JP2003039845A - Lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive lithographic printing plate which is excellent in scratch resistance, sensitivity, fouling preventive properties during printing, and plate wear properties and has a heat sensitive layer which is made alkali- soluble by the photothermal conversion of laser light. SOLUTION: In the lithographic printing plate, the heat sensitive layer containing a water-insoluble, alkali-soluble resin and an infrared absorbent dye and increasing its solubility in an alkaline aqueous solution by heating is formed on a support in which aluminum or an aluminum alloy is subjected to surface roughening and anodic oxidation treatment. The surface-roughened shape of the support has a pebble shape of at least large and small double complex structures comprising a large-wave structure and a small-wave structure. The large wave structure has an average wavelength of 0.5-30 μm, and the small wave structure has a pit structure 0.05-0.2 μm in average diameter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate, and more particularly, it is solubilized with alkali by photothermal exchange of laser light, which can improve both scratch resistance and sensitivity, and is excellent in stain resistance during printing and printing durability. The present invention relates to a positive lithographic printing plate having a photosensitive layer.

[0002]

2. Description of the Related Art In recent years, with the development of image forming technology, a laser beam with a narrow beam is scanned on the plate surface to directly form a character manuscript, an image manuscript, etc. on the plate surface without directly using a film manuscript. It is becoming possible to make a plate. In the so-called thermal positive type lithographic printing plate which causes alkali-solubilization of the recording layer by causing photothermal conversion in the recording layer by laser light irradiation, so-called thermal positive type lithographic printing plate, Since the subtle changes in the intermolecular interaction of the binder are utilized, the difference in the on / off degree of the alkali solubilization of the exposed / unexposed portion is small. Therefore, for the purpose of obtaining a clear discrimination that can withstand practical use,
A means of forming a recording layer structure in which the surface hardly soluble layer in a developing solution is provided as the uppermost layer of the recording layer and the developing solubility of the unexposed portion is suppressed is used.

However, if the surface-insoluble layer is damaged for some reason, even the portion that is originally the image portion will be easily dissolved in the developing solution. In other words, it is a printing plate that is very easily damaged in practical use. For this reason, collisions during printing plate handling, subtle rubbing on the interleaving paper,
Even a slight contact such as a finger contact with the plate surface may cause a scratch-shaped image omission, which is currently difficult to handle during the printing plate work. In order to improve the scratch resistance, it has been attempted to reduce the friction coefficient by providing a layer of a fluorine-based surfactant or a wax agent on the surface of the recording layer, but this is not yet a sufficient countermeasure. .

On the other hand, it has been considered to improve the developability in order to increase the discrimination, and a hydrophilic layer or an alkali-soluble undercoat layer (alkali-solubilizing layer) by a silicate treatment is provided between the recording layer and the support. Have been attempted. According to these methods, the developability can be ensured to some extent, and the development latitude in the practical range can be obtained, but the adhesion between the recording layer and the support is lowered. In addition, in order to improve the stain resistance, smoothing the shape of the surface of the support in an attempt to eliminate the deep recesses that exist on the surface of the support, which causes residual film, greatly reduces printing durability. , It will be practically unusable. For this reason, a lithographic printing plate that has satisfactory printing durability and is less likely to become dirty and that is satisfactory in terms of ease of printing has not yet been realized.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a heat-sensitive layer which is excellent in both scratch resistance and sensitivity, and is excellent in stain resistance during printing and printing durability and is alkali-solubilized by photothermal conversion of laser light. The object is to provide a positive planographic printing plate having

[0006]

Means for Solving the Problems The present inventor has diligently studied to achieve the above object. The details will be described below. In the thermal positive type lithographic printing plate, as described above, a hydrophilic layer or an alkali solubilizing layer is provided at the interface between the heat sensitive layer and the support in order to secure the area of the development latitude within the practical range. For this reason, if the shape of the surface of the support is smoothed in an attempt to improve the stain resistance, the printing durability is significantly reduced. Here, the printing durability is largely dependent on the adhesion between the heat-sensitive layer and the support, and the adhesion changes substantially in correlation with the contact area between the heat-sensitive layer and the support, thus improving the printing durability. For this purpose, the surface area of the support may be increased to increase the contact area between the heat sensitive layer and the support.

On the other hand, in order to improve the stain resistance, it is necessary that the mist of the ink is less likely to be retained in the non-image area of the plate surface during printing. I thought it was necessary to reduce it. It has been found that stain resistance and printing durability can be maintained by making the surface shape of the aluminum support into a composite grain shape having a large wave structure having a specific average wavelength and a fine structure having a specific average pit diameter. The present invention has been completed. Furthermore, the inventors have found that by defining the crystal grain size and the alloy components contained in the aluminum plate, the graining property can be made uniform and stain resistance and printing durability can be further improved, and the present invention has been completed.

That is, according to the present invention, 1) a water-insoluble and alkali-soluble resin and an infrared absorbing dye are provided on a support obtained by roughening and anodizing aluminum or an aluminum alloy, and the solubility in an alkaline aqueous solution is increased by heating. In the lithographic printing plate provided with the heat-sensitive layer, the roughened shape of the support has a grainy shape of a composite structure of large and small double or more composed of a large wave structure and a small wave structure, and the large wave structure is 0.
Provided is a lithographic printing plate having an average wavelength of 5 to 30 µm and a wavelet structure having a pit structure having an average diameter of 0.01 to 0.3 µm.

The present invention also provides 2) mechanical roughening treatment of aluminum or aluminum alloy, electrochemical roughening treatment with an electrolytic solution containing nitric acid, and electrochemical roughening treatment with an electrolytic solution containing hydrochloric acid. The planographic printing plate according to 1) is treated by two or more treatment methods selected from the group consisting of chemical treatment and chemical dissolution treatment with an alkaline aqueous solution.

Here, it is preferable that the amount of aluminum dissolved in the chemical dissolution treatment with the alkaline aqueous solution, which is performed after the electrochemical graining treatment, is 0.5 g / m ² or less.

The aluminum plate used in the present invention is JIS
It is A1050 material, and the average crystal grain size is 2 to 20 with a minor axis.
It is preferably 0 μm and the major axis is 50 to 1500 μm. Further, Si is 0.02 to 0.1% and Cu is 0.00.
It is preferable to use an aluminum material containing 5% or less and 0.1 to 0.5% Fe.

The present invention further provides 3) a lithographic printing plate as described in 1) or 2), wherein the recording layer writable by laser exposure is a multi-layered photosensitive layer formed by coating a plurality of times. To do.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. [Aluminum support] <Aluminum plate (rolled aluminum)> The aluminum plate used in the lithographic printing plate of the present invention is a dimensionally stable metal containing aluminum as a main component, and is made of aluminum or an aluminum alloy. Besides pure aluminum plate,
It is also possible to use an alloy plate containing aluminum as a main component and a slight amount of a different element.

In the following description, the above-mentioned various substrates made of aluminum or aluminum alloy will be collectively referred to as aluminum plates. The foreign elements that may be contained in the aluminum alloy include silicon, iron, manganese,
There are copper, magnesium, chromium, zinc, bismuth, nickel, titanium, etc., and the content of foreign elements in the alloy is 10% by mass or less. Among them, the aluminum plate used in the present invention is preferably made of aluminum having a Cu content of 0.005 mass% or less. Si content is 0.1
Mass% or less, Cu content 0.005 mass% or less, Fe
More preferably, the content is 0.5 mass% or less of aluminum. It is an alloy classified as JIS 1050 to 1070, and improves the stain resistance by reducing the pit diameter especially in the electrolytic surface roughening, and achieves a balance between stain resistance and printing durability in combination with non-silicate development. Suitable for lithographic printing plates.

In the present invention, it is preferable to use a pure aluminum plate, but since completely pure aluminum is difficult to produce due to refining technology, it may contain a slightly different element. As described above, the composition of the aluminum plate used in the present invention is not specified, and a conventionally publicly known material such as JIS A105 is used.
0, JIS A1100, JIS A3005, JIS
Aluminum alloy plates such as A3004 and internationally registered alloy 3103A can be appropriately used. Among them, in terms of making the pit shape for electrolytic surface roughening small and deep, J
ISA1050 material is preferable, and the average crystal grain size of aluminum has a short diameter of 2 to 200 μm and a long diameter of 50 to 1
It is preferably 500 μm. If the crystal grains become large, the etching properties will differ depending on the crystal orientation, making uniform roughening difficult, and if the crystal grains become small, the strength will increase and the handling aptitude will deteriorate.

The aluminum plate used in the present invention is
Si 0.02-0.1%, Cu 0.005% or less,
More preferably, it is made of aluminum containing 0.1 to 0.5% of Fe. It is an alloy classified as JIS 1050 to 1070, and improves the stain resistance by reducing the pit diameter especially in the electrolytic surface roughening, and achieves a balance between stain resistance and printing durability in combination with non-silicate development. Suitable for lithographic printing plates.

The manufacturing method of the aluminum plate may be either a continuous casting method or a DC casting method, and an aluminum sheet without intermediate annealing of the DC casting method or soaking may be used. In the final rolling, it is also possible to use an aluminum plate having irregularities formed by lamination rolling or transfer. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm. This thickness can be appropriately changed according to the size of the printing machine, the size of the printing plate, and the desire of the user.

The aluminum support used in the lithographic printing plate of the present invention is obtained by providing the aluminum plate with a specific surface shape. The aluminum support used in the lithographic printing of the present invention is obtained by subjecting the aluminum plate to a roughening treatment and an anodizing treatment. In addition to the above, various commonly used steps (for example, alkali etching treatment, desmutting treatment with acid, etc.) may be included. The preferred method for producing the aluminum support of the present invention includes mechanical roughening treatment of aluminum or aluminum alloy, electrochemical roughening treatment with an electrolytic solution containing nitric acid, and electrical treatment with an electrolytic solution containing hydrochloric acid. Examples include a method of performing two or more kinds of treatments selected from the group consisting of a chemical surface roughening treatment and a chemical dissolution treatment with an alkaline aqueous solution. By combining multiple treatments in this way, it is possible to form complex shapes that cannot be obtained by a single treatment. Can be improved. Less than,
Various surface treatments performed on the aluminum plate will be described.

<Roughening treatment (graining treatment)> The aluminum plate is grained to a more preferable shape. The grain shape of the aluminum support used in the present invention must have a large and small double structure.
Specifically, the roughened shape of the aluminum support has a large wave structure with an average wavelength of 0.5 to 30 μm and an average pit diameter of 0.01.
It is a grain shape of a large and small double structure composed of a small wave structure of ˜0.3 μm.

The graining method is disclosed in JP-A-56-288.
There are mechanical graining, chemical etching, electrolytic graining, etc. as disclosed in Japanese Patent Laid-Open No. 93. Furthermore, an electrochemical graining method (electrochemical graining treatment, electrolytic graining treatment) in which a grain is electrochemically grained in a hydrochloric acid electrolytic solution or a nitric acid electrolytic solution, or a wire that is scratched with a metal wire on an aluminum surface Mechanical graining methods (mechanical graining treatment) such as brush grain method, ball grain method of graining the aluminum surface with abrasive balls and abrasives, brush grain method of graining the surface with nylon brush and abrasives Can be used. These graining methods can be used alone or in combination. For example, a combination of a mechanical surface roughening treatment with a nylon brush and an abrasive and an electrolytic surface roughening treatment with a hydrochloric acid electrolyte solution or a nitric acid electrolyte solution, or a combination of a plurality of electrolytic surface roughening treatments can be mentioned.

In the case of the brush grain method, the surface of the aluminum support is appropriately selected by appropriately selecting the conditions such as the average particle size of the particles used as the abrasive, the maximum particle size, the bristle size of the brush used, the density and the pressing pressure. It is possible to control the average depth of the concave portion having a long wavelength component (large wave). The concave portion obtained by the brush grain method has an average wavelength of 0.5 to
It is preferably 30 μm, and the average depth is 0.3 to 2.
It is preferably 0 μm. More preferably, the average wavelength is 1 to 15 μm.

As the electrochemical graining method, an electrochemical method of chemically graining in a hydrochloric acid electrolytic solution or a nitric acid electrolytic solution is preferable. A preferable power supply amount is 50 to 400 C / dm ² at the anode. More specifically, for example, in an electrolytic solution containing 0.1 to 50% by mass of hydrochloric acid or nitric acid, a temperature of 20 to 100 ° C., a time of 1 second to 30 minutes, a power supply amount of 100 to 400 C / dm ² , and a current density. 1-100A / d
It is performed using direct current or alternating current under the condition of m ² . According to the electrolytic surface roughening treatment, since it is easy to give fine irregularities to the surface, it is possible to enhance the adhesion between the heat sensitive layer and the support.

By the electrolytic graining treatment after the mechanical graining treatment, the average diameter is about 0.01 to 0.3 μm, more preferably 0.05 to 0.2 μm, and the average depth is 0.01 to 0. .4
Crater-shaped or honeycomb-shaped pits of μm can be formed on the surface of the aluminum plate at an area ratio of 90 to 100% to form a large and small double pit structure. The pits provided have the function of improving the stain resistance and printing durability of the non-image area of the printing plate. In the electrolytic surface roughening treatment, the amount of electricity required to provide sufficient pits on the surface, that is, the product of the current and the time when the current is passed is an important condition in the electrochemical roughening. It is desirable to form sufficient pits with a smaller amount of electricity from the viewpoint of energy saving. The surface roughness after the surface roughening treatment is JIS B0601.
The arithmetic mean roughness ( _Ra ) measured with a cutoff value of 0.8 mm and an evaluation length of 3.0 mm in accordance with -1994 is 0.
It is preferably 2 to 0.6 μm.

