JP2003005366A - Planographic printing original plate for heat mode laser pattern forming - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem of a performance enhancing technique in microfabrication of a semiconductor device using an electron beam or X-ray and to provide a negative type resist composition for an electron beam or X-ray satisfying such characteristics as sensitivity and resist shape when an electron beam or X-ray is used. SOLUTION: The negative type resist composition contains (A) a compound which generates an acid when irradiated with an electron beam or X-ray, (B) a resin soluble in an aqueous alkali solution and (D) at least one compound represented by a specified structure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a negative lithographic printing plate precursor comprising a support having a hydrophilic surface and a hydrophilic image forming layer. More specifically, the present invention relates to a lithographic printing plate precursor capable of producing a plate by scanning exposure based on a digital signal, and having high sensitivity and high printing durability and capable of giving a printed material having no residual color or stain.

[0002]

2. Description of the Related Art In recent years, digitization techniques for electronically processing, accumulating and outputting image information using a computer have become widespread, and various new image output methods corresponding to such digitization techniques are available. It is becoming practical. Along with this, computer-to-plate (CTP) technology, which scans active radiation having a high directivity such as laser light according to digitized image information and directly produces a printing plate without passing through a lith film, has long been desired. However, obtaining an original plate for a printing plate adapted to this has become an important technical issue.

On the other hand, in recent years, consideration of the global environment has become a great concern of the entire industry, and there has been a demand for simplification of processing in the plate making process, dry processing, and no processing. There is. Therefore, the development of a technology provided with both the environmental conservation suitability of the printing / plate-making system and the suitability of the digitized information processing system has been strongly desired more than ever before.

From this point of view, as one of the methods for eliminating the conventional processing steps, a lithographic printing plate making method for obtaining a final printing plate by developing it on a printing machine after exposure, that is, an on-press developing method. However, it is being accepted. However,
When applying a conventional PS plate to an on-press development printing plate,
Since the photosensitive layer is not fixed on the original plate even after exposure, for example,
There was a big problem that the plate had to be completely protected from light and / or kept at a constant temperature until it was mounted on the printing machine.

In response to the above technical problems, recently, as a method of manufacturing a printing plate by scanning exposure, a semiconductor laser, YA
Since high-power solid-state lasers such as G lasers have become available at low cost, methods using these lasers have been particularly promising. In a high power density exposure system using these high-power lasers, in many cases, the light energy absorbed in the photosensitive material is converted into heat, and the generated heat causes a desired phenomenon, resulting in a low level of light intensity. Images that utilize various thermal phenomena different from the photoreactions used in light-sensitive material systems for medium power density exposure, specifically, structural changes such as phase changes and morphological changes in addition to chemical changes Recording is done. Generally, a recording method in which light received by such high power density exposure is converted into energy and thermally recorded is called heat mode recording.

A major advantage of the heat mode recording system is that fixing of an image after exposure is not essential. That is, the heat mode photosensitive material does not substantially change under irradiation with light having a normal intensity for the photon mode photosensitive material or at a normal environmental temperature, so that fixing of the image after exposure is not essential. Therefore, according to the heat mode recording, it is possible to obtain a lithographic printing plate precursor which is desirable for the on-press development method described above.

As one of the preferable methods for producing a lithographic printing plate based on heat mode recording, a hydrophilic image forming layer is provided on a hydrophilic support, and the image is exposed to heat mode to expose the hydrophilic layer for dissolution. A method has been proposed in which dispersibility is changed and, if necessary, the unexposed portion is removed by wet development.
However, the conventional heat mode system original plate has another serious problem that the non-image part has poor stain resistance or the image part has low strength. One of the causes is that the change in solubility due to exposure in the vicinity of the support in the image forming layer is smaller than that in the vicinity of the surface of the image forming layer, and the improvement was necessary. In this heat mode method original plate, since the heat generation during the heat mode exposure is based on the light absorption of the light absorber in the recording layer, the heat generation amount is large on the recording layer surface and small in the vicinity of the support. Therefore, the degree of change in solubility of the recording layer in the vicinity of the support becomes relatively small. As a result, in the heat mode negative type master plate, the ink receiving layer may be removed during the developing and / or printing process in the exposed portion where the originally hydrophobic ink receiving region should be formed. Such removal of the ink-receptive layer in the image area of the negative original plate causes problems such as deterioration of printing durability and increase of printing stains in terms of printing performance. In particular, when a metal support having high thermal conductivity such as an aluminum plate, which is preferable in terms of printability, is used, thermal diffusion further hinders the temperature rise due to exposure in the vicinity of the support, and thus the above-mentioned print stains are prevented. Increase and decrease in printing durability are remarkable. In order to obtain a sufficient change in the solubility in the vicinity of the substrate, extremely large exposure energy was required, or post-treatment such as heating after exposure had to be performed.

For example, as described in Japanese Patent No. 2938397, thermoplastic hydrophobic polymer fine particles are thermally fused by infrared laser exposure to form an image,
There is a method of mounting the plate on a cylinder of a printing machine and performing on-press development with dampening water and / or ink. However, in such a method of simply forming an image by heat fusion, although a good on-press developability is exhibited, when a heat-sensitive layer is directly provided on an aluminum substrate, the heat generated is absorbed by the aluminum substrate, so that the substrate- Fusing does not occur on the interface of the heat-sensitive layer, resulting in insufficient printing durability. Similarly, JP-A-9-
No. 127683 or WO99 / 10186 also describes that thermoplastic fine particles are heat-sealed to form an image by on-press development, but similarly, printing durability becomes insufficient.

[0009]

As described above, a heat-sensitive photosensitive material having good on-press developability, high sensitivity, and high printing durability can be obtained in spite of strong market demand. I haven't got it yet. Therefore, an object of the present invention is to solve them, and specifically, after recording an image in a heat mode, it can be mounted on a printing machine as it is without being developed, and a lithographic printing plate precursor can be printed. It is also an object of the present invention to provide a lithographic printing plate precursor capable of giving a printed matter having high sensitivity, good printing durability, and no stain.

[0010]

Means for Solving the Problems In order to achieve the above object, the inventors of the present invention have keenly searched for a means for increasing the strength of a binding medium by a heat mode crosslinking reaction, and have searched for it, and planed it. As a result of studying application to the present invention, the inventors have found that the problems of the invention can be solved by the following, and have completed the present invention. That is, the present invention is as follows.

(1) On a support having a hydrophilic surface,
A layer containing resin fine particles and microcapsules is provided, and the microcapsules are characterized by including a compound having a reactive group that is bonded to the reactive group of the resin fine particles by the action of heat. Heat mode Master plate for lithographic printing plate for laser drawing.

(2) On a support having a hydrophilic surface, a layer containing fine resin particles and a layer containing microcapsules are provided in this order, and the microcapsules have A lithographic printing plate precursor for heat mode laser drawing, which comprises a compound having a reactive group which is bonded to the reactive group.

According to the lithographic printing plate precursor of the present invention, heat in the heat mode is not generated in the unexposed portion, and therefore,
The reaction between the reactive group of the resin fine particles (hereinafter referred to as reactive group A) and the reactive group of the microcapsule-encapsulating compound (hereinafter referred to as reactive group B) does not occur, and the resin fine particles and micro The capsules retain their morphology and the layers containing them can be easily removed from the support by water and / or ink. on the other hand,
In the exposed portion, thermal energy generated by photothermal conversion of light energy of irradiation light progresses fusion of the resin fine particles having the reactive group A, and the microcapsules are destroyed or the holes of the microcapsule wall are enlarged. By doing so, the compound having the reactive group B is released.
The released compound having the reactive group B reacts with the resin fine particles having the reactive group A to form a bond between the resin having the reactive group A and the compound having the reactive group B. Therefore, a three-dimensional crosslinked coating film in which the resin having the reactive group A is connected to the compound having the reactive group B is formed. In addition, since the layer containing the microcapsules encapsulating the resin fine particles having the reactive group A and the compound having the reactive group B is substantially composed of the resin fine particles and the microcapsule particles, voids are present in the layer. It has a sparse structure with some parts. Therefore, since the compound having the reactive group B penetrates to the substrate through this sparse structure, the resin fine particles having the reactive group A existing in the vicinity of the substrate also undergo a binding reaction with the compound having the reactive group B. You can keep it. Therefore, in the exposed portion, the image portion of the crosslinked coating firmly bonded in the depth direction is formed, so that a printing plate having extremely high printing durability can be obtained without being removed on the printing machine.

Further, since the lithographic printing plate precursor of the invention can form an image only by destroying at least the microcapsules, if the photothermal conversion dye is contained in the microcapsules, the image can be formed with very little exposure energy. Can be formed. Further, in the lithographic printing plate precursor of the form in which the layer containing microcapsules is provided on the layer containing fine particles, the thermal diffusion to the aluminum substrate is blocked by the layer containing fine particles, so that the energy consumption is further reduced. With this, image formation becomes possible. For the above reasons, the lithographic printing plate precursor of the present invention is capable of image formation with very little exposure energy, by recording using a solid-state laser and a semiconductor laser that emits infrared light, digital data of a computer or the like. A lithographic printing plate that can be directly plate-made from the above, has good printing durability, and is free from stains.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The lithographic printing plate precursor according to the present invention comprises a support having a hydrophilic surface and a layer containing microcapsules containing organic resin fine particles having a reactive group A and a compound having a reactive group B provided on the support. A lithographic printing plate precursor.
In the constitution of the printing plate precursor for the printing plate of the present invention, the resin fine particles and the microcapsules may be contained in the same layer or may be contained in another layer. In the latter case, the microcapsule layer may be on the support side or may be the upper layer. However, for the reasons described above, it is preferable that the microcapsule layer is the upper layer because it is advantageous in terms of sensitivity. Also,
A photothermal conversion agent which is a photosensitizer, for example, an infrared absorbing dye, may be contained in microcapsules, may be added in the microcapsule layer, or may be contained in the resin fine particle layer, and It may be included in one or more of them. When it is contained in the microcapsule layer, thermal destruction or embrittlement of the microcapsule wall occurs sensitively, which is advantageous. At the same time, the sensitivity can be further improved by allowing a photothermal conversion agent to be present near the microcapsules. In the following description of the present specification, each of the microcapsule-containing layer and the resin fine particle-containing layer, or a combination thereof, or a layer containing both microcapsules and resin fine particles may be referred to as an image forming layer. A layer substantially containing a heat-sensitive agent, such as a layer containing microcapsules containing a heat-sensitive agent, is also called a heat-sensitive layer. The individual components of the lithographic printing plate precursor according to the invention will be described below. First, the reactive group A and the reactive group B will be described.

[Reactive Group A and Reactive Group B] The reactive group A and the reactive group B introduced into the organic resin particles and the microcapsule-encapsulating compound used in the present invention are, respectively,
It is a functional group characterized in that it is a combination which is bonded to each other by a reaction represented by the following formula.

[0017]

[Chemical 1]

That is, the reactive group A and the reactive group B react with each other to form a new linking group C,
It is a functional group that bonds the residue R ^{1 of} the polymer compound (1) forming the resin fine particles and the residue R ² of the compound (2) included in the microcapsule. In the present invention, any combination of such functional groups can be preferably used, but from the viewpoint of sensitivity, the functional groups in which the above reaction proceeds at a temperature of 300 ° C. or lower. Sets are particularly preferred.

