules of a hydrophilic binder and a lipophilic component described in JP-A-7-1849, and JP-A-7-56330
JP-A-8-305012 discloses a constitution of an image forming material using a diazo resin in which the total amount of free water is specified, a photosensitive layer containing a diazonium salt and a hydrophilic layer containing tetraorthosilicate. Of a radiation-sensitive layer containing a diazonium salt condensation product and a mineral acid described in (1) above, and Japanese Patent Application No. 10-22 previously proposed by the present inventors.
No. 9783, a decarboxylation reaction of a polymer having a carboxyl group or a carboxylate,
JP-A-158699, the constitution of an image forming material utilizing the desulfonation reaction of a polymer having a sulfonic acid group, and the like. Specifically, the cationic polymer having an ammonium side group is a group represented by the following general formula in the side chain described in paragraph numbers [0012] to [0023] of JP-A-6-317899. A water-soluble polymer having, for example, a reaction with a carboxylic acid or a mineral acid, or a reaction with an alkylating group containing 7 or less carbon atoms, and a reaction between a monomer containing a quaternized amine and methyl methacrylate. And copolymers.

[0009] -N _{[(R 1) (R 2)} (R 3) ] ⁺ X ^-

Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
X represents an alkyl group, an alkenyl group, or an aryl group, and X represents an anion, preferably a halide, an alkyl sulfate, or a carboxylate.

The recording layer described in Japanese Patent Application Laid-Open No. 7-1849 includes a phenylisocyanate in a hydrophilic layer comprising a three-dimensionally crosslinked hydrophilic binder polymer such as a poly (meth) acrylate or polyoxyalkylene. ,
Microcapsules that contain lipophilic components such as polyethylene glycol diisocyanate and are destroyed by heat to form an image are dispersed, and after the microcapsule wall collapses, the hydrophilic polymer and the lipophilic component chemically bond to form an image. As hydrophilic polymers having such a structure, paragraph numbers [0012] to [0013] of the same publication, and as specific examples, paragraph numbers [00]
17] to [0033], as the lipophilic component, paragraphs [0048] to [0056] of the same publication.
Described in (1). Of these, a system using a material that undergoes polarity conversion using a diazonium group, a decarboxylation reaction, and a desulfonation reaction is preferable, and particularly preferably a decarboxylation reaction described in Japanese Patent Application No. 10-229783 is used. Of the image forming material obtained. here,
The polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group that undergoes decarboxylation by heat is preferably selected from the group represented by the following general formulas (1) and (2).

[0012]

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(Wherein X is selected from the group consisting of elements of groups 4 to 6, oxides, sulfides, selenides and tellurides, P represents a polymer main chain, and -L- Represents a divalent linking group, R ¹ and R ² each represent a monovalent group which may be the same or different, M represents an alkali metal,
Represents any one selected from the group consisting of alkaline earth metals and onium. )

Hereinafter, preferred examples of the polarity conversion layer include monomers, polymers, compounds, and the like having a partial structure having the above-mentioned functions. The structure of the polarity conversion layer of the present invention is not limited thereto. There is no restriction. Examples of the monomer having a carboxylic acid group or a carboxylic acid group include the following.

[0015]

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The structure of a copolymer obtained by using a monomer having such a partial structure in combination with another monomer is as follows.

[0017]

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[0018]

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Examples of the monomer having a sulfonic acid group structure include the following.

[0020]

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Examples of the polymer having a carboxylic acid group or a carboxylic acid group include the following.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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Examples of the polymer having a sulfonic acid group or a sulfonic acid group include the following.

[0034]

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[0035]

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[0036]

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[0037]

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[Acid Cross-Linking Layer] The acid cross-linking layer in the present invention comprises a compound which generates an acid by light or heat (hereinafter referred to as an acid generator) and a compound which cross-links by the generated acid (hereinafter referred to as a cross-linking agent). And a binder polymer which may react with a crosslinking agent in the presence of an acid to form a layer containing these. In this acid cross-linked layer, the acid generated by the decomposition of the acid generator by light irradiation or heating promotes the action of the cross-linking agent, and a strong cross-linking structure between the cross-linking agents or between the cross-linking agent and the binder polymer. Is formed, whereby the alkali solubility decreases and the developer becomes insoluble.

As the acid crosslinking agent layer having such properties, a known layer having similar properties can be used. For example, a layer composed of a radiation-sensitive composition containing a resole resin, a novolak resin, a latent Bronsted acid, and an infrared absorber described in JP-A-7-20629 can be mentioned. This composition contains both an alkali-resistant resol resin and a highly alkali-soluble novolak resin, and further contains a latent Bronsted acid. Here, the “latent Bronsted acid” refers to a precursor that decomposes to generate a Bronsted acid, and is a compound having both characteristics of an acid generator and an acid crosslinking agent in the present invention. Bronsted acids are believed to catalyze the matrix-forming reaction between resole resins and novolak resins, and examples of suitable Bronsted acids for this purpose are trifluoromethanesulfonic acid and hexafluorophosphonic acid. Further, ionic latent Bronsted acids are preferred, examples of which are onium salts, especially iodonium, sulfonium, phosphonium,
Includes selenonium, diazonium, and arsonium salts. Specific examples of particularly useful onium salts are: diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, phenylmethyl-ortho-cyanobenzylsulfonium trifluoromethanesulfonate, and 2-methoxy-
4-aminophenyldiazonium hexafluorophosphate. Non-ionic latent Bronsted acids can also be suitably used, for example, the following compounds: RCH ₂ X, RCHX ₂ , RCX ₃ , R (CH ₂ X)
₂ , and R (CH ₂ X) ₃ , wherein X is Cl, B
r, F, or CF ₃ or SO ₃ , and R is an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group).

Further, an image recording material containing an acid-crosslinkable compound and a high-molecular-weight binder described in JP-A-11-95415 is also mentioned as a suitable material. This is a compound capable of generating an acid upon irradiation with actinic rays, for example, salts such as diazonium, phosphonium, sulfonium, and iodonium, organic halogen compounds, and orthoquinone-.
Diazide sulfonyl chloride, and an organic metal / organic halogen compound, for example, an amino compound having at least two alkoxymethyl, methylol, and acetoxymethyl groups as functional groups, and an alkoxymethyl group, a methylol group, and acetoxymethyl as functional groups The photosensitive layer contains at least a disubstituted aromatic compound having a group or the like, a resole resin and a furan resin, an acrylic resin synthesized from a specific monomer, and the like, and can be used.

Other known recording materials applicable to a layer having the same function include, as described in JP-A-8-276558, a negative-type noble image recording material containing a phenol derivative and JP-A-7-306528. Negative recording material containing diazonium compound described in Japanese Patent Application Laid-Open
JP-A-203037 discloses a negative-type image-forming material utilizing a polymer having a heterocyclic group having an unsaturated bond in a ring and utilizing an acid-catalyzed crosslinking reaction. A layer can be applied as the acid crosslinked layer of the present invention.