<Alkali Etching Treatment> The aluminum plate thus grained is preferably chemically etched with alkali. The alkaline agent preferably used in the present invention is not particularly limited,
Examples thereof include sodium hydroxide, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, and lithium hydroxide. Alkaline etching conditions are that the amount of Al dissolved is 0.05 to 5.0 g / m.
^It is preferable to carry out under the condition such that the amount of Al dissolved is 0.5 g /
It is preferable to carry out under the condition of m ² or less. It is known that when the amount of alkali etching after the electrolytic surface roughening treatment is more than 0.5 g / m ² , the grain shape becomes smoother and the adhesion of the photosensitive layer is significantly reduced. Further, other conditions are not particularly limited, but the alkali concentration is 1 to 5
It is preferably 0% by mass, more preferably 5 to 30% by mass, and the temperature of the alkali is 20 to 100%.
C. is preferable, and 30 to 50.degree. C. is more preferable. The alkali etching treatment is not limited to one method, and a plurality of steps can be combined.

The alkali etching treatment is not limited to the one-step treatment. For example, after carrying out mechanical surface roughening treatment, alkali etching treatment is carried out, followed by desmutting treatment (pickling for removing smut described later), further electrolytic roughening treatment, and then alkali etching again. Alkaline etching treatment and desmut treatment such as performing treatment and subsequent desmut treatment,
Both can be performed in combination a plurality of times.

After the alkali etching treatment, acid cleaning (desmut treatment) may be performed to remove stains (smut) remaining on the surface. Examples of the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and hydrofluoric acid. In particular, as a method for removing smut after electrolytic surface roughening treatment, 5 as described in JP-A-53-12739 is preferable.
A method of contacting with sulfuric acid of 15 to 65 mass% at a temperature of 0 to 90 ° C can be mentioned.

<Anodizing Treatment> It is preferable that the aluminum plate treated as described above is further subjected to anodizing treatment. At this time, it is necessary to reduce the number of micropores as much as possible in order to suppress the decrease in sensitivity due to the micropores. The anodizing treatment can be performed by a method conventionally used in this field. Specifically, sulfuric acid as a main component, phosphoric acid, chromic acid, oxalic acid, sulfamic acid,
When a direct current or an alternating current is applied to the aluminum plate in an aqueous solution containing a combination of benzenesulfonic acid and the like, an anodized film can be formed on the surface of the aluminum plate.

At this time, at least the components usually contained in the Al alloy plate, the electrode, the tap water, the groundwater, etc. may be contained in the electrolytic solution. Furthermore, the second and third components may be added. Examples of the second and third components here include Na, K, Mg, Li, Ca, Ti, and A.
Ions of metals such as l, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; cations such as ammonium ions; nitrate ions, carbonate ions, chloride ions, phosphate ions,
Anions such as fluoride ion, sulfite ion, titanate ion, silicate ion, and borate ion are included, and 0 to
It may be contained at a concentration of about 10,000 ppm.

The conditions of the anodizing treatment cannot be unconditionally determined because they vary depending on the electrolytic solution used, but generally the electrolytic solution concentration is 1 to 15% by mass, and the liquid temperature is -5 to 60.
C, current density 5 to 60 A / dm ² , voltage 1 to 200 V,
An electrolysis time of 10 to 200 seconds is suitable.

In the present invention, the amount of anodized film is 1
It is preferably ˜5 g / m ² . If it is less than 1 g / m ² , the plate is likely to be scratched, while if it exceeds 5 g / m ² , a large amount of electric power is required for production, which is economically disadvantageous. The amount of the anodized film is more preferably 1.5 to 4 g / m ² .

<Alkali metal silicate treatment> The aluminum support on which the anodized film obtained by the above treatment is formed is, if necessary, dipped in an aqueous solution of an alkali metal silicate. . The treatment conditions are not particularly limited, but, for example, using an aqueous solution having a concentration of 0.01 to 5.0 mass% at a temperature of 5 to 40 ° C. for 1 to 60 seconds, and then washing with running water. A more preferable dipping treatment temperature is 10 to 40 ° C., and a more preferable dipping time is 2 to 20 seconds.

Examples of the alkali metal silicate used in the present invention include sodium silicate, potassium silicate, and lithium silicate. The aqueous solution of alkali metal silicate may contain an appropriate amount of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like. Further, the aqueous solution of alkali metal silicate may contain an alkaline earth metal salt or a Group 4 (Group IVA) metal salt. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate; sulfates; hydrochlorides; phosphates; acetates; oxalates; borate. Examples of Group 4 (Group IVA) metal salts include:
Examples thereof include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride oxide, zirconium dioxide, zirconium oxychloride, and zirconium tetrachloride. These alkaline earth metal salts and Group 4 (Group IVA) metal salts may be used alone or in combination of two or more.

The amount of Si adsorbed by the alkali metal silicate treatment is measured by a fluorescent X-ray analyzer, and the adsorbed amount is preferably about 1.0 to 15.0 mg / m ² . By this alkali metal silicate treatment, the effect of improving the dissolution resistance of the aluminum support surface to the alkali developing solution is obtained, the elution of the aluminum component into the developing solution is suppressed, and the development residue caused by the fatigue of the developing solution is suppressed. Can be reduced.

[Image-Forming Layer] The lithographic printing plate of the present invention contains a water-insoluble and alkali-soluble resin and an infrared absorbing dye on the aluminum support obtained as described above and is heated to an alkaline aqueous solution. It is provided with a heat-sensitive layer whose solubility is increased. As such a heat sensitive layer, a heat sensitive layer composed of two or more layers is preferable. Since the alkali-soluble layer and the surface hardly-solubilized layer can be provided separately,
Greater day discrimination is obtained. As the heat-sensitive layer composed of two or more layers, for example, a heat-sensitive layer having an interlayer easily soluble alkali and a heat-sensitive layer sequentially solubilized by heating and a heat-sensitive layer having a multi-layer structure are provided separately from the intermediate layer. Is preferred. Hereinafter, the alkali-soluble intermediate layer and the heat-sensitive layer which is solubilized by heating will be described. The lithographic printing plate of the present invention has a two-layer structure such as an "intermediate layer" and a "heat-sensitive layer" described below, as well as one layer of the heat-sensitive layer, which is soluble in alkali on the aluminum support side. However, those having a structure in which the solubility is higher than that on the surface side are included.

<Intermediate Layer> In the planographic printing plate of the present invention,
Lucari easily soluble middle layer is a layer easily alkali soluble
Although not particularly limited, the weight of a monomer having an acid group is
It is preferable to contain a polymer, and a monomer having an acid group or
And a polymer containing a monomer having an onium group
More preferably. Below, the polymerization contained in the intermediate layer
Describe your body in detail. Polymer contained in the intermediate layer
Is a compound formed by polymerizing a monomer having at least an acid group.
And preferably a monomer having an acid group and
A compound obtained by polymerizing a monomer having an onium group.
It Here, the acid group has an acid dissociation index (pKa) of 7
The following acid groups are preferable, more preferably -COOH,-
SO₃H, -OSO₃H, -PO₃H₂, -OPO ₃H
₂, -CONHSO₂, -SO₂NHSO₂−,
Particularly preferred is -COOH. Also, with an onium group
Preferred are those of Group 15 of the Periodic Table (Group VB)
Is an onium group containing an atom of Group 16 (Group VIB)
And more preferably nitrogen atom, phosphorus atom or sulfur
An onium group containing an atom, particularly preferably nitrogen
It is an onium group containing an atom.

The polymer used in the present invention is preferably a polymer compound whose main chain structure is a vinyl-based polymer such as acrylic resin, methacrylic resin or polystyrene, urethane resin, polyester or polyamide. is there. More preferably, it is a polymer compound characterized in that the main chain structure of this polymer is a vinyl polymer such as an acrylic resin, a methacrylic resin or polystyrene. Particularly preferably, the monomer having an acid group is a compound represented by the following general formula (1) or general formula (2), and the monomer having an onium group is a general formula (3) or a general formula (4) described below. Alternatively, it is a polymer compound characterized by being a compound represented by the general formula (5).

[0037]

[Chemical 1]

In the formula, A represents a divalent linking group. B represents an aromatic group or a substituted aromatic group. D and E each independently represent a divalent linking group. G represents a trivalent linking group. X and X'independently represent an acid group having a pKa of 7 or less, or an alkali metal salt or ammonium salt thereof. R ₁ represents a hydrogen atom, an alkyl group or a halogen atom. a, b, d and e each independently represent 0 or 1. t is an integer of 1 to 3. Among the monomers having an acid group, more preferably, A represents —COO— or —CONH—, B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. D and E each independently represents a divalent linking group alkylene or molecular formula of _{C n H 2n O, C n} H 2n S or C _n H _{2n + 1} N. G represents a trivalent connecting group molecular formula is represented by _{C n H 2n-1, C} n H 2n-1 O, C n H 2n-1 S or C _n H _2n N. However,
Here, n represents an integer of 1 to 12. X and X ′ are each independently carboxylic acid, sulfonic acid, phosphonic acid,
Represents a sulfuric acid monoester or a phosphoric acid monoester. R
₁ represents a hydrogen atom or an alkyl group. a, b, d and e each independently represent 0 or 1, but a and b are not 0 at the same time. Among the monomers having an acid group, the compound represented by the general formula (1) is particularly preferable, B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. D and E each independently represent an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom. R ₁ represents a hydrogen atom or an alkyl group. X represents a carboxylic acid group. a is 0 and b is 1.

Specific examples of the monomer having an acid group are shown below. However, the present invention is not limited to this specific example. (Specific examples of monomers having an acid group) acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid, maleic anhydride

[0040]

[Chemical 2]

[0041]

[Chemical 3]

[0042]

[Chemical 4]

Next, the polymer represented by the following general formula (3), (4) or (5), which is an onium group-containing monomer, will be described.

[0044]

[Chemical 5]

In the formula, J represents a divalent linking group. K is fragrance
It represents a group group or a substituted aromatic group. M independently
It represents a divalent linking group. Y₁Is the periodic table 15 group (VB
Group) atom, Y₂Is the periodic table 16 group (VIB
Group) represents an atom. Z^-Represents a counter anion. R₂Is water
Represents an elementary atom, an alkyl group or a halogen atom. R₃,
R _Four, R_FiveAnd R₇Are each independently a hydrogen atom or
Is an alkyl optionally substituted with a substituent
Represents a group, an aromatic group or an aralkyl group, and R₆Is al
Represents a pyridyl group or a substituted alkylidyne, R₃And R
_FourOr R₆And R₇Are bonded together to form a ring
Good. j, k, and m are each independently 0 or 1.
Represent u represents an integer of 1 to 3. Model with onium group
More preferably among the nomers, J is -COO- or-.
Represents CONH-, and K is a phenylene group or a substituted phenyl group.
Represents a len group, the substituent of which is a hydroxyl group, a halogen atom or
Is an alkyl group. M is an alkylene group or a molecular formula
C_nH_2nO, C_nH_2nS or C_nH_{2n + 1}Represented by N
Represents a divalent linking group. However, here, n is 1 to 12
Represents the integer. Y₁Represents a nitrogen atom or a phosphorus atom,
Y₂Represents a sulfur atom. Z^-Is halogen ion, PF
₆ ^-, BF _Four ^-Or R₈SO₃ ^-Represents R₂Is hydrogen
Represents an atom or an alkyl group. R₃, R_Four, R_Fiveand
R₇Are each independently a hydrogen atom, or
Is an alkyl having 1 to 10 carbon atoms to which a substituent may be bonded.
Represents a group, an aromatic group or an aralkyl group, and R₆Is carbon
The number 1-10 alkylidyne group or substituted alkylidyne
Represents, but R₃And R_Four, And R₆And R₇Are each
They may combine to form a ring. j, k and m are respectively
Independently represent 0 or 1, but j and k are not 0 at the same time
Yes. R₈Is an alkyl group having 1 to 10 carbon atoms to which a substituent may be bonded.
It represents a rualkyl group, an aromatic group or an aralkyl group. Oniu
Particularly preferably among the monomers having a group, K is a phenol group.
Represents a nylene group or a substituted phenylene group, and the substituent is
It is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M is
Linked by an alkylene group having 1 to 2 carbon atoms or an oxygen atom
It represents an alkylene group having 1 to 2 carbon atoms. Z^-Is chlorine ion
Or R₈SO₃ ^-Represents R₂Is a hydrogen atom or methyl
Represents a radical. j is 0 and k is 1. R₈Is carbon
Represents an alkyl group of formulas 1 to 3.

Specific examples of the monomer having an onium group are shown below. However, the present invention is not limited to this specific example. (Specific examples of monomers having an onium group)

[0047]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8]

Even if the monomer having an acid group is used alone,
Two or more kinds may be used in combination, and the monomers having an onium group may be used alone or in combination of two or more kinds. Further, the polymer used in the present invention may be a mixture of two or more kinds having different monomers, composition ratios or molecular weights. At this time, the polymer having a monomer having an acid group as a polymerization component preferably contains 1 mol% or more of a monomer having an acid group, more preferably 5 mol% or more, and further contains a monomer having an onium group. The polymer as a polymerization component preferably contains an onium group-containing monomer in an amount of 1 mol% or more, more preferably 5 mol% or more.

