JP2003285569A - Support for lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a support for a lithographic printing plate to be used as an original plate for the lithographic printing plate showing outstanding resistance to dirt and plate wear when the plate is obtained. <P>SOLUTION: The support for a lithographic printing plate is manufactured by roughening the surface of an aluminum sheet and oxidizing an anode, then making the sheet hydrophilic in an aqueous alkali metallic silicate solution with a concentration of 0.6 to 5.0 mass%, and treating the sheet in an aqueous solution containing carboxylic acid and/or carboxylate. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a support for a lithographic printing plate.
Body and lithographic printing plate precursor, especially lithographic printing plate
Can achieve both stain resistance and printing durability.
Lithographic printing plate support and planographic printing plate precursor using the same
About. [0002] Conventionally, the developability of lithographic printing plate precursors has been improved.
The surface of the lithographic printing plate support after anodizing
Apply hydrophilization treatment as represented by silicate treatment
It has been known. Hydrophilization treatment on the surface of the lithographic printing plate support
If applied, the non-image area of the planographic printing plate is hydrophobic during printing.
The ink is difficult to adhere and the stain resistance is improved.
It is. However, the surface of the lithographic printing plate support is hydrophilized.
When processed, the image that is hydrophobic in the lithographic printing plate precursor
Adhesion between the image recording layer and the support is reduced, and a lithographic printing plate is obtained.
In some cases, the printing durability was reduced. Therefore
Stain resistance and printing durability when using a lithographic printing plate
There is a demand for a lithographic printing plate precursor that is excellent in deviation. By the way, the infrared absorption present in the heat-sensitive layer.
The agent exhibits its photothermal conversion effect and generates heat upon exposure.
The exposed part of the heat-sensitive layer is alkali-solubilized by heat, and a positive image
So-called thermal positive type image recording layer
The radical generator and acid generator are radicalized by the heat.
And acid generation, thereby causing radical polymerization reaction and acid crosslinking
Thermal reaction that insolubilizes and forms a negative image
Contains infrared absorbers such as negative-type image recording layers
A lithographic printing plate precursor having an image recording layer
This is likely to occur. One of the reasons is that these pictures
The infrared absorber used in the image recording layer has a relatively low molecular weight.
Because it is a large compound, it is difficult to dissolve in the developer and during development
It is easy to adsorb on the surface of the non-image area of the lithographic printing plate.
I can get lost. Conventionally, images containing such infrared absorbers
In a lithographic printing plate precursor having an image recording layer, the above-mentioned
A lithographic printing plate precursor with excellent stain resistance and printing durability
Realizing the version was particularly difficult. In Japanese Patent Laid-Open No. 10-171104
Before or after treatment with aqueous carboxylate solution
And SiO₂/ M₂O (M represents an alkali metal)
Ratio is 0.3-4.0, the concentration of alkali metal silicate is
With an aqueous metal silicate solution of 0.05 to 0.5 wt%
Hydrophilic treatment or carboxylate aqueous solution
Hydrophilic treatment with liquid, then hydrophilic polymer aqueous solution
By performing the hydrophilic treatment with, stop dirtiness,
A method for improving printing durability and the like has been proposed. But
However, the method described in the above publication is a so-called control.
Stop for the image recording layer of the conventional positive type
The purpose is to improve stain resistance, printing durability, etc.
Images containing infrared absorbers that are prone to smudges during printing
For the recording layer, both stain resistance and printing durability
It was not excellent. [0005] Therefore, the present invention is not intended to be achieved.
For stain resistance and printing durability when used as a printing plate
Excellent lithographic printing plate precursor, especially containing infrared absorber
Lithographic printing plate precursor having an image recording layer and use thereof
It is intended to provide a lithographic printing plate support
The [0006] [Means for Solving the Problems] The present inventor
As a result, the planographic printing plate precursor and the aluminum plate are roughened
And after anodizing treatment, the concentration is 0.6-5.0 quality
Hydrophilic treatment with aqueous solution of alkali metal silicate
Carboxylic acid and / or carboxylate
Planar obtained by treatment with aqueous solution
When using a plate printing plate support, a planographic printing plate
Both stain resistance and printing durability should be excellent
I found. In addition, the present inventor has determined that the lithographic printing plate precursor is infrared.
When having an image recording layer containing a line absorber
In addition, the inventors have found that the above effect is particularly great. Inventor
Completed the present invention based on these findings. That is, the present invention provides the following (1) to (4).
provide. (1) A roughening treatment on an aluminum plate and
After anodizing, the concentration is 0.6 to 5.0% by mass
Hydrophilic treatment with alkali metal silicate aqueous solution,
Further, it contains carboxylic acid and / or carboxylate
Support for lithographic printing plates obtained by treatment with aqueous solution
body. (2) The lithographic printing plate support described in (1) above
A lithographic printing plate precursor comprising an image recording layer provided on a holder. (3) The lithographic printing plate support and the image
Between the recording layer, the component having an acid group and the onium group
An intermediate containing a polymer compound having a constituent component
The lithographic printing plate precursor as described in (2) above having a layer. (4) The flat surface described in (2) or (3) above.
After exposure to the plate printing plate precursor, the alkali metal
Of a lithographic printing plate developed using a developer containing no acid salt
Processing method. [0012] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below.
To do. [Support for lithographic printing plate] <Surface treatment> In the lithographic printing plate support of the present invention,
By applying a surface treatment to the aluminum plate described later
Then, a grain shape is formed on the surface of the aluminum plate. Book
The lithographic printing plate support of the invention is roughened on an aluminum plate
After the treatment and the anodizing treatment, the concentration is 0.6 to 5.
Hydrophilization treatment with 0% by weight alkali metal silicate aqueous solution
In addition, carboxylic acid and / or carboxylic acid
It can be obtained by treatment with an aqueous solution containing salt.
The manufacturing process of the support is not particularly limited,
Various other processes may be included. The surface grain shape
As a typical method for forming aluminum plates
Mechanical surface roughening, alkali etching, acid
Electrochemical roughening using desmut treatment and electrolyte
Method of sequentially applying treatment, mechanical roughening treatment on aluminum plate
, Alkaline etching treatment, desmutting treatment with acid
And electrochemical roughening treatment using different electrolytes.
Several times, alkali etching treatment on aluminum plate
Electricity, desmutting with acid and electrolyte
A method of sequentially performing chemical surface roughening treatments, aluminum plate
Lukari etching treatment, acid desmutting treatment and
Perform electrochemical surface roughening multiple times using different electrolytes
The present invention is not limited to these methods.
Yes. In these methods, the electrochemical roughening treatment
Thereafter, alkaline etching treatment and acid
Smut treatment may be applied. Hereafter, each process of surface treatment
Will be described in detail. <Mechanical roughening treatment> Mechanical roughening treatment
Is cheaper and average compared to electrochemical roughening treatment
Form an uneven surface with a wavelength of 5 to 100 μm
Therefore, it is effective as a roughening treatment means. machine
As an example of a rough surface treatment method, for example, an aluminum surface
The wire brush grain method, scratched with metal wire
A bow that grinds the aluminum surface with an abrasive ball and abrasive.
Lugrain method, JP-A-6-135175 and special
Nylon described in Japanese Patent Publication No. 50-40047
Brush grain method with grained surface with brush and abrasive
Can be used. Also, the uneven surface is an aluminum plate
It is also possible to use a transfer method that is pressed against the substrate. That is,
Sho 55-74898, JP-A 60-36195, Special
Those described in each publication of Japanese Utility Model Publication No. 60-20396
In addition to the above method, the transfer is performed several times.
No. 55871, characterized in that the surface is elastic
Japanese Patent Application No. 4-204235 (Japanese Patent Laid-Open No. 6-2416)
The method described in the publication No. 8) is also applicable. Also, electric discharge machining, shot blasting, laser
Using a laser, plasma etching, etc.
A method of performing repetitive transfer using an engraved transfer roll,
The uneven surface with fine particles applied to the aluminum plate
Contact the surface and repeatedly apply pressure several times above it.
Uneven pattern corresponding to the average diameter of fine particles on a minium plate
It is also possible to use a method of transferring the ink repeatedly multiple times.
The As a method of imparting fine irregularities to the transfer roll,
JP-A-3-8635, JP-A-3-66404, JP-A-3-66404
Known in Japanese Laid-Open Patent Publication No. 63-65017
This method can be used. Also, the die on the roll surface
Fine grooves from two directions using tools, tools, lasers, etc.
You may cut and give a square unevenness to the surface. This role table
The surface was formed by performing a known etching process or the like.
You may perform the process in which a square unevenness | corrugation is rounded.
In addition, to increase the hardness of the surface,
You may perform rom plating etc. In addition, mechanical coarse
As the surface treatment, Japanese Patent Laid-Open No. 61-162351,
Those described in Japanese Patent Application Laid-Open No. 63-104889
The method can also be used. In the present invention, productivity, etc.
Can be used in combination with each of the methods described above
Yes. These mechanical roughening treatments are electrochemical roughening
It is preferably done before treatment. Hereinafter, it is preferably used as a mechanical surface roughening treatment.
The brush grain method will be described. Bracelet
The in method generally uses nylon (a quotient) on the surface of a cylindrical body.
Name), from synthetic resins such as propylene and vinyl chloride resin
Roller-shaped bush with a lot of brush hairs such as synthetic resin hair
Use a brush to contain abrasive in the rotating roller brush
While spraying the slurry liquid
This is done by rubbing one or both of the surfaces. Above
A polishing layer on the surface instead of a brush and slurry.
It is also possible to use a polishing roller that is a roller provided with
The Flexural modulus is preferred when using a roller brush
Or 10,000-40,000kg / cm²More like
Preferably 15,000-35,000kg / cm²In
And the strength of the hair is preferably 500 g or less, more
Brush hair that is preferably 400 g or less is used. bra
The diameter of the bristle is generally 0.2 to 0.9 mm
The The length of the brush bristles depends on the outer diameter and body of the roller brush.
Can be appropriately determined according to the diameter of the
Is 10 to 100 mm. Known abrasives can be used.
For example, pumiston, quartz sand, aluminum hydroxide, aluminum
Lumina powder, silicon carbide, silicon nitride, volcanic ash, carbora
Abrasives such as second-hand and dam sand; use a mixture of these
You can. Of these, pumiston and silica sand are preferable.
In particular, silica sand is harder and less likely to break than Pamiston.
Therefore, it is preferable in terms of excellent surface roughening efficiency. Average grain of abrasive
The diameter is excellent in roughening efficiency and the graining pitch is narrow.
It is preferably 3 to 50 μm because it can be used.
6 to 45 μm is more preferable. Abrasive
For example, it is suspended in water and used as a slurry liquid.
In addition to abrasives, slurry liquids include thickeners and dispersants (eg
For example, surfactants), preservatives, etc. can be included.
The The specific gravity of the slurry is preferably 0.5-2
Yes. As an apparatus suitable for the mechanical surface roughening treatment,
For example, the device described in Japanese Patent Publication No. 50-40047 is disclosed.
Can be listed. <Electrochemical roughening treatment> Electrochemical roughening
Generalization treatment (hereinafter also referred to as “electrolytic roughening treatment”)
Electricity used in electrochemical surface roughening using ordinary alternating current
Dissolution can be used. Among them, hydrochloric acid or nitric acid
It is preferable to use a main electrolyte. In the present invention
Electrolytic surface roughening treatment is acidic before and after cathodic electrolysis.
First and second electrolytic treatments with alternating waveform current in solution
It is preferable to perform the operation. Aluminum by cathodic electrolysis
Hydrogen gas is generated on the surface of the nium plate to generate smut.
The surface condition is made uniform, and the subsequent alternating waveform
Uniform electrolytic surface roughening is possible during electrolysis with current.
The This electrolytic surface roughening treatment is, for example, Japanese Patent Publication No. 48-28.
No. 123 and British Patent No. 896,563
Electrochemical grain method (electrolytic grain) described in
Law). This electrolytic grain method uses sine
A waveform alternating current is used.
Using special waveforms as described in the 8602 publication
You may go. Japanese Patent Laid-Open No. 3-79799
Can also be used. Also special
No. 55-158298, Japanese Patent Laid-Open No. 56-28898
JP, 52-58602, JP 52-1523
02, JP 54-85802, JP 60-19
0392, JP 58-120531, JP 63
JP-A-176187, JP-A-1-5889, JP-A-1-5889
280590, JP-A-1-118489, JP-A-1
-148592, JP-A-1-17896, JP-A-1
1-188315, JP-A 1-154797, JP
Hei-2-235794, JP-A-3-260100,
Kaihei 3-253600, JP-A-4-72079,
Kaihei 4-72098, JP-A-3-267400,
The method described in each gazette of Kaihei 1-141094
Applicable. In addition to the above,
Alternating current of special frequency proposed as a manufacturing method
It is also possible to perform electrolysis using. For example, US patents
Nos. 4,276,129 and 4,676,4.
No. 879. Various proposals have been made for electrolytic cells and power sources.
However, U.S. Pat.
Sho 56-123400, JP-A 57-59770,
JP-A-53-12738, JP-A-53-32821
No., JP-A 53-32822, JP-A 53-3282
No. 3, JP-A 55-122896, JP-A 55-13
2884, JP-A-62-2127500, JP-A-1-
No. 52100, JP-A-1-52098, JP-A-60-
67700, JP-A-1-230800, JP-A-3-230
Use those described in each publication of No. 257199
Can be. JP-A 52-58602, JP
No. 52-152302, JP-A 53-12738
, JP-A-53-12739, JP-A-53-3282
No. 1, JP-A 53-32822, JP-A 53-328
33, JP-A 53-32824, JP-A 53-32
825, JP 54-85802, JP 55-1
No. 22896, Japanese Patent Laid-Open No. 55-132848, Japanese Patent Publication No. 4
No. 8-28123, Japanese Examined Patent Publication No. 51-7081, JP-A-5
2-133838, JP-A-52-133840,
JP-A-52-133844, JP-A-52-13384
5, JP 53-149135, JP 54-14
Those described in each publication of No. 6234 are also used.
be able to. Examples of acidic solutions that are electrolytes include nitric acid and salts.
In addition to acids, U.S. Pat. No. 4,671,859,
4,661,219, 4,618,405,
No. 4,600,482, No. 4,566,960,
No. 4,566,958, No. 4,566,959
No. 4,416,972, No. 4,374,71
No. 0, No. 4,336,113, No. 4,184,9
Use the electrolyte described in each specification of No. 32 etc.
You can also. The concentration of the acidic solution is 0.01 to 2.5% by mass.
Is preferred, but it is used in the above smut removal process.
Considering the application, it is 0.05 to 1.0% by mass.
Is preferred. The liquid temperature is preferably 20 to 80 ° C.
Moreover, it is more preferable that it is 30-60 degreeC. An aqueous solution mainly composed of hydrochloric acid or nitric acid is concentrated.
Nitric acid in an aqueous solution of hydrochloric acid or nitric acid with a degree of 1-100 g / L
Such as aluminum, sodium nitrate, ammonium nitrate
Nitrate compounds with nitrate ions or aluminum chloride
Hydrochloric acid ions such as sodium chloride, sodium chloride and ammonium chloride
1 g / L of at least one hydrochloric acid compound having
It can be added and used within the range up to the sum. Ma
In addition, aqueous solutions mainly composed of hydrochloric acid or nitric acid include iron, copper,
Manganese, nickel, titanium, magnesium, silica, etc.
Even if the metal contained in the aluminum alloy is dissolved
Good. Preferably, the concentration of hydrochloric acid or nitric acid is 0.5 to 2
3-50 g / L of aluminum ions in the aqueous solution
So that aluminum chloride, aluminum nitrate, etc.
It is preferable to use the added liquid. Further, a compound capable of forming a complex with Cu is added.
Aluminum containing a large amount of Cu
Uniform graining is also possible for um plates. Cu and
Examples of compounds that can form complexes include, for example, ammonia.
A; methylamine, ethylamine, dimethylamine, di
Ethylamine, trimethylamine, cyclohexylamine
, Triethanolamine, triisopropanolamine
Ammoni such as EDTA (ethylenediaminetetraacetic acid)
A hydrogen atom is placed in a hydrocarbon group (aliphatic, aromatic, etc.)
Amines obtained by conversion; sodium carbonate, potassium carbonate
And metal carbonates such as potassium hydrogen carbonate.
In addition, ammonium nitrate, ammonium chloride, ammonium sulfate
Such as ammonium, ammonium phosphate, ammonium carbonate
Also included are ammonium salts. The temperature is preferably 10-60 ° C.
More preferably, 20 to 50 ° C is more preferable. AC power used for electrochemical surface roughening treatment
Source wave is not particularly limited, sine wave, rectangular wave, trapezoidal wave,
Triangular waves are used, but rectangular or trapezoidal waves are preferred.
And trapezoidal waves are particularly preferred. The trapezoidal wave is shown in FIG.
Say things. In this trapezoidal wave, the current peaks from zero
Time to reach (TP) is 1-3msec
Is preferred. If it is less than 1 msec, an aluminum plate
A chatter mark that occurs perpendicular to the direction of travel
Is likely to occur. When TP exceeds 3 msec, especially
When nitric acid electrolyte is used, spontaneous increase in electrolytic treatment
In electrolytes represented by ammonium ions
It becomes easy to be affected by ingredients, and uniform graining is performed.
It becomes difficult. As a result, stain resistance when using a lithographic printing plate
Tend to decrease. The duty ratio of trapezoidal wave alternating current is 1: 2 to 2: 1.
Can be used, but JP-A-5-195300
As described in the official gazette,
Duty ratio in indirect power supply method without talol
Is preferably 1: 1. Trapezoidal AC frequency is 0.
It is possible to use one of 1 to 120 Hz, but 5
0-70Hz is preferable on an installation. Lower than 50Hz
And the carbon electrode of the main electrode is easily dissolved, and 7
If the frequency is higher than 0 Hz, the inductance component on the power supply circuit
The power supply cost becomes high. However
By setting the frequency to 100-300 Hz,
The standard deviation of the wave structure opening diameter can be set to 0.2 or less.
Yes. One or more AC power supplies are connected to the electrolytic cell.
be able to. Join the aluminum plate facing the main pole
Controls the current ratio between the anode and cathode of the alternating current and makes it uniform
Graining and melting main pole carbon
For the purpose of installing an auxiliary anode as shown in FIG.
However, it is preferable to divert part of the alternating current. FIG.
11 is an aluminum plate and 12 is a radius.
Rudrum roller, 13a and 13b are main poles
14 is an electrolytic treatment solution, and 15 is an electrolyte supply port.
16 is a slit, 17 is an electrolyte passage,
18 is an auxiliary anode, 19a and 19b are siris
20 is an AC power source, and 40 is a main electrolytic cell.
50 is an auxiliary anode tank. Rectifier or switch
A part of the current value is separated from the two main electrodes through the winding element.
To divert as a direct current to the auxiliary anode provided in the tank
Anodic acting on the aluminum plate facing the main pole
The current value for the cathode reaction and the cathode reaction
The ratio with the current value can be controlled. Opposite the main pole
Take part in the anodic and cathodic reactions on an aluminum plate
The ratio of electricity (cathode electricity / anode electricity) is 0.3.
It is preferably ˜0.95. The electrolytic cell is vertical type, flat type, radial type.
Electrolyzers used for known surface treatment such as can be used
Is described in JP-A-5-195300
Such a radial electrolytic cell is particularly preferred. Pass through the electrolytic cell
The electrolyte to be used is in the direction of the aluminum web
It may be a parallel or a counter. (Nitric acid electrolysis) An electrolytic solution mainly composed of nitric acid is used.
The average opening diameter of 0.5 to
5 μm pits can be formed. However, electricity
When the amount is relatively large, the electrolytic reaction is concentrated and 5 μm
The honeycomb pits exceeding are also generated. Like this
To obtain the aluminum at the end of the electrolytic reaction
The total amount of electricity involved in the anode reaction of the steel plate is 1-1.
000C / dm²Is preferably 50 to 300C.
/ Dm²It is more preferable that The current density at this time is
20-100A / dm²Is preferred. Also high
When using concentrated or high-temperature nitric acid electrolyte, the average opening diameter
A small wave structure of 0.2 μm or less can also be formed. (Hydrochloric acid electrolysis) Hydrochloric acid is its own aluminum.
Because of its strong dissolving power, the surface can be applied with a slight amount of electrolysis
It is possible to form fine irregularities on the surface. This fine
The irregularities have an average opening diameter of 0.01 to 0.2 μm,
It is uniformly formed on the entire surface of the aluminum plate. This
In order to obtain such grain,
Total amount of electricity involved in the anodic reaction of the ruminium plate
1-100 C / dm²It is preferable that
70 C / dm²It is more preferable that Current at this time
Density is 20-50A / dm²Is preferred. Electricity in an electrolyte mainly composed of such hydrochloric acid is used.
In the gas chemical roughening treatment, the electricity involved in the anode reaction
The total amount is 400-1000 C / dm²And make it bigger
And form a large crater-like swell at the same time
Is also possible. In this case, the average opening diameter is 10 to 30 μm.
Superposed on crater-like undulations, average opening diameter 0.01 ~
Fine irregularities of 0.4 μm are generated on the entire surface. In the present invention, the first electrolytic surface roughening treatment
As described above, electrolysis using the above-described electrolytic solution mainly composed of nitric acid
Roughening treatment (nitric acid electrolysis) is performed, and the second electrolytic roughening treatment
Electrolysis using the above-mentioned electrolyte mainly composed of hydrochloric acid
Roughening treatment (hydrochloric acid electrolysis) is preferably performed. Performed in the above electrolytic solution such as nitric acid, hydrochloric acid, etc.
During the first and second electrolytic surface roughening treatments, aluminum
The plate is preferably subjected to cathodic electrolysis. This cathode electrolysis
Processing generates smut on the surface of the aluminum plate.
At the same time, hydrogen gas is generated to produce a more uniform electrolytic roughening treatment.
It becomes possible. This cathodic electrolysis is performed in an acidic solution.
The amount of polar electricity is preferably 3 to 80 C / dm²More preferred
Or 5-30 C / dm ²Done in Cathode electricity is 3C
/ Dm²If the amount of smut is less than
There is also 80C / dm²With smut
There is a case where the amount of wearing is excessive, and neither is preferred.
The electrolytic solution is obtained by the first and second electrolytic surface-roughening processes.
The solution used may be the same or different. <Alkaline etching treatment> Alkali etching
Chinching is performed by contacting the aluminum plate with an alkaline solution.
It is a process of dissolving the surface layer by touching. Alkali performed before electrolytic surface roughening treatment
Etching is performed when mechanical surface roughening is not performed.
The pressure on the surface of the aluminum plate (rolled aluminum).
The purpose is to remove oil spread, dirt, natural oxide film, etc.
In addition, when mechanical surface roughening has already been performed
Is the uneven edge generated by mechanical surface roughening
Surface that dissolves the minute and has smooth undulations of steep irregularities
It is done for the purpose of changing. Mechanical rough surface before alkali etching treatment
In the case where the crystallization treatment is not performed, the etching amount is 0.1 to 10
g / m²1 to 5 g / m is preferable.²Is
Is more preferable. Etching amount is 0.1g / m²Less than
If there is, the surface rolling oil, dirt, natural oxide film, etc. remain.
In the subsequent electrolytic surface roughening treatment.
Pits cannot be generated and unevenness may occur.
The On the other hand, the etching amount is 1 to 10 g / m.²Is
Thorough removal of surface rolling oil, dirt, natural oxide film, etc.
Is called. Etching amount exceeding the above range
It will be disadvantageous. Mechanical rough surface before alkali etching treatment
The etching amount is 3 to 20 g / m when the crystallization treatment is performed²
Is preferably 5 to 15 g / m.²Is more
preferable. Etching amount is 3g / m²Less than
Unevenness formed by mechanical surface roughening can be smoothed.
There may be no, uniform pits in the subsequent electrolytic treatment
It may not be possible to form. Also, stains deteriorate during printing
There is a case. On the other hand, the etching amount is 20 g / m.²The
If it exceeds, the concavo-convex structure may disappear. Alkaline etching performed immediately after the electrolytic surface roughening treatment
Chinching dissolves smut generated in acidic electrolyte
And pits formed by electrolytic surface roughening
It is performed for the purpose of dissolving the edge portion of the.
The pits formed by the electrolytic surface roughening treatment depend on the type of electrolyte.
However, the optimum etching amount is different because it is different,
Alkali etching process performed after electrolytic surface roughening
Ching amount is 0.1-5g / m²Is preferred.
When using nitric acid electrolyte, compared with using hydrochloric acid electrolyte
However, it is necessary to set a large etching amount. Electrolytic rough surface
If multiple processes are performed, after each process
In addition, alkali etching treatment may be performed if necessary.
it can. As an alkali used in an alkaline solution
Examples include caustic alkali and alkali metal salts.
It is. Specifically, as caustic alkali, for example,
Examples include caustic soda and caustic potash. Arca
Examples of the metal salt include sodium silicate and sodium silicate.
Alkaline metal such as potassium carbonate, metasilicate potassium, and potassium silicate
Irate: Alkali metal carbonate such as sodium carbonate and potassium carbonate
Salt: Alkaline gold such as sodium aluminate and potassium aluminate
Genus aluminate; sodium gluconate, potassium gluconate, etc.
Alkali metal aldonates; dibasic sodium phosphate, second
Potassium phosphate, sodium triphosphate, potassium tertiary phosphate, etc.
Lucari metal hydrogen phosphate is mentioned. Above all, etch
Caseial is fast and inexpensive.
Potash solution and caustic alkali and alkali metal
A solution containing both luminate and salt is preferred. In particular,
An aqueous solution of caustic soda is preferred. The concentration of the alkaline solution depends on the etching amount.
However, it is 1 to 50% by mass.
Is preferable, and it is more preferable that it is 10-35 mass%.
Yes. Aluminum ions are dissolved in the alkaline solution
The concentration of aluminum ions is 0.01 to
It is preferably 10% by mass, 3-8% by mass
Is more preferable. The temperature of the alkaline solution is 20 to 90 ° C.
Preferably there is. Processing time is 1 to 120 seconds
preferable. An aluminum plate is brought into contact with an alkaline solution.
For example, an aluminum plate is dissolved in an alkali solution.
A method of passing through a tank containing liquid, an aluminum plate
A method of soaking in an alkaline solution tank
One method is to spray the potash solution onto the surface of the aluminum plate.
