JP2003287894A - Planographic printing plate original - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high sensitivity thermal negative type planographic printing plate original capable of ensuring both high adhesion of an image recording layer to a support and high stain resistance of a non-image area and capable of efficiently using energy by exposure in image formation, that is, excellent in thermal diffusion inhibiting effect. <P>SOLUTION: The planographic printing plate original is obtained by disposing an image recording layer which is cured by infrared laser exposure on a metallic support obtained by forming a hydrophilic film whose heat conductivity in the film thickness direction is 0.05-0.5 W/(m×K) on a surface-roughened metallic substrate. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Relating to a lithographic printing plate precursor having a negative type image recording layer
The [0002] In recent years, with the development of image forming technology,
A laser beam with a focused beam is scanned over the plate surface,
Create originals, image originals, etc. directly on the plate surface,
The technology that makes the plate directly without using the paper is drawing attention. This
Image recording, which is a typical embodiment of direct plate making technology such as
Photothermal conversion occurs in the recording layer, and the image is recorded by the generated heat.
Form negative images by reducing the alkali solubility of the layer
To the so-called thermal negative type lithographic printing plate precursor
In the case of red light in the image recording layer by laser light irradiation, etc.
Heat is generated by a photothermal conversion material such as an external absorber, and the heat
As a result, an image forming reaction (curing reaction) occurs. Therefore
If the image formation reaction due to heat is insufficient,
Problems arise. First, a metal support on which an anodized film is formed
On the body, the thermal conductivity of the support is extremely higher than that of the image recording layer.
Heat generated near the interface between the image recording layer and the support.
Move into the support before the image formation reaction has progressed sufficiently.
May end up. Then, especially with the image recording layer.
In the vicinity of the interface with the holder, the image recording layer does not cure.
The image recording layer and the support in the image area
Inadequate adhesion will result in a decrease in printing durability. Also, the current
When the liquid sensitivity expressed by the conductivity of the image liquid increases,
Even the image recording layer of the image area after the curing reaction that should not have
Dissolve and ink inking properties will decrease, or the image described above
Insufficient curing reaction near the interface between the recording layer and the support
May cause a decrease in printing durability.
The As a means to solve these problems, image recording
To accelerate the curing reaction in the exposed part of the recording layer, exposure
Post-heat treatment is generally performed.
The However, post-heating treatment requires special equipment, and
In order to complicate the process, such post-heating treatment is performed.
Thermal negative type that can form a good image without any trouble
Currently, the planographic printing plate precursor is desired. Thermal negative type lithographic printing plate precursor
In addition, there are the following problems. First, thermal
Ga type lithographic printing plate precursors have unexposed areas (non-image areas)
The uncured image recording layer is removed by the developer and supported.
The support surface is exposed and becomes a hydrophilic region.
Insufficient aqueous properties can cause oleophilic properties that are not desired during printing.
Due to the adhesion of the ink, the non-image area is likely to become dirty.
The On the other hand, after the anodizing treatment,
Kate treatment etc. is performed to improve hydrophilicity
However, further improvements are required. Also develop
If the liquid becomes fatigued and the liquid sensitivity decreases, the solubility of the image recording layer
Decreases and a residual film is generated, and as a result, non-image areas are stained.
It tends to occur. Means to solve these problems
For example, various undercoats have been studied,
In any case, we can reach a satisfactory level
Not in. On the other hand, as a recent market trend,
Because of the above, shortening the exposure time and extending the life of the laser
Therefore, there is a strong demand to use as low output as possible.
Even if the laser beam energy is lowered, the energy of the laser beam
Can be used in the image formation reaction efficiently.
Highly sensitive thermal negative lithographic printing plate precursor
It has been. [0006] An image recording layer, a support, and
The adhesion and non-image area stain resistance are trade-offs.
Have a high level of compatibility between these properties, and
Use energy from exposure efficiently for image formation
Thermal negative type lithographic printing plate with excellent sensitivity
The original version has not been realized yet. Therefore, the present invention
Is the adhesion between the image recording layer and the support and the resistance to non-image areas.
Achieving both a high level of dirtiness and energy from exposure
Can be used efficiently for image formation, i.e. thermal expansion.
High-sensitivity thermal negative type flat with excellent scattering suppression effect
The purpose is to provide a printing plate precursor. [0007] The present inventor has achieved the above object.
As a result of earnest study to achieve, the image recording layer and the support
To improve adhesion, sensitivity and stain resistance of non-image areas
The heat generated from photothermal conversion materials such as infrared absorbers
The efficiency of the image formation reaction
A hydrophilic coating with a specific range of thermal conductivity on a metal substrate
Image recording layer cured by infrared laser exposure after being provided
By providing this, the hydrophilic film has an effect of suppressing thermal diffusion
The present invention has been found to achieve the above object, and the present invention
Was completed. That is, the present invention relates to a roughened gold.
The thermal conductivity in the film thickness direction on the metal substrate is 0.05 to 0.5 W /
(M · K) Metal support obtained by forming a hydrophilic film
Image recording layer cured by infrared laser exposure on the holder
Provides a lithographic printing plate precursor. The lithographic plate of the present invention
Because the printing plate precursor has a high effect of suppressing thermal diffusion,
The curing reaction in the exposed part of the image recording layer is supported by the image recording layer.
Since it is sufficiently advanced near the interface with the holder, the image
Excellent adhesion between the recording layer and the support, and
High sensitivity. In the planographic printing plate precursor of the present invention,
As described above, the image recording layer has a thermal diffusion suppressing effect.
Since the adhesion between the substrate and the support is excellent, the support surface
Even if the hydrophilicity of the surface is increased, the printing durability is sufficient.
By improving the hydrophilicity of the body surface, resistance to non-image areas
The dirtiness can be improved. [0009] DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below.
The [Metal support] <Metal substrate> The metal substrate used in the present invention is particularly limited.
Not, for example, iron, stainless steel, aluminum
It is done. Among these, aluminum is preferable. Arminius
The aluminum plate used as a substrate is dimensionally cheap.
It is a metal mainly composed of regular aluminum.
Made of aluminum or aluminum alloy. Pure aluminum
In addition to plates, it contains aluminum as a main component and contains trace amounts of foreign elements.
Alloy plate or aluminum or aluminum alloy
Minated or vapor-deposited plastic film
Or paper can be used. Furthermore, Japanese Patent Publication 48-18
Polyethylene telescope as described in Japanese Patent No. 327
An aluminum sheet is bonded on the phthalate film.
A composite sheet can also be used. The aluminum plate used in the present invention has a special feature.
Although not limited to this, it is preferable to use a pure aluminum plate.
It is. Completely pure aluminum is manufactured by scouring technology
It is difficult to use those that contain slightly different elements.
May be. For example, Aluminum Handbook 4th edition
Known materials described in (Light Metals Association (1990))
Specifically, JIS1050 material, JIS1100
Material, JIS3003 material, JIS3103 material, JIS30
05 material or the like can be used. Also aluminum
The content of (Al) is 99.4 to 95% by mass, and iron
(Fe), silicon (Si), copper (Cu), magnesium
(Mg), manganese (Mn), zinc (Zn), chromium
(Cr) and at least five of titanium (Ti)
Aluminum alloy, sc
Aluminum using wrap aluminum or secondary metal
A board can also be used. In the present invention, the cost reduction effect
Aluminum with an Al content of 95-99.4% by mass
A nickel plate can also be used. Al content is 99.
If it exceeds 4% by mass, the allowable amount of impurities decreases.
Therefore, the cost reduction effect may be reduced. Ma
In addition, if the Al content is less than 95% by mass, many impurities are contained.
Will cause defects such as cracks during rolling.
There is a case. More preferable Al content is 95-9.
9 mass%, particularly preferably 95-97 mass%
The The Fe content is 0.3 to 1.0% by mass.
It is preferable. Fe is 0.1-0.
An element contained around 2% by mass, the amount dissolved in Al is
There are few, and most remain as an intermetallic compound. Fe
If the content of the steel exceeds 1.0% by mass, cracks occur during rolling.
It becomes easy to produce, and the cost is reduced if it is less than 0.3%
This is not preferable because the effect is reduced. More preferable Fe
Content rate is 0.5-1.0 mass%. The Si content is 0.15 to 1.0% by mass.
Preferably there is. Si is JIS2000 series, 4000
Element contained in many scraps of 6000 and 6000 series materials
is there. Si is also 0.03 to 0.1 in the new bullion.
It is an element that is contained around mass% and is in a solid solution state in Al.
Or as an intermetallic compound. Armini
When the steel plate is heated during the manufacturing process of the support,
Si may be precipitated as simple Si. Single Si
And FeSi-based intermetallic compounds have poor resistance to severe ink stains
It is known to have an impact. Here, "Severe Inn
“Stained” means that printing is interrupted many times.
Ink easily adheres to the surface of non-image areas of planographic printing plates
As a result, a dot or ring appearing on the printed paper
Dirty. Si content exceeds 1.0 mass%
And, for example, treatment with sulfuric acid (desmut treatment) described later.
May not be able to be completely removed in step (5).
If it is less than mass%, the cost reduction effect will decrease.
Yeah. More preferable Si content is 0.3 to 1.0 mass%.
It is. The Cu content is 0.1 to 1.0% by mass.
It is preferable. Cu is JIS2000 series, 4000 series
It is an element contained in many scraps of materials. Cu is the ratio
It is easy to dissolve in Al. Cu content is 1.0 quality
When the amount exceeds 50%, for example, it can be treated with sulfuric acid described later.
Less than 0.1% by mass
If it is, the cost reduction effect will decrease. More preferred
The content of fresh Cu is 0.3 to 1.0% by mass. The Mg content is 0.1 to 1.5% by mass.
It is preferable. Mg is JIS2000, 3000
Highly contained in scraps of 5000 series, 7000 series materials
It is an element. Especially in can end materials
Therefore, one of the major impurity metals contained in scrap materials
One. Mg is relatively easy to dissolve in Al.
An intermetallic compound is formed. Mg content is 1.5 mass%
Exceeding this, for example, this is treated with sulfuric acid described later.
It may become impossible to remove, and is less than 0.1% by mass
Then, the cost reduction effect will decrease. More preferable
Mg content is 0.5-1.5 mass%, more preferred
Or 1.0 to 1.5 mass%. The Mn content is 0.1 to 1.5% by mass.
It is preferable. Mn is a JIS 3000 series material
It is an element contained in a lot. Mn is especially can b
Included in scrap material because it is included in many ody materials
One of the main impurity metals. Mn is relatively in Al
Easy to dissolve, Al, Fe and Si and intermetallic compounds
Form. If the Mn content exceeds 1.5% by mass,
For example, it can not be completely removed by the treatment with sulfuric acid described later.
If the amount is less than 0.1% by mass, cost reduction
Decrease effect will decrease. More preferable Mn content is
0.5 to 1.5 mass%, more preferably 1.0 to
1.5% by mass. The Zn content is 0.1 to 0.5% by mass.
It is preferable. Zn is especially a JIS 7000 series scrubber.
It is an element contained in a lot. Zn is relatively in Al
Easy to dissolve. Zn content exceeds 0.5 mass%
For example, this is removed by treatment with sulfuric acid described later.
If it is less than 0.1% by mass,
This reduces the strike reduction effect. More preferable Zn content
The percentage is 0.3 to 0.5% by mass. The Cr content is 0.01-0.1% by mass.
Preferably there is. Cr is JISA5000 series, 600
Impurity gold contained in a small amount in 0 series and 7000 series scrap
It is a genus. When the Cr content exceeds 0.1% by mass,
For example, it can not be completely removed by the treatment with sulfuric acid described later.
If it is less than 0.01% by mass, the cost
Reduction effect will decrease. More preferable Cr content
Is 0.05-0.1 mass%. The Ti content is 0.03 to 0.5% by mass.
Preferably there is. Ti is usually 0.
It is an element added in an amount of 01 to 0.04% by mass. JIS5
Not suitable for 000, 6000 and 7000 scraps
It is contained in a relatively large amount as a pure metal. Ti content is
When it exceeds 0.5% by mass, for example, by sulfuric acid described later
In some cases, it may not be possible to remove this by processing.
If it is less than mass%, the cost reduction effect will decrease.
Yeah. A more preferable Ti content is 0.05 to 0.5 mass.
%. The aluminum plate used in the present invention is
Appropriately rolled into one that has been cast using the raw materials
Or heat treatment, the thickness is, for example, 0.1-0.7 mm
However, it is manufactured by performing a flatness correction process as necessary.
This thickness depends on the size of the printing press, the size of the printing plate and the unit.
It can be changed as needed by the user. Na
As a method for manufacturing the aluminum plate, for example,
DC casting method, soaking and / or firing from DC casting method
Use the method that omits the blunt treatment and the continuous casting method
be able to. The metal support used in the present invention comprises the above gold.
The metal substrate is roughened, and a specific hydrophilic film is applied.
It is obtained by forming a rough surface in the metal support manufacturing process.
Includes various processes other than chemical treatment and hydrophilic film formation
It may be. Hereinafter, an aluminum plate as a metal substrate
As an example, a metal support used in the present invention is used.
The holding body will be described. The aluminum plate is attached to the rolled
Degreasing process to remove oil, smut on the surface of aluminum plate
Dissolving desmut treatment process, aluminum plate surface
Roughening process to roughen the surface of the aluminum plate
After the anodizing process, etc., covered with a chemical film, it is used as a support.
It is preferable. Production of metal support used in the present invention
The process uses aluminum in an acidic aqueous solution with alternating current
Surface roughening treatment (electrochemical roughening)
It is preferable to include a surface treatment. Also used in the present invention
The manufacturing process of the metal support is the electrochemical roughening treatment described above.
Besides roughening, mechanical surface roughening, acid or alkaline aqueous solution
Aluminum combined with chemical etching process in
It may include a surface treatment step of the um plate. Used in the present invention
The manufacturing process such as roughening the metal support is a continuous process.
However, it is preferable to use the continuous method industrially.
Good. The metal support used in the present invention has a specific heat transfer.
A hydrophilic coating of conductivity can be provided. In addition, if necessary,
Pore wide treatment (acid treatment or alkali treatment), sealing treatment
A support is formed through a surface treatment and a hydrophilic surface treatment. Further
In addition, if necessary, an undercoat layer may be provided after forming the support.
Yes. <Roughening treatment (graining treatment)> First, roughening
The imposition process will be described. The aluminum plate is
It is grained to a more preferable shape. Grain processing method
The method is described in JP-A-56-28893
Mechanical graining (mechanical roughening), chemical
There are etching and electrolytic grain. Furthermore, in hydrochloric acid electrolyte
Or electrochemical graining in nitric acid electrolyte electrochemically
Graining method (electrochemical roughening, electrolytic roughing)
Or the aluminum surface with a metal wire.
Aluminum brush with ear brush grain method, polishing ball and abrasive
Ball grain method, nylon bra
Such as brush grain method where the surface is grained with sand and abrasive
Using mechanical graining (mechanical roughening)
it can. These graining methods can be used alone or in combination.
Can be used. For example, nylon brush and sharpening
Mechanical roughening with abrasive and hydrochloric acid electrolyte or glass
Combination with acid roughening treatment with acid electrolyte or multiple
And a combination of the electrolytic surface roughening treatment. Above all,
An electrochemical roughening treatment is preferred. Mechanical roughening
It is also possible to combine treatment with electrochemical roughening treatment
In particular, electrochemical roughening after the mechanical roughening treatment
It is preferable to perform the surface treatment. The mechanical surface roughening treatment is performed using a brush or the like.
It is a treatment to mechanically roughen the aluminum plate surface,
It is preferably performed before the electrochemical surface roughening process described above.
That's right. In a preferred mechanical roughening treatment, the bristle diameter is 0.
Rotating nylon brush low which is 07-0.57mm
And slurry of abrasive supplied to the surface of the aluminum plate
-Treat with liquid. Nylon brushes with low water absorption are preferred
For example, nylon bristle 200T manufactured by Toray Industries, Inc.
(6,10-nylon, softening point: 180 ° C., melting point: 21
2 to 214 ° C., specific gravity: 1.08 to 1.09, moisture content: 2
1.4-1.8, 20 ° C at 0 ° C and 65% relative humidity
・ 2.2-2.8 at 100% relative humidity, dry pull
Tensile strength: 4.5-6 g / d, dry tensile elongation: 20-3
5%, boiling water shrinkage: 1-4%, dry tensile resistance: 3
9 to 45 g / d, Young's modulus (dry): 380 to 440 kg
/ Mm²) Is preferred. As the abrasive, a known one may be used.
However, JP-A-6-135175 and Shoko
Silica sand and stone described in Japanese Patent No. 50-40047
British, aluminum hydroxide, or a mixture of these
It is preferable. The slurry liquid has a specific gravity of 1.05 to 1.05.
Those within the range of 1.3 are preferred. Add slurry liquid
As a method for supplying to the surface of the ruminium plate, for example,
A method of spraying rally liquid, using a wire brush
Method, the surface shape of the rolling roll with unevenness is aluminum
The method of transferring to a board is mentioned. Also, JP-A-55-0
No. 74898, No. 61-162351, No. 6
Using the method described in Japanese Patent No. 3-104889
Also good. Further, it is described in JP-T-9-509108.
As shown, the mixture of particles of alumina and quartz
The compound is included at a mass ratio in the range of 95: 5 to 5:95.
Brush the aluminum plate surface in an aqueous slurry.
The method can also be used. Of the above mixture at this time
The average particle size is in the range of 1-40 μm, especially 1-20 μm
Is preferably within. Electrochemical roughening treatment is performed in an acidic aqueous solution.
Then, through an alternating current using an aluminum plate as an electrode,
This is a process of electrochemically roughening the surface of a ruminium plate.
This is different from the mechanical surface roughening process described later. In the present invention
In the above electrochemical surface roughening treatment, aluminum
The amount of electricity when the metal plate becomes the cathode, that is, the cathode current
Q_CAnd the amount of electricity when it becomes the anode,
Extreme electricity quantity Q_ARatio Q with_C/ Q_AFor example, 0.95
The surface of the aluminum plate by being in the range of ~ 2.5
And uniform honeycomb pits. Q_C
/ Q_AIs less than 0.95, uneven honeycomb pipe
In addition, even if it exceeds 2.5, non-uniform
It tends to be a Nikamppit. Q_C/ Q_A1.5 ~
It is preferable to be within the range of 2.0. AC power used for electrochemical roughening treatment
Current waveforms include sine, rectangular, triangular, and trapezoidal
Etc. Of these, rectangular or trapezoidal waves are preferred.
Yes. The frequency of the alternating current is the same as the frequency of the power supply device.
