JP2001042508A - Image forming material - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming material which can be used as a lithographic printing plate material, a color proof, a photoresist and a color filter. In particular, the present invention relates to a negative type image forming material which can be directly used for making a plate by using various lasers from a digital signal of a computer or the like, and which is preferably used as a so-called direct plate making planographic printing plate.

[0002]

2. Description of the Related Art Solid-state lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm can be easily obtained with high output and small size. Is very useful as a recording light source when making a plate directly from digital data of a computer or the like. Various researches have been made on recording materials sensitive to these various laser beams. Representative examples of the materials that can be recorded with an infrared laser having a photosensitive wavelength of 760 nm or more include positive recording materials described in US Pat. No. 4,708,925, There is an acid-catalyzed crosslinked negative recording material described in JP-A-8-276558. U.S. Pat. No. 2,850,445 discloses a recording material compatible with an ultraviolet or visible light laser of 300 to 700 nm.
And a large number of radical polymerization type negative recording materials as described in JP-B-44-18989.
Such a recording material utilizing radical polymerization can achieve high sensitivity, but has the problem that the adhesion between the recording layer and the support at the interface of the support is insufficient due to volume shrinkage during polymerization. there were. When such a recording material is used for a printing plate, it causes a large problem that a defect occurs in an image portion at the time of printing due to a decrease in adhesion.
At present, after image formation, the entire surface is exposed again by ultraviolet light, heat treatment, and the like are performed to enhance image adhesion.

On the other hand, a material recordable by short-wavelength light of 300 nm or less and an electron beam is particularly important as a photoresist material. In recent years, the degree of integration of integrated circuits has been further increased, and the processing of ultra-fine patterns having a line width of less than half a micron has been required even in the manufacture of semiconductor substrates such as VLSI. The wavelength used by an exposure apparatus used for lithography is becoming shorter and shorter, and far ultraviolet light or excimer laser light (XeCl, Kr
F, ArF, etc.), and the formation of an ultrafine pattern using an electron beam has been studied. In particular, electron beams are promising as light sources for next-generation pattern formation technology. The problem common to all of these image forming materials is that the adhesion to the support in the various energy irradiation sections described above is reduced. Particularly, in writing a fine pattern, the support of the recording layer having a small area is preferable. If the adhesion to the low, high sensitivity, the effect of high resolution can not be obtained sufficiently, in terms of this adhesion point is not obtained satisfactory enough, there is no conventional New technology was required.

[0004]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a negative type image forming material having improved image adhesion at various energy irradiation portions, and particularly to a solid-state laser and a semiconductor laser which emit infrared rays. An object of the present invention is to provide a negative-type image forming material which can be directly made from digital data by a computer or the like, and has good adhesion to a support and good storage stability.

[0005]

Means for Solving the Problems The present inventors focused on the layer constitution of the image forming material, formed a recording layer utilizing radical polymerization with excellent sensitivity near the exposed surface, and formed a recording layer adjacent to the support. Forming an acid-crosslinkable recording layer with excellent adhesion
The present inventors have found that the above problems can be solved and completed the present invention. That is, the image forming material of the present invention comprises, on a support, a first layer containing a compound capable of generating an acid by light or heat and a compound capable of being crosslinked by the generated acid, and having reduced alkali solubility due to the crosslinking. (Hereinafter, appropriately referred to as an acid crosslinked layer)
And a second layer containing a compound that generates a radical by light or heat and a compound capable of undergoing radical polymerization and having a reduced alkali solubility due to polymerization (hereinafter, appropriately referred to as a radical polymerization layer). It is characterized by becoming.
The image forming material preferably contains an infrared absorber from the viewpoint of improving sensitivity. The infrared absorbing agent may be contained in either or both of the acid cross-linking layer and the radical polymerization layer, or may be contained in another layer provided adjacent thereto. Further, in the present invention, that the layers are sequentially provided means that the acid cross-linking layer and the radical polymerization layer are provided on the support in this order, and other auxiliary layers are provided according to the purpose. Layers, for example, an intermediate layer,
It does not exclude the presence of a protective layer, an undercoat layer and the like.

