JP2003034091A - Lithographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat sensitive lithographic printing original plate, which has favorable press developability, high sensitivity and, at the same time, high plate werability and, in addition favorable hardness to be stained by printing such as favorable ink repelling properties or the like under the condition that this lithographic printing plate can execute printing being installed as it is without being processed after the scanning exposure of infrared ray based on digital signals. SOLUTION: In this lithographic printing original plate, an image recording layer including thermally amalgamable self-water-dispersible resin particulates and allowing to be written through infrared laser exposure is provided on an aluminum board having a hydrophilic film obtained by being electrochemically roughening treated in a hydrochloric acid-containing aqueous solution and having the thermal conductivity of 0.05 to 0.5 W/mk.

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 precursor for a computer-to-plate system that does not require development. More specifically, it is possible to record an image by infrared scanning exposure based on a digital signal, and the image-recorded product can be directly mounted on a printing machine and printed without undergoing a conventional liquid development process. A possible heat-sensitive lithographic printing plate precursor.

[0002]

2. Description of the Related Art Many studies have been conducted on a lithographic printing plate precursor for a computer to plate (CTP) system, which has made remarkable progress in recent years. Among them, in order to further rationalize the process and solve the problem of waste liquid treatment, a lithographic printing plate that can be mounted on a printing machine as it is and printed after exposure has been studied, and various methods have been proposed.
One of the promising methods is a heat-sensitive lithographic printing plate precursor having an image recording layer comprising a layer in which hydrophobic thermoplastic polymer particles are dispersed in a hydrophilic binder polymer. When the heat is applied to the image recording layer, the hydrophobic thermoplastic polymer particles are fused and coalesced, and the surface of the hydrophilic image recording layer is converted into a lipophilic image portion.

Among the methods utilizing thermal fusion of the hydrophobic thermoplastic polymer particles, one of the methods for eliminating the processing step is to mount the exposed printing original plate on the plate cylinder of the printing machine, There is a method called on-press development in which the non-image portion of the printing plate precursor is removed by supplying dampening water and ink while rotating, or further supplying printing paper. That is, this is a method in which the printing plate precursor is exposed and then mounted in a printing machine as it is, and the removal of the non-image portion is completed in a normal printing process.

A lithographic printing plate suitable for such on-press development has an image recording layer soluble in at least one of dampening water and an ink solvent, and on a printing machine placed in a bright room. Characteristics that fog does not occur even when exposed to visible light during development
It is necessary to have so-called light room handling.

For example, Japanese Patent No. 2938397 discloses a lithographic printing plate having a hydrophilic substrate on which a photosensitive layer (image recording layer) in which fine particles of a thermoplastic hydrophobic polymer are dispersed is provided on a hydrophilic substrate. Is listed. In this publication, in the lithographic printing plate precursor, infrared laser exposure is carried out to combine fine particles of a thermoplastic hydrophobic polymer by heat to form an image, and then the plate is attached to a plate cylinder of a printing machine, and a fountain solution and It is described that on-press development can be carried out by supplying an ink. In addition, since it is infrared-sensitive, it has good light-room handling properties without being fogged in a light room.

JP-A-9-127683 describes that a printing plate can be prepared by on-press development using self-water-dispersible resin particles. Further, in this printing plate, since the unfused resin particles have high hydrophilicity, it is easy to cause the resin particles to separate from the substrate surface in the non-image area, and there is an advantage that there is little non-image area ink stain. ing.

[0007]

However, such a method of forming an image by combining fine particles due to heat shows a good on-machine developability when a metal substrate having high dimensional stability is used. Since heat escapes to the substrate, the sensitivity is low, and the image strength is weak due to insufficient coalescence of fine particles.
There was a problem that printing durability was insufficient. As a measure against this,
A method of providing an organic resin on a metal substrate has been proposed. Although this method has high sensitivity, it has a problem of causing print stains.

The object of the present invention is to provide a lithographic printing plate precursor that overcomes the above-mentioned drawbacks of the prior art.
That is, it is to provide a heat-sensitive lithographic printing plate precursor having good on-press developability, high sensitivity, high printing durability, and good stain resistance during printing, such as ink wiping property. .

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventor has roughened an aluminum plate which has been roughened, and provided a hydrophilic film having physical properties such as thermal conductivity or density in a specific range on the roughened aluminum plate. By providing an image recording layer containing self-water-dispersible resin fine particles that are coalesced by heat on the substrate provided, the diffusion of heat to the aluminum substrate is suppressed, the sensitivity is increased, and the coalescence of the particles by heat of the particles is suppressed. It has been found that the above object can be achieved by improving efficiency and improving image strength to secure printing durability, and further improving printing stains by using a hydrophilic film. That is, the present invention is as follows.

1. Electrochemical surface roughening treatment in an aqueous solution containing hydrochloric acid with a thermal conductivity of 0.05 to 0.5 W / mK
A lithographic printing original plate having an image recording layer which is writable by infrared laser exposure, containing self-water-dispersible resin fine particles which coalesce by heat, on an aluminum substrate having a hydrophilic film.

2. Electrochemical surface roughening treatment in an aqueous solution containing hydrochloric acid with a density of 1000 to 3200 kg / m ³
And / or for lithographic printing, which comprises an aluminum substrate having a hydrophilic film having a porosity of 20 to 70%, containing self-water-dispersible resin fine particles that coalesce by heat, and having an image recording layer writable by infrared laser exposure. Original plate.

3. The average opening diameter of the roughened small pits is 0.01 to 3 μm, the ratio of the average depth of the small pits to the average opening diameter is 0.1 to 0.5, and the thermal conductivity is 0.05.
A lithographic printing original plate comprising an aluminum substrate having a hydrophilic film of about 0.5 W / mK, containing self-water-dispersible resin particles which are coalesced by heat, and having an image recording layer writable by infrared laser exposure.

4. The average opening diameter of the small pits having a roughened shape is 0.01 to 3 μm, the ratio of the average depth of the small pits to the average opening diameter is 0.1 to 0.5, and the density is 1000 to 3.
An image recording layer containing self-water-dispersible resin fine particles which coalesce by heat and which is writable by infrared laser exposure is provided on an aluminum substrate having a hydrophilic film of 200 kg / m ³ and / or a porosity of 20 to 70%. The original plate for lithographic printing.

5. The above-mentioned 1 characterized in that the large opening of the aluminum substrate has an average opening diameter of 3 to 20 μm.
To the original plate for lithographic printing according to any one of 4 above.

6. 6. The lithographic printing plate precursor as described in any one of 1 to 5 above, wherein the hydrophilic film is an anodized film.

7. 7. The lithographic printing plate precursor as described in 6 above, which has an anodized film amount of 3.2 g / m ² or more.

8. The surface pore size of the anodized film is 40n
The lithographic printing plate precursor as described in 6 or 7 above, which is m or less.

9. 9. The lithographic printing plate precursor as described in any one of 6 to 8 above, wherein the anodized film is subjected to a sealing treatment.

10. Average particle size 8-80 on the anodized film
10. The lithographic printing plate precursor as described in any one of 6 to 9 above, wherein a layer of particles of 0 nm is provided.

11. 11. The lithographic printing plate precursor as described in any one of 6 to 10 above, wherein the anodized film is formed by two or more steps of anodizing treatment.

12. For lithographic printing according to the above 11, wherein the anodic oxidation is carried out in the electrolytic solution containing sulfuric acid in the 12.1st step and the anodic oxidation is carried out in the electrolytic solution containing phosphoric acid in the 2nd step and thereafter. Original plate.

13. 13. The lithographic printing plate precursor as described in any one of 1 to 12 above, wherein the image recording layer contains a photothermal conversion agent.

14. 14. The lithographic printing plate precursor as described in 13 above, wherein the photothermal conversion agent is contained in the self-water-dispersible resin fine particles which are coalesced by heat.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. Here,% means mass% unless otherwise specified.

[Aluminum Substrate] The aluminum substrate used in the present invention is an aluminum substrate which has been subjected to electrochemical graining treatment using an aqueous solution containing hydrochloric acid and which has a hydrophilic film having a thermal conductivity in a specific range. The aluminum substrate used in the present invention is an aluminum substrate which has been subjected to electrochemical graining treatment using an aqueous solution containing hydrochloric acid and which has a hydrophilic film having a density or porosity within a specific range. The aluminum substrate used in the present invention is an aluminum substrate in which the ratio of the average opening diameter of the small pits having the roughened shape and the average depth of the small pits to the average opening diameter is within a specific range. less than,
Such an aluminum substrate will be described in detail.

Generally, a roughened structure of an aluminum substrate which is suitably used for a lithographic printing plate has a large wave structure having an average opening diameter (average diameter) of several μm to several tens of μm and an average opening diameter of 0.01 to several. It is a superposed structure with pits of μm. In the present invention, a pit in which a large wave structure has a large undulation and no smaller pit exists inside is called a small pit. Further, the micropores of the anodized film are also simply called pores.

The aluminum plate used as a raw material for the aluminum substrate of the present invention is a dimensionally stable metal whose main component is aluminum, and is made of aluminum or an aluminum alloy. In addition to pure aluminum plates, alloy plates containing aluminum as a main component and containing trace amounts of foreign elements, aluminum or aluminum alloys are laminated,
Alternatively, a vapor deposited plastic film or paper can be used. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 can be used.

As a method of manufacturing the above aluminum plate,
For example, DC casting method, soaking treatment from DC casting method and /
Alternatively, a method in which the annealing treatment is omitted and a continuous casting method can be mentioned. In the following description, the above-mentioned substrates made of aluminum or aluminum alloy will be generically referred to as aluminum substrates.

The different elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium, and the content of the different elements in the alloy is 10% or less. is there. 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,
You may use the thing containing a little foreign element. As described above, the aluminum plate applied to the present invention is not specified in its composition, and is made of a conventionally publicly known material described in Aluminum Handbook 4th Edition (Light Metals Association (1990)), for example, JIS. A 1050, J
IS A 1100, JIS A 3103, JIS
A 3005 and the like can be appropriately used.

The aluminum plate used in the present invention has a thickness of about 0.1 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. For aluminum plate,
The surface treatment described below is performed.

Generally, an aluminum substrate for a lithographic printing plate has a degreasing process for removing rolling oil adhering to the aluminum plate, a pre-roughening process such as a desmutting process for dissolving smut on the surface of the aluminum plate, and an aluminum plate. It is manufactured through a roughening treatment step of roughening the surface of.

The aluminum substrate of the present invention is further provided with a hydrophilic film having a specific thermal conductivity after the above treatment. Further, if necessary, an acid / alkali treatment step, a sealing treatment step, and a hydrophilization treatment step are performed to form a substrate used for the lithographic printing plate precursor. Further, if necessary, an undercoat layer may be provided after forming the substrate.

The production method including the surface-roughening treatment of the present invention may be a continuous method or an intermittent method, but it is industrially preferable to use the continuous method. Hereinafter, each surface treatment step will be described in detail.

<Pre-roughening treatment> The aluminum plate is subjected to dissolution treatment using an alkaline aqueous solution such as caustic soda to remove strong dirt and natural oxide film, and the residual alkali components after the dissolution treatment are removed. In order to neutralize, it is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, colomilic acid or a mixed acid thereof to carry out a neutralization treatment. If necessary, in order to remove oils and fats, rust, dust and the like on the surface of the aluminum plate, solvent degreasing with trichlene, thinner or the like, or emulsion degreasing treatment with an emulsion of kerosene, triethanol or the like may be carried out. It is particularly preferable that the type and composition of the acid used in the neutralization treatment are matched to those of the acid used in the electrochemical graining treatment in the next step.

<Roughening Treatment> The present invention is characterized by using a substrate roughened by an electrochemical treatment using an aqueous solution containing hydrochloric acid as an electrolytic solution. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added to the electrolytic solution, and acetic acid is particularly preferable.

In the electrochemical graining treatment, the applied voltage is preferably 1 to 50V, more preferably 5 to 30V. Current density (peak value) is 5 to 200 A / dm ²
Is preferred, and 20 to 150 A / dm ² is more preferred. Electricity is 10 to 2000C in total for all processing steps
/ Dm ² is preferable, and 200 to 1000 C / dm ² is more preferable. The temperature is preferably 10 to 60 ° C., and 15 to 4
5 ° C. is more preferable. The frequency is preferably 10 to 200 Hz, more preferably 40 to 150 Hz.

The hydrochloric acid concentration is preferably 0.1 to 5%, and the current waveform used for electrolysis is appropriately selected depending on the desired roughening shape such as sine wave, rectangular wave, trapezoidal wave, sawtooth tooth, etc. Square waves are preferred.

The electrochemically roughened aluminum plate is subjected to surface etching treatment by immersing it in an acid or alkali aqueous solution in order to remove smut on the surface and control the shape of the rough surface pit. Done. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and examples of the alkali include sodium hydroxide, potassium hydroxide and the like. Among these, it is preferable to use an aqueous alkali solution, and to use an aqueous solution of 0.05 to 40% of the alkali for 20 to 9
It is preferable to perform treatment for 5 seconds to 5 minutes at a liquid temperature of 0 ° C., and after surface etching with the alkaline aqueous solution with the alkaline aqueous solution,
Neutralization treatment is performed by immersing in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof.

As the electrolysis device used in the roughening treatment step, known electrolysis devices such as a vertical type, a flat type and a radial type can be used, but the radial type as described in JP-A-5-195300 is used. An electrolysis device is particularly preferred.

FIG. 1 is a schematic view of a radial type electrolysis apparatus preferably used in the present invention. In FIG. 1, in the radial type electrolysis apparatus, an aluminum plate 11 is wound around a radial drum roller 12 arranged in a main electrolysis tank 21, and main electrodes 13a and 13 connected to an AC power source 20 in a conveying process.
Electrolyzed by b. The acidic aqueous solution 14 is supplied from a solution supply port 15 through a slit 16 to a solution passage 17 between the radial drum roller 12 and the main poles 13a and 13b.