From the standpoint of strike, it is preferable to be 30-200Hz
40 to 120 Hz is more preferable. The present invention
FIG. 1 shows an example of a trapezoidal wave suitably used for the above. Figure 1
Here, the vertical axis represents the current value, and the horizontal axis represents time. Ta
Is the anode reaction time, tc is the cathode reaction time, tp
And tp ′ until the current reaches a peak from 0
Ia is the power at peak time on the anode cycle side.
Current, Ic is the peak current on the cathode cycle side
The When using a trapezoidal wave as the AC current waveform,
Times tp and tp 'from 0 to the peak are
Each is preferably 0.1 to 2 msec, 0.3
More preferably, it is -1.5 msec. tp and
If tp ′ is less than 0.1 msec, the power
Influenced by the impedance, large when the current waveform rises
When the power supply voltage is required and the equipment cost of the power supply is high
There is a match. Also, tp and tp 'exceed 2msec
As a result, the influence of trace components in the acidic aqueous solution increases,
One roughening process may be difficult to perform. Also used for electrochemical roughening treatment.
The AC current duty is uniformly rough on the aluminum plate surface.
It is preferable to be within the range of 0.25 to 0.5 from the point of surface formation.
More preferably, it should be in the range of 0.3 to 0.4.
Yes. The duty referred to in the present invention is the period T of the alternating current.
The duration of the anodic reaction of the aluminum plate
Ta / T when (anode reaction time) is ta
Yeah. In particular, on the aluminum plate surface during the cathode reaction,
For generation of smut components mainly composed of aluminum hydroxide
In addition, dissolution and destruction of the oxide film occurred, and the following aluminum
Initiation of pitting reaction during anode reaction
Since the point becomes a point, the selection of the alternating current duty is a uniform rough surface
Great effect on conversion. The current density of the alternating current is trapezoidal or rectangular
In the case of a wave, the peak current density I on the anode cycle side
ap and cathode cycle side peak current density I
cp is 10 to 200 A / dm each²Prefer to be
That's right. Icp / Iap is in the range of 0.9 to 1.5
Preferably within. In electrochemical roughening treatment
At the point when the electrochemical roughening treatment is completed.
The total amount of electricity used in the anodic plate anode reaction is 50-
1000 C / dm ²Is preferred. Electrochemical rough
The surface treatment time is preferably 1 second to 30 minutes. Acidic water used for electrochemical roughening treatment
As the solution, normal direct current or alternating current was used.
It is possible to use what is used for the electrochemical roughening treatment.
Among them, acidic aqueous solution or hydrochloric acid mainly composed of nitric acid
It is preferable to use an acidic aqueous solution mainly composed of. here
“Mainly” means the main component in the aqueous solution.
Is 30% by mass or more, preferably 5%, based on the entire component.
It means 0% by mass or more. Other ingredients below
The same applies to. As an acidic aqueous solution mainly composed of nitric acid,
As stated, normal DC current or AC current was used.
Those used for electrochemical surface roughening can be used.
The For example, aluminum nitrate, sodium nitrate, nitric acid
One or more of nitric acid compounds such as ammonium, 0.0
Concentration from 1 g / L to saturation, nitric acid concentration 5
Can be used by adding to 15 g / L nitric acid aqueous solution
The In acidic aqueous solution mainly composed of nitric acid, iron, copper, man
Gun, nickel, titanium, magnesium, silicon, etc.
Even if the metal contained in the ruminium alloy is dissolved
Good. As an acidic aqueous solution mainly composed of nitric acid,
But it contains nitric acid, aluminum salt, and nitrate,
And aluminum ion is 1-15 g / L, preferably
1-10 g / L, ammonium ion 10-300
Nitric acid water with a nitric acid concentration of 5 to 15 g / L so as to achieve ppm
Add aluminum nitrate and ammonium nitrate to the solution.
It is preferable to use what was obtained by adding. The above
Aluminum ions and ammonium ions are
Spontaneous increase during aerochemical roughening
It is something to do. The liquid temperature at this time is 10 to 95.
Is preferable, and is preferably 20 to 90 ° C.
A temperature of 40 to 80 ° C. is particularly preferable. In the electrochemical surface roughening treatment, the vertical type,
Use a known electrolytic device such as a flat type or radial type.
However, it is described in JP-A-5-195300.
A radial type electrolyzer as described above is particularly preferred. Figure
2 is a radial type electrolysis apparatus preferably used in the present invention.
FIG. In FIG. 2, the radial electrolyzer is
A radiator in which the aluminum plate 11 is disposed in the main electrolytic cell 21
Wound around the Aldrum roller 12 and AC power supply in the transport process
Electrolysis by main poles 13a and 13b connected to 20
It is processed. The acidic aqueous solution 14 is discharged from the solution supply port 15.
Radial drum roller 12 and main pole 1 through lit 16
To the solution passage 17 between 3a and 13b
The Next, the aluminum plate treated in the main electrolytic cell 21
11 is electrolyzed in the auxiliary anode tank 22. This auxiliary yang
The auxiliary anode 18 faces the aluminum plate 11 in the electrode chamber 22.
The acidic aqueous solution 14 is connected to the auxiliary anode 18 and the
It is supplied so as to flow between the luminium plates 11. Na
The current flowing through the auxiliary electrode is the thyristor 19a and 1
9b. The main electrodes 13a and 13b are made of carbon, white
Gold, titanium, niobium, zirconium, stainless steel, fuel
Can be selected from electrodes used for battery cathodes
However, carbon is particularly preferred. General carbon
Impregnated graphite for chemical equipment and resin core
Graphite or the like can be used. Auxiliary anode 18 is blowjob
Ite, iridium oxide, platinum, or platinum to titanium,
Niobium, zirconium and other valve metals clad or
Is selected from known oxygen generating electrodes such as plated ones
be able to. Through the main electrolytic cell 21 and the auxiliary anode cell 22
The direction of supply of the excess acidic aqueous solution is the progress of the aluminum plate 11
It can be parallel to the line or counter. Aluminum plate
The relative flow rate of the acidic aqueous solution is 10 to 1000 cm
/ Sec is preferred. One for one electrolyzer
The above AC power supply can be connected. 2 or more
The above electrolyzer may be used, and the electrolysis strip in each device
The matters may be the same or different. Also,
After the electrolytic treatment is completed, take the treatment solution to the next process.
Because there is no nip roller draining and spraying
It is preferable to perform washing with water. In the case of using the above electrolytic apparatus,
Acidic water solution in which the aluminum plate in the cracker reacts with the anode
For example, (i) introduction of acidic aqueous solution
Electricity, (ii) ultrasonic wave propagation speed, (iii) temperature, etc.
Based on the nitric acid and aluminum ion concentration obtained from
Add nitric acid and water while adjusting the amount of nitric acid and water.
Sequentially exceed the volume of acidic aqueous solution from the electrolyzer
By letting it flow and discharge, the concentration of the acidic aqueous solution
It is preferable to keep it constant. Next, in an acidic aqueous solution or an alkaline aqueous solution
Table of chemical etching process and desmut process in liquid
The surface processing will be described in order. The surface treatment is
Before the electrochemical roughening treatment, or
After the electrochemical surface roughening treatment, the anodizing treatment described later
It takes place before the reason. However, each of the following surface treatments
The explanation is an example, and the present invention includes the following contents of each surface treatment.
It is not limited to. In addition, the above surface treatment
The following processes are optionally performed. <Alkaline etching treatment> Alkali etching
Chinching is performed on an aluminum plate surface in an alkaline aqueous solution.
Is a process of chemically etching the above-mentioned electrochemical
Preferably before and after roughening.
Yes. In addition, the mechanical roughening treatment is performed before the electrochemical roughening treatment.
When performing the processing, it is preferable to perform it after the mechanical roughening treatment.
Good. Alkaline etching process has a fine structure in a short time
Acid etching, which will be described later
There is an advantage over processing. Used for alkali etching
Examples of alkaline aqueous solutions that can be used include caustic soda and sodium carbonate.
, Sodium aluminate, sodium metasilicate, sodium phosphate
1 type such as lithium hydroxide, potassium hydroxide, lithium hydroxide, etc.
An aqueous solution containing two or more types can be mentioned. In particular, hydroxylation
An aqueous solution mainly composed of sodium (caustic soda) is preferred.
That's right. Alkaline aqueous solution is not only aluminum but also aluminum.
0.5 to 10 alloy components contained in the luminium plate
% May be contained. The concentration of the alkaline aqueous solution is
It is preferably 1 to 50% by mass, and 1 to 30% by mass
More preferably. Alkali etching treatment is performed using alkaline water
The liquid temperature is 20-100 ° C, preferably 40-80 ° C.
Between 1 and 120 seconds, preferably 2 to 60 seconds
It is preferable to do so. Aluminum melting
The amount is 5 to 20 g / in after the mechanical roughening treatment.
m²Preferably after electrochemical graining treatment
0.01 to 20 g / m when performing²Is preferred
Yes. First, use a chemical etchant in an alkaline solution.
When mixing, use liquid sodium hydroxide (cassette)
Isoda) and sodium aluminate (sodium aluminate)
It is preferable to prepare a treatment solution using Ma
In addition, after the alkaline etching treatment is completed, the treatment liquid
In order not to take it out to the next process,
It is preferable to perform cutting and water washing by spraying. Alkaline etching treatment with electrochemical rough surface
When performed after the graining treatment,
The smut can be removed. Such al
As the potash etching treatment, for example, JP-A-53-1
50-90 ° C. as described in Japanese Patent No. 2739
A method of contacting with 15 to 65% by weight of sulfuric acid at a temperature, and
Alkaline described in Japanese Patent Publication No. 48-28123
A method of re-etching is preferable. <Acid etching process> Acid etching process
The chemical etching of the aluminum plate in an acidic aqueous solution
After the electrochemical roughening treatment.
It is preferred to do so. In addition, the electrochemical surface roughening treatment
Perform the alkali etching process before and / or after
If so, acid etch after alkali etching
It is also preferable to perform the processing. The above aluminum plate
After the potash etching treatment, the above acidic etching
When treated, a metal containing silica on the aluminum plate surface
Intercalation compound or simple substance Si can be removed, and then
Defects in the anodized film formed in the anodizing treatment of
Can be eliminated. As a result, when printing,
Trouble that dot ink adheres to the non-image area called
Can be prevented. Acidic water used for acid etching treatment
Liquids include phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid,
Or an aqueous solution containing two or more of these mixed acids.
It is. Of these, a sulfuric acid aqueous solution is preferable. Concentration of acidic aqueous solution
The degree is preferably 50 to 500 g / L. Acid water
Solution is not only aluminum but also aluminum plate
The alloy component to be contained may be contained. In the acidic etching treatment, the liquid temperature is set to 60 to 90.
℃, preferably 70-80 ℃, treated for 1-10 seconds
It is preferable to do so. Aluminium at this time
The dissolution amount of the steel plate is 0.001 to 0.2 g / m²Is
preferable. Also, acid concentration, such as sulfuric acid concentration and aluminum
Select the ion concentration from the range that does not crystallize at room temperature.
It is preferable. The preferred aluminum ion concentration is
0.1 to 50 g / L, particularly preferably 5 to 15 g
/ L. Also, after the acid etching process is finished
In order not to take the processing liquid to the next process,
It is preferable to perform draining with water and washing with spray.
That's right. <Desmutting> Electrochemical surface roughening
The alkali etching treatment before and / or after the treatment
In general, by alkaline etching treatment,
In addition, smut is generated on the surface of the aluminum plate.
Acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid, hydrofluoric acid, borofluoride
Hydrofluoric acid or an acid containing a mixture of two or more of these
So-called desmatter, which dissolves the above smut in an aqueous solution
It is preferable to perform the etching process after the alkali etching process
Yes. Note that after the alkali etching treatment, an acidic etchant is used.
One of Ching process and Desmut process
Is sufficient. The concentration of the acidic solution is 1 to 500 g / L.
It is preferable. Aluminum is used in acidic solutions.
The alloy component contained in the aluminum plate is 0.00
1 to 50 g / L may be dissolved. Liquid temperature of acidic solution
Is preferably 20 to 95 ° C, 30 to 70 ° C
It is more preferable that The processing time is 1 to 120.
Preferably 2 seconds, more preferably 2 to 60 seconds
That's right. Moreover, as a desmut treatment liquid (acidic solution),
The acidic aqueous solution used in the electrochemical surface roughening treatment
It is preferable to use it for reducing the amount of waste liquid. Death Mat
After finishing the process, do not take the treatment liquid to the next process.
For example, liquid draining with a nip roller and washing with spray
Is preferably performed. As a combination of these surface treatments, preferred
Preferred embodiments are shown below. First, mechanical roughening and
And / or alkaline etching treatment,
Perform smut processing. Next, electrochemical surface roughening treatment
After that, acid etching treatment, alkaline etching
Ching process and subsequent desmut process,
Lucari etching process and subsequent acidic etching
One of the processing is performed. <Formation of hydrophilic film>
Aluminum with surface treatment and other treatment as required
Treatment for providing a hydrophilic film with low thermal conductivity on a nium plate
To do things. The hydrophilic film has a thermal conductivity in the film thickness direction of 0.0.
5 W / (m · K) or more, preferably 0.08 W /
(M · K) or more, and 0.5 W / (m · K) or more
Below, preferably 0.3 W / (m · K) or less
More preferably, it is 0.2 W / (m · K) or less.
Thermal conductivity in the film thickness direction is 0.05 to 0.5 W / (m · K)
Then, the heat generated in the recording layer by the laser light exposure
Diffusion to the support can be suppressed. The result
Results in excellent printing durability, stain resistance and sensitivity.
-Marnega type lithographic printing plate precursor is obtained. Hereinafter, the film thickness of the hydrophilic film defined in the present invention
The thermal conductivity in the direction will be described. Measurement of thermal conductivity of thin film
Various methods have been reported so far.
In 1986, ONO et al.
The thermal conductivity in the plane direction is reported. In addition, thin film
Attempts have also been made to apply the AC heating method to the measurement of fertility.
The The origin of the AC heating method was reported in 1863.
In recent years, lasers have been used.
In combination with the development of heating methods and Fourier transform
Various measurement methods have been proposed. Laser Ong Straw
Devices using the method are also commercially available. these
All methods have thermal conductivity in the plane direction (in-plane direction) of the thin film
Is what you want. However, when considering the thermal conduction of thin films,
Thermal diffusion in the depth direction is an important factor. Various reports
It is said that the thermal conductivity of thin films is not isotropic
Especially in the case of the present invention, the film thickness direction is directly
It is very important to measure the thermal conductivity. like this
From the viewpoint of measuring the thermophysical properties of thin films in the thickness direction
The method using a thermocomparator is Lambropo
ulos et al. (J. Appl. Phys., 66
(9) (1 November 1989)) and H
paper of energer et al. (APPLIED OPTIC
S, Vol. 32, no. 1 (1 January 1
993)). Furthermore, in recent years, polymer thin
Thermal diffusivity of film for temperature wave thermal analysis using Fourier analysis
Hashimoto et al. Reported a method of measuring more (N
etu Sukutei, 27 (3) (200
0)). In the film thickness direction of the hydrophilic film defined in the present invention
The thermal conductivity is measured by the method using the above thermo-comparator.
Determined. The above method will be specifically described below.
For the basic principle of the method, see Lambro mentioned above.
In the papers of poulos et al. and Hengager et al.
It is described in detail. In addition, the device used in the above method.
The device is not limited to the following devices. FIG. 3 shows the hydrophilicity of the lithographic printing plate precursor according to the present invention.
Can be used to measure the thermal conductivity in the film thickness direction
2 is a schematic diagram of a thermocomparator 30. FIG. Thermocomp
In the method using a vibrator, the contact area and contact with the thin film
Largely affected by surface condition (roughness). Therefore, support
-As long as the top of the comparator 30 can contact the thin film
It is important to make it smaller. For example, anoxia
A chip made of copper and having a minute tip with a radius r1 = 0.2 mm.
A wire (wire) 31 is used. This chip 31 is constant
Fixed to the center of the reservoir 32 made of tongue, the reservoir 3
2 is an oxygen-free copper heater having an electric heater 33.
The thermal jacket 34 is fixed. This heating jacket
34 is heated by an electric heater 33,
While feeding back the output of the attached thermocouple 35
Control the reservoir 3 to 60 ± 1 ° C.
31 is heated to 60 ± 1 ° C. On the other hand, radius 10c
m, Oxygen-free copper heat sink 36 with a thickness of 10 mm
The metal substrate 38 having the film 37 to be measured is healed.
Tosink 36 is installed. Of the surface of the heat sink 36
The temperature is measured using a contact thermometer 39. Thus, the thermo comparator 30 is set.
After that, the tip of the heated tip 31 is attached to the surface of the film 37.
Contact so that it is in close contact. Thermocomparator 30
For example, the tip of a dynamic microhardness meter
Instead, it is attached and driven up and down, and the film 37
The chip 31 hits the surface of the surface and a load of 0.5 mN is applied.
Until it is pressed. This
Variation in contact area between the film 37 to be measured and the chip 31
Tack can be minimized. Heated tip 31
When the tip is brought into contact with the film 37, the tip temperature of the tip 31 decreases.
However, it reaches a steady state at a certain temperature. This is electric heat
Heater 33 to heating jacket 34 and reservoir 3
2 and the amount of heat given to the chip 31 through
Diffuses to the heat sink 36 through the metal substrate 38
This is because the amount of heat is balanced. Tip tip temperature at this time
Temperature, heat sink temperature and reservoir temperature respectively.
Tip temperature recorder 40, heat sink temperature recorder 41
And recording using the reservoir temperature recorder 42. The relationship between the above temperatures and the thermal conductivity of the film is as follows.
It becomes like Formula (1). [0056] [Expression 1] However, the sign in the above formula (1) is the following:
Street. T_t: Tip tip temperature, T_b: Heat sink temperature,
T_r: Reservoir temperature, K_tf: Thermal conductivity of film, K₁: Reservoir thermal conductivity, K₂: Chip thermal conductivity (in the case of oxygen-free copper, 400 W /
(M · K)), K_Four: Metal substrate thermal conductivity (when no coating is provided), r₁: Tip radius of curvature, A₂: Contact area between reservoir and tip, A_Three: Chip and
Contact area with the coating, t: film thickness, t₂: Contact thickness (≒ 0) By changing the film thickness (t), each temperature (T_t, T
_bAnd T_r) To measure and plot
The slope of equation (1) is obtained, and the film thermal conductivity (K_tf)
be able to. That is, this inclination is clear from the above equation (1).