I can get lost. <Desmutting treatment> Electrolytic roughening treatment or
After alkali etching treatment, stains remaining on the surface
Pickling (desmut treatment) to remove smut
Is performed. Examples of the acid used include glass.
Acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoride
A hydrofluoric acid is mentioned. The above desmut process is
If the above aluminum plate has a concentration of hydrochloric acid, nitric acid, sulfuric acid, etc.
0.5-30 mass% acidic solution (aluminum ion
Contains 0.01 to 5 mass%. To contact)
Do more. Method of contacting an aluminum plate with an acidic solution
As an example, an acidic solution was put into an aluminum plate
How to pass through the tank, aluminum plate with acidic solution
A method of soaking in a tank that contains water
The method of spraying on the surface of a um plate is mentioned. Desma
In the treatment, the above-mentioned electrolytic rough surface is used as the acidic solution.
Aqueous solution mainly composed of nitric acid discharged in the treatment
Or waste solution of aqueous solution mainly composed of hydrochloric acid, or described later
Water solution mainly composed of sulfuric acid discharged in anodizing treatment
Liquid waste can be used. Liquid temperature of desmut treatment
Is preferably 25 to 90 ° C. Also processing time
Is preferably 1 to 180 seconds. Death mat processing
The acidic solution used for
The nium alloy component may be dissolved. <Anodizing treatment> Treated as described above.
The aluminum plate is further subjected to an anodizing treatment.
Anodizing is performed by a method conventionally used in this field.
be able to. In this case, for example, sulfuric acid concentration 50-30
In a solution with an aluminum concentration of 5% by mass or less at 0 g / L
Then, the anodic oxide film was energized with the aluminum plate as the anode.
Can be formed. Used for anodizing treatment
Solutions include sulfuric acid, phosphoric acid, chromic acid, oxalic acid,
Rufamic acid, benzenesulfonic acid, amidosulfonic acid
May be used alone or in combination of two or more.
it can. At this time, at least the aluminum plate, the electric
Components normally contained in poles, tap water, groundwater, etc. are contained in the electrolyte.
It may be included. Furthermore, the second and third components
It may be added. The second and third components here
For example, Na, K, Mg, Li, Ca, T
i, Al, V, Cr, Mn, Fe, Co, Ni, Cu,
Metal ions such as Zn; positive ions such as ammonium ions
Nitrate ion, carbonate ion, chloride ion, phosphate ion
ON, fluoride ion, sulfite ion, titanate ion
And anions such as silicate ions and borate ions.
Even if it is contained at a concentration of about 0 to 10,000 ppm
Good. The conditions for the anodizing treatment are as follows.
However, it cannot be determined in general.
Generally, the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C.,
Current density 0.5-60A / dm², Voltage 1-100V,
An electrolysis time of 15 seconds to 50 minutes is appropriate and desired
The amount is adjusted so as to be the amount of the anodized film. In addition, Japanese Patent Laid-Open No. 54-81133, Japanese Patent Laid-Open No.
57-47894, JP 57-51289, JP
Sho-57-51290, JP-A-57-54300, Special
No. 57-136596, JP-A 58-107498
JP, 60-600025, JP 62-136
No. 596, JP-A 63-176494, JP-A 4-1
No. 76897, JP-A-4-280997, JP-A-6-280997
207299, JP-A-5-24377, JP-A-5-24377
32083, JP-A-5-125597, JP-A-5-125597
Use the method described in each publication of 195291
You can also Of these, Japanese Patent Laid-Open No. 54-12853.
And JP-A-48-45303.
Thus, it is preferable to use a sulfuric acid solution as the electrolytic solution. Electric
The sulfuric acid concentration in the solution is 10 to 300 g / L (1 to 30 quality).
%)), And aluminum ions
The concentration is 1 to 25 g / L (0.1 to 2.5% by mass).
2-10 g / L (0.2-1% by mass)
It is more preferable that Such electrolytes are
For example, sulfuric acid is added to dilute sulfuric acid having a sulfuric acid concentration of 50 to 200 g / L.
It can be prepared by adding aluminum etc.
Yes. Anodizing treatment in an electrolyte containing sulfuric acid
When doing so, apply direct current between the aluminum plate and the counter electrode.
You may apply, and you may apply alternating current. Aluminum plate
When a direct current is applied to the current density, the current density is 1-6.
0A / dm²Is preferably 5 to 40 A / dm.²
It is more preferable that Continuous anodizing treatment
In some cases, the current is concentrated on a part of the aluminum plate.
In order to prevent loose “burning”, start the anodizing process.
First 5-10A / m²Current at a low current density of
As polar oxidation progresses, 30-50A / dm²Ma
It is preferable to increase the current density more than that. Communicating
When anodizing is performed continuously, an aluminum plate
In addition, it is performed by a liquid power feeding method in which power is fed through an electrolytic solution.
preferable. To perform anodizing under these conditions
Many more pores called micropores
Although a porous film is obtained, the average pore diameter is usually 5-5.
It is about 0 nm, and the average pore density is 300 to 800 /
μm²Degree. The amount of the anodized film is 1 to 5 g / m.²Is
Is preferred. 1g / m²If it is less than
On the other hand, 5g / m²Exceeding power
Power is needed and it is economically disadvantageous. Of anodized film
The amount is 1.5-4 g / m²It is more preferable that Ma
In addition, an anodic acid between the center of the aluminum plate and the vicinity of the edge
Difference in chemical film amount is 1 g / m²It is preferable to do so
Good. As an electrolysis apparatus used for anodizing treatment
Are disclosed in JP-A 48-26638 and JP-A 47-1873.
9 and published in Japanese Patent Publication No. 58-24517
Can be used. Above all, it is shown in FIG.
A device is preferably used. Figure 4 shows a table of aluminum plates
It is the schematic which shows an example of the apparatus which anodizes the surface.
In the anodizing apparatus 410, the aluminum plate 41
6 is conveyed as shown by the arrow in FIG. Electrolytic solution 41
In the power supply tank 412 in which 8 is stored, the aluminum plate 416
Is charged to (+) by the feeding electrode 420. So
The aluminum plate 416 is
The nip roller 42 is conveyed upward by the roller 422.
4, the electrolyte solution 426 is stored.
The roller 4 is conveyed toward the accumulated electrolytic treatment tank 414.
The direction is changed horizontally by 28. Then Al
The minium plate 416 is moved to (−) by the electrolytic electrode 430.
Anodized film is formed on the surface by being charged
The aluminum plate 416 exiting the electrolytic treatment tank 414 is
It is conveyed to the subsequent process. In the anodizing apparatus 410,
Roller 422, nip roller 424 and roller
428 constitutes the direction changing means, and aluminum
The plate 416 is between the feeding tank 412 and the electrolytic treatment tank 414.
The rollers 422, 424 and 428
Therefore, it is conveyed to a mountain shape and an inverted U shape. Feed electrode 42
0 and the electrolytic electrode 430 are connected to a DC power source 434.
Yes. The characteristics of the anodizing apparatus 410 shown in FIG.
The feeding tank 412 and the electrolytic treatment tank 414 are combined into one tank wall 432.
And the aluminum plate 416 is mountain-shaped between the tanks.
And it has been transported in an inverted U shape. by this,
Minimize the length of the aluminum plate 416 between the tanks
Can. Therefore, all of the anodizing apparatus 410
Since the body length can be shortened, the equipment cost can be reduced.
The In addition, the aluminum plate 416 has a mountain shape and an inverted U shape.
Each tank 412 and 414 tanks by being transported to
An opening for passing the aluminum plate 416 through the wall
No need to form. Therefore, each tank 412 and 4
14 required to maintain the liquid level in 14 at the required level
Since the liquid volume can be reduced, the operating cost should be reduced.
Can do. <Sealing treatment> In the present invention, if necessary,
Sealing hole that seals micropores in the anodized film
Processing may be performed. Sealing treatment includes boiling water treatment and hot water treatment.
Steam treatment, Sodium silicate treatment, Nitrite treatment, Acetic acid
It can be performed according to known methods such as ammonium treatment.
Yes. For example, Japanese Patent Publication No. 56-12518,
No. 4-4194, Japanese Patent Application No. 4-33952
(Japanese Patent Laid-Open No. 5-20296), Japanese Patent Application No. 4-339
No. 51 (JP-A-5-179482) etc.
Sealing treatment may be performed using the equipment and methods provided.
Yes. <Hydrophilic treatment> In the present invention,
The aluminum plate was roughened and anodized.
And other treatments as necessary
After, an alkali metal silicate having a concentration of 0.6 to 5.0% by mass
A hydrophilic treatment with an aqueous solution is performed. Alkali metal silicate
Hydrophilic treatment with an aqueous solution is described in U.S. Pat. No. 2,714,0.
No. 66 and U.S. Pat. No. 3,181,461
Follow the methods and procedures described in the booklet
In the present invention, alkali metal silicate can be used.
The concentration of the aqueous solution is 0.6% by mass or more, preferably 0.8
% By mass or more, and 5.0% by mass or less, preferably
It is 3.0 mass% or less. If it is in the above range, image recording
When using an image recording layer containing an infrared absorber as the layer
Even if it is a lithographic printing plate, it has excellent stain resistance
It will be. Alkali metal silicates are particularly limited
For example, sodium silicate, potassium silicate,
A lithium acid is mentioned. These can be used alone or in combination
Used in combination. Alkali metal silicate water
The solution is sodium hydroxide, potassium hydroxide,
An appropriate amount of thium or the like may be contained. Also alkaline
Metal silicate aqueous solutions are alkaline earth metal salts or Group 4
(Group IVA) may contain a metal salt. alkali
Examples of the earth metal salt include calcium nitrate and nitrate.
Glass such as trontium, magnesium nitrate, barium nitrate
Acid salt; Sulfate; Hydrochloride; Phosphate; Acetate; Oxalic acid
Salt; borate. Group 4 (Group IVA) metal salts
For example, titanium tetrachloride, titanium trichloride,
Titanium potassium fluoride, Titanium potassium oxalate, Titanium sulfate
Titanium tetraiodide, zirconium chloride oxide, dioxide
Luconium, zirconium oxychloride, zirconium tetrachloride
Um. These alkaline earth metal salts and
Group 4 (Group IVA) metal salts may be used alone or in combination of two or more
Used together. Hydrophilization with aqueous alkali metal silicate solution
Treatment is roughening treatment, anodizing treatment and if necessary
Concentration of aluminum plate with other treatments
0.6% to 5.0% by weight aqueous alkali metal silicate solution
This is done by contact. Aluminum plate with alkali
The method of contacting the metal silicate aqueous solution is particularly limited.
For example, an aluminum plate is placed in a tank containing the above aqueous solution.
Method of passing inside, put the above aqueous solution into the aluminum plate
Soaking in the bath
The method of spraying on the surface of a um plate is mentioned. alkali
Various conditions for hydrophilization treatment with aqueous metal silicate solution
Although not limited, the liquid temperature is preferably 10 to 80 ° C.
More preferably 15 to 30 ° C., and treatment
The time is preferably 1 to 100 seconds, and 5 to 20 seconds.
More preferably. Hydrophilization with aqueous alkali metal silicate solution
The amount of Si adsorbed by the treatment is measured by an X-ray fluorescence analyzer
The amount of adsorption can be about 1.0-15.0
mg / m²Preferably, 2.5 to 5.0 mg /
m²Is more preferable. This alkali metal silicic acid
Lithographic printing plate support by hydrophilization treatment with aqueous salt solution
The effect of improving the dissolution resistance to alkaline developer on the surface of
The dissolution of the resulting aluminum component into the developer is suppressed.
To reduce development debris caused by developer fatigue.
Can. <Carboxylic acid and / or carboxylate
In the present invention, the treatment with an aqueous solution containing
After the hydrophilization treatment, further carboxylic acid and / or calcium
A treatment with an aqueous solution containing a borate is performed. Carvone
The acid is not particularly limited, and for example, formic acid, aliphatic carvone
Acid, aromatic carboxylic acid, heterocyclic carboxylic acid
The The carboxylic acid may be a monocarboxylic acid,
It may be a polybasic acid such as rubonic acid or tricarboxylic acid
Yes. Examples of the aliphatic carboxylic acid include carbon.
The linear or branched optionally substituted 1 to 22
Alkanecarboxylic acids, substituted with 3 to 22 carbon atoms
Linear or branched alkenes or alkynes
These carboxylic acids are mentioned. These carboxylic acids are mono
In the case of a carboxylic acid, it preferably has 12 or less carbon atoms.
Good. Examples of other aliphatic carboxylic acids include:
Ring member carbon atoms having 5 to 22 carbon atoms which may be substituted
And carboxylic acid of hydrogen fluoride. Monocarboxylic acid
In this case, the number of carbon atoms is preferably 12 or less. Alicyclic
Examples of hydrocarbons include monocyclic, polycyclic and bridged
Each cyclic alicyclic hydrocarbon is mentioned. Specific alicyclic
Examples of the hydrocarbon include cyclopentane and cyclopenta.
N-ten, cyclopentadiene, cyclohexane, cyclo
Hexene, cyclohexadiene, cycloheptane, cycl
Loheptene, cycloheptadiene, cyclooctane,
Crooctene, cyclooctadiene, cyclooctatri
Ene, cyclononane, cyclononene, cyclodecane,
Clodecene, cyclodecandiene, cyclodecantrie
, Cycloundecane, cyclododecane, bicyclohept
Tan, bicyclohexane, dicyclohexene, trisic
Rohexane, norcaran, norpinane, norbornane,
Norbornene, norbornadiene, tricyclohepta
, Tricycloheptene, decalin, adamantane, etc.
Can be mentioned. As the aromatic carboxylic acid, for example, each
Optionally substituted monocyclic, 2-5 condensed rings, aromatic
Polycyclic hydrocarbons formed by direct bonding of rings (for example, bif
Carboxylic acid). Concrete aromatic charcoal
Examples of hydrides include benzene, naphthalene, and dihydrogen.
Dronaphthalene, tetralin, indene, indane,
Nzocyclobutene, benzocycloheptene, benzocycl
Looctene, hydrobenzocycloheptene, hydroben
Zocyclooctene, anthracene, phenanthrene, fu
Enalen, Indacene, Fluorene, Acenaphthylene,
Acenaphthene, biphenylene, naphthacene, pyrene, benzene
Nzophenanthrene, benzopyrene, biphenyl, ter
Examples thereof include phenyl and binaphthyl. As the heterocyclic carboxylic acid, for example, acid
At least one of elementary atom, sulfur atom and nitrogen atom
Monocyclic (for example, 5- to 10-membered ring), polycyclic
Heterocyclic carvone consisting of a ring structure of formula or bridged cyclic
Examples include acids. These heterocycles may be substituted
Yes. Specific heterocycles include, for example, tetrahydrofluoro
Orchid, dihydrofuran, furan, pyrrole, pyrroline,
Pyrrolidine, pyrazole, pyrazoline, pyrazolidine,
Imidazole, imidazoline, imidazolidine, tria
Sol, triazoline, triazolidine, tetrazo
, Tetrazoline, tetrazolidine, thiophene, dihi
Drothiophene, teratohydrothiophene, isoxa
Sol, isoxazoline, isoxazolidine, oxy
Sazole, oxazoline, oxazolidine, isothiazo
, Isothiazoline, isothiazolidine, thiazole
, Thiazoline, thiazolidine, pyridine, hydropyri
Gin, piperidine, pyridazine, hydropyridazine, pipe
Limidine, pyrazine, piperazine, pyran, hydropyra
Thiopyran, hydrothiopyran, oxazine, mol
Holin, azepine, hydroazepine, azocine, azesi
, Diazepine, diazocine, hydrodiazocine, dia
Zonin, diazemine, oxepin, hydrooxepin,
Oxocin, oxonine, oxesin, thiepine, thio
Syn, hydrothiocin, thionine, thiecin, dithiepi
, Dithiocin, dithionin, dithiecin, oxazepi
, Thiazepine, oxathiepine, hydroxathiepi
, Oxathiocin, hydrooxathiocin, isoin
Dole, indoline, indole, isoindoline, mosquito
Rubazole, indazole, benzimidazole, hydride
Lobenzimidazole, benzotriazole, invene
Zofuran, dibenzofuran, hydrobenzofuran, ben
Zoxazole, benzothiophene, benzodithio
, Hydrobenzoxazole, benzisoxazol
, Benzothiazole, benzoisothiazole, benzo
Oxathiol, quinoline, isoquinoline, acrid
Phenanthridine, quinazoline, phenazine, ben
Zopyran, xanthene, benzothiopyran, hydroben
Zopyran, benzoxazine, benzothiazine, thiox
Santen, phenoxazine, phenothiazine, benzoa
Zepin, benzodiazepine, pyrrolidine, quinolidine,
Quinolizidine, indolizine, pyrrolizidine, purine,
Isochroman, chroman, bipyridine, bithiophene,
Examples include quinuclidine and piverazine. These carboxylic acids can be substituted.
Examples of the substituent include a monovalent nonmetallic atomic group excluding hydrogen.
It is done. For example, halogen atom (fluorine atom, chlorine source
Child, bromine atom, iodine atom), -CN, -NO₂, Hor
Mill group, -SH, -OH, -OR¹, -SR¹, -CO
OR¹, -OCOR¹, -SO₂R¹, -COR¹,-
NHCONHR¹, -CON (R²) (R^Three), -SO
₂N (R²) (R^Three), -N (R^Four) COR¹, -N
(R^Four) SO₂R¹, -N (R²) (R^Three), -N
⁺(R²) (R^Three) (R^Five), -P (= O) (R⁶)
(R⁷), -Si (R⁸) (R⁹) (R^Ten), Aryl
Preferred examples include groups and heterocyclic groups. In the above, R¹Is substituted
Good linear or branched alkyl group having 1 to 22 carbon atoms
(Examples of the alkyl group include a methyl group, an ethyl group,
Propyl, butyl, pentyl, hexyl, hep
Til, octyl, nonyl, decyl, undecyl
Group, dodecyl group, tridecyl group, tetradecyl group, pen
Tadecyl group, hexadecyl group, heptadecyl group, octa
Decyl group, nonadecyl group, eicosanyl group, heneicosa
Nyl group and docosanyl group can be mentioned. ), Replaced
A linear or branched alkene having 2 to 22 carbon atoms
Nyl group or alkynyl group (Examples of alkenyl group include
For example, vinyl, propenyl, butenyl, penteni
Group, hexenyl group, octenyl group, decenyl group, dode
Cenyl group, tridecenyl group, tetradecenyl group, hexa
Decenyl group, octadecenyl group, eicosenyl group, doco
Cenyl group, butadienyl group, heptadienyl group, hexa
Dienyl group, octadienyl group, etc.
Examples of the alkyl group include ethynyl group, propynyl group, and butyl group.
Tinyl group, hexynyl group, octanyl group, decanyl group,
A dodecanyl group etc. are mentioned. ), Setting of 5 to 22 carbon atoms
Monocyclic, polycyclic or bridged cyclic fats that may be substituted
Cyclic hydrocarbons (specifically, each alicyclic carbon listed above)
And monovalent organic residues of hydrogen fluoride. ), Replaced
An aromatic group having 6 to 14 carbon atoms (specifically,
Examples of monovalent organic residues of each aromatic hydrocarbon listed above
It is done. ) And an optionally substituted heterocyclic group
(Specifically, the monovalent organic residue of each heterocyclic ring enumerated above.
Groups. ) R²And R^ThreeAre independently hydrogen
Atom or R¹Represents the same content as Also,
R²And R^ThreeAnd form a ring structure containing a nitrogen atom
It may be a thing. For example, pyrazine ring, piperidine
Ring, morpholine ring, pyrrole ring, pyrazole ring, imida
Zole ring, imidazolidine ring, oxazolidine ring, thia
Zolidine ring, azepine ring, hydroazepine ring, etc.
It is. R^FourIs a hydrogen atom or R¹Of the same content
Represents a thing. R^FiveIs a hydrogen atom or R¹Same as
Represents content. Substituent -N⁺(R²) (R^Three) (R
^Five), R², R^ThreeAnd R^FiveAre the same each
It may be different or different. R⁶Is —OH, a hydrocarbon group, or the —
OR¹Represents R⁷Is a hydrocarbon group or -OR¹
Represents. The hydrocarbon group is used in the aliphatic carboxylic acid.
And groups used for aromatic carboxylic acids.
I can get lost. Substituent -P (= O) (R⁶) (R⁷)smell
R⁶And R⁷Each may be the same or different
It may be. R⁸, R⁹And R^TenEach
A hydrocarbon group or the -OR¹Represents. hydrocarbon
The groups are those used for the aliphatic carboxylic acid, and
Examples include groups used for aromatic carboxylic acids. Substituent
-Si (R⁸) (R⁹) (R^Ten) -OR¹Is
The number is preferably 2 or less. As the aryl group, specifically,
Residues obtained by removing one hydrogen atom from the aromatic hydrocarbon nucleus
It is. Specific examples of the heterocyclic group include a nucleus of the above heterocyclic ring.
And residues obtained by removing one hydrogen atom from the above. In addition, each of the above substituents is further substituted.
May be. Each substituent can be substituted and
As a substituent capable of substituting carboxylic acid,
Are the same as those listed above. Specific examples of carboxylic acids used in the present invention
Although enumerated below, the present invention is not limited to these.
There is no. Examples of monocarboxylic acids include formic acid and vinegar
Acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid
Acid, pivalic acid, hexanoic acid, heptanoic acid, octanoic acid,
Nonanoic acid, decanoic acid, lauric acid, crotonic acid, sorbi
Acid, vinyl acetate, butenic acid, pentene carboxylic acid,
Propionyl acid, phenylacetic acid, 3-phenylpropio
Acid, naphthylacetic acid, cyclohexanecarboxylic acid,
Rohexylmethylcarboxylic acid, cyclopentanecarboxylic acid
Acid, cyclooctanecarboxylic acid, cyclodecanecarboxylic acid
Acid, adamantanecarboxylic acid, isobornenecarboxylic acid
Acid, benzoic acid, naphthalenecarboxylic acid, toluic acid, keto
Cinnamic acid, tropic acid, salicylic acid, acetylsalicylic acid,
Aminosalicylic acid, anisic acid, vanillic acid, nitrobenzoic acid
Perfume acid, cyanobenzoic acid, veratric acid, piperonic acid,
Protocatechuic acid, gallic acid, homovanillic acid, cafe
Acid, ferulic acid, benzoylbenzoic acid, acetylbenzoic acid
Acid, chlorobenzoic acid, dichlorobenzoic acid, trimethyl ammonium
Benzoic acid, N, N-dimethylaminobenzoic acid, aminonaphth
Talencarboxylic acid, chloroacetic acid, dichloroacetic acid, trichl
Loroacetic acid, trifluoroacetic acid, 3-methylthiopropion
Acid, 3-phenylthiopropionic acid, 3-oxovalery
Acid, methoxycarbonylacetic acid, 3,5-dioxovale
Phosphoric acid, β-oxocyclohexanepropionic acid, β-
Oxo-3-pyridinepropionic acid, furancarboxylic
Acid, pyridinecarboxylic acid, picolinic acid, nicotinic acid,
Sonicotinic acid, quinolinecarboxylic acid, indoleacetic acid,
4-isoindolebutanoic acid, thiophenecarboxylic acid,
Glyoxylic acid, proline pyruvic acid, acetoacetic acid, le
Brinic acid, glycolic acid, mercaptoacetic acid, lactic acid, glycine
Serine acid, succinic acid monoamide, carbamoyl benzoate
Acid, camphoric acid, benzylic acid, orotic acid, N-methyl
Rucarbamoylglutaric acid, acetamidoacetic acid, 3-
(Trimethylsilicyl) propionic acid, uroxanoic acid
(Uroxic Acid), uronic acid (Uronic Acid)
ic Acid), α-aminocarboxylic acids (eg,
Glycine, alanine, aminobutyric acid, vanillin, leuci
, Sarcosine, aminopropionic acid, aminohippuric acid,
Isovaline, norvaline, isoleucine, norleucine
, Ornithine, lysine, homolysine, asparagine,
Glutamine, lysine, creatine, norarginine, shi
Tolrin, serine, azaserine, threonine, homoseri
, Carnitine, cysteine, acetylcysteine,
Mocysteine, methionine, ethionine, penis lice
, Phenylalanine, tyrosine, thyronine, trypto
Fan, histidine, valine, etc.). Examples of polybasic acids (polycarboxylic acids)
For example, oxalic acid, malonic acid, succinic acid, glutaric acid,
Dipic acid, pimelic acid, suberic acid, azelaic acid,
Vacic acid, maleic acid, fumaric acid, citraconic acid, mesa
Conic acid, acetylenedicarboxylic acid, itaconic acid, alkyl
R-substituted succinic acid (as alkyl group, methyl group, ethyl
Group, butyl group, oxyl group, octyl group, decyl group),
Cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid
Acid, cyclohexanedicarboxylic acid, cycloheptanedica
Rubonic acid, cyclooctane dicarboxylic acid, cyclohexa
Tricarboxylic acid, norbornene dicarboxylic acid, bicycl
B [2.2.2] Oct-7-ene-tetracarboxylic
Acid, tricyclo [5.2.1.0^2,6] Decandicarbo
Acid, cyclohexanetetracarboxylic acid, benzenedica
Rubonic acid (eg phthalic acid, isophthalic acid, terephthalic acid)
Acid), biphenyldicarboxylic acid, tetrachlorobenze
Dicarboxylic acid, Hensentricarboxylic acid, benzene ester
Tracarboxylic acid, naphthalene dicarboxylic acid, anthrace
Dicarboxylic acid, naphthalenetricarboxylic acid, naphthalene
Tetracarboxylic acid, anthracentricarboxylic acid, te
Trahydrophthalic acid, hexahydrophthalic acid, imino di
Acetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, asthma
Paraginic acid, glutamic acid, lanthionine, cystathio
Nin, kainic acid, mesooxalic acid, oxalacetic acid, glycine
Serine acid, malic acid, tartaric acid, gluconic acid, citric acid,
Shikimic acid, quinic acid, thiophene dicarboxylic acid, pyridine
Dicarboxylic acid, 4,4'-oxodibenzoic acid, bicyclo
[2.2.2] Oct-5-ene-dicarboxylic acid, 2,
2-biquinoline-4,4'-dicarboxylic acid, Cheli
Examples thereof include damic acid and coumaric acid. these
These carboxylic acids are used alone or in combination of two or more.