Specific examples of the reactive group used in the present invention as shown in the above reaction formula include a functional group such as a carbon-carbon double bond which carries out a polymerization reaction, an isocyanate group or a block thereof. Body and functional groups having active hydrogen atoms (eg amino groups, hydroxyl groups, carboxyl groups, hydrazide groups, hydrazine groups, thiol groups, amide groups, etc.), epoxy groups and functional groups having active hydrogen atoms, lactone groups and active hydrogen atoms A functional group having an addition reaction such as an oxazoline group and a functional group having an active hydrogen atom, or an active ester group (for example, N-hydroxyphthalimide ester group, N-hydroxysuccinimide ester group, p- Nitrophenyl ester group, p-chlorophenyl ester group, p-methoxycarbonylphenyl ester group,
p-sulfonium phenyl ester group, -CONHCH
(OMe) COOMe group) and a functional group having an active hydrogen atom (for example, a hydroxyl group, an amino group having at least one hydrogen atom, a thiol group, a hydrazine group, a hydrazide group, an amide group, etc.), an acid halide group And a functional group having an active hydrogen atom, a combination of an acid anhydride group and a functional group having an active hydrogen atom, a leaving group that causes a nucleophilic substitution reaction (for example, a halogen atom, an alkylsulfonyloxy group, an arylsulfonyloxy group, Azido group) and nucleophilic groups (eg, hydroxyl group, amino group,
A combination of a thiol group, a sulfide group, a phosphino group, a hydrazine group, a hydrazide group, an amide group, etc., and a combination of reactive groups for dehydration condensation [eg, a heterocyclic group having an unsaturated bond in the ring (eg, N- An alkylindole group, an N-alkylpyrrole group, an N-alkylimidazole group, a furanyl group, an oxazole group, etc.) and a carbonyl group, a heterocyclic group and an acetal group having an unsaturated bond in the ring, and a phenol having a hydrogen at the ortho position. Group and a phenol group having a hydroxymethyl group at the ortho position, a phenol group having a hydrogen at the ortho position and an aniline group having a hydroxymethyl group at the ortho position, a carboxyl group and an N-methylol group, a carboxyl group and an N-alkoxymethyl group, Carbonyl group and hydrazide group, primary amino group, hydrazine group, ketimine group] Combination, may be mentioned condensation reaction or the like, such as a combination of a diazo group and an active methylene group, they what combination with or reactive groups if chemical bond is formed.

[Resin Fine Particles Having Reactive Group] Next, the resin fine particles having a reactive group will be described. The resin fine particles having a reactive group used in the lithographic printing plate precursor of the present invention are resin fine particles in which the polymer compound having a functional group described above is finely divided and exists in a dispersed state. Such resin fine particles can also be obtained by emulsion polymerization or suspension polymerization of the above-mentioned functional group-containing monomer, or after dissolving the above-mentioned functional group-containing polymer compound in an organic solvent, an emulsifier or dispersion. It can also be obtained by emulsifying and dispersing in water with the agent and then evaporating the organic solvent. Further, the polymer compound having the above functional group is obtained by polymerizing the monomer having the above functional group in an organic solvent as usual, or polymerizing the monomer having a functional group derivable to the above functional group as usual. It can be obtained by derivatizing the inducible functional group in the obtained polymer compound into the above functional group by a polymer reaction. Specific examples of the monomer having the above functional group used for synthesizing the resin fine particles having a reactive group used in the present invention and the monomer having a functional group derivable to the above functional group are as follows. And various monomers. However, the present invention is not limited to these.

[0021]

[Chemical 2]

[0022]

[Chemical 3]

[0023]

[Chemical 4]

The resin having a reactive group used in the present invention can be obtained by polymerizing these monomers alone or copolymerizing two or more kinds thereof. Further, the resin having a reactive group used in the present invention is not particularly limited as long as it has the reactive group as described above, and may have a functional group other than the reactive group. Therefore, even a copolymer with a monomer having a functional group other than the reactive group can be suitably used as long as the effect of the present invention is not impaired. Examples of the radically polymerizable monomer that can be used as the copolymerization component include the following monomers.

Radical-polymerizable monomers used when the resin fine particles are a copolymer include acrylic acid, acrylic acid esters, acrylamides, methacrylic acid, methacrylic acid esters, methacrylamides, maleic acid, Maleic anhydride, maleic acid esters, maleic acid amides, maleic acid imides, itaconic acid, itaconic anhydride, itaconic acid esters, itaconic acid amides, itaconic acid imides, crotonic acid, crotonic acid esters, Crotonic acid amides, fumaric acid,
Fumaric acid esters, fumaric acid amides, mesaconic acid,
Mesaconic acid esters, Mesaconic acid amides, α, β-
Unsaturated lactones, α, β-unsaturated lactams, unsaturated hydrocarbons, vinyl ethers, vinyl esters,
Known monomers such as α, β-unsaturated ketones and styrenes can be mentioned.

Specific examples of acrylic acid esters include:
Methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate , Amyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate , Benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxyben Acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl acrylate, etc. .

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N- (n- or i-) propylacrylamide, N- (n-, i-, sec- or t-). Acrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N -
(Tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like can be mentioned.

Specific examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate,
(N- or i-) propyl methacrylate, (n-, i-,
sec- or t-) butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, amyl methacrylate,
2-ethylhexyl methacrylate, dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxy Benzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, Sulfamoyl phenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N- (n- or i-) propylmethacrylamide, N- (n-, i-, sec. -Or t-) methacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N-phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) Methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-
Examples thereof include methyl-N-phenylmethacrylamide and N-hydroxyethyl-N-methylmethacrylamide.

Specific examples of crotonic acid esters include:
Methyl crotonate, ethyl crotonate, (n- or i-) propyl crotonate, (n-, i-, sec- or t-) butyl crotonate, pentyl crotonate, hexyl crotonate, heptyl crotonate, octyl Crotonate, nonyl crotonate, decyl crotonate, amyl crotonate, 2-ethylhexyl crotonate, dodecyl crotonate, chloroethyl crotonate, 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 5-hydroxypentyl crotonate , Cyclohexyl crotonate, allyl crotonate, trimethylolpropane monocrotonate, pentaerythritol monocrotonate, benzyl crotonate, methoxybenzyl crotonate, chlorobenzyl crotonate, hydroxyben Lucrotonate, hydroxyphenethyl crotonate, dihydroxyphenethyl crotonate, furfuryl crotonate, tetrahydrofurfuryl crotonate, phenyl crotonate, hydroxyphenyl crotonate, chlorophenyl crotonate, sulfamoylphenyl crotonate, 2- (hydroxyphenylcarbonyloxy) ) Ethyl crotonate and the like.

Specific examples of crotonic acid amides include crotonic acid amide, N-methyl crotonic acid amide, N-ethyl crotonic acid amide, N- (n- or i-) propyl crotonic acid amide, N- (n- , I-, sec- or t-) crotonic acid amide, N-benzyl crotonic acid amide, N-hydroxyethyl crotonic acid amide, N-phenyl crotonic acid amide, N-tolyl crotonic acid amide, N- (hydroxyphenyl) crotone Acid amide, N- (sulfamoylphenyl) crotonic acid amide, N- (phenylsulfonyl) crotonic acid amide, N- (tolylsulfonyl) crotonic acid amide, N, N-dimethylcrotonic acid amide, N-
Examples thereof include methyl-N-phenylcrotonic acid amide and N-hydroxyethyl-N-methylcrotonic acid amide.

Specific examples of maleic acid esters include:
Dimethyl maleate, diethyl maleate, di (n- or i-) propyl maleate, di (n-, i-) maleate
sec- or t-) butyl, diphenyl maleate, diallyl maleate, monomethyl maleate, monoethyl maleate, mono (n- or i-) propyl maleate, mono (n-, i-, sec- or maleate. -) Butyl, dibenzyl maleate, monobenzyl maleate, methyl ethyl maleate, methyl propyl maleate, ethyl propyl maleate and the like.

Specific examples of maleic acid amides include maleic acid amide, N-methyl maleic acid amide, N-ethyl maleic acid amide, N- (n- or i-) propyl maleic acid amide, N- (n- , I-, sec- or t-) butyl maleic acid amide, N-benzyl maleic acid amide,
N-hydroxyethyl maleic acid amide, N-phenyl maleic acid amide, N-tolylmaleic acid amide, N- (hydroxyphenyl) maleic acid amide, N- (sulfamoylphenyl) maleic acid amide, N- (phenylsulfonyl) Maleic acid amide, N- (tolylsulfonyl) maleic acid amide, N, N-dimethyl maleic acid amide, N-methyl-N-phenyl maleic acid amide, N-hydroxyethyl-N-methyl maleic acid amide, N-methyl maleic acid amide Examples thereof include acid monoamide, N-ethylmaleic acid monoamide, N, N-dimethylmaleic acid monoamide, N-methyl-N′-ethylmaleic acid amide and N-methyl-N′-phenylmaleic acid amide.

Specific examples of maleic imides include maleic imide, N-methyl maleic imide, N-ethyl maleic imide, N- (n- or i-) propyl maleic imide, N- (n- , I-, sec- or t-) butyl maleic imide, N-benzyl maleic imide,
N-hydroxyethyl maleic acid imide, N-phenyl maleic acid imide, N-tolylmaleic acid imide, N- (hydroxyphenyl) maleic acid imide, N- (sulfamoylphenyl) maleic acid imide, N- (phenylsulfonyl) Examples thereof include maleic acid imide and N- (tolylsulfonyl) maleic acid imide.

Specific examples of itaconic acid esters include:
Dimethyl itaconic acid, diethyl itaconic acid, di (n- or i-) propyl itaconic acid, di (n-, i-) itaconic acid
sec- or t-) butyl, diphenyl itaconate, diallyl itaconate, monomethyl itaconate, monoethyl itaconate, mono (n- or i-) propyl itaconate, mono (n-, i-, sec- or itaconate itaconate -) Butyl, dibenzyl itaconate, monobenzyl itaconate, methylethyl itaconate, methylpropyl itaconate, ethylpropyl itaconate and the like.

Specific examples of itaconic acid amides include itaconic acid amide, N-methylitaconic acid amide, N-ethylitaconic acid amide, N- (n- or i-) propyl itaconic acid amide, and N- (n- , I-, sec- or t-) butyl itaconic acid amide, N-benzyl itaconic acid amide,
N-hydroxyethylitaconic acid amide, N-phenylitaconic acid amide, N-tolylutaconic acid amide, N- (hydroxyphenyl) itaconic acid amide, N- (sulfamoylphenyl) itaconic acid amide, N- (phenylsulfonyl) Itaconic acid amide, N- (tolylsulfonyl) itaconic acid amide, N, N-dimethylitaconic acid amide, N-methyl-N-phenylitaconic acid amide, N-hydroxyethyl-N-methylitaconic acid amide, N-methylitacone Examples thereof include acid monoamide, N-ethylitaconic acid monoamide, N, N-dimethylitaconic acid monoamide, N-methyl-N′-ethylitaconic acid amide, and N-methyl-N′-phenylitaconic acid amide.

Specific examples of the itaconic acid imides include itaconic acid imide, N-methylitaconic acid imide, N-ethylitaconic acid imide, N- (n- or i-) propyl itaconic acid imide, and N- (n- , I-, sec- or t-) butylitaconimide, N-benzylitaconimide,
N-hydroxyethyl itaconic acid imide, N-phenyl itaconic acid imide, N-tolulytaconic acid imide, N- (hydroxyphenyl) itaconic acid imide, N- (sulfamoylphenyl) itaconic acid imide, N- (phenylsulfonyl) Examples thereof include itaconic acid imide and N- (tolylsulfonyl) itaconic acid imide.

Specific examples of the fumarate esters include dimethyl fumarate, diethyl fumarate, and di (n-fumarate).
Or i-) propyl, di (n-, i-, sec- or t-) butyl fumarate, diphenyl fumarate, diallyl fumarate, monomethyl fumarate, monoethyl fumarate, monofumarate (n- or i-) Propyl, fumarate mono (n-,
i-, sec- or t-) butyl, dibenzyl fumarate,
Examples include monobenzyl fumarate, methylethyl fumarate, methylpropyl fumarate, ethylpropyl fumarate and the like.

Specific examples of fumaric acid amides include fumaric acid amide, N-methyl fumaric acid amide, N-ethyl fumaric acid amide, N- (n- or i-) propyl fumaric acid amide, N- (n-, i -, Sec- or t-) butyl fumarate amide, N-benzyl fumarate amide, N-hydroxyethyl fumarate amide, N-phenyl fumarate amide, N-
Tolyl fumarate amide, N- (hydroxyphenyl) fumarate amide, N- (sulfamoylphenyl) fumarate amide, N- (phenylsulfonyl) fumarate amide, N- (tolylsulfonyl) fumarate amide, N, N-
Dimethyl fumarate amide, N-methyl-N-phenyl fumarate amide, N-hydroxyethyl-N-methyl fumarate amide, N-methyl fumarate monoamide, N-ethyl fumarate monoamide, N, N-dimethyl fumarate monoamide, N- Methyl-N'-ethyl fumarate amide, N-methyl
-N'-phenyl fumarate amide and the like can be mentioned.