Next, the aluminum plate 11 treated in the main electrolytic bath 21 is subjected to electrolytic treatment in the auxiliary anode bath 22. In this auxiliary anode tank 22, the auxiliary anode 18 is the aluminum plate 1
1, and the acidic aqueous solution 14 is supplied so as to flow between the auxiliary anode 18 and the aluminum plate 11. The current flowing through the auxiliary electrode is the thyristor 19a.
And 19b.

The main electrodes 13a and 13b can be selected from carbon, platinum, titanium, niobium, zirconium, stainless steel, an electrode used for a fuel cell cathode, etc., but carbon is particularly preferable. As the carbon, generally commercially available impermeable graphite for chemical devices, resin-containing graphite and the like can be used. The auxiliary anode 18 may be ferrite, iridium oxide, platinum, or platinum in titanium,
It can be selected from known oxygen generating electrodes such as those obtained by clad or plating valve metals such as niobium and zirconium.

The supply direction of the hydrochloric acid-containing aqueous solution passing through the main electrolytic bath 21 and the auxiliary anode bath 22 is the aluminum plate 11.
It may be parallel or counter with the progress of. The relative flow rate of the hydrochloric acid-containing aqueous solution to the aluminum plate is 10 to 10
It is preferably 00 cm / sec.

One or more AC power sources can be connected to one electrolysis device. Also, two or more electrolysis devices may be used, and the electrolysis conditions in each device may be the same or different. Further, after the electrolytic treatment is completed, it is preferable to perform draining with a nip roller and washing with water by spraying in order to prevent the treatment liquid from being taken out to the next step.

Further, in the roughening treatment, the aluminum plate in the electrolyzer is proportional to the energization amount of the hydrochloric acid-containing aqueous solution which undergoes an anodic reaction, for example, (i) the conductivity of the hydrochloric acid-containing aqueous solution and (ii) Based on the concentration of hydrochloric acid and aluminum ions determined from the velocity of sound wave propagation and (iii) temperature, add hydrochloric acid and water while adjusting the amount added, and add an aqueous solution containing hydrochloric acid in the same amount as the volume of hydrochloric acid and water added. It is preferable to keep the concentration of the hydrochloric acid-containing aqueous solution constant by overflowing the electrolytic solution from the electrolysis device and discharging it.

Further, in the present invention, a pause time of 0.2 to 10 seconds is provided in the course of the electrochemical graining treatment in the hydrochloric acid-containing electrolytic solution, and the electrochemical graining treatment is performed once. It is preferable that the amount of electricity is 100 C / dm ² or less. When the electrochemical surface roughening treatment is carried out in a plurality of times as described above, when the rest time is less than 0.2 seconds and the amount of electricity in the electrochemical surface roughening treatment exceeds 100 C / dm ^2. However, it is not possible to suppress the formation of coarse pits having an opening diameter of more than 20 μm, and if the pause time exceeds 10 seconds, it takes too much time to manufacture the aluminum substrate, and the productivity deteriorates.

The above-mentioned electrochemical graining treatment using an aqueous solution containing hydrochloric acid as an electrolytic solution can be used in combination with mechanical graining treatment or electrochemical graining treatment under different conditions.

The mechanical surface roughening treatment is preferably carried out before the electrochemical surface roughening treatment and prior to the dissolution treatment using the alkaline aqueous solution. The method of mechanical surface roughening treatment is not particularly limited, but brush polishing and honing polishing are preferable.
In brush polishing, for example, a cylindrical brush having bristles of 0.2 to 1 mm in diameter is rotated, and a slurry in which an abrasive is dispersed in water is supplied to the contact surface and pressed against the surface of an aluminum plate to roughen the surface. Perform processing. In the honing polishing, a slurry in which an abrasive is dispersed in water is injected from a nozzle under pressure, and the slurry is made to collide obliquely with the surface of an aluminum plate for roughening treatment. Further, mechanical roughening treatment can also be performed by laminating a sheet which has been roughened in advance on the surface of the aluminum plate and applying pressure to transfer the roughened surface pattern.

When carrying out the mechanical surface roughening treatment, the solvent degreasing treatment or the emulsion degreasing treatment can be omitted.

Examples of the electrochemical graining treatment under different conditions include an electrochemical graining treatment mainly containing nitric acid.

The acidic aqueous solution containing nitric acid as a main component may be one that is used for an ordinary electrochemical roughening treatment using a direct current or an alternating current. For example, one or more nitric acid compounds such as aluminum nitrate, sodium nitrate, and ammonium nitrate are added to a nitric acid aqueous solution having a nitric acid concentration of 5 to 15 g / l at a concentration from 0.01 g / l to saturation. be able to. Metals and the like contained in aluminum alloys such as iron, copper, manganese, nickel, titanium, magnesium and silicon may be dissolved in the acidic aqueous solution containing nitric acid as a main component.

The acidic aqueous solution containing nitric acid as a main component contains, among others, nitric acid, aluminum salts and nitrates,
And, aluminum ion is 1 to 15 g / l, preferably 1 to 10 g / l, and ammonium ion is 10 to 300.
It is preferable to use a product obtained by adding aluminum nitrate and ammonium nitrate to a nitric acid aqueous solution having a nitric acid concentration of 5 to 15 g / l so that the concentration becomes ppm. The aluminum ions and ammonium ions spontaneously increase during the electrochemical graining treatment. The liquid temperature at this time is 10 to 95.
C. is preferable, and 40 to 80.degree. C. is more preferable.

In the lithographic printing plate precursor of the present invention which has been subjected to the above-mentioned roughening treatment, the average opening diameter of the small pits having the roughened shape is preferably 0.01 to 3 μm. It is more preferably 0.05 to 2 μm, and particularly preferably 0.05 to 1.
It is 0 μm. Within this range, satisfactory stain resistance and printing durability in printing can be secured, and good printing durability can be obtained.

The ratio of the average depth of the small pits to the average opening diameter is preferably 0.1 to 0.5. It is more preferably 0.1 to 0.3, and particularly preferably 0.15 to 0.2. Within this range, stain resistance and printing durability are good,
Also, the stain resistance is good, which is preferable.

The average opening diameter of the undulations having a roughened shape is preferably 3 to 20 μm. More preferably 3 to 17 μm
And particularly preferably 4 to 10 μm. Within this range, the stain resistance and printing durability during printing are good, and the stain resistance is also good, which is preferable.

<Formation of Hydrophilic Film> The aluminum substrate of the present invention has a thermal conductivity of 0.05 on the aluminum plate which has been subjected to the surface roughening treatment as described above and, if necessary, other treatments.
It is characterized in that a hydrophilic film of 0.5 W / mK is provided.

The hydrophilic film has a thermal conductivity of 0.05 in the film thickness direction.
W / (m · K) or more, preferably 0.08 W /
(M · K) or more, and 0.5 W / (m · K) or less, preferably 0.3 W / (m · K) or less, and more preferably 0.2 W / (m · K). ) Below.
Thermal conductivity in the film thickness direction is 0.05 to 0.5 W / (mK)
Then, the heat generated in the recording layer due to the laser light exposure can be prevented from diffusing into the substrate. As a result, the sensitivity is increased, the efficiency of heat fusion of the fine particles is increased, the image strength is improved, and the printing durability can be improved.

The thermal conductivity in the film thickness direction of the hydrophilic film specified in the present invention will be described below. Various methods have been reported so far for measuring the thermal conductivity of thin films. 19
In 1986, ONO et al. Reported the thermal conductivity in the planar direction of a thin film using a thermograph. An attempt to apply the AC heating method to the measurement of thermophysical properties of thin films has also been reported.
The origin of the AC heating method can be traced back to the report of 1863, but in recent years, various measurement methods have been proposed by developing a heating method using a laser and combining with a Fourier transform. A device using the laser angstrom method is actually commercially available. In all of these methods, the thermal conductivity in the plane direction (in-plane direction) of the thin film is obtained.

However, when considering the heat conduction of the thin film, heat diffusion in the depth direction is an important factor. It is said that the thermal conductivity of a thin film is not isotropic as reported variously, and particularly in the case of the present invention, it is extremely important to directly measure the thermal conductivity in the film thickness direction. From such a viewpoint, a method using a thermocomparator is a method using Lambropo as an attempt to measure the thermophysical properties of the thin film in the film thickness direction.
ulos et al. (J. Appl. Phys., 66.
(9) (1 November 1989)) and H
a paper by Enger et al. (APPLIED OPTIC
S, Vol. 32, No. 1 (1 January 1
993)). Furthermore, in recent years, a method of measuring the thermal diffusivity of a polymer thin film by temperature wave thermal analysis applying Fourier analysis has been reported by Hashimoto et al.
etsu Sokutei, 27 (3) (200
0)).

The thermal conductivity in the film thickness direction of the hydrophilic film defined in the present invention is measured by the method using the thermocomparator. Hereinafter, the above method will be described in detail, but the basic principle of the above method will be described with reference to Lambpropo described above.
It is described in detail in the article by ulos et al. and the article by Henager et al. The device used in the above method is not limited to the following device.

FIG. 2 is a schematic diagram of a thermocomparator 30 which can be used for measuring the thermal conductivity in the film thickness direction of the hydrophilic film of the lithographic printing plate precursor of the present invention. The method using the thermocomparator is greatly affected by the contact area with the thin film and the state (roughness) of the contact surface. Therefore, it is important to make the tip of the thermocomparator 30 in contact with the thin film as small as possible. For example, a chip (wire material) 31 made of oxygen-free copper and having a minute tip with a radius r ₁ = 0.2 mm is used.

This chip 31 is fixed to the center of a constantan reservoir 32, and the periphery of the reservoir 32 is
An oxygen-free copper heating jacket 34 having an electric heater 33 is fixed. The heating jacket 34 is heated by the electric heater 33, and the output of the thermocouple 35 mounted inside the reservoir 32 is fed back to the reservoir 3
When the temperature is controlled to be 60 ± 1 ℃, the chip 31 becomes 60
Heated to ± 1 ° C. On the other hand, radius 10 cm, thickness 10 m
A heat sink 36 made of oxygen-free copper of m is prepared, and a metal substrate 38 having a film 37 to be measured is placed on the heat sink 36. The temperature of the surface of the heat sink 36 is measured using a contact thermometer 39.

After the thermocomparator 30 is set in this way, the tip of the heated chip 31 is brought into close contact with the surface of the film 37. Thermo comparator 30
Is attached, for example, to the tip of a dynamic micro hardness tester instead of an indenter and is driven up and down.
The chip 31 hits the surface of and is pressed until a load of 0.5 mN is applied. As a result, the variation in the contact area between the film 37 to be measured and the chip 31 can be minimized.

When the heated chip 31 is brought into contact with the film 37, the tip temperature of the chip 31 decreases, but reaches a steady state at a certain constant temperature. This is the chip 31 from the electric heater 33 through the heating jacket 34 and the reservoir 32.
This is because the amount of heat applied to the heat sink 36 is balanced with the amount of heat diffused from the chip 31 to the heat sink 36 through the metal base 38. The tip tip temperature, heat sink temperature, and reservoir temperature at this time are respectively indicated by the tip tip temperature recorder 4
0, heat sink temperature recorder 41 and reservoir temperature recorder 42 are used for recording.

The relationship between each temperature and the thermal conductivity of the film is as shown in the following mathematical expression (1).

[0066]

[Equation 1]

However, the symbols in the above equation (1) are as follows. T _t : chip tip temperature, T _b : heat sink temperature, T
_r : reservoir temperature, K _tf : thermal conductivity of film, K ₁ : thermal conductivity of reservoir, K ₂ : thermal conductivity of chip (400 W / (mK) for oxygen-free copper), K ₄ : (coating film Metal substrate thermal conductivity (when not provided), r ₁ : tip tip radius of curvature, A ₂ : contact area between reservoir and tip, A ₃ : contact area between tip and film, t: film thickness, t ₂ : contact Thickness (≒
0)

By changing the film thickness (t), each temperature (T _t , T
By measuring and plotting _b and T _r ), the slope of the above equation (1) can be obtained and the film thermal conductivity (K _tf ) can be obtained. That is, this slope is, as is clear from the above formula (1), the reservoir thermal conductivity (K ₁ ), the tip radius of curvature (r ₁ ), the film thermal conductivity (K _tf ), and the contact between the chip and the film. Since the values are determined by the area (A ₃ ), and K ₁ , r ₁ and A ₃ are known values, the value of K _tf can be obtained from the slope.

The present inventors determined the thermal conductivity of the anodic oxide film (Al ₂ O ₃ ) provided on the aluminum substrate using the above measuring method. The temperature was measured while changing the film thickness, and the thermal conductivity of Al ₂ O ₃ obtained from the slope of the resulting graph was 0.69 W / (m · K). This is in good agreement with the results of the above-mentioned Lambropoulos et al. This result shows that the thermophysical property value of the thin film is the bulk thermophysical property value (the thermal conductivity of the bulk Al ₂ O ₃ is 2
It also shows that it is different from 8 W / (mK).

When the above-mentioned method is used for measuring the thermal conductivity in the film thickness direction of the hydrophilic film of the lithographic printing plate precursor of the present invention, the tip of the chip is made fine and the pressing load is kept constant, whereby It is preferable that the surface roughened for the printing plate can obtain a result without variation.
The value of thermal conductivity is measured at different points on the sample, eg 5
It is preferable to measure at points and obtain the average value.

The film thickness of the hydrophilic film is preferably 0.1 μm or more in view of scratch resistance and printing durability, and is 0.3.
It is more preferably at least 5 μm, particularly preferably at least 0.6 μm, and from the viewpoint of manufacturing cost, in view of the fact that a large amount of energy is required to provide a thick film, it is at most 5 μm. Preferably 3μ
It is more preferably m or less, and particularly preferably 2 μm or less.

The hydrophilic film of the present invention has a density of 1000 from the viewpoint of the effect on heat insulation, film strength, and stain resistance during printing.
It is preferably ˜3200 kg / m ³ .