I can. The carboxylate is not particularly limited,
Examples include carboxylic acid anion and counter cation salts.
The The counter cation is not particularly limited, and the inorganic cation and
And any organic cation. Inorganic cations
For example, non-metal element cations (for example, Na
⁺, Li ⁺, K⁺), Metal element cations (eg, Zr
⁺), NH_Four ⁺Ions. As an organic cation
For example, HN⁺(R¹¹) (R¹²) (R¹³)
It is done. In the above, R¹¹, R¹²And R¹³Is
R², R^ThreeAnd R^FiveRepresents the same content as Organic
The amine compound to be an amine may be a monoamine
Or polyamines such as diamine and triamine
Yes. Specific examples include pyridine. These cal
Bonates may be used alone or in combination of two or more.
It is. Also, one or more carboxylic acids and one of the carboxylic acid salts
A combination of more than one species may be used. Carboxylic acid and / or carboxylate
The concentration of the aqueous solution to be contained is not particularly limited, but 0.0
It is preferably 1% by mass or more, and 0.05% by mass or more
It is more preferable that it is 10% by mass or less.
Is preferable, and it is more preferable that it is 1 mass% or less.
Within the above range, the printing durability when using a lithographic printing plate is excellent.
It will be. Carboxylic acids and / or carboxylates
Treatment with aqueous solution containing alkali metal silicate water
An aluminum plate that has been hydrophilized with a solution
In aqueous solution containing boric acid and / or carboxylate
This is done by contact. Carbox aluminum plate
Contact with aqueous solution containing acid and / or carboxylate
There are no particular restrictions on the method used, for example, aluminum
A method of passing a plate through a tank containing the above aqueous solution,
Immerse the minium plate in the tank containing the above aqueous solution.
Method, the above aqueous solution is sprayed on the surface of an aluminum plate
A method is mentioned. Carboxylic acid and / or carvone
Conditions for treatment with aqueous solutions containing acid salts are particularly limited
Although it is not, the liquid temperature is preferably 15-100 ° C
More preferably 20 to 50 ° C., and treatment
The time is preferably 1 to 100 seconds, and 5 to 20 seconds.
More preferably. In the present invention, as described above,
Minium plate was roughened and anodized
After, an alkali metal silicate having a concentration of 0.6 to 5.0% by mass
Hydrophilic treatment with aqueous solution, and carboxylic acid and
And / or treatment with an aqueous solution containing carboxylate
The image is recorded on the resulting lithographic printing plate support.
A lithographic printing plate precursor provided with a recording layer contains an infrared absorber.
Even if it has an image recording layer, a lithographic printing plate
Excellent stain resistance and printing durability when
It will be a thing. <Washing treatment> After completion of the above-described treatment steps
It is preferable to perform washing with water. For washing, pure water, well water,
Tap water or the like can be used. Holding the treatment liquid to the next process
A nip device may be used to prevent pinching. <Aluminum plate (rolled aluminum)> The present invention
In order to obtain a lithographic printing plate support, known aluminum
Plate can be used. Aluminum used in the present invention
The nickel plate is mainly composed of dimensionally stable aluminum.
Metal or aluminum or aluminum alloy
It becomes. In addition to pure aluminum plate, the main component is aluminum.
It is also possible to use alloy plates that contain minute amounts of foreign elements.
The In the present specification, the above-described aluminum is used.
Various substrates made of aluminum or aluminum alloy
Used generically as a nium plate. Included in the aluminum alloy
The different elements that may be rare include silicon, iron, manganese, copper,
Magnesium, chromium, zinc, bismuth, nickel, titanium
The content of foreign elements in the alloy is 10% by mass or less.
It is below. Thus, the aluminum used in the present invention
As for the board, the composition is not specified, for example,
Aluminum Handbook 4th Edition (1990, light metal
Previously known materials described in the association), for example,
JIS A1050, JISA1100, JIS A1
070, JIS A3004 containing Mn, internationally registered alloy
  3103A or other Al-Mn based aluminum plate
Can be used. Also, for the purpose of increasing the tensile strength,
These aluminum alloys have a magnesi content of 0.1% by mass or more.
Al-Mg based alloy with addition of hum, Al-Mn-Mg based
An alloy (JISA3005) can also be used. Further
In addition, Al-Zr alloys and Al-Si alloys containing Zr and Si
An alloy can also be used. Furthermore, Al-Mg-Si system
An alloy can also be used. Regarding the JIS 1050 material, the applicant of the present application.
The technique proposed by JP-A-59-153861
, JP-A 61-51395, JP-A 62-1466
94, JP-A-60-215725, JP-A-60-2
15726, JP-A-60-215727, JP-A-6
0-216728, JP-A 61-272367, special
No. 58-11759, JP 58-42493,
JP-A-58-212254, JP-A-62-14829
No. 5, JP-A-4-254545, JP-A-4-1650
41, JP-B-3-68939, JP-A-3-2345
94, JP-B-1-47545 and JP-A-62-1
It is described in each publication of No. 40894. Also, fairness
No. 1-35910, Japanese Patent Publication No. 55-28874
The techniques described in the above are also known. Regarding the JIS1070 material, the applicant of the present application.
The technique proposed by JP-A-7-81264,
JP-A-7-305133, JP-A-8-49034,
JP-A-8-73974, JP-A-8-108659
And JP-A-8-92679.
The Regarding the Al-Mg alloy, the applicant of the present application.
The technology proposed by SHO 62-5080,
JP-B 63-60823, JP-B 3-61753,
JP-A-60-203396, JP-A-60-20349
No. 7, Japanese Patent Publication No. 3-11635, JP-A 61-2749
93, JP 62-23794, JP 63-47
347, JP-A 63-47348, JP-A 63-4
7349, JP-A 64-1293, JP-A 63-1
35294, JP-A 63-87288, JP 4-B
73392, Japanese Patent Publication No. 7-100904, Japanese Patent Laid-Open No. Sho 62
-149856, JP-B-4-73394, JP-A-6
No. 2-181191, Japanese Patent Publication No. 5-76530, Japanese Patent Laid-Open No.
Each of 63-30294 and 6-37116
It is described in the publication. Also, JP-A-2-215599.
Described in Japanese Patent Laid-Open No. 61-201747, etc.
It is. Regarding the Al-Mn alloy, the applicant of the present application.
The technique proposed by JP-A-60-230951
No. 1, JP-A-1-306288 and JP-A-2-293.
It is described in each publication of No. 189. In addition, Shoko 54
-42284, JP 4-19290, JP 4-
19291, Japanese Patent Publication No. 4-19292, JP-A 61-
No. 35995, Japanese Unexamined Patent Publication No. 64-51592, Japanese Unexamined Patent Publication No. Hei 4-
No. 226394, US Pat. No. 5,009,72
Also described in No. 2, No. 5,028,276, etc.
It is listed. Regarding the Al-Mn-Mg alloy, the present application
The technique proposed by the applicant is disclosed in Japanese Patent Laid-Open No. 62-861.
43 and JP-A-3-22279
Has been. JP-B 63-60824, JP-A
JP 60-63346, JP 60-63347, JP
Japanese Laid-Open Patent Publication No. 1-293350, European Patent No. 223,7
37, U.S. Patent No. 4,818,300, British Patent No.
Also described in each specification of No. 1,222,777
The Regarding the Al-Zr alloy, the applicant of the present application.
The technology proposed by Tokushima is Japanese Patent Publication No. 63-15978
Described in Japanese Patent Laid-Open No. 61-51395
Yes. Also, JP-A-63-143234, JP-A-63.
It is also described in each publication of 143,235. Regarding the Al-Mg-Si alloy, the United Kingdom
It is described in the patent 1,421,710 specification etc.
The In order to use an aluminum alloy as a plate material, for example,
For example, the following method can be employed. First, given
Always use the molten aluminum alloy adjusted to the alloy content.
Clean and cast according to the law. For cleaning process
In order to remove unnecessary gases such as hydrogen in the molten metal,
Degassing using oxygen treatment, argon gas, chlorine gas, etc.
Processing, ceramic tube filter, ceramic four
So-called rigid media filters such as
Fibres that use alumina flakes, alumina balls, etc. as filter media
Filtering using a filter or glass cloth filter
Processing, or degassing and filtering
Combined processing is performed. These cleaning treatments are carried out with non-metallic intermediaries in the molten metal.
Defects caused by foreign objects such as natural objects and oxides, or melted into the molten metal
It is preferred to be implemented to prevent defects caused by gas.
Yes. Regarding filtering of molten metal, JP-A-6-57
No. 432, JP-A-3-162530, JP-A-5-14
0659, JP-A-4-231425, JP-A-4-2
No. 76031, Japanese Patent Laid-Open No. 5-311261, Japanese Patent Laid-Open No.
No. 136466, for example. Also melt
Regarding degassing of hot water, JP-A-5-51659,
It is described in Japanese Utility Model Laid-Open No. 5-49148. This application
The applicant also disclosed in Japanese Unexamined Patent Publication No. 7-40017
It proposes technology for degassing. Next, the cleaning process is performed as described above.
Casting is performed using the molten metal. Regarding casting method, D
A method using a solid mold represented by the C casting method, and a continuous casting
There is a method using a driving mold represented by a manufacturing method. DC casting
In the manufacturing process, the cooling rate is in the range of 0.5 to 30 ° C./second.
Solidify. Coarse intermetallic compound when the temperature is less than 0.5 ° C / second
Many objects may be formed. When DC casting was performed
Can produce ingots with a thickness of 300-800mm.
Yes. The ingot is chamfered as necessary according to conventional methods.
Usually, 1-30 mm of the surface layer, preferably 1-10 m
m is cut. Before and after that, soaking as needed
Process. When soaking treatment, intermetallic compounds are
1 to 48 hours at 450 to 620 ° C. to avoid coarsening
The heat treatment is performed. If the heat treatment is shorter than 1 hour,
The effect of heat treatment may be insufficient. Thereafter, hot rolling and cold rolling are performed.
A rolled plate of a minium plate. Hot rolling start temperature is 35
0-500 degreeC is suitable. Before or after hot rolling,
Alternatively, intermediate annealing may be performed in the middle
Yes. The conditions for the intermediate annealing treatment are 2 using a batch annealing furnace.
2 to 20 hours at 80 to 600 ° C., preferably 350 to 5
Heat at 00 ° C. for 2-10 hours or use a continuous annealing furnace
6 minutes or less at 400 to 600 ° C., preferably 450 to 55
Heating at 0 ° C. for 2 minutes or less. Using a continuous annealing furnace
The crystal structure is heated by heating at a heating rate of 10 to 200 ° C./second.
It can be made fine. Through the above process, a predetermined thickness, for example,
For example, an aluminum plate finished to 0.1 to 0.5 mm
Furthermore, straightening devices such as roller levelers and tension levelers
The flatness may be improved. The improvement in flatness is
It may be performed after the ruminium plate is cut into a sheet.
However, in order to improve productivity,
It is preferable to carry out in the state. Also processed to a predetermined plate width
Therefore, a slitter line may be used. Also alumni
In order to prevent scratches due to friction between
A thin oil film may be provided on the surface of the ruminium plate. Oil film
If necessary, volatile or non-volatile
Used as appropriate. On the other hand, as a continuous casting method, a twin roll method is used.
(Hunter method) Using a cooling roll represented by the 3C method
Method, twin belt method (Hasley method), Al Swiss Cas
Use cooling belts and cooling blocks represented by type II
The method is being carried out industrially. Using continuous casting
The cooling rate is in the range of 100 to 1000 ° C./sec.
To solidify. The continuous casting method is generally used as a DC casting method.
Compared to the aluminum matrix because the cooling rate is faster than
The alloy component has a high solid solubility.
Have. Regarding the continuous casting method, it is proposed by the applicant of the present application.
The proposed techniques are disclosed in JP-A-3-79798 and JP-A-5-
2011166, JP-A-5-156414, JP-A-6
-262203, JP-A-6-122949, JP-A-6-122949
JP-A-6-210406 and JP-A-6-26308
Etc. are described. When continuous casting is performed, for example,
If a method using a cooling roll such as the Hunter method is used,
Direct casting of cast plates with a thickness of 1-10mm is possible.
That the hot rolling process can be omitted.
Can be obtained. Also, use a cooling belt such as the Husley method.
Is used to cast a cast plate having a thickness of 10 to 50 mm.
In general, hot rolling
Thickness 1-10mm
A continuous cast and rolled plate is obtained. These continuous cast and rolled plates are suitable for DC casting.
Cold rolling, intermediate annealing, flatness
Through a process such as slitting, slitting, etc., a given thickness, for example
For example, the sheet thickness is 0.1 to 0.5 mm. Continuous casting
For intermediate annealing conditions and cold rolling conditions when using the manufacturing method
As for the technology proposed by the applicant of the present application,
Hei 6-220593, JP-A 6-210308,
Each of Kohei 7-54111 and JP-A-8-92709
It is described in the news. Aluminum plate manufactured in this way
The following various characteristics are desired. Arminius
The strength of the board is the strength required for a lithographic printing plate support.
In order to obtain the thickness, the 0.2% proof stress is 140 MPa or more.
Is preferred. Also when burning process is performed
In order to obtain a certain level of waist strength, 3 to 1 at 270 ° C.
0.2% proof stress after heat treatment for 0 minutes is 80 MPa or more
It is preferable that the pressure is 100 MPa or more.
preferable. Especially when you want the strength of your waist on an aluminum plate
Use aluminum material with added Mg or Mn.
However, if you are stiff, it is difficult to
Depending on the application, the material
And the addition amount of a trace component is selected suitably. Related to these
The technique proposed by the present applicant is disclosed in
JP-A-126820, JP-A-62-140894
It is described in the news. The crystal structure of the aluminum plate is a chemically rough surface.
If aluminum treatment or electrochemical surface roughening is performed, aluminum
The crystal structure on the surface of the aluminum plate causes the occurrence of poor surface quality.
It may not be very rough on the surface.
preferable. The crystal structure on the surface of the aluminum plate has a width of 2
It is preferably 00 μm or less, and is 100 μm or less
More preferably 50 μm or less.
Moreover, the length of the crystal structure is 5000 μm or less.
Is preferable, and is preferably 1000 μm or less.
More preferably, it is 500 μm or less. To these
Regarding the technique proposed by the applicant of the present application,
6-218495, JP-A-7-39906,
7-124609 and the like. The alloy composition distribution of the aluminum plate is chemically
If roughening or electrochemical roughening is performed,
Due to non-uniform distribution of alloy components on the surface of the minium plate
Since surface quality defects may occur,
It is preferable that it is not uneven. In this regard, this application
The technique proposed by the applicant is disclosed in JP-A-6-4805.
No. 8, JP-A-5-301478, JP-A-7-1326
No. 89, for example. The intermetallic compound of the aluminum plate is its gold
The size and density of the intergeneric compounds are controlled by chemical roughening and electrical
It may affect the chemical roughening treatment. To these
Regarding the technique proposed by the applicant of the present application,
7-138687 and JP-A-4-254545
It is described in the news. In the present invention, as shown above
In the final rolling process of aluminum plates,
It can also be used with unevenness by rolling, transferring or the like. The aluminum plate used in the present invention is continuous.
It is a continuous belt-like sheet material or plate material. That is, aluminum
It may be a nitro web and is shipped as a product.
A sheet-like sheet cut to a size corresponding to the printing plate precursor
It may be a port. The scratches on the surface of the aluminum plate are flat.
There is a possibility of defects when processed into a printing plate support.
Before the surface treatment process to make a lithographic printing plate support
It is necessary to suppress the occurrence of scratches at this stage as much as possible.
The To that end, it is stable and difficult to be damaged during transportation.
It is preferable that it is a package. Aluminum web field
For example, the package of aluminum is, for example, an iron pallet.
Lay hardboards and felt on the cardboard and cardboard
Apply the donut plate, wrap the whole with a polytube,
Insert a wooden donut into the inner diameter of the coil and
Apply the felt, squeeze it with a band, and display it on the outer periphery.
In addition, as packaging material, polyethylene film, cushioning material
For example, needle felt or hard board can be used.
You can. There are many other forms, but stable
If it can be transported without scratches, it is limited to this method.
It is not something. Thickness of the aluminum plate used in the present invention
Is about 0.1 mm to 0.6 mm, and 0.15 mm
~ 0.4mm is preferred, 0.2mm ~ 0.3mm
More preferably, it is mm. This thickness is the size of a printing press.
Depending on the size, size of the printing plate, user's request, etc.
Can be changed. [Lithographic printing plate precursor] For the lithographic printing plate of the present invention
The support is provided with an image recording such as a photosensitive layer and a thermosensitive layer exemplified below.
A recording layer can be provided to provide a lithographic printing plate precursor according to the present invention.
The The image recording layer is not particularly limited.
Conventional positive type, conventional negative tie
Type, photopolymer type, thermal positive type, sensor
Marnega type, non-processing type that can be developed on the machine is suitable
Can be mentioned. Hereinafter, these suitable image recording layers will be described.
This will be described in detail. <Conventional positive type> Conventional
Lithographic printing of the present invention having a photosensitive layer of national positive type
As a positive photosensitive resin composition used for the plate precursor,
Change in solubility or swelling in developer before and after exposure
Can be used as long as
As an example, o-quinonediazide compound is mentioned.
The For example, water-insoluble and alkali-soluble polymer compounds
(Hereinafter referred to as “alkali-soluble polymer compound”)
And positive-type photosensitivity containing o-quinonediazide compound
In the case of the resin composition, the o-quinonediazide compound is a small amount.
A compound having at least one o-quinonediazide group,
Increases solubility in alkaline aqueous solution by actinic rays
Is preferred. As such, various structures can be used.
For example, J. KOSAR "Lig
ht-Sensitive Systems "(Joh
nWiley & Sons, Inc, 1965
Line) p. 336-352. o-
As quinonediazide compounds, various hydroxy compounds are used.
Compound and o-benzoquinonediazide or o-naphtho
Sulfonic acid esters made from non-diazide are preferred
It is. O-quinonediazide compounds as described above and
For example, 1,2-naphthoquinone-2-diazide
-5-sulfonyl chloride and phenol / formal
With aldehyde resin or cresol / formaldehyde resin
Esters in U.S. Pat. No. 3,635,709
1,2-Naphthoquinone-2-diazide described
5-sulfonyl chloride and pyrogallol / acetone tree
Esters with fat; described in Japanese Patent Publication No. 63-13528
1,2-Naphthoquinone-2-diazide-5
-Sulfonyl chloride and resorcin-benzaldehyde
Esters with resin; Japanese Patent Publication No. 62-44,257
1,2-naphthoquinone-2-diazide described in
-5-sulfonyl chloride and resorcin-pyrogalo
Esters with ru-acetone co-condensation resin; As described in Japanese Examined Patent Publication No. 56-45,127.
A polyester having a hydroxy group at its terminal
1,2-naphthoquinone-2-diazide-5-sulfonyl
Esterified from chloride;
N- (4-hydroxyl) described in Japanese Patent No. 4,641.
Siphenyl) methacrylamide homopolymer or others
1,2-naphtho to a copolymer with a copolymerizable monomer
Quinone-2-diazide-5-sulfonyl chloride
Stylized; Japanese Patent Publication No. 54-29,922
1,2-naphthoquinone-2-diazide described in
-5-sulfonyl chloride and bisphenol form
Esters with aldehyde resins;
Of p-hydroxystyrene described in Japanese Patent No. 3
Copolymerization with mopolymers or other copolymerizable monomers
1,2-naphthoquinone-2-diazide-5-sulfo
Nyl chloride esterified; 1,2-naphth
Toquinone-2-diazide-5-sulfonyl chloride and
There are esters with polyhydroxybenzophenone. Other known o-keys that can be used in the present invention.
Non-diazide compounds include those disclosed in JP-A-63-80254.
, JP 58-5737, JP 57-11153
No. 0, JP-A-57-111531, JP-A-57-11
No. 4138, Japanese Patent Laid-Open No. 57-142635, Japanese Patent Laid-Open No. 51
-36129, Shoko 62-3411, Shoko 62
Described in publications such as -51459 and Shokoku 51-483
What is listed can be listed. o-quinone
The content of the diazide compound is the total solid content of the photosensitive resin composition.
Usually, it is 5 to 60% by weight, preferably
It is 10-40 mass%. Sensitization other than o-quinonediazide compounds
As a compound, an alkali-soluble group was protected with an acid-decomposable group.
Chemical amplification system consisting of a combination of a compound and a photoacid generator
Photosensitive material (light irradiation sensitive mixture) can be used
The Photoacid generation used for chemically amplified photosensitive materials
A well-known thing can be used as an agent. example
S. I. Schlesinger, Photog
r. Sci. Eng. , 18, 387 (1974),
T.A. S. Bal et al, Polymer, 21,
Diazonium described in 423 (1980)
Salt, U.S. Pat. No. 4,069,055, 4,0
69,056 specification, Unexamined-Japanese-Patent No. 3-140140
Ammonium salts described in the above, and the like. C. Neck
er et al, Macromolecules, 1
7, 2468 (1984), C.I. S. Wen et a
l, Teh, Proc. Conf. Rad. Curin
g ASIA, p. 478 Tokyo, Oct (19
88), U.S. Pat. Nos. 4,069,055 and 4,062.
Phosphonium described in each specification of No. 9,056
Mu salt, J.M. V. Crivello et al, Mac
romolecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 2
8, p. 31 (1988), European Patent No. 104,143
No., U.S. Pat. Nos. 339,049 and 410,201.
No. 1, No. 2-150848, JP-A No. 2-150848
Iodonium described in each publication of No. 296514
Mu salt, J.M. V. Crivello et al, Pol
ymer J.M. 17, 73 (1985), J. Am. V. Cr
ivello et al. J. et al. Org. Chem. ,
43, 3055 (1978), W.W. R. Wattet
al, J. et al. Polymer Sci. , Polymer
  Chem. Ed. , 22, 1789 (1984),
J. et al. V. Crivello et al, Polyme
r Bull. 14, 279 (1985), J. Am. V.
Crivello et al, Macromorec
ules, 14 (5), 1141 (1981), J. Am.
V. Crivello et al, J.A. Polyme
r Sci. , Polymer Chem. Ed. , 1
7, 2877 (1979), European Patent No. 370,693
No. 3, US Pat. No. 3,902,114, European Patent No. 23
3,567, 297,443, 297,442
U.S. Pat. Nos. 4,933,377 and 410,20
No. 1, No. 339,049, No. 4,760,013,
4,734,444, 2,833,827, Germany
Japanese Patent Nos. 2,904,626 and 3,604,580
No. 3,604,581 etc., etc.
Sulfonium salt, J. J. et al. V. Crivello et al,
Macromolecules, 10 (6), 1307
(1977), J.M. V. Crivello et a
l, J. et al. Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979) etc.
A selenonium salt, C.I. S. Wen et
al, Teh, Proc. Conf. Rad. Curi
ng ASIA, p. 478 Tokyo, Oct (1
988), etc.
Mu salt; U.S. Pat. No. 3,905,815, Shoko
46-4605, JP-A 48-36281, JP-A
55-32070, JP-A-60-239736, Special
Japanese Utility Model Publication No. 61-169835, Japanese Patent Application Laid-Open No. 61-169837
JP, 62-58241, JP 62-2124
01, JP-A 63-70243, JP-A 63-29
Organic halogenation described in each publication of No. 8339
Compound; K. Meier et al, J.A. Rad. Cu
ring, 13 (4), 26 (1986), T. P. G
ill et al, Inorg. Chem. , 19,
3007 (1980), D.M. Astruc, Acc. C
hem. Res. , 19 (12), 377 (189
6), described in JP-A-2-161445, etc.
Organometallic / organic halides; Hayase e
t al, J. et al. Polymer Sci. , 25, 75
3 (1987), E.I. Reichmaniset a
l, J. et al. Polymer Sci. , Polymer
  Chem. Ed. , 23, 1 (1985), Q.M. Q.
Zhu et al, J.A. Photochem. , 3
6, 85, 39, 317 (1987), B.I. Amit
et al, Tetrahedron Lett. ,
(24), 2205 (1973), D.M. H. R. Bar
ton et al, J.A. ChemSoc. , 3571
(1965), p. M.M. Collins et al,
J. et al. Chem. Soc. Perkin I, 1695
(1975), M.M. Rudinstein et a
l, Tetrahedron Lett. , (17),
1445 (1975), J. MoI. W. Walker et
al J. et al. Am. Chem. Soc. , 110,717
0 (1988), S.A. C. Busman et al,
J. et al. ImagingTechnol. , 11 (4), 1
91 (1985), H.C. M.M. Houlihan et
al, Macormolecules, 21, 2001.
(1988), p. M.M. Collins et al,
J. et al. Chem. Soc. , Chem. Commun. ,
532 (1972), S.A. Hayase et al,
Macromolecules, 18, 1799 (19
85), E.I. Reichmanis et al.
Electrochem. Soc. , Solid St
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F. M.M. Houlihan et al, Macrom
olcules, 21, 2001 (1988), European special
No. 0290,750, 046,083, 15
No. 6,535, No. 271,851, No. 0,388,3
43, U.S. Pat.Nos. 3,901,710, 4,18
Nos. 1,531 and JP-A-60-198538
No., JP-A-53-133302, etc.
Photoacid generation with o-nitrobenzyl type protecting group
Agent; M.M. Tunook et al, Poly
mer Preprints Japan, 35
(8) G. Berner et al, J.A. Rad.
Curing, 13 (4), W.M. J. et al. Mijs et
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7), 45 (1983), Akzo, H .; Adachi
  etal, Polymer Preprints, J
apan, 37 (3), European Patent No. 0199,672.
No., No. 84515, No. 199,672, No. 044
115, 0101,122, US Pat. No. 4,61
8,564, 4,371,605, 4,43
Nos. 1,774, JP-A No. 64-18143,
JP-A-2-245756, JP-A-4-365048
In the imino sulfonates described in the above publications, etc.
Representative compounds that generate sulfonic acid by photolysis;
Jiss described in Japanese Utility Model Publication No. 61-166544
Examples include luphone compounds. By irradiation with these actinic rays or radiations
Amount of compound (photoacid generator) that decomposes and generates acid
Is generally 0. 0 with respect to the total solid content of the photosensitive resin composition.
001 to 40% by mass, 0.01 to 20% by mass
Preferably 0.1 to 5% by mass.