Specific examples of mesaconic acid esters include:
Dimethyl mesaconate, diethyl mesaconate, di (n- or i-) propyl mesaconate, di (n-, i-, mesaconate
sec- or t-) butyl, diphenyl mesaconate, diallyl mesaconate, monomethyl mesaconate, monoethyl mesaconate, mono (n- or i-) propyl mesaconate, mono (n-, i-, sec- or t-mesaconate -) Butyl, dibenzyl mesaconate, monobenzyl mesaconate, methylethyl mesaconate, methylpropyl mesaconate, ethylpropyl mesaconate and the like.

Specific examples of mesaconic acid amides include mesaconic acid amide, N-methyl mesaconic acid amide, N-ethyl mesaconic acid amide, N- (n- or i-) propyl mesaconic acid amide, N- (n-, i-, sec- or t-) butyl mesaconic acid amide, N-benzyl mesaconic acid amide,
N-hydroxyethyl mesaconic acid amide, N-phenyl mesaconic acid amide, N-tolyl mesaconic acid amide, N- (hydroxyphenyl) mesaconic acid amide, N- (sulfamoylphenyl) mesaconic acid amide, N- (phenylsulfonyl ) Mesaconic acid amide, N- (tolylsulfonyl) mesaconic acid amide, N, N-dimethyl mesaconic acid amide, N-methyl-N-phenyl mesaconic acid amide, N-hydroxyethyl-N-methyl mesaconic acid amide, N- Examples thereof include methyl mesaconic acid monoamide, N-ethyl mesaconic acid monoamide, N, N-dimethyl mesaconic acid monoamide, N-methyl-N'-ethyl mesaconic acid amide, N-methyl-N'-phenyl mesaconic acid amide and the like.

Specific examples of styrenes include styrene,
Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Examples thereof include iodostyrene, fluorostyrene, carboxystyrene, sodium 4-vinylbenzenesulfonate and the like. The following compounds may be mentioned as specific examples of the α, β-unsaturated lactones.

[0043]

[Chemical 5]

Specific examples of α, β-unsaturated lactams include the following compounds.

[0045]

[Chemical 6]

Specific examples of unsaturated hydrocarbons include the following compounds.

[0047]

[Chemical 7]

Specific examples of vinyl ethers include the following compounds.

[0049]

[Chemical 8]

Specific examples of the vinyl esters include the following compounds and the like.

[0051]

[Chemical 9]

Specific examples of the α, β-unsaturated ketones include the following compounds.

[0053]

[Chemical 10]

The proportion of the monomer having a reactive group used for synthesizing the resin having a reactive group used in the present invention is preferably 5 mol% or more, more preferably 10 mol% or more of all the constituent monomers. . If 5 mol% or more of the monomer having a reactive group is used, the reactive group B
And can be sufficiently crosslinked. The ratio of the monomer when another monomer having no reactive group is used to form a copolymer may be any ratio as long as the monomer having a reactive group is used in a preferable ratio. . Only one type of these other copolymerizable monomers may be used, or two or more types may be mixed and used.

Specific examples of the resin having a reactive group used in the present invention are shown below. However, the present invention is not limited to these. The following specific examples show repeating structural units, and the subscripts indicate the molar ratio of each repeating structural unit,
Those without a subscript indicate a resin composed only of the indicated repeating structural unit.

[0056]

[Chemical 11]

[0057]

[Chemical 12]

[0058]

[Chemical 13]

[0059]

[Chemical 14]

[0060]

[Chemical 15]

The weight average molecular weight of the resin having a reactive group used in the lithographic printing plate precursor of the present invention measured by GPC is preferably 2,000 or more, more preferably 5,000 to 1,000,000. The number average molecular weight is preferably 800 or more, more preferably 10
The range is from 00 to 1,000,000. The polydispersity (= weight average molecular weight / number average molecular weight) is preferably 1 or more, and 1.1 to 1
The range of 0 is more preferable. The resin having these reactive groups may be any of a random polymer, a block polymer, a graft polymer, etc., but a random polymer is preferable.

Solvents used when synthesizing the resin having a reactive group and the fine particles thereof used in the lithographic printing plate precursor of the invention include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N
-Dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, ethyl lactate, methyl lactate,
Dimethyl sulfoxide, water, etc. may be mentioned. You may use these solvent individually or in mixture of 2 or more types.

As the radical polymerization initiator used when synthesizing the polymer compound having a reactive group constituting the resin fine particles used in the lithographic printing plate precursor of the present invention, an azo-based initiator and a peroxide are used. Known compounds such as an initiator can be used. The heat softening temperature of the resin fine particles having these reactive groups is preferably 70 ° C. or higher, but more preferably 100 ° C. or higher in consideration of stability over time. The average particle size of the resin fine particles having these reactive groups is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm. When the average particle size is in the range of 0.01 to 20 μm, a lithographic printing plate precursor having good resolution, stability over time, and developability can be obtained. The content of the resin fine particles having a reactive group used in the lithographic printing plate precursor of the present invention in the image forming layer, in terms of solid content,
The amount is preferably 10 to 80% by weight or more, more preferably 20 to 70% by weight. Within this range, good on-press developability, sensitivity and printing durability can be obtained.

[Microcapsules Encapsulating Compound Having Reactive Group] Next, microcapsules encapsulating a compound having a reactive group will be described. The compound having a reactive group encapsulated in the microcapsules used in the present invention has a reactive group shown as a combination of the reactive groups involved in the reaction of the polymer compound (1) and the compound (2) described above. Any compound can be preferably used. In the lithographic printing plate precursor of the invention, the compound having a reactive group released from the microcapsules reacts with the resin fine particles having a reactive group to form an image, so that the microcapsules are encapsulated. As the compound having a reactive group, a compound having a melting point of 100 ° C. or lower is particularly preferable, but even a compound having a melting point of 100 ° C. or higher is suitable by dissolving it in a suitable solvent and encapsulating it in a microcapsule. Can be used. Among the compounds having a reactive group contained in such microcapsules, specific examples of the polymer compound include the polymer compounds constituting the resin fine particles described above.
On the other hand, as the low molecular weight compound, any compound having two or more reactive groups in the molecule as described above can be preferably used, and specific examples thereof include the following compounds. To be The present invention is not limited to these.

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

The microcapsule containing the compound having a reactive group used in the present invention may be any microcapsule as long as it contains the high molecular compound and / or the low molecular compound having the above reactive group. It can be used preferably. As a method of microencapsulating the compound having the reactive group, a known method can be applied.

For example, as an example of a method for producing microcapsules, US Pat.
Method utilizing coacervation, which is found in U.S. Pat. No. 5,839,099, British Patent 990443, U.S. Pat.
Method by the interfacial polymerization method found in US Pat. No. 11, US Pat.
No. 18250, No. 3660304, a method by precipitation of a polymer, a method using an isocyanate polyol wall material found in US Pat. No. 3,796,669, a method using an isocyanate wall material found in US Pat. No. 3,914,511, US Pat. 4087
No. 40254, Urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall forming materials found in U.S. Pat.
No. 45, a method using a wall material such as melamine-formaldehyde resin and hydroxycellulose, JP-B-36.
No. 9163, No. 51-9079, in-situ method by monomer polymerization, British patent No. 930422, spray drying method seen in US Pat. No. 3,111,407, electrolytic dispersion cooling method seen in British patent Nos. 952807, 967074, etc. However, the present invention is not limited to these.

The preferred microcapsule wall used in the present invention has a function of causing changes such as expansion, destruction, melting and the like due to heat to release the inclusion. From this point of view, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, or a mixture thereof, particularly preferably polyurea or polyurethane. The average particle size of the microcapsules is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm. If the average particle size is 0.01 μm or more, the on-press developability and stability over time are good, and if the average particle size is 20 μm or less, the resolution is good. The content of the microcapsules containing the compound having a reactive group used in the lithographic printing plate precursor of the invention in the image forming layer is preferably 10 to 80% by weight or more in terms of solid content, and 20 to 70% by weight. % Or more is more preferable. Within this range, good on-press developability, sensitivity and printing durability can be obtained.

When the microcapsules are added to the heat-sensitive layer, a solvent that dissolves the inclusions and swells the wall material can be added to the microcapsule dispersion medium. Such a solvent promotes the diffusion of the encapsulated compound having the heat-reactive functional group to the outside of the microcapsules. Such a solvent depends on the microcapsule dispersion medium, the material of the microcapsule wall, the wall thickness and the inclusions, but can be easily selected from many commercially available solvents. For example, cross-linked polyurea, in the case of water-dispersible microcapsules consisting of polyurethane walls, alcohols,
Ethers, acetals, esters, ketones, polyhydric alcohols, amides, amines, fatty acids and the like are preferable.

Specific compounds include methanol, ethanol, tert-butanol, n-propanol, tetrahydrofuran, methyl lactate, ethyl lactate, methyl ethyl ketone, propylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, γ-butyl lactone. , N, N-dimethylformamide, N, N-dimethylacetamide and the like, but are not limited thereto. Moreover, you may use 2 or more types of these solvents.

A solvent that does not dissolve in the microcapsule dispersion but dissolves if the above solvent is mixed can be used. The addition amount depends on the combination of the constituent components, but if it is less than the appropriate value, image formation becomes insufficient, and if it is more than the appropriate value, the stability of the dispersion liquid deteriorates. Usually, 5 to 95% by weight of the coating solution is effective, a preferable range is 10 to 90% by weight, and a more preferable range is 15 to 85%.
% By weight.

[Others] Next, other components contained in the image forming layer of the lithographic printing plate precursor according to the invention will be described. (Photothermal conversion agent) In many aspects of the lithographic printing plate precursor according to the invention, the photothermal conversion agent is encapsulated in microcapsules. Is. In addition, a mode in which the photothermal conversion agent is added to the resin fine particle layer can be employed. The heat sensitive layer is usually also the image forming layer. When the image forming layer contains a photothermal conversion material, image writing can be performed by laser light irradiation. As a special example, a photothermal conversion agent may be contained in a layer adjacent to the image forming layer. For example, the photothermal conversion agent may be contained in an overcoat layer described later. Any material that absorbs light of 700 nm or more may be used as the photothermal conversion material, and various pigments and dyes can be used. As pigments, commercially available pigments and color index (CI) handbook, "Latest pigment handbook" (edited by Japan Pigment Technology Association, published in 1977), "Latest pigment application technology" (CM
C publication, published in 1986), "printing ink technology" CMC publication, published in 1984).

Examples of pigments include black pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments. , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.

These pigments may be used without surface treatment or may be used after surface treatment. When added to the resin fine particle layer, it is preferably subjected to a surface treatment. The surface treatment method includes a method of surface-coating a hydrophilic resin or a lipophilic resin, a method of attaching a surfactant, and a reactive substance (for example, A method of binding a silica sol, an alumina sol, a silane coupling agent, an epoxy compound, an isocyanate compound or the like) to the pigment surface can be considered. The above surface treatment method is described in "Properties and Applications of Metal Soap" (Koshoubo), "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986). There is. Among these pigments, those that absorb infrared light or near infrared light are preferable because they are suitable for use in a laser that emits infrared light or near infrared light. Carbon black is preferred as the pigment that absorbs such infrared light or near infrared light.
The particle size of the pigment is preferably in the range of 0.01 μm to 1 μm, and more preferably in the range of 0.01 μm to 0.5 μm.

As the dye, commercially available dyes and known dyes described in the literature (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes. Among these dyes, those that absorb infrared light or near infrared light are particularly preferable because they are suitable for use in a laser that emits infrared light or near infrared light.

Examples of dyes that absorb infrared light or near infrared light include, for example, JP-A-58-125246 and JP-A-59-
84356, JP-A-60-78787, US Pat. No. 4,973,572, JP-A-10-26851.
Cyanine dyes described in JP-A-58-1
73696, JP-A-58-181690, JP-A-5
Methine dyes described in JP-A-8-194595, JP-A-58-112793 and JP-A-58-224793.
JP-A-59-48187 and JP-A-59-7399.
6, JP-A-60-52940, and JP-A-60-637.
Naphthoquinone dyes described in JP-A-44, etc.
8-112792 and the like, squarylium dyes, cyanine dyes described in British Patent 434,875, dyes described in U.S. Pat. No. 4,756,993, U.S. Pat. No. 4,973,572. Examples thereof include the cyanine dyes described in JP-A-10-268512.