Further, these polymers have the following (1) to
At least one selected from the polymerizable monomers shown in (14) may be contained as a copolymerization component. (1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o- or Acrylamides, methacrylamides, acrylic esters, methacrylic acid esters and vidroxystyrenes having aromatic hydroxyl groups such as m-chloro-p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate. (2) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and its half ester, itaconic acid, itaconic anhydride and its half ester,

(3) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl)) Naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonyl) Phenyl) methacrylamide, N- [1- (3-aminosulfonyl)
Naphthyl] methacrylamide, methacrylamides such as N- (2-aminosulfonylethyl) methacrylamide, o-aminosulfonylphenyl acrylate, m-aminosulfonylphenyl acrylate, p-
Aminosulfonylphenyl acrylate, unsaturated sulfonamides such as acrylic acid esters such as 1- (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, Unsaturated sulfonamides such as methacrylic acid esters such as 1- (3-aminosulfonylphenylnaphthyl) methacrylate,

(4) Phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide,
And phenylsulfonyl methacrylamide optionally having a substituent such as tosyl methacrylamide, (5) acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. ,
(6) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, (Substituted) acrylic acid esters such as 4-hydroxybutyl acrylate, glycidyl acrylate and N-dimethylaminoethyl acrylate, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, methacrylic acid Hexyl, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid-2-
(Substituted) methacrylic acid esters such as chloroethyl, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate,

(8) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N
-Phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide. Or vinyl ethers such as methacrylamide, (9) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether,

(10) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, (11) styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene, (12) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone, (13) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene,
(14) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

The polymer used here preferably contains 1 mol% or more of a monomer having an acid group, more preferably 5 mol% or more, and 1 mol% or more of a monomer having an onium group. It is preferable to contain 5 mol%
It is more preferable to include the above. Further, when the content of the monomer having an acid group is 20 mol% or more, the dissolution and removal during alkali development is further promoted, and the monomer having an onium group is 1% or less.
When it is contained in an amount of more than mol%, the adhesiveness is further improved by the synergistic effect with the acid group. The constituent component having an acid group may be used alone or in combination of two or more kinds.
The onium group-containing monomer may be used alone or in combination of two or more kinds. Further, the polymer used in the present invention may be a mixture of two or more kinds having different monomers, composition ratios or molecular weights. Next, typical examples of the polymer used in the present invention are shown below. The compositional ratio of the polymer structure represents a molar percentage.

[0057]

[Chemical 9]

[0058]

[Chemical 10]

[0059]

[Chemical 11]

[0060]

[Chemical 12]

[0061]

[Chemical 13]

[0062]

[Chemical 14]

[0063]

[Chemical 15]

[0064]

[Chemical 16]

[0065]

[Chemical 17]

The polymer used in the present invention can be generally produced by a radical chain polymerization method ("T
extbook of Polymer Science
e "3rd ed. (1984) FW Billme.
yer, A Wiley-Interscience
Publication)).

The molecular weight of the polymer used in the present invention may be in a wide range, but when measured by a light scattering method,
Weight average molecular weight (M _w ) is 500 to 2,000,000
Is preferable, and the range of 1,000 to 600,000 is more preferable. Further, the number average molecular weight (M _n ) calculated from the integrated intensity of the terminal group and the side chain functional group in the NMR measurement is preferably 300 to 500,000, and preferably 500 to 100,000. More preferable. When the molecular weight is smaller than the above range, the adhesion to the substrate becomes weak and the printing durability may deteriorate. On the other hand, when the molecular weight becomes larger than the above range,
In some cases, the adhesion to the support becomes too strong, and the residue of the heat-sensitive layer in the non-image area cannot be sufficiently removed. The amount of unreacted monomer contained in the polymer may be in a wide range, but is preferably 20% by mass or less, more preferably 10% by mass or less.

The polymer having a molecular weight in the above range can be obtained by using a polymerization initiator and a chain transfer agent together and adjusting the addition amount when copolymerizing the corresponding monomers. The chain transfer agent refers to a substance that moves the active point of the reaction by a chain transfer reaction in the polymerization reaction, and the easiness of the transfer reaction depends on the chain transfer constant C
It is represented by s. The chain transfer constant Cs × 10 ⁴ (60 ° C.) of the chain transfer agent used in the present invention is preferably 0.01 or more, more preferably 0.1 or more, 1
The above is particularly preferable. As the polymerization initiator, peroxides, azo compounds, and redox initiators that are commonly used in radical polymerization can be used as they are. Of these, azo compounds are particularly preferable.

Specific examples of the chain transfer agent include halogen compounds such as carbon tetrachloride and carbon tetrabromide, alcohols such as isopropyl alcohol and isobutyl alcohol, and 2-
Olefins such as methyl-1-butene and 2,4-diphenyl-4-methyl-1-pentene, ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercapto Propionic acid, thioglycolic acid, ethyl disulfide,
Examples thereof include, but are not limited to, sulfur-containing compounds such as sec-butyl disulfide, 2-hydroxyethyl disulfide, thiosalicylic acid, thiophenol, thiocresol, benzyl mercaptan and phenethyl mercaptan. More preferably, ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyl disulfide, sec-butyl disulfide, 2-hydroxyethyl disulfide. , Thiosalicylic acid, thiophenol,
Thiocresol, benzyl mercaptan, phenethyl mercaptan, particularly preferably ethanethiol,
Butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyl disulfide, sec-butyl disulfide and 2-hydroxyethyl disulfide.

The amount of unreacted monomer contained in this polymer may be in a wide range, but it is preferably 20% by mass or less, and more preferably 10% by mass or less.

Next, synthesis examples of the polymer used in the present invention will be shown. [Synthesis Example 1] Synthesis of polymer (No. 1) 50.4 g of p-vinylbenzoic acid (manufactured by Kitako Chemical Co., Ltd.), triethyl (p
-Vinylbenzyl) ammonium chloride 15.2 g,
Mercaptoethanol 1.9 g and methanol 15
3.1 g was placed in a 2 L three-necked flask, and heated at 60 ° C. with stirring under a nitrogen stream. To this solution, 2.8 g of 2,2'-azobis (isobutyric acid) dimethyl was added, and stirring was continued for 30 minutes. Then, 201.5 g of p-vinylbenzoic acid and 60. triethyl (p-vinylbenzyl) ammonium chloride were added to the reaction solution.
9 g, mercaptoethanol 7.5 g and 2,2'-
A solution prepared by dissolving 11.1 g of dimethyl azobis (isobutyrate) in 612.3 g of methanol was added dropwise over 2 hours. After the dropping is completed, the temperature is raised to 65 ° C. and the temperature is raised to 10 ° C. under a nitrogen stream.
Continued stirring for hours. When the reaction solution was left to cool to room temperature after completion of the reaction, the yield of this reaction solution was 1132 g, and the solid content concentration was 30.5% by mass. Further, the number average molecular weight ( _Mn ) of the obtained product was determined from ¹³ C-NMR spectrum, and as a result, the value was 2,100.

[Synthesis Example 2] Synthesis of Polymer (No. 2) Instead of triethyl (p-vinylbenzyl) ammonium chloride, a mixture of triethyl (vinylbenzyl) ammonium chloride in the m / p form (2/1) was used. A polymer having a number average molecular weight (M _n ) of 4,800 was obtained by performing the same operation as in Synthesis Example 1, except that ethyl mercaptopropionate was used instead of mercaptoethanol.

[Synthesis Example 3] Synthesis of polymer (No. 25) 146.9 g of p-vinylbenzoic acid (manufactured by Kitako Chemical Co., Ltd.)
(0.99 mol), 44.2 g (0.21 mol) of vinylbenzyltrimethylammonium chloride and 2
-Methoxyethanol (446 g) was placed in a 1 L three-necked flask and heated at 75 ° C. with stirring under a nitrogen stream.
Kept at. Next, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added and stirring was continued. Two hours later, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added. Further, after 2 hours, 2,2-azobis (isobutyric acid) dimethyl 2.76.
g (12 mmol) was added. After stirring for 2 hours, the mixture was allowed to cool to room temperature. Stir this reaction mixture for 12 hours
Pour into L ethyl acetate. The precipitated solid was collected by filtration and dried. The yield was 189.5 g. As a result of measuring the molecular weight of the obtained solid by a light scattering method, the weight average molecular weight (M _w ) was 32,000.

The other polymers used in the present invention are synthesized in the same manner.

The intermediate layer of the lithographic printing plate of the present invention comprises
In addition to the polymer, a compound represented by the following general formula (6) can be added.

[0076]

[Chemical 18]

(In the formula, R ₁ represents an arylene group having 6 to 14 carbon atoms, and m and n independently represent an integer of 1 to 3.) Regarding the compound represented by the general formula (6), Explained. The arylene group represented by R ₁ has 6 to ₁ carbon atoms.
It is preferably 4 and more preferably 6 to 10. Specific examples of the arylene group represented by R ₁ include a phenylene group, a naphthyl group, an anthryl group, and a phenathryl group. The arylene group represented by R ₁ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and 6 carbon atoms.
10 aryl groups, carboxylic acid ester groups, alkoxy groups, phenoxy groups, sulfonic acid ester groups, phosphonic acid ester groups, sulfonylamide groups, nitro groups, nitrile groups, amino groups, hydroxy groups, halogen atoms, ethylene oxide groups, It may be substituted with a propylene oxide group, a triethylammonium chloride group or the like.

Specific examples of the compound represented by the general formula (6) include, for example, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, salicylic acid and 1-hydroxy-2-.
Examples thereof include naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydrosikyl-3-naphthoic acid, 2,4-dihydroxybenzoic acid and 10-hydroxy-9-anthracenecarboxylic acid. However, the present invention is not limited to the above specific example. Further, the compound represented by the general formula (6) may be used alone or in combination of two or more kinds.

The intermediate layer containing the above-mentioned polymer used in the present invention and the compound represented by the above-mentioned general formula (6) which is optionally added is coated on the above-mentioned aluminum support by various methods. It is provided.

As the method for providing this intermediate layer, for example, an organic solvent such as methanol, ethanol or methyl ethyl ketone, a mixed solvent thereof or a mixed solvent of these organic solvent and water and the polymer used in the present invention and, if necessary, A coating method in which a solution of the compound represented by the general formula (6), which is added in accordance with the above, is coated on an aluminum support and dried, an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof, or these After immersing the aluminum support in a solution prepared by dissolving the polymer used in the present invention and the compound represented by the general formula (6), which is optionally added, in a mixed solvent of the organic solvent and water of Examples of the method include washing with water, washing with air or the like and drying.

In the former method, the total amount of the above compounds is 0.
A solution having a concentration of 005 to 10% by mass can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, or curtain coating may be used.
Moreover, in the latter method, the concentration of the solution is 0.005 to 20.
% By mass, preferably 0.01% to 10% by mass, the dipping temperature is 0 ° C. to 70 ° C., preferably 5 to 60 ° C., and the dipping time is 0.1 seconds to 5 minutes, preferably 0.5. Seconds to 120 seconds.

The above solution contains basic substances such as ammonia, triethylamine and potassium hydroxide, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid, organic sulfonic acids such as nitrobenzenesulfonic acid and naphthalenesulfonic acid, and phenylphosphone. Organic phosphonic acids such as acids, benzoic acid, coumaric acid, various organic acidic substances such as organic carboxylic acids such as malic acid,
Adjust the pH with organic chloride such as naphthalene sulfonyl chloride, benzene sulfonyl chloride,
It can also be used in the range of pH = 0 to 12, more preferably pH = 0 to 6. Further, in order to improve the tone reproducibility of the lithographic printing plate, a substance that absorbs ultraviolet light, visible light, infrared light or the like can be added.

The total amount of the compound constituting the intermediate layer of the lithographic printing plate of the present invention after drying is 1 to 100 mg / m ^2.
Is suitable, and preferably ² to 70 mg / m ² .
If the coating amount is less than 1 mg / m ² , sufficient effects may not be obtained. The same applies when the amount is more than 100 mg / m ² .

<Heat-sensitive layer 1> The heat-sensitive layer of the lithographic printing plate of the present invention, which is alkali-solubilized by heating, contains a positive photosensitive composition for infrared laser (hereinafter, also simply referred to as "photosensitive composition"). To do. The positive photosensitive composition for infrared laser contained in the heat-sensitive layer is at least (A) an alkali-soluble polymer compound, and (B) is compatible with the alkali-soluble polymer compound to form an alkaline aqueous solution of the polymer compound. And a compound which reduces the solubility of the compound and reduces the solubility-decreasing effect by heating, and (C) a compound which absorbs light and generates heat, and further, if necessary,
(D) Contains other components.

(A) Alkali-Soluble Polymer Compound The alkali-soluble polymer compound used in the present invention is not particularly limited, and conventionally known compounds can be used.
(1) Phenolic hydroxyl group, (2) Sulfonamide group,
And (3) a polymer compound having any of the functional groups of the active imide group in the molecule is preferable. For example, the following may be mentioned, but the invention is not limited thereto.