The acid-crosslinked layer of the present invention contains an acid generator, a crosslinking agent, a binder polymer and others.
These compounds will be individually described. In the present invention, the compound that generates an acid by light or heat (acid generator) refers to a compound that is decomposed by irradiation with infrared rays or heated at 100 ° C. or more to generate an acid. The generated acid is preferably a strong acid having a pKa of 2 or less, such as sulfonic acid and hydrochloric acid. Examples of the acid generator suitably used in the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts. Specifically, US Pat. No. 4,708,925 and JP-A-7-20
No. 629. Particularly, an iodonium salt, a sulfonium salt, and a diazonium salt having a sulfonate ion as a counter ion are preferable.
As diazonium salts, US Pat. No. 3,867,14
7, the diazonium compound described in US Pat.
Also preferred are diazonium compounds described in 2,703 and diazo resins described in JP-A-1-102456 and JP-A-1-102457. Also, U
Benzyl sulfonates described in S5,135,838 and US 5,200,544 are also preferred. Further, JP-A-2-100054, JP-A-2-1000
Active sulfonic acid esters and disulfonyl compounds described in No. 55 and Japanese Patent Application No. 8-9444 are also preferable. Besides, haloalkyl-substituted S-triazines described in JP-A-7-271029 are also preferable.

These acid generators are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, based on the total solid content of the acid-crosslinked layer. It is added in the crosslinked layer. If the amount is less than 0.01% by weight, no image can be obtained. On the other hand, if the amount exceeds 50% by weight, non-image areas are stained during printing.

These compounds may be used alone,
Also, two or more kinds may be used in combination. Since the acid generators listed here can be decomposed by irradiation with ultraviolet rays, the image recording material of the present invention can record images not only with infrared rays but also with irradiation with ultraviolet rays.

The crosslinking agent that can be used in the acid crosslinking layer of the present invention is not particularly limited as long as it is a compound capable of crosslinking with an acid, but a phenol derivative represented by the following general formula (I) (hereinafter referred to as a low molecular weight compound) A phenol derivative), a polynuclear phenolic crosslinking agent having at least three phenol rings having two or three hydroxymethyl groups on the ring, represented by the following general formula (II), and a resol resin. Or a mixture thereof.

[0046]

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In the formula, Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. R ¹ and R ² may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. R ³ represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. m is 2 to 4
Indicates an integer. n shows the integer of 1-3. X represents a divalent linking group, and Y represents a monovalent to 4 group having the above partial structure.
A valent linking group or a functional group whose terminal is a hydrogen atom,
Z represents a monovalent to tetravalent linking group or a functional group that is absent when Y is a terminal group, or exists depending on the number of linking groups of Y.

[0048]

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In the formula, A represents an r-valent hydrocarbon linking group having 1 to 20 carbon atoms, and r represents an integer of 3 to 20. p is
Shows an integer of 2 to 3. First, the phenol derivative represented by the general formula (I) will be described in detail. Formula (I)
In the formula, Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. From the availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Preferred examples of the substituent include a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group, and a trifluoromethyl group. Is mentioned. Because of its high sensitivity, Ar ¹
Benzene ring and naphthalene ring having no substituent,
Or a halogen atom, a hydrocarbon group having 6 or less carbon atoms,
A benzene ring and a naphthalene ring having an alkoxy group having 6 or less carbon atoms, an alkylthio group having 6 or less carbon atoms, or a nitro group as a substituent are particularly preferable. R ¹ and R ²
May be the same or different, and represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. It is particularly preferable that R ¹ and R ² are a hydrogen atom or a methyl group because of easy synthesis. R ³ represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. R3 is particularly preferably a hydrocarbon group having 7 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a benzyl group, etc., because of its high sensitivity.
m shows the integer of 2-4. n shows the integer of 1-3.

X represents a divalent linking group, Y represents a monovalent to tetravalent linking group having the above partial structure or a functional group having a terminal hydrogen atom, and Z represents a terminal group. A monovalent to tetravalent linking group or functional group that does not exist or exists depending on the number of Y linking groups.

Next, X in the general formula (I) will be described in detail. X is a divalent linking group, and represents a single bond or a hydrocarbon linking group which may have a substituent. As the hydrocarbon linking group, straight-chain alkylene having 1 to 18 carbon atoms, branched-chain alkylene and cyclic alkylene, straight-chain alkylene having 2 to 18 carbon atoms,
Branched, cyclic alkenylene, alkynylene having 2 to 8 carbon atoms and arylene having 6 to 20 carbon atoms are preferred. Specifically, more preferred examples include methylene, ethylene, propylene, butylene, isopropylene, cyclohexylene, phenylene, tolylene, biphenylene, and groups represented by the following structures.

[0052]

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When these linking groups have a substituent, preferred substituents include an alkoxy group having 12 or less carbon atoms, a halogen atom and a hydroxyl group.

Next, Y in the general formula (I) will be described in detail. Y is a functional group which may be a linking group accompanied by Z as described later, and may be monovalent, divalent, trivalent or tetravalent as described above, and in particular, may have a mutual function with a phenolic hydroxyl group. It is a group known to have a strong effect. Specifically, a functional group having the following partial structure is preferably exemplified.

[0055]

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Here, that the exemplified structure is a partial structure of Y means that the linking group or the functional group Y whose terminal is a hydrogen atom has at least one exemplified partial structure. Accordingly, Y includes a group in which a plurality of the exemplified partial structures are linked, or a group in which the exemplified partial structure is linked to a normal hydrocarbon group or the like. Particularly preferred compounds having these functional groups, specifically, amide, sulfonamide, imide, urea,
Examples thereof include urethane, thiourea, carboxylic acid, carboxylic acid ester, and sulfonic acid ester.

Next, Z in the general formula (I) will be described in detail. Z represents a monovalent to tetravalent linking group or a functional group that does not exist when the functional group Y is a terminal group, or exists depending on the number of linking groups of the functional group Y. Z is preferably a hydrocarbon linking group or group which may have a substituent, and examples of the hydrocarbon linking group include linear alkylene or alkyl having 1 to 18 carbon atoms, branched alkylene or alkyl, Preferred are cyclic alkylene, alkyl, alkyl, arylene or aryl having 6 to 20 carbon atoms, linear or branched, cyclic alkenylene or alkenyl having 2 to 18 carbon atoms, alkynylene or alkynyl having 2 to 18 carbon atoms.

As more preferred specific examples of Z, when monovalent, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, octyl, benzyl, phenyl, Examples include naphthyl, anthracenyl, allyl, vinyl and the like. Also,
In the case of divalent or higher valence, it is preferable to remove a hydrogen atom from these monovalent groups according to the valence to form a linking group. When Z has a substituent, preferred substituents include alkoxy having 12 or less carbon atoms, a halogen atom, and a hydroxyl group.

Specific examples of the low-molecular-weight phenol derivative suitably used in the present invention are shown below for convenience by dividing into several patterns, for example, with functional groups, but the present invention is not limited to these. Not something.

[0060]

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[0061]

[Table 1]

[0062]

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[0063]

[Table 2]

[0064]

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[0065]

[Table 3]

[0066]

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[0067]

[Table 4]

[0068]

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[0069]

[Table 5]

[0070]

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[0071]

[Table 6]

[0072]

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[0073]

[Table 7]

[0074]

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[0075]

[Table 8]

[0076]

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[0077]

[Table 9]

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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Of these, low molecular weight phenol derivatives having an amide structure and a urea structure are preferred from the viewpoint of the effect.