As a dye, US Pat. No. 5,156,56
The near-infrared absorption sensitizer described in US Pat. No. 938 is also preferably used, and the substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, JP-A-57-1.
No. 42645 (US Pat. No. 4,327,169), a trimethine thiapyrylium salt, JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363.
No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, and the pyrylium compounds described in JP-A-59-2161.
46, cyanine dyes, US Pat. No. 4,283,4
No. 75 pentamethine thiopyrylium salt, etc., and the pyrylium compounds disclosed in Japanese Examined Patent Publication Nos. 5-13514 and 5-19702, Epolig manufactured by Eporin.
ht III-178, Epolight III-130,
Epolight III-125 and the like are particularly preferably used. Among these dyes, water-soluble cyanine dyes are particularly preferable. The specific compounds are listed below.

[0080]

[Chemical 19]

[0081]

[Chemical 20]

[0082]

[Chemical 21]

[0083]

[Chemical formula 22]

[0084]

[Chemical formula 23]

[0085]

[Chemical formula 24]

[0086]

[Chemical 25]

[0087]

[Chemical formula 26]

[0088]

[Chemical 27]

Next, the photothermal conversion metal fine particles will be described. The metal used for the fine metal particles in the present invention may be any fine metal particle as long as it is a light-heat convertible metal particle that is heat-fused by irradiation with light. However, the metal constituting the preferable fine particles is group 8 or 1B. Fine particles of a simple metal or alloy selected from the group, and more preferably fine particles of a simple metal or alloy of Ag, Au, Cu, Pt, and Pd. In the present invention, the metal colloid dispersed particles are
It is obtained by adding an aqueous solution of the above metal salt or metal complex salt to an aqueous solution containing a dispersion stabilizer, further adding a reducing agent to form metal colloid dispersed particles, and then removing unnecessary salts. The dispersion stabilizer used in the present invention, citric acid,
Carboxylic acid such as oxalic acid and its salts, PVP, PV
Polymers such as A, gelatin and acrylic resins can be used. As the reducing agent used in the present invention, FeSO
_4, base metal salt such as SnSO _4, borohydride compound, formalin, dextrin, glucose, Rochelle salt, tartaric acid, sodium thiosulfate, and the like hypophosphite.

The average particle size of the metal colloid dispersed particles used in the present invention is 1 to 500 nm, preferably 1 to 100 nm, more preferably 1 to 50 n.
m. The degree of dispersion may be polydisperse, but monodisperse with a coefficient of variation of 30% or less is preferable. As a method of removing salts used in the present invention, there are an ultrafiltration method and a method of adding methanol / water or ethanol / water to a colloidal dispersion system and spontaneously precipitating or centrifuging to remove the supernatant.

The amount of the light-heat converting agent added to the image forming layer (heat-sensitive layer) may be up to 30% by weight of the total solid content of the heat-sensitive layer in the organic light-heat converting agent. It is preferably 5 to 25% by weight, and particularly preferably 7 to 20% by weight. In the case of the fine metal particle-based light-heat converting agent, it is used in an amount of 5% by weight or more, preferably 10% by weight or more, particularly preferably 20% by weight or more, based on the solid content of the heat-sensitive layer gold. If it is less than 5% by weight, the sensitivity tends to be low.

(Hydrophilic Resin) A hydrophilic resin may be added to the image forming layer (heat-sensitive layer) of the lithographic printing plate precursor according to the invention. The addition of the hydrophilic resin not only improves the on-press developability, but also improves the film strength of the heat-sensitive layer itself. Further, the resin can be crosslinked and cured to give a lithographic printing plate precursor that does not require development. Examples of the hydrophilic resin include those having a hydrophilic group such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl and carboxymethyl,
Hydrophilic sol-gel conversion binder resins are preferred.

Specific examples of the hydrophilic resin include gum arabic, casein, gelatin, starch derivatives, carboxymethyl cellulose and Na salts thereof, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers. , Polyacrylic acids and their salts, polymethacrylic acids and their salts, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers of hydroxypropyl acrylate And copolymers, hydroxybutyl methacrylate homopolymers and copolymers, hydroxybutyl acrylate homopolymers and copolymers , Polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and homopolymers of hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide with a degree of hydrolysis of at least 60% by weight, preferably at least 80% by weight, and Examples thereof include copolymers, methacrylamide homopolymers and polymers, and N-methylolacrylamide homopolymers and copolymers.

Further, the above hydrophilic resin may be cross-linked and used as a water-proofing agent to be cured, aldehydes such as glyoxal, melamine formaldehyde resin and urea formaldehyde resin, N-methylol urea and N-methylol melamine, Methylol compounds such as methylolated polyamide resin, active vinyl compounds such as divinyl sulfone and bis (β-hydroxyethyl sulfonic acid), epichlorohydrin and polyethylene glycol diglycidyl ether, polyamide / polyamine / epichlorohydrin adduct, polyamide epichlorohydride Epoxy compounds such as phosphorus resin, ester compounds such as monochloroacetic acid ester and thioglycolic acid ester, polycarboxylic acids such as polyacrylic acid and methyl vinyl ether / maleic acid copolymer, Acid, titanyl sulfates, Cu,
Inorganic cross-linking agents such as Al, Sn, V and Cr salts, modified polyamide polyimide resin, etc. may be mentioned. The hydrophilic resin may be added to the image forming layer (heat-sensitive layer) in the range of 0 to 40% by weight based on the total solid content of the heat-sensitive layer. In addition, a crosslinking catalyst such as ammonium chloride, a silane coupling agent, or a titanate coupling agent can be used in combination.

(Components other than the above) In the present invention, the image forming layer (thermosensitive layer) has a large absorption in the visible light region in order to make it easy to distinguish the image area from the non-image area after the surface image formation. The dyes that it possesses can be used as image colorants. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above Orient Chem. Industrial Co., Ltd., Victoria Pure Blue, Crystal Violet (CI
42555), methyl violet (CI4253
5), ethyl violet, rhodamine B (CI145
170B), malachite green (CI42000),
Methylene blue (CI52015), etc.
The dyes described in 2-293247 can be mentioned. Also, phthalocyanine pigments, azo pigments,
Pigments such as titanium oxide can also be preferably used. The addition amount is 0 to 10% by weight based on the total solid content of the heat-sensitive layer coating liquid.
Is the ratio.

Further, in the present invention, a plasticizer may be added to the image forming layer (heat sensitive layer), 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. The amount of the plasticizer added to the heat-sensitive layer may be 0 to 10% by weight based on the total solids of the heat-sensitive layer.

In the present invention, the image forming layer (heat sensitive layer) is
Each of the necessary components described above is dissolved in a solvent to prepare a coating solution, which is coated on a support described later. As the solvent used here, 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, dimethyl sulfoxide, sulfolane, γ-butyl lactone, toluene,
Examples thereof include water, but are not limited thereto. These solvents are used alone or as a mixture. The solid content concentration of the coating solution is preferably 1 to 50% by weight.
Is.

The coating amount (solid content) of the image-forming layer (heat-sensitive layer) on the support obtained after coating and drying varies depending on the use, but is generally 0.5 to 5.0 g / m ^2. . If the coating amount is less than this range, the apparent sensitivity will be high, but the film characteristics of the heat-sensitive layer which functions as an image recording will be deteriorated. Various methods can be used as a coating method. Examples include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating.

The coating solution for the image forming layer (heat sensitive layer) according to the present invention contains a surfactant for improving the coating property, such as a fluorine-based interface as described in JP-A-62-170950. Activators can be added. The preferable addition amount is 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight based on the total solid content of the heat-sensitive layer.

[Overcoat Layer] The lithographic printing plate precursor of the invention comprises a water-soluble resin for the purpose of preventing adhesion of stains, scratches and abrasion on the surface of the heat-sensitive layer on the image forming layer such as the heat-sensitive layer. Can be provided. As the water-soluble resin, any water-soluble organic polymer can be preferably used, but celluloses are particularly preferable. Examples of the water-soluble celluloses used in the present invention include carboxymethyl cellulose (serogen 5A etc.), carboxyethyl cellulose,
Resins obtained by water-solubilizing cellulose such as methyl cellulose (Tylose MH200K and the like), hydroxyethyl cellulose, hydroxypropyl cellulose (Metroze 50 and the like), sulfated cellulose and modified products thereof are preferable. A particularly preferred water-soluble cellulose is carboxymethyl cellulose. The number of substituted three hydroxyl groups in the 6-membered ring of cellulose is 0.
5 to 3.0 is preferable. More preferably 0.6-2.
It is 5. These resins must be contained in an amount of 40% by weight or more of the overcoat layer. If it is less than that, the inking property deteriorates. The content is preferably 60% by weight, particularly preferably 80% by weight or more.

Further, a water-soluble resin different from celluloses can be added to the overcoat layer for the purpose of improving the developability. Specifically, polyvinyl acetate (provided that the hydrolysis rate is 65% or more), polyacrylic acid and its alkali metal salt or amine salt, polyacrylic acid copolymer and its alkali metal salt or amine salt, and polymethacrylic acid. And alkali metal salts or amine salts thereof, polymethacrylic acid copolymers and alkali metal salts or amine salts thereof, polyacrylamide and copolymers thereof, polyhydroxyethyl acrylate, polyvinylpyrrolidone and copolymers thereof, polyvinyl methyl ether, polyvinyl Methyl ether / maleic anhydride copolymer, poly-2-acrylamido-2-methyl-1-propanesulfonic acid and its alkali metal salts or amine salts, poly-2-acrylamido-2-methyl-1-propanesulfonic acid copolymer Polymer and its al Li metal salt or amine salt, gum arabic, white dextrin,
Examples thereof include pullulan and enzyme-decomposed etherified dextrin. 40 for these overcoat layers
It can be added in less than wt%. If it is more than this, the receptiveness becomes poor. It is preferably less than 30% by weight, more preferably less than 20% by weight.

Further, in order to prevent stickiness, a fluorine-based compound, a silicone-based compound, or a wax agent emulsion may be added to these overcoat layers. When these are added, they float on the surface of the overcoat layer to eliminate stickiness due to the hydrophilic resin. The amount of these compounds added was 0.
1% to 5% by weight is required. Preferably 0.5-
It is 2.0% by weight.

The overcoat layer preferably contains a water-soluble photothermal conversion agent described later. Further, for the purpose of ensuring coating uniformity, a nonionic surfactant such as polyoxyethylene nonylphenol or polyoxyethylene dodecyl ether may be added to the overcoat layer in the case of coating with an aqueous solution. The dry coating amount of the overcoat layer is preferably 0.1 to 2.0 g / m ² . It is more preferably 0.5 to 1.2 g / m ² . If it is less than that range, fingerprint adhesion stains occur, and if it is more than that range, the on-press developability deteriorates.

[Support] The hydrophilic support which can be coated with the heat-sensitive layer (image forming layer) in the lithographic printing plate precursor of the invention is a dimensionally stable plate-like material.
Paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, butyric acid) Cellulose, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and a paper or plastic film laminated or vapor-deposited with the above metals. A preferable support includes a polyester film or an aluminum plate.

As the support used in the lithographic printing plate precursor of the invention, it is preferable to use an aluminum plate which is lightweight and has excellent surface treatment property, processability and corrosion resistance. As an aluminum material provided for this purpose, JIS 105
0 material, JIS 1100 material, JIS 1070 material, Al
-Mg-based alloy, Al-Mn-based alloy, Al-Mn-Mg-based alloy, Al-Zr-based alloy, Al-Mg-Si-based alloy and the like can be mentioned.

Known techniques regarding aluminum materials that can be used for the support are listed below. (1) Regarding JIS 1050 material, the following technology is disclosed. JP-A-59-153861, JP-A-6-
1-51395, JP-A-62-146694, JP-A-6-
0-215725, JP-A-60-215726, JP-A-60-215727, JP-A-60-215728, JP-A-61-272357, JP-A-58-11759, JP-A-58-42493, JP-A-58-42493. -212254, JP-A-62-148295, JP-A-4-254545, JP-A-4-165041, JP-B-3-68939, JP-A-3.
-234594, Japanese Patent Publication No. 1-447545, Japanese Patent Laid-Open No. 62-
140894, etc. In addition, Japanese Patent Publication No. 1-3591
No. 0, Japanese Patent Publication No. 55-28874 and the like are also known.

(2) Regarding JIS 1070 material, the following techniques are disclosed. JP-A-7-81264, JP-A-7-305133, JP-A-8-49034, JP-A-8-73974, JP-A-8-108659, JP-A-8-
92679, etc.