(1) As the polymer compound having a phenolic hydroxyl group, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m
Any of-, p- and m- / p-mixtures may be used. ) Examples include novolac resins such as mixed formaldehyde resins and pyrogallol acetone resins. In addition to the above, the polymer compound having a phenolic hydroxyl group is preferably a polymer compound having a phenolic hydroxyl group in the side chain. As the polymer compound having a phenolic hydroxyl group in the side chain, a polymerizable monomer consisting of a low molecular weight compound having one or more unsaturated bonds capable of polymerizing with a phenolic hydroxyl group is homopolymerized, or other monomer is added to the monomer. Examples thereof include polymer compounds obtained by copolymerizing a polymerizable monomer.

Examples of the polymerizable monomer having a phenolic hydroxyl group include acrylamide, methacrylamide, acrylic acid ester having a phenolic hydroxyl group,
Methacrylic acid ester; hydroxystyrene can be mentioned. Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3 -Hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate,
m-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene,
m-hydroxystyrene, p-hydroxystyrene, 2
-(2-hydroxyphenyl) ethyl acrylate, 2
-(3-hydroxyphenyl) ethyl acrylate, 2
-(4-hydroxyphenyl) ethyl acrylate, 2
-(2-hydroxyphenyl) ethyl methacrylate,
2- (3-Hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate, etc. can be used conveniently. The resin having such a phenolic hydroxyl group may be used in combination of two or more kinds. Further, as described in US Pat. No. 4,123,279, phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin. You may use together the condensation polymer with.

(2) The alkali-soluble polymer compound having a sulfonamide group is obtained, for example, by homopolymerizing a polymerizable monomer having a sulfonamide group or copolymerizing the monomer with another polymerizable monomer. Examples of the polymer compound include: Examples of the polymerizable monomer having a sulfonamide group include a sulfonamide group —NH—SO ₂ — having at least one hydrogen atom bonded to a nitrogen atom in one molecule and a polymerizable unsaturated bond. Examples of the polymerizable monomer include a low molecular weight compound having three or more. Among them, a low molecular weight compound having an acryloyl group, an allyl group or a vinyloxy group and a mono-substituted aminosulfonyl group or a substituted sulfonylimino group is preferable. Examples of such a compound include compounds represented by the following general formulas (I) to (V).

[0089]

[Chemical 19]

In the formula, X¹And X²Are respectively -O-
Or -NR₇-Indicates. R₁And R_FourRespectively
Hydrogen atom or -CH₃Represents R₂, R_Five, R₉, R
₁₂And R₁₆Is an optionally substituted charcoal
An alkylene group having a prime number of 1 to 12, a cycloalkylene group,
It represents a rylene group or an aralkylene group. R₃, R₇Oh
And R₁₃Have a hydrogen atom or a substituent respectively
Optionally an alkyl group having 1 to 12 carbon atoms, cycloalkyl
Represents a group, an aryl group or an aralkyl group. Also, R₆
And R₁₇Are each optionally substituted carbon
Number 1 to 12 alkyl group, cycloalkyl group, aryl
Represents a group or an aralkyl group. R₈, R _TenAnd R
₁₄Is a hydrogen atom or -CH₃Represents R₁₁And R₁₅
May each have a single bond or a substituent.
An alkylene group having 1 to 12 carbon atoms, a cycloalkylene group,
Represents an arylene group or an aralkylene group. Y¹And
And Y²Each represent a single bond or -CO-. Concrete
Specifically, m-aminosulfonylphenyl methacrylate
G, N- (p-aminosulfonylphenyl) methacryl
Amide, N- (p-aminosulfonylphenyl) acry
Lamide and the like can be preferably used.

(3) The alkali-soluble polymer compound having an active imide group is preferably one having an active imide group represented by the following formula in its molecule. With an active imide group represented by, homopolymerizing a polymerizable monomer consisting of a low molecular weight compound having one or more polymerizable unsaturated bonds, respectively, or
Examples thereof include polymer compounds obtained by copolymerizing the monomer with other polymerizable monomers.

[0092]

[Chemical 20]

Specific examples of such a compound include:
N- (p-toluenesulfonyl) methacrylamide, N
-(P-toluenesulfonyl) acrylamide etc. can be used conveniently.

Further, as the alkali-soluble polymer compound used in the present invention, two of the above-mentioned polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, and a polymerizable monomer having an active imide group are used. Preferable are polymer compounds obtained by polymerizing one or more kinds, or polymer compounds obtained by copolymerizing other polymerizable monomers with two or more kinds of polymerizable monomers.
When a polymerizable monomer having a phenolic hydroxyl group and a polymerizable monomer having a sulfonamide group and / or a polymerizable monomer having an active imide group are copolymerized, the compounding mass ratio of these components is from 50:50 to 5: 5. 95
The preferred range is 40:60 to 10:90
Is more preferably in the range.

The alkali-soluble polymer compound is a copolymer of the above-mentioned polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group, and another polymerizable monomer. In some cases, those containing 10 mol% or more of the monomer imparting alkali solubility are preferable, and those containing 20 mol% or more are more preferable. When the content of the copolymerization component is less than 10 mol%, the alkali solubility tends to be insufficient, and the effect of improving the development latitude may not be sufficiently achieved.

Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group include the following (1) to (1
The monomers mentioned in 2) can be used, but the monomers are not limited to these. (1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylate such as acrylate. (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl. Alkyl methacrylate such as methacrylate.

(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N -Acrylamide and methacrylamide such as ethyl-N-phenylacrylamide. (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether. (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(7) Styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene. (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (12) acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid.

In the present invention, the alkali-soluble polymer compound is a homopolymer or copolymer of the above-mentioned polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group. In some cases, it is preferable that the weight average molecular weight is 2,000 or more and the number average molecular weight is 500 or more. More preferably, the weight average molecular weight is 5,000 to
300,000 and a number average molecular weight of 800 to 25
And the degree of dispersion (weight average molecular weight / number average molecular weight) is 1.1 to 10. In the present invention, when the alkali-soluble polymer compound is a resin such as phenol formaldehyde resin or cresol aldehyde resin, the weight average molecular weight is 500 to 20,000.
It is 0, and those having a number average molecular weight of 200 to 10,000 are preferable.

These alkali-soluble polymer compounds may be used alone or in combination of two or more, and are preferably 30 to 99 in the total solid content of the heat-sensitive layer.
It is used in an amount of 100% by mass, more preferably 40 to 95% by mass, and particularly preferably 50 to 90% by mass. When the amount of the alkali-soluble polymer compound added is less than 30% by mass, the durability of the heat-sensitive layer deteriorates, and when it exceeds 99% by mass, it is not preferable in terms of both sensitivity and durability.

(B) A compound which, when compatible with the alkali-soluble polymer compound, reduces the solubility of the polymer compound in an aqueous alkaline solution and reduces the solubility-reducing action by heating. Has a good compatibility with the (A) alkali-soluble polymer compound due to the action of the hydrogen-bonding functional group present in the molecule, and can form a uniform coating solution, It refers to a compound having a function of suppressing alkali solubility of the polymer compound by interaction. Further, although this compound loses its solubility-reducing effect by heating, when the component (B) itself is a compound that decomposes by heating, sufficient energy for decomposition is not imparted depending on conditions such as laser output and irradiation time. If so, the effect of suppressing the solubility becomes insufficient and the sensitivity may decrease. Therefore, the thermal decomposition temperature of the component (B) is preferably 150 ° C. or higher.

Suitable component (B) used in the present invention includes, for example, sulfone compounds, ammonium salts, phosphonium salts, amide compounds, and other compounds that interact with component (A). As described above, the component (B) should be appropriately selected in consideration of the interaction with the component (A). Specifically, for example, when a novolac resin is used alone as the component (A). The cyanine dye A and the like exemplified below are preferably used.

The compounding ratio of the component (A) and the component (B) is usually preferably in the range of 99/1 to 75/25.
When the amount of the component (B) is less than 99/1, the interaction with the component (A) becomes insufficient, alkali solubility cannot be hindered, and it is difficult to form a good image. Further, when the amount of the component (B) is more than 75/25, the interaction is excessive and the sensitivity is remarkably lowered, which is not preferable.

(C) Compound that absorbs light and generates heat: The compound that absorbs light and generates heat in the present invention is 70
There is a light absorption region in the infrared region of 0 nm or more, preferably 750 to 1200 nm, and in the light of the wavelength of this range, light /
Refers to those that exhibit heat conversion ability. Specifically, various pigments or dyes that absorb light in this wavelength range and generate heat can be used. Examples of the pigment include commercially available pigments or color index (CI) handbooks, "latest pigment handbook" (edited by Japan Pigment Technology Association, 1977), "latest pigment application technology" (CMC Publishing, 1986) and " The pigments described in "Printing Ink Technology", CMC Publishing Co., Ltd., 1984) can be used.

Examples of the pigment include black pigment, yellow pigment, orange pigment, brown pigment, red pigment,
Examples include 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. A quinophthalone pigment, a dyed lake pigment, an azine pigment, a nitroso pigment, a nitro pigment, a natural pigment, a fluorescent pigment, an inorganic pigment, and carbon black can be used.

These pigments may be used without surface treatment or may be subjected to surface treatment before use. Examples of the surface treatment method include a method of surface-coating a resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate) to the pigment surface. Be done. 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.

The particle size of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. . When the particle size of the pigment is less than 0.01 μm, it is not preferable from the viewpoint of stability of the dispersion in the heat-sensitive layer coating liquid, and when it exceeds 10 μm, it is not preferable from the viewpoint of uniformity of the heat-sensitive layer.

As a method of dispersing the pigment, a known dispersion technique used in ink production, toner production, etc. can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three roll mill, and a pressure kneader. For details, see "Latest Pigment Application Technology" (CM
C Publishing, 1986).

As the dyes, commercially available dyes and literatures (for example, "Dye Handbook" edited by the Society of Organic Synthetic Chemistry, Showa 4)
The publicly known thing described in the 5-year publication can be used. Specifically, 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 can be used.

In the present invention, among these pigments or dyes, those absorbing infrared light or near infrared light are
It is particularly preferable in that it is suitable for use with a laser that emits infrared light or near infrared light.

Carbon black is preferably used as such a pigment that absorbs infrared light or near infrared light.
Further, as the dye that absorbs infrared light or near infrared light,
For example, JP-A-58-125246 and JP-A-59.
-84356, JP-A-59-202829, JP-A-60-78787, and other cyanine dyes, JP-A-58-173696, JP-A-58-181690, and JP-A-58-181690. Kaisho 58-19459
No. 5, methine dyes described in JP-A-58-
112793, JP-A-58-224793, JP-A-59-48187, and JP-A-59-73.
996, JP-A-60-52940, JP-A-60-63744, and the like, naphthoquinone dyes, JP-A-58-112792, and the like, squarylium dyes, British Patent No. 434,875
Cyanine dyes described in U.S. Pat.
The dihydroperimidine squarylium dyes described in the specification of No. 0,635 can be mentioned.

Further, as the dye, US Pat.
The near infrared absorption sensitizer described in US Pat. No. 6,938, is also preferably used, and the substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, especially Trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, JP-A-58-220143, and JP-A-58-220143. 59-41363
JP-A-59-84248, JP-A-59-84248
84249, JP-A-59-146063,
Pyrylium compounds described in JP-A-59-146061, cyanine dyes described in JP-A-59-216146, and pentamethinethiopyrylium described in U.S. Pat. No. 4,283,475. Salts and the like, pyrilium compounds disclosed in JP-B-5-13514 and JP-B-5-19702, and Epolyight I
II-178, Epolight III-130, Epol
light III-125, Epolight IV-62A
Etc. are particularly preferably used.

Another particularly preferable example of the dye is a near-infrared absorbing dye described as the formula (I) or (II) in US Pat. No. 4,756,993. it can.

These pigments or dyes are preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the heat-sensitive layer. 5 to 10% by mass, and in the case of a pigment, particularly preferably 3.1 to 10% by mass, can be added to the photosensitive composition. Addition amount of pigment or dye is 0.0
If it is less than 1% by mass, the sensitivity will be low, and if it exceeds 50% by mass, the uniformity of the heat-sensitive layer will be lost and the durability of the heat-sensitive layer will be deteriorated. These dyes or pigments may be added to the same layer as other components, or may be added to another layer provided separately. When it is formed as a separate layer, it is preferably added to a layer adjacent to the layer containing a substance which is a substance which substantially decomposes the solubility of the alkali-soluble polymer compound in the state of being thermally decomposable and not decomposed. Further, the dye or pigment and the alkali-soluble polymer compound are preferably contained in the same layer, but they may be contained in different layers.

Component (B + C) In the present invention, the solubility of the polymer compound in an alkaline aqueous solution is reduced by being compatible with the alkali-soluble polymer compound (B). Instead of the compound that decreases and the compound (C) that absorbs light and generates heat, one compound having both properties (hereinafter, also referred to as “(B + C) component”) may be contained. Such compounds include, for example:
The thing represented by the following general formula (Z) is mentioned.