These low-molecular-weight phenol derivatives useful as crosslinking agents can be synthesized by a conventionally known method. The general synthetic method is shown in the following schemes I and II.

[0104]

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In the formula, base represents a strong alkali, for example, KOH, NaOH, Me ₄ N ⁺ OH and the like.

That is, the compound of the general formula (I) can be synthesized from the corresponding phenol derivative by hydroxyalkylation and alkoxylation with a carbonyl compound. These low-molecular-weight phenol derivatives may be used alone or in combination of two or more. Further, when synthesizing these phenol derivatives, the phenol derivatives may condense with each other to produce by-products such as dimers and trimers, but the phenol derivatives may be used while containing these impurities. In this case, the impurity is 3
It is preferably at most 0%, more preferably at most 20%.

Next, the polynuclear phenolic crosslinking agent represented by the general formula (II) will be described. As is apparent from the structural formula, the polynuclear phenolic crosslinking agent represented by the general formula (II) has three or more phenol rings having two or three hydroxymethyl groups on the ring in the molecule. It is a polynuclear phenolic crosslinking agent. A in the general formula (II) has an r value of 1
A hydrocarbon linking group having from 20 to 20 carbon atoms, which is obtained by removing hydrogen from a skeleton composed of a straight-chain, branched-chain, or cyclic alkyl group or aryl group so as to have an r value.
More preferable specific examples of the linking group A include those represented by the following structures.

[0108]

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The compound represented by the general formula (I) having the linking group A in the molecule.
Preferred specific examples of the polynuclear phenolic crosslinking agent represented by I) include (II-1) to (II-6) shown below, but are not limited thereto.

[0110]

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[0111]

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These compounds are obtained by subjecting the corresponding polynuclear phenols to a methylolation reaction, and by the same route as in the scheme described above for the low molecular weight phenol derivatives. In use, it may be used while containing by-products such as oligomers generated during the methylolation reaction. Also in this case, the content of the by-product is preferably 10% by weight or less.

Now, the resole resin will be described.
The resole resin that can be used in the present invention is not particularly limited, but a compound disclosed as a resole resin in British Patent No. 2,082,339 is preferable, and among these, a weight average molecular weight of 500 to 100,000 and a number average molecular weight of 200 are preferable. 50,000 to 50,000 are preferred examples. If the molecular weight is too small, the crosslinkability is low, resulting in low printing durability. If the molecular weight is too large, it is unstable and the storage stability may be reduced.

The crosslinking component of the present invention includes (1) a mixture of a low-molecular phenol derivative and a polynuclear phenolic crosslinking agent, (2) a mixture of a low-molecular phenol derivative and a resole resin, and (3) a low-molecular phenol derivative. And a mixture of a polynuclear phenolic crosslinking agent and a resole resin.

Other crosslinking agents suitably used in the present invention include two or more hydroxymethyl groups in the molecule,
It is a compound having an alkoxymethyl group, an epoxy group, an aldehyde group, a ketone group or a vinyl ether group. Preferably, a compound in which these crosslinkable functional groups are directly bonded to an aromatic ring is used. Specifically, methylol melamine,
Epoxidized novolak resins, urea resins, and the like are included. Further, compounds described in "Crosslinking Agent Handbook" (written by Shinzo Yamashita and Tosuke Kaneko, Taiseisha Co., Ltd.) are also preferable. In particular, a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule is preferable because the strength of the image area when an image is formed is good.

However, these crosslinking agents are unstable to heat, and the storage stability after the formation of the acid crosslinking layer is not so good. On the other hand, the molecule has two or more hydroxymethyl or alkoxymethyl groups bonded to the benzene ring in the molecule, and contains 3 to 5 benzene nuclei,
Further, a phenol derivative having a molecular weight of 1,200 or less has good stability during storage and is most preferably used in the present invention. The alkoxymethyl group preferably has 6 or less carbon atoms. Specifically, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, and t-butoxymethyl are preferred. Further, alkoxy-substituted alkoxymethyl groups such as 2-methoxyethoxymethyl group and 2-methoxy-1-propoxymethyl group are also preferable. Specific examples include compounds described in JP-A-6-282067, JP-A-7-64285, and EP632003A1.

In the present invention, the crosslinking agent is used in an amount of 5 to 70% by weight, preferably 10 to 65% by weight, based on the total solid content of the acid crosslinking layer. If the amount of the cross-linking agent is less than 5% by weight, the film strength of the image portion at the time of image recording is deteriorated, and if it exceeds 70% by weight, the stability during storage is not preferable.

These crosslinking agents may be used alone.
Also, two or more types may be used in combination.

Examples of the binder polymer that can be used in the acid cross-linking layer of the present invention include polymers having an aromatic hydrocarbon ring, to which a hydroxy group or an alkoxy group is directly bonded, in a side chain or a main chain. As the alkoxy group, those having 20 or less carbon atoms are preferable from the viewpoint of sensitivity. As the aromatic hydrocarbon ring, a benzene ring, a naphthalene ring or an anthracene ring is preferable from the viewpoint of availability of raw materials. These aromatic hydrocarbon rings may have a substituent other than a hydroxy group or an alkoxy group, for example, a substituent such as a halogen group or a cyano group, but from the viewpoint of sensitivity, other than a hydroxy group or an alkoxy group. It is preferable not to have a substituent of

In the present invention, a binder polymer that can be suitably used is a polymer having a structural unit represented by the following general formula (III) or a phenol resin such as a novolak resin.

[0121]

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In the formula, Ar^TwoIs a benzene ring, naphthalene
A ring or an anthracene ring. R ^FourIs a hydrogen atom or
Represents a methyl group. R^FiveIs a hydrogen atom or carbon number 20
Represents up to alkoxy groups. X1 is a single bond or
Containing one or more atoms selected from C, H, N, O, and S
And a divalent linking group having 0 to 20 carbon atoms. k
Represents an integer of 1 to 4.

First, in the present invention, preferred examples of the structural unit represented by the general formula (III) ([BP-1]
To [BP-6]) below, but the invention is not limited thereto.

[0124]

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[0125]

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The polymer having these structural units can be obtained by subjecting the corresponding monomer to radical polymerization by a conventionally known method.

In the present invention, as the binder polymer,
A homopolymer composed of only the structural unit represented by the general formula (III) may be used, or a copolymer having a structural unit derived from another known monomer may be used together with the specific structural unit. good. Other known monomers used at this time include, for example, acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, and benzyl acrylate; Methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 2
-Methacrylic esters such as hydroxyethyl methacrylate and benzyl methacrylate; styrene, acrylonitrile, and monomers having an acidic group such as acrylic acid and methacrylic acid; and sodium salts of p-styrenesulfonic acid and 2-acrylamide-2-methyl Monomers containing a salt of a strong acid such as an alkali metal salt of propanesulfonic acid, a tetraalkylammonium salt, and a potassium salt of 3-sulfopropylacrylate are exemplified.

The proportion of the structural unit represented by the general formula (III) contained in the copolymer using these is 50 to 100.
% By weight, more preferably 60 to 60% by weight.
100% by weight. The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more,
More preferably, it is in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, and more preferably in the range of 2000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10.

These polymers are random polymers,
Any of a block polymer and a graft polymer may be used, but a random polymer is preferred.