(3) The following techniques have been disclosed for Al-Mg alloys. Japanese Patent Publication No. 62-5080, Japanese Patent Publication No. 63-60823, Japanese Patent Publication No. 3-61753, and Japanese Unexamined Patent Publication No.
0-203496, JP-A-60-203497, JP-B-3-11635, JP-A-61-274993, JP-A-6-63.
2-23794, JP-A-63-47347, JP-A-63.
-47348, JP-A-63-47349, JP-A-64-
61293, JP-A-63-135294, JP-A-63-135294
87288, Japanese Patent Publication 4-73392, Japanese Patent Publication 7-100
844, JP-A-62-149856, JP-B-4-733.
94, JP-A-62-181191, JP-B-5-7653.
0, JP-A-63-30294, JP-B-6-37116 and the like. Further, JP-A-2-215599 and JP-A-61-2
No. 01747 is also known.

(4) Regarding Al-Mn alloys, the following techniques have been disclosed. Japanese Unexamined Patent Publication No. 60-230951,
JP-A-1-306288, JP-A-2-293189 and the like. In addition, Japanese Examined Patent Publication No. 54-42284, Japanese Examined Patent Publication No. 4-192
90, Japanese Patent Publication No. 4-19291, Japanese Patent Publication No. 4-19292,
JP-A-61-35995, JP-A-64-51992, U
S5009722, US5028276, Japanese Patent Laid-Open No. 4-2
26394 and the like are also known. (5) Regarding the Al-Mn-Mg-based alloy, the following techniques are disclosed. JP-A-62-86143, JP-A-3
-222796, JP-B-63-60824, JP-A-60
-63346, JP-A-60-63347, EP2237.
37, JP-A-1-283350, US4818300,
BR1222777 and the like are known.

(6) The following techniques are known for Al-Zr alloys. JP-B-63-15978, JP-A-61-51395, JP-A-63-143234 and JP-A-63-143235 are known. (7) Regarding the Al-Mg-Si alloy, BR142
1710 and the like are known.

The following contents can be used as the method for producing the aluminum plate for the support. The aluminum alloy melt having the above-mentioned content components and alloy component ratios is subjected to a cleaning treatment according to a conventional method and cast. For the cleaning process,
In order to remove unnecessary gas such as hydrogen in the molten metal, flux treatment, degassing treatment using Ar gas, Cl gas, etc., so-called rigid media filter such as ceramic tube filter, ceramic foam filter, etc.
Filtering using filters such as alumina flakes and alumina balls, a glass cloth filter, or a combination of degassing and filtering is performed. These cleaning treatments are
It is desirable to carry out in order to prevent defects due to non-metallic inclusions, foreign substances such as oxides, and defects due to gas melted in the molten metal.

Regarding the filtering of the molten metal, JP-A-6-57342, JP-A-3-162530, and JP-A-5-34230.
140659, JP-A-4-231425, JP-A-4-4-2
76031, JP-A-5-311261, JP-A-6-13
6466 and the like are known. Regarding degassing of molten metal,
Japanese Patent Laid-Open Nos. 5-51659, 5-51660, 5-49148, and 7-40017 are known. As described above, casting is performed using the molten metal that has been subjected to the cleaning treatment. Regarding the casting method, there are a method using a fixed mold represented by a DC casting method and a method using a driving mold represented by a continuous casting method. When the DC casting method is used, the cooling rate is solidified in the range of 1 to 300 ° C / sec. If it is less than 1 ° C./sec, many coarse intermetallic compounds are formed.

As the continuous casting method, a method using a cooling roll, represented by the Hunter method and the 3C method, a Hazley method, a method using a cooling belt represented by the Alswier caster type II, and a cooling block are used. Is done in a regular manner. The cooling rate when the continuous casting method is used is 100 to 1000 ° C /
It solidifies in the range of seconds. Generally, since the cooling rate is higher than that of the DC casting method, the solid solubility of the alloy component with respect to the aluminum matrix is high. Regarding the continuous casting method, the inventors of the present invention disclosed in JP-A-3-7
9798, JP-A-5-201166, JP-A-5-156
414, JP-A-6-262203, and JP-A-6-1229.
49, JP-A-6-210406, JP-A-6-26230.
8 etc. are disclosed.

When DC casting is performed, the plate thickness is 300 to 80.
A 0 mm ingot can be manufactured. The ingot, according to the usual method,
The surface is chamfered, and the surface layer is 1 to 30 mm, preferably 1 to 30 mm.
10 mm is cut. After that, soaking treatment is performed if necessary. When carrying out soaking treatment, it should be done at 450-620 ° C. for 1 hour so that the intermetallic compound does not become coarse.
The heat treatment is performed for not less than 48 hours and not more than 48 hours. If it is shorter than 1 hour, the effect of soaking treatment becomes insufficient. Then, hot rolling and cold rolling are performed to obtain an aluminum rolled plate. The starting temperature of hot rolling is 350 to 500
It shall be in the range of ° C. Intermediate annealing treatment may be performed before, after, or during the cold rolling. The intermediate annealing condition in this case is 280 ° C. to 6 using a batch type annealing furnace.
2 to 20 hours at 00 ° C, preferably 350 to 500 ° C
By heating for 2 to 10 hours or using a continuous annealing furnace.
360 seconds or less at 00 to 600 ° C., preferably 450 to
Heat treatment at 550 ° C. for 120 seconds or less can be adopted. The crystal structure can be made finer by heating at a temperature rising rate of 10 ° C./sec or more using a continuous annealing furnace.

Through the above steps, the predetermined thickness of 0.1 to 0.1 is obtained.
In order to improve the flatness of the aluminum plate finished to 0.5 mm, the flatness may be improved by a straightening device such as a roller leveler or a tension leveler. The flatness may be improved after cutting the plate into a sheet,
In order to improve the productivity, it is desirable to improve the flatness in a continuous coil state. Further, in order to process the plate width to a predetermined width, a slitter line is usually passed. The end face of the plate cut by the slitter is one of the shear surface and the fracture surface when cut by the slitter blade,
Or both occur.

The accuracy of the plate thickness is within ± 10 μm, preferably within ± 6 μm over the entire length of the coil.
Also, the thickness difference in the width direction is within 6 μm, preferably 3 μm.
Within is good. Moreover, the accuracy of the plate width is within ± 1.0 mm,
Desirably, within ± 0.5 mm. The surface roughness of the aluminum plate is easily affected by the surface roughness of the rolling roll, but finally the center line surface roughness (Ra) is Ra =
It is preferable to finish it to about 0.1 to 1.0 μm. If Ra is too large, the original roughness of the aluminum plate, that is, the rough rolling streaks transferred by the rolling rolls on the image forming layer when the surface is roughened for the lithographic printing plate and applied to the image forming layer. Since it is visible from the outside, it is not desirable in appearance. The roughness of Ra = 0.1 μm or less is industrially undesirable because it is necessary to finish the surface of the rolling roll to an excessively low roughness.

Further, in order to prevent the occurrence of scratches due to the friction between the aluminum plates,
You may have a thin oil film. In the oil film, if necessary,
A volatile one or a non-volatile one is appropriately used. If the oil content is too high, although the slip failure occurs in the production line, since failure of scratches generated in the coil transport amount of oil that it none occurs, the amount of oil is 100m at 3 mg / m ² or more
g / m ² or less, a desirable upper limit is 50 mg / m ² or less, and more desirably 10 mg / m ² or less. Regarding cold rolling, JP-A-6-210308 and the like are disclosed.

When continuous casting is performed, for example, by using a cooling roll such as a Hunter method, a cast plate having a plate thickness of 1 to 10 mm can be directly continuously cast-rolled, and there is an advantage that the hot rolling step can be omitted. Further, if a cooling roll such as the Hazley method is used, a cast plate having a plate thickness of 10 to 50 mm can be cast,
Generally, a continuous casting and rolling plate having a plate thickness of 1 to 10 mm is obtained by placing a hot rolling roll immediately after casting and continuously rolling. These continuously cast rolled plates are finished to a plate thickness of 0.1 to 0.5 mm through the steps of cold rolling, intermediate annealing, flatness improvement, slitting, etc. as described in the case of DC casting. To be Regarding the intermediate annealing condition and the cold rolling condition in the case of using the continuous casting method, see JP-A-6-2205.
93, JP-A-6-210308, JP-A-7-5411
1, JP-A-8-92709 and the like are disclosed.

The aluminum plate produced by the above method may be subjected to surface treatment such as surface roughening treatment and then coated with an image forming layer to prepare a lithographic printing plate precursor. The surface roughening treatment includes mechanical surface roughening, chemical surface roughening, and electrochemical surface roughening, either alone or in combination. In addition, it is also preferable to perform anodizing treatment for ensuring the scratch resistance of the surface and treatment for increasing the hydrophilicity.

The surface treatment of the support will be described below. Prior to roughening the aluminum plate, if necessary, for example, a surfactant for removing rolling oil on the surface,
Degreasing treatment with an organic solvent or an alkaline aqueous solution may be performed. In the case of alkali, a treatment such as neutralization and smut removal with an acidic solution may be performed next.

Next, in order to improve the adhesion between the support and the image forming layer and to impart water retention to the non-image area, the surface of the support is roughened, that is, a so-called graining treatment is performed. Specific means of this graining method include sand blasting, ball grain, wire grain, nylon brush and brush grain with abrasive / water slurry,
There is a mechanical graining method such as honing grain which sprays abrasive / water slurry onto the surface at high pressure, and there is also a chemical graining method where the surface is roughened with an etching agent consisting of alkali or acid or a mixture thereof. . Also, British Patent No. 896,563 and JP-A-5
3-67507, JP-A-54-146234 and JP-B-48-28123, or an electrochemical graining method, or JP-A-53-1232.
No. 04, JP-A-54-63902, a method combining a mechanical graining method and an electrochemical graining method, and a mechanical method described in JP-A-56-55261. It is also known to combine a graining method and a chemical graining method with a saturated aqueous solution of an aluminum salt of a mineral acid. Further, to the support material, a method of adhering a granular material with an adhesive or a method having its effect to roughen the surface, or a continuous band or roll having fine unevenness is pressure-bonded to the support material to form unevenness. A rough surface may be formed by transferring.

A plurality of such surface roughening methods may be carried out in combination, and the order, the number of repetitions, etc. can be arbitrarily selected. When a plurality of surface-roughening treatments are combined, chemical treatment with an acid or alkali aqueous solution can be performed during that time so that the subsequent surface-roughening treatment can be performed uniformly. Specific examples of the acid or alkali aqueous solution include acids such as hydrofluoric acid, zirconic acid fluoride, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid, and aqueous alkali solutions such as sodium hydroxide, sodium silicate and sodium carbonate. . These acid or alkali aqueous solutions may be used alone or in combination of two or more. The chemical treatment is carried out using a 0.05 to 40% by weight aqueous solution of these acids or alkalis at 40 ° C to 1
Generally, the treatment is performed at a liquid temperature of 00 ° C. for 5 to 300 seconds.

Since smut is formed on the surface of the support obtained by the above-mentioned roughening treatment, that is, graining treatment, appropriate treatment such as washing with water or alkali etching is performed to remove the smut. It is generally preferred to do As such a process, for example, Japanese Patent Publication No.
Treatment methods such as the alkali etching method described in JP-A-8-28123 and the sulfuric acid desmutting method described in JP-A-53-12739 are mentioned. In the case of the aluminum support used in the present invention, after the pretreatment as described above, an oxide film is usually formed on the support by anodization in order to improve wear resistance, chemical resistance and water retention. To form.

As the electrolyte used for the anodizing treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film. 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 electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but generally, the electrolyte concentration is 1 to 80% solution, the liquid temperature is 5 to 70 ° C,
A current density of 5 to 60 A / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are suitable. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. If the anodic oxide film is less than 1.0 g / m ² , printing durability is insufficient, or the non-image area of the lithographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. "Scratch stains" easily occur.

Such an anodizing treatment is applied to the surface of the lithographic printing plate support used for printing. However, due to the reverse rotation of the lines of electric force, an anode of 0.01 to 3 g / m ² is also applied to the back surface. An oxide film is generally formed. Further, an anodizing treatment in an alkaline aqueous solution (for example, a caustic soda aqueous solution of several%) or a molten salt, or an anodizing treatment for forming a nonporous anodized film using an ammonium borate aqueous solution, for example, can be performed. .. The hydrated oxide film described in JP-A-4-148991 and JP-A-4-97896 may be formed before the anodizing treatment, and also JP-A-63-56497 or JP-A-63-56497. The treatment in a metal silicate solution described in JP-A-63-67295, the hydrated oxide film formation treatment, the chemical conversion film formation treatment described in JP-A-56-144195, and the like can also be performed.