Although the function of the present invention is not clear, first, an acid cross-linking layer is provided on a support, and a radical polymerization layer is used on the acid cross-linking layer. As the sensitivity is increased, the lower layer continuously undergoes acid-catalyzed curing with good adhesion. In addition, since the lower layer is originally made of an acid-crosslinked layer having high storage stability, the adhesion of the recording layer in the exposed area can be improved while maintaining the high sensitivity of radical polymerization. It is considered that the stability was improved. For this reason, when the image forming material of the present invention is used for a printing plate such as a lithographic printing plate, a disadvantage of the radical polymerizable recording layer, which is particularly problematic, is that there is insufficient adhesion due to volume shrinkage during polymerization. It effectively reduces image skipping (especially small spots) and printing durability caused by printing due to this, and pattern skipping during dry etching when forming small spots and isolated patterns when used as a resist. Can be prevented. In the present invention, the acid cross-linking system that cross-links and cures using an acid as a catalyst includes a cationic polymerization system that does not involve shrinkage during polymerization.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The image-forming material of the present invention is provided with an acid-crosslinked layer on a support and a radical polymerized layer in the vicinity of an exposed surface. Hereinafter, the configuration of the image forming material of the present invention will be described in detail. <Radical polymerization layer> The radical polymerization layer in the image forming material of the present invention includes a compound that generates a radical by light or heat (hereinafter, referred to as a radical generator) and a compound that can undergo radical polymerization (hereinafter, referred to as a polymerizable compound). Containing, for example, a radical is generated from a radical generator in an exposed portion by irradiation with an infrared laser or the like, which serves as an initiator, and the polymerizable compound is cured by a radical polymerization reaction,
An image area is formed. The combination of the radical generator and the polymerizable compound used here may be appropriately selected from known ones as long as the strength of the film formed by radical polymerization satisfies the requirements as an image forming material. it can. Further, in order to improve the reactivity of the radical generator, an accelerator such as an onium salt or an infrared absorber may be used in combination. Examples of the components that can be used in the radical polymerization layer include compounds described in JP-A-8-108621 as constituents of the thermopolymerizable recording layer, and compounds described in JP-A-9-108621.
In JP-A-34110, compounds described as components of the photosensitive layer can also be preferably used.

(Radical Generator) As the radical generator used in the radical polymerization layer, a known radical polymerization initiator generally used for a polymer synthesis reaction by radical polymerization can be used without particular limitation. Azobisnitrile compounds such as 2'-azobisisobutyronitrile and 2,2'-azobispropionitrile, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, perbenzoic acid-t
Organics such as -butyl, α-cumyl hydroperoxide, di-t-butyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, peracids, alkyl peroxycarbamates, nitrosoaryl acylamines Inorganic peroxides such as peroxides, potassium persulfate, ammonium persulfate and potassium perchlorate; azo or diazo compounds such as diazoaminobenzene, p-nitrobenzenediazonium, azobis-substituted alkanes, diazothioethers and arylazosulfones Compounds, tetraalkylthiuram disulfides such as nitrosophenylurea and tetramethylthiuram disulfide, diaryl disulfides such as dibenzoyl disulfide, dialkyl xanthogenic disulfides, and aryl sulfinic acid , Arylalkyl sulfones include a 1-alkanoic sulfinic acids and the like.

When the image forming material of the present invention is recorded with an infrared laser, the ultimate temperature of the exposed surface can be as high as 600 ° C. or more, depending on the energy of the laser, so that a radical generator having a large activation energy is sufficient. Sensitivity can be obtained. The activation energy for radical generation of the radical generator is preferably 30 Kcal / mol or more, and examples thereof include azobisnitrile compounds and organic peroxides. Among them, compounds which are excellent in stability at room temperature, have a high decomposition rate upon heating, and become colorless upon decomposition are preferable, and examples thereof include benzoyl peroxide and 2,2′-azobisisobutyronitrile. The above radical generators may be used alone or in combination of two or more. They are used in an amount of about 0.5 to 30% by weight, preferably 2 to 10% by weight, based on the total solid content of the radical polymerization layer. Further, a compound that generates a radical by interaction with an onium salt described later can also be suitably used. Specifically, halides (α-haloacetophenones, trichloromethyltriazines, etc.), azo compounds, aromatic carbonyl compounds (benzoin esters, ketals, acetophenones, o-acyloxyimino ketones, acylphosphine oxides) Etc.), hexaarylbisimidazole compounds, peroxides and the like.
(A-1) to (A-).
Bisimidazole derivatives disclosed as 4). The latter radical generator achieves high sensitivity by interaction with an onium salt. Examples of the onium salt that can be used in combination with the radical generator include phosphonium salts described in paragraphs [0022] to [0049] of the same publication;
Each compound includes a sulfonium salt, an iodonium salt, and an ammonium salt. The amount of the onium salt added,
Although it depends on the type and use form of the onium salt, it is preferably 0.05 to 50% by weight based on the total solid content of the image forming material.