Examples of the solvent used for synthesizing the polymer used in the present invention include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, -Methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-
Examples include dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.

As the radical polymerization initiator used for synthesizing the polymer used in the present invention, known compounds such as an azo initiator and a peroxide initiator can be used.

Next, novolaks will be described. The novolak resin preferably used in the present invention includes phenol novolak, o-, m-, p- various cresol novolaks, and copolymers thereof, novolaks using phenol substituted with a halogen atom, an alkyl group, and the like. Can be The weight average molecular weight of these novolak resins is preferably at least 1,000, more preferably 2,000.
And a number average molecular weight of preferably 100
0 or more, more preferably 2000 to 15000
Range. The polydispersity is preferably 1 or more, more preferably in the range of 1.1 to 10.

In a preferred embodiment, a polymer having a heterocyclic group having an unsaturated bond in the ring is used as the binder polymer. Here, the term "heterocycle" refers to a ring that contains one or more heteroatoms other than carbon among the atoms constituting the ring system. As the hetero atom to be used, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom are preferable. It is considered that by using such a polymer having a heterocyclic group, the function of the lawn pair present in the present heterocyclic ring facilitates a chemical structural reaction, and a film having good printing durability is formed.

The heterocyclic ring having an unsaturated bond in the ring (hereinafter, simply referred to as "heterocyclic ring") preferably used in the present invention is a 5-membered ring having two conjugated double bonds or a three-membered ring having two conjugated double bonds. 6-membered ring having a conjugated double bond, and a heterocycle obtained by condensing these heterocycles. Since these heterocycles have aromaticity, they are called aromatic heterocycles. further,
A particularly preferred heterocyclic ring is a heterocyclic ring in which an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring is further condensed to the above heterocyclic ring. As the heterocycle suitably used in the present invention, for example, pyrrole, furan, thiophene, oxazole, isoxazole, thiazole, isothiazole,
Monocyclic heterocycles such as imidazole, pyrazole, furazane, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, and silabenzene, and indole, isoindole, benzofuran, benzothiophene, indolizine, quinoline, isoquinoline, purine,
Indazole, benzimidazole, benzothiazole, benzoxazole, quinazoline, cinnoline, quinoxaline, phthalazine, pteridine, carbazole,
Examples include fused heterocycles such as acridine, phenanthridine, xanthene, phenazine, and phenothiazine. These heterocycles may have a substituent. Preferred substituents include a hydrocarbon group having 20 or less carbon atoms and 2 carbon atoms.
Examples include 0 or less alkoxy groups, aryloxy groups having 20 or less carbon atoms, and halogen atoms.

In this polymer having a heterocyclic group,
The heterocyclic group may be introduced into the polymer as a component constituting the main chain of the polymer, but is preferably bonded to the side chain of the polymer in a pendant manner because the film strength of the image is high. . In this case, the heterocyclic group may be directly bonded to the polymer main chain, but it is more preferable that the heterocyclic group is bonded in a pendant manner via an appropriate connecting chain because the film strength of the image portion is also high. . Preferred linking chains include, for example, ester bonds, carboxylic acid amide bonds, sulfonic acid amide bonds, ether bonds, thioether bonds, and organic groups having 20 or less carbon atoms that may contain these bonds. it can. Examples of the polymer main chain include vinyl polymers, polyesters, and polyurethanes, which are main chains such as poly (meth) acrylate, polystyrene, and polyvinyl acetal. Is preferred.

The binder polymers used in the present invention described above may be used alone or as a mixture of two or more. These polymers are added at a ratio of 20 to 95% by weight, preferably 40 to 90% by weight based on the total solid content of the acid crosslinked layer. When the addition amount is less than 20% by weight, the strength of the image portion is insufficient when an image is formed. When the amount exceeds 95% by weight, no image is formed. The acid crosslinked layer is provided on the polarity conversion layer, but an intermediate layer may be provided between the two if desired.

It is preferable to use an infrared absorber in the polarity conversion layer and / or the acid crosslinked layer of the present invention in view of improving the light / heat conversion efficiency in a recording material capable of recording an image with a laser emitting infrared rays. That is, the infrared absorbent has a function of converting the absorbed infrared rays into heat, and the heat generated at this time decomposes the acid generator to generate an acid.
It promotes a thermal crosslinking function such as crosslinking reactivity and a polarity conversion function such as decarboxylation reactivity. Hereinafter, the polarity conversion layer and / or the acid cross-linked layer will be simply referred to as “recording layer” as appropriate. The infrared absorber used in the present invention is a dye or pigment that effectively absorbs infrared rays having a wavelength of 760 nm to 1200 nm. Preferably, the wavelength 760
It is a dye or pigment having an absorption maximum from nm to 1200 nm.

As the dye, commercially available dyes and known dyes described in literatures such as “Dye Handbook” (edited by The Society of Synthetic Organic Chemistry, Japan, 1970) can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes Is mentioned.

Preferred dyes include, for example, those described in
Cyanine dyes described in JP-A-8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, etc .;
No. 96, JP-A-58-181690, JP-A-58-1
No. 94595, etc., methine dyes described in
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940 and JP-A-60-63744;
Squarylium dyes described in No. 12792, etc.,
Cyanine dyes described in British Patent 434,875 and the like can be mentioned.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted aryl benzo (thio) described in US Pat. No. 3,881,924 is also preferable. Pyrylium salt, JP-A-57-142645
No. (U.S. Pat. No. 4,327,169) described in JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, and JP-A-59-41363.
Nos. -84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranyl compounds, cyanine dyes described in JP-A-59-216146, pentamethinethiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-13
Pyrylium compounds disclosed in JP-A-514 and JP-A-5-19702 are also preferably used.

Further, as another preferred example of the dye, US Pat. No. 4,756,993 discloses a compound represented by the formula (I):
Near-infrared absorbing dyes described as (II) can be mentioned. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

Preferred examples of the infrared absorber used in the present invention include an infrared absorber having an onium salt structure as shown below. Specific examples (A-1 to A-56) of such an infrared absorber are shown, but the present invention
It is not limited to these.

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[0158] In the structural formulas of A-1~A-56, T ^- A,
Represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a Lewis acid anion (B
F ₄ ⁻ , PF ₆ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ ), an alkyl sulfonate anion and an aryl sulfonate anion.
The alkyl herein refers to a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group,
Examples thereof include a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable. In addition, the aryl referred to herein refers to those composed of one benzene ring, those formed by condensing two or three benzene rings, and those formed by condensing a benzene ring and a 5-membered unsaturated ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

Examples of the pigment used for the infrared absorbent in the present invention include commercially available pigments and Color Index (CI) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, published in 1977), "Latest Pigment" Application Technology ”(CMC
Publishing, 1986) and "Printing Ink Technology", CMC Publishing, 1984).

The types of the pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyeing lake pigments,
Azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.
Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
If less than 10 m, it is not preferable in view of the stability of the dispersion in the coating solution of the acid-crosslinked layer or the polarity conversion layer.
Is not preferable in view of the uniformity of these recording layers.

As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

These dyes or pigments are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the recording layer.
% By weight, particularly preferably 0.5 to 10% by weight for dyes, and particularly preferably 1.0 to 10% by weight for pigments. If the amount of the pigment or dye is less than 0.01% by weight, the sensitizing effect is insufficient, and if it exceeds 50% by weight, the non-image area tends to be stained during printing. .