The aluminum support used in the lithographic printing plate precursor according to the invention may be treated with an organic acid or a salt thereof after anodizing, or the organic acid or a salt thereof may be used as an undercoat layer for coating an image forming layer. it can. Examples of the organic acid or its salt include organic carboxylic acid, organic phosphonic acid, organic sulfonic acid and its salt, and the like, and preferably organic carboxylic acid or its salt. Organic carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid, and stearic acid; unsaturated aliphatic monocarboxylic acids such as oleic acid and linoleic acid; oxalic acid and succinic acid. Acids, adipic acid, maleic acid, and other aliphatic dicarboxylic acids; lactic acid,
Oxycarboxylic acids such as gluconic acid, malic acid, tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid, mandelic acid, salicylic acid and phthalic acid, and Ia, IIb, IIIb, IV
Mention may be made of Group a, VIb and VIII metal salts and ammonium salts. Among the above organic carboxylic acid salts, preferred are the above-mentioned metal salts and ammonium salts of formic acid, acetic acid, butyric acid, propionic acid, lauric acid, oleic acid, succinic acid and benzoic acid. You may use these compounds individually or in combination of 2 or more types.

These compounds were dissolved in water and alcohol at 0.0
It is preferably dissolved to a concentration of 01 to 10% by weight, particularly 0.01 to 1.0% by weight, and the treatment conditions are 25 to 95 ° C., preferably 50 to 95 ° C., p
H is 1 to 13, preferably 2 to 10 and 10 seconds to 20 minutes,
The support is preferably immersed for 10 seconds to 3 minutes or the treatment liquid is applied to the support.

Further, after the anodizing treatment, the following treatment with a compound solution or these compounds can be used as an undercoat layer for coating the image forming layer. Suitable compounds include, for example, phenylphosphonic acid which may have a substituent, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and other organic phosphonic acids, substituted Phenylphosphoric acid which may have a group, naphthylphosphoric acid, organic phosphoric acid such as alkylphosphoric acid and glycerophosphoric acid, phenylphosphinic acid which may have a substituent,
Organic phosphinic acids such as naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, glycine, β-alanine, valine, serine, threonine, aspartic acid, glutamic acid, arginine, lysine, tryptophan, parahydroxyphenylglycine, dihydroxyethylglycine, anthranyl Amino acids such as acids;
Aminosulfonic acids such as sulfamic acid and cyclohexylsulfamic acid; 1-aminomethylphosphonic acid, 1-dimethylaminoethylphosphonic acid, 2-aminoethylphosphonic acid, 2-aminopropylphosphonic acid, 4-aminophenylphosphonic acid, 1-aminoethane -1,1-diphosphonic acid, 1-amino-1-phenylmethane-1,1-diphosphonic acid, 1-dimethylaminoethane-1,1-diphosphonic acid, 1-dimethylaminobutane-1,1-diphosphonic acid, Examples include compounds such as aminophosphonic acid such as ethylenediaminetetramethylenephosphonic acid.

In addition, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid (methanesulfonic acid, etc.) or oxalic acid, alkali metal,
Salts with ammonia, lower alkanolamines (triethanolamine, etc.), lower alkylamines (triethylamine, etc.), etc. can also be used suitably.

Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine and its mineral acid salt, poly (meth) acrylic acid and its metal salt, polystyrenesulfonic acid and its metal salt, (meth) acrylic acid alkyl ester and 2-acrylamide. 2-Methyl-1-propanesulfonic acid and metal salts thereof, polymers of trialkylammonium methylstyrene chloride and copolymers thereof with (meth) acrylic acid, and water-soluble polymers such as polyvinylphosphonic acid are also preferably used. it can. Furthermore, soluble starch, carboxymethyl cellulose, dextrin, hydroxyethyl cellulose, gum arabic, guar gum, sodium alginate, gelatin, glucose, sorbitol and the like can be preferably used. These compounds may be used alone or in combination of two or more kinds.

In the case of treatment, these compounds are preferably dissolved in water and / or methyl alcohol to a concentration of 0.001 to 10% by weight, particularly 0.01 to 1.0% by weight. The temperature is in the range of 25 to 95 ° C., preferably 50 to 95 ° C., and the pH is 1 to 13, preferably 2 to 10, 10 seconds to 20 minutes, and preferably 10 seconds to 3 minutes.

When it is used as an undercoat layer for coating an image forming layer, it is similarly diluted with water and / or methyl alcohol to 0.0.
It is dissolved so as to have a concentration of 01 to 10% by weight, particularly 0.01 to 1.0% by weight, and if necessary, a basic substance such as ammonia, triethylamine or potassium hydroxide, or
Adjust the pH with acidic substances such as hydrochloric acid and phosphoric acid
It can also be used in the range of 1 to 12. Further, a yellow dye may be added to improve the tone reproducibility of the lithographic printing plate precursor. The coating amount of the organic undercoat layer after drying is 2
~ 200 mg / m ² is suitable, preferably 5 ~ 10
It is 0 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient effects cannot be obtained for the original purpose of preventing stains. Further, when it exceeds 200 mg / m ² , the printing durability is lowered.

An intermediate layer may be provided to enhance the adhesion between the support and the image forming layer. In order to improve the adhesion, the intermediate layer is generally made of a diazo resin, a phosphoric acid compound adsorbed on aluminum, or the like. The thickness of the intermediate layer is arbitrary, and it must be a thickness capable of performing a uniform bond forming reaction with the upper image forming layer when exposed. Usually, a coating rate of about 1 to 100 mg / m ² as a dry solid is good, and 5 to 40 mg / m ² is particularly good. The use ratio of the diazo resin in the intermediate layer is 30 to 100.
%, Preferably 60 to 100%.

Prior to the above-mentioned treatment and application of an undercoat layer, the anodized support is washed with water, then the dissolution of the anodized film in dampening water is suppressed, and the remaining film of image forming layer components is left. For the purpose of suppressing, improving the strength of the anodized film, improving the hydrophilicity of the anodized film, and improving the adhesion to the image forming layer, the following treatments can be carried out. One of them is a silicate treatment in which the anodic oxide film is treated by bringing it into contact with an aqueous solution of an alkali metal silicate. In this case, the concentration of the alkali metal silicate is 0.1 to 30% by weight, preferably 0.5 to 15% by weight, and the aqueous solution having a pH of 10 to 13.5 at 25 ° C. is 5 to 80 ° C. The contact is preferably performed at 10 to 70 ° C., more preferably 15 to 50 ° C. for 0.5 to 120 seconds. The contacting method may be dipping or spraying, or any method. Alkali metal silicate solution is p
When H is lower than 10, the liquid gels, and when H is higher than 13.5, the anodized film is dissolved.

As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. P of alkali metal silicate solution
The hydroxide used for H adjustment includes sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The above treatment liquid contains alkaline earth metal salt or IVb
You may mix | blend a group metal salt. The alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. Is mentioned. Examples of the Group IVb metal salt include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride oxide and the like. The alkaline earth metal or Group IVb metal salts can be used alone or in combination of two or more kinds. The preferable range of these metal salts is 0.01 to 10% by weight, and more preferably 0.05 to 5.0% by weight.

In addition to the above, various sealing treatments can be cited, and steam sealing, boiling water (hot water) sealing, metal salt sealing ( Chromate / dichromate sealing, nickel acetate sealing, etc.), oil-impregnated sealing, synthetic resin sealing, low temperature sealing (such as red blood salt or alkaline earth salt) can be used. From the viewpoints of performance as a printing plate support (adhesion and hydrophilicity with the image forming layer), high-speed processing, low cost, low pollution, etc., water vapor sealing is relatively preferable. As the method, for example, the relative humidity of 7 or less can be obtained by continuously or discontinuously applying pressurized or normal-pressure steam, which is also disclosed in JP-A-4-176690.
Examples include a method of contacting the anodic oxide film at 0% or more and a steam temperature of 95 ° C. or more for about 2 seconds to 180 seconds. As another sealing treatment method, a method of immersing or spraying the support in hot water or an alkaline aqueous solution at about 80 to 100 ° C., or a method of substituting for it or subsequently immersing or spraying in a nitrous acid solution is used. it can. Examples of nitrites are Ia, IIa, IIb, IIIb, IVb, IV of the Periodic Table.
Examples thereof include nitrite salts or ammonium salts of metals of a, VIa, VIIa, and VIII, that is, ammonium nitrite, and examples of the metal salts include LiO ₂ , NaNO ₂ , and KNO.
₂ , Mg (NO ₂ ) ₂ , Ca (NO ₂ ) ₂ , Zn (N
O ₃ ) ₂ , Al (NO ₂ ) ₃ , Zr (NO ₂ ) ₄ , Sn (NO
₂ ) ₃ , Cr (NO ₂ ) ₃ , Co (NO ₂ ) ₂ , Mn (N
O ₂ ) ₂ , Ni (NO ₂ ) _{2 and the} like are preferable, and alkali metal nitrite is particularly preferable. Two or more kinds of nitrites can be used in combination.

The treatment conditions cannot be uniquely determined because they differ depending on the state of the support and the type of alkali metal.
For example, when sodium nitrite is used, the concentration is generally 0.001-10% by weight, more preferably 0.0
1-2% by weight, bath temperature generally from room temperature to about 100 ° C
Before and after, more preferably 60 to 90 ° C., the treatment time may be generally selected from the range of 15 to 300 seconds, more preferably 10 to 180 seconds. P of nitrous acid aqueous solution
H is preferably adjusted to 8.0 to 11.0, and particularly preferably adjusted to 8.5 to 9.5. To adjust the pH of the nitrous acid aqueous solution to the above range,
For example, it can be suitably prepared using an alkaline buffer or the like. Examples of the alkaline buffer include, but are not limited to, a mixed aqueous solution of sodium hydrogen carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydrogen carbonate, and sodium chloride and sodium hydroxide. Mixed aqueous solution,
A mixed aqueous solution of hydrochloric acid and sodium carbonate, a mixed aqueous solution of sodium tetraborate and sodium hydroxide, and the like can be preferably used. In addition, an alkali metal salt other than sodium, such as potassium salt, can be used as the above alkaline buffer solution.

After the silicate treatment or the pore-sealing treatment as described above, in order to improve the adhesion to the heat-sensitive layer, the acidic aqueous solution treatment and the hydrophilic undercoating disclosed in JP-A-5-278362 are applied. What to do and JP-A-4-
An organic layer disclosed in Japanese Patent No. 282637 or Japanese Patent Laid-Open No. 7-314937 may be provided.

After the surface of the support is subjected to the above treatment or undercoating, a back coat is provided on the back surface of the support, if necessary. As such a back coat, a coating layer made of a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 is used. It is preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si (OC)
Silicon alkoxy compounds such as ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ and Si (OC ₄ H ₉ ) ₄ are inexpensive and easily available, and the metal oxide coating layer obtained therefrom can be used as a developer-proof solution. It is excellent and particularly preferable.

A preferable characteristic of the support for a lithographic printing plate is a center line average roughness of 0.10 to 1.2 μm. If it is less than 0.10 μm, the adhesiveness to the heat-sensitive layer decreases
This causes a marked decrease in printing durability. If it is larger than 1.2 μm, the stain resistance during printing will deteriorate. Further, the color density of the support is 0.15 to 0.
When it is 65 and is whiter than 0.15, halation during image exposure is too strong, which hinders image formation.
When it is blacker than 0.65, the image is difficult to see in the plate inspection work after development, and the plate inspection property is remarkably poor.

The lithographic printing plate precursor of the present invention has a better on-press developability by using, as its support, an aluminum substrate which has been roughened and then anodized. be able to. In that case, it is more preferable to use an aluminum substrate further subjected to a silicate treatment.