As the method for measuring the density, for example, from the weight measurement by the Mason method (the weight method of the anodic oxide film by dissolving the chromic acid / phosphoric acid mixture solution) and the film thickness obtained by observing the cross section by SEM, It can be calculated by a formula.

Density (kg / m ³ ) = (weight of hydrophilic film per unit area / film thickness)

The density of the formed hydrophilic film is 1000 kg / m.
^If it is less than ³ , the film strength will be low, which may adversely affect the image forming properties and printing durability, and the stain resistance during printing will also deteriorate. If it exceeds 3200 kg / m ³ , sufficient heat insulation cannot be obtained, and the effect of improving sensitivity decreases.

In the present invention, the porosity of the hydrophilic film is 20.
˜70% is preferable, 30 to 60% is more preferable, and 40 to 50% is particularly preferable.
If the porosity of the hydrophilic film is less than 20%, the thermal diffusion to the aluminum substrate cannot be sufficiently suppressed, and the effects of increasing the sensitivity and improving the printing durability are insufficient. When the porosity exceeds 70%, the problem of stains on the non-image area is likely to occur.

The method for providing the hydrophilic film is not particularly limited, and an anodic oxidation method, a vapor deposition method, a CVD method, a sol-gel method, a sputtering method, an ion plating method, a diffusion method or the like can be appropriately used. Alternatively, a method of applying a solution in which hollow particles are mixed with a hydrophilic resin or a sol-gel solution can be used.

Among them, it is most preferable to use a treatment for forming an oxide by the anodizing method, that is, anodizing treatment. The anodizing treatment can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to an aluminum plate in an aqueous solution or a non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., alone or in combination of two or more kinds. An anodized film, which is a hydrophilic film, can be formed on the surface of the aluminum plate.

The conditions of the anodic oxidation treatment cannot be unconditionally determined because they vary depending on the electrolytic solution used, but generally, the electrolytic solution concentration is 1 to 80% by mass, the liquid temperature is 5 to 70 ° C.
Current density 0.5 to 60 A / dm ² , voltage 1 to 200 V,
A suitable electrolysis time is 1 to 1000 seconds.

Among these anodizing treatments, a method of anodizing treatment at a high current density in a sulfuric acid electrolytic solution described in British Patent No. 1,412,768 and US Pat. No. 3,511,511 The method described in No. 661, in which phosphoric acid is used as an electrolytic bath and anodizing treatment is preferable. It is also possible to carry out a multi-stage anodizing treatment such as anodizing in sulfuric acid and then in phosphoric acid.

In the present invention, the anodic oxide film has a sensitivity
And in terms of printing durability, 3.2 g / m ²It is better to be above
Much better, 4.0 g / m²More preferably,
5 g / m²It is especially preferable that it is above, and thick skin
A great amount of energy is required to form the film
Considering that, 50g / m²The following is preferable and 3
0 g / m²The following is more preferable, and 20 g / m²Since
Especially preferred is below.

On the surface of the anodic oxide film, fine recesses called micropores are uniformly distributed and formed. The diameter density of the micropores present in the anodized film is
It can be adjusted by appropriately selecting the processing conditions. By increasing the diameter density of the micropores, the thermal conductivity in the film thickness direction of the anodized film is 0.05 to 0.5W.
It can be / (m · K).

Further, by increasing the micropore diameter density of the anodized film, the density becomes 1000 to 3200 kg.
/ M can ³ to be.

In the present invention, it is preferable to carry out a pore widening treatment for expanding the pore diameter of the micropores after the anodizing treatment for the purpose of lowering the thermal conductivity and density and increasing the porosity. In the pore widening treatment, the aluminum substrate having the anodic oxide film formed thereon is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodic oxide film, thereby expanding the pore size of the micropores. In the pore widening treatment, the dissolved amount of the anodized film is preferably 0.01 to 2
0 g / m ^2, more preferably 0.1-5 g / m ^2, particularly preferably at a range of a 0.2~4g / m ^2.

The pore diameter of the micropores is preferably 0 to 40 nm from the viewpoints of print stains and on-machine developability. The thickness is more preferably 15 nm or less, and particularly preferably 7 nm or less. Within this range, good print stain and on-press developability can be obtained. Further, from the viewpoint of sensitivity and printing durability, the pore diameter at a position 0.4 μm lower from the surface is 7 to 200 n.
m is preferred. The thickness is more preferably 15 to 100 nm, and particularly preferably 30 to 100 nm. Within this range, good heat insulation can be obtained, and the effects of improving sensitivity and printing durability can be obtained.

When an aqueous acid solution is used for the pore widening treatment, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or a mixture thereof. The concentration of the aqueous acid solution is preferably 10 to 1000 g / l, 20
More preferably, it is about 500 g / l. The temperature of the aqueous acid solution is preferably 10 to 90 ° C, and 30 to 70 ° C.
Is more preferable. Immersion time in acid aqueous solution is 1
It is preferably ˜300 seconds, more preferably 2 to 100 seconds.

On the other hand, when an alkaline aqueous solution is used for the pore widening treatment, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The alkaline aqueous solution preferably has a pH of 10 to 13.
It is more preferably from 1.5 to 13.0. The temperature of the alkaline aqueous solution is preferably 10 to 90 ° C., and 30
More preferably, it is -50 ° C. The immersion time in the alkaline aqueous solution is preferably 1 to 500 seconds, and 2 to 1
More preferably, it is 00 seconds.

Further, the hydrophilic film may be an inorganic film provided by a sputtering method, a CVD method or the like in addition to the above-mentioned anodic oxide film. Examples of the compound forming the inorganic film include oxides, nitrides, silicides, borides, and carbides. Further, the inorganic film may be composed of only a single compound, or may be composed of a mixture of compounds.

Specific examples of the compound forming the inorganic film include aluminum oxide, silicon oxide, titanium oxide,
Zirconium oxide, hafnium oxide, vanadium oxide,
Niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, chromium oxide; aluminum nitride, silicon nitride, titanium nitride, zirconium nitride, hafnium nitride, vanadium nitride, niobium nitride, tantalum nitride, molybdenum nitride. , Tungsten nitride, chromium nitride, silicon nitride, boron nitride; titanium silicide,
Zirconium silicide, hafnium silicide, vanadium silicide, niobium silicide, tantalum silicide, molybdenum silicide, tungsten silicide, chromium silicide; titanium boride, zirconium boride, hafnium boride, vanadium boride, boride Niobium, tantalum boride, molybdenum boride, tungsten boride, chromium boride; aluminum carbide, silicon carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, molybdenum carbide, tungsten carbide, chromium carbide Is mentioned.

<Sealing Treatment> In the present invention, in order to improve the stain resistance and the on-machine developability of the lithographic printing plate substrate of the present invention obtained by providing the hydrophilic film as described above, Sealing treatment may be performed. The sealing treatment used in the present invention can be carried out by a conventionally known method, but in order to achieve both sensitivity, printing durability and stain resistance, and on-press developability, it is necessary to use the fine pores of the sealing treatment film. The opening diameter is 0-40 in the surface layer
nm, 7 to 200 nm at a position 0.4 μm below the surface layer
Is preferred.

The sealing treatment used in the present invention is described in JP-A-4-176690 and Japanese Patent Application No. 10-106.
The sealing treatment of the anodized film with pressurized steam or hot water described in Japanese Patent No. 819 (JP-A-11-301135) is mentioned. Also, silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment, electrodeposition sealing treatment, triethanolamine treatment, barium carbonate treatment, hot water treatment containing a trace amount of phosphate. It can also be carried out using a known method such as. Among them, especially preferred is
Average particle size 8 to 800 n described in Japanese Patent Application No. 2001-9871
A sealing treatment using particles of m can be mentioned.

The pore-sealing treatment using particles has an average particle size of 8 to 8
00 nm, preferably 10-500 nm average particle size, more preferably 10-150 nm average particle size. Within this range, there is little risk that particles will enter the inside of the micropores present in the hydrophilic film, the effect of high sensitivity can be sufficiently obtained, and the adhesiveness with the image recording layer will be sufficient, resulting in printing durability. Will be excellent. The thickness of the particle layer is preferably 8 to 800 nm, and 10 to 50 nm.
More preferably, it is 0 nm.

The particles used in the present invention have a thermal conductivity of 6
It is preferably 0 W / (m · K) or less, and 40 W /
It is more preferably (m · K) or less, and 0.3 to 10
It is particularly preferably W / (m · K) or less. When the thermal conductivity is 60 W / (m · K) or less, the thermal diffusion to the aluminum substrate is sufficiently suppressed, and the effect of increasing the sensitivity is sufficiently obtained.

As the method for providing the particle layer, for example, dipping treatment with a solution, spraying treatment, coating treatment,
Electrolytic treatment, vapor deposition treatment, sputtering, ion plating, thermal spraying, plating and the like can be mentioned, but not limited thereto.

Direct current or alternating current can be used for the electrolytic treatment. Examples of the waveform of the alternating current used for the electrolytic treatment include a sine wave, a rectangular wave, a triangular wave, and a trapezoidal wave. The frequency of the alternating current is preferably 30 to 200 Hz, and more preferably 40 to 120 Hz, from the viewpoint of the cost of manufacturing the power supply device. When a trapezoidal wave is used as the waveform of the alternating current, the time tp until the current reaches the peak from 0 is 0.1 to 2 mse.
c is preferable, and 0.3 to 1.5 msec is more preferable. If the tp is less than 0.1 msec, the impedance of the power supply circuit influences, a large power supply voltage is required when the current waveform rises, and the equipment cost of the power supply may increase.

As the hydrophilic particles, Al ₂ O ₃ and Ti are used.
It is preferable to use O ₂ , SiO ₂ and ZrO ₂ alone or in combination of two or more kinds. The electrolytic solution is, for example,
It is obtained by suspending the hydrophilic particles in water or the like so that the content of the hydrophilic particles is 0.01 to 20% of the whole. The electrolytic solution has a positive or negative electric charge, for example,
The pH can also be adjusted by adding sulfuric acid. The electrolytic treatment is performed by using, for example, direct current, an aluminum plate as a cathode, the above electrolytic solution, and a voltage of 10 to 200 V.
At 1 to 600 seconds. According to this method, it is possible to easily close the mouth of the micropore existing in the anodized film while leaving a void inside the micropore.

As another method of sealing treatment, carboxymethyl cellulose; dextrin; gum arabic; phosphonic acids having an amino group such as 2-aminoethylphosphonic acid; phenylphosphonic acid which may have a substituent and naphthylphosphone. Organic phosphonic acids such as acids, alkylphosphonic acids, glycerophosphonic acids, methylenediphosphonic acids, ethylenediphosphonic acids; phenylphosphoric acids which may have a substituent, naphthylphosphoric acids, alkylphosphoric acids, glycerophosphoric acids, etc. Phosphoric acid ester; Organic phosphinic acid such as optionally substituted phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid; Amino acids such as glycine and β-alanine;
There is also a method of providing a layer of a compound selected from a hydrochloride of an amine having a hydroxy group such as a hydrochloride of triethanolamine.

Further, the sealing treatment may be carried out by applying a silane coupling agent having an unsaturated group. Examples of the silane coupling agent include N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (3-acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) methyldimethoxy. Silane, (3-acryloxypropyl) trimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyldimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, 3-
Butenyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, methacrylamidopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) Dimethylethoxysilane, Methacryloxymethyltriethoxysilane, Methacryloxymethyltrimethoxysilane, Methacryloxypropyldimethylethoxysilane, Methacryloxypropyldimethylmethoxysilane, Methacryloxypropylmethyldiethoxysilane, Methacryloxypropylmethyldimethoxysilane, Methacryloxypropyl Methyltriethoxysilane, methacryloxypropylmethyltrimethoxysilane, methacryloxypropyltris (methoxyethoxy) si Emissions, methoxy dimethylvinylsilane, 1-methoxy-3- (trimethylsiloxy) butadiene, styrylethyltrimethoxysilane, 3- (N-
Styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, vinyldimethylethoxysilane, vinyldiphenylethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, O
-(Vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-t-butoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, vinyltris (2-methoxyethoxy) ) Silane and diallylaminopropylmethoxysilane. Of these, a silane coupling agent having a methacryloyl group or an acryloyl group, which has a fast unsaturated group reactivity, is preferable.

In addition, the sol-gel coating treatment described in JP-A-5-50779,
-246171, coating treatment of phosphonic acids, JP-A-6-234284, JP-A-6-191173 and JP-A-6-2305.
Japanese Patent Laid-Open No. 6-262872, which is a method for treating a backcoat material by coating.
Treatment of phosphonic acids described in Japanese Patent Laid-Open No. Hei 6 (1999)
-297875, the method of anodizing treatment described in JP-A-10-109480, Japanese Patent Application No. 10-252078 (Japanese Patent Application Laid-Open No. 2000-81704) and Japanese Patent Application Laid-Open No. 2000-81704. Japanese Patent Application No. 10-253411 (Japanese Patent Laid-Open No. 2000-8946)
The dipping treatment method described in Japanese Patent No. 6) may be used, and any method may be used.

<Hydrophilic surface treatment> In the present invention, the lithographic printing plate substrate of the present invention obtained by providing the hydrophilic film as described above is further treated with an aqueous solution containing one or more hydrophilic compounds. It is preferable to perform hydrophilic surface treatment by dipping.

A method of treatment with an alkali metal silicate (alkali metal silicate) described in US Pat. Nos. 2,714,066 and 3,181,461, JP-B-36-22063. A method of treating with potassium fluorozirconate described in Japanese Patent Publication No.
A method of treatment with polyvinylphosphonic acid described in U.S. Pat. No. 4,153,461, JP-A-9-2
Japanese Patent Laid-Open No. 44227/1992, a method of treating with an aqueous solution containing a phosphate and an inorganic fluorine compound.
No. 0-252078 and JP-A-10-26341.
The method of treatment with an aqueous solution containing titanium and fluorine described in Japanese Patent No. 1 is cited. Among them, the method of treating with an alkali metal silicate and the method of treating with polyvinylphosphonic acid are preferable.