Like, the reservoir thermal conductivity (K₁) Of tip
Radius of curvature (r₁), Film thermal conductivity (K_tf) And chips
Contact area (A_Three)
K₁, R₁And A_ThreeIs a known value,
R K_tfCan be obtained. The present inventors have used the above-described measurement method to make an adjustment.
Anodized film on aluminum substrate (Al₂O_Three)
The thermal conductivity of was determined. Change the film thickness and measure the temperature.
Al obtained from the slope of the resulting graph₂O_ThreeHeat conduction
The rate was 0.69 W / (m · K). This is the above
Good result with the paper of Lambropoulos et al.
Indicates a match. And this result shows the thermophysical value of the thin film
Is the bulk thermophysical value (bulk Al₂O_ThreeThermal conductivity of
Indicates that it is different from 28W / (m · K))
The Hydrophilic film of the lithographic printing plate precursor according to the present invention
Using the above method to measure the thermal conductivity in the thickness direction, the chip
Make the tip minute and keep the pressing load constant.
The surface roughened for lithographic printing plates.
However, it is preferable because you can get results without variation.
Yes. Thermal conductivity values can be measured at different points on the sample, for example
For example, it is preferable to measure at 5 points and obtain the average value.
Yes. The film thickness of the hydrophilic film is such that it is difficult to scratch and
In terms of printing durability, it is preferably 0.1 μm or more,
More preferably, it is 0.3 μm or more, and 0.6 μm or more.
It is particularly preferable that
In order to provide a thick film, a lot of energy is required
In view of the above, it is preferable that the thickness is 5 μm or less.
More preferably 3 μm or less, and 2 μm or less.
It is particularly preferred. The method for providing the hydrophilic film is particularly limited.
Not specified, anodic oxidation method, vapor deposition method, CVD method, sol-gel
Method, sputtering method, ion plating method, diffusion
Laws and the like can be used as appropriate. Also hydrophilic resin or
Is a method of applying a solution in which hollow particles are mixed with a sol-gel solution
Can also be used. Among them, an oxide is formed by an anodic oxidation method.
It is most preferable to use an anodizing process.
The Anodizing is a conventional method in this field.
It can be carried out. Specifically, sulfuric acid, phosphoric acid, chromium
Acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc.
A single or a combination of two or more aqueous solutions or non-
Direct a direct current or an alternating current through an aluminum plate in an aqueous solution
And an anodic acid that is a hydrophilic film on the surface of the aluminum plate.
A chemical film can be formed. Conditions for anodizing
Varies widely depending on the electrolyte used.
Cannot be determined, but generally electrolyte concentration 1-80 mass
%, Liquid temperature 5 to 70 ° C., current density 0.5 to 60 A / d
m², Voltage 1-200V, electrolysis time 1-1000 seconds
It is appropriate. Among these anodizing treatments,
It is described in Japanese Patent No. 1,412,768
Anodizing at high current density in sulfuric acid electrolyte
And US Pat. No. 3,511,661.
Anodic oxidation treatment using phosphoric acid as an electrolytic bath
Is preferable. In addition, anodization is performed in sulfuric acid.
Multi-stage anodizing treatment such as anodizing in phosphoric acid
Can also be applied. In the present invention, the anodized film is scratched.
0.1 g / m in terms of hardness and printing durability²That's it
Preferably 0.3 g / m²More is better
2g / m²It is particularly preferable that
In addition, enormous energy is required to provide a thick film.
In view of the above, 100 g / m²The following is
Preferably 40 g / m²More preferably,
20 g / m²It is particularly preferred that The anodized film has a micropore on its surface.
The fine recesses called a are uniformly distributed.
The The density of micropores present in the anodized film is
It can be adjusted by selecting the appropriate conditions.
The Anodic acid by increasing the density of micropores
The thermal conductivity in the film thickness direction of the chemical film is 0.05 to 0.5 W /
(M · K). In the present invention, the purpose of reducing the thermal conductivity is
Then, after anodizing, expand the pore diameter of the micropore
It is preferable to perform pore wide processing. This pore wide
The treatment is performed on an aluminum substrate on which an anodized film is formed.
By soaking in an aqueous acid or alkaline solution
Dissolve the anodic oxide film and expand the pore diameter of the micropores.
It ’s a big deal. The pore wide treatment is applied to the anodized film.
The dissolution amount is preferably 0.01 to 20 g / m.²More like
Preferably 0.1-5g / m², Particularly preferably 0.2 to
4g / m²It is performed in the range. When using an acid aqueous solution for pore wide treatment
Is an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or these
It is preferable to use an aqueous solution of the above mixture. Acid aqueous solution
The concentration is preferably 10 to 1000 g / L, 20
More preferably, it is -500 g / L. Temperature of aqueous acid
The degree is preferably 10 to 90 ° C, and 30 to 70 ° C.
It is more preferable that The immersion time in the acid aqueous solution is
It is preferably 1 to 300 seconds, and 2 to 100 seconds
Is more preferable. Meanwhile, alkaline water for pore wide treatment
When using a solution, use sodium hydroxide or potassium hydroxide.
Selected from the group consisting of lithium and lithium hydroxide
It is preferable to use one alkali aqueous solution.
The pH of the alkaline aqueous solution is preferably 10-13.
And more preferably 11.5 to 13.0. Al
The temperature of the aqueous potassium solution is preferably 10 to 90 ° C.
More preferably, the temperature is 30 to 50 ° C. Alkaline water
The immersion time in the solution is preferably 1 to 500 seconds.
2 to 100 seconds is more preferable. Further, the hydrophilic film is composed of the above-described anodized skin.
In addition to the film, provided by sputtering, CVD, etc.
An inorganic film may be used. Composition of inorganic coating
Examples of compounds include oxides, nitrides, silicides,
Examples thereof include borides and carbides. In addition, inorganic coatings are
It may be composed of only a single compound, or a mixture of compounds.
You may be comprised with the compound. Construct inorganic coating
Specific compounds include aluminum oxide, oxidation
Silicon, titanium oxide, zirconium oxide, hafnium oxide
, Vanadium oxide, niobium oxide, tantalum oxide, oxidation
Molybdenum, tungsten oxide, chromium oxide; nitride
Luminium, silicon nitride, titanium nitride, zirconium nitride
Conium, hafnium nitride, vanadium nitride, nitrogen
Niobium fluoride, tantalum nitride, molybdenum nitride, nitride
Tungsten, chromium nitride, silicon nitride, silicon nitride
U: Titanium silicide, Zirconium silicide, Silicide Hough
Ni, Vanadium silicide, Niobium silicide, Tan silicide
Tall, molybdenum silicide, tungsten silicide, silicide
Chromium; Titanium boride, Zirconium boride, Ha boride
Funium, vanadium boride, niobium boride, titanium boride
Tantalum, molybdenum boride, tungsten boride, boron
Chromium carbide; aluminum carbide, silicon carbide, titanium carbide
, Zirconium carbide, hafnium carbide, vanadium carbide
, Niobium carbide, tantalum carbide, molybdenum carbide, carbonization
Examples include tungsten and chromium carbide. <Sealing Treatment> In the present invention, the above-mentioned
In this way, the metal support obtained by providing a hydrophilic film is sealed.
A hole treatment may be performed. Sealing treatment used in the present invention;
Japanese Patent Application Laid-Open No. 4-176690 and Japanese Patent Application No. 1
No. 0-106819 (JP-A-11-301135)
Anodized film with pressurized steam or hot water
The sealing treatment is included. Also, silicate treatment, heavy black
Aqueous salt treatment, nitrite treatment, ammonium acetate
Treatment, electrodeposition sealing treatment, triethanolamine treatment, carbonic acid treatment
Barium salt treatment, hydrothermal treatment containing a very small amount of phosphate, etc.
It can also be performed using a known method. Sealing treatment film
For example, if electrodeposition sealing is applied,
In the case of water vapor sealing treatment,
It is formed from the top of the seal, and depending on the method of sealing treatment, sealing treatment
The way the film is formed is different. Besides that, depending on the solution
Immersion treatment, spray treatment, coating treatment, vapor deposition treatment
, Sputtering, ion plating, thermal spraying, spear
Although gold etc. are mentioned, it is not specifically limited. As a specific processing method, for example, JP-A-6
0-149491, at least
1 amino group, carboxyl group and salt group
Selected from the group consisting of Rabi and sulfo groups and salts thereof.
A layer composed of a compound having at least one group,
As described in Japanese Utility Model Publication No. 60-232998,
At least one amino group and at least one hydroxy group
A compound selected from a compound having a salt and a salt thereof.
Described in JP-A-62-19494
Phosphate-containing layer, disclosed in JP 59-101651 A
Less of the monomer units with sulfo groups described
Polymerization with 1 type as a repeating unit in the molecule
A method of providing a compound layer or the like by coating
Can be mentioned. In addition, carboxymethylcellulose;
String; gum arabic; 2-aminoethylphosphonic acid
Phosphonic acids having an amino group such as
Phenylphosphonic acid, naphthylphosphonic acid,
Rualkylphosphonic acid, glycerophosphonic acid, methylenediphos
Organic phosphonic acids such as sulfonic acid and ethylenediphosphonic acid;
Optionally substituted phenylphosphoric acid, naphthylyl
Organic phosphoric acid such as acid, alkyl phosphoric acid, glycerophosphoric acid
Ester; phenylphosphie optionally having substituent (s)
Acid, naphthylphosphinic acid, alkylphosphinic acid,
Organic phosphinic acids such as glycerophosphinic acid;
And amino acids such as β-alanine;
Hydrochlorides of amines having a hydroxy group, such as hydrochlorides of amines
The method of providing the layer of the compound chosen from is also mentioned. For the sealing treatment, a silane compound having an unsaturated group is used.
A coating agent may be applied. Silane coupling
Examples of the adhesive include N-3- (acryloxy-2-
Hydroxypropyl) -3-aminopropyltriethoxy
Sisilane, (3-acryloxypropyl) dimethylmeth
Xylsilane, (3-acryloxypropyl) methyldimethyl
Toxisilane, (3-acryloxypropyl) trimeth
Xylsilane, 3- (N-allylamino) propyltrime
Toxisilane, allyldimethoxysilane, allyltrie
Toxisilane, allyltrimethoxysilane, 3-buteni
Rutriethoxysilane, 2- (chloromethyl) allylto
Limethoxysilane, methacrylamide propyltriet
Xysilane, N- (3-methacryloxy-2-hydroxy
Cypropyl) -3-aminopropyltriethoxysila
(Methacryloxymethyl) dimethylethoxysila
, Methacryloxymethyltriethoxysilane, methacrylate
Liloxymethyltrimethoxysilane, methacryloxyp
Lopyldimethylethoxysilane, methacryloxypropi
Didimethylmethoxysilane, methacryloxypropylme
Tildiethoxysilane, methacryloxypropylmethyl
Dimethoxysilane, methacryloxypropylmethyltri
Ethoxysilane, methacryloxypropylmethyl trime
Toxisilane, Methacryloxypropyl Tris (Metoki
Siethoxy) silane, methoxydimethylvinylsilane,
1-methoxy-3- (trimethylsiloxy) butadiene
, Styrylethyltrimethoxysilane, 3- (N-styrene)
Tyrylmethyl-2-aminoethylamino) -propylto
Limethoxysilane hydrochloride, vinyldimethylethoxysila
Vinyl diphenylethoxysilane, vinyl methyldi
Ethoxysilane, vinylmethyldimethoxysilane, O-
(Vinyloxyethyl) -N- (triethoxysilylpro
Pill) urethane, vinyltriethoxysilane, vinyltol
Limethoxysilane, vinyltri-t-butoxysilane,
Vinyl triisopropoxy silane, vinyl tripheno
Xysilane, vinyltris (2-methoxyethoxy) silane
Orchid, diallylaminopropylmethoxysilane
It is. Above all, methacryloyl with fast reactivity of unsaturated groups
And silane coupling agents having an acryloyl group are preferred.
Good. In addition, JP-A-5-507779
Sol-gel coating treatment described in the
Phosphonic acids described in Japanese Patent No. 5-246171
Coating treatment, JP-A-6-234284,
JP-A-6-191173 and JP-A-6-230
The backcoat material described in Japanese Patent No. 563
For processing by sheeting, JP-A-6-26287
Treatment of phosphonic acids described in Japanese Patent No. 2
Coating described in JP-A-6-297875
Processing, described in JP-A-10-109480
Anodizing method, Japanese Patent Application No. 10-252078
Specification (Japanese Patent Laid-Open No. 2000-81704) and Japanese Patent Application
Hei 10-253411 (Japanese Patent Laid-Open No. 2000-894)
66)), and so on.
Any method may be used. <Hydrophilic surface treatment> In the present invention,
Metal support obtained by providing a hydrophilic coating as described
The body into an aqueous solution further containing one or more hydrophilic compounds
Hydrophilic surface treatment may be performed by soaking
Yes. Examples of hydrophilic compounds include polyvinyl phospho
Acid, sulfonic acid group-containing compound, saccharide compound, silica
Preferable examples include acid salt compounds. Compounds having a sulfonic acid group include aromatic
Sulfonic acid, its formaldehyde condensates, their derivatives
Conductors and their salts are included. Aromatic sulfonic acid
For example, phenolsulfonic acid, catechol
Sulfonic acid, resorcinol sulfonic acid, benzenesulfuric acid
Phosphonic acid, toluene sulfonic acid, lignin sulfonic acid, sodium
Phthalenesulfonic acid, acenaphthene-5-sulfonic acid,
Phenanthrene-2-sulfonic acid, benzaldehyde
2 (or 3) -sulfonic acid, benzaldehyde-2,
4 (or 3,5) -disulfonic acid, oxybenzyls
Sulfonic acids, sulfobenzoic acid, sulfanilic acid, naphthy
Examples include on acid and taurine. Among them, benzenesulfur
Phosphonic acid, naphthalene sulfonic acid, lignin sulfonic acid
preferable. Benzene sulfonic acid, naphthalene sulphate
Formaldehyde condensate of phonic acid and lignin sulfonic acid
Is also preferable. In addition, they are used as sulfonates
May be. For example, sodium salt, potassium salt, lithi
Um salt, calcium salt, and magnesium salt.
Of these, sodium salts and potassium salts are preferred. Sulfo
The pH of the aqueous solution containing the compound having an acid group is 4 to
6.5, preferably sulfuric acid, sodium hydroxide,
It can be adjusted to the above pH range using ammonia, etc.
Yes. Saccharide compounds include monosaccharides and their sugar alcohols.
Contains cole, oligosaccharides, polysaccharides, and glycosides
It is. Examples of monosaccharides and their sugar alcohols include
For example, trioses such as glycerol and its sugar alcohol
Tetrols such as threose and erythritol
And their sugar alcohols; arabinose, arabitol
Pentoses and sugar alcohols thereof;
And hexoses such as sorbitol and its sugar alcohol
D-glycero-D-galactoheptose, D-g
Heptose such as lysero-D-galactoheptitol and
Sugar alcohols thereof; D-erythro-D-galacto
Octose such as cutitol and sugar alcohols thereof;
Nonoses such as D-erythro-L-gluco-nonurose
And sugar alcohols thereof. As oligosaccharides
For example, saccharose, trehalose, lacto
And disaccharides such as raffinose.
Examples of polysaccharides include amylose, arabinan,
Clodextrin, cellulose alginate
The In the present invention, “glycoside” means a sugar moiety.
And a non-sugar moiety bonded via an ether bond etc.
Say things. Glycosides can be classified by non-sugar moieties
The For example, alkyl glycosides, phenol glycosides, bears
Phosphorus glycoside, oxycoumarin glycoside, flavonoid glycoside
Body, anthraquinone glycoside, triterpene glycoside,
Examples include Lloyd glycosides and mustard oil glycosides. Sugar part and
The monosaccharide and its sugar alcohol;
Polysaccharides. Among them, monosaccharides and oligos
Saccharides are preferable, and monosaccharides and disaccharides are more preferable. Like
As an example of a new glycoside, a compound represented by the following formula (I)
Is mentioned. [0078] [Chemical 1] In the above formula (I), R represents 1 to 2 carbon atoms.
0 linear or branched alkyl group, alkeni
Represents a ru group or an alkynyl group. 1-20 carbon atoms
Examples of alkyl groups include methyl, ethyl, and
Propyl, butyl, pentyl, hexyl, heptyl
Group, octyl group, nonyl group, decyl group, undecyl group
Group, dodecyl group, tridecyl group, tetradecyl group, pen
Tadecyl group, hexadecyl group, heptadecyl group, octa
Decyl, nonadecyl, and eicosyl groups.
They may be straight or branched.
Further, it may be a cyclic alkyl group. 1 to 2 carbon atoms
Examples of the alkenyl group of 0 include, for example, an allyl group and 2-butyl group.
Terenyl groups, which are straight-chained,
It may have a cyclic alkenyl group
Good. Examples of alkynyl groups having 1 to 20 carbon atoms include
For example, 1-pentynyl groups are mentioned and these are linear
Or may have a branch, and a cyclic alkyn
It may be a ru group. Specific compounds represented by the above formula (I)
For example, methyl glucoside, ethyl glucosi
Propyl glucoside, isopropyl glucoside,
Tyl glucoside, isobutyl glucoside, n-hexyl
Glucoside, Octyl glucoside, Capryl glucosi
Dodecyl glucoside, 2-ethylhexyl glucosi
, 2-pentylnonyl glucoside, 2-hexyldecyl
Luglucoside, lauryl glucoside, myristyl gluco
Sid, stearyl glucoside, cyclohexyl glucosi
And 2-butynyl glucoside. These
A compound is a glucoside, a type of glycoside, that is made up of glucose.
Hemiacetal hydroxyl group ethers other compounds
For example, glucose and alcohol
Can be obtained by a known method of reacting
The Some of these alkyl glucosides are found in German He
The trade name Glucopon (GLUCOPO) by nkel
N) and is used in the present invention.
You can. Another example of a preferred glycoside is saponi.
, Rutin trihydrate, hesperidin methyl carbonate
Lucon, Hesperidin, Narizine hydrate, Feno
-Β-D-glucopyranoside, salicin, 3 ′,
5,7-methoxy-7-rutinoside. The pH of the aqueous solution containing the saccharide compound is 8
~ 11, preferably potassium hydroxide, sulfuric acid, charcoal
Use acid, sodium carbonate, phosphoric acid, sodium phosphate, etc.
And can be adjusted to the above pH range. The aqueous solution of polyvinylphosphonic acid has a concentration of
It is preferably 0.1 to 5% by mass, 0.2 to 2.5
% Is more preferred. Immersion temperature is 10 ~ 70 ℃
It is preferable that it is 30-60 ° C.