This printing plate comprises a hydrophilic layer which is insoluble in water on an aluminum substrate or a layer which is hydrophilic and insoluble in water when heated by laser exposure, or an organic polymer in order to impart heat insulating property to the aluminum substrate. In addition to the above heat insulating layer, a water-insoluble hydrophilic layer or a water-insoluble hydrophilic layer that generates heat by laser exposure may be provided. For example, a silica fine particle and a hydrophilic layer of a hydrophilic resin may be provided on an aluminum substrate. Further, the above-mentioned photothermal conversion material may be introduced into this hydrophilic layer to form an exothermic hydrophilic layer. This makes it difficult for heat to escape to the aluminum substrate, or can be used as a hydrophilic substrate that generates heat by laser exposure. Further, when an intermediate layer made of an organic polymer is provided between the hydrophilic layer and the aluminum substrate, it is possible to further prevent heat from escaping to the aluminum substrate. From the viewpoint of on-press developability, the support is preferably not porous, and a support that swells with water containing 40% or more of a hydrophilic organic polymer material is inconvenient because ink is hard to be removed. is there.

The hydrophilic layer used in the present invention is three-dimensionally crosslinked, and is a lithographic printing plate using water and / or ink,
It is a layer that is insoluble in immersion water and is preferably composed of the following colloids. It is a colloid comprising a sol-gel conversion system of oxides or hydroxides of beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony or transition metals. In some cases, it may be a colloid composed of a complex of these elements. These colloids have a structure in which the above-mentioned elements form a network structure via oxygen atoms and at the same time have unbonded hydroxyl groups and alkoxy groups, and these are mixed. From the initial hydrolysis-condensation stage where there are many active alkoxy groups and hydroxyl groups, the particle size increases and becomes inactive as the reaction proceeds. The colloidal particles are generally 2 nm to 500 nm, and in the case of silica, spherical particles of 5 nm to 100 nm are preferable in the present invention. 100x like a colloidal dispersion of aluminum
A feather-like material such as 10 nm is also effective. Furthermore,
Spherical particles from 10 nm to 50 nm have particle sizes from 50 nm to 400
A pearl-neck-shaped colloidal dispersion having a length of nm can also be used.

The colloidal dispersion may be used alone or in combination with a hydrophilic resin. Further, in order to accelerate the crosslinking, a crosslinking agent for the colloidal dispersion may be added. Usually, the colloidal dispersion is often stabilized by a stabilizer. A compound having an anion group is added to the cation-charged colloidal dispersion, while a compound having a cation group is added to the anion-charged colloidal dispersion. For example, since silicon colloidal dispersions are charged with anions, amine-based compounds are added as stabilizers, and aluminum colloidal dispersions are charged with cations, so strong acids such as hydrochloric acid and acetic acid are added. ing. When such a colloidal dispersion is coated on a substrate,
Many of them form a transparent film at room temperature, but gelation is not complete when the dispersion medium of the colloidal dispersion is evaporated, and heating is performed to a temperature at which the stabilizer can be removed, resulting in strong tertiary crosslinking. The hydrophilic layer is preferable for the present invention.

A hydrolytic condensation reaction is carried out directly from a starting material (for example, di-, tri- and / or tetraalkoxysilane) without using the above-mentioned stabilizer, and an appropriate sol state is produced and directly placed on the substrate. The reaction may be completed by coating and drying. In this case, three-dimensional crosslinking can be carried out at a lower temperature than in the case where a stabilizer is included.

In addition to the above, a colloid obtained by dispersing and stabilizing an appropriate hydrolysis-condensation reaction product in an organic solvent is also suitable for the present invention. A three-dimensionally crosslinked film is obtained simply by evaporating the solvent. If a low boiling point solvent such as methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or methyl ethyl ketone is selected for these solvents,
It can be dried at room temperature. In particular, colloids of methanol and ethanol solvents are useful in the present invention because they can be easily cured at low temperatures.

The hydrophilic resin used together with the colloidal dispersion is preferably one having a hydrophilic group such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl or carboxymethyl. Specific hydrophilic resins include gum arabic, casein, gelatin, starch derivatives,
Carboxymethyl cellulose and their Na salts, cellulose acetate, sodium alginate, vinyl acetate-
Maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and their salts, polymethacrylic acids and their salts, hydroxyethyl methacrylate homopolymers and copolymers, hydroxyethyl acrylate homopolymers and copolymers, hydroxypropyl methacrylate Homopolymers and copolymers, hydroxypropyl acrylate homopolymers and copolymers, hydroxybutyl methacrylate homopolymers and copolymers, hydroxybutyl acrylate homopolymers and copolymers, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols and At least 60% by weight, preferably at least 80% by weight of hydrolyzed polyvinyl acetate Polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, homopolymers and copolymers of acrylamide, homopolymers and polymers of methacrylamide, homopolymers and copolymers of N- methylol acrylamide, 2-acrylamide -
Examples thereof include homopolymers and copolymers of 2-methylpropanesulfonic acid or salts thereof.

Particularly preferred hydrophilic resins are hydroxyl group-containing polymers that are not water-soluble, specifically homopolymers and copolymers of hydroxyethyl methacrylate and copolymers of hydroxyethyl acrylate. These hydrophilic resins are used together with the colloidal dispersion, and the addition ratio thereof is preferably 40% by weight or less of the total solid content of the hydrophilic layer when the hydrophilic resin is water-soluble, and when the hydrophilic resin is not water-soluble. 20% by weight or less of the total solid content is preferable.

These hydrophilic resins can be used as they are, but a crosslinking agent for hydrophilic resins other than the colloidal dispersion may be added for the purpose of increasing printing durability during printing.
Examples of the crosslinking agent for such a hydrophilic resin include formaldehyde, glyoxal, polyisocyanate, an initial hydrolysis / condensation product of tetraalkoxysilane, dimethylol urea, and hexamethylol melamine. In addition to the above-mentioned colloidal dispersion of oxide or hydroxide and the hydrophilic resin, a cross-linking agent that promotes cross-linking of the colloidal dispersion may be added to the hydrophilic layer according to the present invention. As such a crosslinking agent, an initial hydrolysis-condensation product of tetraalkoxysilane, trialkoxysilylpropyl-N, N, N-trialkylammonium halide or aminopropyltrialkoxysilane is preferable. The addition ratio is preferably 5% by weight or less of the total solid content of the hydrophilic layer.

Further, a hydrophilic photothermal conversion material may be added to the hydrophilic layer according to the present invention in order to enhance the heat sensitivity. A particularly preferable photothermal conversion material is a water-soluble infrared absorbing dye, and is a cyanine dye having the above-mentioned sulfonic acid group or alkali metal base of sulfonic acid or amine base. The addition ratio of these dyes is based on the total amount of the hydrophilic layer,
1 wt% to 20 wt%, more preferably 5 wt% to 1
It is 5% by weight.

The coating thickness of the three-dimensionally crosslinked hydrophilic layer according to the present invention is preferably 0.1 μm to 10 μm. More preferably, it is 0.5 μm to 5 μm. If it is too thin, the durability of the hydrophilic layer is poor and the printing durability during printing is poor. If it is too thick, the resolution will decrease. Hereinafter, the intermediate layer made of an organic polymer will be described. The organic polymer that can be used in the intermediate layer can be used without problems as long as it is a commonly used organic polymer such as polyurethane resin, polyester resin, acrylic resin, cresol resin, resole resin, polyvinyl acetal resin, and vinyl resin. It is preferred that these are the coating weight of ^{0.1g / m 2 ~5.0g / m 2} . If it is 0.1 g / m ² or less, the heat insulating effect is small, and if it is more than 5.0 g / m ² , the printing durability of the non-image area is deteriorated.

The lithographic printing plate precursor according to the invention can form an image by high power laser exposure, but a writing machine such as a thermal head may be used. Particularly in the present invention, it is preferable to use a laser emitting in the infrared or near infrared region. Particularly preferred is a laser diode which emits light in the near infrared region. In the present invention, the wavelength 76
Image exposure is preferably performed by a solid-state laser and a semiconductor laser that emit infrared rays of 0 nm to 1200 nm. The laser output is preferably 100 mW or more, and it is preferable to use a multi-beam laser device in order to shorten the exposure time. Also, the exposure time per pixel is 2
It is preferably within 0 μsec. The energy applied to the recording material is preferably 10 to 300 mJ / cm ² . Further, the lithographic printing plate precursor according to the invention can be used for image formation by an ultraviolet lamp.

The plate thus exposed is mounted in the cylinder of the printing press without processing.
The plate thus mounted can be printed by the following procedure. (1) A method of supplying dampening water to the printing plate, developing on the machine, and then supplying ink to start printing, (2) supplying dampening water and ink to the printing plate, and developing on the machine After that, there is a method of starting printing, (3) a method of supplying ink to the plate, supplying dampening water, and simultaneously supplying paper to start printing. In addition, these plates are patent No. 2938398.
It is also possible to carry out on-press development with a laser mounted on the printing machine, followed by dampening water and / or ink after mounting on the cylinder of the printing machine as described in No. Preferably, it can be developed with water or an aqueous solution, or can be mounted on a printing machine as it is without performing development and printing.

[0154]

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

Examples 1 to 6 Comparative Examples 1 to 3 Preparation of Support (1) (Preparation of Aluminum Substrate) Aluminum of 99.5% or more, Fe 0.30%, S
The molten metal of JIS A1050 alloy containing i0.10%, Ti0.02%, and Cu0.013% is subjected to a cleaning treatment,
Cast. For the cleaning treatment, degassing treatment was performed to remove unnecessary gas such as hydrogen in the molten metal, and ceramic tube filter treatment was performed. The casting method was a DC casting method. Solidified ingot with a thickness of 500 mm is 10 m from the surface
The surface was m-faced and homogenized at 550 ° C. for 10 hours to prevent the intermetallic compound from coarsening. Then 40
After hot rolling at 0 ° C., intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain a rolled aluminum plate having a plate pressure of 0.30 mm. The center line average surface roughness Ra after cold rolling was controlled to 0.2 μm by controlling the roughness of the rolling roll. Then, a tension leveler was applied to improve the flatness.

Next, a surface treatment was carried out to prepare a support for a lithographic printing plate. First, in order to remove the rolling oil on the surface of the aluminum plate, a 10% sodium aluminate aqueous solution is used at 50 ° C.
Degreasing treatment was performed for 2 seconds, neutralization was performed with a 30% sulfuric acid aqueous solution at 50 ° C. for 30 seconds, and smut removal treatment was performed.

Next, in order to improve the adhesion between the support and the heat-sensitive layer and to impart water retention to the non-image area, the surface of the support was roughened, that is, a so-called graining treatment was performed. 1%
45 nitric acid and an aqueous solution containing 0.5% aluminum nitrate
While maintaining the temperature at ℃, while flowing the aluminum web in the aqueous solution, the anode side electricity quantity of 240 C / dm with an alternating waveform with a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect power supply cell.
Electrolytic graining was performed by giving ² . Then 10%
Etching treatment was performed for 30 seconds at 50 ° C. with an aqueous solution of sodium aluminate, neutralization was performed for 30 seconds at 50 ° C. for 30 seconds with an aqueous 30% sulfuric acid solution, and smut removal treatment was performed.

Further improved abrasion resistance, chemical resistance and water retention
To form an oxide film on the support by anodization.
I made it. Use 20% sulfuric acid aqueous solution as electrolyte at 35 ° C
Indirect power supply while carrying the aluminum web through the electrolyte
14A / dm depending on cell²Electrolysis with direct current
2.5 g / m²The anodic oxide film of was prepared. After this
To ensure the hydrophilicity of the plate non-image area,
Processing was performed. Treatment is No. 3 sodium silicate 1.5% water soluble
Keeping the liquid at 70 ℃, the contact time of aluminum web is 15 seconds.
And then washed with water. Adhesion amount of Si is 10m
g / m ²Met. Ra of the support prepared as described above
(Centerline surface roughness) was 0.25 μm.

[Synthesis of Microcapsules (1)] D-110N [manufactured by Takeda Pharmaceutical Co., Ltd.] as an oil phase component: 40
g, blocked isocyanate (1): 10 g, IR-3
3: 5.0 g, Pionin A41C (manufactured by Takemoto Yushi):
0.1 g was dissolved in 60 g of anisole. As a water phase component, 120% of a 4% aqueous solution of PVA205 (manufactured by Kuraray)
g was produced. The oil phase component and the water phase component were emulsified at 10,000 rpm using a homogenizer. After that, water: 40
g was added, and the mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours. The microcapsules thus obtained had an average particle size of 0.5 μm and a solid content concentration of 40% by weight.