Examples of the alkali metal silicate used in the method of treating with an alkali metal silicate include sodium silicate, potassium silicate, and lithium silicate.

The method of treatment with an alkali metal silicate is as follows:
For example, the alkali metal silicate concentration is 0.01 to 30% by mass, preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, and the pH at 25 ° C is 10 to 13%.
A method of immersing the aluminum substrate provided with the above-mentioned particle layer at 4 to 80 ° C., preferably 0.5 to 120 seconds, more preferably 2 to 30 seconds in the alkali metal silicate aqueous solution. The processing conditions such as the above-mentioned alkali metal silicate concentration, pH, temperature and processing time can be appropriately selected. If the pH of the aqueous alkali metal silicate solution is lower than 10, the solution tends to gel and the pH is 1 or less.
If it is higher than 3, the particle layer and the anodic oxide film may be dissolved, so attention must be paid to this point.

In the above hydrophilic treatment, if necessary,
In order to adjust the pH of the alkali metal silicate aqueous solution to a high level, a hydroxide can be added. Examples of the hydroxide include sodium hydroxide, potassium hydroxide and lithium hydroxide.

If necessary, an alkaline earth metal salt and / or Group 4 (group I
You may mix | blend a VA group) metal salt. Examples of the alkaline earth metal salts include nitrates of alkaline earth metals (eg, calcium nitrate, strontium nitrate, magnesium nitrate, barium nitrate), sulfates, hydrochlorides, phosphates,
Water-soluble salts such as acetate, oxalate, borate and the like can be mentioned. Examples of the Group 4 (Group IVA) metal salt include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium tetraiodide, and the like.
Examples thereof include zirconium chloride oxide, zirconium dioxide, zirconium oxychloride, and zirconium tetrachloride. Alkaline earth metal salts and Group 4 (Group IVA) metal salts are
They may be used alone or in combination of two or more. The amount of these metal salts used is preferably 0.01
10 to 10% by mass, more preferably 0.05 to 5.0
It is% by mass.

The aqueous solution used in the method for treating with polyvinylphosphonic acid has a polyvinylphosphonic acid concentration of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.2 to 2. 5% by mass, temperature 10
C. to 70.degree. C., preferably 30.degree. C. to 60.degree. In the hydrophilic treatment, the aluminum substrate provided with the particle layer is immersed in the aqueous solution, for example, for 0.5 seconds to 10 minutes, preferably 1
It can be performed by dipping for 30 seconds to 30 seconds.

The treatment with an aqueous solution of potassium zirconium fluoride is preferably carried out with an aqueous solution of potassium zirconium fluoride having a concentration of 0.1 to 10% by mass, more preferably 0.5 to 2% by mass, and the substrate, preferably 30 to 80%. It is carried out by immersing at 60 ° C., preferably for 60 to 180 seconds.

In the phosphate / inorganic fluorine compound treatment, the phosphate compound concentration is preferably 5 to 20% by mass, the inorganic fluorine compound concentration is 0.01 to 1% by mass, and the pH is preferably 3 to 5. An aluminum substrate is added to the aqueous solution, preferably at 20 to 100 ° C, more preferably at 40 to 80 ° C.
The immersion is preferably carried out for 2 to 300 seconds, more preferably 5 to 30 seconds.

Examples of the phosphate used in the present invention include phosphates of metals such as alkali metals and alkaline earth metals. Specifically, for example, zinc phosphate,
Aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, potassium dihydrogenphosphate, dipotassium hydrogenphosphate, calcium phosphate, phosphorus Sodium ammonium hydrogen hydride,
Magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, lead phosphate, diammonium phosphate, dihydrogen phosphate Calcium, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate;
Examples include sodium phosphite, sodium tripolyphosphate, and sodium pyrophosphate. Among them, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate are preferable.

Further, as the inorganic fluorine compound used in the present invention, metal fluoride is preferably mentioned. Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium hexafluorozirconium, potassium hexafluorozirconium, sodium hexafluorotitanate, potassium hexafluorotitanate, hexafluorozirconium oxyhydroxide , Hexafluorotitanium hydrogen acid, hexafluorozirconium ammonium, hexafluorotitanate ammonium, hexafluorosilicic acid, nickel fluoride, iron fluoride, fluorophosphoric acid, and ammonium fluorophosphate.

The aqueous solution used for the phosphate / inorganic fluorine compound treatment may contain one or more phosphates and two or more inorganic fluorine compounds, respectively.

In the present invention, in addition to the above-mentioned aqueous solution,
Suitable compounds include compounds having a sulfonic acid group and sugar compounds.

The compounds having a sulfonic acid group include aromatic sulfonic acids, their formaldehyde condensates, their derivatives, and their salts.

Examples of the aromatic sulfonic acid include phenol sulfonic acid, catechol sulfonic acid, resorcinol sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, lignin sulfonic acid, naphthalene sulfonic acid, acenaphthene-5-sulfonic acid and phenanthrene-2. -Sulfonic acid, benzaldehyde-2 (or 3) -sulfonic acid, benzaldehyde-2,4 (or 3,5) -disulfonic acid, oxybenzyl sulfonic acids, sulfobenzoic acid, sulfanilic acid, naphthoic acid, and taurine. Of these, benzenesulfonic acid, naphthalenesulfonic acid, and ligninsulfonic acid are preferable. Further, formaldehyde condensates of benzenesulfonic acid, naphthalenesulfonic acid and ligninsulfonic acid are also preferable. Furthermore, they may be used as sulfonates. For example, sodium salt, potassium salt, lithium salt, calcium salt,
Magnesium salt may be mentioned. Among them, sodium salt,
The potassium salt is preferred.

The pH of the aqueous solution containing the compound having a sulfonic acid group is preferably 4 to 6.5, and sulfuric acid,
The pH range can be adjusted using sodium hydroxide, ammonia or the like.

The saccharide compounds include monosaccharides and sugar alcohols thereof, oligosaccharides, polysaccharides, and glycosides.

As the monosaccharide and its sugar alcohol,
For example, trioses such as glycerol and sugar alcohols thereof; tetroses such as threose and erythritol and sugar alcohols thereof; pentoses such as arabinose and arabitol and sugar alcohols thereof; hexoses such as glucose and sorbitol and sugar sugars thereof; D -Glycero-D-galactoheptose, D-
Heptose such as glycero-D-galactoheptitol and sugar alcohols thereof; octose such as D-erythro-D-galactooctitol and sugar alcohols thereof; nonose such as D-erythro-L-gluco-nonulose and sugars thereof Examples include alcohols.

Examples of oligosaccharides include disaccharides such as saccharose, trehalose and lactose; and trisaccharides such as raffinose.

Examples of the polysaccharides include amylose, arabinan, cyclodextrin and cellulose alginate.

In the present invention, the "glycoside" refers to a compound in which a sugar moiety and a non-sugar moiety are bound via an ether bond or the like. Glycosides can be classified by the non-sugar moiety. For example, alkyl glycosides, phenol glycosides, coumarin glycosides, oxycoumarin glycosides, flavonoid glycosides, anthraquinone glycosides, triterpene glycosides, steroid glycosides, mustard oil glycosides Can be mentioned.

Examples of the sugar moiety include the above-mentioned monosaccharides and sugar alcohols thereof; oligosaccharides and polysaccharides. Among them, monosaccharides and oligosaccharides are preferable, and monosaccharides and disaccharides are more preferable.

Examples of preferred glycosides include the following formula (I)
The compound represented by

[0123]

[Chemical 1]

In the above formula (I), R represents 1 to 2 carbon atoms.
Represents an alkyl group, an alkenyl group, or an alkynyl group having 0 straight chain or branching.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Dodecyl group,
Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group may be mentioned, and these may be linear or branched, and cyclic alkyl It may be a group.

Examples of the alkenyl group having 1 to 20 carbon atoms include an allyl group and a 2-butenyl group, which may be linear or branched and may be cyclic. It may be an alkenyl group.

Examples of the alkynyl group having 1 to 20 carbon atoms include a 1-pentynyl group, which may be linear or branched, and are cyclic alkynyl groups. It may be.

Specific compounds represented by the above formula (I) include, for example, methylglucoside, ethylglucoside, propylglucoside, isopropylglucoside, butylglucoside, isobutylglucoside, n-hexylglucoside, octylglucoside, caprylglucoside, Examples include decyl glucoside, 2-ethylhexyl glucoside, 2-pentylnonyl glucoside, 2-hexyl decyl glucoside, lauryl glucoside, myristyl glucoside, stearyl glucoside, cyclohexyl glucoside, and 2-butynyl glucoside. These compounds are glucosides, which are a type of glycoside, in which the hemiacetal hydroxyl group of glucose is bound to another compound in an ether form, and obtained by, for example, a known method of reacting glucose with alcohol be able to. Some of these alkyl glucosides are found in German He
Trade name GLUCOPO by Nkel
N), which is commercially available and can be used in the present invention.

Other examples of preferred glycosides include saponins, rutin trihydrate, hesperidin methyl chalcone, hesperidin, naridin hydrate, phenol-β-D-glucopyranoside, salicin, 3 ',
5,7-methoxy-7-rutinoside may be mentioned.

The pH of the aqueous solution containing the saccharide compound is 8
It is preferably -11 and can be adjusted to the above pH range using potassium hydroxide, sulfuric acid, carbonic acid, sodium carbonate, phosphoric acid, sodium phosphate and the like.

An aqueous solution of a compound having a sulfonic acid group is
The concentration is preferably 0.02 to 0.2% by mass. The immersion temperature is preferably 60 to 100 ° C. The immersion time is preferably 1 to 300 seconds, more preferably 10 to 100 seconds.

Further, the aqueous solution of the saccharide compound has a concentration of 0.
It is preferably 5 to 10% by mass. Immersion temperature is 40 ~
It is preferably 70 ° C. The immersion time is preferably 2 to 300 seconds, more preferably 5 to 30 seconds.

The substrate is immersed in an aqueous solution containing these hydrophilic compounds, then washed with water or the like, and dried.

By the hydrophilic surface treatment described above, the sensitivity (improvement in printing durability in the case of a negative type photosensitive layer) improved by the pore widening treatment after the anodizing treatment and the printing stain such as deterioration of ink repellency which occurs in exchange. The problem goes away.
That is, due to the increase in the pore diameter, it becomes difficult to remove the ink during printing, especially when the printing machine is stopped and the lithographic printing plate is left on the printing machine and then restarted (deterioration of ink-repelling property). However, when the hydrophilic surface treatment is applied, the above problems are alleviated.

<Undercoat Layer> In the present invention, before providing a recording layer writable by infrared laser exposure on the lithographic printing plate substrate of the present invention thus obtained,
If necessary, a water-soluble metal salt such as zinc borate, an inorganic undercoat layer such as a phosphate described in JP-A-62-19494, or an organic undercoat layer described below is provided. May be.

Examples of the organic undercoat layer include those disclosed in Japanese Patent Laid-Open No.
Compounds having at least one amino group and at least one group selected from the group consisting of a carboxyl group and a salt group thereof, and a sulfo group and a salt group thereof, which are described in JP-A 0-149491. A layer comprising a compound selected from compounds having at least one amino group and at least one hydroxy group described in JP-A-60-232998 and salts thereof; JP-A-59-59 Examples of the layer include a polymer compound having at least one kind of a monomer unit having a sulfo group described in JP-A-101651 as a repeating unit in a molecule.

Specific organic compounds used in the organic undercoat layer include, for example, glycine, p-hydroxyphenylglycine, dihydroxyethylglycine, β-alanine, lysine, aspartic acid, and other amino acids, and their sodium salts and potassium. Salts, salts such as ammonium salts, aliphatic aminosulfonic acids such as sulfamic acid and cyclohexylsulfamic acid and salts thereof such as sodium salts, potassium salts and ammonium salts, monoethanolamine,
Amine having a hydroxyl group such as diethanolamine, triethanolamine, and tripropanolamine, and salts thereof such as hydrochloride, oxalate, and phosphate, p-styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Allyl sulfonic acid, methallyl sulfonic acid, ethylene sulfonic acid or a polymer or copolymer containing a salt thereof as a monomer unit, further,
Carboxymethyl cellulose; Dextrin; Gum arabic; Polyacrylic acid; Phosphonic acids having an amino group such as 2-aminoethylphosphonic acid; Phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid which may have a substituent Acids, methylenediphosphonic acid, organic phosphonic acids such as ethylenediphosphonic acid;
Organic phosphoric acid such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid, glycerophosphoric acid which may have a substituent; phenylphosphinic acid which may have a substituent,
Examples thereof include organic phosphinic acids such as naphthylphosphinic acid, alkylphosphinic acid, and glycerophosphinic acid. These may be used alone or in combination of two or more.

The organic undercoat layer is formed by applying a solution prepared by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, methyl ethyl ketone or the like, or a mixed solvent thereof onto an aluminum plate and drying it. The concentration of the solution in which the above organic compound is dissolved is 0.0
It is preferably from 05 to 10% by mass. The application method is
The method is not particularly limited, and any method such as bar coater coating, spin coating, spray coating, and curtain coating can be used.

The coated amount of the organic undercoat layer after drying is 2 to 20.
It is preferably 0 mg / m ² , and 5 to 100 mg / m ^2.
Is more preferable. Within the above range, printing durability will be better.

<Backcoat Layer> When the aluminum substrate obtained as described above is used as a lithographic printing plate precursor, the back surface (the side where the recording layer is not provided is provided so that the recording layer is not scratched even when stacked. A coating layer (hereinafter also referred to as a "backcoat layer") made of an organic polymer compound may be provided on the surface of (2).

The main component of the back coat layer is a saturated copolyester resin having a glass transition point of 20 ° C. or higher,
It is preferable to use at least one resin selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin and a vinylidene chloride copolymer resin.

The saturated copolymerized polyester resin comprises a dicarboxylic acid unit and a diol unit. Examples of the dicarboxylic acid unit include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid and tetrachlorophthalic acid; adipic acid, azelaic acid, succinic acid, oxalic acid, suberic acid and sebacic acid. And saturated aliphatic dicarboxylic acids such as malonic acid and 1,4-cyclohexanedicarboxylic acid.