(Polymerizable compound) As the polymerizable polymer compound which is polymerized and cured by a radical generated from a radical generator, a known monomer having a polymerizable group can be used without any particular limitation. Specific examples of such a monomer include, for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate,
Monofunctional acrylates such as hydroxypropyl acrylate and derivatives thereof or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc .; polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A diacrylate, neohydroxypivalate neoate Bifunctional acrylates such as diacrylate of ε-caprolactone adduct of pentyl glycol and derivatives thereof, or compounds in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, etc .; or trimethylolpropane tri (meth) acrylate, Pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pyrogallol tria Polyfunctional acrylic acid esters and derivatives thereof or methacrylate these acrylates such relations, can be given itaconate, crotonate, the compound was changed to maleate or the like or the like. Further, a so-called prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can also be suitably used.

[0011] In addition, JP-A-58-212994,
Nos. 61-6649, 62-46688 and 62-
No. 48589, No. 62-173295, No. 62-18
Nos. 7092 and 63-67189, JP-A-1-244
No. 891 and the like, and furthermore, "11290 Chemical Products", Chemical Daily, 286-
Compounds described on page 294, compounds described in “UV / EB Curing Handbook (Raw Materials Edition)”, Polymer Publishing Association, pages 11 to 65, and the like can also be suitably used.

Among them, compounds having two or more acrylic or methacrylic groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are desirable. In the present invention, the polymerizable compound is selected from among monomers having a polymerizable group, including those exemplified above, and prepolymers.
Two or more kinds can be used in combination. The compound having an ethylenically unsaturated group is preferably 20 to 80% by weight, more preferably 3% by weight, as a solid content in the radical polymerization layer.
It is contained in an amount of 0 to 60% by weight.

(Binder Resin) A binder resin is used in the photosensitive layer if necessary. Examples of the binder resin include polyester resin, polyvinyl acetal resin, polyurethane resin, polyamide resin, cellulose resin, olefin resin, vinyl chloride resin, (meth) acrylic resin, styrene resin, polycarbonate, and polyvinyl alcohol. , Polyvinylpyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, rubber resin and the like. Further, a resin having an unsaturated bond in the resin, for example, diallyl phthalate resin and its derivative, chlorinated polypropylene, etc., can be polymerized with the compound having an ethylenically unsaturated bond described above, and is suitably used depending on the application. Can be used. As the binder resin, one or more of the above resins can be used in combination. These binder resins are preferably used in an amount of 500 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the polymerizable compound.

(Infrared Absorber) In the present invention, the radical polymerization layer contains an infrared absorber that efficiently converts the light of an infrared laser into heat in order to improve the sensitivity of the radical generator and promote the radical polymerization reaction. Is preferred. The infrared absorber used here has a wavelength of 760 nm to 1
It is a dye or pigment that effectively absorbs infrared rays of 200 nm. Preferably, the dye or the pigment has an absorption maximum at a wavelength of 760 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, published in 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 arylbenzo (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. By using such an infrared absorber, the addition of the onium salt can be omitted or the amount added can be reduced. Specific examples (A-1 to A-56) of the infrared absorber having an onium salt structure are shown, but the present invention is not limited thereto.

[0020]

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[0021]

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[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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[0033]

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[0034]

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[0035] 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.

In the present invention, commercially available pigments and Color Index (CI) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), and "Latest Pigment" Application Technology ”(CMC
Publishing, 1986) and "Printing Ink Technology", CMC Publishing, 1984).