[0116]

[Chemical 21]

In the general formula (Z), R _{1 to} R ₄ are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group,
Represents a cycloalkyl group or an aryl group, R ₁ and R
₂ , R ₃ and R ₄ may be bonded to each other to form a ring structure. Here, as R _{1 to} R ₄ , specifically,
Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group, an allyl group and a cyclohexyl group. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester. R _{5 to} R ₁₀ each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent, and
Specific examples of R _{5 to} R ₁₀ include a methyl group, an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group,
Examples thereof include allyl group and cyclohexyl group. Further, when these groups have a substituent, as the substituent,
Halogen atom, carbonyl group, nitro group, nitrile group,
Sulfonyl group, carboxyl group, carboxylic acid ester,
Examples thereof include sulfonic acid ester.

R _{11 to} R ₁₃ are each independently a hydrogen atom,
1-8 carbon atoms which may have a halogen atom or a substituent
Represents an alkyl group of R ₁₂ and R ₁₂ is R ₁₁ or R ₁₃
May combine with each other to form a ring structure, and in the case of m> 2, plural R _{12 s} may combine with each other to form a ring structure. Specific examples of R _{11 to} R ₁₃ include a chlorine atom, a cyclohexyl group, a cyclopentyl ring formed by combining R _12's , a cyclohexyl ring, and the like. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester. Moreover, m represents the integer of 1-8, Preferably it is 1-3. R ₁₄ and R
₁₅ independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent,
R ₁₄ may combine with R ₁₅ to form a ring structure, m
In the case of> 2, a plurality of R _14's may combine with each other to form a ring structure. Specific examples of R ₁₄ and R ₁₅ include a chlorine atom, a cyclohexyl group, a cyclopentyl ring formed by combining R _14's , a cyclohexyl ring, and the like. When these groups have a substituent, the substituent may be a halogen atom, a carbonyl group, a nitro group,
Examples thereof include a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester. Moreover, m represents the integer of 1-8, Preferably it is 1-3.

In the general formula (Z), X ⁻ represents an anion. Specific examples of the compound that becomes an anion include:
Perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4. 6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-
Chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, para Toluenesulfonic acid may be mentioned. Among these, in particular, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, and alkyl aromatic sulfonic acids such as 2,5-dimethylbenzenesulfonic acid are preferably used.

The compound represented by the general formula (Z) is a compound generally called a cyanine dye, and specifically, the following compounds are preferably used, but the present invention is not limited to this specific example. Not something.

[0121]

[Chemical formula 22]

The component (B + C) has a property of absorbing light to generate heat (that is, the property of the component (C)), has an absorption region in the infrared region of 700 to 1200 nm, and is alkali-soluble. Good compatibility with high molecular compounds,
Since it is a basic dye and has a group that interacts with an alkali-soluble polymer compound such as an ammonium group and an iminium group in the molecule (that is, it has the characteristic of the component (B)),
It can interact with the polymer compound to control its alkali solubility and can be preferably used in the present invention.

In the present invention, the component (B) and the component (C)
When a compound (B + C) component having both properties such as the above cyanine dye is used instead of the component, the addition amount of this compound is 99/1 to 7 with respect to the component (A).
The range of 0/30 is preferable from the viewpoint of sensitivity, and 9
The range of 9/1 to 75/25 is more preferable.

(D) Other Components Various additives may be added to the photosensitive composition used in the present invention, if necessary. For example, cyclic acid anhydrides, phenols, organic acids, and sulfonyl compounds can be used together for the purpose of improving sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 3,6-endooxy-Δ4-tetrahydroanhydride described in US Pat. No. 4,115,128. Examples thereof include phthalic acid, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic dianhydride.
Examples of phenols include bisphenol A and p
-Nitrophenol, p-ethoxyphenol, 2,
4,4'-trihydroxybenzophenone, 2,3,4
-Trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyl Triphenylmethane may be mentioned.

Examples of organic acids include, for example, JP-A-60-
Examples thereof include sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric acid esters and carboxylic acids described in JP-A-88942 and JP-A-2-96755. Specifically, for example, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipine. Acid, p-
Toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid,
Examples thereof include terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid, bishydroxyphenyl sulfone, methylphenyl sulfone and diphenyldisulfone.

The ratio of the above cyclic acid anhydride, phenols, organic acids and sulfonyl compounds in the solid content of the above-mentioned photosensitive composition is preferably 0.05 to 20% by mass and 0.1 It is more preferably -15% by mass, and particularly preferably 0.1-10% by mass.

In the photosensitive composition of the present invention, in order to extend the stability of processing under developing conditions, JP-A-62-251740 and JP-A-3-20851 are incorporated.
A nonionic surfactant as described in JP-A-
JP-A-59-121044 and JP-A-4-1314
Amphoteric surfactants such as those described in JP 9 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, and 2-alkyl-N-.
Examples thereof include carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name "Amorgen K", manufactured by Dai-ichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and the amphoteric surfactant in the solid content of the photosensitive composition is
It is preferably 0.05 to 15% by mass, and 0.1 to 5
More preferably, it is mass%.

In the above-mentioned photosensitive composition used in the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure and a dye or pigment as an image colorant can be added. Examples of the print-out agent include a combination of a compound that releases an acid when heated by exposure (photo-acid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, and JP-A- 53-36223, JP-A-54-74
728, JP 60-3626, and JP 6
A combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A-1-143748, JP-A-61-151644 and JP-A-63-58440 can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give a clear printout image.

As the image colorant, a dye other than the above-mentioned salt-forming organic dye can be used. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, for example, 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 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI. 42555). , Methyl violet (CI. 42535), ethyl violet, rhodamine B (CI. 145170B), malachite green (CI. 42000), methylene blue (CI.
I. 52015). In addition, JP-A-62-2
The dyes described in JP-A-93247 and JP-A-5-313359 are particularly preferable. These dyes are preferably added to the solid content of the photosensitive composition in an amount of 0.
It can be added to the photosensitive composition at a rate of 01 to 10% by mass, more preferably 0.1 to 3% by mass.

A plasticizer may be added to the photosensitive composition used in the present invention, if necessary, in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid. Oligomers and polymers are used. Further, if necessary, a compound such as a quinonediazide compound or a diazo compound which is decomposed by light may be added to the photosensitive composition used in the present invention. The addition amount of these compounds is preferably 1 to 5 mass% with respect to the solid content of the photosensitive composition.

The heat-sensitive layer according to the present invention can be usually prepared by dissolving each of the above components in a solvent and coating the solution on a suitable support. Examples of the solvent used here include 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,
Dimethoxyethane, methyl lactate, ethyl lactate, N, N-
Dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone,
Toluene may be mentioned, but not limited to. These solvents are used alone or as a mixture. The above components in the solvent (total solids including additives)
The concentration is preferably 1 to 50% by mass.

The coating amount (solid content) of the heat-sensitive layer on the support obtained after coating and drying is preferably 0.5 to 5.0 g / m ² .

Various methods can be used for coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate.

A surfactant for improving the coating property, for example, a fluorine-based surfactant as described in JP-A-62-170950 can be added to the heat-sensitive layer. The preferable addition amount is 0.01 to 1% by mass, and more preferably 0.05 to 0.5% by mass, based on the total solid content of the heat-sensitive layer.

<Heat-sensitive layer 2> The heat-sensitive layer preferably used in the lithographic printing plate precursor according to the invention has a laminated structure and is provided at a position close to the surface (exposed surface). A heat-sensitive layer having a lower layer containing an alkali-soluble resin provided on the side closer to the support can be mentioned. Each of these layers contains a water-insoluble and alkali-soluble resin, and the upper heat-sensitive layer contains an infrared absorbing dye. Hereinafter, each component of the heat sensitive layer will be described.

[Alkali-Soluble Polymer] In the present invention, the water-insoluble and alkali-water-soluble polymer compound used in the heat-sensitive layer and the lower layer (hereinafter appropriately referred to as alkali-soluble polymer) means A homopolymer containing an acidic group in the main chain and / or side chain, a copolymer thereof, or a mixture thereof is included. Therefore, the polymer layer according to the present invention has a property of dissolving when contacted with an alkaline developer. The alkali-soluble polymer used in the lower layer of the present invention and the heat-sensitive layer is not particularly limited as long as it is a conventionally known polymer, but (1) a phenolic hydroxyl group,
It is preferable that the polymer compound has a functional group of either (2) sulfonamide group or (3) active imide group in the molecule. For example, the following are exemplified, but the invention is not limited thereto.

(1) As the polymer compound having a phenolic hydroxyl group, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m
-, P-, or m- / p-mixture may be used) Novolak resins such as mixed formaldehyde resins and pyrogallol acetone resins. In addition to the above, the polymer compound having a phenolic hydroxyl group is preferably a polymer compound having a phenolic hydroxyl group in the side chain. As the polymer compound having a phenolic hydroxyl group in the side chain, a polymerizable monomer composed of a low molecular weight compound having at least one unsaturated bond capable of polymerizing with the phenolic hydroxyl group is homopolymerized, or another polymerizable compound is added to the monomer. Examples thereof include polymer compounds obtained by copolymerizing monomers.

Examples of the polymerizable monomer having a phenolic hydroxyl group include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene having a phenolic hydroxyl group. Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3 -Hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate,
m-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene,
m-hydroxystyrene, p-hydroxystyrene, 2
-(2-hydroxyphenyl) ethyl acrylate, 2
-(3-hydroxyphenyl) ethyl acrylate, 2
-(4-hydroxyphenyl) ethyl acrylate, 2
-(2-hydroxyphenyl) ethyl methacrylate,
2- (3-Hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate, etc. can be used conveniently. The resin having such a phenolic hydroxyl group may be used in combination of two or more kinds. Further, U.S. Pat. No. 4,123,279.
As described in the specification, even if a condensation polymer of phenol and formaldehyde having a C3-8 alkyl group as a substituent, such as t-butylphenolformaldehyde resin and octylphenolformaldehyde resin, is used in combination. Good.

(2) As the alkali-soluble polymer compound having a sulfonamide group, a polymer compound obtained by homopolymerizing a polymerizable monomer having a sulfonamide group or copolymerizing the polymerizable monomer with another polymerizable monomer. Is mentioned. Examples of the polymerizable monomer having a sulfonamide group include a sulfonamide group —NH—SO ₂ — having at least one hydrogen atom bonded to a nitrogen atom in one molecule.
And a polymerizable monomer composed of a low molecular weight compound each having one or more polymerizable unsaturated bonds. Among them, a low molecular weight compound having an acryloyl group, an allyl group or a vinyloxy group and a substituted or mono-substituted aminosulfonyl group or a substituted sulfonylimino group is preferable.

(3) The alkali-soluble polymer compound having an active imide group is preferably one having an active imide group in the molecule, and as the polymer compound, an unsaturated compound capable of polymerizing with the active imide group in one molecule is used. Examples thereof include a polymer compound obtained by homopolymerizing a polymerizable monomer composed of a low molecular weight compound having one or more bonds, or by copolymerizing the polymerizable monomer with another polymerizable monomer.

Specific examples of such a compound include:
N- (p-toluenesulfonyl) methacrylamide, N
-(P-toluenesulfonyl) acrylamide etc. can be used conveniently.

Further, as the alkali-soluble polymer compound of the present invention, two or more kinds of the above-mentioned polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, and a polymerizable monomer having an active imide group are used. It is preferable to use a polymer compound obtained by polymerizing the above, or a polymer compound obtained by copolymerizing another polymerizable monomer with these two or more polymerizable monomers. When a polymerizable monomer having a phenolic hydroxyl group is copolymerized with a polymerizable monomer having a sulfonamide group and / or a polymerizable monomer having an active imide group, the blending weight ratio of these components is 50:50 to 5: 5. It is preferably in the range of 95, particularly preferably in the range of 40:60 to 10:90.

In the present invention, the alkali-soluble polymer is a copolymer of the above-mentioned polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group, and another polymerizable monomer. When it is a polymer, the content of the alkali-solubilizing monomer is preferably 10 mol% or more, more preferably 20 mol% or more. When the content of the copolymerization component is less than 10 mol%, the alkali solubility tends to be insufficient, and the effect of improving the development latitude may not be sufficiently achieved.

The monomer components to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group are listed in the following (m1) to (m12). Examples of the compound include, but are not limited to, these. (M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (M2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Alkyl acrylates such as hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate and glycidyl acrylate. (M3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2-
Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, etc. (M4) acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N
-Acrylamide or methacrylamide such as phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide.

(M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether. (M6) vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate. (M7) Styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene. (M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (M10) N-vinylpyrrolidone, acrylonitrile,
Methacrylonitrile etc. (M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (M12) An unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride or itaconic acid.

As the alkaline water-soluble polymer compound,
It is preferable to have a phenolic hydroxyl group from the viewpoint of excellent image formability upon exposure with an infrared laser or the like. For example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde. Resin, phenol / cresol (m-, p-, or m- /
Preference is given to novolak resins such as mixed formaldehyde resins and pyrogallolacetone resins.

Further, as the alkaline water-soluble polymer compound having a phenolic hydroxyl group, further, as described in US Pat. No. 4,123,279,
Carbon number 3 ~, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin
Examples thereof include a condensation polymer of phenol and formaldehyde having the alkyl group of 8 as a substituent.

As a method for copolymerizing the alkaline water-soluble polymer compound, a graft copolymerization method known in the art,
A block copolymerization method, a random copolymerization method, etc. can be used.