That's right. The immersion time is preferably 1 to 20 seconds. Ma
An aqueous solution of a compound having a sulfonic acid group has a concentration of
It is preferable that it is 0.02-0.2 mass%. Soaking temperature
The degree is preferably 60 to 100 ° C. Soaking time
1 to 300 seconds is preferable, and 10 to 100 seconds.
More preferably. Further, the aqueous solution of saccharide compound is concentrated.
The degree is preferably 0.5 to 10% by mass. Soaking temperature
The degree is preferably 40 to 70 ° C. Soaking time is 2
~ 300 seconds are preferred, and 5-30 seconds
More preferred. In the present invention, a water solution containing a hydrophilic compound is used.
In addition to the above-mentioned aqueous solutions of organic compounds,
In addition, alkali metal silicate aqueous solution, zirconium fluoride
Potassium (K₂ZrF₆) Aqueous solution, phosphate / inorganic fluoride
Also suitable for aqueous solutions of inorganic compounds such as aqueous solutions containing elemental compounds
I can. The alkali metal silicate aqueous solution treatment is preferred.
Or a concentration of 0.01 to 30% by mass, more preferably
0.1 to 10% by mass, preferably pH at 25 ° C.
Is an aqueous solution of alkali metal silicate that is 10-13.
The support is preferably 30-100 ° C, more preferably
50-90 ° C, preferably 0.5-40 seconds
It is preferably performed by dipping for 1 to 20 seconds. Alkali metal silicate used in the present invention
For example, sodium silicate, potassium silicate,
A lithium acid is mentioned. Among them, sodium silicate,
Potassium silicate is preferred. Alkali metal silicate water
The solution should be sodium hydroxide, water to increase the pH.
Contains appropriate amounts of hydroxides such as potassium oxide and lithium hydroxide
You may have. Among them, sodium hydroxide and potassium hydroxide
Um is preferred. Also, alkali metal silicate aqueous solution
Is an alkaline earth metal salt or a Group 4 (Group IVA) metal
A salt may be contained. Examples of alkaline earth metal salts
For example, calcium nitrate, strontium nitrate, mug nitrate
Nitrates such as nesium and barium nitrate; sulfates; hydrochlorides;
Phosphate; acetate; oxalate; water-soluble salt such as borate
Is mentioned. Examples of Group 4 (Group IVA) metal salts include:
For example, titanium tetrachloride, titanium trichloride, titanium fluoride potassium
Um, potassium titanium oxalate, titanium sulfate, tetraiodide
Titanium, chlorinated zirconium oxide, zirconium dioxide,
Examples include zirconium oxychloride and zirconium tetrachloride
It is. These alkaline earth metal salts and Group 4 (Group IV
Group A) metal salts are used alone or in combination of two or more.
I can. Treatment with potassium fluoride zirconium aqueous solution
Preferably has a concentration of 0.1 to 10% by mass, more preferably
Or 0.5 to 2 mass% potassium zirconium fluoride
The support is preferably in aqueous solution, preferably at 30-80 ° C.
Alternatively, it is performed by dipping for 60 to 180 seconds. Phosphate / inorganic fluorine compound treatment is preferred
Alternatively, the phosphate compound concentration is 5 to 20% by mass, inorganic fluoride.
The elemental compound concentration is 0.01 to 1% by mass, preferably
The support is preferably added to an aqueous solution having a pH of 3 to 5, preferably 20 to
100 ° C, more preferably 40-80 ° C, preferably
Immerse for 2 to 300 seconds, more preferably 5 to 30 seconds
To do. Examples of the phosphate used in the present invention include
For example, phosphorous of metals such as alkali metals and alkaline earth metals
Acid salts. Specifically, for example, zinc phosphate,
Aluminum phosphate, ammonium phosphate, hydrogen phosphate
Diammonium, ammonium dihydrogen phosphate, monophosphate
Ammonium, monopotassium phosphate, monosodium phosphate
, Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, lithium
Calcium phosphate, sodium ammonium hydrogen phosphate,
Magnesium hydrogen phosphate, magnesium phosphate, phosphoric acid
Ferrous, ferric phosphate, sodium dihydrogen phosphate, phosphorus
Sodium phosphate, disodium hydrogen phosphate, lead phosphate, lithium
Diammonium phosphate, calcium dihydrogen phosphate, phosphoric acid
Lithium, phosphotungstic acid, phosphotungstic acid
Numonium, sodium phosphotungstate, phosphorus
Ammonium budenate, sodium phosphomolybdate;
Sodium phosphite, sodium tripolyphosphate, pyro
A sodium phosphate is mentioned. Among them, dihydrogen phosphate
Sodium, disodium hydrogen phosphate, dihydrogen phosphate
Rium and dipotassium hydrogen phosphate are preferred. In addition, the inorganic fluorinated compound used in the present invention.
As the product, a metal fluoride is preferably exemplified. concrete
For example, sodium fluoride, potassium fluoride,
Calcium fluoride, magnesium fluoride, hexafluoro
Zirconium sodium, hexafluorozirconium
Potassium, sodium hexafluorotitanate, hexa
Potassium fluorotitanate, hexafluorozirconium
Humic acid, hexafluorotitanium hydric acid, hexafluoro
Rozirconium ammonium, hexafluorotitanic acid
Ammonium, hexafluorosilicic acid, Nicke fluoride
Iron, iron fluoride, phosphoric acid phosphate, ammonium fluoride phosphate
Can be mentioned. Used for phosphate / inorganic fluorine compound treatment
Aqueous solution that contains phosphate and inorganic fluorine compounds
One or two or more of them can be contained. The support contains these hydrophilic compounds.
After soaking in an aqueous solution, it is washed with water,
Dried. Anodizing by the hydrophilic surface treatment described above
Improved sensitivity and printing durability due to pore-wide processing after processing
Ink repellency deterioration, etc. that occurs in exchange for improvement
The problem of smudges is solved. In other words, the pore diameter has increased.
With this, when printing, especially the printing machine stops and the lithographic printing plate
When printing is restarted after being left on the printing press, the ink
Phenomenon that makes it difficult to remove (degradation of ink repellency)
There is a problem that makes it easier, but it has a hydrophilic surface treatment
The above problems are alleviated. <Undercoat layer> In the present invention,
On the metal support obtained by infrared laser exposure.
Before providing a hardened image recording layer, for example, if necessary
Inorganic subbing layers such as water-soluble metal salts such as zinc borate
Or, an organic undercoat layer may be provided. As an organic compound used in an organic undercoat layer
For example, carboxymethylcellulose; dextri
Gum arabic; polymer having sulfonic acid groups in the side chain
And copolymers; polyacrylic acid; 2-aminoethyl phosphate
Phosphonic acids having an amino group such as sulphonic acid;
Phenylphosphonic acid and naphthylphospho which may have
Acid, alkylphosphonic acid, glycerophosphonic acid, methyl
Organic phosphines such as rangephosphonic acid and ethylenediphosphonic acid
Phosphonic acid; phenylphosphonic acid optionally substituted
Presence of phthalyl phosphate, alkyl phosphate, glycerophosphate, etc.
Phosphoric acid; phenylphosphie which may have a substituent
Acid, naphthylphosphinic acid, alkylphosphinic acid,
Organic phosphinic acids such as glycerophosphinic acid;
And amino acids such as β-alanine;
Hydrochloric acid of amines having hydroxyl groups such as hydrochloride
Salt; a yellow dye. These can be used alone
In addition, two or more kinds may be mixed and used. The organic subbing layer is made of water or methanol,
Organic solvents such as ethanol and methyl ethyl ketone, or
A solution in which the above organic compound is dissolved in these mixed solvents is used.
It is provided by applying and drying on an aluminum plate
The The concentration of the solution in which the organic compound is dissolved is 0.0.
It is preferable that it is 05-10 mass%. The method of application is
Not particularly limited, bar coater coating, spin coating, spray
-Any method such as coating or curtain coating can be used.
it can. The coating amount after drying of the organic undercoat layer is 2 to 200 m.
g / m²Is preferably 5 to 100 mg / m²so
More preferably. Within the above range, printing durability is good.
It becomes better. <Backcoat layer> Obtained as described above.
When the lithographic printing plate precursor is used,
Even if the recording layer is not damaged,
Coating layer made of organic polymer compound
(Hereinafter also referred to as “back coat layer”) as required
It may be provided. The main component of the backcoat layer is glass
Saturated copolymer polyester tree having a transition point of 20 ° C or higher
Fats, phenoxy resins, polyvinyl acetal resins and
A small amount selected from the group consisting of vinylidene chloride copolymer resins
It is preferable to use at least one kind of resin. Saturated copolymer polyester resin is dicarbohydrate.
It consists of an acid unit and a diol unit. Dicarbo
Examples of acid units include phthalic acid and terephthalic acid.
Acid, isophthalic acid, tetrabromophthalic acid, tetrachloro
Aromatic dicarboxylic acids such as ruphthalic acid; adipic acid, aze
Rhine acid, succinic acid, oxalic acid, suberic acid, sebatin
Acid, malonic acid, 1,4-cyclohexanedicarboxylic acid, etc.
Of saturated aliphatic dicarboxylic acids. The back coat layer is further dyed for coloring.
Silanes for improving adhesion to pigments, pigments and supports
A coupling agent, a diazo resin comprising a diazonium salt,
Organic phosphonic acid, organic phosphoric acid, cationic polymer, lubrication
Wax, higher fatty acid, higher grade
Silicone made of fatty acid amide and dimethylsiloxane
Compound, modified dimethylsiloxane, polyethylene powder, etc.
Can be contained appropriately. The thickness of the back coat layer is basically a slip sheet.
Even if there is no damage, it is difficult to damage the recording layer described later.
What is necessary is just 0.01-8 micrometers. Thickness is
If the thickness is less than 0.01 μm, remove the planographic printing plate precursor
It is difficult to prevent the recording layer from being scratched when handled.
The If the thickness exceeds 8 μm, lithographic printing is in progress
Backcoat layer swells due to chemicals used around the plate
The thickness varies, and the printing pressure changes, deteriorating the printing characteristics.
Sometimes. A method of providing a back coat layer on the back surface of the support.
Various methods can be used as the method. example
For example, the above components for the back coat layer are dissolved in an appropriate solvent.
Apply as a liquid, or apply as an emulsified dispersion and dry
How to do; Adhering previously formed film
Bonding to a support with heat agent or heat; melting with a melt extruder
Examples include forming a melt film and attaching it to a support.
The The most preferable way to ensure a suitable thickness is
Dissolve the components for the back coat layer in a suitable solvent and apply as a solution.
It is a method of cloth and drying. In this method,
Existence as described in Sho 62-251739
Use the solvent as a solvent alone or in combination
Can do. In the production of a lithographic printing plate precursor,
Either the backcoat layer or the surface recording layer first on the support
Or both of them may be provided at the same time. [Lithographic printing plate precursor] For the lithographic printing plate of the present invention
The original plate is formed on the metal support described above by infrared laser exposure.
It can be obtained by providing a hardened image recording layer. [Image Recording Layer] The image recording layer used in the present invention is an infrared
Especially if it is an image recording layer that is cured by linear laser exposure
Not limited. Such direct infrared laser exposure
Close contact recording is possible, and the exposed area is soluble in alkaline developer.
An image recording layer with reduced solutionability is suitably used as a thermal negative below.
This is called a type of image recording layer (heat-sensitive layer). Thermal negative
In the image recording layer
Radicals or acids that act as initiators and catalysts to record images
The compound contained in the layer causes a polymerization reaction or a crosslinking reaction,
The image portion is formed by curing. Hereinafter, preferred image recording layers will be described in detail.
explain. Thermal negative type image used in the present invention
One of the image recording layers is a photopolymerization layer. Photopolymerization
The layers are (A) an infrared absorber and (B) a radical generator.
(Radical polymerization initiator) and generated radicals
(C) radically polymerizable compound that cures by causing a combined reaction
Preferably (D) a binder polymer
Containing. In the photopolymerization layer, the infrared absorber absorbs
Infrared light is converted into heat, and the heat generated at this time
Radical polymerization initiators such as nium salts decompose and radicals
Occur. The radically polymerizable compound has at least one
Has an ethylenically unsaturated double bond and has terminal ethylenically unsaturated
A compound having at least one, preferably two or more union bonds
Polymerized in a chain by selected radicals selected from compounds
A reaction takes place and cures. In addition to the photopolymerization layer, a suitable thermal
One of the negative type image recording layers is an acid cross-linked layer.
It is done. Acid cross-linking layer (E) generates acid by light or heat
Compound (hereinafter referred to as “acid generator”), (F)
A compound that crosslinks with the generated acid (hereinafter referred to as “crosslinking agent”)
Yeah. And a layer containing these is formed.
To react with the crosslinker in the presence of acid (G)
Contains potash-soluble polymer compound. In the acid crosslinking layer
Is generated by decomposition of the acid generator by light irradiation or heating.
Acid promotes the function of the cross-linking agent and
Is a strong cross-linking structure between the cross-linking agent and the binder polymer
This reduces the alkali solubility,
Insoluble in developer. At this time, the energy of the infrared laser
In order to use ghee efficiently, the acid cross-linking layer has (A) infrared
A line absorber is blended. In addition, thermal negative type
As one of the heat-sensitive layers, (H) hydrophobic hot-melt resin fine particles
The child is dispersed in the (J) hydrophilic polymer matrix and the
Hydrophobic polymers are melted by the heat of the light part and fused together
And the hydrophobic (ink-philic) region of the polymer, that is,
A heat-sensitive layer that forms an image portion is also preferably exemplified. This heat
A lithographic printing plate precursor having a layer is printed after image recording (exposure).
Mount on the press cylinder, fountain solution and / or ink
Do not perform special development processing by supplying
And can be developed on-press. For each compound used in the photopolymerization layer,
Described below. (A) Infrared absorber Infrared absorbers have the function of converting absorbed infrared light into heat.
Have. Radicals generated by the heat generated by the infrared absorber
The generator and acid generator are decomposed to generate radicals and acids.
The The infrared absorber used in the present invention has a wavelength of 7
Dye or pigment having absorption maximum at 60-1200 nm
It is. Examples of the dye include commercially available dyes and literature.
(For example, “Handbook of Dyes” edited by the Society of Synthetic Organic Chemistry, Showa 4
The publicly known thing described in the 5th year publication can be used. Ingredients
Specifically, for example, the stage of JP-A-10-39509 is disclosed.
Also listed in the drop numbers [0050] to [0051]
Can be mentioned. Particularly preferred among these dyes
As cyanine dyes, squarylium dyes, pyririu
Salts and nickel thiolate complexes. Above all,
Cyanine dyes are preferred, particularly those represented by the following general formula (I)
Most preferred are cyanine dyes. [0109] [Chemical 2] In the general formula (I), X¹Is a halogen atom
Or -X²-L¹Represents. Where X²Is an oxygen atom or
Represents a sulfur atom, L¹Is a hydrocarbon having 1 to 12 carbon atoms
Represents a basic group. R¹And R²Each independently of carbon
A hydrocarbon group having 1 to 12 atoms is shown. Storage of heat-sensitive layer coating solution
From stability, R¹And R²Is the number of carbon atoms
It is preferably two or more hydrocarbon groups, and further R
¹And R²Bind to each other to form a 5- or 6-membered ring
It is particularly preferable. Ar¹And Ar²Is
Aromatic carbonization which may have a substituent each independently
Represents a hydrogen group. Y¹And Y²Each independently
Dialkyl methylene having 12 or less carbon atoms or yellow atoms
Represents a group. R^ThreeAnd R^FourAre each independently substituted
Hydrocarbon having 20 or less carbon atoms, which may have a group
Represents a group. Preferred substituents are 12 carbon atoms
The following alkoxy, carboxy and sulfo groups are listed.
I can get lost. R^Five, R⁶, R⁷And R⁸Each
Vertically, a hydrogen atom or a hydrocarbon having 12 or less carbon atoms
In view of the availability of raw materials, it is preferably a hydrogen atom.
That's right. Z^1-Represents a counter anion. However, R¹~ R⁸
Z is substituted with a sulfo group^1-Is
unnecessary. Z^1-Because of the storage stability of the thermosensitive layer coating solution,
Logen ion, perchlorate ion, tetrafluoro volley
Ion, hexafluorophosphate ion or
Preferably, it is a sulfonate ion, a perchlorate ion,
Hexafluorophosphate ion or aryls
More preferably, it is a sulfonic acid ion. In the present invention, it can be suitably used.
Specific examples of the cyanine dye represented by the general formula (I)
Japanese Patent Application No. 11-310623 (Japanese Patent Laid-Open No. 2001-310623).
No. 133969), paragraph numbers [0017] to [0]
019] can be mentioned. As the pigment, commercially available pigments, as well as
And Color Index (CI) Handbook, “Latest Pigment
Handbook "(edited by Japan Pigment Technology Association, published in 1977)," Latest
Pigment Application Technology "(CMC Publishing, 1986) and
Described in “Printing Ink Technology” published by CMC, published in 1984)
The pigments that are used can be used. As the types of pigments, black pigment, yellow face
, Orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Examples include polymer-bound dyes. Details of these pigments
Is the paragraph number [005] of JP-A-10-39509.
2] to [0054], which are described in detail.
The present invention can also be applied. Of these pigments
Preferred is carbon black. The content of the dye or pigment is the total solid content of the heat sensitive layer.
It is preferable to be 0.01 to 50% by mass with respect to the shape.
More preferably 0.1 to 10% by weight,
Furthermore, in the case of dyes, it is further 0.5 to 10% by mass.
In the case of a pigment, 1.0 to 10 mass is preferable.
% Is more preferable. Content is not 0.01% by mass
If it is full, the sensitivity may be low, and 50% by mass
If this is exceeded, the non-image area will become dirty when using a lithographic printing plate.
May occur. (B) Radical generator Examples of radical generators include onium salts and organic phosphors.
Examples include an urine complex and a halomethylated triazine. Inside
Also preferred are onium salts. Specific examples of onium salts
For example, iodonium salts, diazonium salts,
A ruphonium salt is mentioned. These onium salts are
Although it also has a function as a raw material, the radical polymerizability described later
When used in combination with a compound, it functions as a radical polymerization initiator.
The The onium salt suitably used in the present invention is
An onium salt represented by the general formulas (III) to (V)
The [0116] [Chemical 3] In the general formula (III), Ar¹¹And A
r¹²Each independently represents an optionally substituted carbon.