These dyes or pigments may be added to the same layer as other components, or another layer may be provided and added thereto.

The acid crosslinked layer / polarity conversion layer (recording layer) of the present invention
In addition, various compounds other than the above may be added as necessary. For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5
05 (manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI4255)
5), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170B),
Malachite green (CI42000), methylene blue (CI52015), Aizen spiron blue CR
H (manufactured by Hodogaya Chemical Co., Ltd.) and JP-A-62-29
And dyes described in No. 3247.

The addition of these dyes makes it easier to distinguish between an image area and a non-image area after image formation. Therefore, it is preferable to add these dyes. The amount of addition is 0.01 to 10% by weight based on the total solid content of the recording layer.

In the recording layer of the present invention, in order to widen the stability of processing under development conditions, Japanese Patent Application Laid-Open No.
Nonionic surfactants described in JP-A-251740 and JP-A-3-208514;
No. 044 and JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether and the like.

Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N , N-betaine type (for example,
(Trade name: Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the recording layer is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer is added to the recording layer of the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and the like are used.

In the recording layer of the present invention, each of the above-mentioned components is usually dissolved in a solvent and coated on a suitable support. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate,
N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, water and the like, but are not limited thereto. Absent. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. Coating amount (solid content) on support obtained after coating and drying
Varies depending on the use, but generally speaking, as for the lithographic printing plate material, the polarity conversion layer is 0.01 to 5.0 g /
m ² is preferable, and 0.1 to 3.0 g / m ² is more preferable. Preferably 0.5 to 5.0 g / m ² as acid crosslinking layer, further 0.5 to 3.0 g / m ² is preferred. Various methods can be used as the method of coating, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating,
Examples include blade coating and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the recording layer deteriorate.

The recording layer coating solution of the present invention may contain a surfactant for improving coating properties, for example, JP-A-62-1.
No. 70950 can be added. A preferable addition amount is 0.01 to 1% by weight based on the total solid content of the recording layer, and more preferably 0.1 to 1% by weight.
0.5 to 0.5% by weight.

[Support] As the image recording material of the present invention,
The support to which the acid cross-linking layer and the polarity conversion layer can be applied is a dimensionally stable plate-like material, for example, paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, Metal plate (for example,
Aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate)
Polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited.

Preferred examples of the support include a polyester film and an aluminum plate. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in aluminum alloys include silicon, iron, manganese,
Copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The total content of foreign elements in the alloy is 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like is performed to remove rolling oil on the surface. The surface roughening treatment of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating current or a direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment, if necessary, in order to increase the water retention and abrasion resistance of the surface. You. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes forming a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte used and thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is a 1 to 80% by weight solution, the liquid temperature is 5 to 70 ° C.,
Current density 5 to 60 A / dm ^2, voltage 1 to 100 V, which is an electrolyzing time of 10 seconds to 5 minutes.

When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, and the non-image area of the lithographic printing plate is easily scratched. The so-called "scratch dirt" to which is adhered easily occurs.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment as required. U.S. Pat. No. 2,714,075 discloses a hydrophilic treatment that can be used in the present invention.
No. 66, No. 3,181,461, No. 3,280,
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in U.S. Pat. Nos. 734 and 3,902,734. In this method, the support is immersed or electrolytically treated with an aqueous solution of sodium silicate. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063, U.S. Pat.
No. 76,868, No. 4,153,461, No. 4,
No. 689,272, a method of treating with polyvinyl phosphonic acid or the like is used.

[Others] An undercoat layer can be provided on a support, if necessary, before applying and forming each constituent layer in the image recording material of the present invention. As the undercoat layer component, various organic compounds are used, for example, phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid;
Optionally substituted phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid,
Organic phosphonic acids such as methylene diphosphonic acid and ethylene diphosphonic acid; phenylphosphoric acid which may have a substituent,
Organic phosphoric acids such as naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid; organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent; glycine and β-alanine And amino acid salts having a hydroxyl group such as triethanolamine hydrochloride, but may be used in combination of two or more. It is also preferable to undercoat the aforementioned diazonium compound. The coating amount of the organic undercoat layer is 2-200 mg.
/ M ² is appropriate.

As described above, the negative image recording material of the present invention can be obtained. The negative-type image recording material can be recorded with an infrared laser. Also, thermal recording with an ultraviolet lamp or a thermal head is possible. In the present invention, it is preferable that the image is exposed by a solid-state laser or a semiconductor laser that emits infrared rays having a wavelength of 760 nm to 1200 nm. In the present invention, the developing treatment may be performed immediately after the exposure, or a heat treatment may be performed between the exposure step and the developing step. When performing heat treatment, the conditions are:
It is preferable to carry out in a range of 60 ° C. to 150 ° C. for 5 seconds to 5 minutes. As a heating method, various conventionally known methods can be used. For example, a method of heating while contacting the recording material with a panel heater or a ceramic heater,
And a non-contact heating method using a lamp or warm air. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

After performing a heat treatment as required, the image recording material of the present invention is preferably developed with water or an alkaline aqueous solution.

When an alkaline aqueous solution is used, a conventionally known alkaline aqueous solution can be used as a developer and a replenisher for the image recording material of the present invention. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium,
Same ammonium, sodium hydroxide, same ammonium,
And inorganic alkali salts such as the same potassium and the same lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. An example of a particularly preferable developer among these alkaline agents is an aqueous solution of a silicate such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and the concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O which are the components of the silicate. An alkali metal silicate described in JP-B-57-7427 is effectively used.

When developing using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is added to the developing solution to replace the developing solution in the developing tank for a long time. It is known that a large amount of lithographic printing plate material can be processed without the need. This replenishment system is also preferably applied in the present invention.

Various surfactants and organic solvents can be added to the developing solution and the replenishing solution, if necessary, for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. . Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred organic solvents include benzyl alcohol and the like. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof.

Further, the developing solution and the replenisher may contain, if necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcin, sodium or potassium sulfite or bisulfite, an organic carboxylic acid, an antifoaming agent, a hard water Softeners can also be added.

Examples of such a developer containing a surfactant, an organic solvent, a reducing agent and the like include, for example, those described in
Benzyl alcohol described in No. 77401,
A developer composition comprising an anionic surfactant, an alkali agent and water, comprising an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite as described in JP-A-53-44202; Developer composition,
Examples thereof include a developer composition containing an organic solvent, an alkali agent, and water having a solubility in water of 10% by weight or less at room temperature described in JP-A-55-155355, which is also suitable for the present invention. Used for

The printing plate developed using the developing solution and the replenisher described above is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. You. As the post-processing when the image recording material of the present invention is used as a printing plate material, these processings can be used in various combinations.

In recent years, in the plate making and printing industry, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally includes a developing section and a post-processing section, and includes a device for transporting a printing plate material, each processing solution tank, and a spray device. The developing process is performed by spraying each pumped processing liquid from a spray nozzle. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like into a processing liquid tank filled with a processing liquid to perform processing. In such automatic processing,
Processing can be performed while replenishing each processing solution with a replenisher according to the processing amount, operating time, and the like.