That's right. In addition, alkali-soluble groups are protected with acid-decomposable groups.
The compound (compound that can be cleaved by an acid) is -C-O.
Compound having —C— bond or —C—O—Si— bond
The following examples can be given. (A) at least one orthocarboxylic acid ester and
And those selected from the group of carboxylic acid amide acetals
The compound can have polymerizability, and the above group
As a bridging element in the main chain or as a lateral substituent
(B) a repeating acetal in the main chain
And oligomeric substances including those selected from the ketal group
Or a polymer compound, (c) at least one enol enol
Compounds containing stealth or N-acylamino carbonate groups
Compound (d) of β-ketoester or β-ketoamide
Cyclic acetal or ketal, (e) silyl ether
Group-containing compounds, including (f) silyl enol ether group
Compound (g) aldehyde or ketone component is developed
A solvent having a solubility of 0.1 to 100 g / L with respect to the agent.
Noacetal or monoketal, (h) tertiary alcohol
Ether, (i) tertiary allylic position or benzil
Carboxylic acid ester and carbonic acid ester
Le. As a component of the light-sensitive mixture, an acid is used.
The compound of the above (a) which is a compound that can be cleaved is
Patent Application Publication No. 2,610,842 and the same
No. 2,928,636. the above
A mixture containing the compound of (b) is described in German Patent 2,30.
No. 6,248 and No. 2,718,254
It is described in the booklet. The compound of the above (c)
Patent Application Publication No. 0,006,626 and No. 1
No. 0,006,627. the above
The compound of (d) is EP 0,202,1
No. 96 specification. Compound (e) above
German Patent Application Publication No. 3,544,165
And in the specification of US Pat. No. 3,601,264
The The compound of the above (f) is German Patent Application Publication No. 3,7.
No. 30,785 and No. 3,730,783
It is described in the specification. The compound of (g) above is Germany
Described in Japanese Patent Application No. 3,730,783
ing. The compound of (h) is, for example, U.S. Pat.
No. 4,603,101. the above
The compound (i) is, for example, U.S. Pat. No. 4,491,6.
28 and J.P. M.M. Frechet et al.
(J. Imaging Sci. 30, 59-64 (1
986)). These alkali soluble
The content of the compound whose group is protected with an acid-decomposable group is the photosensitive resin
It is usually 1 to 60% by mass with respect to the total solid content of the composition.
Preferably, it is 5-40 mass%. The photosensitive resin composition has a high alkali soluble content.
You may contain a child compound. Alkali-soluble polymer compound
For example, phenol formaldehyde tree
Fat, Cresol / Formaldehyde resin, Phenol /
Cresol / formaldehyde co-condensation resin, phenol
Modified xylene resin, polyhydroxystyrene, polyhalo
Genated hydroxystyrene, N- (4-hydroxyphene
Nyl) methacrylamide copolymer, hydroquinone
Nomethacrylate copolymer, Japanese Patent Laid-Open No. 7-28244
Sulfonylimide-based polymers described in
Carboxy group described in JP-A-7-36184
And containing polymers. Also, JP-A 51-34.
Phenolic hydride as described in Japanese Patent No. 711
Acrylic resin containing a roxy group, JP-A-2-866
Acrylic having sulfonamide group described in No.
Various alkali-soluble materials such as polyurethane resins and urethane resins
These polymer compounds can also be used. These arcas
The resoluble polymer compound has a weight average molecular weight of 500-2.
It is preferably 00,000, and the number average molecular weight
Is preferably 200 to 60,000. alkali
Soluble polymer compounds may be used alone or in combination of two or more
May be used in combination, the entire photosensitive resin composition
Used at a content of 80% by weight or less based on solid content
The Furthermore, US Pat. No. 4,123,279 Akira
As described in the details,
Lumaldehyde resin, octylphenol formaldehyde
Alkyl group having 3 to 8 carbon atoms such as hydride resin as a substituent
Condensation product of phenol and formaldehyde
Is used in order to improve the oil sensitivity of the image.
Good. Such an alkali-soluble polymer compound is usually
90% by mass or less based on the total solid content of the photosensitive resin composition
Is used at a content of. In the photosensitive resin composition, if necessary, further.
Cyclic acid anhydride to increase sensitivity, possible immediately after exposure
Print-out agent for obtaining visual image, dyeing as image colorant
Materials, other fillers, etc. can be added. In the photosensitive resin composition, the sensitivity is increased.
Add cyclic acid anhydrides, phenols, and organic acids
It is preferable. Specifically, as the cyclic acid anhydride,
Described in US Pat. No. 4,115,128.
Compounds. Examples of organic acids include JP-A-60-8894.
2 and JP-A-2-96755
Sulfonic acids, sulfinic acids, alkyl sulfuric acid
, Phosphonic acids, phosphinic acids, phosphate esters
And carboxylic acids. The above cyclic acid anhydrides, phenols and
The total content of organic acids is the total solid content of the photosensitive resin composition.
It is preferably 0.05 to 15% by mass based on the shape.
More preferably 0.1 to 5% by mass. Printout to obtain a visible image immediately after exposure
As a rusting agent, a photosensitive compound that releases an acid upon exposure
And organic dyes that change color by forming salts with acids
Can be mentioned. The acid used by the exposure used in the print-out agent
As the photosensitive compound to be released, for example, JP-A-50-
Described in 36209, 55-62444, etc.
O-Naphthoquinonediazide compounds which have been used;
Trihalomethyl described in Japanese Patent No. 3-36223
2-Biron and trihalomethyl-s-triazine;
2-Toriha described in Japanese Patent Publication No. 55-77742
Romethyl-5-aryl-1,3,4-oxadiazo
A diazonium salt; and the like. This
These compounds can be used alone or in combination.
The content is based on the total solid content of the photosensitive resin composition.
It is preferably 0.3 to 15% by mass. In the photosensitive resin composition, it is photodecomposed.
Interacts with photodegradation products of compounds that generate acidic substances
At least organic dyes that change their color
Also, it is preferable to use one or more. Such organic dye
Examples of materials include diphenylmethane and triary
Lumethane, thiazine, oxazine, phenazine
, Xanthene, anthraquinone, iminonaphtho
Non- and azomethine dyes can be used. Ingredients
Specifically, for example, JP-A-50-36209,
The compounds described in JP-A-55-77742 are listed.
I can get lost. Particularly preferred organic dyes are triaryl dyes.
Tan dye. Among triarylmethane dyes
Are disclosed in JP-A-62-2932471 and JP-A-5-3.
Counter anion as described in US Pat. No. 13359
Those having a sulfonic acid compound are particularly useful. These dyes are used alone or in combination.
The content of the photosensitive resin composition
It is preferable that it is 0.3-15 mass% with respect to solid content.
Yes. Also, use with other dyes and pigments as necessary.
The amount used is based on the total mass of dyes and pigments.
It is preferably 70% by mass or less, and 50% by mass or less.
More preferably. Each component of the photosensitive resin composition is dissolved in a solvent.
The lithographic printing plate support of the present invention is dissolved or dispersed.
The lithographic printing plate precursor of the present invention is applied to the holder by coating
A version is obtained. Specific examples of the solvent include a solvent.
Lucols (methanol, ethanol, isopropano
, Tetrahydrofurfuryl alcohol, diacetone
Lucol, ethylene glycol, propylene glycol
, Ethylene glycol monomethyl ether, ethylene
Glycol monoethyl ether, 1-methoxy-2-propyl
Ropanol, etc.), hydrocarbons (toluene, cyclohexa
), Halogenated hydrocarbons (ethylene dichloride)
Etc.), ketones (acetone, acetylacetone, methyl)
Ethyl ketone, methyl isobutyl ketone, cyclohexa
Non), esters (ethyl acetate, methyl lactate, lactic acid)
Ethyl, 2-methoxyethyl acetate, 1-methoxy
-2-propyl acetate), ethers (ethylene)
Glycol dimethyl ether, diethylene glycol di
Methyl ether, propylene glycol diethyl ether
), Amides (dimethylacetamide, dimethylphenol, etc.)
Lumamide, N-methylpyrrolidone, etc.), γ-butyrolas
Kuton, dimethyl sulfoxide, water and their solvents
It can be used by appropriately selecting from a mixture of As the coating method, various methods are used.
For example, bar coater coating, spin coating
Cloth, spray coating, curtain coating, dip coating, air
-Knife coating, blade coating, roll coating, etc.
You can. <Conventional negative type> Conventional
Lithographic printing of the present invention having a photosensitive layer of the negative type
As a negative photosensitive resin composition used for the plate precursor,
For example, diazo resin and alkali-soluble or highly swellable
What contains a molecular compound (binder) is mentioned.
As a diazo resin used in negative photosensitive resin compositions
For example, aromatic diazonium salt and formaldehyde
Condensates with active carbonyl group-containing compounds such as
It is. Examples of the diazo resin include p-diazof.
Enylamines and formaldehyde, acetaldehyde
Condensates with aldehydes such as hexafluorophosphate
Or organic product of reaction with tetrafluoroborate
Solvent-soluble diazo resin inorganic salt; Japanese Examined Patent Publication No. 47-1167
The condensate as described in the publication and sulfone
Acid salts such as p-toluenesulfonic acid, propylna
Phthalenesulfonic acid, butylnaphthalenesulfonic acid, di
Butylnaphthalenesulfonic acid, dodecylbenzenesulfone
Acid, 2-hydroxy-4-methoxybenzophenone-
Organic solvent soluble disulfide that is a reaction product with 5-sulfonic acid
An azo resin organic salt is mentioned. In particular, JP-A-59-78.
20 mol% of hexamer or more described in No. 340
The high molecular weight diazo compound contained above is preferred. Ma
It is described in JP-A-58-27141.
Such 3-methoxy-4-diazo-diphenylamine
4,4'-bis-methoxy-methyl-diphenyl ether
Also suitable are mesitylene sulfonates condensed with water.
It is right. Further, described in Japanese Patent Publication No. 49-48001
Co-condensed diazo resins with aromatic compounds and
It has an acid group described in JP-A-2-29650
Co-condensed diazo resins with aromatic compounds are also preferably used
The Further, it is described in JP-A-4-18559.
With an aldehyde or acetal compound having an acid group
The combined diazo resin can be preferably used as well.
The Furthermore, a carboxy group, a sulfo group, a sulfinic acid group,
Selected from the group consisting of oxyacid group and hydroxy group of phosphorus
An aromatic compound having at least one organic group,
Diazonium compounds, preferably aromatic diazonium
A cocondensate containing a compound as a structural unit is also preferred. Na
These diazo resins may be used alone or in two kinds
You may use as a mixture of the above. Diazo resin content
Is 1 to 70% by mass relative to the total solid content of the photosensitive layer
Is preferable, and 3 to 60% by mass is more preferable.
Yes. Al used for negative photosensitive resin composition
Potassium-soluble or swellable polymer compounds include acid-containing compounds.
Abundance is preferably 0.1-5.0 meq / g, more preferred
Or 0.2 to 3.0 meq / g, substantially water-free.
Soluble (ie, insoluble in neutral or acidic aqueous solutions) and skin
An organic polymer compound having film-forming properties, comprising an alkali
Can be dissolved or swelled in the developer, and
Insoluble in the above developer by photocuring in the presence of a diazo resin
Those that become non-swelled are preferred. Acid content
When it is less than 0.1 meq / g, it becomes difficult to develop
If it exceeds 5.0 meq / g, the image strength during development
The degree may be significantly weakened. Particularly suitable binders include acrylic acid,
Methacrylic acid, crotonic acid or maleic acid is an essential ingredient
The multi-component copolymer contained as is mentioned. For example, JP
50-118802, JP-A-53-120903,
JP-A-54-98614 and JP-A-56-4144
And multi-component copolymers described in each publication
The Further, as the binder, acidic polyvinyl polymers are used.
Lucol derivatives and acidic cellulose derivatives are also useful.
Polyvinyl acetal and polyurethane
Japanese Patent Publication No. 54-19773, Japanese Patent Publication No. 57-9
4747, 60-182437, 62-582
42 and 62-123453
Also useful are binding agents. The molecular weight of the binder is 0.5 to 200,000
Is more preferable, and 2 to 150,000 is more preferable. this
These binders may be used alone or in combination of two or more.
It may be used. Of diazo resin and binder in photosensitive layer
The content is based on the total amount of both, and the diazo resin
Is 3 to 60% by mass, and the binder is 97 to 40% by mass.
It is appropriate. Less content of diazo resin
However, if the sensitivity is less than 3% by mass, the binder is light-cured.
The photocured film is not suitable for development.
It swells with the image liquid and the film becomes weak. Conversely, diazo resin
If the content of exceeds 60% by mass, the sensitivity decreases and the actual
Useful points come out. Preferably, the diazo resin is 5-4.
0% by mass and the binder is 95-60% by mass. Dissolve each component of the photosensitive resin composition.
Dissolve in solvent and apply on lithographic printing plate support of the present invention
By doing so, the lithographic printing plate precursor of the present invention is obtained.
The The solvent contains an alkali-soluble polymer compound.
When providing an interlayer, an alkali-soluble polymer compound
Those that do not dissolve are selected. Specifically, for example,
Same as the conventional positive type photosensitive layer described above.
The following solvents are mentioned. As a method of applying, as described above.
The same as for conventional positive-type photosensitive layers
Various methods can be used. The concentration (solid content) of the above components is 2-50.
It is appropriate that the amount is%. As coating amount (solid content)
0.5-4.0 g / m²Is preferred. 0.5g
/ M ²If it is less, the printing durability may deteriorate.
4.0 g / m²If it is more, the printing durability will be improved, but
The degree may decrease. In the photosensitive resin composition, the coatability is improved.
Surfactants, for example, JP-A-62-1709
Fluorosurfactant as described in Japanese Patent No. 50
Can be added. Amount of fluorosurfactant added
Is 0.01 to the total solid content of the photosensitive resin composition
It is preferably 1% by mass, 0.05 to 0.5% by mass
It is more preferable that It should be noted that the conventional negative tie described above.
Arbitrary layers may be provided under the photosensitive layer. For example,
It is described in JP 2000-105462 A,
A component having an acid group and a component having an onium group;
An intermediate layer containing a polymer compound having
The <Photopolymer type> (Photosensitive layer) The present invention having a photopolymer type photosensitive layer
Photopolymerization type photosensitive composition used for lithographic printing plate precursor
(Hereinafter referred to as “photopolymerizable composition”) is capable of addition polymerization.
A compound containing an ethylenically unsaturated bond (hereinafter simply referred to as “eth
It is referred to as “lenic unsaturated bond-containing compound”. ) And photopolymerization
Contains an initiator and a polymer binder as essential ingredients
Depending on the type, various colorants, plasticizers, thermal polymerization inhibitors, etc.
Contains compound. [0136] Ethylenic polymers contained in the photopolymerizable composition
Saturated bond-containing compounds are those whose photopolymerizable composition is irradiated with
Addition polymerization by the action of photoinitiator when irradiated
Have an ethylenically unsaturated bond that crosslinks and cures
It is a compound. The ethylenically unsaturated bond-containing compound is
At least one terminal ethylenically unsaturated bond, preferably
Can be arbitrarily selected from compounds having two or more
For example, monomers, prepolymers (ie, 2 quantities)
, Trimers and oligomers), mixtures thereof, this
And other chemical forms such as copolymers. Examples of monomers and copolymers thereof
Unsaturated carboxylic acids (e.g. acrylic acid, methacrylate)
Formic acid, itaconic acid, crotonic acid, isocrotonic acid, male
Esters of aliphatic acid and aliphatic polyhydric alcohol compounds,
Amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds
Is mentioned. Unsaturated carboxylic acid and ester monomers
Specific examples of aliphatic polyhydric alcohol compounds that form
Are ethylene glycol, triethylene glycol,
1,3-propanediol, 1,3-butanediol,
Tetramethylene glycol, propylene glycol, ne
Opentyl glycol, trimethylolpropane, tri
Methylolethane, hexanediol, 1,4-cyclo
Hexanediol, pentaerythritol, dipentae
Lithitol, sorbitol, tri (2-hydroxy ester
Til) isocyanurate, bis [p- (3-hydroxy
-2-Hydroxypropoxy) phenyl] dimethylmeta
Bis- [p- (2-hydroxyethyloxy) fe
Nil] dimethylmethane and the like. However, trivalent or more
There are at least two alcohol compounds in the molecule
Any of the polymerizable unsaturated groups may be used.
In the present invention, these ester monomers
Mixtures can also be used. Formation of amide monomer with unsaturated carboxylic acid
Specific examples of the aliphatic polyamine compound to be used include methyl
Diamine, ethanediamine, propanediamine, teto
Ramethylene diamine, hexamethylene diamine, diethyl
Rentriamine, xylylenediamine, cyclohexane
Diamine, cyclohexanedimethylamine, etc.
The As another example, Japanese Patent Publication No. 48-417.
Two or more isoforms in one molecule described in JP 08
Polyisocyanate compounds having cyanate groups
1 minute after adding vinyl monomer having droxy group
Vinylureta having two or more polymerizable vinyl groups in the core
Compounds, Japanese Patent Application Laid-Open No. 51-37193, and Japanese Patent
Urethanes as described in Japanese Patent No. 2-332293
Acrylates, JP-A-48-64183, JP-B-4
No. 9-43191 and Japanese Patent Publication No. 52-30490
Polyester acrylates as described in
Epoxy with epoxy resin and (meth) acrylic acid reacted
Polyfunctional (meth) acrylates such as acrylates
Can be mentioned. In addition, Japan Adhesion Association Magazine Vo1.2
0, No. 7, p. Light on 300-308 (1984)
Introduced as curable monomers and oligomers
Things can also be used. These ethylenically unsaturated bond-containing compounds
The content of is 5 to 5 with respect to the total solid content of the photopolymerizable composition.
80% by mass is preferable, and 30 to 70% by mass.
More preferably. Photopolymerization initiator contained in the photopolymerizable composition
According to the wavelength of the light source used, in patents, literature, etc.
Various known photopolymerization initiators or two or more photopolymerizations
Use the initiator combination system (photoinitiation system) as appropriate.
Can do. Specific examples of the photopolymerization initiator are listed below,
The present invention is not limited to these. 400nm
Second of visible light, Ar laser, semiconductor laser
When using a harmonic, SHG-YAG laser as the light source,
Various photoinitiation systems have been proposed. Photoinitiator below
Specific examples are listed below, but the present invention is not limited to these.
Not. Specific examples of photopolymerization initiators include photoreducibility
Dye (described in US Pat. No. 2,850,445: B)
Bengal, Eosin, Erythrosin, etc.), amine
(Described in Japanese Patent Publication No. 44-20189), radical generation
Agent (Japanese Patent Publication No. 45-37377, Japanese Patent Laid-Open No. 52-1126)
81, 58-15503, JP-A-2-17964
3 and 2-244050), hex
Saarylbiimidazole (Japanese Examined Publication No. 47-2528)
And described in JP 54-155292 A), cyclic
Cis-α-dicarbonyl compounds (JP-A-48-8418)
3), cyclic triazine (JP-A-54-151)
No. 024), Bimidazir (JP 59-1)
40203), organic peroxides (Japanese Patent Laid-open No. Sho 59-
1504, 59-140203, 59-189
No. 340, No. 62-174203, and Shoko 62-
No. 1641 and U.S. Pat. No. 4,766,0
55), an active halogen compound (Japanese Patent Laid-Open No. Sho 63)
No. -259033 and JP-A-2-63054
Report), borate compounds (JP-A-62-143044)
No., No. 62-150242, No. 64-13140,
64-13141, 64-13142, 64
-13143, 64-13144, 64-17
No. 048, JP-A-1-229003, JP-A-1-29
No. 8348, No. 1-138204 and No. 11-84
No. 647), thiol compounds (Japanese Unexamined Patent Publication No. 59)
-140203, etc.), disulfone compounds (special
No. 61-166544), titanocene compound
(Japanese Patent Laid-Open Nos. 59-152396 and 61-15119)
7, JP-A-4-219756, and 4-221958.
No., No. 6-295061, No. 8-334897, Special
Kai 2000-147663 and 2001-042
No. 524), an iron-arene complex (Japanese Patent Laid-Open No. Hei 1)
-304453, 1-152109, etc.
Listed). In the present invention, in particular, the titanocene compound is used.
Since the system using is excellent in terms of sensitivity,
It is. Various titanocene compounds are used.
For example, JP 59-152396 A
Described in Japanese Patent Laid-Open No. 61-151197.
Select from various titanocene compounds
Can do. In these photoinitiating systems, exposure to light (light weight)
The image recording layer further enhances the sensitizing color.
It preferably contains elemental or sensitization aids. Photopolymerization started
By using a sensitizing dye in combination with the photosensitizer,
The long region can be adjusted. As a combination dye
Preferred are cyanine, merocyanine, oxa
Nten, ketocoumarin and benzopyran dyes
The Although the cyanine dye is not particularly limited,
No. 2-143044, Japanese Examined Patent Publication No. 46-42363
What is described in the report etc. is illustrated suitably. Merosi
The anine-based pigment is not particularly limited,
Described in Japanese Patent No. 621, Japanese Patent Laid-Open No. 2-17943, etc.
What is done is illustrated suitably. In the methine chain
, Thiazolidinone ring, imidazoliquinone ring, oxazo
Merocyanines containing lysine or dithiolanone rings
Dyes (for example, JP-A-2-244050, JP-B-59)
-28326, JP-A-59-89303, JP-A-8
-129257, etc.) is also preferably exemplified. Ki
Santen dyes are not particularly limited, but rhodamine
B, rhodamine 6G, ethyl eosin, alcohol soluble
Preferred examples are sex eosin, pyronin Y, and pyronin B.
The Ketocoumarin dyes and benzopyran dyes
Although not particularly limited, Japanese Patent Application Laid-Open No. 8-3344897
The compounds described are preferably exemplified. Furthermore, the photopolymerizable composition has the above-described photopolymerization initiation.
In addition to the agent, the effect of further improving the sensitivity, or oxygen
Known compounds having an action of suppressing polymerization inhibition by
May be contained as a co-sensitizer. Such co-sensitizers
Examples of amines include amines (eg, MR Sande
r et al., “Journal of Polymer So
city ", Vol. 10, p. 3173 (1972), special
Kosho 44-20189, JP-A 51-82102,
JP 52-134692 A, JP 59-13820 A
5, JP 60-84305, JP 62-185
37 and JP-A 64-33104
Bini, Research Disclosure 33
Compounds described in No. 825), thiol and
Sulfides (for example, JP-A-53-702 and
Described in Japanese Patent Publication No. 55-500806
Compound, etc.), described in JP-A-5-142773
Thiol compounds, disclosed in JP-A-56-75643
The disulfide compounds and amino acid compounds described
(For example, N-phenylglycine, etc.), JP-B 48-4
No. 2965, organometallic compounds (for example,
Tributyltin acetate, etc.), JP-B 55-34
The hydrogen donor described in Japanese Patent No. 414,
Sulfur compounds described in Japanese Patent No. 308727
(E.g., Tritian etc.), JP-A-6-250389
Phosphorus compounds described in (diethyl phosphite
Etc.). These photopolymerization initiators or photoinitiators are included.
The content is 100% of the ethylenically unsaturated bond-containing compound.
It is preferable that the amount is 0.05 to 100 parts by mass with respect to the amount part.
More preferably, it is 0.1 to 70 parts by mass.
More preferably, it is 2-50 mass parts. Polymeric binder contained in photopolymerizable composition
Only functions as a film-forming agent for the photopolymerizable composition.
The photosensitive layer must be dissolved in an alkaline developer.
High organic content that is soluble or swellable in alkaline water
A child polymer is used. Such organic polymer and
For example, when a water-soluble organic polymer is used,
Development is possible. As such an organic polymer
Is an addition polymer having a carboxy group in the side chain, for example,
JP 59-44615, JP-B 54-34327
No., JP-B 58-1277, JP-B 54-2595
7, JP 54-92723, JP 59-538
36 and JP-A-59-71048
That is, methacrylic acid copolymer, acrylic
Luric acid copolymer, Itaconic acid copolymer, Crotonic acid copolymer
Body, maleic acid copolymer, partially esterified maleic acid copolymer
A polymer etc. are mentioned. Further, as a polymer binder, a side chain contains a cal
It is also possible to use acidic cellulose derivatives having a boxy group
it can. In addition, the addition polymer having a hydroxy group is cyclic.
What added the acid anhydride is also useful. Among them, [benzyl (meth) acrylate
/ (Meth) acrylic acid / other addition polymerization as required
Vinyl monomer] copolymer and [allyl (meth) a]
Acrylate (meth) acrylic acid / other as required
Addition-polymerizable vinyl monomer] is preferable. Ma
Polyvinyl pyrrole as a water-soluble organic polymer
Don, polyethylene oxide and the like are useful. Also,
In order to improve the strength of the cured film, alcohol soluble
Polyamide, 2,2-bis- (4-hydroxypheny
E) Polyether of propane and epichlorohydrin
Le; No. 7-120040, No. 7-12004
No. 1, No. 7-120042, No. 8-1224
No. 4, JP-A 63-287944, JP-A 63-28
7947, Japanese Patent Laid-Open No. 1-271741 and Japanese Patent Laid-Open No. 1
Polyure described in each publication of No. 1-352691
Tan resins are also useful. These organic polymer polymers have a side chain with a label.
Strength of cured film by introducing dical reactive groups
Can be improved. Functional group capable of addition polymerization reaction
As an ethylenically unsaturated bond group, amino group, epoxy
A functional group that can become a radical when irradiated with light.
Mercapto group, thiol group, halogen atom, tria
Gin structure, onium salt structure, etc. are
Examples thereof include a xy group and an imide group. Addition polymerization reaction
Examples of functional groups that can be used include acrylic groups, methacryl groups,
Special feature is ethylenically unsaturated bond group such as allyl group and styryl group.
Preferred for amino group, hydroxy group, phosphonic acid
Group, phosphate group, carbamoyl group, isocyanate group,
Raid, ureylene, sulfo and ammonio groups
A functional group selected from the group consisting of is also useful. In order to maintain the developability of the photopolymerizable composition
The polymer binder in the present invention has an appropriate molecular weight and
It preferably has an acid value. The weight average molecular weight is 500
It is preferably 0 to 300,000, and the acid value is 20 to 2
00 is preferred. The polymeric binder is optional in the photopolymerizable composition.