An aryl group having 20 or less elementary atoms is represented. This aryl
Preferred substituents when the group has a substituent include
Rogen atom, nitro group, alkyl having 12 or less carbon atoms
Group, alkoxy group having 12 or less carbon atoms and carbon
An aryloxy group having 12 or less atoms is exemplified. Z
^11-Is halogen ion, perchlorate ion, tetrafluoro
Roborate ion, hexafluorophosphate ion
And a sulfonate ion selected from the group consisting of sulfonate ions
ON, preferably perchlorate ion, hexaflur
Orofophosphate ion, aryl sulfonate ion
It is. In the above general formula (IV), Ar^{twenty one}Is a substituent
An aryl group having 20 or less carbon atoms, which may have
Represents. Preferred substituents include halogen atoms and nitro
B group, alkyl group having 12 or less carbon atoms, carbon atom number
12 or less alkoxy groups, 12 or less carbon atoms
Reeloxy group, alkylamine having 12 or less carbon atoms
Group, dialkylamino group having 12 or less carbon atoms, charcoal
Arylamino groups and carbon atoms having up to 12 atoms
A diarylamino group of several 12 or less is mentioned. Z
^{twenty one-}Is Z^11-Represents a counter ion having the same meaning as. In the general formula (V), R³¹, R³²And R
³³Each independently represents an optionally substituted carbon.
A hydrocarbon group having 20 or less atoms is represented. Preferred substituents
As halogen atoms, nitro groups, 12 carbon atoms
The following alkyl groups and alkoxy having 12 or less carbon atoms
Groups and aryloxy groups having 12 or less carbon atoms.
I can get lost. Z^31-Is Z^11-Represents a counter ion having the same meaning as. In the present invention, it can be suitably used.
Specific examples of the onium salt include Japanese Patent Application No. 11-3106.
No. 23 (Japanese Patent Laid-Open No. 2001-133969)
Those described in paragraph numbers [0030] to [0033]
Can be mentioned. The onium salt used in the present invention is:
The maximum absorption wavelength is preferably 400 nm or less.
More preferably, it is 60 nm or less. Absorbed in this way
The lithographic printing of the present invention by setting the wavelength in the ultraviolet region
The original plate can be handled under white light. [0122] The content of these onium salts depends on the heat sensitive layer.
It is preferable that it is 0.1-50 mass% with respect to the total solid content.
More preferably, it is 0.5 to 30% by mass.
More preferably, it is -20 mass%. Content is 0.1
If it is less than mass%, the sensitivity is lowered, and 50 mass%.
Otherwise, the non-image area may become dirty during printing.
The These onium salts may be used alone.
Two or more kinds may be used in combination. Also these oniyu
The salt may be added to the same layer as the other components, or another layer
And may be added thereto. (C) Radical polymerizable compound The radically polymerizable compound has at least one ethylenic compound
A radically polymerizable compound having an unsaturated double bond,
At least one terminal ethylenically unsaturated bond, preferably
Is selected from compounds having two or more. Such a compound
A group of things is widely known in the industry,
In the present invention, these can be used without any particular limitation.
Yes. These include, for example, monomers, prepolymers (immediate
Dimer, trimer and oligomer), and their mixture
And chemical forms of these copolymers. Examples of monomers and copolymers thereof
Unsaturated carboxylic acids (e.g. acrylic acid, methacrylate)
Formic acid, itaconic acid, crotonic acid, isocrotonic acid, male
Inic acid), its esters, and amides.
Preferably, unsaturated carboxylic acid and aliphatic polyhydric alcohol
Esters with compounds, unsaturated carboxylic acids and aliphatic polyvalents
Amides with amine compounds are used. Hydro
Has nucleophilic substituents such as xy group, amino group, mercapto group
Unsaturated carboxylic esters, amides, monofunctional
Or with polyfunctional isocyanates or epoxies
Dehydration condensation with addition product, monofunctional or polyfunctional carboxylic acid
Combined reactants and the like are also preferably used. Also isocyanate
Unsaturated carbons having electrophilic substituents such as epoxy groups
Bonic acid esters or amides and mono- or polyfunctional
Addition reaction with alcohols, amines or thiols
In addition, leaving groups such as halogen groups, tosyloxy groups, etc.
Unsaturated carboxylic acid ester or amide having a substituent
Monofunctional or polyfunctional alcohols, amines or
Also suitable are substitution reaction products with thiols. Another
As an example, instead of the above unsaturated carboxylic acid, unsaturated
Use compounds that have been replaced with phosphonic acid, styrene, etc.
It is also possible. Aliphatic polyhydric alcohol compounds and unsaturated cal
It is a radical polymerizable compound that is an ester with boronic acid.
Acrylic acid ester, methacrylic acid ester, itacone
Acid ester, crotonic acid ester, isocrotonic acid ester
Specific examples of ter and maleate esters include, for example:
Japanese Patent Application No. 11-310623 (JP 2001-1)
No. 33969), paragraph numbers [0037] to [004]
2]. Examples of other esters include, for example, special
Kosho 46-27926, JP-B 51-47334
And JP-A-57-196231.
Aliphatic alcohol esters, JP-A-59-52
No. 40, JP-A 59-5241 and JP-A 2-22
It has an aromatic skeleton described in each publication of No. 6149.
What is described in JP-A-1-165613
Suitable examples include those containing an amino group. In addition, an aliphatic polyvalent amine compound and an unsaturated catalyst.
Specific examples of amide monomers with rubonic acid include
Renbis-acrylamide, methylenebis-methacrylic
Amide, 1,6-hexamethylenebis-acrylamid
1,6-hexamethylenebis-methacrylamide,
Diethylenetriaminetrisacrylamide, Xylile
Bisacrylamide, Xylylenebismethacrylami
Do. Examples of other preferred amide monomers
Is described in Japanese Patent Publication No. 54-21726.
And those having a cyclohexylene structure. In addition, an isocyanate group and a hydroxy group
Of urethane-based addition polymerization using an addition reaction
A compound is also suitable.
2 molecules per molecule described in Sho 48-41708
Polyisocyanate having at least one isocyanate group
The compound contains a hydroxy group represented by the following formula (VI):
2 or more per molecule with added vinyl monomer
Vinyl urethane compounds containing polymerizable vinyl groups above
Is mentioned. [0130]   CH₂= C (R⁴¹) COOCH₂CH (R⁴²) OH (VI) (In the above formula (VI), R⁴¹And R⁴²Respectively
Or CH_ThreeRepresents. ) Japanese Patent Laid-Open No. 51-37193, Japanese Patent
No. 2-332293 and JP-B-2-16765
Urethane acrylates,
No. 58-49860, No. 56-17654,
JP-B-62-39417 and JP-B-62-3941
Ethylene oxide bone described in each publication of No. 8
Urethane compounds having a rating are also suitable. Further, JP-A 63-277653, JP-A 63-277653
Sho 63-260909 and JP-A-1-105238
As described in each publication, the amino structure and
Using radically polymerizable compounds having a rufido structure
You can also Other examples include Japanese Patent Laid-Open No. 48-641.
83, JP-B 49-43191 and JP-B 52-
Police as described in each publication of 30490
Teracrylates, epoxy resins and (meth) acrylic
Multifunctional such as epoxy acrylates reacted with acid
Examples include acrylate and methacrylate. Also special
No. 46-43946, No. 1-40337 and
And Japanese Patent Publication No. 1-40336
Certain unsaturated compounds and those described in JP-A-2-25493
Examples thereof include vinyl phosphonic acid compounds. Ma
In some cases, it is described in JP-A-61-22048.
The structures containing perfluoroalkyl groups listed are
It is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 2
0, No. 7, p. 300-308 (1984)
And introduced as photocurable monomers and oligomers.
It is also possible to use what has been used. With respect to these radical polymerizable compounds,
What kind of structure is used, whether it is used alone or two or more
Details of how to use, such as
The details are optional depending on the performance design of the final recording material.
Can be set. For example, it is selected from the following viewpoints.
In terms of sensitivity, a structure with a high content of unsaturated groups per molecule
In many cases, bifunctional or more is preferred. Also,
To increase the strength of the image area, that is, the cured film,
Better than performance, and different functional numbers and different polymerizations
A compound having a functional group (for example, an acrylic ester-based compound)
Compound, methacrylate ester compound, styrene compound
In combination with the photosensitivity and strength.
A method of adjusting the direction is also effective. Large molecular weight compounds
Highly hydrophobic compounds are excellent in sensitivity and film strength,
It is preferable in terms of development speed and precipitation in the developer.
There is a case. Also, other components in the heat sensitive layer (e.g.
Compatibility with inder polymers, initiators, colorants, etc.)
Selection and use of radically polymerized compounds for dispersibility
Method is an important factor, for example the use of low purity compounds
Or by using two or more compounds in combination to improve compatibility
There is a possibility. In addition, support, overcoat layer, etc.
Selecting a specific structure for the purpose of improving adhesion
There is also a possibility. Arrangement of radical polymerizable compounds in the image recording layer
As for the ratio, a larger number is more advantageous in terms of sensitivity.
If this is the case, undesirable phase separation may occur or image recording may occur.
Problems in the manufacturing process due to adhesiveness of the recording layer (for example, recording layer
Inferior manufacturing due to component transfer and adhesion) and from developer
This may cause problems such as precipitation. From these viewpoints, radically polymerizable compounds
In many cases, the mixing ratio of is based on the total solid content of the heat-sensitive layer,
It is preferably 5 to 80% by mass, and 20 to 75% by mass.
It is more preferable that These can be used alone
Or two or more of them may be used in combination. In addition, radio
The use method of the polymerizable compound is a large amount of polymerization inhibition against oxygen.
Small, resolution, fog, refractive index change, surface adhesiveness, etc.
From the point of view, it is possible to arbitrarily select an appropriate structure, composition, and addition amount.
In some cases, the layer structure such as undercoating and overcoating
A coating method can also be implemented. (D) Binder polymer In the present invention, a binder polymer is further used.
Is preferred. As a binder polymer, a linear organic polymer is used.
It is preferable to use a remer. As a linear organic polymer
Any of them can be used. Preferably water development
Or water or weak to allow weak alkaline water development.
Linear organic polymers that are soluble or swellable in alkaline water
Is selected. Linear organic polymer forms a heat-sensitive layer
Not only as a film-forming agent for water or weak al
Depending on the type of potash water and its use as an organic solvent developer
Select used. For example, using a water-soluble organic polymer
Then, water development becomes possible. Such a linear organic polymer
As a radical polymerization having a carboxy group in the side chain
Bodies, for example, JP 59-44615, JP-B 54-
No. 34327, No. 58-12777, No. 54
25957, JP 54-92723, JP 5
Japanese Patent Publication Nos. 9-53836 and 59-71048
Described in methacrylic acid copolymer,
Acrylic acid copolymer, itaconic acid copolymer, crotonic acid
Copolymer, maleic acid copolymer, partially esterified male
An acid copolymer etc. are mentioned. Similarly, the side chain
Examples include acidic cellulose derivatives having a ruboxy group.
The In addition, a cyclic acid is added to the polymer having a hydroxy group.
What added the anhydride etc. is useful. Of these, in particular, benzyl groups or ants
(Meth) acrylate having a benzene group and a carboxy group in the side chain
Resin has excellent balance of film strength, sensitivity and developability
It is suitable. Also, Japanese Patent Publication No. 7-12004 and Japanese Patent Publication No. 7
-120041, JP 7-120042, JP
8-12424, JP 63-287944, JP
Sho 63-287947, JP-A 1-271744,
It is described in JP-A-11-352691, etc.
Urethane binder polymer containing acid groups
Since it is always excellent in strength, it has printing durability and low exposure suitability.
Is advantageous. Further, in addition to this, a water-soluble linear organic polymer.
-Polyvinylpyrrolidone, polyethylene oxa
Id etc. are useful. Also to increase the strength of the cured film
For example, alcohol-soluble nylon, 2,2-bis- (4
-Hydroxyphenyl) -propane and epichlorohydride
Polyethers and the like are also useful. The weight of the linear organic polymer used in the present invention
The weight average molecular weight is preferably 5000 or more, more
Preferably it is 10,000 to 300,000, and the number average molecular weight
Is preferably 1000 or more, more preferably 2
000-250,000. Polydispersity (weight average molecular weight / number
(Average molecular weight) is 1 or more, preferably 1.1 to 10
It is. These linear organic polymers are random polymers.
Rimmer, block polymer, graft polymer, etc.
However, it is preferable to use a random polymer.
That's right. The polymers used in the present invention are conventionally known.
It can be synthesized by the method. Used when synthesizing
Examples of the solvent to be used include tetrahydrofuran and ethyl.
Range chloride, cyclohexanone, methyl ethyl keto
, Acetone, methanol, ethanol, ethylene glycol
Cole monomethyl ether, ethylene glycol monoe
Chill ether, 2-methoxyethyl acetate, diethyl
Lenglycol dimethyl ether, 1-methoxy-2-
Propanol, 1-methoxy-2-propyl acetate
, N, N-dimethylformamide, N, N-dimethyl
Acetamide, toluene, ethyl acetate, methyl lactate, milk
Examples include ethyl acid, dimethyl sulfoxide, and water.
These solvents may be used alone or in combination of two or more.
The In the synthesis of the polymer used in the present invention
As radical polymerization initiators, azo initiators, peracids
Known compounds such as compound initiators can be used. A binder polymer may be used alone.
It is also possible to use a mixture. Contains binder polymer
The amount is 20 to 95% by mass with respect to the total solid content of the heat-sensitive layer.
Preferably, it is more preferably 30 to 90% by mass.
Good. When the content is less than 20% by mass, an image is formed.
The strength of the image area may be insufficient. Also included
If the amount exceeds 95% by mass, images may not be formed.
The Also, radically polymerizable compounds and linear organic polymers
The mass ratio is preferably 1/9 to 7/3. [Overcoat layer] Thermal negative type
An overcoat layer may be provided on the image recording layer.
preferable. Overcoat layer suitably used in the present invention
Is for actinic rays, i.e. rays used for image exposure.
Transparent and has some adhesion to the adjacent heat sensitive layer
If it does, it will not specifically limit, Select a well-known thing
Can be used. Overcoat layer is in heat sensitive layer
And compounds produced by exposure to actinic rays
It is provided to inhibit the influence of outside air. That
Therefore, it is generated in low-molecular compounds existing in the air and in the heat-sensitive layer.
Preferably, the low molecular weight compound has low permeability. That is,
-Bar coat layer is a compound generated during exposure in the heat sensitive layer.
Substances that trap things and reactions that occur in the heat-sensitive layer
Inhibits water, bases, acids, oxygen, etc. present in the air
Mixing of the compound into the heat-sensitive layer can be prevented, and
Remove the non-image area overcoat layer before or during development.
If it can be left, it will not be specifically limited. That is,
A film with low permeability or a film forming film
preferable. As a compound for forming an overcoat layer
Specifically, for example, polyvinyl alcohol, poly
Vinylidene chloride, poly (meth) acrylonitrile, poly
Sulphone, acetyl cellulose, polyvinyl chloride, poly
Vinyl acetate, ethylene-vinyl alcohol copolymer,
Reethylene, polycarbonate, polystyrene, polyester
Tylene, polyamide, cellophane, acrylic resin, gelatin
And gum arabic. Use these alone
Or two or more of them may be used in combination. Above all, during development
Polyvinyl alcohol in terms of removability and ease of coating
, Water-soluble acrylic resin, polyvinylpyrrolidone, z
Water-soluble polymers such as latin and gum arabic are preferred.
In particular, it can be applied using water as a solvent, and water-based
Polyvinyl alcohol that can be removed with a developer
, Polyvinylpyrrolidone, gelatin, gum arabic
preferable. To improve the removability of the overcoat layer
Therefore, partial structures such as amines are added to these water-soluble polymers.
Nitrogen-containing water-soluble polymer having acid groups such as sulfo groups
A water-soluble polymer may be used in combination. Poly used suitably for overcoat layer
Vinyl alcohol has the necessary water solubility.
Containing an amount of unsubstituted vinyl alcohol units
For example, some vinyl alcohol units are esters and ethers.
Alternatively, it may be substituted with acetal. Also the same
In addition, some may contain other copolymerization components. Poly
Specific examples of vinyl alcohol include 71 to 100%
Those that are hydrolyzed and have a degree of polymerization in the range of 300-2400
can give. Specifically, for example, PVA-105, P
VA-110, PVA-117, PVA-117H, P
VA-120, PVA-124, PVA-124H, P
VA-CS, PVA-CST, PVA-HC, PVA-
203, PVA-204, PVA-205, PVA-2
10, PVA-217, PVA-220, PVA-22
4, PVA-217EE, PVA-220, PVA-2
24, PVA-217EE, PVA-217E, PVA
-220E, PVA-224, PVA-405, PVA
-420, PVA-613, L-8 (all trade names,
Kuraray Co., Ltd.). Examples of copolymers include
88-100% hydrolyzed polyvinyl acetate
Toto chloroacetate or propionate, polyvinyl chloride
Luformal, polyvinyl acetal and their
A polymer is mentioned. The overcoat layer is prepared by dissolving the above components in a solvent.
Dissolve or disperse the coating solution obtained by image recording
It can be applied on the layer and dried. Coating liquid
As a solvent used in the above, pure water is preferably mentioned.
Alcohols such as methanol and ethanol, acetone,
Used by mixing ketones such as methyl ethyl ketone with pure water
You can also. The concentration of solid content in the coating solution is 1-20.
It is preferable that it is mass%. Further, the overcoat layer is further coated.
To improve the physical properties of surfactants and coatings
Add known additives such as water-soluble plasticizer for
Can do. Examples of water-soluble plasticizers include propio
Amide, cyclohexanediol, glycerin, sol
Bitol is mentioned. Water-soluble (meth) acrylic
It is also possible to add a polymer or the like. The coating amount of the overcoat layer is the quality after drying.
About 0.1 to about 15 g / m in quantity²Preferably,
About 1.0 to about 5.0 g / m²It is more preferable that Next, each compound used in the acid cross-linking layer is changed to
This is described below. (A) Infrared absorber The infrared absorber used for the acid crosslinking layer as needed
(A) Same as the infrared absorber described in the photopolymerization layer
Can be used. Infrared absorber content
Is 0.01 to 50% by mass relative to the total solid content of the heat-sensitive layer
Preferably, it is 0.1 to 10% by mass.
More preferably, in the case of a dye, 0.5 to 10 mass.
%, And in the case of pigments,
More preferably, it is 1.0-10 mass%. Content
However, if it is less than 0.01% by mass, the sensitivity will be low.
When it exceeds 50% by mass, it is a planographic printing plate
In addition, stains may occur in the non-image area. (E) Acid generator An acid generator refers to light in the wavelength region of 200 to 500 nm.
By heating or heating to 100 ° C or higher.
This refers to the compound that occurs. As an acid generator, a photocation
Polymerization photoinitiator, radical photopolymerization photoinitiator, dyes
Used for photo-decoloring agent, photo-discoloring agent, micro resist, etc.