Further, a so-called disposable processing method in which the processing is performed with a substantially unused processing solution can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum if desired. Is subjected to a burning process. When burning a lithographic printing plate, before burning,
No. 2518, No. 55-28062, JP-A-62-3
It is preferable to treat with a surface-regulating liquid as described in JP-A Nos. 1859 and 61-159655.

[0194] As a method for this, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied onto a lithographic printing plate,
A method in which a printing plate is immersed in a vat filled with a surface conditioning liquid to apply the printing plate, an application using an automatic coater, or the like is applied. Further, it is preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. The application amount of the surface conditioning liquid is generally 0.03 to 0.8 g / m ^2.
(Dry weight) is appropriate.

The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then burned with a burning processor (for example,
It is heated to a high temperature by a burning processor (BP-1300) sold by Fuji Photo Film Co., Ltd. The heating temperature and time in this case depend on the type of the component forming the image, but may be 1 to 180 ° C. to 300 ° C.
A range of up to 20 minutes is preferred.

The burn-processed lithographic printing plate can be subjected to a conventional treatment such as washing with water or gumming if necessary. When a liquid is used, a so-called desensitizing treatment such as gumming can be omitted.

The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0198]

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

(Example 1) [Production of support] Aluminum plate having a thickness of 0.30 mm
(Material 1050) is washed with trichlorethylene and degreased
Nylon brush and 400 mesh pamistone-
Use a water suspension to grain the surface, wash well with water
Was. Put this plate in a 25% aqueous solution of sodium hydroxide at 45 ° C.
After immersion for 9 seconds, etching and washing with water, 2% H
NO _ThreeFor 20 seconds and washed with water. Graining at this time
The amount of etching on the surface is about 3 g / m^TwoMet. Then this
7% H_TwoSO_FourCurrent density 15A / dm
^Two3g / m^TwoWas provided. Then 7
After immersing in a 2.5% aqueous solution of sodium silicate at 0 ° C for 1 minute, washing with water
Dried. Next, the aluminum plate was subbed with the following composition
And dried at 80 ° C. for 30 seconds. Coating after drying
The amount is 20mg / m^TwoMet. [Composition of undercoat liquid] 0.1 g of dibutylnaphthalenesulfonic acid as a condensate of 4-diazodiphenylamine and phenoxyacetic acid with formaldehyde 100 g of methanol

[Formation of Polarity Conversion Layer] Next, a polarity conversion layer coating solution I having the following composition was prepared, and this solution was applied to the above-mentioned primed aluminum plate and dried at 140 ° C. for 2 minutes. 0.5 g / m ² of plate material (I) was obtained. (Exemplified Compound CCP-1) The Exemplified Compound CCP-1
Is the synthesis example 1 in the examples of JP-A-64-32255.
In the same manner as the polymer (A) described in (1). The ratio of the structural unit having a polarity conversion group is 10 parts, and the weight average molecular weight is 58,000. [Composition of the polarity conversion layer coating solution I]-Exemplified compound CCP-1 2.0 g-Anthracene 0.7 g-N, N-dimethylacetamide 15 ml-Methyl ethyl ketone 15 ml

[Formation of Acid-Crosslinking Layer] Next, an acid-crosslinking layer coating solution (p) having the following composition was prepared, and this solution was applied on the plate (I) and dried at 100 ° C. for 1 minute. Thus, an image recording material (Ip) of 1.5 g / m ² in which a polarity conversion layer and an acid cross-linking layer were sequentially formed on a support having an undercoat layer formed thereon was obtained. [Composition of the acid cross-linking layer coating solution (p)]-Novolak resin (m / p = 6/4, Mw = 10,000) 3 g-Resol resin 1.5 g (resin obtained from bisphenol A and formaldehyde, weight average molecular weight) : 2,000, number average molecular weight: 1,000) Triphenylsulfonium p-toluenesulfonate 0.5 g Methanol 25 ml Methyl ethyl ketone 20 ml 1-nitronaphthalene 0.5 g

Example 2 In Example 1, a plate material (II) of 0.2 g / m ² was obtained by using a polarity conversion layer coating solution II having the following composition for forming a polarity conversion layer. In the same manner as in Example 1, a polarity conversion layer (II) and an acid crosslinked layer (p) were sequentially formed on a support having an undercoat layer formed thereon, at a rate of 1.7 g /.
m ² of the image recording material (II-p) was obtained. [Polar Conversion Layer Coating Solution II] Polymer compound containing N- (2-hydroxy-3-methacryloxypropyl) -N-phenyl glycine as a structural unit described in Example 1 of JP-A-2-238002 ( A-1) 2.5 g ・ Michler's ketone 1.0 g ・ N, N-dimethylacetamide 15 ml ・ Methyl ethyl ketone 15 ml

(Example 3) [Preparation of support] An aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichlorethylene and degreased, and then a nylon brush and a 400-mesh paminestone-water suspension were used. The surface was grained and washed well with water. This plate was immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds, etched, washed with water, and further washed with 2% water.
% HNO ₃ for 20 seconds and washed with water. At this time, the etching amount on the back surface of the graining was about 3 g / m ² .
Next, this plate was subjected to a current density of 1% using 7% H ₂ SO ₄ as an electrolytic solution.
After providing a direct current anodic oxide film of 5 A / dm ^2, the film was washed with water and dried. Next, the following undercoat liquid was applied to this aluminum plate, and dried at 80 ° C. for 30 seconds. The coating weight after drying is 1
It was 0 mg / m ² . (Composition of undercoat liquid) ・ β-alanine 0.1 g ・ Phenylphosphonic acid 0.05 g ・ Methanol 40 g ・ Pure water 60 g

[Formation of Polarity Conversion Layer] Next, a polarity conversion layer coating solution III having the following composition was prepared, and this solution was applied to the undercoated aluminum plate (support).
Drying at 2 ° C. for 2 minutes gave 0.3 g / m ² of plate material (III). [Polar Conversion Layer Coating Solution III]-Exemplified compound CP-1 (polymer having a carboxylic acid group) 2.4 g-Infrared absorber DX-1 (structure shown below) 0.7 g-Fluorinated surfactant (MegaFac F) -177, Dainippon Ink and Chemicals, Inc.) 0.06 g-Dimethyl sulfoxide 20 ml-Methyl ethyl ketone 20 ml-Colorant (VPB-Naps: 0.04 g from Hodogaya Chemical Co., Ltd.)