The amount of the photopolymerizable composition can be
It is preferably 10 to 90% by mass based on the shape.
It is more preferably 0 to 80% by mass. 90% by mass
Exceeding this is not preferable in terms of the strength of the formed image.
In addition, an ethylenically unsaturated bond-containing compound and a polymer binder
Is preferably 1/9 to 9/1.
/ 8 to 8/2 is more preferable, and 3/7 to 7/3
More preferably. In the present invention, the photopolymerizable composition contains
An infrared absorber can also be contained. Infrared absorber
As a specific example, a thermal positive type thermosensitive layer described later
Various infrared absorbers used in the above are mentioned. In addition to the above essential components, the photopolymerizable composition comprises
During the production or storage of the photopolymerizable composition.
Prevent unnecessary thermal polymerization of compounds containing lentic unsaturated bonds
Therefore, it is preferable to contain a small amount of a thermal polymerization inhibitor.
Suitable thermal polymerization inhibitors include hydroquinone and p-me
Toxiphenol, di-t-butyl-p-cresol,
Pyrogallol, t-butylcatechol, benzoquinone,
4,4-thiobis (3-methyl-6-tert-butylpheno
2,2'-methylenebis (4-methyl-6-t)
-Butylphenol), N-nitrosophenylhydroxy
Silamine primary cerium salt, N-nitrosophenyl hydride
Roxylamine aluminum salt etc. are mentioned. Thermal polymerization
The content of the inhibitor is based on the total solid content of the photopolymerizable composition.
About 0.01 to about 5 mass%. In addition, if necessary, the photopolymerizable composition may be used.
In order to prevent polymerization inhibition by oxygen,
Contains higher fatty acid derivatives such as behenamide.
Even if it is unevenly distributed on the surface of the photosensitive layer during the drying process after coating,
Good. Inclusion of higher fatty acid derivatives, etc.
It is about 0.5 to about 10% by mass with respect to the total solid content.
preferable. Furthermore, the photopolymerizable composition contains a coloring of the photosensitive layer.
For the purpose, a colorant may be contained. As a colorant
The conventional positive type and conventional
Dyes and dyes used in conventional negative type photosensitive layers
Pigments (for example, phthalocyanine pigments, azo pigments,
Carbon black). The colorant content is
About 0.5 to about 20 relative to the total solids of the photopolymerizable composition
It is preferable that it is mass%. In addition, the photopolymerizable composition
Is an inorganic filler to improve the physical properties of the cured film;
Cutyl phthalate, dimethyl phthalate, tricresyl
It may contain additives such as plasticizers such as phosphate
Yes. These contents are based on the total solid content of the photopolymerizable composition.
And it is preferable that it is 10 mass% or less. The photopolymerizable composition is applied on the adhesive layer described later.
When cloth is used, it is dissolved in various solvents and used.
As a solvent, the above-mentioned conventional negative type
Similar to those exemplified as the solvent used in the photosensitive layer
Is mentioned. These solvents can be used alone or in combination
Can be used. The concentration (solid content) of the coating solution is
It is preferable that it is 1-50 mass%. For photopolymerizable composition
Contains surfactant to improve the coating surface quality
Can be made. The coating amount (solid content) of the photosensitive layer is about 0.1 to 0.1%.
About 10g / m²Preferably, 0.3 to 5 g / m
²More preferably, 0.5-3 g / m²Is
Is more preferable. (Oxygen-blocking protective layer)
On the light layer, in order to prevent the inhibition of oxygen polymerization,
An oxygen barrier protective layer is provided. Included in oxygen barrier protective layer
Examples of water-soluble vinyl polymers that can be used include polyvinyl alcohol.
Coal, its partial esters, ethers, acetals,
Substantial amount of undissolved water that makes them necessary water-soluble
Examples of such copolymers containing vinyl alcohol units
It is done. As polyvinyl alcohol, 71-100
% Hydrolyzed and having a polymerization degree of 300-2400.
I can get lost. Other useful polymers include polyvinyl
Examples include pyrrolidone, gelatin, and gum arabic. This
These may be used alone or in combination of two or more
Yes. The solution used when applying the oxygen barrier protective layer
The medium is preferably pure water, but methanol, ethanol
Alcohols such as acetone; acetone, methyl ethyl ketone, etc.
These ketones may be mixed with pure water. Coating solution
The concentration (solid content) of 1 to 20% by mass is preferred
Yes. The oxygen barrier protective layer further improves coatability.
Surfactant, water-soluble to improve film properties
You may add well-known additives, such as a plasticizer. Oxygen barrier
The coating amount of the protective layer is about 0.1 to about 15 g in mass after drying.
/ M²Preferably, about 1.0 to about 5.0 g / m
²It is more preferable that (Adhesive layer) Photopolymer type photosensitive layer
The adhesive layer shown below is provided as the lower layer of the present invention.
This is one of the preferred embodiments. Adhesive layer is alkenyl
Group, alkynyl group and other radicals
Functional group (hereinafter referred to as “addition-reactive functional group”)
Contains a silicon compound. The adhesive layer must be applied
Additive functional groups and governments that can hydrolyze alkoxy groups, etc.
Organosilicon compounds having functional groups (hereinafter referred to as “organic silicon
Compound (S) ". ) For lithographic printing plate
By treating the surface of the carrier, the hydrolyzable government
Active groups and metals, metal oxides, hydroxides,
Siloxy formed by chemical conversion treatment of droxy group and support
Reacts with a diol group to support the organosilicon compound
A covalent bond is formed with the body surface, and an addition reactive functional group
May be bonded to or planted on the support surface. Yes
Specific examples of the silicon compound (S) include Trialco
Xylyl compounds (hereinafter referred to as “organic silicon compounds (S-
1) ". ), Tetraalkoxysilane compounds (hereinafter
Hereinafter referred to as “organosilicon compound (S-2)”. ) Etc.
A run coupling agent is mentioned. As the organosilicon compound (S), a lithographic plate
From the viewpoint of improving stain resistance when used as a printing plate
Silicon compound (S-1) and organic silicon compound (S
-2) are preferably used in combination. The above-mentioned organosilicon compound has a central S.
Of 1 to 4 addition-reactive functional groups bonded to i atom
A lithographic plate with at least one remaining unhydrolyzed
It is applied to a printing plate support. Organosilicon compound
When coating on a plate printing plate support, it may be used as is.
In addition, it may be diluted with an appropriate solvent. For lithographic printing plates
Bond organic silicon compounds more firmly on the support
For this purpose, water and / or a catalyst can be added.
Solvents include methanol, ethanol, and propano
, Isopropanol, ethylene glycol, hexile
Preferred examples include alcohols such as glycols.
Further, as the catalyst, acids such as hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid;
Ammonia, tetramethylammonium hydroxide, etc.
The base is preferably exemplified. Addition-reactive functional groups on a lithographic printing plate support
The amount depends on the type of addition-reactive functional group to be bound.
Usually 10nm²0.01-1000 per
It is preferably 0.05 to 200, and
More preferably, it is 1-50. Addition functional group
The amount is 10nm²If it is less than 0.01 per one, it is enough
It is difficult to obtain photoadhesive strength. Thick organosilicon compound
10nm by recoating²Per addition reaction
The amount of functional groups can be increased substantially
However, the attachment that can be exposed on the outermost surface
Additive functional group amount is 10nm²10 at most
So it is useless even if it is too thick. Addition functional group
Make sure that the amount is not too high and the hydrophilicity of the non-image area is insufficient.
10nm for²Amount of addition-reactive functional group
Is preferably 1000 or less. Existence for organic silicon compound (S-1)
Specific mixing molar ratio of the silicon compound (S-2)
Is preferably 0.05 to 500, 0.2 to 2
00 is more preferable, and 1 to 100 is more preferable.
Is preferred. Also, within the above range, organosilicon compound
If the amount of the hydrophilic group derived from (S-2) is increased,
The hydrophilicity of the non-image area is increased. However, the density of hydrophilic groups is
Hydrophilic treatment of addition-reactive functional groups even if low
The density of the hydrophilic group can be improved. Addition reactivity to the surface of a lithographic printing plate support
Specific embodiments of the introduction of the functional group and the organosilane compound are as follows:
For example, JP-A-7-159983 and 8-3
Use the contents described in the publication No. 20551
it can. There is no uneven distribution of the adhesive layer used in the present invention.
In order to prevent this, apply these treatment solutions to the support.
It is preferable to adjust the concentration by adding a solvent before the preparation. This
Solvents used for this purpose include alcohols, especially meta
Nord is preferred, but other solvents, organic compounds, inorganic additives
Additives, surfactants and the like can also be added. Of other solvents
For example, the conventional negative type feeling described above
What was illustrated as a solvent used for an optical layer is mentioned.
The Examples of organic compounds that can be added include
Poxy resin, acrylic resin, butyral resin, urethane
Resin, novolac resin, pyrogallol-acetone resin,
Polyvinyl pyrrolidone, polyvinyl alcohol, poly vinyl
Nyl methyl ether, polypropylene glycol
It is done. Examples of inorganic additives include colloidal silica,
A colloidal alumina is mentioned. The liquid composition used in the present invention (present
Application of silicon compound or its solution or sol solution)
Construction methods include brushing, dipping, atomizing, and cleaning.
Various types such as pin coating, doctor blade application, etc.
Can be used, taking into account the required film thickness, etc.
Can be decided. In addition, it has the above-mentioned addition-reactive functional group.
The adhesive layer containing the silicon compound is a photopolymer film.
As well as conventional positive type and convex
National negative type, thermal positive type, thermal
In each negative and non-processing type image recording layer
Can also be provided. <Thermal positive type> (Thermosensitive layer) Thermal positive type feeling used in the present invention
The thermal layer is composed of an alkali-soluble polymer compound and an infrared absorber.
Containing. Here, the alkali-soluble polymer compound is
Contains acidic groups in the main chain and / or side chain in the polymer
Homopolymers, copolymers thereof, and mixtures thereof
Is included. Therefore, thermal positive type heat sensitive layer
Has the property of dissolving when in contact with alkaline developer
The As the alkali-soluble polymer compound, the following (1)
To (6) at least one of the acidic groups is a polymer main chain
And / or an alkali developer in the side chain
It is preferable from the viewpoint of solubility. (1) Phenolic hydroxy group (-Ar
-OH) (2) Sulfonamide group (—SO₂NH-R) (3) Substituted sulfonamide acid group (—SO₂NHCO
R, -SO₂NHSO₂R, -CONHSO₂R) (
Hereinafter referred to as “active imide group”. ) (4) Carboxy group (—CO₂H) (5) Sulfo group (—SO_ThreeH) (6) Phosphate group (-OPO_ThreeH₂) In the above (1) to (6), Ar represents a substituent.
It represents a divalent aryl linking group that may have. R is
The hydrocarbon group which may have a substituent is represented. An acidic group selected from the above (1) to (6)
Among the alkali-soluble polymer compounds possessed by (1)
Enol group, (2) sulfonamide group and (3) activity
An alkali-soluble polymer compound having an imide group is preferred.
In particular, (1) phenol group or (2) sulfone
An alkali-soluble polymer compound having an amide group is
Is it sufficient to ensure sufficient solubility in re-developer and film strength?
Most preferred. Next, these alkali-soluble polymers are formed.
A typical example of the polymerization component of the compound will be described. (1) Polymerizable monomer having a phenolic hydroxy group
As for, it can be polymerized with phenolic hydroxy group
Is it a low molecular weight compound with at least one unsaturated bond?
For example, phenol
Acrylamides having a functional hydroxy group, methacryl
Amides; acrylic acid esters, methacrylic acid esters
And various derivatives of hydroxystyrene and the like.
These monomers having a phenolic hydroxy group are
Two or more kinds may be used in combination. (2) Polymerizable module having a sulfonamide group
Nomers include at least one nitrogen atom in one molecule.
Sulfone amide group (—NH—SO
₂-) And at least one polymerizable unsaturated bond
And polymerizable monomers comprising low molecular weight compounds
For example, acryloyl group, allyl group or vinyloxy
And a mono-substituted aminosulfonyl group or substituted sulfo group
A low molecular weight compound having a nilimino group is preferred. this
As such a compound, for example, JP-A-8-12302
Indicated by general formulas (I) to (V) described in No. 9 publication
And the like. Of these compounds,
As a polymerizable monomer having a honamide group, specifically
Is m-aminosulfonylphenyl methacrylate, N
-(P-aminosulfonylphenyl) methacrylami
N- (p-aminosulfonylphenyl) acrylic
A mid or the like can be suitably used. (3) Polymerizable monomer having an active imide group
As described in JP-A-11-84657.
Preferably have an active imide group in the molecule,
In one molecule, an active imide group and a polymerizable unsaturated bond
Polymerizability consisting of one or more low molecular weight compounds
Monomer. Polymerizable module having an active imide group
Specific examples of the nomer include N- (p-toluenesulfur
Phonyl) methacrylamide, N- (p-toluenesulfo
Nyl) acrylamide etc. can be preferably used
The In addition, the above (4) carboxy group, (5)
Alkali having rupho group and / or (6) phosphate group
Examples of the soluble polymer compound include this in one molecule.
Each of these acidic groups and one polymerizable unsaturated group
The smallest structural unit derived from the compound
A polymer to be used can be mentioned. Used for thermal positive type heat sensitive layer
The above (1) to constituting the alkali-soluble polymer compound
(6) The minimum structural unit having an acidic group selected from
It is not necessary to have only one kind in the
2 or more kinds of small structural units or the most
It is also possible to use a copolymer of two or more small structural units
it can. As a copolymerization method, a conventionally known graft copolymer is used.
Use polymerization, block copolymerization, random copolymerization, etc.
Can be. The copolymer is copolymerized (1) above.
A compound having an acidic group selected from (6) is a copolymer.
It is preferable that 10 mol% or more is contained in
More preferably, it is contained in an amount of at least 1%. 10 mol% not yet
If it is full, sufficiently improve the development latitude
There is a tendency not to. Also, a compound is copolymerized to form a copolymer.
In this case, as the compound, the acid of the above (1) to (6)
Other compounds that do not contain a sex group can also be used. As an alkali-soluble polymer compound, red is used.
Excellent image formability during exposure with external laser
In U.S. Pat. No. 4,123,279, etc.
Novolac with phenolic hydroxy group
Resins and pyrogallol acetone resin are preferred. The alkali-soluble polymer compound has its weight
The average molecular weight is preferably 500 or more, and 1.0
More preferably, it is 00-700,000. Ma
The number average molecular weight is preferably 500 or more.
More preferably 750 to 650,000.
Yes. Dispersity (weight average molecular weight / number average molecular weight) is 1.1.
10 is preferable. The alkali-soluble polymer compound is
It may be used alone or in combination of two or more.
The total content is 1 to 90 with respect to the total solid content of the heat-sensitive layer.
It is preferable that it is mass%, and it is 2 to 70 mass%.
More preferably, it is more preferably 2 to 50% by mass.
Yes. When the content is less than 1% by mass, durability deteriorates.
Tend to be greater than 90% by mass and sensitivity and
This is not preferable because the image formability tends to decrease. The infrared absorber used in the present invention emits light.
It is a substance that absorbs heat and generates heat. Infrared absorber
Interaction of exposed area of heat-sensitive layer by converting energy to heat
The release can be performed efficiently. In the present invention
The infrared absorber has a wavelength of 700 to 1 from the viewpoint of recording sensitivity.
A pigment or dye having a light absorption region in the 200 nm infrared region
preferable. Examples of the pigment include commercially available pigments, as well as
And Color Index (CI) Handbook, “Latest Pigment
Handbook "(edited by the 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. Examples of the pigment include black face.
Materials, yellow pigments, orange pigments, brown pigments, red pigments,
Purple pigment, blue pigment, green pigment, fluorescent pigment, metal powder face
And polymer-bound dyes. Specifically, insoluble
Azo pigments, azo lake pigments, condensed azo pigments, chelates
Azo pigment, phthalocyanine pigment, anthraquinone face
, Perylene and perinone pigments, thioindigo face
Materials, quinacridone pigments, dioxazine pigments, isoi
Ndrinon pigments, quinophthalone pigments, dyed lakes
Pigment, azine pigment, nitroso pigment, nitro pigment, natural face
Use of pigments, fluorescent pigments, inorganic pigments, carbon black
You can. These pigments can be used without surface treatment.
Alternatively, a conventionally known surface treatment may be applied. The particle size of the pigment is 0.01 to 10 μm.
Is preferably in the range, and in the range of 0.05 to 1 μm.
More preferably, it is in the range of 0.1 to 1 μm.
Further preferred. Heat sensitivity of the pigment dispersion is within the above range.
Preferred in terms of stability in layer coating solution, uniformity of heat-sensitive layer, etc.
Yes. As a method for dispersing the pigment, for example,
"The latest pigment application technology" (CMC Publishing, 1986)
For ink production and toner production, etc.
Any known dispersion technique can be used. Examples of the dyes include commercially available dyes and literature.
(For example, “Dye Handbook” published by Kodansha (19
1986), “Dye Handbook”, edited by the Society of Synthetic Organic Chemistry, Showa 4
The publicly known thing described in the 5th year publication can be used. Ingredients
Physically, azo dyes, metal complex azo dyes, pyrazolones
Zo dye, naphthoquinone dye, anthraquinone dye, lid
Russianine dye, carbonium dye, azulenium dye
, Quinoneimine dye, methine dye, cyanine dye,
Quaryllium dyes, pyrylium salts, metal-metal complexes (eg
Dithiol metal complexes, metal-containing phthalocyanines)
Dyes can be used. In the present invention, these pigments or dyes are used.
Among the materials that absorb infrared light or near infrared light,
Suitable for use with lasers emitting infrared or near infrared light
Particularly preferred in terms. Absorb such infrared light or near infrared light
As pigments, phthalocyanine (metal-containing phthalocyanine)
Including ), Carbon black is preferably used.
In addition, as a dye that absorbs infrared light or near infrared light,
For example, cyanine dyes, merocyanine dyes, iminium
Dyes, oxonol dyes, pyrylium (thiopyrilyu
, Serenapyrylium, Ternapyrylium. )system
Dye, naphthoquinone dye, squarylium dye, phthalo
Cyanine (including metal-containing phthalocyanine) dye, organic
Metal complexes (metal complex compounds with dithiols, diamines, etc.
Etc.). Specifically, for example, JP-A-7-
No. 285275, paragraph numbers [0020] to [002]
1] and “Electronic
Related dyes-present status and future prospects-Chapter 16 C Co., Ltd.
It is described in publicly known materials such as MC (published in 1998).
Compounds. Further, as another preferred example of the dye,
In U.S. Pat. No. 4,756,993.
Near-infrared absorption described as (I) or (II)
Dye, described in JP 2000-267265 A
IR-absorbing dye that is soluble in alkaline aqueous solution
Due to the heat described in Japanese Patent Laid-Open No. 11-309952
Infrared absorbing dyes containing functional groups that change to hydrophilic properties,
Kai 2000-160131, 2000-33027
1, 2001-117216 and 2001-
Polymethine color described in each publication of 174980
Described in JP 2000-352817 A
Phthalocyanine dyes. However, in the present invention
The dyes used as infrared absorbers are limited to these
Is not to be done. The content of these pigments or dyes is determined by heat sensitivity.
Preferably 0.01 to 50 mass with respect to the total solid content of the layer
%, More preferably 0.01-30% by weight, even more preferred
0.1 to 10% by weight, particularly preferably in the case of dyes
In the case of 0.5 to 10% by weight, pigment, particularly preferably 1 to
10% by mass. The pigment or dye content is 0.01
If it is less than mass%, the sensitivity may be low,
If it exceeds 50 mass%, the uniformity of the heat sensitive layer will be lost and the heat sensitive layer will be lost.
There is a case where the durability of becomes worse. These dyes or pigments are the same as the other components
May be added to another layer, or another layer may be provided and added to it.
May be. If it is in a separate layer, it is thermally decomposable and decomposes
In the state where
Added to a layer adjacent to a layer containing a substantially reducing substance
It is preferable. [0195] The heat-sensitive layer may further contain various additives as required.
Additives can be included. For example, it is pyrolytic
In the state that does not decompose, the alkali-soluble polymer compound
When a substance that substantially reduces solubility is used in combination,
Can improve the dissolution inhibition property of
It is preferable. Examples of such substances include oni
Um salt, quinonediazide, aromatic sulfone compound, aromatic
An aromatic sulfonic acid ester compound is mentioned. Examples of onium salts include diazonium.
Salt, ammonium salt, phosphonium salt, iodonium
Salt, sulfonium salt, selenonium salt, arsonium salt
Is mentioned. Among them, preferable specific examples are described above.
Light used for conventional positive-type photosensitive layers
The same compounds as those exemplified as the acid generator
I can get lost. The counter ion of the onium salt is an inorganic ion or
Is an organic ion, specifically described in each of the above known documents.
Those listed can be used. Suitable quinonediazides include o-quino.
And diazide compounds. Used in the present invention
The o-quinonediazide compound obtained is at least one
It is a compound having o-quinonediazide group.
Compounds with various structures that increase alkali solubility
Can be used. That is, o-quinonediazide is
Losing the ability to inhibit the dissolution of the binder by thermal decomposition;
Non-diazide itself turns into an alkali-soluble substance.
Helps the solubility of the sensitive material system by both effects. O-Quinonediazide used in the present invention
As a compound, the above-mentioned conventional positive type
The same compounds as those used for the photosensitive layer can be mentioned. Onium salts and o-quinonediazide compounds
The addition amount is preferably 1 to the total solid content of the heat-sensitive layer.
50% by weight, more preferably 5-30% by weight, even more preferred
Or it is the range of 10-30 mass%. These compounds
Can be used alone, but as a mixture of two or more
May be. Included in thermal positive type heat sensitive layer
Other components can be recorded with actinic radiation such as infrared rays.
Various components of known image recording layer materials are appropriately selected and used
Can be. Thermal positive thermal layer is required
Depending on the, it can contain various additives.
For example, other onium salts, aromatic sulfone compounds, aromatic
Group sulfonic acid ester compounds, polyfunctional amine compounds, etc.
When included, to developer of alkali-soluble polymer compound
It is preferable because it can improve the dissolution inhibiting function of
Yes. [0202] The heat-sensitive layer further improves the sensitivity.
Phenols, US Pat. No. 4,115,128
Cyclic acid anhydrides described in the specification, etc.
-88942 and JP-A-2-96755
It is also possible to contain the described organic acids. Ring
The content of acid anhydrides, phenols and organic acids is
0.05 to 20 mass with respect to the total solid content of the layer to be added
%, Preferably 0.1 to 15% by mass.
More preferred is 0.1 to 10% by mass.
That's right. In addition to these, epoxy compounds,
Vinyl ethers, described in JP-A-8-276558
Phenolation with hydroxymethyl groups listed
Compound and phenol compound having alkoxymethyl group
, JP-A-62-251740 and JP-A-3-
Non-ion field as described in 208514
Surfactant, JP 59-121044 A and JP
Amphoteric world as described in Japanese Patent Laid-Open No. 4-13149
Surfactant, European Patent Application No. 950,517
Siloxane compounds as described in JP-A-6
No. 2-170950 and JP-A-11-28809
Fluorine-containing monomers as described in Japanese Patent No. 3
Copolymer, described in JP-A-11-160860
A crosslinkable compound having an alkaline dissolution inhibiting action
Plasticizers (eg, polyethylene glycol; carvone
Depending on the purpose, alkyl esters such as acid and phosphoric acid)
It can contain suitably. These additives are used in the photosensitive layer.
It can be added arbitrarily as long as other performance is not degraded.
Yes. Specifically, the total solid content of the added layer, respectively.
Is preferably 0.01 to 15% by mass,
More preferably, it is 0.1-5 mass%. Further, the heat sensitive layer is formed immediately after heating by exposure.
As a print-out agent for obtaining a visible image or as an image colorant
Dyes and pigments can be contained. As a baking-out agent
Is a compound that releases acid by heating by exposure (photoacid
Release agent) and organic dyes that can form salts
Indicated. Specifically, JP-A-50-36209,
Kaisho 53-8128, JP-A 53-36223, Special
Kaisho 54-74728, JP-A-60-3626, Special
No. 61-143748, JP-A 61-151644
No. and JP-A 63-58440, etc.
The compound currently mentioned is mentioned. As the image colorant, the above-mentioned salt-forming organics are used.
Other dyes can be used in addition to the dye. Salt formation
Oil-soluble dyes and basic dyes as suitable dyes, including machine dyes
Dyes. Also, JP-A-62-293247
Described in Japanese Patent Laid-Open No. 5-313359
Particularly preferred are dyes. The amount of these dyes added is
0.01 to 10% by mass relative to the total solid content of the layer to be added
It is preferable that it is 0.1 to 3% by mass.
preferable. The heat-sensitive layer of the present invention may be a single layer or
2 layers as described in Japanese Patent Publication No. 11-218914
It may be provided as a structure. The heat sensitive layer is usually prepared by dissolving the above components in a solvent.
The heat-sensitive layer coating solution obtained on the lithographic printing plate support
It can be manufactured by coating. Used here
As the solvent to be used, the above-mentioned conventional negative tie
The same solvents as those used in the photosensitive layer
However, the present invention is not limited to this. These solvents are simple
Used alone or mixed. The above components in the solvent
The concentration of the total solid content including additives is 1 to 50% by mass.
Is preferred. As a method of applying, the above-mentioned conveyor
Various types as in the case of national positive type photosensitive layer
Can be used. Further, the coating amount (solid content) of the heat sensitive layer is determined by the usage.
Generally 0.5 to 5.0 g / m, depending on²so
Preferably there is. Less application amount than the above range
The apparent sensitivity increases, but the image recording function is fulfilled.
The film properties of the heat-sensitive layer are reduced. (Undercoat layer) Thermal positive type thermosensitive layer and
Provide an undercoat layer between the support and the support as necessary.
Can do. Components contained in the primer layer include various organic materials
Compounds. For example, carboxymethylcellulose
Dextrin; gum arabic; 2-aminoethyl
Phosphonic acids having an amino group such as phosphonic acid, substituents
Phenylphosphonic acid, naphthylphos
Phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, meso
Organic phosphoric acid such as tylene diphosphonic acid and ethylene diphosphonic acid
Sulfonic acid; phenylphosphoric acid which may have a substituent,
Naphthyl phosphate, alkyl phosphate, glycerophosphate, etc.