The back coat layer further comprises a dye or pigment for coloring, a silane coupling agent for improving adhesion to the substrate, a diazo resin containing a diazonium salt, an organic phosphonic acid, an organic phosphoric acid, a cationic A polymer, a wax usually used as a slip agent, a higher fatty acid, a higher fatty acid amide, a silicone compound composed of dimethylsiloxane, a modified dimethylsiloxane, a polyethylene powder and the like can be appropriately contained.

The thickness of the back coat layer may basically be 0.01 to 8 μm as long as it does not scratch the recording layer described later even if there is no interleaving paper. When the thickness is less than 0.01 μm, it is difficult to prevent scratches on the recording layer when the lithographic printing plate precursors are stacked and handled. If the thickness exceeds 8 μm, the back coat layer may swell due to chemicals used around the planographic printing plate during printing, the thickness may change, and the printing pressure may change to deteriorate the printing characteristics.

Various methods can be used for providing the back coat layer on the back surface of the aluminum substrate. For example, a method in which the components for the back coat layer are dissolved in a suitable solvent and applied as a solution, or an emulsified dispersion is applied and then dried; a film previously formed into a film by an adhesive or heat. And a method of forming a molten coating with a melt extruder and then laminating it to a substrate. The most preferable method for ensuring a suitable thickness is a method in which the components for the backcoat layer are dissolved in a suitable solvent to form a solution, which is then applied and dried. In this method, an organic solvent as described in JP-A No. 62-251739 can be used alone or in combination as a solvent.

In the production of the lithographic printing plate precursor, either the back coat layer on the back side or the recording layer on the front side may be provided on the substrate first, or both may be provided at the same time.

[Image-Recording Layer] The image-recording layer of the present invention contains self-water-dispersible resin particles which coalesce by heat. As such self-water-dispersible resin fine particles, a raw material resin having a lipophilic resin portion and a hydrophilic group in the molecule is disclosed in JP-A-3-22.
Resin fine particles dispersed in water without an emulsifier or a protective colloid by the phase inversion emulsification method as described in 1137 and JP-A-5-66600 can be mentioned.

Examples of the hydrophilic group in the raw material resin molecule used in the phase inversion emulsification method include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, an amide group, a sulfonamide group and an amino group. Specific examples of the monomer having a hydrophilic group include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, monobutyl maleate, acid phosphooxyethyl methacrylate, acid phosphooxypropyl. Methacrylate, 3-chloro-2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethylmethacrylate, acrylamide, N-vinylpyrrolidone, N-vinylimidazole, hydroxyethyl acrylate and the like can be mentioned.

As an example of the lipophilic resin portion in the raw material resin molecule used in the phase inversion emulsification method, a polymer portion obtained by polymerizing or copolymerizing the following polymerizable monomers (A) to (J) is mentioned. be able to.

(A) Acrylic acid esters. Examples of this monomer group include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate,
Octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, o-, m- and p-hydroxyphenyl acrylate, glycidyl acrylate, N -Dimethylaminoethyl acrylate and the like.

(B) Methacrylic acid esters. Examples of this monomer group include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, Methacrylic acid-2-
Chloroethyl, 2-hydroxyethyl methacrylate,
4-hydroxybutyl methacrylate, o-, m- and p-hydroxyphenyl methacrylate, glycidyl methacrylate, N, N-dimethylaminoethyl methacrylate and the like can be mentioned.

(C) Substituted acrylamides and substituted methacrylamides. Examples of this monomer group include N-methylol acrylamide, N-methylol methacrylamide, N
-Ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-
Cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide , N-ethyl-N-phenylacrylamide and N-ethyl-N-
Examples thereof include phenylmethacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

(D) Vinyl ethers. Examples of this monomer group include ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

(E) Vinyl esters. Examples of this group of monomers include vinyl acetate, vinyl chloroacetate,
Examples thereof include vinyl butyrate and vinyl benzoate.

(F) Styrenes. Examples of this monomer group include styrene, methylstyrene, t-butylstyrene,
Examples include chloromethylstyrene, o-, m- and p-hydroxystyrene.

(G) Vinyl ketones. Examples of this monomer group include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, and the like.

(H) Olefins. Examples of this group of monomers include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

(I) N-containing monomer. Examples of this monomer group include N-vinylcarbazole, acrylonitrile, methacrylonitrile, and the like.

(J) Unsaturated sulfonamide. Examples of this monomer group include N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl).
Acrylamides such as acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide, N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonyl) Phenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl)
Naphthyl] methacrylamide, methacrylamides such as N- (2-aminosulfonylethyl) methacrylamide, o-aminosulfonylphenyl acrylate, m-aminosulfonylphenyl acrylate, p-
Unsaturated sulfonamides such as acrylic acid esters such as aminosulfonylphenyl acrylate and 1- (3-aminosulfonylphenylnaphthyl) acrylate, o
-Aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate and the like can be mentioned.

The lipophilic resin moiety in the raw material resin molecule used in the phase inversion emulsification method may be a copolymer of the above-mentioned polymerizable monomers and a polymerizable unsaturated group-containing oligomer in some cases. Good. Examples of the polymerizable unsaturated group-containing oligomer include vinyl-modified polyester, vinyl-modified polyurethane, vinyl-modified epoxy resin, vinyl-modified phenol resin, and the like. Specific examples include maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, endomethylenetetrahydromaleic anhydride,
A polymerizable unsaturated bond (vinyl group) is introduced by polycondensation or addition of various compounds such as α-terpinene maleic anhydride adduct, monoallyl ether of triol, pentaerythrite diallyl ether or allyl glycidyl ether.

The vinyl-modified polyurethane can be obtained, for example, by addition polymerization of various polyols such as glycerin monoallyl ether or 1,2-bond-containing butadiene polyol with diisocyanate. Alternatively, the vinyl bond is also introduced by an addition reaction of urethane having an isocyanate group at the terminal and a hydroxyl group-containing polymerizable monomer. Also, by adding dimethylolpropionic acid or the like as a polyol component,
An acid component can be introduced into polyurethane.

Examples of the vinyl-modified epoxy resin include those obtained by reacting a terminal epoxy group of an epoxy resin with a carboxyl group of acrylic acid or methacrylic acid.

Examples of the vinyl-modified phenol resin include those obtained by reacting a hydroxyl group of a phenol resin with a (meth) acrylic acid halide or glycidyl (meth) acrylate.

Further, an oligomer of a polymerizable monomer having a polymerizable vinyl group, which is obtained by adding a polymerizable monomer containing a glycidyl group to a vinyl copolymer containing a carboxyl group, can be obtained. The polymerizable monomers used here are selected from those listed above. However, the oligomer and the polymerizable vinyl group are not limited to the above-described types and methods.

By copolymerizing at least one selected from these monomers and a polymerizable unsaturated group-containing oligomer with the above-mentioned monomer having a hydrophilic group, self-water-dispersible resin fine particles are obtained by phase inversion emulsification method. A raw material resin is obtained. This raw material resin has a weight average molecular weight of 500 to 500,000,
The number average molecular weight is preferably 200 to 60,000.

Further, the raw material resin of the self-water-dispersible resin fine particles may have a thermoreactive functional group. Examples of the heat-reactive functional group include an ethylenically unsaturated group that undergoes a polymerization reaction (eg, acryloyl group, methacryloyl group, vinyl group, allyl group), an epoxy group that undergoes an addition reaction, an isocyanate group, or a block thereof. be able to.

The introduction of the heat-reactive functional group is effective in increasing the strength of the image area after exposure and improving the printing durability. The heat-reactive functional group can be introduced by, for example, the polymer reaction described in WO96-34316.

In addition to the above, examples of the self-water-dispersible resin fine particles used in the present invention include, for example, JP-A-1-287.
Resin fine particles obtained by phase inversion emulsification of the urethane resin having an acidic group described in No. 183, the epoxy resin having an acidic group described in JP-A-55-3481, or the polyester resin having an acidic group. It is suitable.

Introduction of an acid group into the polyester can be carried out by a known method. For example, an excess amount of a dibasic acid such as phthalic acid may be used, whereby a product having a terminal carboxyl group can be obtained. Alternatively, by using trimellitic anhydride, one having an acid group in the main chain can be obtained.

The coagulation temperature of the self-water-dispersible resin fine particles is preferably 70 ° C. or higher.
More preferably, the temperature is 00 ° C. or higher.

The amount of the self-water-dispersible resin fine particles added to the image recording layer is preferably 50% or more, more preferably 60% or more of the solid content of the image recording layer. Within this range, good image formation can be achieved and good printing durability can be obtained.

Since the self-water-dispersible resin fine particles of the present invention enhance the action of melting, diffusing, and leaching by heat generation by light irradiation to make the neighborhood hydrophobic (lipophilic), a hydrophobic organic low-molecular compound is contained in the fine particles. Can be included. Examples of such organic low molecular weight compounds include components for printing inks, plasticizers, high-boiling aliphatic and aromatic hydrocarbons, carboxylic acids, alcohols, esters, ethers, amines and derivatives thereof. be able to.

Specific examples include oils and fats such as linseed oil, soybean oil, poppy seed oil and safflower oil, plasticizers such as tributyl phosphate, tricresyl phosphate, dibutyl phthalate, butyl laurate and dioctyl phthalate, carnauba wax, Castor wax, microcrystalline wax, paraffin wax, shellac wax, palm wax,
Fine particles dispersion of waxes such as beeswax, low molecular weight polyethylene, silver behenate, calcium stearate, metal salts of long-chain fatty acids such as magnesium palmitate,
n-nonane, n-decane, n-hexadecane, octadecane, eicosane, caproic acid, capric acid, stearic acid, oleic acid, dodecyl alcohol, octyl alcohol, n-octadecyl alcohol, 2-octanol, lauryl alcohol, lauryl methyl ether, Stearyl methyl ether, stearyl amide, etc. are mentioned.

The inclusion of the above hydrophobic organic compound in the self-water-dispersible resin fine particles can be carried out by adding the self-water-dispersible resin to an organic solvent in which the self-water-dispersible resin is dissolved and performing phase inversion emulsification during the synthesis of the resin fine particles. .

The image recording layer of the present invention may contain a photothermal conversion agent having a function of converting light into heat in order to enhance sensitivity. The photothermal conversion agent may be any substance as long as it absorbs light of 700 nm or more, and various pigments and dyes can be used. As pigments, commercially available pigments and color index (CI) handbook, "Latest pigment handbook" (edited by Japan Pigment Technology Association, 1977), "Latest pigment application technology" (CMC Publishing, 1986), "Printing" The pigments described in "Ink Technology" (CMC Publishing, 1984) can be used.

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

These pigments may be used without being surface-treated, or may be used after being surface-treated. The surface treatment method is a method of surface-coating a hydrophilic resin or a lipophilic resin,
A method of attaching a surfactant, a method of binding a reactive substance (for example, silica sol, alumina sol, a silane coupling agent, an epoxy compound, an isocyanate compound, etc.) to the pigment surface can be considered. The above surface treatment method,
It is described in “Properties and Applications of Metal Soap” (Koshoubo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Among these pigments, those that absorb infrared rays are preferable because they are suitable for use in a laser that emits infrared rays. Carbon black is particularly preferable as such an infrared absorbing pigment.

As the pigment to be added to the image recording layer of the present invention and the overcoat layer described later, a hydrophilic resin or silica sol is particularly used so as to be easily dispersed in a water-soluble or hydrophilic resin and not to impair the hydrophilicity. Surface coated carbon black is useful.

The particle size of the pigment is preferably in the range of 0.01 μm to 1 μm, more preferably in the range of 0.01 μm to 0.5 μm. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production or the like can be used. As the disperser, an ultrasonic disperser,
Sand mill, attritor, pearl mill, super mill, ball mill, impeller, desperser, KD mill, colloid mill, dynatron, three roll mill, pressure kneader and the like can be mentioned. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

As the dyes, commercially available dyes and literatures (for example, "Handbook of Dyes" edited by the Society of Synthetic Organic Chemistry, published in 1945,
"Chemical Industry" May 1986 issue P. Known dyes described in "Near-infrared absorbing dyes" of 45 to 51, "Development and market trends of 90's functional dyes", Chapter 2, Section 2.3 (1990) CMC) or patents can be used. . Specifically, infrared absorbing dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, polymethine dyes, and cyanine dyes are preferable.

For example, JP-A-58-125246, JP-A-59-84356, JP-A-60-78787,
JP-A-58-173696, JP-A-58-19459
5, JP-A-59-216146, British Patent 434.
875, U.S. Pat. No. 4,973,572 and other cyanine dyes, U.S. Pat. No. 4,756,993
Cyanine dyes and azomethine dyes described in JP-A-58-
181690 and the like, methine dyes, JP-A-58-112793, JP-A-58-224793,
JP-A-59-48187, JP-A-59-73996
JP-A-60-52940, JP-A-60-6374
Naphthoquinone dyes described in JP-A No. 4-4, JP-A-58
Examples thereof include squarylium dyes described in JP-A-112792, phthalocyanine compounds described in JP-A No. 11-235883, and various dyes described in JP-A No. 10-268512.

Further, as a dye, US Pat. No. 5,156,
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.
Trimethine thiapyrylium salt described in JP-A-42645, JP-A-58-181051, and JP-A-58-220143.
JP-A-59-41363, JP-A-59-8424
No. 8, JP-A-59-84249, JP-A-59-146.
063, JP-A-59-146061, JP-B 5-1.
No. 3514, Japanese Patent Publication No. 5-19702, pyrilium compounds, pentamethine thiopyrylium salts described in US Pat. No. 4,283,475, Eporite III-178, Eporite III- 130,
Epolite III-125 and the like are also preferably used.

Of these, a particularly preferable dye to be added to the image recording layer is a dye having a water-soluble group, and specific examples are listed below by structural formula.