The publicly known acid generators that can generate acid by thermal decomposition
And known compounds and mixtures thereof. Specifically, S.M. I. Schlesing
er, Photogr. Sci. Eng. , 18, 38
7 (1974), T.W. S. Bal et al, Pol
ymer, 21, 423 (1980)
Diazonium salt, US Pat. No. 4,069,055
And Japanese Patent Application Laid-Open No. 4-365049.
Ammonium salt, U.S. Pat. No. 4,069,055, ibid.
The phosphine described in each specification of US Pat. No. 4,069,056
Honium salt, European Patent No. 104,143, US Patent
339,049, 410,201,
JP-A-2-150848, JP-A-2-296514
The iodonium salts described in the publications of the European Patent No.
370,693, 390,214, 233,5
67, 297,443, 297,442, rice
National Patent Nos. 4,933,377 and 161,811,
410,201, 339,049, 4,76
0,013, 4,734,444, 2,83
3,827, German Patent 2,904,626, the same
Each light of 3,604,580 and 3,604,581
Examples include sulfonium salts described in the booklet. In addition, J.A. V. Crivello et
al, Macromolecules, 10 (6), 1
307 (1977), J. MoI. V. Crivello et
  al, J. et al. Polymer Sci. , Polyme
r Chem. Ed. , 17, 1047 (1979)
The selenonium salts described, C.I. S. Wen et
  al, Teh, Proc. Conf. Rad. Cur
ing ASIA, p478 Tokyo, Oct (1
988), such as arsonium salts
Salt, US Pat. No. 3,905,815, Japanese Patent Publication No. 4
6-4605, JP-A 48-36281, JP-A 5
No. 5-232070, JP-A-60-239736, JP-A-60-39736
Sho 61-169835, JP-A 61-169837
JP, 62-58241, JP 62-2124
01, JP-A 63-70243, JP-A 63-29
Organic halogen compounds described in each publication of No. 8339
Products described in JP-A-2-161445
Machine metal / organic halide, European Patent 0290,75
0, 046,083, 156,535, 2
71,851, No. 0,388,343, US Patent No.
Each light of 3,901,710 and 4,181,531
Book, JP-A-60-198538, JP-A-53-13
O-Nitrobenzen described in each publication of No. 3022
A photoacid generator having a protecting group, European Patent 0199,
No. 672, No. 84515, No. 199,672, No. 0
44,115, 0101,122, US Patent
4,618,564, 4,371,605,
No. 4,431,774, JP-A 64-181
43, JP-A-2-245756, JP-A-4-365
Iminosulfonate described in each publication of No. 048
Compounds that generate sulfonic acid by photolysis, such as
Described in Japanese Patent Application Laid-Open No. 61-166544
A disulfone compound is also mentioned. Further, groups or compounds that generate these acids.
Also suitable is a compound in which is introduced into the main chain or side chain of the polymer
It is mentioned in. For example, US Pat. No. 3,849,137
No. 1, German Patent No. 3,914,407, JP, JP,
Sho 63-26653, JP-A 55-164824,
JP-A-62-69263, JP-A-63-146037
No., JP-A 63-163452, JP-A 62-153
No. 853 and JP-A 63-146029
The compound currently made is mentioned. Further, V.V. N. R. Pillai, Syn
thesis, (1), 1 (1980), A.M. Abad
  et al, Tetrahedron Lett. ,
(47) 4555 (1971), D.M. H. R. Bart
on et al, J.A. Chem, Soc,. (B),
329 (1970), U.S. Pat. No. 3,779,778.
No., European Patent No. 126,712, etc.
Also included are compounds that generate an acid by light. Among them, as the acid generator, the following formula (I)
The compound represented by-(V) is preferable. [0158] [Formula 4] In the above formulas (I) to (V), R¹, R², R
^FourAnd R^FiveEach independently has a substituent.
Represents a hydrocarbon group having 20 or less carbon atoms. R^ThreeHa
Rogen atom, optionally having 10 or less carbon atoms
Represents a hydrocarbon group or an alkoxy group having 10 or less carbon atoms.
The Ar¹And Ar²Each independently represents a substituent.
An aryl group having 20 or less carbon atoms which may be present.
R⁶Is an optionally substituted 2 having 20 or less carbon atoms.
Represents a valent hydrocarbon group. n represents an integer of 0 to 4. R
¹, R², R^FourAnd R^FiveEach has 1 to 14 carbon atoms
The hydrocarbon group is preferably. Acid generators represented by the above formulas (I) to (V)
The preferred embodiment of the present invention is a patent application proposed by the applicant of the present application.
Hei 11-320997 (Japanese Patent Laid-Open No. 2001-142)
230)), paragraph numbers [0197] to [0222].
Are described in detail. These compounds are, for example,
Japanese Patent Laid-Open Nos. 2-100054 and 2-100
Synthesis by the method described in No. 055
Can do. Further, as acid generators, halides and soot are used.
It is also possible to use onium salts with counter ions such as sulfonic acid
it can. Among them, in the following general formulas (VI) to (VIII)
Iodonium salt, sulfonium salt and diazo represented
Preferred examples include those having any structural formula of a nium salt
Can be. [0162] [Chemical formula 5] In the above general formulas (VI) to (VIII), X
^-Is a halide ion, ClO _Four ^-, PF₆ ^-, S
bF₆ ^-, BF_Four ^-Or R⁷SO_Three ^-Represents. here
And R ⁷Is an optionally substituted carbon group of 20 or less
Represents a hydrocarbon group. Ar^ThreeAnd Ar^FourRespectively
Independently, the carbon atom having 20 or less carbon atoms which may have a substituent.
Represents a reel group. R⁸, R⁹And R^TenEach
The carbonization having 18 or less carbon atoms which may have a substituent.
Represents a hydrogen group. Such an onium salt is disclosed in
No. 39509, paragraph numbers [0010] to [003]
5] as compounds of general formulas (I) to (III)
It is. The content of the acid generator is the total solid content of the heat sensitive layer.
On the other hand, it is preferably 0.01 to 50% by mass,
It is more preferably 0.1 to 25% by mass, 0.5 to
More preferably, it is 20 mass%. Content of acid generator
If the content is less than 0.01% by mass, images cannot be obtained.
If the amount exceeds 50% by mass, a lithographic printing plate is obtained.
When printing, stains may occur in the non-image area.
There is. The acid generator may be used alone or in combination of two or more.
A combination of the above may be used. (F) Crosslinking agent The crosslinking agent is as follows.
Is mentioned. (I) a hydroxymethyl group or an alkoxymethyl group
Substituted aromatic compounds, (ii) N-hydroxymethyl
Group, N-alkoxymethyl group or N-acyloxy
A compound having a methyl group, (iii) an epoxy compound. The compounds (i) to (iii) above are
The details will be described. (I) a hydroxymethyl group or an alkoxymethyl group
Examples of substituted aromatic compounds include hydroxy
Methyl, acetoxymethyl or alkoxymethyl
Aromatic or heterocyclic compounds polysubstituted by groups
Things. However, known as resole resin
Polycondensation of phenols and aldehydes under basic conditions
Also included are resinous compounds. Hydroxymethyl group
Or aromatic compounds poly-substituted with alkoxymethyl groups
Or a heterocyclic compound adjacent to a hydroxy group
Hydroxymethyl or alkoxymethyl group
A compound having is preferred. In addition, alkoxymethyl group
Of aromatic or heterocyclic compounds poly-substituted with
However, compounds having an alkoxymethyl group of 18 or less carbon atoms
Preferably, compounds represented by the following general formulas (1) to (4)
Is more preferable. [0167] [Chemical 6] [0168] [Chemical 7]In the general formulas (1) to (4), L₁~ L₈
Are each independently methoxymethyl, ethoxymethyl
A hydride substituted with an alkoxy group having 18 or less carbon atoms, such as
Roxymethyl group or alkoxymethyl group is represented. this
These crosslinking agents have high crosslinking efficiency and can improve printing durability.
It is preferable at the point which can be. (Ii) N-hydroxymethyl group, N-a
Has a alkoxymethyl group or an N-acyloxymethyl group
As the compound to be used, European Patent Application Publication No. 0,133,
216, West German Patent 3,634,671 and the same
No. 3,711,264, each described in the specification
Polymers and oligomers-melamine-formaldehyde condensation
Compounds and urea-formaldehyde condensates, European patents
It is described in the specification of published application 0,212,482
And alkoxy-substituted compounds. Above all, for example
At least two free N-hydroxymethyl groups, N
-Alkoxymethyl group or N-acyloxymethyl group
Melamine-formaldehyde derivatives having
N-alkoxymethyl derivatives are more preferable. (Iii) As an epoxy compound, one
Monomers, dimers and oligomers having the above epoxy groups
Examples include epoxy compounds such as sesame and polymers.
For example, the reaction between bisphenol A and epichlorohydrin
Products, low molecular weight phenol-formaldehyde resins and resins
A reaction product with piclohydrin is mentioned. That
Crab, US Pat. No. 4,026,705 and English
It is described in Japanese Patent No. 1,539,192
An epoxy resin can be mentioned. As the crosslinking agent, the above (i) to (iii)
The content when using a compound is relative to the total solid content of the heat sensitive layer.
And preferably 5 to 80% by mass,
More preferably, it is 20% by mass to 20% by mass.
More preferably. Addition amount of crosslinking agent is less than 5% by mass
The heat-sensitive layer of the resulting image recording material has low durability.
In addition, if it exceeds 80% by mass, it is preserved.
Time stability may be reduced. In the present invention, (i
v) Phenol derivatives represented by the following general formula (5) are also preferred.
Can be used appropriately. [0174] [Chemical 8] In the general formula (5), Ar¹Is substituted
It represents an aromatic hydrocarbon ring that may have. The aromatic
The hydrocarbon ring is benzene in terms of availability of raw materials.
A ring, naphthalene ring or anthracene ring is preferred. Ma
The substituent includes a halogen atom, 12 or more carbon atoms.
Lower hydrocarbon group, alkoxy group having 12 or less carbon atoms, carbon
An alkylthio group, cyano group, nitro group,
A trifluoromethyl group and the like are preferable. Of the above, Ar¹
As, it has a substituent in that it can be highly sensitive.
Benzene ring or naphthalene ring; halogen atom,
Hydrocarbon group having 6 or less carbon atoms, alkoxy having 6 or less carbon atoms
Group, alkylthio group with 6 or less carbon atoms, nitro group, etc.
More preferred is a benzene ring or naphthalene ring as a group.
Good. R¹, R²And R^ThreeAre independent
Represents hydrogen or a hydrocarbon group having 12 or less carbon atoms. R
¹, R²And R^ThreeAs hydrogen atom,
The ru group is preferred. m and n are each independently 1 to
Represents an integer of 8. (G) Alkali-soluble polymer compound Examples of alkali-soluble polymer compounds include novolak trees
A polymer having a hydroxyaryl group in the side chain
Can be mentioned. As novolak resin, phenols and
Resins obtained by condensing aldehydes with acidic conditions
It is. Among them, phenol and formaldehyde
Novolak resins obtained from m-cresol and form
Novolak resin obtained from aldehyde, p-creso
Novolac tree obtained from corn and formaldehyde
Obtained from fat, o-cresol and formaldehyde
Novolac resin, octylphenol and formaldehyde
Novolac resin obtained from the
Novolac tree obtained from sol and formaldehyde
Fat, phenol / cresol (m-, p-, o-, m-
/ P-mix, m- / o-mix and o- / p-mix
Obtained from a mixture of formaldehyde)
Novolac resin, phenol and paraformaldehyde
Using hydride as a raw material, without using a catalyst, in a sealed state under high pressure
High molecular weight novola with high ortho bond ratio obtained by reaction
A cuck resin or the like is preferable. Novolac resin is weight average
The molecular weight is 40 to 300,000 and the number average molecular weight is 40.
Select from 0 to 60,000 according to purpose.
It is preferable to select and use an appropriate one. Further, it has a hydroxyaryl group in the side chain
As with novolak resins, the polymers used are also suitable.
The As the hydroxyaryl group, a hydroxy group
An aryl group in which one or more are bonded. Said ants
Examples of the alkyl group include a phenyl group, a naphthyl group, and an aryl group.
Examples thereof include an nthracenyl group and a phenanthrenyl group.
Among these, phenyl is easy to obtain and from the viewpoint of physical properties.
And naphthyl groups are preferred. Hydroxy ali on the side chain
Specific examples of the polymer having an alkyl group include the following formula (I
Any one of the structural units represented by X) to (XII)
Mention may be made of polymers comprising one species. However, the book
The invention is not limited to these examples. [0180] [Chemical 9] In the above formulas (IX) to (XII), R¹¹Is
Represents a hydrogen atom or a methyl group. R ¹²And R¹³The
Independently, a hydrogen atom, a halogen atom, 10 or more carbon atoms
Lower hydrocarbon group, alkoxy group having 10 or less carbon atoms, or
An aryloxy group having 10 or less carbon atoms is represented. Where R
¹²And R¹³And are condensed to form a benzene ring, cyclohexane
A sun ring or the like may be formed. R¹⁴Is a single bond or
A divalent hydrocarbon group having 20 or less carbon atoms is represented. R¹⁵Is simply
A bond or a divalent hydrocarbon group having 20 or less carbon atoms is represented.
R¹⁶Is a single bond or a divalent hydrocarbon having 10 or less carbon atoms
Represents a group. X¹Is a single bond, ether bond, thioate
Represents an alkyl bond, an ester bond or an amide bond. p is
The integer of 1-4 is represented. q and r are each independently
Represents an integer of 0 to 3; As the alkali-soluble polymer compound,
Japanese Patent Application No. 11-320997 proposed by the applicant
Paragraph (Japanese Patent Laid-Open No. 2001-142230)
Numbers [0130] to [0163] are described in detail.
The Alkali-soluble polymer compounds may be used alone
In addition, two or more kinds may be used in combination. The content of the alkali-soluble polymer compound is
It is 5 to 95 mass% with respect to the total solid content of the heat-sensitive layer.
Preferably, it is more preferably 10 to 95% by mass,
More preferably, it is 20-90 mass%. Alkaline water
When the content of the soluble resin is less than 5% by mass, the heat-sensitive layer
Durability may deteriorate and over 95% by mass
The image may not be formed. In addition to the above, the acid crosslinking layer
Are also described in JP-A-8-276558.
Negative image recording material containing an enol derivative,
Diazonium described in JP-A-7-306528
Negative recording material containing a compound, JP-A-10-203
Has an unsaturated bond in the ring described in No. 037
Acid-catalyzed bridges using polymers with heterocyclic groups
It is also possible to use negative-type image forming materials that use the bridge reaction.
it can. Next, (H) hydrophobic heat-meltable resin fine particles
And (J) a thermosensitive layer using a hydrophilic polymer matrix
Each compound used is described below. (H) Hydrophobic hot-melt resin fine particles Hydrophobic hot-melt resin fine particles (hereinafter referred to as “fine particle polymer”)
Say. ), The fine particle polymers melt and coalesce by heat
Preferably, the surface is hydrophilic and hydrophilic such as fountain solution
What disperse | distributes to a component is more preferable. Form fine particles
Examples of the resin include polyethylene, polystyrene,
Polyvinyl chloride, polyvinylidene chloride, poly (meth) a
Methyl crylate, poly (meth) ethyl acrylate, poly
(Meth) butyl acrylate, polyacrylonitrile, poly
Vinyl acetate; their copolymer latex is preferred
It is listed as a new one. Fine particles with hydrophilic surface
The polymer itself is hydrophilic because the polymer that makes up the particles is hydrophilic.
Some introduce hydrophilic groups in the main or side chain of the polymer
The polymer itself, such as those imparted hydrophilicity, is hydrophilic.
Some; polyvinyl alcohol, polyethylene glycol
Hydrophilic polymers such as
By adsorbing low molecular weight compounds on the surface of fine polymer particles
Including those with hydrophilic surfaces, but not limited to these
It is not something. Other preferred properties of the fine particle polymer
From the viewpoint of improving the film strength of the image area,
The child polymer is composed of a polymer having a thermally reactive functional group.
Can be mentioned. As the thermoreactive functional group
Is an ethylenically unsaturated group (e.g.
Liloyl group, methacryloyl group, vinyl group, allyl group
Etc.); Isocyanate group for carrying out addition reaction or its bromide
A functional group having an active hydrogen atom as a reaction partner
Group (for example, amino group, hydroxy group, carboxy group)
Etc.); an epoxy group that undergoes an addition reaction, its reaction partner
Amino group, carboxy group or hydroxy group; condensation reaction
Carboxy group and hydroxy group or amino group
Acid anhydride and amino group or hydroxy for the cycloaddition reaction
Groups and the like. However, chemical bonding is caused by heating.
What has the function to form a bond
It may be a functional group that performs the reaction. Of these thermally reactive functional groups
The introduction to the fine particle polymer may be performed at the time of polymerization,
You may carry out using a polymer reaction after superposition | polymerization. [0187] The content of the fine particle polymer is determined based on the total solid content of the heat sensitive layer.
It is preferably 50% by mass or more based on the shape,
It is more preferably 0 to 95% by mass. The heat-sensitive functional group as described above is added to the heat-sensitive layer.
When using a fine particle polymer having, if necessary,
Adding compounds that initiate or accelerate these reactions
Also good. Compounds that initiate or accelerate the reaction include
Compounds that generate radicals or cations by heat
You can list things. Specifically, Lofine Dimmer
ー 、 Trihalomethyl compound 、 Peroxide 、 Azo compound 、 Di
Contains azonium salt or diphenyliodonium salt
Onium salt, acylphosphine, imide sulfonate
Etc. The content of these compounds is
It is preferably 1 to 20% by mass based on the total solid content.
3 to 10% by mass is more preferable. Above range
If it is within, on-machine development is impaired even when on-machine development is performed.
Good reaction initiation effect or reaction promotion effect
The (J) Hydrophilic polymer matrix The fine particle polymer is a matrix made of a hydrophilic resin.
If you want to develop on-machine,
The image quality is improved and the film strength of the thermosensitive layer itself is improved.