Organophosphoric acid; phenylphosphine optionally having substituent
Phosphoric acid, naphthylphosphinic acid, alkylphosphine
Acid, organic phosphinic acid such as glycerophosphinic acid;
Amino acids such as syn and β-alanine;
Hydrochlorides of amines having hydroxy groups, such as hydrochloride of min
Etc. These may be used alone or in combination of two or more.
You may mix and use it. As the undercoat layer, JP-A 2000-1
Structure having an acid group described in Japanese Patent No. 05462
Polymerization having component and component having onium group
An intermediate layer containing a compound is also preferably used. This middle layer
Provides sufficient alkali developability and resistance to printing.
Clear without causing stain and image strength degradation
A large number of printed images can be obtained. Na
This primer layer is not only a thermal positive type but also a co
Conventional positive type, conventional negative tie
, Photopolymer type, thermal negative type and
It can also be provided in each non-process type image recording layer.
it can. The undercoat layer can be provided by the following method.
Yes. That is, water or methanol, ethanol, methyl
For organic solvents such as ruethyl ketone or mixed solvents
Support for lithographic printing plate with solution of above organic compound dissolved
Applying and drying on the body, water or meta
Organic solvents such as diol, ethanol, methyl ethyl ketone
Or the above organic compound is dissolved in a mixed solvent thereof.
Immerse an aluminum plate in
Adsorb, then wash with water and dry
Is the method. The former method favors the above organic compounds.
Or a solution with a concentration of 0.005 to 10% by mass in various ways
It can be applied by the method. In the latter method,
The concentration of the liquid is preferably 0.01 to 20% by mass, more preferably
It is 0.05 to 5% by mass, and the immersion temperature is preferable.
Or 20 to 90 ° C., more preferably 25 to 50 ° C.
The immersion time is preferably 0.1 second to 20 minutes, more preferably
It is preferably 2 seconds to 1 minute. The solution used in the above method is
Ammonia, triethylamine, potassium hydroxide, etc.
PH 1 due to basic substances and acidic substances such as hydrochloric acid and phosphoric acid
It can also be adjusted to a range of ˜12. Also, image recording
Containing yellow dye to improve tone reproducibility of materials
You can also. The coating amount of the undercoat layer is 2 to 200 mg / m²so
Appropriately, 5 to 100 mg / m²Is
preferable. Covering amount is 2mg / m²Less than enough
Printing durability may not be obtained. 200 mg / m
²It is the same even if it exceeds. <Thermal negative type> (Thermosensitive layer) The thermal negative type thermal layer absorbs infrared rays.
Contains an agent and the infrared laser irradiation part is cured to form an image part.
Any negative heat-sensitive layer can be applied.
Can be. Such a thermal negative thermal type
One of the layers is preferably 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 thermal negative
As one of the heat sensitive layers, an acid cross-linked layer is preferably mentioned.
The The acid cross-linking layer (E) generates an acid by light or heat.
A compound (hereinafter referred to as “acid generator”) and (F)
A compound that crosslinks with an acid (hereinafter referred to as “crosslinking agent”)
In order to form a layer containing these
(G) Alkaline capable of reacting with a crosslinking agent in the presence of an acid
Contains a soluble polymer compound. In the acid crosslinking layer, light
Acid generated by decomposition of the acid generator by irradiation or heating
Promotes the function of the cross-linking agent, and between or between cross-linking agents
A strong cross-linking structure is formed between the agent and the binder polymer
As a result, the alkali solubility is reduced, and the developer
Becomes insoluble. At this time, the energy of the infrared laser
In order to use efficiently, the acid cross-linked layer has (A) infrared absorption
An agent is blended. 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 thermal positive
As an infrared absorber contained in the type heat sensitive layer, the above
And the dyes exemplified in the above. Especially among these dyes
Preferred are oxonol dyes, cyanine color
Element, squarylium dye, pyrylium salt, organometallic complex
(Phthalocyanine metal salts, dithiolate metal complexes, etc.)
Is mentioned. Specifically, JP-A-11-119421.
No. 11-95421, JP-A 2000-26726
5, 2000-338651, 2000-34
Nos. 7393 and 2001-125260
Infrared absorbing dyes described in the above. Examples of the pigment include commercially available pigments, as well as
And Color Index (CI) Handbook, “Latest Pigment
Handbook "(edited by the 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. In particular,
For example, infrared contained in a thermal positive type heat-sensitive layer
Examples of the line absorber include the pigments exemplified above. This
Details of these pigments are used for thermal positive-type heat-sensitive layers.
It is the same as the pigment that can be used. 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 Radical generator generates radicals by thermal energy
Polymerization of the compound having a polymerizable unsaturated group is started.
It is a compound that promotes and promotes. As radical generator
Is a conventionally known thermal polymerization initiator with a low bond dissociation energy.
To appropriately select and use a compound having a bond
it can. For example, an onium salt compound (specifically, the above-mentioned
Used for conventional positive-type photosensitive layers
Onium salt compounds exemplified as photoacid generators), cal
Bonyl compounds, organic peroxides, organic halogen compounds,
Zo polymerization initiators, azide compounds, titanocene compounds,
Hexaarylbiimidazole compounds, organoborates
Compounds and disulfone compounds are mentioned. Specifically, an example
For example, it is used for the photopolymer type photosensitive layer described above.
What was illustrated as a photoinitiator to be mentioned is mentioned. In addition, as a radical generator, organoboron
Complexes can also be used. As an organic boron complex,
For example, JP-A-6-157623, JP-A-6-175
564 and JP-A-6-175561.
Organoboron sulfonium complex or organoboron
Oxosulfonium complex, JP-A-6-175554
And JP-A-6-175553.
Organoboron iodonium complex, JP-A-9-18871
Organoboron phosphonium complex described in No. 0 publication
Body, JP-A-6-348011, JP-A-7-12878
5, JP-A-7-140589, JP-A-7-3065
27, JP-A-7-292014, etc.
And organoboron transition metal coordination complexes. Among these radical generators, in particular,
Nium salt compounds are preferred. Suitable for use in the present invention
Specific examples of onium salt compounds that can be
Paragraph No. [003] of Japanese Patent Laid-Open No. 2001-133969
Names described in [0] to [0033]
Can do. Onium salt compounds used in the present invention
Preferably has a maximum absorption wavelength of 400 nm or less.
More preferably, it is 360 nm or less. like this
In the present invention, the absorption wavelength is set in the ultraviolet region.
The printing plate precursor can be handled under white light.
The The content of these radical generators is determined by heat sensitivity.
It is 0.1-50 mass% with respect to the total solid of a layer.
Preferably, 0.5 to 30% by mass is more preferable
1 to 20% by mass is more preferable. Content is
If it is less than 0.1% by mass, the sensitivity is low, and 50
If the mass exceeds 50%, stains will occur on the non-image area during printing.
There is. These radical generators use only one kind
Alternatively, two or more kinds may be used in combination. Also these
The radical generator may be added to the same layer as other components
However, another layer may be provided and 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. As a more specific embodiment, a photopolymer is used.
-Type photosensitive layer containing ethylenically unsaturated bonds
Examples of the compound include the same contents as exemplified above.
It is done. With respect to these radically 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
Goods: For example, Japanese Patent Publication No.49-43191, 52-3
0490, 46-43946, 1-403
37, 1-40336, JP-A-2-25493
, JP-A-61-22048, Japanese Adhesive Society
Magazine, vol. 20 (No. 7) (1984) etc.)
Use together to adjust both photosensitivity and intensity
The method is also effective. Large molecular weight compounds and hydrophobic
Higher compounds have better sensitivity and film strength, but development speed
Or in terms of precipitation in the developer.
The In addition, other components in the heat sensitive layer (for example, binder binder)
Compatibility and dispersibility with limer, initiator, colorant, etc.)
However, the selection and use of radical polymerization compounds is important.
Factors such as the use of low-purity compounds and two or more
Compatibility with compounds may improve compatibility.
The Also improved adhesion of support, overcoat layer, etc.
It is possible to select a specific structure for the purpose.
Regarding the mixing ratio of radically polymerizable compounds in the image recording layer
Is more advantageous in terms of sensitivity, but if too much
May cause undesirable phase separation or adhesion of the image recording layer.
Problems in the manufacturing process due to the property (for example,
Production defects due to copying and sticking) and precipitation from the developer.
May cause problems. 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 undercoat and overcoat
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. As such a linear organic polymer
Is a radical polymer having a carboxy group in the side chain, for example
For example, JP-A-59-44615 and JP-B-54-3432
No.7, Shoko 58-12777, Shoko 54-259
57, JP 54-92723, JP 59-53
836 and JP-A-59-71048.
Methacrylic acid copolymer, acrylic
Acid copolymer, itaconic acid copolymer, crotonic acid copolymer
Body, maleic acid copolymer, partially esterified maleic acid copolymer
A polymer etc. are mentioned. Similarly, the side chain
Examples include acidic cellulose derivatives having a silyl group. this
In addition, a cyclic acid anhydride is added to the polymer having a hydroxy group.
Those added are 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. In addition, Japanese Patent Publication No.7-12004, 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 Japanese Patent Application Laid-Open No. 11-352691
The urethane-based binder polymer containing acid groups
Since it is always excellent in strength, printing durability and low exposure suitability
Is advantageous. In addition to these, water-soluble linear organic polymers.
-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.
It may be. The 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. Next, each compound used in the acid crosslinking 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. example
Onium salt compounds, o-quinonediazide compounds,
And halogenated compounds and disulfone compounds.
These specific examples are illustrated as the radical generators described above.
The same as those mentioned above. Of onium salt compounds
As a preferred embodiment, for example, JP-A-10-3950
Described in paragraphs [0010] to [0035] of No. 9 publication
And the like. o-quinonediazide
As a compound, it is used for a thermal positive type thermosensitive layer.
The same compounds as exemplified above are listed as examples.
It is done. As another example, the above-described conventioner is used.
Examples of photoacid generators used in photopositive photosensitive layers
Organometallic / organic halide, o−, similar to that shown
Iminos, a photoacid generator with a nitrobenzyl-type protecting group
Photolysis, such as sulfonate, generates sulfonic acid
Compounds, disulfone compounds; generating these acids
Group or compound introduced into the main or side chain of the polymer
Compound. 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), US Pat. No. 3,779,7798.
Described in European Patent No. 126,712, etc.
It is possible to use a compound that generates acid by light.
You can also. Among the acid generators described above, Japanese Patent Application Laid-Open No. 2001-2001.
No. 142230, paragraph numbers [0197] to [02
22] is preferred. 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 following are mentioned as a crosslinking agent. (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. Hereinafter, the above compounds (i) to (iii) are converted into
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
preferable. Specifically, for example, JP 2000-267 A
In paragraph Nos. [0077] to [0083] of No. 265
Examples of the compounds of the general formulas (8) to (11) described
It is done. These cross-linking agents have high cross-linking efficiency and improve printing durability.
This is preferable in that it can be improved. (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 application publication No. 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, as a crosslinking agent, JP-A-2
No. 000-267265, paragraph number [0088] to
[0097] represented by the general formula (12) described in [0097]
Phenol derivatives that can be used are also suitable. (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
Novolak 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. In addition, 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 a diol group include
Paragraph Nos. [0130] to [0]
163] are described in detail. A
Lucari-soluble polymer compound may be used alone or 2
You may use combining more than a seed. 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. (H) Other components In addition to the above components, the thermal negative thermal layer is
If necessary, various compounds may be further added.
For example, the above-mentioned dyes having large absorption in the visible light region and
And pigments can be used as image colorants. This
These colorants distinguish between image and non-image areas after image formation.
It is preferable to add it. Including colorant
The amount is 0.01 to 10 quality with respect to the total solid content of the heat sensitive layer.
The amount is preferably%. Further, when the heat-sensitive layer is a photopolymerization layer, the coating is applied.
During the preparation or storage of liquids, radically polymerizable compounds
In order to prevent unnecessary thermal polymerization of materials,
It can be used for photopolymerizable compositions of limer type photosensitive layers.
Addable thermal polymerization inhibitor as a small amount of thermal polymerization inhibitor
It is preferable to do. The content of the thermal polymerization inhibitor is the heat sensitive layer.
About 0.01 to about 5% by mass based on the total solid content of
Is preferred. 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%. In the heat sensitive layer, if necessary,
Various additives can be used in combination. Specifically, the above
Which can be optionally added to the thermal positive layer
The compound used as a minute is mentioned. The lithographic printing plate precursor of the present invention provided with the above heat-sensitive layer
To obtain a plate, the same method as the thermal positive type thermal layer
The method may be used. Coating amount of heat-sensitive layer obtained by coating and drying
(Solid content) varies depending on the application, but usually 0.5 to
5.0 g / m²Is preferred. Within the above range
And various performances are suitable. <Non-treatment type> Non-treatment type heat-sensitive layer
For example, irradiation by heating or radiation irradiation
The moiety is a specific acidic group (for example, phospho group, sulfo group,
A polymer that generates (ruboxy groups) and solubilizes, or
A compound in which the irradiated part can form a hydrophobic region (hereinafter “hydrophobic”
It is also referred to as “chemical precursor”. ) Containing hydrophilic polymer
A heat-sensitive layer containing a trick is mentioned. Polymers that generate and solubilize specific acidic groups
-Is preferably a sulfonic acid generation type, for example
For example, it is described in JP-A-10-282672.
Sulfonic acid ester group, disulfone group or sec-
Or a poly having a tert-sulfonamide group in the side chain.
And the like. Examples of hydrophobizing precursors include: (A) Hydrophobic fine particle polymer (B) Microcapsules enclosing a hydrophobic substance Is mentioned. These were fused to each other by heating.
The hydrophobized precursor contained in the microcapsule
Causing a more chemical reaction, resulting in an image area,
An aqueous region (parent ink region) can be formed. And this
These hydrophobized precursors are preferably hydrophilic binders
Since it is dispersed inside, printing after image recording (exposure)
Install the lithographic printing plate precursor on the machine cylinder,
And / or special development processing by supplying ink
It is possible to perform on-press development without carrying out the process. Hydrophobic fine particle polymer and hydrophobic substance
The average particle diameter of the encapsulated microcapsules is 0.
It is preferably 01-20 μm, 0.05-5.0
More preferably, it is μm. Within the above range, high precision
Fine image formation is possible.
Time stability is good. As the hydrophobic fine particle polymer, thermoplasticity is used.
Fine particle polymer, thermosetting fine particle polymer, heat reactive agent
Examples thereof include fine particle polymers having functional groups. Thermoplasticity
As a fine particle polymer, Research Discl
osureNo. 33303 (January 1992), JP
Hei 9-123387, 9-131850, 9-
Nos. 171249 and 9-171250, Europe
It is described in patent application publication 931,647 specification etc.
Suitable examples of the thermoplastic fine particle polymer
be able to. Examples of thermosetting fine particle polymers include
For example, a resin having a phenol skeleton, a urea resin (for example,
For example, urea or urea derivatives such as methoxymethylated urea
Resinized with aldehydes such as formaldehyde
), Melamine resins (eg melamine or its inducement)
Resin conductor with aldehydes such as formaldehyde
), Alkyd resin, unsaturated polyester resin,
Polyurethane resin and epoxy resin can be used. In addition, a microcap containing a hydrophobic substance.
As the cell, for example, the hydrophobic fine particle polymer described above is contained.
Encapsulating microcapsules, ie thermoplastic particulate polymer
ー, thermosetting fine particle polymer, with heat-reactive functional group
Examples include microcapsules that contain fine particle polymers.
It is. However, it is particularly preferred as a hydrophobizing precursor.
The reason is that a fine particle polymer having a thermally reactive functional group or
A microcap containing a compound having a heat-reactive functional group
Cell. Thermally reactive functional groups commonly used for these
As an ethylenically unsaturated group (for example, a polymerization reaction)
Acryloyl group, methacryloyl group, vinyl group,
Isyl to carry out addition reaction
Nate group or its block, the activity that is its reaction partner
A functional group having a hydrogen atom (for example, an amino group, hydro
Xy group, carboxy group, etc.); epoxy that performs addition reaction
Group, amino group, carboxy group or the reaction partner
Hydroxyl group; Carboxyl group and hydroxyl group for condensation reaction
Si group or amino group; acid anhydride and a
Mino group, hydroxy group or vinyloxy group
be able to. However, chemical bonds are formed by heating.
If there is a function that
It may be Noh. Fine particles having such heat-reactive functional groups
Polymers include acryloyl groups and methacryloyl
Group, vinyl group, allyl group, vinyloxy group, epoxy
Group, amino group, hydroxy group, carboxy group, isocyanate
Nate groups, acid anhydrides; having groups protecting them
Can be mentioned. To these polymer particles
The introduction may be performed during the polymerization, or after the polymerization, the polymer reaction
You may use it. When introduced during polymerization, these groups are present.
It is preferable to carry out emulsion polymerization or suspension polymerization of the monomer to be
Good. As a specific example of a monomer having such a group
For example, paragraphs of JP 2001-293971 A
Compounds described in the numbers [0018] to [0035]
Although the thing is mentioned, this invention is not limited to these. This
Has heat-reactive functional groups that can be copolymerized with these monomers.
Non-monomers include, for example, styrene, alkyl amines
Acrylate, alkyl methacrylate, acrylonitrile
, Vinyl acetate, etc.
The monomer is not limited to these as long as it does not have a functional group.
Yes. Used when heat-reactive functional groups are introduced after polymerization
Examples of the polymer reaction include International Publication No. 96/343.
List polymer reactions described in pamphlet No. 16.
Can. Of fine particle polymer having heat-reactive functional group
The coagulation temperature is preferably 70 ° C. or higher.
Considering qualitative properties, it is more preferably 100 ° C. or higher. The content of the hydrophobic fine particle polymer is determined by the heat sensitive layer.
50% by mass or more based on the total solid content of
More preferably 60% by mass or more. The microcapsules used in the present invention are:
Hydrophobic substances, preferably those having the above heat-reactive functional groups
Contains compound. Compounds with this thermally reactive functional group
Products include polymerizable unsaturated groups, hydroxy groups,
Si group, carboxylate group, acid anhydride, amino group, epoxy
Xyl group and isocyanate group and block body thereof
A compound having at least one functional group selected from
Can be mentioned. As the compound having a polymerizable unsaturated group,
Ethylenically unsaturated bonds such as acryloyl groups, meta
At least one acryloyl group, vinyl group, allyl group, etc.
Compounds, preferably two or more, are preferred.
Such compounds are widely known in the industry.
In the present invention, these are not particularly limited.
Can be. These chemical forms include mono
Polymers, prepolymers, ie dimers, trimers and oligos
Gomer or a mixture thereof or a copolymer thereof
Is mentioned. Specifically, for example, JP-A-2001-2
No. 77742, paragraph numbers [0016] to [003]
2]. Specific examples of compounds having a polymerizable unsaturated group
Unsaturated carboxylic acids (eg acrylic acid,
Crylic acid, itaconic acid, crotonic acid, isocrotonic acid,
Maleic acid etc.), its esters and amides
Preferably, unsaturated carboxylic acid and aliphatic polyvalent alcohol
Esters and unsaturated carboxylic acids and aliphatic polyvalent
Examples include amides with amines. A hydroxy group,
Saturation with nucleophilic substituents such as amino and mercapto groups
Japanese carboxylic acid ester or unsaturated carboxylic acid amide
Monofunctional or polyfunctional isocyanate or epoxy
Addition reaction with side and monofunctional or polyfunctional
A dehydration condensation reaction product with rubonic acid is also preferred. Ma
Electrophilic substituents such as isocyanate groups and epoxy groups
An unsaturated carboxylic acid ester or amide having
Functional or polyfunctional alcohols, amines and thiols
Addition reaction products, and halogen groups, tosyloxy groups, etc.
An unsaturated carboxylic acid ester having a leaving substituent of
Is an amide, monofunctional or polyfunctional alcohol, amine
Also preferred are substitution reaction products with thiols. Ma
As another preferred example, the unsaturated carboxylic acid is
Replaced with unsaturated phosphonic acid or chloromethylstyrene
The obtained compound is mentioned. Unsaturated carboxylic acid and aliphatic polyhydric alcohol
Of a compound having a polymerizable unsaturated group, which is an ester with
Specific examples of monomers include photopolymer type
As an ethylenically unsaturated bond-containing compound used in the optical layer
Each acrylic ester and each methacrylate exemplified above
Luric acid ester, each itaconic acid ester, each crotonic acid ester
Steal, each isocrotonic acid ester and each maleic acid
Examples include esters. Specifically, for example, JP-A-20
No. 01-293971, paragraph number [0021] to
And the compounds described in [0030]. Other compounds having a polymerizable unsaturated group
As an example, it is used for thermal negative type heat sensitive layer
The same as those exemplified above as the radical polymerizable compound
Things. As the compound having an epoxy group,
Serine polyglycidyl ether, polyethylene glycol
Rudiglycidyl ether, polypropylene diglycidyl
Ether, trimethylolpropane polyglycidyl ether
Tellurite, sorbitol polyglycidyl ether, bisphe
Nords or polyphenols or their hydrogen
Preferred examples include polyglycidyl ether as an additive.
The As a compound having an isocyanate group
Is tolylene diisocyanate, diphenylmethane dii
Socynate, polymethylene polyphenyl polyisocyanate
Nate, xylylene diisocyanate, naphthalene diis
Socynate, cyclohexanephenylene diisocyanate
, Isophorone diisocyanate, hexamethylene di
Isocyanate, cyclohexyl diisocyanate;
Compounds that block them with alcohol or amine
Preferably mentioned. Examples of the compound having an amino group include ethylene.
Diamine, diethylenetriamine, triethylenetet
Lamin, hexamethylenediamine, propylene diamine
Preferable examples include polyethylene and imine. Hydro
A compound having a xy group has a terminal methylol group.
Compound, polyvalent alcohol such as pentaerythritol
Preferable examples include bisphenol and polyphenols
It is done. As compounds having a carboxy group,
Many aromatics such as lomellitic acid, trimellitic acid, phthalic acid
Aliphatic carboxylic acid such as polyvalent carboxylic acid, adipic acid, etc.
Are preferable. As a compound having an acid anhydride
Pyromellitic anhydride, benzophenone tetracar
Preferable examples include boronic acid anhydride. Vinyloxy group
As the compound having, for example, JP-A-2002-291
Preferred examples include compounds described in No. 62.
The Coordination of compounds having an ethylenically unsaturated bond
As the polymer, an allyl methacrylate copolymer is preferred.
Named appropriately. Specifically, allyl methacrylate /
Methacrylic acid copolymer, allyl methacrylate / ethyl
Methacrylate copolymer, allyl methacrylate / buty
And dimethacrylate copolymer. A microcapsule containing a hydrophobic substance
Production methods include interfacial polymerization to produce capsule membranes, in
-Situ method, complex coacervate method, organic
It is possible to use a known method such as a phase separation method from a solvent system.
Yes. Specifically, for example, JP 2001-29397 A
Method described in paragraph No. [0036] of No. 1 publication
Etc. can be used. A microcapsule containing a hydrophobic substance
The microcapsule wall used has three-dimensional crosslinking,
It is preferable that it has a property of swelling with a solvent.
That's right. From this point of view, the wall material of the microcapsule is
Urea, polyurethane, polyester, polycarbonate
Preferred are polyamides, polyamides, or mixtures thereof.
But polyurea and / or polyurethane are more preferred
Good. The micro-capsule wall has the heat-reactive agent.
A compound having a functional group may be introduced. [0280] Micro containing such a hydrophobic substance
Capsule unites microcapsules by heat
It may or may not be merged
Yes. In short, of the microcapsule inclusions,
Also exuded out of the surface of the psel or outside the microcapsule
Or infiltrated into the microcapsule wall
It is sufficient to cause a chemical reaction. Also added hydrophilic
Even if it reacts with a functional resin or an added low-molecular compound
Good. Also, each of two or more types of microcapsules
Provide functional groups that react thermally with different functional groups
Even if microcapsules react with each other
Good. Therefore, microcapsules are heated by heat
However, melting and coalescence with heat is preferable for image formation.
Yes, but not essential. My encapsulating a hydrophobic substance in the heat sensitive layer
The content of black capsules is based on the total solid content of the heat sensitive layer.
It is preferable that it is 10-60 mass%, and 15-40 mass
% Is more preferred. Within the above range, good
Good on-press developability and good sensitivity and printing durability
It is. A microcapsule enclosing a hydrophobic substance
When included in the heat sensitive layer, the inclusions can be dissolved.
And solvent that can swell the wall material
It can be added to the locapsule dispersion medium. like this
With a thermally reactive functional group encapsulated by a simple solvent
Diffusion of compounds and the like outside the microcapsules is promoted. This
The choice of solvent such as microcapsule dispersion medium,
Depends on black capsule wall material, wall thickness and inclusions
Is easy to choose from many commercially available solvents
Can do. For example, cross-linked polyurea or polyurethane walls
For water dispersible microcapsules consisting of alcohol
, Ethers, acetals, esters, ketones
, Polyhydric alcohols, amides, amines, fatty acids
Etc. are preferred. Specifically, the conventional policy described above is used.
The same as those exemplified as the solvent used for the ditype
However, the present invention is not limited to these. Ma
Two or more of these solvents may be used. In addition, it dissolves in the microcapsule dispersion.
However, it is also possible to use a solvent that dissolves when the solvent is mixed.
You can. The amount added depends on the combination of materials.
If it is round but less than the suitability value, image formation
If the amount is too large, the stability of the dispersion will deteriorate.
The Usually, it is effective to be 5 to 95% by mass of the coating solution.
10 to 90% by mass is preferable.
More preferably, it is mass%. An untreated type heat-sensitive layer has a heat-reactive functional group.
Fine particle polymer and / or thermally reactive functional group
Containing microcapsules enclosing a compound having
In some cases, these reactions can be initiated as needed.
May be added with a promoting compound. Start the reaction
Alternatively, the compound to be promoted may be radical or radical by heat.
Or compounds that generate cations.
Yes. For example, lophine dimer, trihalomethyl compound
, Peroxides, azo compounds, onium salts (diazonium
Salt, sulfonium salt, iodonium salt, etc.), acylphos
Examples include fins and imide sulfonates. Specifically
For example, radicals used in thermal negative types
Compounds exemplified as generators, and conventional converters
Exemplified as a photoacid generator used in the positive type
Compound may be mentioned. The content of these compounds is
1 to 20% by mass based on the total solid content of
3 to 10% by mass is more preferable. Above range
If it is within the range, the on-press developability is not impaired and good reaction initiation
A fruit or reaction promoting effect is obtained. As a hydrophobizing precursor, the periphery is hydrophilic.