In the present invention, the alkali-soluble polymer is
In the case of a homopolymer or a copolymer of the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group, the weight average molecular weight is 2,000 or more and the number average is Those having a molecular weight of 500 or more are preferable. More preferably, the weight average molecular weight is 5,000 to 300,000, the number average molecular weight is 800 to 250,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to 10. . In the present invention, when the alkali-soluble polymer is a resin such as phenol formaldehyde resin or cresol aldehyde resin, the weight average molecular weight is 500 to
20,000 and a number average molecular weight of 200 to 10,0.
00 is preferable.

As the alkali-soluble polymer used in the lower layer, the acrylic resin can well maintain the solubility of the lower layer in the alkaline developer mainly containing the organic compound having a buffering action and the base. It is preferable from the viewpoint of image formation during development. Further, the acrylic resin having a sulfamide group is particularly preferable. Further, as the alkali-soluble polymer used in the heat-sensitive layer, strong hydrogen-bonding property is generated in the unexposed area, and part of the hydrogen-bonding is easily released in the exposed area, and it is used in the present invention. Since there is a large difference in development between the unexposed portion and the exposed portion with respect to the non-silicate developer, the image forming property is improved,
A resin having a phenolic hydroxyl group is desirable. More preferably, it is a novolac resin.

These alkali-soluble polymer compounds may be used either individually or in combination of two or more, and in the total solid content of the heat-sensitive layer, 30 to 99% by mass, preferably 40 to 95% by mass, especially Preferably 50-90
Used in an amount of addition of mass%. When the amount of the alkali-soluble polymer added is less than 30% by mass, the durability of the heat-sensitive layer deteriorates, and when it exceeds 99% by mass, it is not preferable in terms of both sensitivity and durability.

[Infrared absorbing dye] In the present invention, the infrared absorbing dye used in the heat-sensitive layer is not particularly limited as long as it is a dye that absorbs infrared light and generates heat, and various dyes known as infrared absorbing dyes. Can be used.

As the infrared absorbing dye according to the present invention, commercially available dyes and known dyes described in the literature (for example, "Handbook of Dyes" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes,
Examples include dyes such as methine dyes and cyanine dyes. In the present invention, 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 such a dye that absorbs infrared light or near infrared light include, for example, JP-A-58-125246.
JP-A-59-84356 and JP-A-59-2028.
29, JP-A-60-78787, and other cyanine dyes, JP-A-58-173696, and JP-A-5-173966.
8-181690, methine dyes described in JP-A-58-194595, and JP-A-58-112793.
JP-A-58-224793, JP-A-59-481
87, JP-A-59-73996, JP-A-60-52.
940, naphthoquinone dyes described in JP-A-60-63744 and the like, squarylium dyes described in JP-A-58-112792 and the like, British Patent 434.
Examples thereof include cyanine dyes described in No. 875.

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.
Cyanine dye described in US Pat. No. 4,283,4
The pentamethine thiopyrylium salt described in No. 75, the Japanese Patent Publication No. 513514, and the pyrylium compound disclosed in No. 5-19702 are commercially available products, such as Epolight III-178 manufactured by Eporin Co., Epoli
ght III-130, Epolight III-125 and the like are particularly preferably used. Another particularly preferable example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.

These infrared absorbing dyes can be added not only to the heat-sensitive layer but also to the lower layer. The lower layer can also function as a heat-sensitive layer by adding an infrared absorbing dye to the lower layer. When the infrared absorbing dye is added to the lower layer, the same materials as those in the upper heat-sensitive layer may be used, or different materials may be used. Further, these infrared absorbing dyes may be added to the same layer as other components, or may be added to another layer provided separately. When it is formed as another layer, it is preferably added to the layer adjacent to the heat-sensitive layer. The dye and the alkali-soluble resin are preferably contained in the same layer, but they may be contained in different layers. The addition amount is 0.01 to 50% by mass, preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 10% by mass, based on the total solid content of the printing plate material, in the printing plate material. can do. If the amount of the dye added is less than 0.01% by mass, the sensitivity will be low, and if it exceeds 50% by mass, the uniformity of the heat-sensitive layer will be lost and the durability of the heat-sensitive layer will be deteriorated.

[Other Components] In forming the positive heat-sensitive layer or the lower layer, various additives may be added, if necessary, in addition to the above-mentioned essential components unless the effects of the present invention are impaired. can do. The additive may be contained only in the lower layer or only in the heat sensitive layer. Further, it may be contained in both layers. less than,
An example of the additive will be described. For example, onium salt, o-
The use of a substance such as a quinonediazide compound, an aromatic sulfone compound, an aromatic sulfonic acid ester compound, which is thermally decomposable and which substantially reduces the solubility of the alkaline water-soluble polymer compound when not decomposed, causes It is preferable from the viewpoint of improving the dissolution inhibiting property of the above in the developing solution. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts.

Suitable onium salts used in the present invention are, for example, SI Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), TS Bal et a
l, Polymer, 21, 423 (1980), JP-A-5-158230
Diazonium salt described in U.S. Pat. No. 4,069,055
No. 4,069,056, ammonium salts described in JP-A-3-140140, DC Necker et al, Macromolecul
es, 17, 2468 (1984), CS Wen et al, Teh, Proc. Co
nf.Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31.
(1988), European Patent 104,143, U.S. Patent 339,049.
No. 410,201, JP-A No. 2-150848, and JP-A No. 2-2965.
Iodonium salt described in No. 14, JVCrivello et al, P
olymer J. 17, 73 (1985), JV Crivello et al. J.
Org. Chem., 43, 3055 (1978), WR Watt et al, J.
Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JV Crivello et al, Polymer Bull., 14, 279 (198
5), JV Crivello et al, Macromorecules, 14 (5),
1141 (1981), JV Crivello et al, J. Polymer Sci.,
Polymer Chem. Ed., 17, 2877 (1979), European Patent No. 370,
693, 233,567, 297,443, 297,442,
U.S. Pat.Nos. 4,933,377, 3,902,114, 410,201
No., No. 339,049, No. 4,760,013, No. 4,734,444,
No. 2,833,827, German Patent No. 2,904,626, No. 3,604,58
0, 3,604,581 sulfonium salts, JV
Crivello et al, Macromorecules, 10 (6), 1307 (197
7), JV Crivello et al, J. Polymer Sci., Polymer
Chem. Ed., 17, 1047 (1979) described selenonium salt,
CS Wen et al, Teh, Proc.Conf.Rad. Curing ASIA,
Examples include arsonium salts described in p478 Tokyo, Oct (1988). Among the onium salts, the diazonium salt is particularly preferable. Further, particularly preferable diazonium salts include those described in JP-A-5-158230.

As counter ions of the onium salt, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5- Examples thereof include benzoyl-benzenesulfonic acid and paratoluenesulfonic acid. Among these, alkylaromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide assists the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder by thermal decomposition and the effect of changing o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include those described in J. The compounds described on pages 339 to 352 of "Light-Sensitive Systems" (John Wiley & Sons. Inc.) by Coser can be used, but in particular, they have been reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. -Sulfonic acid esters or sulfonic acid amides of quinonediazide are preferred. Further, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,3) as described in JP-B-43-28403.
2) -Diazido-5-sulfonic acid chloride ester with pyrogallol-acetone resin, US Pat. No. 3,046,12
0 and benzoquinone- (1,2) -diazide sulfonic acid chlorides or naphthoquinone- (1,2) -diazide-5-sulfonic acid chlorides and esters of phenol-formaldehyde resins described in No. 3,188,210 It is preferably used.

Further, an ester of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride and a phenol formaldehyde resin or a cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-
Esters of 4-sulfonic acid chloride and pyrogallol-acetone resin are likewise preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, and JP-A-48-96.
575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481
U.S. Pat.Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, 3,674,495.
No. 3,785,825, British Patent No. 1,227,602, No.
1,251,345, 1,267,005, 1,329,888,
Mention may be made, for example, of those described in the respective specifications such as 1,330,932 and German Patent No. 854,890.

The amount of the o-quinonediazide compound added is preferably 1 to 50% by mass, based on the total solid content of the layer.
More preferably 5 to 30% by mass, particularly preferably 10 to
It is in the range of 30% by mass. These compounds can be used alone, but may be used as a mixture of several kinds.

The addition amount of the additives other than the o-quinonediazide compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass. The additive of the present invention and the alkali-soluble polymer are preferably contained in the same layer.

For the purpose of enhancing the discrimination of images and the resistance to scratches on the surface, a polymer having 3 to 20 carbon atoms in the molecule as described in JP-A-2000-187318 is used. It is preferable to use a polymer having a (meth) acrylate monomer having 2 or 3 fluoroalkyl groups as a polymerization component. Such a compound may be contained in either the lower layer or the heat-sensitive layer, but it is more effective that it is contained in the heat-sensitive layer located above. The addition amount is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass in the heat-sensitive layer material.

A compound which lowers the coefficient of static friction of the surface may be added to the printing plate material of the present invention for the purpose of imparting resistance to scratches. In particular,
Examples thereof include esters of long-chain alkylcarboxylic acids as used in US Pat. No. 6,117,913. Such a compound may be contained in either the lower layer or the heat-sensitive layer, but it is more effective that it is contained in the heat-sensitive layer located above. The amount of addition is preferably 0.1 to 10% by mass in the material forming the layer. More preferably, it is 0.5 to 5 mass%.

The lower layer or heat-sensitive layer in the present invention may contain a compound having a low molecular weight acidic group, if necessary. Examples of the acidic group include sulfonic acid, carboxylic acid and phosphoric acid groups. Of these, compounds having a sulfonic acid group are preferable. Specific examples thereof include aromatic sulfonic acids such as p-toluenesulfonic acid and naphthalenesulfonic acid, and aliphatic sulfonic acids. Such a compound may be contained in either the lower layer or the heat sensitive layer. The amount of addition is preferably 0.05 to 5 mass% in the material forming the layer. More preferably, it is 0.1 to 3 mass%. If it exceeds 5%, the solubility of each layer in the developing solution increases, which is not preferable.

Further, in the present invention, various dissolution inhibitors may be contained for the purpose of adjusting the solubility of the lower layer or the heat sensitive layer. As a dissolution inhibitor, JP-A-11-11941
A disulfone compound or a sulfone compound as disclosed in Japanese Patent Laid-Open No. 8 is preferably used, and as a specific example, 4,4′-bishydroxyphenyl sulfone is preferably used. Such a compound may be contained in either the lower layer or the heat sensitive layer. The addition amount is preferably 0.05 to 20% by mass, and more preferably 0.5 to 10% by mass, in the material constituting each layer.

Further, cyclic acid anhydrides, phenols and organic acids may be used in combination for the purpose of further improving the sensitivity. Examples of cyclic acid anhydrides are phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride and tetrachlorophthalic anhydride described in U.S. Pat. No. 4,115,128. , Maleic anhydride, chloromaleic anhydride, α-phenyl maleic anhydride, succinic anhydride, pyromellitic dianhydride, etc. can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-
Ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "
-Trihydroxytriphenylmethane, 4,4 ',
3 ", 4" -tetrahydroxy-3,5,3 ', 5'-
Examples thereof include tetramethyltriphenylmethane. Further, as organic acids, there are JP-A-60-88942 and JP-A-2.
-96755, sulfonic acids,
There are sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric acid esters, carboxylic acids and the like. Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, Phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-
1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned. The proportion of the cyclic acid anhydride, phenols and organic acids in the material constituting the layer is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1. It is 1 to 10 mass%.

In the lower layer or heat-sensitive layer coating solution according to the present invention, in order to enhance the stability of processing under developing conditions, JP-A-62-251740 and JP-A-3-20 are provided.
Nonionic surfactants as described in JP-A-8514, JP-A-59-121044, and JP-A-4-1-1.
An amphoteric surfactant as described in JP 3149, a siloxane compound as described in EP 950517, and a fluorine-containing monomer copolymer as described in JP-A No. 11-288093. It can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride and polyoxyethylene nonylphenyl ether. Specific examples of the double-sided active agent include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Examples include molds (for example, trade name “Amorgen K”: manufactured by Daiichi Kogyo Co., Ltd.). As the siloxane-based compound, a block copolymer of dimethylsiloxane and polyalkylene oxide is preferable, and specific examples include DBE manufactured by Chisso Corporation.
-224, DBE-621, DBE-712, DBP-
732, DBP-534, Tego, Germany, Tego
Mention may be made of polyalkylene oxide-modified silicones such as Glide 100. The ratio of the nonionic surfactant and the amphoteric surfactant in the coating liquid material is
0.05 to 15% by mass is preferable, and more preferably 0.
It is 1 to 5 mass%.

In the lower layer or heat-sensitive layer of the present invention,
A print-out agent for obtaining a visible image immediately after heating by exposure or a dye or pigment as an image colorant can be added. A typical example of the print-out agent is a combination of a compound that releases an acid when heated by exposure (photo-acid releasing agent) and an organic dye capable of forming a salt. Specifically, o-naphthoquinonediazide-4 described in JP-A Nos. 50-36209 and 53-8128 are disclosed.
-A combination of a sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-36223 and 54-74728.
No. 60-3626, No. 61-143748, No. 61-151644, and No. 63-58440, and combinations of trihalomethyl compounds and salt-forming organic dyes. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give a clear printout image.