[0184]

[Chemical 2]

[0185]

[Chemical 3]

The light-heat converting agent may be contained in the resin fine particles and used in the image recording layer, which is preferable from the viewpoint of thermal efficiency. In this case, the light-heat converting agent may be the above infrared absorbing pigment or dye, More lipophilic photothermal conversion agents are preferred. The dyes exemplified below are preferable.

[0187]

[Chemical 4]

[0188]

[Chemical 5]

The addition ratio of the photothermal conversion agent to the image recording layer is
0.1 to 50% by weight of the solid content of the image recording layer is preferable and 3
-25% is more preferable. Within this range, good sensitivity can be obtained without impairing the film strength of the image recording layer.

A hydrophilic resin may be added to the image recording layer of the present invention. The addition of the hydrophilic resin not only improves the on-press developability, but also improves the film strength of the image recording layer itself.

Examples of the hydrophilic resin include hydroxyl group, hydroxyethyl group, hydroxypropyl group, amino group, aminoethyl group, aminopropyl group, carboxyl group, carboxylato group, sulfo group, sulfonato group, and phosphoric acid group. Those having a hydrophilic group are preferable.

Specific examples of the hydrophilic resin include gum arabic, casein, gelatin, starch derivative, carboxymethyl cellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers,
Polyacrylic acids and salts thereof, polymethacrylic acids and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers of hydroxypropyl acrylate and Copolymers, homopolymers and copolymers of hydroxybutyl methacrylate, homopolymers and copolymers of hydroxybutyl acrylate, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and hydrolysis with a degree of hydrolysis of at least 60%, preferably at least 80% Polyvinyl acetate, polyvinyl formal, polyvinyl butyral, poly Nirupiroridon, homopolymers and copolymers of acrylamide, mention may be made of homopolymers and copolymers of methacrylamide, the N- methylol acrylamide homopolymers and copolymers, and the like.

The addition amount of the hydrophilic resin to the image recording layer is preferably 5 to 40% of the solid content of the image recording layer, and 10 to 30%.
Is more preferable. Within this range, good on-machine developability and film strength can be obtained.

If necessary, various compounds other than the above may be added to the image recording layer of the present invention. For example, a polyfunctional monomer can be added to the image recording layer in order to further improve printing durability. As the polyfunctional monomer, a polyfunctional monomer commercially available as a monomer for the photopolymerizable composition can be used. Trimethylolpropane triacrylate may be mentioned as a particularly preferred monomer.

The image recording layer of the present invention may contain a crosslinking agent, if necessary. Suitable cross-linking agents include low molecular compounds having a methylol group, such as melamine-formaldehyde resin, hydantoin-formaldehyde resin,
Thiourea-formaldehyde resin, benzoguanamine-
Formaldehyde resins can be mentioned.

Further, in the image recording layer of the present invention, a compound capable of generating an acid or a radical by heat and a dye discolored by the acid or the radical are provided in order to distinguish the image area from the non-image area after image exposure. Can be included.

As the compound which generates an acid or a radical by heat, for example, US Pat. No. 3,729,313,
No. 4,058,400, No. 4,058,401, No. 4,460,154 and No. 4,921,827, diallyliodonium salts and triallylphosphonium salts, US Pat. No. 3,987, 037, 4,476,2
No. 15, No. 4,826,753, No. 4,619,99
No. 8, No. 4,696,888, No. 4,772,534
No. 4, No. 4,189,323, No. 4,837,128
No. 5,364,734, No. 4,212,970, and the like, and halomethyl-1--3-triazine compounds and halomethyloxadiazole compounds.

As the dye that changes color by an acid or a radical, for example, various dyes such as diphenylmethane type, triphenylmethane type, thiazine type, oxazine type, xanthene type, anthraquinone type, iminoquinone type, azo type and azomethine type dyes are effective. Used.

As a specific example, brilliant green,
Ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2
B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, paramethyl red, congo fred, benzopurpurin 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl Violet, Malachide Green, Parafuchsin, Victoria Pure Blue BOH [Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Co., Ltd.], Oil Pink # 312 [Orient Chemical Co., Ltd.], Oil Red 5B [made by Orient Chemical Industry Co., Ltd.], oil scarlet # 308 [Orient Chemical Industry Co., Ltd.]
Made], Oil Red OG [Orient Chemical Industry Co., Ltd.
Made], Oil Red RR [Orient Chemical Industry Co., Ltd.]
], Oil Green # 502 [produced by Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [produced by Hodogaya Chemical Industry Co., Ltd.], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-
4-p-diethylaminophenyliminonaphthoquinone,
2-Carbostearylamino-4-p-dihydrooxyethylamino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylamino Dyes such as phenylimino-5-pyrazolone, p, p ', p "hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascrip
Examples include leuco dyes such as Blue SRB (manufactured by Ciba Geigy).

The suitable addition amount of the compound generating an acid or radical and the dye discoloring by the acid or radical is 0.01 to 10% with respect to the solid content of the image recording layer.

In the present invention, when an ethylenically unsaturated group is used as the heat-reactive group or a polyfunctional monomer is used in the image recording layer, it is unnecessary during preparation or storage of the image recording layer coating solution. In order to prevent thermal polymerization, it is desirable to add a small amount of thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol,
t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like can be mentioned. The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to 5% based on the weight of the entire composition.

If necessary, a higher fatty acid such as behenic acid or behenic acid amide or a derivative thereof is added in order to prevent polymerization inhibition by oxygen, and the surface of the image recording layer is dried in the drying process after coating. May be unevenly distributed. The amount of higher fatty acid or its derivative added is about 0.1 to about 0.1% of solid content of the image recording layer.
About 10% is preferred.

Inorganic fine particles may be added to the image recording layer of the present invention. Examples of the inorganic fine particles include silica, alumina,
Suitable examples include magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, and mixtures thereof. These are used for strengthening the film even if it is not light-heat convertible and for strengthening the interfacial adhesion by roughening the surface. be able to.

The average particle size of the inorganic fine particles is 5 nm to 10 μm.
Those having a thickness of 10 nm to 1 μm are more preferable. When the particle size is within this range, both the resin fine particles and the metal fine particles of the photothermal conversion agent are stably dispersed in the hydrophilic resin, the film strength of the image recording layer is sufficiently retained, and the printing stains are less likely to cause hydrophilicity. A non-image area can be formed.

Such inorganic fine particles can be easily obtained as a commercial product such as a colloidal silica dispersion. The content of the inorganic fine particles in the image recording layer is preferably 1.0 to 70% of the total solid content of the image recording layer, and more preferably 5.0 to 70%.
50%.

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

In the image recording layer of the present invention, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene may be added, if necessary, for improving the on-press developability. Glycol, tetrapropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol,
A polyhydric alcohol such as tetrabutylene glycol, pentylene glycol, dipentylene glycol, tripentylene glycol or tetrapentylene glycol may be contained.

When resin fine particles having a heat-reactive group are used in the image recording layer of the present invention, a compound which initiates or accelerates these reactions may be added if necessary. Examples of the compound that initiates or accelerates the reaction include compounds that generate a radical or a cation by heat, and examples thereof include a lophine dimer, a trihalomethyl compound, a peroxide, an azo compound, a diazonium salt or a diphenyliodonium salt. And an onium salt, an acylphosphine, an imidosulfonate, and the like.

These compounds have a solid content of 1% of the image recording layer.
It can be added in the range of up to 20%. Preferably 3
It is in the range of -10%. Within this range, a good reaction initiation or acceleration effect can be obtained without impairing the on-press developability.

The image recording layer of the present invention is prepared by dissolving each of the necessary components described above in a solvent to prepare a coating solution and coating the solution on the image recording layer. 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, N-
Examples thereof include methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene and water, but are not limited thereto. These solvents are used alone or as a mixture. The solid content concentration of the coating liquid is preferably 1 to 50%.

The coating amount (solid content) of the image recording layer on the substrate obtained after coating and drying varies depending on the application, but is generally preferably 0.5 to 5.0 g / m ² . When the coating amount is less than this range, the apparent sensitivity is high,
The film properties of the image recording layer that performs the function of image recording are deteriorated. Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating.

The image recording layer coating solution according to the present invention includes
Surfactants for improving coatability, for example, JP-A-6-61
Fluorine-based surfactants such as those described in 2-170950 can be added. The preferred addition amount is
The total solid content of the image recording layer is 0.01 to 1%, more preferably 0.05 to 0.5%.

[Overcoat Layer] In the lithographic printing plate precursor of the invention, in order to prevent the surface of the image recording layer from being contaminated with a lipophilic substance during storage or handling, for example, in the form of fingerprints, it is formed on the image recording layer. In addition, a water-soluble overcoat layer can be provided. The water-soluble overcoat layer used in the present invention can be easily removed during printing, and contains a resin selected from water-soluble organic polymer compounds.
As the water-soluble organic polymer compound used here, a film formed by coating and drying has a film-forming ability. Specifically, polyvinyl acetate (however, the hydrolysis rate is 65% or less) is used.
% Or more), acrylic acid homopolymers or copolymers and alkali metal salts or amine salts thereof, methacrylic acid homopolymers or copolymers and alkali metal salts or amine salts thereof, acrylamide homopolymers and copolymers. , Polyhydroxyethyl acrylate, N
-Vinylpyrrolidone homopolymer and copolymer, polyvinyl methyl ether, vinyl methyl ether / maleic anhydride copolymer, 2-acrylamido-2-methyl-1
-Homopolymers or copolymers of propanesulfonic acid and alkali metal salts or amine salts thereof, gum arabic, fibrin derivatives (for example, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, etc.) and modified products thereof, white dextrin, Examples thereof include pullulan and enzyme-decomposed etherified dextrin. In addition, two or more kinds of these resins may be mixed and used depending on the purpose.

The above photothermal conversion agent may be added to the overcoat layer. Infrared absorbing dyes having a water-soluble group are particularly suitable. Further, in order to ensure coating uniformity, a nonionic surfactant such as polyoxyethylene nonylphenyl ether or polyoxyethylene dodecyl ether may be added to the overcoat layer in the case of coating with an aqueous solution. .

The dry coating amount of the overcoat layer was 0.1.
˜2.0 g / m ² is preferred. Within this range, it is possible to prevent good contamination of the surface of the image recording layer by lipophilic substances such as fingerprint stains without impairing the on-press developability.

[Plate making and printing] The lithographic printing plate precursor of the invention is image-formed by heat. Specifically, direct image-like recording with a thermal recording head, scanning exposure with an infrared laser, high-illuminance flash exposure with a xenon discharge lamp, infrared lamp exposure, or the like is used.
Exposure with a solid-state high-power infrared laser such as a semiconductor laser or a YAG laser that emits 0 nm infrared is suitable.

The lithographic printing plate precursor of the present invention subjected to image exposure can be mounted on a printing machine without any further treatment, and can be printed by a usual procedure using ink and fountain solution. Further, these lithographic printing plate precursors are disclosed in Japanese Patent No. 293839.
As described in No. 8, after being mounted on the plate cylinder of the printing machine, exposed by a laser mounted on the printing machine,
After that, it is also possible to apply fountain solution and / or ink and perform on-press development. Further, these lithographic printing plate precursors can also be used for printing after development using water or a suitable aqueous solution as a developing solution.

[0218]

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

Production Example of Aluminum Substrate Using a JIS 1050 aluminum plate having a thickness of 0.24 mm, pretreatment, surface roughening treatment, hydrophilic film formation treatment and, if necessary, posttreatment were carried out in this order, and the planographic printing plate of the embodiment was used. An aluminum substrate used as a printing original plate was produced. Up to the roughening treatment, any one of the following A to I was performed, and the hydrophilic film forming treatment and the post-treatment were performed by the method described in the production example of each substrate.

<Roughening Treatments A, B and C> An aluminum plate was immersed in a 1% sodium hydroxide aqueous solution kept at 50 ° C. and subjected to a dissolution treatment so that the dissolution amount became 2 g / m ² . . After washing with water, it was immersed for 10 seconds in an aqueous solution having the same composition as the electrolytic solution used in the subsequent electrochemical graining treatment for neutralization treatment, and then washed with water.

Next, this aluminum substrate material was subjected to electrochemical roughening treatment divided into a plurality of times with a current density of 50 A / dm ² and a sine wave alternating current, with a rest period interposed. Table 1
The electrolytic solution composition, the amount of electricity processed per time, the number of times of electrolytic treatment, and the dwell time are shown. After the electrochemical graining treatment,
It is immersed in a 1% sodium hydroxide aqueous solution kept at 50 ° C., alkali-dissolved so that the amount of dissolution becomes 2 g / m ² , washed with water, and then 10 times in a 10% sulfuric acid aqueous solution kept at 25 ° C. It was immersed for 2 seconds for neutralization, and then washed with water.

[0222]

[Table 1]

<Roughening treatment D> The aluminum plate is heated to 50 ° C.
Dipped in 10% aqueous sodium hydroxide solution for 20 seconds,
After degreasing and etching, rinse with running water, then 25
% Aqueous solution of sulfuric acid for 20 seconds for neutralization and washing with water. Then, using a 1% hydrochloric acid aqueous solution (containing 0.5% of aluminum ion), a trapezoidal rectangular wave having a frequency (60) of 2 msec and a duty ratio of 1: 1 while the current value reaches a peak from 0. With a carbon electrode as a counter electrode, the average current density at the time of aluminum anode was 27 A / dm ² (the ratio of the current density at the time of anode and cathode of aluminum was 1: 0.9.
5), average electricity quantity at aluminum anode 350C / dm ²
So that the surface roughening treatment was performed at 20 ° C.
Then, using a 26% aqueous solution of sodium hydroxide and a 6.5% aluminum ion solution, a spray etching treatment was performed at a liquid temperature of 45 ° C. so that the total etching amount including smut was 0.7 g / m ² . Subsequently, desmutting treatment was carried out by spraying treatment at 60 ° C. for 10 seconds with a 25% nitric acid aqueous solution (containing 0.3% of aluminum ions).