Self-dispersing fine particles that are water-soluble and dispersible in water
Is particularly preferred. Self-water dispersion type fine particles are self-water dispersion
The heat sensitivity used when forming the heat sensitive layer
Easily and uniformly dispersed in the layer coating, and
In the heat-sensitive layer (dry film) after applying and drying the coated material
In the hydrophilic binder matrix
Without being uniformly dispersed. Therefore high
Fine printing is possible, and excellent dry film stability over time
It is. Self-water-dispersed fine particles include (1) molecules
Structure part having lipophilic resin structure part and hydrophilic group inside
Japanese Patent Laid-Open No. 3-221137
Information, JP-A-5-66600, etc.
Water without an emulsifier or protective colloid
Fine particles obtained by dispersing in (2) core / shell
It has a structure, the core part is lipophilic resin, and the shell part is hydrophilic.
(3) Hydrophobic material
Obtained by protecting the surface with a hydrophilic wall material
Preferred examples include microcapsule fine particles. these
The method of making the periphery of the fine particles hydrophilic is not particularly limited.
However, for example, the stage of Japanese Patent Application Laid-Open No. 2001-315452
Are listed in the drop numbers [0052] to [0056]
The same method is mentioned. The fine particle polymer and / or the microphone
Locapsules are distributed in a matrix made of hydrophilic resin.
When developing on-machine, good on-machine developability
Furthermore, the film strength of the thermosensitive layer itself is improved. Ma
In addition, lithographic plates that do not require development processing by crosslinking and curing hydrophilic resins
A printing plate precursor can be obtained. As hydrophilic resin,
For example, paragraph number of JP 2001-293971 A
[0043] The hydroxy group or carboxy group described in [0043]
Si group, hydroxyethyl group, hydroxypropyl group,
Mino group, aminoethyl group, aminopropyl group, carboxyl
Those having a hydrophilic group such as a dimethyl group, JP-A-2000-
No. 335131, paragraph numbers [0063] to [007]
7] The hydrophilic sol-gel conversion binder resin described in [7]
Is preferred. The hydrophilic resin content is determined by 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. In addition, the hydrophilic resin is crosslinked and cured.
It may be used. As a crosslinking agent that crosslinks and cures hydrophilic resins
Examples include compounds that are usually used as crosslinking agents.
It is done. Specifically, Shinzo Yamashita and Tosuke Kaneko, “Crosslinking Agent Ha
Book, published by Taiseisha (1981), edited by the Society of Polymer Science, Japan
"Polymer Data Handbook, Basic Reduction" Baifukan (198
6 years) etc. can be used
The Specifically, for example, JP-A-2002-36745
The compound described in paragraph [0053] of the publication is
Can be mentioned. In addition, ammonium chloride, silane
Cross-linking catalysts such as coupling agents and titanate coupling agents
Can be used in combination. In the untreated type heat-sensitive layer, hydrophilicity is required.
Among the resins, it is preferable to use a sol-gel conversion binder resin.
Good. Details will be described below. Non-treatment type heat-sensitive layer
As a sol-gel conversion binder resin suitably used for
Bonding groups from polyvalent elements are networked via oxygen atoms
Hydroxy with structure and unbound polyvalent element
Group, alkoxy group, etc.
A polymer that has a greasy structure,
At the stage where there are many groups, alkoxy groups, etc., it is in a sol state and
As the ether linkage progresses, the network resin structure
Examples thereof include a polymer that is strong. The sol-gel conversion binder resin is a parent of the resin structure.
In addition to the property of changing water content, some hydroxy groups etc.
The surface of the solid fine particles by binding to the solid fine particles
It also has the function of modifying the hydrophilicity.
The Hydroxyl group, alkoxy group, etc. for sol-gel conversion
The polyvalent elements having the following are aluminum, silicon, titanium,
Zirconium etc. are mentioned. Among them, silicon is used
A sol-gel conversion system using a siloxane bond is preferred. Less than
The following explains the sol-gel conversion system using siloxane bonds.
But use aluminum, titanium, zirconium, etc.
Each of the sol-gel conversion systems uses silicon described below for each.
It can replace with an element and can implement. The sol-gel conversion system using a siloxane bond is
At least one silanol group capable of sol-gel conversion
It is a system containing a silane compound having Inorganic hydrophilic formed by sol-gel conversion
The binder resin preferably has a siloxane bond and a silano
It is a resin having a vinyl group. Non-treatment type heat sensitive layer
A silane compound having at least one silanol group;
Coating solution containing sol system is applied to lithographic printing plate support
After application, silanol group hydrolytic condensation proceeds and
That the structure of xane skeleton is formed and that gelation proceeds
Thus formed. In addition, this sol-gel conversion system
The formed heat-sensitive layer has physical properties such as film strength and flexibility.
For the purpose of improving and improving coating properties,
An aqueous polymer, a crosslinking agent, etc. can also be contained. Siloxane resins that form gel structures and
Of a silane compound having at least one silanol group
As a specific example, Japanese Patent Laid-Open No. 2002-6504
Described in paragraph numbers [0054] to [0057]
Compounds. For the formation of the inorganic hydrophilic binder resin, the above-mentioned sila
Ti, Zn, Sn, Zr, Al, etc.
Metallization capable of forming a film by bonding to resin during sol-gel conversion
A compound can be used in combination. Such metal compounds and
For example, Ti (OR ′)_FourTiCl_Four, Zn
(OR ')₂, Zn (CH_ThreeCOCHCOCH_Three)₂,
Sn (OR ')_Four, Sn (CH_ThreeCOCHCOCH_Three)
_Four, Sn (OCOR ')_Four, SnCl4, Zr (O
R ′)_Four, Zr (CH_ThreeCOCHCOCH_Three)_Four, Al
(OR ')_Three, Al (CH_ThreeCOCHCOCH_Three)_Threeetc
Is mentioned. Furthermore, the above silane compound, and
Hydrolysis reaction of the above metal compounds that can be used in combination
In order to accelerate the polycondensation reaction, conventionally known inorganic acids,
Acidic catalyst such as carbonic acid, carboxylic acid, ammonia, organic
It is preferable to use a basic catalyst such as amines in combination. Touch
The medium is an acid or a basic compound as it is, or
Used as a state dissolved in a solvent such as water or alcohol
(Hereinafter referred to as an “acidic catalyst” using an acid,
Those using basic compounds are called basic catalysts.
Yeah. ). The concentration when dissolved in a solvent is particularly limited.
Although the concentration is higher, hydrolysis and polycondensation reactions
Tend to be faster. However, a concentrated base
When a reactive catalyst is used, a precipitate is formed in the sol solution.
Concentration of basic catalyst (concentration in aqueous solution)
Is preferably 1 N or less. As described above, an untreated type heat-sensitive layer and
The heat-sensitive layer (hydrophilic layer created by the sol-gel method)
Heat-sensitive resin containing a sol-gel conversion binder resin
Layer) is preferred. The details of the sol-gel method are as follows.
“Science of Sol-Gel Method” Agne Jofusha (published) (1)
988), Hirashima Satoshi "Functional thin film by the latest sol-gel method
Membrane creation technology ”, General Technology Center (published) (1992), etc.
Is described in detail in the booklet. The hydrophilic resin content is determined by the total solid content of the heat sensitive layer.
Is preferably from 5 to 70% by weight,
More preferably, it is 50 mass%. Within the above range
Good on-press developability and film strength can be obtained. [0300] An infrared absorber is used for the non-treatment type heat-sensitive layer.
It is necessary to add. Infrared absorber has wavelength 7
Any substance that absorbs light of 00 nm or more can be used.
Pigments, dyes and metal fine particles can be used. Examples of the pigment and dye include those described above.
Same as those used for thermal positive type heat sensitive layers
Can be mentioned. Above all, as a pigment, it is water-soluble.
It is easy to disperse with hydrophilic resin and damage hydrophilicity.
The surface is coated with a hydrophilic resin or silica sol.
Carbon black is particularly preferred. The particle size of the pigment is
Preferably it is in the range of 0.01 μm to 1 μm,
More preferably in the range of 0.01 μm to 0.5 μm
That's right. As the dye, a water-soluble dye is particularly preferred.
Yes. Specifically, for example, JP 2001-96936 A
Described in paragraph numbers [0036] to [0041] of the publication
The compound which is mentioned. The metal fine particles are light-to-heat convertible and light.
Especially limited as long as it is a metal fine particle that is thermally fused by irradiation.
Although it is not, paragraph number of JP 2001-293971 A
As described in issue [0081]-[0082]
Belonging to Group 8-11 (Group VIII and Group IB)
It is preferable that the metal is a simple substance or a fine particle of an alloy,
Of a metal selected from Ag, Au, Cu, Pt and Pd
More preferably, they are fine particles of a simple substance or an alloy. metal
Fine particles are added to an aqueous solution containing a dispersion stabilizer.
Add an aqueous solution of a complex salt, and then add a reducing agent to
After making Lloyd, it is used after removing unnecessary salts. Ingredients
Specifically, for example, JP-A-2002-29165,
It is described in JP 2000-335131 A
The The average particle size of the metal colloid is 1 to 500.
nm is preferable, and it is preferably 1 to 100 nm.
More preferably, it is 1-50 nm. So
The degree of dispersion may be polydispersed, but the coefficient of variation is 30% or less
Monodispersion is preferred. The content of the infrared absorber is pigment or dye.
In the case of 30 mass% or less with respect to the total solid content of the heat sensitive layer
It is preferable that it is 5 to 25% by mass.
Further, it is more preferably 7 to 20% by mass. Also,
In the case of metal fine particles, at 5% by mass or more of the total solid content of the heat sensitive layer
It is preferable that it is 10% by mass or more.
More preferably, it is 20% by mass or more. Metal fine
When the content of the particles is less than 5% by mass, the sensitivity is lowered.
May end up. [0305] For the non-treatment type heat-sensitive layer, if necessary,
In addition to the above components, various compounds
Can do. For example, in order to further improve printing durability,
A functional monomer in the matrix of the heat-sensitive layer
Can do. Such polyfunctional monomers include microphones
Exemplified as monomer encapsulated in rocapsule
Can be used. As a particularly preferred monomer
Lists trimethylolpropane triacrylate
be able to. In addition, the non-process type heat sensitive layer has an image shape.
To make it easier to distinguish between image and non-image areas after creation
Therefore, dyes that have a large absorption in the visible light region are used as image colorants.
Can be used. Specifically, the above-mentioned service
Same as image colorant used for heat sensitive layer
The compound of this is mentioned. In addition, phthalocyanine pigments,
Similarly, pigments such as azo pigments and titanium oxide are also used suitably.
Can. These contents are the total solid content of the heat sensitive layer.
It is preferable that it is 0.01-10 mass% with respect to. [0307] Further, the non-treatment type heat-sensitive layer is ethylenic.
When it contains a compound having an unsaturated bond, its unnecessary
Add a small amount of thermal polymerization inhibitor to prevent thermal polymerization
It is preferable. Examples of suitable thermal polymerization inhibitors include
For example, the photopolymerization of the above-described photopolymer type photosensitive layer
Illustrated as a thermal polymerization inhibitor that can be used in the composition
Compounds. Thermal polymerization inhibitor content is heat sensitive
About 0.01 to about 5% by weight, based on total solids of the layer
Is preferred. In addition, the non-treatment type heat sensitive layer is necessary.
In response, behenic acid to prevent polymerization inhibition by oxygen
Or higher fatty acid derivatives such as behenamide.
Even if it is unevenly distributed on the surface of the heat-sensitive layer during the drying process after application
Good. The content of the higher fatty acid derivative is the total solid content of the heat sensitive layer.
Is preferably about 0.1 to about 10% by mass.
Yes. [0309] Furthermore, a non-treatment type heat-sensitive layer is provided as necessary.
It contains a plasticizer to give the film flexibility and the like.
Can. As the plasticizer, the above-mentioned thermal
The same compound as the plasticizer used in the ditype heat sensitive layer
Illustrated. [0310] The non-treatment type heat-sensitive layer is composed of inorganic fine particles.
Can contain children. Examples of inorganic fine particles
Silica, alumina, magnesium oxide, magnesium carbonate
Examples include calcium and calcium alginate. these
Even if it is not photothermal convertible, the film is strengthened and the surface of the heat sensitive layer
There are effects such as enhancement of interfacial adhesion by roughening. inorganic
The content of the fine particles is 1.0 with respect to the total solid content of the heat-sensitive layer.
It is preferable that it is -70 mass%, 5.0-50 mass%
It is more preferable that Expected to be 1% or less
The effect is small, and it is originally necessary to be 70% by mass or more.
In some cases, the content of the infrared absorbing agent is limited. [0311] Further, the non-treatment type heat-sensitive layer is composed of a hydrophilic zone.
It can contain rutile particles. The above hydrophilic sol-like particles
The average particle diameter of the child is preferably 1 to 50 nm.
More preferably, it is ˜40 nm. Hydrophilic sol particles
In the hydrophilic resin, the particle size of is in the above range,
Metal fine particles contained as an infrared absorber, etc.
Hydrophobizing precursors such as fine hydrophobic hot-melt resin particles (exposure
It is hydrophobic when not exposed, and becomes hydrophobic upon exposure
Component) and stable dispersion with sufficient heat-sensitive layer strength
Can also be held by exposure to laser light, etc.
When making a plate and printing it as a lithographic printing plate
Excellent hydrophilicity without ink smudge
The effect that it becomes that which was made is obtained. Hydrophilic sol-like particles
For example, silica sol, alumina sol, oxidation
Magnesium sol, magnesium carbonate sol, alginic acid
Calcium sol is preferred. Among them, Silazo
, Alumina sol, calcium alginate sol or
These mixtures are preferred. These hydrophilic sol-like particles
Are easily available as commercial products.
The [0312] The infrared absorbing agent and the hydrophilic sol-like particles
The existing ratio is 100/0 to 30/70 by mass ratio.
Preferably 100/0 to 40/60
More preferable. Infrared absorbers, hydrophobizing precursors and
And the total content of hydrophilic sol-like particles is the total solid content of the heat-sensitive layer.
It is preferable that it is 2-95 mass% with respect to minutes,
More preferably, it is 85 mass%. The heat sensitive layer is usually prepared by dissolving the above components in a solvent.
The heat-sensitive layer coating solution obtained as described above is converted into a hydrophilic layer (anodized film layer).
Or anodized film layer after hydrophilization treatment)
And can be manufactured. The solvent used here and
Is used for the photopolymer type photosensitive layer described above.
The same solvents are mentioned, but the present invention
It is not limited to. These solvents can be used alone or
Are used as a mixture. The above components in the solvent (total solids)
The concentration of is preferably 1 to 50% by mass. As a coating method, the above-mentioned seeds are used.
Various methods can be used. In addition, the coating amount (solid content) of the heat sensitive layer is
Generally 0.5 to 5.0 g / m, depending on²so
Preferably there is. Less application amount than the above range
The apparent sensitivity increases, but the image recording function is fulfilled.
The film properties of the heat-sensitive layer are reduced. The heat-sensitive layer in the present invention has improved coatability.
Surfactants, for example, JP-A-62-1709
Fluorosurfactant as described in Japanese Patent No. 50
Can be added. The amount of surfactant added is heat sensitive.
It is 0.01-1 mass% with respect to the total solid of a layer.
Preferably, it is 0.05 to 0.5% by mass.
That's right. <Overcoat layer> Thermal positive tie
, Thermal negative type and non-treatment type (hereinafter referred to as total
It is also called “thermal type”. On the heat sensitive layer)
Can be provided with an overcoat layer. In the present invention
The overcoat layer used is a water-soluble layer,
It is easily removed during processing or printing. Oh
The bar coat layer was stored by stacking lithographic printing plate precursors.
Has releasability to prevent sticking in cases
The The main component of the overcoat layer is water-soluble
Or an inorganic polymer compound and its aqueous solution is applied.
Film formed by cloth and drying
It has a forming ability. Specifically, for example,
Paragraph No. [0011] of Japanese Patent Laid-Open No. 2001-162961
Water-soluble resin described in JP-A-2002-1931
Examples include celluloses described in No. 5 publication
The In addition, the overcoat layer has other additives.
You may contain the thing as needed. For example, releasability
Water-soluble or water-dispersible fluorine source to increase
Containing compounds containing silicon atoms and / or silicon atoms
It is preferable. In addition, it preferably contains a photothermal conversion substance.
Good. As the photothermal conversion substance, for example, JP 2001
The compounds described in JP-A-162961 are preferably used.
Can be mentioned. The overcoat layer has a surface dynamic friction coefficient.
(Μk) is preferably 2.5 or less, 0.03 to
More preferably, it is 2.0. High surface friction coefficient
Within the above range, the transportability of the planographic printing plate precursor is good.
In addition, alkali developability or on-press developability and printing durability
The property is also good. Here, the “dynamic friction coefficient” of the surface is the standard
Measured by a measurement method according to quasi-ASTMD 1894
It is. That is, the surface of the underlying material
A lithographic printing plate precursor is placed in contact with the back side.
“Back” refers to the image recording layer on the lithographic printing plate support.
And the surface where no overcoat layer is provided,
“Surface” means an image recording layer on a lithographic printing plate support.
And a surface on which an overcoat layer is provided.
Coefficient of dynamic friction is 3,000 lithographic printing plate precursors stacked
After leaving it at 35 ° C and 75% for 3 days,
It can be determined by measuring the sample below. An overcoat of such a preferred embodiment
The layer increases the type of water-soluble resin, surfactant, etc., and releasability.
Containing fluorine atoms and / or silicon atoms to be added
By appropriately combining the type and amount of compound to be added
Can be obtained. For example, a fluorine atom and / or
Total solidity of the overcoat layer of the compound containing silicon atoms
The ratio to the shape is 0.05 to 5.0% by mass.
Is preferable, and 0.1 to 3% by mass is more preferable.
Yes. <Backcoat layer>
Various image-recording layers are provided on the support for the light planographic printing plate
The back side of the lithographic printing plate precursor of the present invention
Correspondingly, the image recording layer is prevented from being scratched when stacked.
In order to achieve this, a coating layer made of an organic polymer compound
It is called “back coat layer”. ) Can be provided.
The main component of the backcoat layer is a glass transition point of 20 ° C.
Saturated copolymer polyester resin, phenoxy resin
Fat, polyvinyl acetal resin and vinylidene chloride
At least one resin selected from the group consisting of polymerized resins
Are preferably used. Saturated copolymer polyester resin
It consists of a dicarboxylic acid unit and a diol unit.
Dicarboxylic 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.
And saturated aliphatic dicarboxylic acids. The back coat layer is further dyed for coloring.
Materials, pigments, etc .; improved adhesion to lithographic printing plate support
Silane coupling agent for
Diazo resin, organic phosphonic acid, organic phosphoric acid, cation
Polymer, etc .; Wack usually used as a slipping agent
, Higher fatty acid, higher fatty acid amide, dimethylsiloxa
A silicone compound comprising modified dimethylsiloxa
And polyethylene powder and the like can be contained as appropriate. The thickness of the back coat layer is basically a slip sheet.
As long as the image recording layer is not easily damaged
It is preferably 0.01 to 8 μm. The thickness is 0.
If the thickness is 01 μm or less, the planographic printing plate precursors are handled in layers.
It would be difficult to prevent the image recording layer from being scratched.
The When the thickness exceeds 8 μm, the circumference of the lithographic printing plate is being printed.
The back coat layer is swollen by the chemicals used on the side.
The printing characteristics may be deteriorated by changing the thickness and the printing pressure.
There is. [0325] Backcoat layer on back side of planographic printing plate precursor
Various methods can be applied for coating. example
For example, each of the above components is made into a solution of an appropriate solvent or emulsified.
A method of applying a dispersion liquid and drying it.
A method of bonding a molded product with an adhesive or heat.
Method, melt film is formed with a melt extruder and bonded together
Methods and the like. Above all, ensure the above coating amount
It is preferable to apply the solution and dry it.
Is the law. As the solvent, JP-A-62-251739
Organic solvents such as those described in the official gazette
Used together. As the application method and conditions,
Utilize many of the methods and conditions for applying the image recording layer.
You can. That is, for example, using a coating rod
A method using an extrusion type coater,
A method using a slide bead coater can be used. Ba
The back coat layer may be provided before the image recording layer is provided.
May be provided after being provided, or provided at the same time as the image recording layer.
May be. [Image formation and development] Planographic plate of the present invention
Depending on the type of the image recording layer, the printing plate precursor is conventionally known.
Lithographic plate after image formation (for example, exposure) and development processing
It can be a printing plate. Active light used for image exposure
As a light source of the line, for example, a carbon arc lamp, mercury
Lamp, metal halide lamp, xenon lamp, tongue
Ten lamps and chemical lamps may be mentioned. With radiation
For example, electron beam, X-ray, ion beam, far infrared
Line, g-line, i-line, Deep-UV light, high-density energy
Beam (laser beam). With laser beam
For example, helium-neon laser (He-Ne laser)
Laser), argon laser, krypton laser, helium
Mu-cadmium laser, KrF excimer laser, semiconductor
Body laser, YAG laser, YAG-SHG laser
It is done. In the case of a thermal type heat sensitive layer,
A known thermal head system can also be used. Among them, laser light based on digital data
Photopolymer film exposed to the desired image
Type and thermal type plate making
It is preferable to perform development using a method that uses Lucari developer.
Yes. When exposure and development processing are performed in this way,
For positive type lithographic printing plate precursor (thermal positive type)
Depends on the infrared absorber contained in the image recording layer of the exposed area.
The laser beam is absorbed efficiently, and the energy absorbed by exposure
Only the image recording layer in the exposed area
Development process using alkali developer that becomes alkali-soluble
As a result, only the image recording layer of the exposed portion is removed to obtain a desired
An image is formed. In addition, negative planographic printing plate precursor (support
(Marginega type) is included in the image recording layer of the exposed area.
Efficient absorption of laser light by existing infrared absorber
Of the exposed area due to the accumulation of absorbed energy due to exposure.
Only the image recording layer generates heat and generates acid.
The existing crosslinking agent causes a crosslinking reaction, and the image recording layer in the exposed area
Only becomes insoluble in alkali, while image recording of unexposed area
The layer is removed by development using an alkaline developer.
Thus, a desired image is formed. In addition, the image recording layer is
Similarly, if it is a conventional positive type, it will be described later.
An alkaline developer can be preferably used. Image
If the recording is of the conventional negative type, for example
For example, it is described in JP-A-3-103857.
Such a developer can be used. The following is a description of the process used in the development process of the above method.
For Lucari developer (hereinafter also simply referred to as “developer”)
And explain. Alkaline developer used for development is
Alkaline aqueous solution, a conventionally known aqueous alkaline solution
It can be used by appropriately selecting from the above.
Alkaline water solution containing potash or non-reducing sugar and base
The liquid is preferably mentioned, particularly those having a pH of 12.5 to 14.0.
Is more preferable. Alkali silicate is a solution when dissolved in water.
For example, sodium silicate
Alkali metals such as potassium, potassium silicate and lithium silicate
Examples of silicates include ammonium silicate. these
May be used alone or in combination of two or more
Also good. An alkaline aqueous solution using an alkali silicate
In this case, silicon oxide SiO, which is a component of silicate,₂When
Alkali oxide M₂O (M is alkali metal or ammonia
Represents a nium group. ) To adjust the mixing ratio and concentration
Therefore, the developability can be easily adjusted. Above all, acid
Silicon oxide SiO₂And alkali oxide M₂Mixing ratio with O
(SiO₂/ M₂O: molar ratio) of 0.5 to 3.0
Are preferred, and those of 1.0 to 2.0 are more preferred. S
iO₂/ M₂When O is less than 0.5, the alkali strength is
Al is used for lithographic printing plate precursors
The negative effect of etching the minium plate occurs
In addition, if it exceeds 3.0, developability is lowered.
Sometimes. Further, silicic acid in the above alkaline aqueous solution
The alkali concentration is preferably 1 to 10% by mass.
More preferably 3 to 8% by mass, and 4 to 7% by mass.
% Is more preferable. Concentration is less than 1% by mass
Developability and throughput may be reduced.
In addition, if it exceeds 10% by mass, it is easy to form precipitates and crystals.
Furthermore, it becomes easy to gel during neutralization at the time of waste liquid.
It may interfere with liquid processing. Alkaline water solution containing non-reducing sugar and base
In liquid, “non-reducing sugar” means a free aldehyde group.
Or sugars that do not have a ketone group
Taste. Non-reducing sugars are trehalos with reducing groups attached to each other.
Type oligosaccharides, glycosides with saccharide reducing groups and non-saccharides
And sugar alcohols reduced by hydrogenation of sugars
Any of these can be suitably used. Ingredients
Specifically, JP-A-8-305039 and JP-A-8-305039
Examples are compounds described in Japanese Patent Application Publication No. 11-216962.
Indicated. These non-reducing sugars may be used alone.
In addition, two or more kinds may be used in combination. Alkaline water
The content of non-reducing sugar in the solution is 0.1 to 30% by mass
It is preferable that it is 1 to 20% by mass.
Good. With the above alkali silicate or the above non-reducing sugar
Bases used in combination include conventionally known al
A potash agent can be appropriately selected. As alkaline agent
Is, for example, the paragraph number of JP-A-11-216962
Described in Nos. [0083] to [0084]
Is mentioned. These may be used alone or in combination of two or more
May be used in combination. Among them, sodium hydroxide and potassium hydroxide
Are preferred. When these are used, the addition to non-reducing sugars
By adjusting the addition amount, pH in a wide pH range
This is because adjustment is possible. In addition, trisodium phosphate
, Tripotassium phosphate, sodium carbonate, potassium carbonate
Etc. are also preferable because they have a buffering effect. The alkali developer is an alkaline water solution as described above.
It is obtained by adding a surfactant to the liquid. With surfactants
Nonionic surfactants, anionic surfactants,
Thion surfactant, amphoteric surfactant, fluorinated surfactant
Agents and the like. Surfactant may be used alone
In addition, two or more kinds may be used in combination. Nonionic surfactant used in the present invention
Is not particularly limited, and a conventionally known one can be used.