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 being subjected to a surface treatment, or may be used after being subjected to a 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 for producing inks and toners 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).

In addition to the above, for example, see JP-A-8-1
Compounds described as “photothermal conversion substance” in JP 08621, and compounds described as “photothermal conversion element” in JP-A-9-34110 can be used in the same manner. These dyes or pigments are used in an amount of 0.01 to the total solid content of the radical polymerization layer.
To 50% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 10% by weight for dyes, and particularly preferably 1.0 to 10% by weight for pigments. can do. The amount of the pigment or dye added is 0.01
If it is less than 50% by weight, the sensitizing effect is insufficient, and
If it is added in excess of% by weight, there is a tendency for stains to occur easily in the non-image areas during printing.

(Other Compounds) In the radical polymerization layer,
Various additives used in combination with conventionally known photopolymerizable compounds,
As long as the effects of the present invention are not impaired, they can be used as appropriate. Examples of the additive include a thermal polymerization inhibitor. Specifically, hydroquinone, pyrogallol, p-methoxyphenol, catechol, β-naphthol, 2,6-di-t-butyl
quinone-based compounds such as -p-cresol, phenolic compounds, and the like, and a total of 100 parts by weight of a polymerizable compound having an ethylenically unsaturated bond and a binder resin, 10 parts by weight or less, preferably 0.01% by weight. Used at about 5 parts by weight.

Compounds which can be added as an oxygen quencher include those described in US Pat. No. 4,772,541, column 11, lines 58 to 12;
N, N-dialkylaniline derivatives such as the compounds described in the 35th row of the column can be mentioned. In addition, a plasticizer can be used to improve the film quality. For example, phthalates, trimellitates, adipic esters, other saturated or unsaturated carboxylic esters, citrates, and epoxidation can be used. Examples include soybean oil, epoxidized linseed oil, epoxy stearates, orthophosphates, phosphites, and glycol esters.

It is also preferable to use an acid generator in combination as an additive which generates an acid upon heating to accelerate the decomposition of the radical generator. As the acid generator, those described in detail in the following description of the acid crosslinked layer can be used. The radically polymerized layer can be formed by appropriately selecting the above components, dissolving them in an appropriate solvent, and coating the solution on a support. The coating amount after drying is 0.01 to 5. 0g
/ M ² is preferred.

When an infrared absorber is added to the radical polymerization layer, it is preferable to add it so that the optical density at the recording wavelength is in the range of 0.5 to 3. Further, the radical generator, the polymerizable compound, the infrared absorber used as required, and the like may be localized in the microcapsule for the purpose of improving the sensitivity. The microcapsules used here preferably have heat responsiveness (the inclusions are released by heating at the time of exposure), and the method of forming such microcapsules is described in detail in JP-A-1-145190. Has been described.

In the radical polymerization layer, an oxygen-impermeable overcoat layer may be provided adjacent to the radical polymerization layer in order to prevent polymerization inhibition by oxygen. As a material of the overcoat layer, a water-soluble resin such as polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose and polyvinylpyrrolidone is preferable, and a film thickness of about 0.2 to 3 μm is appropriate.

[Acid Crosslinking Layer] In the acid crosslinking layer of the present invention, a compound capable of generating an acid by light or heat (hereinafter, referred to as an acid generator) and a compound capable of crosslinking by using the generated acid as a catalyst (hereinafter, referred to as an acid generator). And a binder polymer capable of reacting with the 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-forming material containing an acid-crosslinkable compound and a high-molecular-weight binder described in JP-A-11-95415 is also preferable. 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-.
Compounds having at least one bond capable of cross-linking in the presence of an acid with diazidosulfonyl chloride and an organometallic / organohalogen compound, for example, at least two functional groups such as an alkoxymethyl group, a methylol group, and an acetoxymethyl group Amino compounds having, an alkoxymethyl group as a functional group, a methylol group, at least a disubstituted aromatic compound having an acetoxymethyl group, a resole resin and a furan resin, an acrylic resin synthesized from a specific monomer, and the like. This is a photosensitive layer that can be used.