The Examples of hydrophilic resins include hydroxy groups,
Boxy group, hydroxyethyl group, hydroxypropyl group
Group, amino group, aminoethyl group, aminopropyl group,
Those having a hydrophilic group such as ruboxymethyl are preferred. Specific examples of hydrophilic resins include Arabico
, Casein, gelatin, starch derivatives, carboxy
Methylcellulose and its sodium salt, cellulose
Acetate, sodium alginate, vinyl acetate-male
Inic acid copolymers, styrene-maleic acid copolymers
, Polyacrylic acids and their salts, polymethacrylic acid
Luric acids and their salts, hydroxyethyl methacrylate
Homopolymers and copolymers of
Acrylate homopolymers and copolymers, hydrides
Roxypropyl methacrylate homopolymer and copolymer
Homopoly of polymer, hydroxypropyl acrylate
And copolymers, hydroxybutyl methacrylate
Homopolymers and copolymers of hydroxybutyl
Acrylate homopolymers and copolymers, polyesters
Tylene glycols, hydroxypropylene polymers
, Polyvinyl alcohol, at least the degree of hydrolysis
60% by weight, preferably at least 80% by weight
Hydrolyzed polyvinyl acetate, polyvinyl formal,
Polyvinyl butyral, polyvinyl pyrrolidone, acrylic
Luamide homopolymers and copolymers, methacryl
Amide homopolymers and polymers, N-methylol
Examples include homopolymers and copolymers of acrylamide.
I can make it. The content of the hydrophilic resin is the total solid content of the heat sensitive layer.
Is preferably 5 to 40% by mass,
More preferably, it is 30% by mass. Within the above range
And good on-press developability is obtained even when developing on-press,
Also, good film strength can be obtained. Such (H) hydrophobic hot-melt resin fine particles
Thermosensitive layer using a child and (J) a hydrophilic polymer matrix
(A) By containing the infrared absorber described above
Thus, image recording by infrared laser irradiation or the like becomes possible.
The infrared absorber used is the same as that exemplified above.
The content of the infrared absorber is based on the total solid content of the heat sensitive layer.
30 mass% or less, preferably 5 to 25 mass
% Is more preferable, and it is 7 to 20% by mass.
Further preferred. Within the above range, good sensitivity can be obtained.
It is. (K) Other components In addition to the above components, the thermal negative thermal layer is
If necessary, various compounds may be further added.
For example, coloring a dye with a large absorption in the visible light range
It can be used as an agent. Also phthalocyanine
Pigments, azo pigments, carbon black, titanium oxide, etc.
These pigments can also be suitably used as colorants. this
These colorants can distinguish between image and non-image areas after image formation.
Since it tends to stick, it is preferable to add it. Inclusion of colorant
The amount is 0.01 to 10 mass based on the total solid content of the heat-sensitive layer.
% Is preferred. Further, when the heat-sensitive layer is a photopolymerization layer, the coating is applied.
During the preparation or storage of liquids, radically polymerizable compounds
A small amount of thermal polymerization prevention to prevent unnecessary thermal polymerization of products
It is preferable to add an agent. As a suitable thermal polymerization inhibitor
Hydroquinone, p-methoxyphenol, di-t
-Butyl-p-cresol, pyrogallol, t-butyl
Catechol, benzoquinone, 4,4'-thiobis (3-
Methyl-6-tert-butylphenol), 2,2'-methyl
Renbis (4-methyl-6-tert-butylphenol),
N-nitroso-N-phenylhydroxylamine aluminum
Examples thereof include nium salts. The content of thermal polymerization inhibitor is
About 0.01 to about 5 mass% with respect to the total solid content of the heat layer
It is preferable. In addition, if necessary, inhibition of polymerization by oxygen
To prevent behenic acid or behenic acid amide high
Adds grade fatty acid derivatives, etc.
It may be unevenly distributed on the surface of the thermal layer. Including higher fatty acid derivatives
The amount is about 0.1 to about 10 with respect to the total solid content of the heat-sensitive layer.
It is preferable that it is mass%. [0196] Furthermore, the heat-sensitive layer can be softened as required.
Can contain plasticizer to give softness etc.
The For example, polyethylene glycol, tribute citrate
Chill, diethyl phthalate, dibutyl phthalate, phthalic acid
Dihexyl, dioctyl phthalate, tricresi phosphate
, Tributyl phosphate, trioctyl phosphate, olein
Acid tetrahydrofurfuryl and the like are used. The lithographic printing plate precursor of the present invention is provided with the heat sensitive layer.
To obtain a plate, dissolve each of the above components in a solvent,
What is necessary is just to apply | coat on a body. As the solvent used here,
Ethylene dichloride, cyclohexanone, methyl ethyl
Ketone, methanol, ethanol, propanol, ethanol
Tylene glycol monomethyl ether, 1-methoxy-
2-propanol, 2-methoxyethyl acetate, 1
-Methoxy-2-propyl acetate, dimethoxyethane
, Methyl lactate, ethyl lactate, N, N-dimethylacetate
Amides, N, N-dimethylformamide, tetramethyl
Urea, N-methylpyrrolidone, dimethylsulfoxy
, Sulfolane, γ-butyl lactone, toluene, water, etc.
The present invention is not limited to these
It is not a thing. Solvents are used alone or mixed
The The concentration in the solvent is preferably 1 to 50% by mass
The In the heat-sensitive layer coating solution, the treatment with respect to the development conditions.
In order to expand the stability of reason, JP-A-62-251740
Described in Japanese Patent Laid-Open No. 3-208514
Nonionic surfactants, such as those disclosed in JP 59-1210
44 and JP-A-4-13149.
Amphoteric surfactants can be added
The As specific examples of the nonionic surfactant,
Rubitan tristearate, sorbitan monopalmitate
, Sorbitan trioleate, monoglyceride stearate
Lido, polyoxyethylene nonylphenyl ether, etc.
Can be mentioned. As specific examples of the amphoteric surfactant,
Rudi (aminoethyl) glycine, alkylpolyamino ester
Tilglycine hydrochloride, 2-alkyl-N-carboxyl
Chill-N-hydroxyethylimidazolinium betai
N-tetradecyl-N, N-betaine type (for example,
Trade name Amorgen K, manufactured by Daiichi Kogyo Co., Ltd.). Nonionic surfactant and amphoteric surfactant
The proportion of the adhesive in the heat-sensitive layer coating solution is the heat-sensitive layer.
It is 0.05 to 15% by mass with respect to the total solid content of
Preferably, it is 0.1-5 mass%. Further, the heat-sensitive layer obtained by applying and drying is used.
The coating amount (solid content) varies depending on the application, but usually
0.5-5.0 g / m²Is preferred. Apply
Various methods can be used as the method, but examples
For example, bar coater coating, spin coating, spray coating,
-Ten coating, dip coating, air knife coating, bracing
Coating, roll coating, and the like. Application amount
As it decreases, the apparent sensitivity increases, but the image
The film properties of the heat-sensitive layer that performs the image recording function are deteriorated. Hereinafter, preferred examples of the metal support used in the present invention will be described.
An apparatus for manufacturing an aluminum support which is a suitable embodiment
explain. Aluminum which is a preferred embodiment of the metal support
The manufacturing process of the support is as follows: (1) Rolled and coiled
An aluminum plate wound on a multi-axis turret
(2) Each of the above treatments (machine
Surface roughening treatment, electrochemical surface roughening treatment, alkali etching
Treatment, acid etching treatment, desmut treatment, low heat
Formation of conductive hydrophilic film, pore wide treatment (acid treatment or
Or alkali treatment), sealing treatment, hydrophilic surface treatment, etc.)
After that, the aluminum plate was dried, and (3) aluminum
Coil the plate with the winding device consisting of the multi-axis turret.
Or rolled up to the flatness of the aluminum plate
After that, it is preferable to cut and accumulate to a predetermined length.
Good. If necessary, in the above process, undercoat layer
And lithographic printing with a process of forming a recording layer and drying treatment
After making the original plate, it is wound into a coil by the above winding device
You may take it. Further, in the production of an aluminum support.
Uses a device to inspect the surface of aluminum plate for defects
The defect is continuously inspected, and the edge of the defect found
Have one or more steps to label the part
Is preferred. Furthermore, in the production of the lithographic printing plate precursor according to the present invention,
The aluminum plate feeding process and winding
In the process, when replacing the aluminum coil, the aluminum coil
Even if the travel of the aluminum plate is stopped, the aluminum
A reservoir device that keeps the traveling speed of the nium plate constant.
It is preferable to provide an aluminum coil feeding work
After the process, the aluminum plate is ultrasonically or arc welded.
It is preferable to provide the process of joining by. Equipment used for the production of aluminum supports
Detects the travel position of the aluminum plate and determines the travel position.
It is preferable to have one or more devices to correct,
For the purpose of cutting the tension and controlling the running speed of the luminium plate
Drive device and dancer roll equipment for tension control
It is preferable to have at least one device. Also,
Whether the state of each process is the desired condition in the racking device
Record and before the aluminum coil is wound
Label the edge of the minium web and label
To be able to determine later whether the desired condition is after
It is also preferable to do this. In the present invention, the aluminum plate is a composite.
Charge together with paper and adsorb each other, then a predetermined length
It is preferable to cut and / or slit
That's right. Also, the label attached to the edge of the aluminum plate
After cutting to a predetermined length based on the information of the bell or
Before cutting the product, use the label as a mark to mark the non-defective part and defective part.
It is preferable to separate only the non-defective parts. In each process including the above-mentioned delivery process, etc.
Luminium plate size (thickness and width), aluminum
Depending on the material of the material or the running speed of the aluminum web,
It is important to set the optimum tension for each condition.
The Therefore, the drive for the purpose of tension cut and traveling speed control.
And a dancer roll for tension control.
Feedback control of the signal from the tension sensing device
It is preferable to provide a plurality of tension control devices. Drive device
Is a control method combining a DC motor and a main drive roller.
The method is generally used. Main drive roller is common
Made of rubber, but the aluminum web is wet
In a process that is in a state, a roller made by laminating non-woven fabric
Can be used. In addition, each pass roller
Generally, aluminum or metal is used.
This slip is used in a place where slippage is likely to occur.
To prevent this, attach a motor or reducer to each pass roller.
Next, rotation control is performed at a constant speed by a signal from the main drive unit.
An auxiliary drive device can be provided. Aluminum support used in the present invention
Is described in JP-A-10-114046
The arithmetic average roughness in the rolling direction (R_a) R₁age,
Arithmetic mean roughness in the width direction (R_a) R₂R
₁-R₂But R₁Is preferably within 30% of the
The average curvature in the rolling direction is 1.5 × 10^-3mm^-1Less than,
Average curvature in the width direction is 1.5 × 10^-3mm^-1Below, how to roll
The average curvature in the direction perpendicular to the direction is 1.0 × 10^-3mm^-1Less than
Is preferred. In addition, the above roughening treatment etc.
The produced aluminum support has a roll diameter of 20-8.
Using a straightening roll with 0 mm and rubber hardness of 50 to 95 degrees
It is preferable to correct. As a result, the planographic printing press
Even in the dynamic conveyance process, exposure deviation of the lithographic printing plate precursor occurs.
Supplying an aluminum coil substrate with flatness
can do. In Japanese Patent Laid-Open No. 9-194093
Web curl measuring method and apparatus, curl correction method
Methods and equipment and web cutting equipment are described.
Thus, these can also be used in the present invention. [0209] Continuously producing an aluminum support.
In doing so, check whether each process is operating under appropriate conditions.
The state of each process is monitored with a tracking device.
Record whether the desired conditions are met and wind the aluminum coil
Label on the edge of the aluminum web before being taken
Past the label to see if the desired condition is after the label.
So that it can be discriminated from the
The quality of the part can be determined. Aluminum used for the above roughening treatment
The plate processing equipment is used for liquid temperature, specific gravity, electrical conductivity, ultrasonic
Measure one or more of the propagation speeds to determine the composition of the liquid,
Feedback control and / or feed-forward
It is preferable to control the liquid concentration to a constant level
That's right. The acidic aqueous solution in the above processing apparatus contains aluminum
Components contained in aluminum plates such as ON
It dissolves as the surface treatment of the ruminium plate proceeds. There
And aluminum ion concentration and acid or alkali concentration
Water and acid or water and alkali
It is preferable to keep the liquid composition constant by adding intermittently. This
The concentration of acid or alkali added here is 10 to 98 quality.
The amount is preferably%. To control the concentration of the acid or alkali
For example, the following method is preferable. First, in advance
Conductivity for each component liquid in the concentration range scheduled for use,
Measure specific gravity or ultrasonic propagation velocity at each temperature
Data table. And the conductivity and ratio of the liquid to be measured
Produced in advance the propagation speed and temperature data of heavy or ultrasonic
Measure the concentration with reference to the data table of the non-measurement solution
To do. Measure the ultrasonic propagation time with high accuracy and high stability.
Is described in JP-A-6-235721.
Yes. Concentration measurement using the ultrasonic wave propagation speed
The system is disclosed in Japanese Patent Application Laid-Open No. 58-77656.
Has been described. In addition, multiple physical quantity data for liquid components
Create a data table showing the correlation between
To measure the concentration of multi-component liquid with reference to data table
Is described in JP-A-4-19559. Concentration measurement method using ultrasonic wave propagation velocity
Combining the method with the conductivity and temperature values of the liquid to be measured.
When applied to the roughening process of the Minium support,
Because it can be managed accurately in real time,
Products can be manufactured, leading to an improvement in yield. Ma
It is a combination of temperature, ultrasonic wave propagation velocity and conductivity.
Not only temperature and specific gravity, temperature and conductivity, temperature and conductivity
For each physical quantity such as specific gravity, data for each concentration and temperature
Create a data table and refer to the data table
The method of measuring the concentration of multi-component liquid by using an aluminum support
When applied to the roughening treatment process, the same effect as above is obtained.
It is done. Measure specific gravity and temperature and create in advance
Referring to the data table, the slurry of the object to be measured
-By determining the concentration, the slurry concentration can also be measured quickly.
You can do it quickly and accurately. The ultrasonic wave propagation velocity is measured by measuring the bubbles in the liquid.
Because it is easily affected, it is placed vertically and below
It is better to carry out in a pipe with a flow velocity upward from the
Good. The ultrasonic propagation velocity is measured when the pressure in the pipe is
1-10kg / cm²Preferably performed within the pressure range of
The ultrasonic frequency is preferably 0.5 to 3 MHz.
That's right. In addition, the specific gravity, conductivity, and ultrasonic propagation velocity are measured.
Because it is easily affected by temperature,
Measured in a pipe whose temperature fluctuation is controlled within ± 0.3 ℃
It is preferable to do this. Furthermore, conductivity and specific gravity, or
Conductivity and ultrasonic propagation velocity are measured at the same temperature.
Preferably in the same pipe or in the same pipe flow
It is particularly preferable to measure with. The pressure fluctuation during measurement is the temperature
Since it leads to the fluctuation | variation of a degree, the lower one is preferable.
Also, the flow velocity distribution in the piping to be measured is as small as possible
Is preferred. In addition, the above measurements include slurry, dust, and
Because it is easily affected by air bubbles, filters, deaerators, etc.
It is preferable to measure the liquid passed through. [Image recording and development processing] Planographic plate of the present invention
The printing plate precursor is recorded and imaged by a conventionally known method.
A lithographic printing plate can be obtained by developing. image
The recording method is not particularly limited, but infrared laser exposure is performed.
The method used is preferred. Specifically, for thermal recording heads, etc.
Direct image-like recording, scanning exposure with infrared laser, key
High intensity flash exposure such as Senon discharge lamp, infrared lamp
The exposure with a solid high-power infrared laser is suitable. Picture
Image recording can be based on digital data
The In addition, as a development process, a commonly used alkali
A method using a developer is preferred. [0215] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. 1. Manufacture of metal support (aluminum support) (Support Production Examples 1 to 5) Alloys of Compositions A to E shown in Table 1
The invention from five types of molten aluminum alloys containing components
The aluminum plate used in the examples and comparative examples of
In this way, it was produced. First, to the aluminum alloy molten metal,
DC casting method with molten metal treatment consisting of degassing and filtration
Thus, an ingot having a thickness of 500 mm was produced. Table of obtained ingots
After chamfering the surface by 10 mm, the ingot is heated to perform a soaking treatment.
Without starting, hot rolling is started at 400 ° C., and the thickness becomes 4 mm.
Until rolled. Next, cold rolled to a thickness of 1.5 mm
Then, after performing the intermediate annealing, 0.24 mm by cold rolling again
Finish and correct flatness to obtain various aluminum plates
It was. Compositions A to D include Al purity and the content of all impurity elements.
The amount is within the preferred range of the present invention. The composition E is A
l purity and 5 types of Fe, Si, Mn, Mg and Zn
Pure elements are within the preferred range of the present invention. [0216] [Table 1]The obtained aluminum plates of the compositions A to E
Each is represented by the procedures (1) to (6) below.
Surface treatment was performed. In addition, after each surface treatment and water washing
The liquid was removed with a nip roller. Wash the water with a spray tube
And sprayed with water. (1) Mechanical surface roughening treatment Silica sand with a specific gravity of 1.12 (abrasive, average particle size 25 μm)
A suspension with water is used as a polishing slurry to
While supplying to the surface of the aluminum plate,
Mechanical surface roughening using brush roller with rotating lash
Went. The nylon brush material used is 6,10-
Nylon, hair length is 50mm, hair diameter is
It was 0.48 mm. This nylon brush is φ300
Drill a hole in a stainless steel tube to make it dense.
It is hair. Also, the brush roller has Nairro
Three brushes are used and are provided at the bottom of the brush.
The distance between the two support rollers (φ200mm) is 300
mm. The brush roller rotates the brush
Nylon brush is made of aluminum
Control and roughen the load before it is pressed against the plate
Arithmetic average roughness (R_a) Is 0.45
It pressed down to become μm. The direction of brush rotation is
The direction of movement of the ruminium plate was the same. Then washed with water
Went. Also, the concentration of the abrasive should be
Refer to the table created from the relationship between degree, temperature and specific gravity
Determine the abrasive concentration from the temperature and specific gravity, and
Water and abrasives are added to the
The concentration was kept constant. Also, the abrasive is pulverized and the particle size is small
The surface shape of the roughened aluminum plate changes when it becomes smaller.
Since the cyclone is used,
Sequentially discharged out of the system. The particle size of the abrasive is in the range of 1 to 35 μm.
It was a go. (2) Alkali etching treatment NaOH 27 mass% and aluminum ion 6.5 quality
An aqueous solution containing 70% of the liquid in a quantity of
Spray on the aluminum plate
I did it. Later electrochemical roughening of aluminum plate
The dissolution amount of the surface to be treated is 8 g / m²And on the back
Dissolved amount is 2 g / m²Met. Alkali etching treatment
The concentration of the etching solution used in the
Degree, aluminum ion concentration, temperature, specific gravity, liquid
Refer to the table created from the relationship with the conductivity of
Determine the etchant concentration from the degree, specific gravity, and conductivity,
Water and 48 mass% NaOH water by feedback control
The solution was kept constant by adding. Then water
Washed. (3) Desmut treatment Use a nitric acid solution with a liquid temperature of 35 ° C to spray aluminum
The sheet was sprayed and desmutted for 10 seconds.