[Synthesis of Microcapsules (2)] D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) as an oil phase component: 40
g, ethylene glycol diglycidyl ether: 10
g, IR-33: 3 g, and Pionin A41C (manufactured by Takemoto Yushi Co., Ltd.): 0.1 g were dissolved in 60 g of ethyl acetate. As a water phase component, a 4% aqueous solution of PVA205 (manufactured by Kuraray) 1
An aqueous solution was prepared by adding 5 g of diethylenetriamine to 20 g. The oil phase component and the water phase component were emulsified at 10,000 rpm using a homogenizer. After that, water: 40
g was added, and the mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours. The microcapsules thus obtained had an average particle size of 0.4 μm and a solid content concentration of 18% by weight.

[Synthesis of Microcapsules (3)] As an oil phase component, phthalic acid dichloride: 40 g, dialdehyde compound (2): 10 g, IR-33: 3 g, acid generator (3): 1.0 g, pyionine A41C (manufactured by Takemoto Yushi Co., Ltd.): 0.1 g was dissolved in 60 g of anisole. As a water phase component, a 4% aqueous solution of sodium dodecyl sulfate 12
An aqueous solution was prepared by adding 2.7 g of pentaerythritol and 0.3 g of diethylene glycol to 0 g. The oil phase component and the water phase component were 10,000 using a homogenizer.
Emulsified at rpm. Then, 100 mL of 4N sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 2 hours and further at 40 ° C. for 3 hours. The aqueous solution thus obtained was filled in a semipermeable membrane and dialyzed against distilled water for 24 hours. The average particle size of the obtained microcapsules was 0.3 μm, and the solid content concentration was 10% by weight.

[Synthesis of Resin Fine Particles (1)] Sodium dodecyl sulfate: 4.32 g and distilled water: 1090 mL were weighed and stirred at 50 ° C. for 10 minutes under a nitrogen stream. To this solution, potassium persulfate: 2.31 g, sodium hydrogencarbonate: 2.15 g was dissolved in distilled water to make a total volume of 50 mL, solution A: 2 mL, and sodium hydrogen sulfite: 0.89 g.
Was dissolved in distilled water to a total volume of 50 mL, and a solution B: 2 mL was added, followed by styrene: 67.7 g and monomer (4): 7
A mixed solution of 0 g and divinylbenzene: 6.5 g was mixed with 3 g.
It dripped over time. During the dropping, the above-mentioned solution A: 2 mL and solution B: 2 mL were added every 20 minutes. After the dropping is completed,
After continuing the stirring for 1 hour, Solution A: 2 mL and Solution B: 2 mL were further added, and the mixture was stirred for 1 hour. Concentrated hydrochloric acid was slowly added to the resulting reaction mixture to bring the pH to about 1, and stirring was continued for another 3 hours. After cooling to room temperature, 1N sodium hydroxide aqueous solution was added to adjust the pH to 8, and the mixture was filtered through a glass filter to obtain fine particles (1). The solid content concentration of the fine particle (1) aqueous solution thus obtained was 11% by weight,
The average particle size was 0.065 μm.

[Synthesis of Resin Fine Particles (2)] Into a 500 ml three-necked flask, 17.17 g of methyl ethyl ketone was weighed and stirred at 65 ° C. under a nitrogen stream for 10 minutes. Here, monomer (5): 57.32 g, ethyl methacrylate: 28.54 g, methyl ethyl ketone: 154.5
A solution prepared by mixing 5 g and 2,2′-azobis-2,4-dimethylvaleronitrile: 0.994 g was added dropwise over 2 hours. After completion of dropping, 2,2'-azobis-2,4 was further added.
-Dimethylvaleronitrile: 0.249 g was added, and the mixture was stirred for 2 hours as it was. After completion of the reaction, 3 L of methanol separately prepared in a 5 L beaker was vigorously stirred, the whole amount of the above reaction solution was slowly poured into the beaker, and the mixture was stirred for 1 hour as it was. After 1 hour, the precipitated solid was filtered,
After washing with methanol, it was dried under reduced pressure to obtain 80 g of a resin having a reactive group. Resin having a reactive group thus obtained: 6.0 g, photothermal conversion agent (I-33): 1.5
g of ethyl acetate / MEK (4/1) solvent: 18.0 g
Dissolved in 4% PVA (manufactured by Kuraray, 205) aqueous solution: 36 g and mixed with a homogenizer to obtain 1000
The emulsion was emulsified at 0 rpm for 10 minutes. Then, ethyl acetate and MEK were evaporated while stirring at 60 ° C. for 90 minutes to obtain fine particles (2) having an average particle diameter of 0.28 μm. The solid content concentration of this aqueous solution was 12.8%.

[Synthesis of Resin Fine Particles (3)] Sodium dodecyl sulfate: 2.23 g and distilled water: 850 mL were weighed and stirred at 75 ° C. for 10 minutes under a nitrogen stream. To this solution was added a solution prepared by mixing potassium persulfate: 0.461 g, 1N sodium hydrogen carbonate aqueous solution: 3.5 mL, and distilled water: 11.3 mL, and then methyl methacrylate: 70.0
A mixed solution of 9 g and sec-butyl methacrylate: 42.6 g was added dropwise over 3 hours. After completion of the dropping, a solution obtained by mixing potassium persulfate: 0.461 g, 1N sodium hydrogen carbonate aqueous solution: 3.5 mL, and distilled water: 14.2 mL was further added, and stirring was continued for 3 hours. After cooling the obtained reaction mixture to room temperature, 15 g of hydrazine monohydrate was slowly added, and stirring was continued for further 3 hours. The obtained solution was filtered with a glass filter to obtain fine particles (3). The solid content concentration of the fine particle (3) aqueous solution thus obtained was 11% by weight, and the average particle size was 0.055 μm.

The blocked isocyanate (1), the dialdehyde compound (2), the acid generator (3), the monomers (4) and (5) used in the synthesis of the microcapsules and resin fine particles are shown below.

[0166]

[Chemical 28]

[Preparation of original plate (1) for lithographic printing plate] The above-mentioned aluminum plate was coated with the solution [1] prepared as follows using a rod bar and dried at 60 ° C for 3 minutes to prepare a lithographic printing plate. A master plate (1) was obtained. The dry coating amount of the heat-sensitive layer at this time was 0.6 g / m ² .

[0168]   Solution [1]   ・ Resin particle (1) dispersion 8.00 g   ・ Microcapsule (1) dispersion 1.00 g   ・ Polyacrylic acid (weight average molecular weight: 25,000) 0.14 g   -Photothermal conversion agent (I-32) 0.05 g   ・ Distilled water 9.00 g

[Preparation of lithographic printing plate precursor (2)] A lithographic printing plate precursor (1) was prepared in the same manner as the lithographic printing plate precursor (1) except that the solution [1] was changed to the following solution [2]. 2) was produced. The dry coating amount of the heat-sensitive layer at this time was 0.7 g.
/ M ² .

[0170] Solution [2]   ・ Resin particle (1) dispersion 8.00 g   ・ Microcapsule (2) dispersion 1.00 g   ・ Polyacrylic acid (weight average molecular weight: 25,000) 0.14 g   -Photothermal conversion agent (I-32) 0.05 g   ・ 3.00g of distilled water

[Preparation of lithographic printing plate precursor (3)] A lithographic printing plate precursor (1) was prepared in the same manner as the lithographic printing plate precursor (1) except that the solution [1] was changed to the following solution [3]. 3) was produced. The dry coating amount of the heat-sensitive layer at this time was 0.8 g.
/ M ² . Solution [3] -Resin fine particle (2) dispersion 8.00 g-Microcapsule (3) dispersion 2.00 g-Water 10.00 g

[Preparation of lithographic printing plate precursor (4)] The lithographic printing plate precursor (1) was prepared in the same manner as the lithographic printing plate precursor (1) except that the solution [1] was changed to the following solution [4]. 4) was produced. The dry coating amount of the heat-sensitive layer at this time was 0.7 g.
/ M ² . Solution [4] -Dispersion of resin fine particles (3) 8.00 g-Dispersion of microcapsules (2) 1.00 g-Photothermal conversion agent (I-3) 0.05 g-Polyacrylic acid (weight average molecular weight: 2.5 10,000) 0.10g-Distilled water 3.00g

[Preparation of lithographic printing plate precursor (5)] The lithographic printing plate precursor (1) was prepared in the same manner as the lithographic printing plate precursor (1) except that the solution [1] was changed to the following solution [5]. 5) was prepared. The dry coating amount of the heat-sensitive layer at this time was 0.8 g.
/ M ² . Solution [5] -Dispersion of resin fine particles (2) 8.00 g-Distilled water 2.00 g

[Preparation of lithographic printing plate precursor (6)] A lithographic printing plate precursor (1) was prepared in the same manner as the lithographic printing plate precursor (1) except that the solution [1] was changed to the following solution [6]. 6) was produced. The dry coating amount of the heat sensitive layer at this time was 0.9 g.
/ M ² . Solution [6] -Resin fine particle (3) dispersion 8.00 g-Photothermal conversion agent (I-32) 0.05 g-Polyacrylic acid (weight average molecular weight: 25,000) 0.10 g-Distilled water 3.00 g

[Examples 1 to 4 and Comparative Examples 1 and 2] The obtained lithographic printing plate precursors (1) to (6) were subjected to a main scanning speed of 2.0 m / s by a semiconductor laser emitting an infrared ray having a wavelength of 840 nm. Exposed. After the exposure, after immersing in distilled water for 1 minute, the line width of the non-image area was observed with an optical microscope. The irradiation energy of the laser corresponding to the line width was obtained, and this was taken as the sensitivity.
Similarly, the lithographic printing plate precursors (1) to (6) were subjected to wavelength
After exposure with a semiconductor laser emitting infrared rays of 840 nm at main scanning speeds of 2.0 m / s and 4.0 m / s, printing was performed by a Heidel KOR-D machine as usual without any processing. At this time, it was evaluated how many good prints could be obtained. The above results are shown in Table 1.

[0176]

[Table 1]

The lithographic printing plate precursor of the present invention has high sensitivity, and even if exposed at any scanning speed of 2.0 m / s or 4.0 m / s, 40,000 or more good printed matter can be obtained and scanned. It did not change with speed. The reason for this is that when the scanning speed is high, the amount of heat generated is insufficient, so that the fusion of the fine particles does not proceed sufficiently, but the fine particle fusion coating film is produced by the compound having a reactive group released from the microcapsules. This is because even if fusion bonding is insufficient, sufficient image strength can be obtained due to the crosslinking of the. On the other hand, the lithographic printing plate precursor of Comparative Example had low sensitivity and 30,000 good prints were obtained at a scanning speed of 2.0 m / s, but when exposed at a scanning speed of 4.0 m / s, Only 10,000 good prints were obtained. This is because in the lithographic printing plate precursor of the comparative example, the image portion is formed only by fusion of fine particles, so that when the scanning speed is high, a sufficient amount of heat cannot be obtained and fusion is insufficient. This is because.

[0178]

INDUSTRIAL APPLICABILITY According to the present invention, a lithographic printing plate precursor which can be developed with water or an aqueous solution or does not require any special treatment such as wet development treatment or rubbing after writing an image, has a higher printing durability. -It is possible to provide a lithographic printing plate precursor which has high sensitivity and can give a printed matter free from printing stains. Further, according to the present invention, it is possible to provide a lithographic printing plate precursor capable of directly making a plate from digital data by recording using a solid-state laser or a semiconductor laser that emits infrared rays.

Continued front page    F-term (reference) 2H025 AA01 AA12 AB03 AC08 AD01                       AD03 CB41 CB42 CB45 CB47                       CC20 DA10 DA18 FA10                 2H096 AA07 AA08 BA16 BA20 CA03                       EA04                 2H114 AA04 AA22 AA24 BA01 DA04                       DA08 DA25 DA26 DA32 DA53                       DA73 DA78 EA01 EA03 EA04                       GA03 GA05 GA06 GA09 GA34                       GA38

Claims (2)

[Claims] 1. A layer containing resin fine particles and microcapsules is provided on a support having a hydrophilic surface,
The lithographic printing plate precursor for heat mode laser drawing, wherein the microcapsules contain a compound having a reactive group that is bonded to the reactive group of the resin fine particles by the action of heat. 2. A support having a hydrophilic surface is provided with a layer containing resin fine particles and a layer containing microcapsules in this order, and the microcapsules are contained in the resin particles by the action of heat. A lithographic printing plate precursor for heat mode laser drawing, which contains a compound having a reactive group that bonds with a reactive group.