Yes. For example, polyoxyethylene alkyl ether
, Polyoxyethylene alkylphenyl ethers,
Polyoxyethylene polystyryl phenyl ethers,
Polyoxyethylene polyoxypropylene alkyl agent
Tells, glycerin fatty acid partial esters, sorbitan
Fatty acid partial esters, pentaerythritol fatty acid part
Esters, propylene glycol mono fatty acid esthetics
Sucrose fatty acid partial esters, polyoxyethylene
N sorbitan fatty acid partial esters, polyoxyethylene
N-sorbitol fatty acid partial esters, polyethylene glycol
Recall fatty acid esters, polyglycerin fatty acid part
Esters, polyoxyethylenated castor oil, polio
Xylethyleneglycerin fatty acid partial esters, fatty acids
Diethanolamides, N, N-bis-2-hydroxy
Alkylamines, polyoxyethylene alkylamino
, Triethanolamine fatty acid ester, trialkyl
And ruamine oxide. Preferably,
No. 11-338126, paragraph number [0062] to
And the compounds described in [0067]. As specific examples of other surfactants,
Paragraph No. [0095] of Kaihei 11-338126
To [0099] are mentioned. The surfactant content is 0.1% in the developer.
˜15% by mass, preferably 0.5˜8.0% by mass
% Is more preferable, and is 1.0 to 5.0% by mass.
More preferably. If the content is too low, developability is low.
Too low and lower solubility of photosensitive layer components, conversely too much
Reducing the printing durability of the lithographic printing plate. The alkali developer contains a chelating agent.
be able to. Examples of chelating agents include Na₂P
₂O₇, Na_FiveP_ThreeO_Three, Na_ThreeP_ThreeO₉, Na₂O_Four
P (NaO_ThreeP) PO_ThreeNa₂, Calgon (Polymetallic
Polyphosphates such as sodium phosphate; ethylenediamine
Tetraacetic acid, its potassium salt, its sodium salt, die
Tylenetriaminepentaacetic acid, its potassium salt, sodium
Um salt, triethylenetetramine hexaacetic acid, its potassium
Um salt, its sodium salt, hydroxyethylethylene
Diamine triacetic acid, its potassium salt, its sodium
Salt, nitrilotriacetic acid, its potassium salt, its sodium
Salt, 1,2-diaminocyclohexanetetraacetic acid,
Potassium salt thereof, its sodium salt, 1,3-diamino-
2-propanoltetraacetic acid, its potassium salt, its sodium
Aminopolycarboxylic acids such as thorium salts; 2-phosphono
Butanetricarboxylic acid-1,2,4, potassium salt thereof,
Its sodium salt, 2-phosphonobutanone tricarboxylic
Acid-2,3,4, its potassium salt, its sodium salt,
1-phosphonoethanetricarboxylic acid-1,2,2, its
Potassium salt, sodium salt thereof, 1-hydroxyethane
-1,1-diphosphonic acid, its potassium salt, its sodium
Um salt, aminotri (methylenephosphonic acid), its potassium
Organic phosphonic acids such as um salt and its sodium salt
It is done. The chelating agent content is determined according to the hard water used.
It is determined according to the hardness and the amount used, but at the time of use
In the developer, it is preferably 0.001 to 5% by mass,
More preferably, the content is 0.01 to 1.0% by mass.
More preferably, it is 05-0.5 mass%. The alkaline developer used in the present invention includes
In order to further improve development performance, the following additives are added.
Can be added. For example, JP-A-58-75152
NaCl, KCl, KBr, etc.
Neutral salt, described in Japanese Patent Application Laid-Open No. 58-190952
Chelating agents such as EDTA and NTA, JP-A-59-1
[Co (NH_Three)₆]
Cl_ThreeCoCl₂・ 6H₂Complexes such as O, JP-A-50-
Alkylnaphthalene described in Japanese Patent No. 51324
Sodium sulfonate, n-tetradecyl-N, N-dihydride
Anionic or amphoteric surface activity such as loxyethyl betaine
Agents described in US Pat. No. 4,374,920
Nonionic interface such as tetramethyldecynediol
Activator, described in JP-A-55-95946
P-dimethylaminomethyl polystyrene methyl chloride
Cationic polymers such as ride quaternary compounds,
Vinylben described in Japanese Patent 56-142528
Zirtrimethylammonium chloride and sodium acrylate
Amphoteric polymer electrolytes such as copolymers with
Such as sodium sulfite described in Japanese Patent No. 192951
Reducing inorganic salt, described in JP-A-58-59444
Inorganic lithium compounds such as lithium chloride,
Organic Si described in 59-75255, Yes
Organometallic surfactants containing machine Ti, etc.
Organoboron compounds described in 84241, etc.
Is mentioned. In addition, the alkaline developer contains the amount of development residue.
Improves dispersion and ink affinity in the image area of the lithographic printing plate precursor
Development stabilizers, organic solvents, etc.
Agent, reducing agent, organic carboxylic acid, water softener, preservative, wear
Coloring agents, thickeners, antifoaming agents and the like may be added. For example, special
Paragraph number [0101] of Kaihei 11-216962
To the compounds described in [0110]
However, the present invention is not limited to these. Use of the alkaline developer used in the present invention
The aspect is not particularly limited. In recent years, in particular, plate making and stamping
In the printing industry, streamlining and standardization of plate making operations
For this reason, automatic developing machines for printing plates are widely used. this
An automatic processor generally consists of a developing section and a post-processing section.
It has a plate transporting device, each processing solution tank, and a spray device.
And pump the exposed printing plate horizontally
Each treatment liquid pumped up is sprayed from the spray nozzle.
Image processing is performed. Recently, the treatment liquid has been filled.
Printing plate with submerged guide rolls in the treated bath
A method of immersing and transporting the material is also known. this
In such automatic processing, each processing solution has a processing amount and an operating time.
Can be processed while replenishing the replenisher according to the interval
The In this case, the alkali strength is higher than that of the developer.
By adding an aqueous solution as a replenisher to the developer.
Without changing the developer in the developer tank for a long time.
An amount of printing plate can be processed. Used in the present invention
This replenishment method is also used when using alkaline developer.
It is a preferable aspect to adopt. As replenisher
Is, for example, the above-mentioned alkaline developer, for development
Use a developer with higher alkali strength than
it can. The developer and replenisher do not promote developability.
Or suppression, dispersibility of development residue, and ink affinity of image area
For the purpose of enhancing various interfaces other than the above as required
An activator, an organic solvent, etc. can also be added. Surface activity
As an agent, anionic surfactant, nonionic surfactant
Or an amphoteric surfactant is preferred. As an organic solvent,
Benzyl alcohol and the like are preferred. Polyethylene
Glycol or its derivatives, polypropylene glycol
It is also preferable to add benzene or a derivative thereof. Furthermore, if necessary
Depending on hydroquinone, resorcin, sulfite or sulfite
Inorganic salts such as sodium or potassium hydrosulfate
System reducing agent; organic carboxylic acid, antifoaming agent, water softener, etc.
Can also be added. Using the alkali developer and replenisher described above
The lithographic printing plate of the present invention obtained by development processing is
In general, rinsing liquid containing washing water, surfactant, etc.
Using desensitized liquid containing beer gum and starch derivatives
And post-processing. In this post-treatment, these treatment liquids
Can be performed in various combinations. Also substantially
So-called disposable treatment with unused alkaline developer
It can also be a processing method. Further, the planographic printing plate precursor as shown below
Contains substantially alkali metal silicate after exposure to
Also used for processing lithographic printing plates that are developed with no developer
I can. With this method, alkali metal silicate
Problems when developing with a developer containing
That is, SiO₂The solid matter caused by
In the neutralization process when processing the waste liquid of the developer, SiO₂
Prevents the occurrence of problems such as gel formation
Can. Note that this method is disclosed in JP-A-11.
-109637, which is described in detail in the present invention.
Use the contents described in the publication.
Can do. Exposure In this method, image exposure is performed before development processing. image
Illustrative examples of actinic light source used for exposure
Can be used. Development Substantially contains an alkali metal silicate after the exposure.
It is preferable to perform development using a non-developing solution. In this method
The preferred developer used is substantially an alkali metal case.
There is no particular limitation as long as the developer does not contain an iodate.
Alkaline aqueous solution substantially free of organic solvent
Is preferred. However, if necessary, include organic solvents.
You may have. This developer contains saccharides.
Is preferred. For example, selected from non-reducing sugars as the main component
At least one compound and at least one base
And a developer having a pH of 9.0 to 13.5.
It is done. Also, when the image recording layer is a non-process type
In this case, after exposure to make a plate making master,
Water or aqueous solution without developing with Lucari developer
Can be made into a lithographic printing plate by simple processing. This place
Aqueous solution substantially free of alkali metal silicate
Is preferably used. For example, if necessary, organic solvent
An alkaline aqueous solution that may contain an agent is included.
This aqueous solution is further made from sugars (eg, non-reducing sugars).
You may contain the compound chosen. In addition, this untreated tag
Ip's planographic printing plate precursor is exposed and image-recorded.
It is attached to the plate cylinder of a printing press without processing, for example
For example, fountain solution is supplied to the lithographic printing plate precursor and developed on the machine.
And then start printing by supplying ink, lithographic
Supply dampening water and ink to the printing plate precursor and develop on-machine
After that, the method of supplying ink and starting printing,
When ink is supplied to the printing plate precursor and fountain solution is supplied
Sometimes the printing is done by feeding paper and starting printing.
can do. Further, the non-process type lithographic printing plate precursor is
As described in Japanese Patent No. 2938398
On the plate cylinder and then installed on the printing press.
Record images with the thermal head or
Developing on-press with water and / or ink
You can also. In other words, an unprocessed lithographic printing plate precursor is preferable.
It can be developed with water or aqueous solution.
Install it in the printing machine without developing it.
It can be printed. [0353] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. 1. Creating a lithographic printing plate precursor Example 1 <Aluminum plate> Si: 0.06 mass%, Fe: 0.
30% by mass, Cu: 0.005% by mass, Mn: 0.00
1% by mass, Mg: 0.001% by mass, Zn: 0.001
% By mass, Ti: 0.03% by mass, the balance being Al
Prepare molten metal using inevitable impurity aluminum alloy
500m thick after molten metal treatment and filtration
An ingot having a width of 1200 mm was prepared by a DC casting method. table
After scraping the surface with an average thickness of 10 mm with a surface grinder,
Keep soaking at 550 ° C for about 5 hours, and drop to 400 ° C
Then, using a hot rolling mill, a pressure of 2.7 mm thick
It was a sheet. Furthermore, heat treatment is performed using a continuous annealing machine.
Finished at 0.24mm in thickness by cold rolling
As a result, a JIS 1050 aluminum plate was obtained. this
After making an aluminum plate width 1030mm, it shows below
It used for surface treatment and the support body for lithographic printing plates was obtained. <Surface Treatment> The surface treatment is carried out as follows:
The various treatments of (i) were performed continuously. Na
After each treatment and water washing, drain the liquid with a nip roller.
went. (A) Mechanical roughening treatment Polishing with a specific gravity of 1.12 using an apparatus as shown in FIG.
A slurry of the agent (pumice) and water is used as a polishing slurry.
Roller shape that rotates while supplying to the surface of the ruminium plate
A mechanical surface roughening treatment was performed with a nylon brush. FIG.
1 is an aluminum plate, 2 and 4 are roller-shaped
Brush 3, polishing slurry liquid, 5, 6, 7 and 8 support
It is a holding roller. The average particle size of the abrasive is 40μm, the largest particle
The diameter was 100 μm. The material of the nylon brush is 6.
10 nylon, hair length is 50 mm, hair diameter is 0.3 mm
Met. Nylon brush is stainless steel of φ300mm
A hole was made in the tube made of the product and the hair was planted so as to be dense. Rotating bra
Three shis were used. Two support rollers (φ
200 mm) was 300 mm. Brush low
The load on the drive motor that rotates the brush
Against the load before pressing the roller against the aluminum plate
It was pressed down until it became 7kW plus. How to rotate the brush
The direction was the same as the moving direction of the aluminum plate. brush
The rotation speed of was 200 rpm. (B) Alkali etching treatment The aluminum plate obtained above was used with caustic soda concentration 26
Mass%, aluminum ion concentration 6.5 mass%, temperature 7
Etching treatment by spraying using aqueous solution at 0 ℃
10g / m of aluminum plate²Dissolved. That
Thereafter, washing with water was performed by spraying. (C) Desmut processing 1% by mass aqueous solution of nitric acid with a temperature of 30 ° C.
Contains 0.5% by mass of ON. )
And then washed with water by spraying. Desma
The nitric acid aqueous solution used in the water treatment is exchanged in the nitric acid aqueous solution.
Using the waste liquid from the process of electrochemical surface roughening using
It was. (D) Electrochemical roughening treatment Continuous electrochemical rough surface using 60Hz AC voltage
The treatment was performed. The electrolyte at this time was 10.5 g of nitric acid.
/ L aqueous solution (aluminum ion 5g / L, ammonia
It contains 0.007% by mass of um ion. ) At a liquid temperature of 50 ° C
there were. The AC power supply waveform is the waveform shown in FIG.
The time TP until the value reaches the peak from zero is 0.8m
sec, duty ratio 1: 1, trapezoidal rectangular wave AC
Electrochemical roughening with carbon electrode as counter electrode
Went. Ferrite was used for the auxiliary anode. use
The electrolytic cell shown in FIG. 3 was used. Current density is electric
30 A / dm at the peak value of the flow²The quantity of electricity is aluminum
The total amount of electricity when the plate is an anode is 220 C / dm²So
It was. The auxiliary anode shunts 5% of the current flowing from the power source
It was. Then, water washing by spraying was performed. (E) Alkali etching treatment Aluminum plate with caustic soda concentration of 26% by mass, aluminum
Spray using an aqueous solution of 6.5% by mass of ionic ions
Etching with-is performed at 60 ° C, aluminum
1.0 g / m of plate²Dissolve and electrify using previous AC
Of aluminum hydroxide produced during surface roughening
Remove and generate smut components mainly composed of um
Smooth the edge by melting the edge of the pit
did. Then, water washing by spraying was performed. (F) Desmut processing 15% by weight aqueous solution of sulfuric acid at a temperature of 30 ° C. (aluminum
It contains 4.5% by mass of ions. ) And spray death
The mat was processed and then washed with water by spraying. death
The aqueous nitric acid solution used for matting is exchanged in aqueous nitric acid solution.
Using the waste liquid of the process of electrochemical surface roughening using
It was. (G) Anodizing treatment Anodizing using the anodizing apparatus having the structure shown in FIG.
went. As electrolyte supplied to the first and second electrolysis parts
Used sulfuric acid. Both electrolytes have a sulfuric acid concentration of 17
0 g / L (containing 0.5 mass% aluminum ions
Mu ) Temperature was 38 ° C. Then by spray
Washed with water. The final oxide film amount is 2.7 g / m²so
there were. (H) Hydrophilization treatment Treatment of 1 mass% aqueous solution of No. 3 sodium silicate with a liquid temperature of 20 ° C
By soaking in the tank for 10 seconds, hydrophilization treatment (A
(Lucali metal silicate treatment). Then use well water
The spray was washed with water. (I) Carboxylic acid and / or carvone
Treatment with aqueous solution containing acid salt In a treatment tank of 0.1% by weight aqueous solution of acetic acid at a liquid temperature of 60 ° C.
By soaking for 10 seconds, carboxylic acid and / or
Was treated with an aqueous solution containing a carboxylate.
Then, wash with water using well water,
A printing plate support was obtained. On the lithographic printing plate support obtained above,
Form the thermal positive type image recording layer as follows.
To obtain a lithographic printing plate precursor. <Formation of image recording layer> On the support for a lithographic printing plate,
Apply the prepared primer and dry at 80 ° C for 15 seconds.
(Intermediate layer) was formed. The coating amount after drying is 20
mg / m²Met. <Undercoat liquid composition> ・ The following polymer compound 0.3g ・ Methanol 100g ・ Water 1g [0365] [Chemical 1] Further, a thermosensitive layer coating solution having the following composition was prepared,
This thermosensitive layer coating solution is applied to an undercoated lithographic printing plate support.
The coating amount after drying (the heat-sensitive layer coating amount) is 1.7 g / m.²Nina
Apply and dry to heat sensitive layer (thermal positive type)
The lithographic printing plate precursor was obtained. <Thermosensitive layer coating solution composition> ・ Novolac resin (m-cresol / p-cresol =
60/40, weight average molecular weight 7,000, unreacted Creso
1.0g) -Cyanine dye A 0.1 g represented by the following structural formula ・ Tetrahydrophthalic anhydride 0.05g ・ 0.002 g of p-toluenesulfonic acid -Ethyl violet counter ion as 6-hydroxy-β
-Naphthalene sulfonic acid 0.02g ・ Fluorine surfactant (Megafac F-177, Dainichi
0.05g made by this ink chemical industry) ・ Methyl ethyl ketone 12g [0368] [Chemical 2] (Examples 2 to 8 and Comparative Example 1 and
2) Aqueous solution concentration, liquid temperature and immersion in (h) above
Time, as well as the solute species of the aqueous solution in (i) above
As shown in Table 1, the concentration, concentration, liquid temperature and immersion time
Except for changes, each planographic printing was performed in the same manner as in Example 1.
I got the original version. In Table 1, “-” indicates the applicable process.
Indicates that no action was taken. (Example 9) Between (f) and (g) above
In addition to the following (j), (k) and (l),
A lithographic printing plate precursor was obtained in the same manner as in Example 1. (J) Electrochemical roughening treatment Continuous electrochemical rough surface using 60Hz AC voltage
The treatment was performed. At this time, the electrolytic solution was 2.5 g of hydrochloric acid /
L aqueous solution (containing 5 g / L of aluminum ions), warm
The temperature was 35 ° C. The AC power supply waveform is the waveform shown in Fig. 2.
Yes, time TP until the current value reaches the peak from zero
Is 0.8msec, duty ratio is 1: 1, trapezoidal rectangular wave
Electrochemical rough surface with carbon electrode as counter electrode
The treatment was performed. Ferrite is used for the auxiliary anode
It was. The electrolytic cell used was the one shown in FIG. Current
The density is 25 A / dm at the peak current value.²The amount of electricity is al
The total amount of electricity when the minium plate is the anode is 30 C / dm²so
there were. Then, water washing by spraying was performed. (K) Alkali etching treatment Aluminum plate with caustic soda concentration of 26% by mass, aluminum
Spray using an aqueous solution of 6.5% by mass of ionic ions
Etching with-is performed at 32 ° C, aluminum
0.10 g / m of plate²Dissolve and electricity using the previous stage alternating current
Aluminum hydroxide produced during chemical roughening
Removal and generation of smut components mainly composed of nitrogen
Dissolve the edge of the pit and smooth the edge
I made it. Then, water washing by spraying was performed. (L) Death mat processing Sulfuric acid concentration 25 mass% aqueous solution (aluminum at 60 ° C.
Contains 0.5% by mass of ions. ) And spray death
Perform mat treatment, then wash with water
It was. (Example 10) Without performing (a) above,
Instead of the above (d), (e) and (f),
Example 1 except that (m), (n) and (o) were performed
A lithographic printing plate precursor was obtained by the same method. (M) Electrochemical roughening treatment Continuous electrochemical rough surface using 60Hz AC voltage
The treatment was performed. The electrolyte at this time was 7.5 g of hydrochloric acid /
L aqueous solution (containing 5 g / L of aluminum ions), warm
The temperature was 35 ° C. The AC power supply waveform is the waveform shown in Fig. 2.
Yes, time TP until the current value reaches the peak from zero
Is 0.8msec, duty ratio is 1: 1, trapezoidal rectangular wave
Electrochemical rough surface with carbon electrode as counter electrode
The treatment was performed. Ferrite is used for the auxiliary anode
It was. The electrolytic cell used was the one shown in FIG. Current
The density is 25 A / dm at the peak current value.²The amount of electricity is al
The total amount of electricity when the minium plate is the anode is 500 C / dm²
Met. 5% of the current flowing from the power supply is distributed to the auxiliary anode
Washed away. Then, water washing by spraying was performed. (N) Alkali etching treatment Aluminum plate with caustic soda concentration of 26% by mass, aluminum
Spray using an aqueous solution of 6.5% by mass of ionic ions
Etching treatment with-is performed at 32 ° C
0.5 g / m of plate²Dissolve and electrify using previous AC
Of aluminum hydroxide produced during surface roughening
Remove and generate smut components mainly composed of um
Smooth the edge by melting the edge of the pit
did. Then, water washing by spraying was performed. (O) Death mat processing Sulfuric acid concentration 25 mass% aqueous solution (aluminum at 60 ° C.
Contains 0.5% by mass of ions. ) And spray death
Perform mat treatment, then wash with water
It was. (Examples 11-14 and Comparative Examples 3 and
4) Aqueous solution concentration, liquid temperature and immersion in (h) above
And the solute of the aqueous solution in (i) above.
Except for changing the type and concentration as shown in Table 1,
Each lithographic printing plate precursor was obtained in the same manner as in Example 10.
In Table 1, “-” indicates that the corresponding processing is not performed.
It shows that. [0379] 2. Exposure and development processing Images are obtained on the planographic printing plate precursors obtained above by the following method.
Exposure and development were performed to obtain a lithographic printing plate. Lithographic seal
Printing plate master output 500mW, wavelength 830nm beam diameter 1
7 μm (1 / e ²CRE equipped with semiconductor laser
Main run using TrendSetter 3244 manufactured by O Company
Inspection speed 5m / sec, plate surface energy 140mJ / cm²
And imagewise exposure. Then combine non-reducing sugar and base
D-sorbite / potassium oxide K₂Potash made of O
Um salt 5.0% by mass and Orphin AK-02 (Nisshin
1L of aqueous solution containing 0.015% by mass)
To C₁₂H_{twenty five}N (CH₂CH₂COONa)₂1g added
Development processing was performed using the alkaline developer prepared. Development
The reason is that the automatic processor PS9 filled with the alkali developer is used.
Development using 00NP (Fuji Photo Film Co., Ltd.)
The test was performed at a temperature of 30 ° C. for 12 seconds. The development process is complete
And then through a water washing step, gum (FP-2W (1: 1))
To obtain a lithographic printing plate on which the plate making was completed. 3. Evaluation of planographic printing plates Ink wiping and printing durability of the lithographic printing plate obtained above
Was evaluated by the following method. (1) Ink repellency Printing using IF2 type 2-color sheet-fed printing machine manufactured by Mitsubishi Heavy Industries
After starting printing under normal printing conditions,
After the prints are available, adjust the water scale.
Stop supplying water to the plate surface and
The ink was allowed to adhere to the ink. Then adjust the water scale again
When the amount of water supplied to the plate is returned to the normal amount
To the amount of waste paper generated until a good print is obtained.
Evaluated by number. When ink repellency is good, there is little waste paper
When the ink repellency is poor, the amount of waste paper increases. Na
Here, ink repellency is one index of stain resistance
It is used as. The results are shown in Table 1. (2) Printing durability A Japanese Lithrone printing machine manufactured by Komori Corporation.
DIC-GEOS (N) ink ink manufactured by Ink Chemical Industry Co., Ltd.
When printing with a key, the density of the solid image starts to fade
Evaluation of printing durability based on the number of copies printed at the time of visual recognition
did. If the printing durability is excellent, the number of printed sheets increases and printing durability increases.
If the performance is inferior, the number of printed sheets is reduced. The results are shown in Table 1.
Show. As is apparent from Table 1, aluminum
After roughening and anodizing the plate, the concentration
0.6% to 5.0% by weight aqueous alkali metal silicate solution
Is subjected to hydrophilization treatment, and further, carboxylic acid and / or
Is obtained by treatment with an aqueous solution containing a carboxylate.
The lithographic printing plate support of the present invention is used.
Plate printing plate precursors (Examples 1 to 14) have ink repellency (resistance to
It is known that both stain resistance and printing durability are excellent.
The In contrast, alkaline gold used for hydrophilic treatment
When the concentration of the aqueous silicate solution is too low (Comparative Example 1 and
3) has a low effect of hydrophilization treatment and ink repellency (resistance to
It is inferior to dirtiness. Also, carboxylic acids and / or cal
When not treated with an aqueous solution containing a borate
(Comparative Examples 2 and 4) are inferior in printing durability. [0383] [Table 1] [0384] As described above, the lithographic seal of the present invention.
Infrared rays are prone to occur when using a printing plate support.
Even when an image recording layer containing an absorbent is provided, it is resistant to contamination.
A lithographic printing plate precursor that is superior in both printability and printing durability.
Can appear.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side view showing the concept of a brush graining process used for mechanical surface roughening in the production of a lithographic printing plate support of the present invention. FIG. 2 is a graph showing an example of an alternating waveform current waveform diagram used for electrochemical surface roughening treatment in producing a lithographic printing plate support of the present invention. FIG. 3 is a side view showing an example of a radial type cell in an electrochemical surface roughening treatment using alternating current in the production of a lithographic printing plate support of the present invention. FIG. 4 is a schematic view of an anodizing apparatus used for anodizing treatment in the production of a lithographic printing plate support of the present invention. [Description of Symbols] 1 Aluminum plate 2, 4 Roller brush 3 Polishing slurry liquid 5, 6, 7, 8 Support roller 11 Aluminum plate 12 Radial drum rollers 13a, 13b Main electrode 14 Electrolytic treatment liquid 15 Electrolyte supply port 16 Slit 17 Electrolyte passage 18 Auxiliary anodes 19 a, 19 b Thyristor 20 AC power supply 40 Main electrolytic tank 50 Auxiliary anode tank 410 Anodizing device 412 Power supply tank 414 Electrolytic treatment tank 416 Aluminum plate 418, 426 Electrolytic solution 420 Power supply electrode 422, 428 Roller 424 Nip roller 430 Electrolytic electrode 432 Tank wall 434 DC power supply

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AB03 DA18 DA20                 2H096 AA06 CA03                 2H114 AA04 AA14 AA22 AA27 BA01                       DA04 DA14 DA64 EA03 EA04                       EA08 GA03 GA08 GA09

Claims (1)

What is claimed is: 1. An aluminum plate is subjected to a surface roughening treatment and an anodizing treatment, followed by a hydrophilization treatment with an aqueous alkali metal silicate solution having a concentration of 0.6 to 5.0% by mass. In addition,
A lithographic printing plate support obtained by treatment with an aqueous solution containing a carboxylic acid and / or a carboxylate.