Other known recording materials applicable to a layer having a similar function include those 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. (Acid Generator) In the present invention, a compound (acid generator) that generates an acid by light or heat is defined as irradiation with infrared rays or 100 ° C.
It refers to a compound that decomposes by heating to generate an acid.
As the generated acid, pKa such as sulfonic acid and hydrochloric acid is 2
The following strong acids are preferred. 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 4,708,9
No. 25 and compounds described in JP-A-7-20629. Particularly, an iodonium salt, a sulfonium salt, and a diazonium salt having a sulfonate ion as a counter ion are preferable. Examples of the diazonium salt include diazonium compounds described in US Pat. No. 3,867,147.
The diazonium compounds described in U.S. Pat. No. 2,632,703 and JP-A-1-102456 and JP-A-1-
The diazo resin described in each publication of 102457 is also preferable. Also, US 5,135,838 and US 5,
Benzyl sulfonates described in JP 200,544 are also preferred. Further, JP-A-2-100054,
Active sulfonic acid esters and disulfonyl compounds described in JP-A-2-100055 and Japanese Patent Application No. 8-94444 are also preferable. In addition, JP-A-7-271029
Also preferred are the haloalkyl-substituted S-triazines described in Ref.

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 mentioned here can be decomposed by irradiation with ultraviolet rays, the image forming material of the present invention can record images not only by irradiation with infrared rays but also by irradiation with ultraviolet rays.

(Acid Crosslinking Agent) 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 being crosslinked by an acid, but a phenol derivative represented by the following general formula (I) (hereinafter referred to as a phenol derivative) , Where appropriate referred to as low molecular weight phenol derivatives),
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) in the molecule, and the low-molecular phenol derivative and the polynuclear compound A mixture with a type phenolic crosslinking agent and / or a resol resin is preferably used.

[0055]

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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.

[0057]

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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.

[0061]

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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.

[0064]

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Here, that the exemplified structure is a partial structure of Y means that the functional group Y having a connecting group or a terminal 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 in some patterns for convenience, for example, with functional groups, but the present invention is not limited to these. Not something.

[0069]

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[0070]

[Table 1]

[0071]

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[0072]

[Table 2]

[0073]

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[0074]

[Table 3]

[0075]

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[0076]

[Table 4]

[0077]

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[0078]

[Table 5]

[0079]

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[0080]

[Table 6]

[0081]

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[0082]

[Table 7]

[0083]

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[0084]

[Table 8]

[0085]

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[0086]

[Table 9]

[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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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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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.

[0113]

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

That is, the compound of the 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.

[0117]

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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.

[0119]

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[0120]

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These compounds are obtained by subjecting the corresponding polynuclear phenol to a methylolation reaction, and by the same route as in the scheme described above for the low molecular weight phenol derivative. 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.

The resole resin which can be used in the present invention is not particularly limited, but is disclosed in British Patent 2,082,3.
No. 39, a compound disclosed as a resole resin is preferable, and among them, a weight average molecular weight of 500 to 100,000,
Those having a number average molecular weight of 200 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 preferably 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 forming the acid-crosslinked layer is not very 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.

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

Examples of the binder polymer which can be used in the acid crosslinked layer of the present invention include a polymer having an aromatic hydrocarbon ring having a hydroxy group or an alkoxy group directly bonded to 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.

[0129]

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

[0132]

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[0133]

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A polymer having these structural units can be obtained by radical polymerization using a corresponding monomer 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. The proportion of the structural unit represented by the general formula (III) contained in the copolymer using these is 50%
It is preferably from 100 to 100% by weight, and more preferably from 60 to 100% by weight. Further, the weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000,
The number average molecular weight is preferably at least 1,000, more preferably in the range of 2,000 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 may be any of a random polymer, a block polymer, a graft polymer and the like, but are preferably a random polymer.

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 the 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.