The aqueous nitric acid solution is overloaded from the electrolyzer used in the next step.
-Flow waste liquid was used. Next, desmut treatment liquid
Set up several spray tubes to be sprayed until the next process
The surface of the aluminum plate was not dried. (4) Electrochemical roughening treatment The trapezoidal alternating current shown in FIG. 1 and the electrolysis apparatus shown in FIG.
Continuous electrochemical surface roughening using 2 tanks
It was. As acidic aqueous solution, nitric acid aqueous solution of nitric acid 1 mass%
(Aluminum ion 0.5 mass% and ammonium
It contains 0.007% by mass of ions. ) Was used. Liquid temperature is 5
It was 0 ° C. In addition, AC current has a current value from zero to the peak.
Time tp and tp 'to reach the peak is 1 msec
The carbon electrode was the counter electrode. AC current peak
Current density when the aluminum plate is anode and cathode
Both 50A / dm²Met. Furthermore, the alternating current cathode
Hourly electricity (Q_C) And anode electricity (Q_A) (Q)_C
/ Q_A), Duty, frequency and total amount of electricity at the time of anode
The sum was as shown in Table 2. Then on the spray
Therefore, it was washed with water. Concentration control of nitric acid aqueous solution
Is a 67% by mass nitric acid stock solution and water in proportion to the amount of electricity applied.
Add an acidic aqueous solution (glass) of the same volume as the addition volume of nitric acid and water.
Acid aqueous solution) is sequentially overflowed from the electrolyzer.
It was discharged outside the disassembly system. Along with this,
Nitric acid concentration, aluminum ion concentration, temperature and liquid
Created from the relationship between the electrical conductivity of the liquid and the ultrasonic wave propagation velocity
Refer to the table, the temperature of the aqueous nitric acid solution, conductivity, ultrasonic transmission
Determine the concentration of the aqueous nitric acid solution from the carrying speed,
The concentration is kept constant by controlling the amount of additive added sequentially.
It was. [0222] [Table 2](5) Alkali etching treatment NaOH 26 mass% and aluminum ion 6.5 quality
An aluminum plate containing an aqueous solution containing 45% by weight and having a liquid temperature of 45 ° C.
Spray with a spray and apply alkali etching treatment.
I did it. The dissolution amount of aluminum plate is 1 g / m²In
It was. The concentration of the etchant is the NaOH concentration in advance.
The aluminum ion concentration, temperature, specific gravity, and liquid conductivity
Refer to the table created from the relationship, temperature, specific gravity and
Obtain etchant concentration from conductivity and feedback
Add water and 48 mass% NaOH aqueous solution.
And kept constant. Then, it washed with water. (6) Acidic etching treatment Sulfuric acid (sulfuric acid concentration 300g / L, aluminum ion concentration
15g / L) as an acidic etchant and spray it
The acid was sprayed onto the aluminum plate from the tube at 80 ° C for 8 seconds.
Etching treatment was performed. Acid etchant concentration
The sulfuric acid concentration, aluminum ion concentration and temperature
A table created from the relationship between the degree of gravity, specific gravity, and liquid conductivity
See, acid etching from temperature, specific gravity and conductivity
The liquid concentration is obtained, and water and 50 quality by feedback control.
A volume% sulfuric acid was added to keep it constant. Then wash with water
went. Subsequently, a hydrophilic film having a low thermal conductivity is provided.
Therefore, the surface treatment is performed according to the following procedures (7) to (9).
Luminium supports [P-1] to [P-5] were obtained. (7) Anodizing treatment Aqueous solution of 170 g / L sulfuric acid (aluminum ion
Including 0.5% by mass. ) As an anodizing solution,
Using DC voltage, current density 30A / dm², Temperature 40
Anodizing of aluminum plate was performed under the conditions of ℃ and 40 seconds.
An anodized film was formed. Concentration of anodizing solution
The sulfuric acid concentration, aluminum ion concentration and temperature
A table created from the relationship between the degree of gravity, specific gravity, and liquid conductivity
Referring to the temperature, specific gravity and conductivity to determine the liquid concentration,
Add water and 50% sulfuric acid by feedback control
And kept constant. Then rinsed by spray
Went. (8) Pore wide processing The anodized aluminum plate is treated with NaOH of pH 13
Immerse in an aqueous solution at 30 ° C for 1 minute for pore wide treatment
went. (9) Hydrophilic surface treatment An aqueous solution with a sodium silicate concentration of 2.5% by mass at 70 ° C.
Hydrophilic surface treatment was performed by treating for 12 seconds. after that,
Washing with water, drying, aluminum support [P-1] ~
[P-5] was obtained. (Support Production Example 6) (1) Mechanical rough surface
The same as in Support Production Example 1 except that the treatment was not performed
By the method, an aluminum support [P-6] was obtained. (Support Production Example 7) (7) Anodizing treatment
In practice, the electrolysis condition is 5 A / dm.²Electrolysis time is 14
0 seconds, and the above (8) pore wide treatment is performed at 60 ° C.
Except for immersion for 1 minute in 170 g / L sulfuric acid,
In the same manner as in Support Production Example 1, aluminum support
Body [P-7] was obtained. (Support Production Example 8) (7) Anodizing treatment
In practice, an aqueous solution of oxalic acid concentration 50 g / L (aluminum
It contains 4.5% by mass of nium ions. ) With anodizing solution
The temperature is 50 ° C. and the current density is 12 A / dm.²,
The electrolysis time is 60 seconds, and the above (8) pore-wide treatment is performed.
Except that the temperature of the NaOH aqueous solution is 50 ° C.
In the same manner as in Support Production Example 1, aluminum was
A support [P-8] was obtained. (Support Production Example 9) (8) Pore wide
After processing, K_ThreeAlF₆/ NaH₂PO_Four(0.1 quality
% By weight / 10% by weight) aqueous solution at 100 ° C. for 10 seconds
After washing with water, in the above (9) hydrophilic surface treatment,
Except for the treatment time of 10 seconds, the same as Support Production Example 1
The aluminum support [P-9] was obtained by the same method.
It was. (Support Production Example 10) K_ThreeAlF₆/ Na
H₂PO_FourInstead of treating with aqueous solution, sodium fluoride
M / 3 sodium silicate (2% by mass / 2.5% by mass)
Made of support except treated with aqueous solution at 100 ° C for 1 minute
In the same manner as in Example 9, the aluminum support [P-
10] was obtained. (Support Production Example 11) (7) Anodization
Instead of processing, S is obtained by magnetron sputtering.
iO₂Support except that the film was made on an aluminum plate
Aluminum support by the same method as body production example 1
[P-11] was obtained. (Support Production Example 12) (8) Pore-wai
(9) Instead of hydrophilic surface treatment,
Dalsilica (ST-20, manufactured by Nissan Chemical Industries, particle size 10-2
0 g) 20 g, polystyrene hollow particle dispersion (JS
R, particle size 0.3 μm, solid content 20%) 10 g
A mixed solution of 4 g of polyvinyl alcohol and 65 g of water
After coating with a wire bar and drying to form a film
The outside is made of aluminum by the same method as in Support Production Example 1.
A support [P-12] was obtained. (Support Production Example 13) (8) Pore-wai
(9) In place of hydrophilic surface treatment,
Tylene hollow particle dispersion (manufactured by JSR, particle size 0.3 μm
m, solid content concentration 20%) as solvent (methanol / water = 9 /
1 (mass ratio)) and the coating solution diluted 10 times
After applying and drying with-, Zirconium fluoride with a concentration of 1 g / L
Treated with aqueous ammonium phosphate solution at 60 ° C. for 30 minutes,
Except for forming a film, the same method as in Support Production Example 1 was used.
As a result, an aluminum support [P-13] was obtained. (Support Production Example 14) (7) Anodization
In the treatment, except that the electrolysis time was 350 seconds
Aluminum support by the same method as body production example 1
[P-14] was obtained. (Comparative Example Support Production Example 1) (7) Positive
In polar oxidation treatment, the electrolysis time is 20 seconds and
(8) Support except that no pore-wide treatment was performed
Aluminum for the comparative example was produced in the same manner as in Production Example 1.
A support [R-1] was obtained. (Comparative Example Support Production Example 2) (7) Positive
For magnetron sputtering instead of polar oxidation treatment
Create a calcium silicate film on the aluminum plate.
Except for the above, in the same manner as in Support Production Example 1, Comparative Example
An aluminum support [R-2] was obtained. 2. Measurement of thermal conductivity in the film thickness direction Aluminum support [P-1] to [P-] obtained above.
14] and [R-1] and [R-2]
Measure the thermal conductivity in the film thickness direction by the following method.
It was. First, aluminum supports [P-1] to [P-1]
4] and [R-1] and [R-2] and only the film thickness
Create two different aluminum supports, two each
did. Aluminum supports that differ only in film thickness are aluminum
Ni supports [P-1] to [P-10] and [P-1]
4] and [R-1]
0.5 times and 2 times the aluminum support [P-1
1] and [R-2], sputtering time
0.5 times and 2 times, and an aluminum support [P-
12] and [P-13], the solid content of the coating solution
Concentrate to 0.5 and 2 times, otherwise each aluminum
It was prepared by the same method as that for the um support. Next, the membrane
Three types of aluminum supports (aluminum
Um supports [P-1] to [P-14] and [R-
1] and [R-2] and the respective aluminum obtained above
Two types of aluminum that differ only in film thickness for the film support
For the measurement with the apparatus shown in FIG.
From the formula (1), the aluminum supports [P-1] to [P
-14] and [R-1] and [R-2]
The thermal conductivity in the film thickness direction was calculated. Note that measurement is performed on the sample.
The measurement was performed at five different points and the average value was used. Table 3 shows the results.
It was shown to. 3. Measurement of film thickness Aluminum support [P-1] to [P-] obtained above.
14] and [R-1] and [R-2]
Cross section using a scanning microscope (T-20, manufactured by JEOL Ltd.)
The film thickness at 50 locations, and calculate the average film thickness.
I put it out. The results are shown in Table 3. [0242] [Table 3] 4. Creating a lithographic printing plate precursor (Example 1) A thermosensitive layer solution [A] having the following composition was prepared, and
Using a wire bar on the ruminium support [P-1]
Apply and dry at 115 ° C for 45 seconds in a warm air dryer
To form a heat-sensitive layer (photopolymerization layer)
Obtained. The coating amount after drying is 1.2 g / m²Met. <Thermosensitive layer solution [A] composition> Infrared absorber [IR-6] represented by the following formula 0.
08g -Radical generator represented by the following formula [IO-6]
0.30g Dipentaerythritol hexaacrylate
00g A molar ratio of allyl methacrylate to methacrylic acid 80:
20 copolymers (weight average molecular weight 120,000) 1.00
g ・ Victoria Pure Blue Naphthalenesulfonate
  0.04g ・ Fluorine surfactant (Megafac F-176, Dainichi
0.01g made by this ink chemical industry) ・ Methyl ethyl ketone 9.0g ・ Methanol 10.0g ・ 4.0-g of 1-methoxy-2-propanol ・ 4.0 g of 3-methoxy-1-propanol [0245] Embedded image (Examples 2 to 14 and Comparative Example 1 and
2) Aluminum support, infrared absorber and radical
Same as Example 1 except that the generator is as shown in Table 4.
Each planographic printing plate precursor was obtained by the same method. Infrared used
The structural formulas of the line absorber and radical generator are as follows:
It is. However, in Examples 7 and 8, heat sensitivity
After forming the layer, polyvinyl alcohol on the heat sensitive layer
3% by weight of water (degree of saponification 98 mol%, degree of polymerization 500)
The dry coating weight of the solution is 2.5 g / m²Apply to be
And dry at 120 ° C for 3 minutes to form an overcoat layer
Thus, a lithographic printing plate precursor was obtained. [0247] Embedded image (Example 15) Thermal layer solution having the following composition
[B] was prepared, and the wax was placed on the aluminum support [P-1].
Apply using an ear bar and use a hot air dryer
Dry at 45 ° C for 45 seconds to form a heat-sensitive layer (acid cross-linked layer)
A lithographic printing plate precursor was obtained. The coating amount after drying is 1.3g
/ M²Met. <Thermosensitive layer solution [B] composition> -Infrared absorber represented by the above formula [IR-6] 0.
07g -Acid generator [SH-1] represented by the following formula 0.3
g ・ Crosslinking agent represented by the following formula [KZ-9] 0.5 g ・ Alkali-soluble polymer (Marcalinker MS-4
P, manufactured by Maruzen Petrochemical Co., Ltd.) 1.5 g ・ Victoria Pure Blue Naphthalenesulfonate
(Hodogaya Chemical Co., Ltd.) 0.035g ・ Fluorine surfactant (Megafac F-177, Dainichi
0.01g made by this ink chemical industry) ・ Phthalic anhydride 0.05g ・ Methyl ethyl ketone 12g ・ Methanol 10g ・ 4g of 1-methoxy-2-propanol ・ 4 g of 3-methoxy-1-propanol [0250] Embedded image (Examples 16 to 28 and Comparative Examples 3 and
4) Aluminum support, infrared absorber and acid generation
The same as in Example 15 except that the agent was as shown in Table 4.
Each planographic printing plate precursor was obtained by this method. Infrared used
The structural formulas of the absorbent and the acid generator are as described above.
The 5. Exposure and development processing Each lithographic printing plate precursor obtained as described above corresponds to the image recording layer.
Next, perform image exposure and development by the following method,
A plate printing plate was obtained. (Examples 1 to 14 and Comparative Example 1 and
2) Lithographic stamps of Examples 1 to 14 and Comparative Examples 1 and 2
The printing plate precursor was equipped with a water-cooled 40W infrared semiconductor laser.
A Trendsetter 3244VFS manufactured by Creo
Using, output 9W, outer drum rotation speed 210rpm, plate
Surface energy amount 100mJ / cm², Resolution 2400d
The exposure was performed under pi conditions. Then Fuji Photo Film
Development using an automatic processor Stablon 900N manufactured by Co., Ltd.
I did it. As a developer, Fuji Photo Film Co., Ltd.
DN-3C 1: 1 water dilution was used, and the developing bath temperature was
The temperature is 30 ° C and the finisher is Fuji Photo Film
A 1: 1 water dilution of FN-6 manufactured by Mu Co., Ltd. was used. (Examples 15 to 28 and Comparative Examples 3 and
4) The flatness of Examples 15 to 28 and Comparative Examples 3 and 4
Examples 1 to 14 and comparison described above
In the same manner as in the planographic printing plate precursors of Examples 1 and 2,
Shined. After exposure, use a Wisconsin oven
Heat treatment at 288 ° F. (142.2 ° C.) for 75 seconds
(Preheating) was performed. Fuji Photo Hui after preheating
Development using Lum's automatic processor LP940H
Went. As a developer, Fuji Photo Film Co., Ltd.
A DP-8 1: 8 water dilution was used, and the temperature of the developing bath was 30.
The finisher is Fuji Photo Film.
A 1: 1 water dilution of FP-2W manufactured by Co., Ltd. was used. 6. Evaluation of planographic printing plate precursors The sensitivity of the lithographic printing plate precursor obtained above, as well as the above
Presence or absence of residual film and printing durability of lithographic printing plates obtained in
Was evaluated by the following method. (1) Sensitivity The lithographic printing plate precursor is equipped with a water-cooled 40W infrared semiconductor laser.
The trend setter 3244V manufactured by Creo
Using FS, exposure is performed at a resolution of 2400 dpi.
It was. At this time, the exposure output and the outer drum rotation speed are changed.
By changing the plate surface energy amount,
Sensitivity was evaluated by the lowest exposure possible. Plate energy
-The smaller the amount, the higher the sensitivity. result
Is shown in Table 4. (2) Presence or absence of residual film View non-image area of planographic printing plate with optical microscope at 100x magnification
The presence or absence of a pot-like residual film in an area of 1 mm square
Solid. The results are shown in Table 4. In Table 4, there is a pot-like residual film.
What was done was marked with ◯, and what was there was marked with x. (3) Printing durability Printing machine made by Komori Corporation using lithographic printing plate
Printing was performed using Lithrone. As an ink, Dainichi
This ink chemical industry company Geos G (N) was used. 500
Remove the printed material every 0 sheets, visually observe the printed material,
Printing durability was evaluated based on the number of sheets that gave a good print. Result
The results are shown in Table 4. As is apparent from Tables 3 and 4,
The lithographic printing plate precursor (Examples 1 to 28) of the present invention is sensitive to sensitivity.
Excellent, difficult to form residual film, and excellent printing durability. This
In contrast, the film thickness of the hydrophilic film on the aluminum support
When the thermal conductivity in the direction is too large (Comparative Examples 1 and 3)
Is inferior in sensitivity and has a plate surface energy amount of 100 mJ / cm.²
With this exposure, image formation is not possible and the printing durability is inferior.
It was. If it is too small (Comparative Examples 2 and 4),
Residual film was generated. [0259] [Table 4][0260] [Table 5] [0261] EFFECT OF THE INVENTION Thermal negative type image on a metal support.
The planographic printing plate precursor of the present invention provided with an image recording layer comprises the gold plate.
The genus support has a thermal conductivity in the film thickness direction of 0.05 to 0.5 W /
Because it has a hydrophilic coating that is (m · K), laser exposure
Insoluble in the developer in the part is high, as a result,
High sensitivity, excellent printing durability and stain resistance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a waveform diagram showing an example of a trapezoidal wave used for electrochemical surface roughening treatment using alternating current preferably used in the present invention. FIG. 2 is a side view showing an example of a radial type cell in an electrochemical surface roughening process suitably used in the present invention. FIG. 3 is a schematic view 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 according to the invention. [Description of Symbols] 11 Aluminum plate 12 Radial drum rollers 13a and 13b Main electrode 14 Acidic aqueous solution 15 Solution supply port 16 Slit 17 Solution passage 18 Auxiliary anodes 19a and 19b Thyristor 20 AC power source 21 Main electrolytic cell 22 Auxiliary anode cell 30 Thermocomparator 31 Chip 32 Reservoir 33 Electric Heater 34 Heating Jacket 35 Thermocouple 36 Heat Sink 37 Film 38 Metal Substrate 39 Contact Thermometer 40 Chip Tip Temperature Recorder 41 Heat Sink Temperature Recorder 42 Reservoir Temperature Recorder

Claims (1)

What is claimed is: 1. A hydrophilic film having a thermal conductivity in the film thickness direction of 0.05 to 0.5 W / (m · K) on a roughened metal substrate. A lithographic printing plate precursor comprising an image recording layer which is cured by infrared laser exposure on a metal support obtained by the formation.