[0205]

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[Formation of Acid Cross-Linked Layer] Next, an acid cross-linked layer coating solution (q) having the following composition was prepared, and this solution was applied to the plate material (II)
I) coated on top and dried at 100 ° C. for 1 minute to form an 1.6 g / m ² image recording material (III-) in which an acid crosslinked layer and a polarity conversion layer were sequentially formed on a support having an undercoat layer formed thereon. q) was obtained. [Composition of coating solution (q) for acid-crosslinking layer] 1.37 g of polyhydroxystyrene (Markarinka-MH2P, Maruzen Petrochemical Co., Ltd.) Synthesis example 1-1 described in Examples of JP-A-8-276558 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis- (4-hydroxyphenyl) ethyl] benzene obtained in the above 0.75 g · (4-octyloxyphenyl) ) Phenyliodonium hexafluoroantimonate 1 g ・ Infrared absorber DX-1 0.7 g ・ Fluorine-based surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.06 g ・ Methanol 15 g ・ 1- Methoxy-2-propanol 5 g, water 5 g, colorant (VPB-Naps: manufactured by Hodogaya Chemical Co., Ltd.) 0.04 g

Example 4 A polarity conversion layer coating solution IV having the following composition was prepared, and this solution was applied to the undercoated aluminum plate (support) used in Example 3,
After drying for ² minutes, a plate material (IV) of 0.2 g / m ² was obtained. [Polar Conversion Layer Coating Solution IV]-Exemplified Compound CP-38 (polymer having a carboxylic acid group) 2.4 g-Infrared absorber DX-1 0.7 g-Fluorinated surfactant (Megafac F-177, large 0.06 g N, N-dimethylformamide 37 ml Colorant (VPB-Naps: Hodogaya Chemical Co., Ltd.) 0.04 g

Next, an acid-crosslinking layer coating solution (q ') having the following composition
Is prepared, and this solution is applied onto the plate (IV), and 1
After drying at 00 ° C. for 1 minute, an acid-crosslinked layer and a polarity conversion layer were sequentially formed on a support having an undercoat layer formed thereon.
m ² of the image recording material (IV-q ′) was obtained. [Composition of the acid-crosslinking layer coating solution (q ')] 1.37 g of polyhydroxystyrene (Markarinka-MH2P, Maruzen Petrochemical Co., Ltd.)-Synthesis example 1 described in Examples of JP-A-8-276558 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis- (4-hydroxyphenyl) ethyl] benzene obtained in 1 0.75 g · (4-octyloxy Phenyl) phenyliodonium hexafluoroantimonate 1g ・ Infrared absorber DX-1 0.7g ・ Fluorine-based surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.06g ・ Methanol 15g ・ 1 -Methoxy-2-propanol 5 g-Water 5 g-Colorant (VPB-Naps: manufactured by Hodogaya Chemical Co., Ltd.) 0.04 g

(Example 5) [Formation of polarity conversion layer] A coating solution V for a polarity conversion layer having the following composition was applied to an aluminum plate (support) which had been treated and treated in the same manner as in Example 3 and was coated at 140 ° C. Dry for 0.3 minutes, 0.3g
/ M ² of plate material V was obtained. [Polar conversion layer coating solution V]-0.7 g of hydrophilic binder polymer P-1 described in Examples of JP-A-7-1849-Microcapsules described in Examples of JP-A-7-1849 Lipophilic component M-1 1.0 g ・ Infrared absorbent DX-2 (structure below) 0.4 g ・ Fluorine-based surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.06 g ・Coloring agent (VPB-Naps: Hodogaya Chemical Co., Ltd.) 0.04 g N, N-dimethylacetamide 20 g Tetrahydrofuran 20 g

[0210]

Embedded image

Next, an acid-crosslinking layer coating solution (r) having the following composition was prepared, and this solution was applied on the plate material (V).
After drying at 0 ° C. for 1 minute, an acid-crosslinked layer and a polarity conversion layer were sequentially formed on the support on which an undercoat layer had been formed, 1.3 g /
m ² of the image recording material (Vr) was obtained. (Synthesis of Crosslinking Agent A-1) p-Aminophenol (1 mo
l), sodium acetate (1 mol) was put into a flask together with acetone (1 liter), and formic acid chloride (1 mol)
Is added dropwise under ice cooling. Five hours later, the mixture was put into ice water to precipitate crystals, and the crystals were collected by filtration to obtain A-1-x in a yield of 75%. The A-1-x (0.75 mol) and KOH (0.
75 mol), 500 ml of water and a 37% aqueous formalin solution (4.0 mol) were placed in a flask, heated at 50 ° C. for 5 hours, and then poured into 5 liters of acetone to precipitate crystals.
The crystals are collected by filtration, dissolved in 100 ml of water, and neutralized with potassium hydrogen sulfate to crystallize. Filter this,
The target product A-1 was obtained in a total yield of 60%. The synthesis scheme is as follows.

[0212]

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The structure of the obtained target product A-1 is represented by ¹ HNM
It was confirmed by R, IR and MASS. [Composition of the acid cross-linking layer coating liquid (r)]-3 g of a polymer of the chemical formula BP-3 described in JP-A-11-102071-1.5 g of the cross-linking agent A-1-2,4,6-tris (hexyl) Oroxy) benzenediazonium 2,4,6-trimethylbenzenesulfonate 0.7 g N, N-dimethylacetamide 30 g Methylethylketone 20 g Infrared absorbent DX-2 0.5 g fluorine-based surfactant (MegaFac F-177 , Dainippon Ink & Chemicals, Inc.) 0.06 g Colorant (VPB-Naps: Hodogaya Chemical Co., Ltd.) 0.04 g

Example 6 A support having an undercoat layer was formed in the same manner as in Example 5 except that a polarity conversion layer coating solution VI having the following composition was used to form the polarity conversion layer. A 1.8 g / m ² image recording material (VI-r), on which a polarity conversion layer (VI) and an acid crosslinked layer (r) were sequentially formed, was obtained. [Polar Conversion Layer Coating Solution VI] Image-forming material 1 in Example 1 of JP-A-8-27287 (composition obtained by adding a cationic fluorine-containing surfactant described in paragraph [0061] of the same publication and water)

(Example 7) A polarity conversion layer coating solution VII having the following composition was applied on an undercoated aluminum plate (support) treated in the same manner as in Example 3 and dried at 140 ° C for 2 minutes.
0.2 g / m ² of printing plate VII was obtained. [Polar Conversion Layer Coating Solution VII]-1.7 g of hydrophilic binder polymer P-1 described in Examples of JP-A-7-1849-Microcapsules described in Examples of JP-A-7-1849 Lipophilic component M-1 1.0 g ・ Infrared absorber DX-1 0.4 g ・ Fluorinated surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.06 g ・ Colorant (VPB) -Naps: Hodogaya Chemical Co., Ltd.) 0.04 g ・ N, N-dimethylacetamide 20 g ・ Tetrahydrofuran 20 g

An acid-crosslinking layer coating solution s having the following composition was applied onto the plate material VII, and dried at 100 ° C. for 1 minute. Then, a polarity conversion layer and an acid-crosslinking layer were successively formed on the support having the undercoat layer formed thereon. 1.3 g / m ² of the formed image forming material (VII-s) was obtained. [Composition of the acid cross-linking layer coating liquid (s)]-Novolak resin (m / p = 6/4, Mw = 10,000) 3 g-Resole resin 1.5 g (resin obtained from bisphenol A and formaldehyde, weight average molecular weight) : 2,000, number average molecular weight: 1,000)-Triphenylsulfonium p-toluenesulfonate 0.5 g-Methanol 25 ml-1-methoxy-2-propanol 10 ml-Water 10 ml-Infrared absorber DX-1 0.5 g

Example 8 The procedure of Example 7 was repeated, except that a polarity conversion layer coating solution VIII having the following composition was used for forming the polarity conversion layer to obtain 0.3 g / m ² of plate material VIII. 1.6 g of a polarity conversion layer (VIII) and an acid crosslinked layer (s) sequentially formed on a support having an undercoat layer formed thereon in the same manner as in Example 7.
/ M ² of the image recording material (VIII-s). [Polar Conversion Layer Coating Solution VIII]-Exemplified compound CP-7 (polymer having a carboxylic acid group) 2.4 g-Infrared absorber DX-2 0.7 g-Fluorinated surfactant (Megafac F-177, large 0.06 g ・ Dimethyl sulfoxide 20 ml ・ Methyl ethyl ketone 20 ml ・ Colorant (VPB-Naps: Hodogaya Chemical Co., Ltd.) 0.04 g