<Roughening treatment E> After roughening the surface of the aluminum plate using a nylon brush having a bristle diameter of 0.72 mm and a bristle length of 80 mm and an aqueous suspension of pumicetone having an average particle diameter of about 15 to 35 μm, Washed well with water. Next, it was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 30 seconds for etching, washed with running water, neutralized with a 20% aqueous nitric acid solution, and washed with water. The aluminum plate thus mechanically roughened was further subjected to the following electrochemical roughening.

The hydrochloric acid concentration was 7.5 g / l, and the liquid temperature was adjusted to 3 g in an aqueous hydrochloric acid solution prepared by adding aluminum chloride to hydrochloric acid so that the aluminum ion concentration became 5 g / l.
AC electrolysis was performed by applying an alternating current to the aluminum plate subjected to the mechanical roughening at 5 ° C. using the radial cell shown in FIG. As the alternating current, commercial alternating current with a frequency of 60 Hz can be used to convert current and current by using an induction voltage regulator and a transformer.
A sine wave generated by adjusting the voltage was used.
The total amount of electricity when the aluminum plate is the anode is 50 C / dm
² and Qc / Qa in one cycle of the alternating current is 0.
It was 95.

Regarding the concentrations of hydrochloric acid and aluminum ions in the above hydrochloric acid aqueous solution, the relationship between the temperature, the conductivity, and the ultrasonic wave propagation velocity and the concentrations of hydrochloric acid and aluminum ions was obtained, and the temperature, conductivity, and Concentrated hydrochloric acid having a concentration of 35% and water were added to the inside of the electrolytic cell main body from the circulation tank so that the sound wave propagation velocity reached a predetermined value, and the excess hydrochloric acid aqueous solution was overflowed to keep it constant. Next, an alkaline solution containing 5% and 0.5% of sodium hydroxide and aluminum ion, respectively, and having a liquid temperature of 45 ° C. was used as a treatment liquid, and the dissolution amount of the roughened surface of the aluminum plate was 0. It was 1 g / m ^2, and the surface such that the dissolution amount 0.05 g / m ² of the surface on the opposite side was subjected to etching treatment.

[0227] Sulfuric acid and aluminum ions were added to both sides of the etched aluminum plate, respectively.
Desmutting treatment was performed by spraying a sulfuric acid aqueous solution containing g / l and 5 g / l at a liquid temperature of 50 ° C.

<Roughening Treatment F> After the roughening treatment A, the following electrochemical roughening treatment in a nitric acid aqueous solution was further performed.

A 1% nitric acid aqueous solution (containing 0.5% of aluminum ions) was used, and the time (TP) between the current value reaching 0 and the peak value was 2 msec.
A trapezoidal rectangular wave with a duty ratio of 1: 1 was used, and the average current density was 27 A / d when the aluminum anode was used with the carbon electrode as the counter electrode.
m ² (ratio of current density at anode and cathode of aluminum 1: 0.95), average electricity at aluminum anode 350
Electrochemical surface roughening treatment was carried out at 50 ° C. using the radial cell shown in FIG. 1 so as to have C / dm ² . Then, sodium hydroxide 26%, aluminum ion 6.
Using a 5% aqueous solution, an etching treatment was performed by spraying at a liquid temperature of 45 ° C. so that the total etching amount including smut was 0.2 g / m ² . Subsequently, desmutting treatment was carried out by spraying treatment at 60 ° C. for 10 seconds with a 25% nitric acid aqueous solution (containing 0.3% of aluminum ions).

<Roughening Treatment G> Among the roughening treatments E, the treatments in which the electrochemical roughening treatment and the subsequent treatments are omitted (mechanical roughening, alkali etching, neutralization, water washing) are carried out. The surface-roughening treatment G was used.

<Roughening treatment H> The aluminum plate is heated to 50 ° C.
It was immersed in a 1% aqueous solution of sodium hydroxide kept in the solution, and a dissolution treatment was performed so that the dissolution amount became 2 g / m ² . After washing with water, it was immersed for 10 seconds in an aqueous solution having the same composition as the electrolytic solution used in the subsequent electrochemical graining treatment for neutralization treatment, and then washed with water.

Next, this aluminum substrate material was used with a 1% nitric acid aqueous solution (containing 0.5% of aluminum ions), a current density of 50 A / dm ² , and a sine wave alternating current, and a dwell time of 1
Times provided 0.5 seconds, once per 250C / dm ^2, an electric quantity of total 500C / dm ^2, after the electrochemical graining treatment, and washed with water. After the electrochemical graining treatment, 5
It was immersed in a 1% sodium hydroxide aqueous solution kept at 0 ° C., subjected to an alkali dissolution treatment so that the amount of dissolution became 5 g / m ² , washed with water, and then 10% in a 10% sulfuric acid aqueous solution kept at 25 ° C. It was immersed for 2 seconds for neutralization, and then washed with water.

<Roughening Treatment I> The same roughening treatment as the roughening treatment H was performed except that the alkali dissolution treatment after the electrochemical roughening treatment was not performed.

Manufacture of Substrates 1 to 6 Substrates A to F which have been subjected to surface roughening treatment were respectively subjected to a sulfuric acid concentration of 170 g / l (containing 0.5% of aluminum ion), a liquid temperature of 40 ° C. and a current density using an anodizing device. 30 A / dm ²
Was anodized for 20 seconds and washed with water. Next, it was immersed in an aqueous solution of sodium hydroxide having a pH of 13 at a liquid temperature of 30 ° C. for 70 seconds and then washed with water. Next, colloidal silica (Snowtex ST-N manufactured by Nissan Chemical Industries, Ltd., particle size of about 2)
(0 nm) was immersed in a 1% aqueous solution at 70 ° C. for 14 seconds and then washed with water. Next, add 7% to 2.5% sodium silicate No. 3.
Substrates 1 to 6 were manufactured by immersing at 0 ° C. for 14 seconds and then washing with water.

Production of Substrate 7 An aluminum plate subjected to surface roughening treatment E was anodized in a 50 g / l solution of oxalic acid at 30 ° C. at a current density of 12 A / dm ² for 2 minutes and washed with water to give 4 g. / M ²
The anodic oxide film of was produced. Next, pH 13, liquid temperature 50 ℃
It was immersed in the aqueous sodium hydroxide solution for 2 minutes and then washed with water. Next, add 2.5% sodium silicate 1 at 70 ° C.
After soaking for 4 seconds, the substrate 7 was manufactured by washing with water.

Manufacture of Substrate 8 An aluminum plate subjected to the surface roughening treatment E is treated with sulfuric acid concentration 170
g / l (containing 0.5% aluminum ion), liquid temperature 3
It was anodized at 0 ° C. and a current density of 5 A / dm ^{2 for} 70 seconds, and washed with water. Next, it was immersed in a sodium hydroxide aqueous solution having a pH of 13 and a liquid temperature of 30 ° C. for 30 seconds, and then washed with water.
Next, the substrate 8 was manufactured by performing sodium silicate treatment and washing with water in the same manner as in Manufacturing Example 7.

Production of Substrates 9 to 13 Except that the anodizing time of Production Example 5 using the substrate subjected to the surface roughening treatment E was changed to 12 seconds, 16 seconds, 24 seconds, 44 seconds and 90 seconds, In the same manner as in Production Example 5, each of the substrates 9
~ 13 were produced.

Production of Substrate 14 Substrate 14 was produced in the same manner as Substrate Production Example 5 except that the immersion treatment of the colloidal silica aqueous solution was not carried out.

Manufacture of Substrate 15 Anodizing was performed on the substrate subjected to the roughening treatment E using an electrolytic solution having a sulfuric acid concentration of 100 g / l and an aluminum ion concentration of 5 g / l at a liquid temperature of 51 ° C. and a current density of 30 A / dm ^2. It was treated and washed with water to form a 2 g / m ² anodized film. Next, sulfuric acid concentration 170g / l, aluminum ion concentration 5
Liquid temperature 40 ° C, current density 30A using g / l electrolyte
/ Dm ² for anodic oxidation and the total oxide film amount is 4.0 g /
It was adjusted to m ² and washed with water to form an anodized film. Next, the substrate 15 was manufactured by immersing in a 2.5% aqueous solution of No. 3 sodium silicate at a liquid temperature of 70 ° C. for 14 seconds and then washing with water.

Production of Substrate 16 Anodizing was performed on the substrate subjected to the surface roughening treatment E using an electrolytic solution having a sulfuric acid concentration of 170 g / l and an aluminum ion concentration of 5 g / l at a liquid temperature of 43 ° C. and a current density of 30 A / dm ^2. It was treated and washed with water to form a 2 g / m ² anodized film. Next, phosphoric acid 120g / l, aluminum ion concentration 5g
/ L electrolyte solution, liquid temperature 40 ℃, current density 18A /
It was anodized at dm ² and washed with water. Next, the substrate 16 was manufactured by immersing it in a 2.5% aqueous solution of No. 3 sodium silicate at a liquid temperature of 70 ° C. for 14 seconds and then rinsing with water.

Manufacture of Substrates for Comparative Example (ratio 1 to ratio 3) Manufactured except that the substrates subjected to the surface-roughening treatments G, H and I were used instead of the surface-roughened substrate of Production Example 14. Substrates 1 to 3 for comparative examples were manufactured in the same manner as in Example 14.

Production of Comparative Example Substrate (Comparative 4) A Comparative Example substrate 4 was produced in the same manner as in Production Example 7 except that the treatment time of sodium hydroxide in Production Example 7 was changed to 3 minutes.

Production of Comparative Example Substrate (Comparative 5) The substrate subjected to the roughening treatment A was treated with a sulfuric acid concentration of 200 g / l,
Using an electrolyte solution with an aluminum ion concentration of 5 g / l,
Temperature 45 ℃, voltage of about 10V and 1.5A / dm ²Current
Anodizing for about 300 seconds at a density of 3g / m²The anode of
An oxide film was prepared and washed with water. Next, sodium bicarbonate
With an aqueous solution containing 20 g / l of water for 30 seconds at a liquid temperature of 40 ° C.
And then rinse with water already at 20 ° C for 120 seconds, and then rinse
And dried. Then, the substrate obtained above was quenched with 5%.
Immerse in acid aqueous solution for 60 seconds, wash with water, and dry at 40 ℃
Then, the substrate 5 for the comparative example was manufactured.

Table 2 shows the roughened shape of the aluminum substrate and the physical properties of the hydrophilic film obtained in the above Production Example. The measuring method of each physical property value is as follows. The density was measured by the method described above.

<Measurement method of average opening diameter of large undulation, average opening diameter of small pits and ratio of average depth of small pits to average opening diameter of small pits> For each value, an SEM photograph of the surface of an aluminum substrate was taken. Measured. For the average opening diameter d ₂ (μm) of the large swell, 1000 times the SEM
Using the photograph, the major axis and the minor axis of each undulation whose contour can be clearly discriminated are measured, and the average is taken as the undulation opening diameter, and the sum of the large undulation opening diameters measured in the SEM photograph is measured. It was calculated by dividing the number of large swells made by 50.
As the SEM, T-20 manufactured by JEOL Ltd. was used.

For the measurement of the average opening diameter d ₁ (μm) of the small pits, a SEM photograph at a magnification of 30,000 was used, and the same method as for the opening diameter with a large waviness was used. The SEM used in this case was Hitachi S-900.

The ratio h / d ₁ between the average depth h (μm) of the small pits and the average opening diameter d ₁ (μm) of the small pits is 3
It was measured using a SEM photograph of 0000 times and measured 50
The average value of several points was used.

<Method of measuring thermal conductivity in the film thickness direction of hydrophilic film>
First, in addition to the aluminum substrates 1 to 16 of the present invention and the substrates 1 to 5 for comparative examples, two types of aluminum substrates having different hydrophilic film thicknesses from these substrates were prepared. Aluminum substrates having different film thicknesses were produced by the same method as the aluminum substrate shown in the production example except that the anodic oxidation time was set to 0.5 times and 2 times, respectively.

Next, three types of aluminum substrates differing only in film thickness were subjected to measurement by the apparatus shown in FIG. 2, and the thermal conductivity in the film thickness direction of the hydrophilic film was calculated by the above mathematical formula (1). The measurement was performed at five different points on the sample, and the average value was used.

Here, the film thickness of the hydrophilic film was obtained by observing the cross section of the hydrophilic film using SEM T-20 manufactured by JEOL Ltd., measuring the film thickness at 50 locations, and using the average value thereof.

<Method of Measuring Pore Diameter of Anodic Oxide Film Micropores> The pore diameter of the anodized film micropores was measured with respect to the surface pore diameter and the pore diameter at a depth of 0.4 μm from the surface layer. For the surface pore size, bend the anodized film surface, and for the 0.4 μm pore size from the surface layer, bend the anodized aluminum substrate, and then bend the side surface of the cracked part (usually a fracture surface). ) Was observed using an ultra high resolution SEM (Hitachi S-900).
The observation was performed at a relatively low accelerating voltage of 12 V and at a magnification of 150,000 times without performing a vapor deposition process for imparting conductivity. For both pore diameters, the average value of the measured values obtained by randomly extracting 50 pores was used. The standard deviation error was less than ± 10% in both cases.

<Measurement Method of Porosity> The porosity of the anodic oxide film was determined by the following formula. Porosity (%) = {1- (oxide film density / 3.98)} x
100 Here, 3.98 is the density (g / cm ³ ) of aluminum oxide according to the Chemical Handbook.

[0253]

[Table 2]

Synthesis Example of Self-Water Dispersible Resin Fine Particles <Synthesis Example 1: Acrylic Resin Fine Particles> 400 g of methyl ethyl ketone was charged into a 1 liter flask equipped with a stirrer, a reflux device, a thermometer, a dry nitrogen introducing tube, and a dropping device. The temperature was raised to 80 ° C. In this, styrene 80 g, methyl methacrylate 238.9 g, methacrylic acid 24.5
g, 56.6 g of butyl acrylate, and 8 g of perbutyl O (a polymerization initiator manufactured by NOF CORPORATION) were well mixed, and a solution was added dropwise over 2 hours. After stirring for 8 hours, perbutyl O
By adding 0.5 g and further stirring for 8 hours, an acrylic resin solution having a dry solid content ratio of 49.5% was obtained. The acrylic resin had an acid value of 39.1 and a number average molecular weight of 20,000. Here, the dry solid content ratio was obtained by weighing about 1 part of the sample solution, weighing the sample after drying at 120 ° C. for 1 hour, and measuring the mass ratio. The number average molecular weight is G
It was measured by PC and the molecular weight in terms of polystyrene was used. The acid value was determined by weighing a predetermined amount of sample solution and titrating it with a methanol solution of potassium hydroxide having a known concentration.