It is preferable that this acid crosslinked layer also contains an infrared absorber from the viewpoint of improving sensitivity. As the infrared absorber that can be used in the acid crosslinked layer, the same ones as those exemplified above in the radical polymerization layer can be used. The preferred content is 0.01 to 50% by weight, preferably 0.1 to 10% by weight based on the total solid content of the acid crosslinked layer, and particularly preferably 0.5 to 10% by weight when a dye is used as an infrared absorbent. When a pigment is used, it can be particularly preferably added to the recording layer at a ratio of 1.0 to 10% by weight. 0.01% by weight of pigment or dye added
If it is less than 50%, the sensitizing effect is insufficient, and 50% by weight.
If it is added in excess of the above range, there is a tendency that stains are likely to occur in the non-image area during printing. In forming the acid crosslinked layer, various additives such as a surfactant can be used in combination for the purpose of improving applicability and film quality.

In the acid crosslinked layer according to the present invention, each of the above components is usually dissolved in a solvent and applied on a suitable support. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The amount of coating (solid content) on the support obtained after coating and drying varies depending on the application. However, in the case of a lithographic printing plate material, the acid crosslinked layer is generally 0.01 to 5.0 g / m ^2. Is preferred. As a method of applying, various methods can be used,
For example, bar coater coating, spin coating, spray coating,
Curtain coating, dip coating, air knife coating, blade coating, roll coating and the like can be mentioned. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the recording layer deteriorate.

[Support] As the image forming 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, for example, a surfactant, an organic solvent or an alkaline aqueous solution 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.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. 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 forming 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 type image forming material of the present invention can be obtained. The negative type image forming 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. After performing a heat treatment as needed, the image forming material of the present invention is preferably developed with water or an aqueous alkaline 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 forming 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 alkali 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.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum if desired. Can be subjected to conventional post-treatments such as burning, heating by a burning processor, washing with water, gumming and the like. 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.

[0153]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. [Preparation of support] 0.30mm thick aluminum plate (Material 1
050) was degreased, and the surface thereof was grained using a nylon brush and a 400 mesh pumistone-water suspension, followed by thorough washing with water. This aluminum plate was immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds to perform etching, washed with water, and further immersed in 2% HNO ₃ for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, this plate was provided with a 3 g / m ² DC anodic oxide coating at a current density of 15 A / dm ² using 7% H ₂ SO ₄ as an electrolytic solution, and then washed and dried. Next, the following undercoating solution was applied to this aluminum plate and dried at 80 ° C. for 30 seconds to obtain a support. The coating amount after drying was 10 mg / m ² .

(Undercoat liquid) ・ Phenylphosphonic acid 0.10 g ・ Polyvinylbenzoic acid (molecular weight 3000) 0.02 g ・ Methanol 40.0 g ・ Pure water 60.0 g

[Examples 1 to 9] The following acid-catalyzed crosslinked layer forming solution 1 was coated on the above-mentioned undercoated support.
After drying for an minute, an acid-catalyzed crosslinked layer was formed. The weight after drying was 0.5 g / m ² . (Solution 1 for forming acid-catalyzed crosslinked layer) 0.5 g of crosslinking agent [X] in Table 10 1.5 g of polymer [Y] in Table 10 0.20 g of acid generator [Z] in Table 10 0.15 g of infrared absorbing agent [A] No. 10 ・ Coloring agent 0.015 g (AIZEN SPLON BLUE C-RH: manufactured by Hodogaya Chemical Co., Ltd.) ・ Fluorine surfactant 0.06 g (Mecha @ Fax F-177: Large -Nippon Ink Chemical Industry Co., Ltd.)-gamma-butyrolactone 15.0 g-methanol 5.0 g-toluene 2.0 g

[0156]

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[0157]

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[0158]

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Subsequently, the following radical polymerization layer forming solution 1 was applied and dried at 130 ° C. for 30 seconds to form a radical polymerization layer on the acid-catalyzed crosslinked layer to obtain an image forming material. The weight after drying was 2.0 g / m ² in total. (Radical polymerizable layer forming solution 1)-1.0 g of polymer [P] in Table 10-0.7 g of dipentaerythritol hexaacrylate (DHPA: manufactured by Nippon Kayaku Co., Ltd.)-Radical generator [Q in Table 10 0.1 g ・ Infrared absorbent [R] rg in Table 10 ・ Additive [S] in Table 10 0.1 g ・ Acetone 15.0 g ・ Methanol 4.0 g ・ Pure water 1.0 g

[0160]

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[0161]

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[0162]

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[0163]

[Table 10]

(Comparative Examples 1 to 9) On the above-mentioned subbed support similar to that used in Example 1, a crosslinking agent, a polymer, an infrared absorbing agent, etc. were prepared in the acid-catalyzed crosslinking layer forming solution 1 as follows. Apply the formulation as described in Table 11 and apply
After drying for 1 minute, an image-forming material having only an acid-catalyzed crosslinked layer formed on a support was obtained. The weight after drying was 0.5 g / m ² .