(Comparative Examples 1 to 4) Plate material p according to Example 1
(Image recording material in which only the acid crosslinked layer (p) was formed on the support having the undercoat layer formed thereon) was used as the image recording material of Comparative Example 1, and the plate material q according to Example 3 (the support having the undercoat layer formed thereon) was used. An image recording material having only the acid crosslinked layer (q) formed thereon was used as the image recording material of Comparative Example 2, and the plate material r according to Example 5 (the acid crosslinked layer (r) was formed on the support having the undercoat layer formed thereon). The image recording material having only the acid crosslinked layer (s) formed on the support having the undercoat layer formed thereon was compared with the plate material s according to Example 7 (compared with the image forming material formed in Example 7). The following evaluations were performed for the image forming material of Example 4 in the same manner as in Example.

(Evaluation of Image Recording Material-1) The photosensitive lithographic printing plates (Ip), (II-p) and (II-p) of Examples 1, Example 2 and Comparative Example 1 obtained as described above. On top of p), a step wedge (density step 0.15, maximum density 15 steps) and a halftone negative film were overlaid, and passed through Kenko Optical Filter BP-40 with a printer FT26V2UPNS (light source; 2KW metal hydride lamp) manufactured by Nuark, USA. Exposure to 50 counts, 25 ° C in the following developer (I)
For 20 seconds, rubbed lightly with absorbent cotton, washed with water, and subjected to the following desensitization treatment to obtain a lithographic printing plate. [Developing solution (I)] _{· [SiO 2] / [K} 2 O] molar ratio of 1.2 cinnamic acid potassium 32 g-ethylenediamine sodium salt 1 g · Water 967g of tetra-acetate [desensitizer] of Gum arabic 5 g-White dextrin 30 g-Ethylene glycol 10 g-Phosphoric acid 3 g-Water 952 g Using these prints, a high quality paper was printed with a commercially available ink using a Heidelberg SOR printer. The obtained images were evaluated according to the following criteria. The results are shown in Table 10 below. [Stability over time] Evaluation was made by comparing the development property and the sensitivity change between the plate immediately after coating the recording layer and the plate stored at 60 ° C. for 3 days after the formation of the recording layer. Developability was defined as "good" when no unexposed portion of the recording layer was observed after development, and "residual" when remaining. [Sensitivity change] It was determined from the change in the maximum number of step wedges. In other words, the portion with the largest numerical value at which an image remains on the step wedge after development is defined as the highest step wedge number, and when this numerical value is larger by two, the sensitivity is doubled. [Adhesion] R201 manufactured by Roland was used as a printing machine, and GEOS-G manufactured by Dainippon Ink was used as the ink.
Using (N), printing was performed using the lithographic printing plate. On the 5,000th sheet from the start of printing, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked in a sponge for printing, halftone dots were wiped off, and the ink on the plate surface was washed. Thereafter, 10,000 sheets were printed, and the presence or absence of halftone dot skipping in the printed matter was visually observed. Those in which no plate skipping was recognized were evaluated as “good”.

[0220]

[Table 10]

As is clear from Table 10, the lithographic printing plate having a recording layer consisting of an acid-crosslinked layer alone has a predetermined performance, but the lithographic printing plate according to the present invention has a polarity conversion layer as a lower layer. The plate material further achieved excellent sensitivity, storage stability and improved adhesion of the recording layer.

(Evaluation of Image Recording Material-2) Example 3,
4, 5, 6, 7, 8 and the lithographic printing plate materials (III-q), (IV-q '), (Vr) obtained in Comparative Examples 2, 3, and 4;
(VI-r), (VII-s), (VIII-s), (q),
(R) and (s) were converted to wavelengths of 830 to 850 nm, respectively.
Exposure was performed with a semiconductor laser that emits infrared light of a degree. After exposure, a heat treatment was performed for 15 seconds at 110 ° C. with a panel heater, and then a developer DN-3C manufactured by Fuji Photo Film Co., Ltd.
(Diluted with water at a ratio of 1: 2) and washed with water. [Sensitivity] Image obtained at these times, line width and laser output,
The amount of energy (sensitivity) required for recording was calculated based on the loss in the optical system and the scanning speed. [Stability over time] In order to examine the storage stability, the plate material before laser exposure was left for 3 days under high temperature conditions (60 ° C.), and then the storage plate material under high temperature conditions was exposed to laser in the same manner as described above. The amount of energy required for recording was calculated, and the difference between the amount of energy before and after aging was examined. Preferably, this difference is substantially 20 mJ / cm ² or less for production,
It is evaluated that the storage stability is good. (Adhesion) After exposing and developing the lithographic printing plate, as a printing machine,
Printing was performed using R201 manufactured by Roland Co. and GEOS-G (N) manufactured by Dainippon Ink Co., Ltd. as the ink. On the 5000th sheet from the start of printing, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked into a printing sponge, halftone dots were wiped off, and the ink on the plate surface was washed. Thereafter, 10,000 sheets were printed, and the presence or absence of halftone dots in the printed matter was visually observed.

[0223]

[Table 11]

As is clear from Table 11, the lithographic printing plate having a recording layer consisting of an acid-crosslinked layer alone has a predetermined performance, but the lithographic printing plate according to the present invention is provided with a polarity conversion layer as an upper layer. As for the plate material, the energy required for recording was also significantly reduced with respect to recording with an infrared laser, achieving excellent sensitivity, and the stability over time and the adhesion of the recording layer were also greatly improved. Was.

[0225]

According to the present invention, recording is performed using a solid-state laser and a semiconductor laser that emit infrared light.
Plate making can be performed directly from digital data from a computer or the like.
A negative type image recording material having excellent adhesion of the recording layer can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 505 G03F 7/004 521 521 B41M 5/26 S (72) Inventor Hitoshi Kunita Haibara-gun, Shizuoka 4000 Kawajiri, Yoshida-machi Fuji Sha Shin Film Co., Ltd. F-term (reference) 2H025 AA01 AA11 AA14 AB03 AB09 AB13 AC08 AD01 BE00 BH03 CC11 CC17 DA03 DA40 2H096 AA06 AA23 BA20 EA04 EA23 2H111 HA14 HA23 HA35 2H114 AA04A30 DA03 DA23 DA27 DA29 DA33 DA34 DA39 DA41 DA52 DA59 EA02 EA08 EA10 FA18 GA01

Claims (2)

[Claims] 1. A first layer, on a support, whose polarity is changed from hydrophilic to hydrophobic by light or heat, a compound that generates an acid by light or heat, and a compound that is cross-linked by the generated acid. An image recording material comprising, in order, a layer which contains and whose alkali solubility is reduced by crosslinking. 2. The method according to claim 1, wherein the first layer contains a compound that generates an acid by light or heat and a compound that is cross-linked by the generated acid. 2. The image recording material according to claim 1, comprising an agent.