As the image colorant, other dyes can be used other than the above-mentioned salt-forming organic dyes. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. 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 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl. Violet (CI42535), ethyl violet, Rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201).
5) etc. can be mentioned. In addition, JP-A-62-2
The dyes described in Japanese Patent No. 93247 are particularly preferable. These dyes are added in an amount of 0.
It can be added to the printing plate material in a proportion of 01 to 10% by mass, preferably 0.1 to 3% by mass. Further, a plasticizer is added to the printing plate material of the present invention, if necessary, in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid. Oligomers and polymers are used.

The method for producing the heat-sensitive layer and the lower layer for forming the multilayer structure described above can be usually formed by dissolving each of the above components in a solvent and coating the solution on a suitable support. 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, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide,
N, N-dimethylformamide, tetramethylurea,
Examples thereof include N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and toluene, but are not limited thereto. These solvents may be used alone or as a mixture. The solvent used for coating is preferably selected from those having different solubilities with respect to the alkali-soluble polymer used in the heat-sensitive layer and the alkali-soluble polymer used in the lower layer. In other words, when the lower layer is applied and then the upper heat-sensitive layer is applied adjacent thereto, if a solvent capable of dissolving the lower layer alkali-soluble polymer is used as the uppermost layer coating solvent, the mixing at the layer interface is ignored. In some extreme cases, it becomes impossible to form multiple layers and a uniform single layer is formed. 2 adjacent to each other
When mixing occurs at the interface of two layers or when they are compatible with each other and behave like a uniform layer, the effect of the present invention due to having two layers may be impaired, which is not preferable. Therefore, the solvent used for coating the upper heat-sensitive layer is preferably a poor solvent for the alkali-soluble polymer contained in the lower layer. When coating each layer, the concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 5
It is 0 mass%. The coating amount (solid content) of the heat-sensitive layer on the support obtained after coating and drying varies depending on the use, but the heat-sensitive layer is 0.05 to 1.0 g / m ² , and the lower layer is 0.3 to 3 It is preferably 0.0 g / m ² . When the heat-sensitive layer is less than 0.05 g / m ^2, the image forming property is lowered, sensitivity exceeds 1.0 g / m ² comes out may be reduced. Further, if the coating amount of the lower layer is out of the above range, the image forming property tends to be deteriorated when the amount is too small or too large. The total of the above two layers is 0.5
It is preferable that the coating amount is 0.1 to 3.0 g / m ² , and the coating amount is 0.1.
If it is less than 5 g / m ² , the coating properties will deteriorate and 3.0 g / m ²
If it exceeds m ² , the sensitivity tends to decrease. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate.

Various methods can be used for coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. You can In the heat-sensitive layer of the present invention, a surfactant for improving the coatability, for example, JP-A-62-1709.
Fluorine-based surfactants such as those described in Japanese Patent Publication No. 50 can be added. The preferable addition amount is 0.01 to 1% by mass, and more preferably 0.05 to 0.5% by mass in the total solid content of the lower layer or the heat-sensitive layer.

The lithographic printing plate precursor of the present invention is made into a lithographic printing plate by various treatment methods depending on the heat-sensitive layer, and a developer containing substantially no alkali metal silicate is prepared as follows. A lithographic printing plate is preferably prepared by a method of developing with. That is, the lithographic printing plate precursor of the present invention,
It is preferably a lithographic printing plate precursor to be processed with a developer containing substantially no alkali metal silicate. Note that this method is described in JP-A-11-10963.
No. 7, which is described in detail, and in the present invention,
The contents described in this publication can be used.

Exposure In this method, image exposure is carried out before the development processing. Examples of the actinic light source used for image exposure include a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, and a chemical lamp. Examples of radiation include electron beams, X-rays, ion beams, far infrared rays, near infrared rays, g rays, i rays, and Dee.
p-UV light, high-density energy beam (laser beam)
Is mentioned. As the laser beam, for example, a helium / neon laser (He-Ne laser), an argon laser, a krypton laser, a helium / cadmium laser,
Examples thereof include KrF excimer laser, semiconductor laser, and YAG laser.

Development After the above exposure, development is carried out using a developer containing substantially no alkali metal silicate. The developing solution used in this method is not particularly limited as long as it is a developing solution containing substantially no alkali metal silicate, but an alkaline aqueous solution containing substantially no organic solvent is preferable. However, an organic solvent may be contained if necessary. Further, this developer preferably contains a saccharide. For example, it contains at least one compound selected from non-reducing sugars and at least one base as main components, and has a pH of 9.0.
A developing solution of 13.5. Further, the developer may contain various surfactants, if necessary, for the purpose of promoting developability, dispersing development residue and improving the ink affinity of the image area of the lithographic printing plate. In the present invention, an anionic surfactant, a cationic surfactant,
Both nonionic and amphoteric surfactants can be used. Further, the developing solution may contain various development stabilizers. Further, the developing solution may contain a reducing agent for the purpose of preventing stains on the lithographic printing plate. Further, the developer may contain an organic carboxylic acid.

[0177]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. 1. Preparation of planographic printing plate precursor <Preparation of support (each processing method)> Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.005 mass%,
Mn: 0.001% by mass, Mg: 0.001% by mass, Z
n: 0.001% by mass, Ti: 0.03% by mass, the balance is prepared using Al and aluminum alloy of unavoidable impurities, and is subjected to melt treatment and filtration.
An ingot having a thickness of 500 mm and a width of 1200 mm was prepared by the DC casting method. After the surface was scraped off by a chamfering machine with an average thickness of 10 mm, it was soaked at 550 ° C. for about 5 hours and kept at a temperature of 4
When the temperature fell to 00 ° C., a hot rolling mill was used to form a rolled plate having a thickness of 2.7 mm. Furthermore, after heat-treating at 500 ° C. using a continuous annealing machine, the thickness is 0.2 by cold rolling.
Finished to a 4 mm aluminum plate. After making this aluminum plate a width of 1030 mm, the following surface treatment was continuously performed. The obtained aluminum plate had an average crystal grain size of aluminum having a short diameter of 100 μm and a long diameter of 1
It was 000 μm.

(A) Mechanical Roughening Treatment Using a device as shown in FIG. 1, a suspension of an abrasive (silica sand) having a specific gravity of 1.12 and water was used as a polishing slurry liquid to form an aluminum plate. While being supplied to the surface, mechanical roughening was performed by a rotating roller nylon brush. In FIG. 1, 1 is an aluminum plate, 2 and 4 are roller brushes, 3 is a polishing slurry liquid, 5, 6, 7 and 8 are support rollers. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of the nylon brush was 6.10 nylon, the bristle length was 50 mm, and the bristle diameter was 0.3 mm. The nylon brush was prepared by forming holes in a stainless steel cylinder having a diameter of 300 mm and densely implanting the bristles. 3 rotating brushes
I used this book. Two support rollers under the brush (φ200
mm) was 300 mm. As for the brush roller, the load of the drive motor that rotates the brush is 7 kW against the load before the brush roller is pressed against the aluminum plate.
Hold down until it becomes positive. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Etching Treatment with Alkaline Agent The aluminum plate obtained above was treated with caustic soda at a concentration of 26.
Mass%, aluminum ion concentration 6.5 mass%, temperature 7
An etching treatment by spraying was performed at 0 ° C. to dissolve an aluminum plate at 6 g / m ² . Then, washing with water was performed by spraying.

(C) Desmutting treatment Desmutting treatment was carried out by spraying with an aqueous 1% by weight nitric acid solution (containing 0.5% by weight of aluminum ion) at a temperature of 30 ° C., and then washing with water was carried out by spraying. As the nitric acid aqueous solution used for the desmut, a waste liquid from the step of electrochemically roughening the surface of the nitric acid aqueous solution using an alternating current was used.

(D) Electrochemical surface roughening treatment Electrochemical surface roughening treatment was continuously carried out using an alternating voltage of 60 Hz. The electrolytic solution at this time was 10.5 g of nitric acid.
/ L aqueous solution (containing 5 g / L of aluminum ion and 0.007 mass% of ammonium ion) and the temperature was 50 ° C. The AC power supply waveform is the waveform shown in FIG. 2, and the time TP from when the current value reaches zero to the peak is 0.8 m.
Using a trapezoidal rectangular wave alternating current with sec, DUTY ratio of 1: 1, electrochemical surface roughening treatment was performed with the carbon electrode as the counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was that shown in FIG. The current density was 30 A / dm ² at the peak value of the current, and the quantity of electricity was 220 C / dm ^{2 as} the total quantity of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, washing with water was performed by spraying.

(E) Alkali etching treatment An aluminum plate was subjected to etching treatment by spraying at a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to give 0.20 g of the aluminum plate.
/ M ² melted and the smut component mainly composed of aluminum hydroxide generated when electrochemical roughening was performed using the alternating current in the previous stage was removed, and the edge portion of the generated pit was melted. To smooth the edges. afterwards,
It was washed with water by spraying. (F) Desmutting treatment Desmutting treatment was carried out by spraying with an aqueous solution of sulfuric acid concentration of 15% by mass (containing 4.5% by mass of aluminum ion) at a temperature of 30 ° C, and then washed with water by spraying. As the nitric acid aqueous solution used for the desmut, a waste liquid from the step of electrochemically roughening the surface of the nitric acid aqueous solution using an alternating current was used.

(G) Electrochemical surface roughening treatment Electrochemical surface roughening treatment was continuously carried out using an alternating voltage of 60 Hz. At this time, the electrolytic solution is hydrochloric acid 7.5 g /
L aqueous solution (containing 5 g / L of aluminum ion) at a temperature of 35 ° C. The AC power supply waveform was a rectangular wave, and electrochemical roughening treatment was performed using the carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was that shown in FIG. In FIG. 3, 11
Is an aluminum plate, 12 is a radial drum roller, 13
Reference numerals a and 13b are main electrodes, 14 is an electrolytic treatment solution, 15 is an electrolytic solution supply port, 16 is a slit, 17 is an electrolytic solution passage, 18 is an auxiliary anode, 19a and 19b are thyristors, and 20 is an AC power supply. Current density is 25 A / d at peak value of current
m ² and the amount of electricity were 50 C / dm ^{2 as} the total amount of electricity when the aluminum plate was the anode. Then, washing with water was performed by spraying.

(H) Alkali etching treatment An aluminum plate was spray-etched at 32 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass to give an aluminum plate of 0.10 g.
/ M ² Melt and remove the smut component mainly composed of aluminum hydroxide generated when electrochemical roughening treatment using the alternating current in the previous stage is performed, and also the edge portion of the generated pit is melted The edges were smoothed. Then, washing with water was performed by spraying. (I) Desmutting treatment Desmutting treatment was performed by spraying with a 25% by weight aqueous solution of sulfuric acid (containing 0.5% by weight of aluminum ion) at a temperature of 60 ° C., and then washing with water was performed by spraying.

(J) Anodizing Treatment The anodizing device of the two-stage power feeding electrolytic treatment method having the structure shown in FIG. 4 (first and second electrolytic portion lengths each 6 m, first and second feeding portion lengths 3 m, first and second Anodizing treatment was performed using two feeding electrodes each having a length of 2.4 m. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis sections. All the electrolytic solutions had a sulfuric acid concentration of 170 g / L (containing 0.5% by mass of aluminum ions) and a temperature of 43 ° C. afterwards,
It was washed with water by spraying.

In the anodizing device, a power source 67a
And the current from 67b flow into the 1st electric power feeding electrode 65a provided in the 1st electric power feeding part 62a, flow into the aluminum plate 11 via an electrolytic solution, and an oxide film is formed on the surface of the aluminum plate 11 in the 1st electrolysis part 63a. To generate the first electrolysis unit 63a
Through the electrolytic electrodes 66a and 66b provided at the power source 67a and 67b. On the other hand, power supplies 67c and 6
The current from 7d flows to the second power supply electrode 65b provided in the second power supply section 62b, flows to the aluminum plate 11 via the electrolytic solution in the same manner as described above, and then to the surface of the aluminum plate 11 at the second electrolytic section 63b. Generates an oxide film. It passes through the electrolytic electrodes 66c and 66d provided in the second electrolytic section 63b and returns to the power supplies 67c and 67d.

From the power sources 67a and 67b to the first power feeding section 6
The amount of electricity supplied to 2a is equal to the amount of electricity supplied from the power sources 67c and 67d to the second power supply section 62b, and the current densities in the first electrolytic section 63a and the second electrolytic section 63b are both about 30 A / It was dm ² . In the second power feeding portion 62b, 1.35 g generated in the first electrolysis portion 63a
Power is supplied through the oxide film surface of / m ² . The final amount of oxide film was 2.7 g / m ² .

(K) Alkali Metal Silicate Treatment By immersing the aluminum support obtained by anodizing treatment in a treated layer of a 1% by mass aqueous solution of No. 3 sodium silicate at 30 ° C. for 10 seconds. Alkali metal silicate treatment (silicate treatment) was performed. After that, washing with well water was performed by spraying.

(L) Formation of Intermediate Layer (Undercoat Layer) An undercoat solution having the following composition was applied onto the aluminum metal silicate-treated aluminum support obtained as described above, and the composition was applied at 80 ° C. for 15 seconds. It was dried to form a coating film. The coating amount of the coating film after drying was 15 mg / m ² .