100 g of the above acrylic resin solution was neutralized with 2.71 g of triethylamine, and water was added dropwise with stirring. The prepolymer solution gradually thickens to about 150 g
From around the point where the water was dropped, the viscosity was remarkably reduced and the phase inversion was completed. After further adding 150 g of water, the resulting dispersion is heated to 30 ° C. to remove the organic solvent and excess water under reduced pressure to obtain a dry solid content ratio of 33.7% and an average particle diameter of 0.12 μm. An aqueous dispersion of acrylic resin fine particles was obtained. The particle size was measured with a laser Doppler particle size distribution analyzer Microtrac UPA-150.

<Synthesis Example 2: Polyester Fine Particles> In a 2-liter four-necked flask equipped with a stirrer, a rectification tube, a dry nitrogen introduction tube, and a thermometer, 397.6 g of terephthalic acid, 397.6 g of isophthalic acid, and ethylene. Glycol 144.
Charge 9g and neopentyl glycol 243.6g,
The temperature was raised to 160 ° C. After adding 0.5 g of dibutyltin oxide and conducting a dehydration reaction while raising the temperature to 260 ° C. over 6 hours, 30 g of xylene was added, and the mixture was further stirred for 4 hours while azeotropically removing water at 160 ° C. After cooling to room temperature, dilute with 500 g of methyl ethyl ketone to obtain an acid value of 1
9.3, a solution of polyester having carboxyl groups at both ends (dry solid content ratio 65.5%) was obtained.

30 g of methyl ethyl ketone was added to 100 g of the above polyester solution, and triethylamine 2.36 was added.
It was neutralized with g and water was added dropwise with stirring. The viscosity of the prepolymer solution gradually increased, and the viscosity was remarkably reduced around the point where about 150 g of water was dropped, and the phase inversion was completed. Further 150
After adding g of water, the resulting dispersion is heated to 30 ° C. to remove the organic solvent and excess water under reduced pressure to obtain a dry solid content ratio of 30.0% and an average particle size of 0.30 μm.
An aqueous dispersion of polyester fine particles was obtained.

<Synthesis Example 3: Polyurethane fine particles> A 1 liter four-necked flask equipped with a stirrer, a reflux device, a dry nitrogen inlet tube, and a thermometer was placed on a barnock DN-980 (manufactured by Dainippon Ink and Chemicals, Inc.). Polyisocyanate) 53
3 g, 33.5 g of 2,2-bis (hydroxymethyl) propionic acid, 0.05 g of dibutyltin dilaurate and 300 g of ethyl acetate were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain an NCO (having a dry solid content ratio of 50.0%). A solution of a polyurethane prepolymer having an isocyanate group content of 6.80% was obtained. To determine the NCO content, a predetermined amount of sample solution is weighed, a certain amount of an ethyl acetate solution of di-n-butylamine having a known excess concentration from the isocyanate group to be measured is added and reacted, and the excess amount of di-n-butylamine is measured. It was determined by back titration with aqueous hydrochloric acid.

Solution 10 of the above polyurethane prepolymer
30 g of methyl ethyl ketone was added to 0 g, neutralized with 3.50 g of triethylamine, and water was added dropwise with stirring.
The viscosity of the prepolymer solution gradually increased, and the viscosity was remarkably reduced around the point where about 150 g of water was dropped, and the phase inversion was completed.
After further adding 150 g of water, an aqueous solution in which 2.51 g of diethylenetriamine was dissolved in 50 g of water was slowly added with stirring. The dispersion obtained is then added to 30
By heating to 0 ° C. and removing the organic solvent and excess water under reduced pressure, an aqueous dispersion of urethane fine particles having an average particle diameter of 0.078 μm (dry solid content ratio 33.5%) was obtained. The acid value of the urethane fine particles was 31.2.

<Synthesis Example 4: Fine resin particles containing a photothermal conversion agent> Carbon black 20 g, styrene acrylic acid resin (styrene / 2-ethylhexyl acrylate / acrylic acid = weight ratio 77/10/13 copolymer, Acid value 100,
A mixture of 20 g of a weight average molecular weight of 40,000, 2 g of an oily phthalocyanine dye (IR-26 described in the specification) and 49 g of methyl ethyl ketone was kneaded for 4 hours with a paint shaker using glass beads having a diameter of 0.2 mm, and 40 g of methyl ethyl ketone was used. , 40 g of isopropyl alcohol was added,
The contents were taken out to obtain 171 g of a mill base solution. To this millbase 171 g, triethanolamine 5.3 g
While adding (corresponding to 100% neutralization ratio of resin) and stirring,
A mixed solution of 50 g of glycerin and 120 g of ion-exchanged water was added dropwise at a rate of 5 ml per minute to obtain an aqueous dispersion of photothermal conversion agent-containing resin fine particles. The aqueous dispersion of the obtained resin fine particles was subjected to a dispersion treatment again using a collision type dispersion device Nanomizer (manufactured by Nanomizer Co., Ltd.) at a pressure of 1500 kg / cm ² . A mixture of 80 g of glycerin and 300 g of ion-exchanged water was added dropwise to the obtained treatment liquid at a rate of 5 ml / min, and then methyl ethyl ketone and isopropyl alcohol were distilled off using a rotary evaporator to obtain a final aqueous dispersion of resin fine particles. Obtained. This aqueous dispersion was filtered using a 1.5 μm filter. The resin fine particles in the obtained dispersion had an average particle diameter of 0.1 μm and showed stable dispersion over a long period without any agglomerates.

Examples 1 to 16 and Comparative Examples 1 to 5 36.0 g of the fine particle water dispersion obtained in Synthesis Example 1 was stirred into a photothermal conversion agent (IR-11 described in the present specification).
0 g, distilled water 75.0 g, methanol 30.0 g, and Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g as a fluorosurfactant were added in this order, and further at room temperature for 10 minutes. The coating liquid was stirred.

The above coating solution was applied onto each of the aluminum substrates (1 to 16) and the comparative example substrates (ratio 1 to ratio 5) in Table 2 by using a wire bar, and dried at 60 ° C. for 4 minutes to give A lithographic printing plate precursor of the invention was obtained. Dry coating amount is 1.0
It was g / m ² . The lithographic printing plate thus obtained was used as a trend setter 3244VFS (40W by Creo).
Plate setter equipped with a 830 nm semiconductor laser) and exposed under the conditions of an outer drum rotation speed of 100 rpm, a plate surface energy of 200 mJ / cm ² , and a resolution of 2400 dpi. The exposed plate was mounted on a Harris Aurelia printing machine as it was without further treatment, and was printed using a fountain solution and an ink containing a 10% by volume isopropyl alcohol aqueous solution containing an etchant. The results obtained with each printing plate are listed in Table 3.

[0263]

[Table 3]

The on-press development sheet number is the number of printing sheets required for complete on-press development, and represents the difficulty of on-press development property. The number of sheets left unpaid is the amount of printing paper required until a good printed matter without stain is obtained when printing is restarted after stopping the printing machine and leaving the printing plate on the plate cylinder for 1 hour at room temperature. It is the number of sheets and indicates the degree of stain resistance of the printing plate.

Examples 17 to 32 and Comparative Examples 6 to 10 Example 1 except that the fine particle water dispersion obtained in Synthesis Example 2 was used in place of the fine particle water dispersion obtained in Synthesis Example 1.
To 16 and Comparative Examples 1 to 5 to prepare coating solutions,
A lithographic printing plate precursor was prepared by coating and drying. Exposure and printing were performed in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 5, and the results are shown in Table 4.

[0266]

[Table 4]

Examples 33 to 48 and Comparative Examples 11 to 15 Example 1 except that the fine particle water dispersion obtained in Synthesis Example 3 was used in place of the fine particle water dispersion obtained in Synthesis Example 1.
To 16 and Comparative Examples 1 to 5 to prepare coating solutions,
A lithographic printing plate precursor was prepared by coating and drying. Exposure and printing were performed in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 5, and the results are shown in Table 5.

[0268]

[Table 5]

Examples 49 to 64 and Comparative Examples 16 to 20 To 36.0 g of the fine particle water dispersion obtained in Synthesis Example 4 was added 75.0 g of distilled water, 30.0 g of methanol and a fluorine-containing surfactant while stirring. MegaFac F-177 0.
02 g was added in this order, and coating and drying were performed in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 5 except that a coating solution obtained by stirring at room temperature for 10 minutes was used to prepare a lithographic printing plate precursor. did. Exposure and printing were performed in the same manner as in Examples 1 to 16 and Comparative Examples 1 to 5, and the results are shown in Table 6.

[0270]

[Table 6]

[0271]

According to the present invention, it is a lithographic printing plate which can be directly mounted on a printing machine for printing without being processed after infrared scanning exposure based on a digital signal, and has a good on-machine development property. It is possible to provide a heat-sensitive lithographic printing plate precursor having a high sensitivity, a high printing durability, and a good stain resistance during printing such as ink wiping property.

[Brief description of drawings]

FIG. 1 is a side view showing an example of a radial type cell for electrochemical graining treatment that is preferably used for manufacturing an aluminum substrate of a lithographic printing plate precursor of the present invention.

FIG. 2 is a schematic diagram of a thermocomparator that can be used for measuring the thermal conductivity in the film thickness direction of the hydrophilic film of the lithographic printing plate precursor of the present invention.

[Explanation of symbols]

11 Aluminum plate 12 radial drum roller 13a, 13b Main pole 14 Acidic aqueous solution 15 Solution supply port 16 slits 17 Solution passage 18 Auxiliary anode 19a, 19b Thyristor 20 AC power supply 21 Main electrolyzer 22 Auxiliary anode tank 30 thermo comparator 31 chips 32 reservoir 33 Electric heater 34 Heating jacket 35 thermocouple 36 heat sink 37 film 38 Metal substrate 39 Contact thermometer 40 tip temperature recorder 41 Heat sink temperature recorder 42 Reservoir temperature recorder

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C25D 11/18 301 C25D 11/18 301A C25F 3/04 C25F 3/04 A G03F 7/00 503 G03F 7 / 00 503 7/004 521 7/004 521 7/09 501 7/09 501 F term (reference) 2H025 AB03 AC08 AD03 BH03 CB54 CC11 DA20 DA36 FA10 2H096 AA06 BA20 CA03 EA04 2H114 AA04 AA14 AA22 AA24 AA27 BA01 DA10 DA10 DA47 DA74 EA01 EA02 FA06 FA07 FA16 GA07

Claims (14)

[Claims] 1. A self-assembled by heat treatment on an aluminum substrate having a hydrophilic film which has been subjected to electrochemical graining treatment in an aqueous solution containing hydrochloric acid and has a thermal conductivity of 0.05 to 0.5 W / mK. A lithographic printing plate precursor containing water-dispersible resin particles and having an image recording layer writable by infrared laser exposure. 2. An aluminum substrate, which has been subjected to electrochemical graining treatment in an aqueous solution containing hydrochloric acid and has a hydrophilic film having a density of 1000 to 3200 kg / m ³ and / or a porosity of 20 to 70%, A lithographic printing original plate containing self-water-dispersible resin particles which coalesce by heat and having an image recording layer writable by infrared laser exposure. 3. The average opening diameter of the roughened small pits is 0.01 to 3 μm, the ratio of the average depth of the small pits to the average opening diameter is 0.1 to 0.5, and the thermal conductivity is 0.05
A lithographic printing original plate comprising an aluminum substrate having a hydrophilic film of about 0.5 W / mK, containing self-water-dispersible resin particles which are coalesced by heat, and having an image recording layer writable by infrared laser exposure. 4. The average opening diameter of the roughened small pits is 0.01 to 3 μm, the ratio of the average depth of the small pits to the average opening diameter is 0.1 to 0.5, and the density is 1000 to. Three
An image recording layer containing self-water-dispersible resin fine particles which coalesce by heat and which is writable by infrared laser exposure is provided on an aluminum substrate having a hydrophilic film of 200 kg / m ³ and / or a porosity of 20 to 70%. The original plate for lithographic printing. 5. An aluminum substrate having a large waviness having an average opening diameter of 3 to 20 μm.
5. The lithographic printing original plate according to claim 4. 6. The lithographic printing plate precursor as claimed in claim 1, wherein the hydrophilic film is an anodized film. 7. The lithographic printing plate precursor as claimed in claim 6, wherein the amount of anodized film is 3.2 g / m ² or more. 8. The pore diameter of the surface layer of the anodized film is 40 nm.
The lithographic printing plate precursor as claimed in claim 6 or 7, wherein: 9. The lithographic printing plate precursor as claimed in claim 6, wherein the anodized film is subjected to a sealing treatment. 10. An average particle size of 8 to 800 on the anodized film.
The lithographic printing plate precursor as claimed in any one of claims 6 to 9, wherein a layer of particles having a thickness of nm is provided. 11. The lithographic printing plate precursor as claimed in claim 6, wherein the anodized film is formed by two or more steps of anodizing treatment. 12. The planographic printing according to claim 11, wherein the first step is anodic oxidation with an electrolytic solution containing sulfuric acid, and the second step and subsequent steps are anodic oxidation with an electrolytic solution containing phosphoric acid. Original edition. 13. The lithographic printing plate precursor as claimed in any one of claims 1 to 12, wherein the image recording layer writable by infrared laser exposure contains a photothermal conversion agent. 14. The lithographic printing plate precursor according to claim 13, wherein the photothermal conversion agent is contained in the self-water-dispersible resin fine particles which are coalesced by heat.