[0165]

[Table 11]

[Comparative Examples 10 to 18] On the undercoated support similar to that used in Example 1, a radical generator, an infrared absorber and the like in the radical polymerization layer forming solution 1 are shown in Table 12 below. Apply the formulation as described and apply 130
It dried at 30 degreeC for 30 second, and obtained the image forming material which formed only the radical polymerization layer on the support body. 1.5 g after drying
/ M ² .

[0167]

[Table 12]

As described above, Examples 1 to 9 and Comparative Example 1
~ 27 kinds of photosensitive / thermal image forming materials of 18
The following evaluation was performed. [Evaluation 1 of Adhesion] Wavelength of 830 nm to 8
Scanning exposure was performed with a semiconductor laser that generates infrared rays of about 50 nm to form 100 dots having a diameter of 20 μm. After exposure, the panel was heated at 110 ° C. for 15 seconds using a panel heater.
Then, DP-4 developed by Fuji Photo Film Co., Ltd.
(1: 8 water dilution). Attach a commercially available cellophane tape to the image area obtained at this time and apply 0.2 kg / cm ²
The film is peeled off after applying the load for 30 minutes. The number of dots remaining on the support after peeling was counted and used as an index of adhesion.

(Evaluation of Adhesion 2: Printing Durability) The image forming material was scanned and exposed with a semiconductor laser that emits infrared light having a wavelength of about 830 nm to 850 nm, and was exposed to 1% halftone dots (highlight).
After the exposure, a heat treatment was performed at 130 ° C. for 75 seconds with a panel heater. Thereafter, development was carried out using a developing solution manufactured by Fuji Photo Film Co., Ltd., DP-4 (a 1: 8 water diluent). The photosensitive material obtained at this time was used as a printing plate and Heidel KO was used.
After printing with an R-D machine, the number of finished sheets was used as an index of adhesion, and a relative comparison was made using Example 2 which is at a practically preferable level as a reference (100). From the viewpoint of production, those having an index of 100 or more are favorable and preferable.

(Evaluation of Storage Stability) The above-mentioned image forming material before laser exposure was subjected to a high humidity condition (75% RH, 45 ° C.).
After storage for a day, the sensitized material after storage was printed in the same manner as described above, and the non-image area was examined for stains. Those having poor storage stability, image forming property and developing property are deteriorated, and non-image areas are stained. Table 13 also shows these evaluation results.

[0171]

[Table 13]

From Table 13, it was confirmed that the photographic material of the present invention had high adhesion (high printing durability) and good storage stability.

[0173]

The image-forming material of the present invention has excellent adhesion between the support and the recording layer in the irradiated part of various energies,
In particular, using an infrared laser, a negative-type image forming material that can be directly made from digital data from a computer or the like, has good adhesion to a support, and has excellent characteristics of good storage stability. It is.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA02 AA11 AA14 AB03 AB13 AC08 AD01 BC13 BC31 BE00 CA00 CC11 CC17 DA13 DA35 DA40 FA10 2H096 AA06 AA23 BA05 BA20 CA05 EA04 EA23 2H114 AA04 BA02 BA05 FA10 GA05

Claims (2)

[Claims] 1. A first layer containing a compound capable of generating an acid by light or heat and a compound capable of being cross-linked by the generated acid on a support, wherein the first layer has a reduced alkali solubility due to the cross-linking. An image forming material comprising: a second layer containing a compound capable of generating a radical by the method and a compound capable of undergoing radical polymerization, and having a reduced alkali solubility due to the polymerization. 2. The image forming material according to claim 1, wherein the image forming material contains an infrared absorbing agent.