<Undercoating liquid composition> ・ The following polymer compound 0.3g ・ Methanol 100g ・ Water 1g

[0191]

[Chemical formula 23]

(M) Formation of Heat-Sensitive Layer A Next, a heat-sensitive layer coating liquid 1 having the following composition was prepared, and the coating amount after drying the heat-sensitive layer coating liquid 1 on the undercoated aluminum support (heat-sensitive layer coating amount). Of 1.0 g / m ² and dried to form a heat-sensitive layer A to obtain a lithographic printing plate precursor of Example 1.

[0193] <1 composition of heat-sensitive layer coating liquid>   ・ Capric acid 0.03g   -N- (p-aminosulfonylphenyl) methacrylamide / methacrylic acid Chill / acrylonitrile (32/43/25 mol%) copolymer (weight average molecule Amount 53,000) 0.75g   M, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight 3,5 00, containing 0.5% by mass of unreacted cresol) 0.25 g   -P-toluenesulfonic acid 0.003 g   ・ Tetrahydrophthalic anhydride 0.03g   ・ 0.017 g of cyanine dye A represented by the following structural formula

[0194]

[Chemical formula 24]

[0195]   ・ The counter ion of Victoria Pure Blue BOH is 1-naphthalenesulfonic acid ani Dye 0.015g turned on   ・ Fluorosurfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc. ) 0.05 g   ・ Γ-Butyl lactone 10 g   ・ Methyl ethyl ketone 10g   ・ 1-Methoxy-2-propanol 1 g

(Example 1) A lithographic printing plate was prepared by preparing a support by removing the mechanical surface roughening treatment (a), and providing the above-mentioned (l) and (m) on the support. . (Example 2) A support was prepared except for the above (d), (e) and (f), and the above (l) and (m) were formed on the support.
Was prepared to prepare a lithographic printing plate.

(Example 3) In Example 1, (h) the amount of aluminum dissolved in the alkali etching treatment was 0.6.
A support was prepared at g / m ² , and (l) and (m) were provided on the support to prepare a lithographic printing plate.

(Example 4) In Example 1, (d),
(E) and (f) were not carried out, and (g) an aluminum plate was used as the support so that the total amount of electricity when the aluminum plate was an anode was 450 C / dm ² and the support was prepared. The above (l) and (m) were provided on the body to prepare a lithographic printing plate.

(Example 5) In Example 4, (h) the amount of aluminum dissolved in the alkali etching treatment was 0.6.
A support was prepared at g / m ² , and (l) and (m) were provided on the support to prepare a lithographic printing plate.

(Example 6) In Example 1, Si:
0.13% by mass, Cu: 0.01% by mass, Fe: 0.2
A support is prepared by using an aluminum plate containing 100% by mass and the balance consisting of Al and unavoidable impurities, and having an average crystal grain size of aluminum having a short diameter of 300 μm and a long diameter of 2000 μm. ) And (m) were prepared to prepare a lithographic printing plate.

(Example 7) In Example 1, after providing (l) on the support, the following heat-sensitive layer B was provided in place of (m) to prepare a lithographic printing plate.

(N) Formation of heat-sensitive layer B The following lower layer coating solution was applied at a coating amount of 0.85 g / m ² and then PERFECT manufactured by TABAI.
Set Wind Control to 7 in OVEN PH200 and dry at 140 degrees for 50 seconds, then apply the heat-sensitive layer coating solution to a coating amount of 0.15 g / m ² and then dry at 120 degrees for 1 minute. Then, a lithographic printing plate of Example 7 having the heat sensitive layer B was obtained.

[0203] <Coating liquid for lower layer> ・ N- (4-aminosulfonylphenyl) methacrylamide /     Acrylonitrile / methyl methacrylate     (36/34/30: weight average molecular weight 50,000) 1.896 g -Cresol novolac (m / p = 6/4 weight average molecular weight 4500,       Residual monomer 0.8wt%) 0.237g ・ Cyanine dye A (the following structure) 0.109 g * 4,4'- bishydroxy phenyl sulfone 0.063g ・ Tetrahydrophthalic anhydride 0.190 g -P-toluenesulfonic acid 0.008 g ・ Ethyl violet counter ion     Replaced with 6-hydroxynaphthalene sulfone 0.05g ・ Fluorosurfactant (MegaFac F176,     Dainippon Ink and Co., Ltd.) 0.035g ・ Methyl ethyl ketone 26.6g ・ 1-Methoxy-2-propanol 13.6 g * Γ-butyrolactone 13.8 g

[0204]

[Chemical 25]

[0205] <Coating liquid for heat sensitive layer> -M, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight     4500, containing 0.8% by weight of unreacted cresol) 0.237 g ・ Cyanine dye A (the above structure) 0.047 g ・ Dodecyl stearate 0.060g ・ 3-Methoxy-4-diazodiphenylamine     Hexafluorophosphate 0.030 g ・ Fluorosurfactant (MegaFac F176,     Dainippon Ink and Chemicals Co., Ltd. 0.110g -Fluorosurfactant [Megafac MCF-312 (30%),     Manufactured by Dainippon Ink Industry Co., Ltd.] 0.120 g ・ Methyl ethyl ketone 15.1 g ・ 1-Methoxy-2-propanol 7.7 g

Comparative Example 1 (a), (g), (h)
A support was prepared except for (i) and (i), and (l) and (m) were provided on the support to prepare a lithographic printing plate.

(Comparative Example 2) A lithographic printing plate was prepared by preparing a support except for the above (g), (h) and (i), and providing the above (1) and (m) on the support. And

2. Development method PS manufactured by Fuji Photo Film Co., Ltd. that does not contain silicate
Using the plate developing solution DT-1 under standard use conditions, development was carried out by an automatic developing machine 900NP.

[0209] 3. Small wave average pit diameter After exposing the support by dissolving and removing the heat-sensitive layer from the lithographic printing plate with γ-butyl lactone, the support surface was magnified 5 times from the vertical direction.
SEM observation was carried out at a magnification of 0000, 100 pit diameters were measured on the photographed image, and the average value was taken as the average pit diameter. At this time, Hitachi S-900 was used. It should be noted that the small wave referred to herein is an SEM image in which the surface of the support is magnified 50,000 times, and the average value of the major axis and the minor axis of the pit shape with a clear contour is 0.01 to.
A small pit having a diameter of 0.5 μm was measured, and 200 small pits were measured, and the average value thereof was used as the small wave pit diameter.

4. After exposing the support by dissolving and removing the photosensitive layer of the large wave average wavelength lithographic printing plate with γ-butyl lactone, the surface of the support was tilted at 45 ° from the vertical direction and observed by SEM at a magnification of 3500. Then, 30 peak intervals were measured in the horizontal direction, and the average value was used as the average wavelength of the large wave. At this time, T-20 manufactured by JEOL Ltd. was used as the scanning electron microscope.

5. Evaluation of scratch resistance of lithographic printing plate precursor The scratch resistance of each lithographic printing plate precursor obtained above was evaluated. Place interleaving paper on the surface of the heat-sensitive layer of the lithographic printing plate, sandwich the top and bottom with corrugated paper, 25 ° C, 50% RH
It was left for 3 days under the environment. Then, the plate surface was rubbed 5 times with cotton gloves and developed by the above developing method. The extent to which the rubbed part was scratched and was missing in white was visually observed and evaluated. Those that did not change at all before development were marked with ◯, those in which the support was almost visible and the color of the heat-sensitive layer was hardly visible, were marked with x, and their intermediate levels were marked with ◯ Δ, Δ, and Δx. The results are shown in Table 1.

6. Evaluation of Sensitivity of Lithographic Printing Plate Each of the lithographic printing plates obtained above was processed by TREO manufactured by CREO.
The plate surface energy amount was changed using dSetter3244, and the entire surface was exposed and developed by the above-described developing method. The sensitivity was evaluated by the plate surface energy amount when it was visually observed that the heat-sensitive layer was completely removed. The results are shown in Table 1.

7. Evaluation of stain resistance of lithographic printing plate Each lithographic printing plate precursor obtained above was processed by Treo manufactured by CREO.
Image exposure was carried out using the nndSetter 3244 at a plate surface energy amount of 140 mJ / cm ² , and then developed by the above-mentioned developing method. A Mitsubishi diamond type F2 printing machine (manufactured by Mitsubishi Heavy Industries, Ltd.) was used to print with DIC-GEOS (s) crimson ink, and stains on the blanket were visually evaluated after printing 10,000 sheets. ○, which was hardly dirty
The one that was slightly soiled was represented by Δ, and the one that was significantly soiled was represented by X. The results are shown in Table 1.

8. Evaluation of printing durability of lithographic printing plate A lithographic printing plate was obtained by the same method as in the above evaluation of stain resistance. The lithographic printing plate thus obtained was applied to a DI manufactured by Dainippon Ink and Chemicals, using a Lithrone printing machine manufactured by Komori Corporation.
Printing was performed using C-GEOS (N) black ink, and printing durability was evaluated by the number of printed sheets at the time when it was visually recognized that the density of the solid image started to decrease. The results are shown in Table 1.

[0215]

[Table 1]

[0216]

The lithographic printing plate of the present invention is excellent in both scratch resistance and sensitivity, and is also excellent in stain resistance during printing and printing durability.

[Brief description of drawings]

FIG. 1 is a side view showing a concept of a step of brush graining used for mechanical surface roughening treatment in producing an aluminum support used for a lithographic printing plate according to the invention.

FIG. 2 is a graph showing an example of an alternating waveform current waveform diagram used in the electrochemical roughening treatment in the production of the aluminum support used in the lithographic printing plate of the present invention.

FIG. 3 is a schematic configuration diagram of an apparatus in which two or more radial drum rollers used for electrochemical roughening treatment in the production of an aluminum support used in the lithographic printing plate of the present invention are connected.

FIG. 4 is a schematic view of an anodizing treatment apparatus of a two-step power supply electrolysis method used for anodizing treatment in producing an aluminum support used in the lithographic printing plate of the present invention.

[Explanation of symbols]

1 Aluminum plate 2, 4 roller brush 3 Polishing slurry liquid 5, 6, 7, 8 Support roller 11 Aluminum plate 12 radial drum roller 13a, 13b Main pole 14 Electrolysis solution 15 Electrolyte supply port 16 slits 17 Electrolyte passage 18 Auxiliary anode 19a, 19b Thyristor 20 AC power supply 40, 41 Main electrolyzer 50, 51 Auxiliary anode tank 62a First power supply unit 62b Second power supply unit 63a First electrolysis unit 63b Second electrolysis section 64a, 64b Nip roller 65a First feeding electrode 65b Second feeding electrode 66a, 66b, 66c, 66d Electrolytic electrode 67a, 67b, 67c, 67d Power supply

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C25D 11/04 C25D 11/04 E 11/16 301 11/16 301 C25F 3/04 C25F 3/04 A G03F 7/00 503 G03F 7/00 503 7/004 505 7/004 505 7/09 501 7/09 501 7/095 7/095 // C23F 1/36 C23F 1/36 F term (reference) 2H025 AA01 AA13 AA14 AB03 AC08 AD03 BG00 CC11 DA11 DA20 DA36 FA10 2H096 AA06 BA09 BA20 CA01 EA04 EA23 GA08 2H114 AA04 AA11 AA14 AA22 AA23 AA27 AA30 BA01 BA10 DA04 EA02 FA06 GA04 GA05 GA07 GA05 GA07 GA05 GA07 4K057 WA05 WB05 WC10 W05K22

Claims (6)

[Claims] 1. A heat-sensitive layer comprising a water-insoluble and alkali-soluble resin and an infrared absorbing dye, which is heated on a support having an aluminum or aluminum alloy surface-roughened and anodized to increase its solubility in an alkaline aqueous solution by heating. A planographic printing plate, wherein the roughened shape of the support has a grain shape of a composite structure of large and small double or more composed of a large wave structure and a small wave structure, and the large wave structure has an average wavelength of 0.5 to 30 μm. A lithographic printing plate having a wavelet structure having a pit structure with an average diameter of 0.01 to 0.3 μm. 2. Aluminum or an aluminum alloy is mechanically roughened, electrolytically roughened with an electrolytic solution containing nitric acid, electrochemically roughened with an electrolytic solution containing hydrochloric acid, and an alkaline aqueous solution. The planographic printing plate according to claim 1, wherein the planographic printing plate is treated by two or more kinds of treatment methods selected from the group consisting of chemical dissolution treatment according to 1. 3. The planographic printing plate according to claim 2, wherein the amount of aluminum dissolved in the chemical dissolution treatment with the alkaline aqueous solution, which is performed after the electrochemical graining treatment, is 0.5 g / m ² or less. Printed version. 4. The aluminum plate according to claim 1, wherein the aluminum material is JIS A1050, and the average crystal grain size is an aluminum plate having a short diameter of 2 to 200 μm and a long diameter of 50 to 1500 μm. The planographic printing plate described in the crab. 5. Si 0.02-0.1%, Cu 0.0
An lithographic printing plate according to any one of claims 1 to 4, wherein an aluminum material containing not more than 05% and 0.1 to 0.5% Fe is used. 6. A recording layer writable by laser exposure,
The lithographic printing plate according to any one of claims 1 to 5, wherein the lithographic printing plate is a multilayer photosensitive layer formed by coating a plurality of times.