JP2003233194A - Support for photosensitive planographic printing plate material, photosensitive planographic printing plate material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate material excellent in the adhesiveness of a photopolymerizable layer to the support, capable of ensuring both printing resistance and improvement in stain of a non-printing area and capable of obtaining a high resolution planographic printing plate and to provide a method for producing the same. <P>SOLUTION: A support for a photosensitive planographic printing plate material is a surface-roughened metal support treated with an aqueous solvent containing at least A) polyvinylphosphonic acid and B) an amino-containing compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a support for a photosensitive lithographic printing plate material which is excellent in printing durability, stain recovery and linearity, a photosensitive lithographic printing plate material and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a photosensitive lithographic printing plate material is known in which a photopolymerizable layer and a protective layer are laminated on a support which has been subjected to a hydrophilic surface treatment. In addition, particularly in recent years, in order to rapidly obtain a high-resolution planographic printing plate material, and for the purpose of filmless, digital exposure is performed based on image information using a laser, and this is developed to obtain a planographic printing plate. The manufacturing method is generalized.

For example, an output signal from an electronic plate making system or an image processing system or an image signal transmitted through a communication line modulates a light source to directly scan and expose a photosensitive lithographic printing plate material. Therefore, a system for forming a lithographic printing plate is known.

The photopolymerizable layer is generally composed of an acrylic monomer, an alkali-soluble resin and a photopolymerizable initiator, and optionally a sensitizing dye for adjusting the wavelength (especially when laser writing is performed). Is known to contain.

It is also known to provide a protective layer (oxygen blocking layer) for the purpose of preventing polymerization inhibition by oxygen.

As a light source for exposing / making a photopolymerizable photosensitive lithographic printing material, an Ar laser (488 nm) or F
A long-wavelength visible light source such as a D-YAG laser (532 nm) is used. More recently, for example, InG
aN-based or ZnSe-based material, 350 nm to 45 nm
A semiconductor laser that can continuously oscillate in the 0 nm range is in a practical stage. Scanning exposure systems that use these short-wave light sources are semiconductor lasers that can be manufactured inexpensively because of their structure.
It has the advantage of being able to build an economical system while having sufficient output. Further, as compared with the conventional system using FD-YAG or Ar laser, there is a possibility that a photosensitive lithographic printing plate material having a shorter photosensitive area capable of working under brighter safe light can be used. .

In the case of a photopolymerizable photosensitive lithographic printing plate material, it is usually subjected to imagewise exposure and, if necessary, heat treatment, followed by washing with water for removing the protective layer, developing treatment for dissolving and removing the unexposed portion, and washing with water. A lithographic printing plate is obtained by performing a treatment and a finisher gum treatment for making the non-image area hydrophilic.

Such a photopolymerizable photosensitive lithographic printing plate material generally has a weak printing endurance, and in order to increase the printing endurance, polyvinyl as described in JP-B-46-35685 is used. The technology of treating the support with phosphonic acid and the technology of silicate treatment are known, but even with such technology, the printing durability is still insufficient and the adhesion between the photosensitive layer and the support is improved. There is a problem in that the non-image portion is contaminated if the amount of such processing is increased in an attempt to do so.

There are also known techniques for providing an intermediate layer between the support and the photosensitive layer, or for subjecting the support to a coupling treatment or a diazonium treatment. However, both of them increase the cost and the printing durability. And the stain on the non-image area was not at a satisfactory level.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems. That is, in the present invention, the adhesiveness between the photopolymerizable layer and the support is excellent, and it is possible to achieve both printing durability and improvement of stains in non-image areas.
An object of the present invention is to provide a support for a photosensitive lithographic printing plate material capable of obtaining a lithographic printing plate having a high resolution, a photosensitive lithographic printing plate material and a method for producing the same.

[0011]

The above objects of the present invention have been achieved by the following.

1. A photosensitive lithographic printing plate material, which is a roughened metal support and is treated with an aqueous solvent containing at least A) polyvinyl phosphonic acid and B) a compound containing an amino group. Support.

2. 2. The support for a photosensitive lithographic printing plate material as described in 1 above, wherein the aqueous solvent further contains C) a compound having an ethylenic addition polymerizable group.

3. The compound having an amino group is D)
2. A support for a photosensitive lithographic printing plate material as described in 1 above, which is a compound having an amino group and an ethylenic addition polymerizable group.

4. A photosensitive lithographic printing plate which is a roughened metal support and is treated with an aqueous solvent containing a reaction product of at least a polyvinyl phosphonic acid and a compound having an amino group. Support for plate material.

5. The addition rate of the compound having an amino group to the repeating unit of polyvinyl phosphonic acid is
The support for the photosensitive lithographic printing plate material as described in 4 above, which is 0.01 to 50 mol%.

6. A photosensitive lithographic printing plate material having, on a roughened metal support, a photopolymerizable layer containing a compound having an ethylenic addition-polymerizable group and a compound capable of generating radicals by actinic rays, the metal comprising: The support is:
A) an aqueous solvent containing polyvinyl phosphonic acid and B) a compound having an amino group, and C: an aqueous solvent further containing a compound having an ethylenic addition-polymerizable group, and: having polyvinyl phosphonic acid and an amino group A photosensitive lithographic printing plate material, which is treated with at least one selected from an aqueous solvent containing a reaction product obtained by reacting a compound.

7. The reaction product of the reaction between the polyvinyl phosphonic acid and the compound having an amino group is in the range of 0.01 to 50 mol% as the addition rate of the compound having an amino group to the repeating unit of polyvinyl phosphonic acid. 7. The photosensitive lithographic printing plate material as described in 6 above, which is characteristic.

8. A method for producing a photosensitive lithographic printing plate material having a photopolymerizable layer containing, on a roughened metal support, a compound having an ethylenic addition-polymerizable group and a compound capable of generating radicals by actinic rays, , A below
1. A method for producing a photosensitive lithographic printing plate material, which comprises steps d to d. a) a step of electrochemically roughening the metal support in an acidic medium b) the surface of the metal support is: A) an aqueous solvent containing polyvinyl phosphonic acid and B) a compound having an amino group: And C) an aqueous solvent containing a compound having an ethylenic addition-polymerizable group; and an aqueous solvent containing a reaction product of a reaction between polyvinyl phosphonic acid and a compound having an amino group, treated with at least one of the above Step c) Step of providing a photopolymerizable layer containing a compound having an ethylenic addition-polymerizable group and a compound that generates a radical by actinic rays d) Step of providing an overcoat layer 9. 9. The method for producing a photosensitive lithographic printing plate material as described in 8 above, wherein the steps a to d further include a step of mechanically roughening the surface of the metal support.

10. 9. The method for producing a photosensitive lithographic printing plate material as described in 8 above, which comprises a step of treating with an aqueous solvent containing polyvinyl phosphonic acid before the step b).

11. 6. The support for a photosensitive lithographic printing plate material as described in any one of 1 to 5 above, wherein the amino group of the compound having an amino group is a primary or secondary amino group.

12. 8. The photosensitive lithographic printing plate material as described in 6 or 7 above, wherein the amino group of the compound having an amino group is a primary or secondary amino group.

13. 11. The method for producing a photosensitive lithographic printing plate material as described in any one of 8 to 10 above, wherein the amino group of the compound having an amino group is a primary or secondary amino group.

That is, in the present invention, PVPA (polyvinyl phosphonic acid) used as a pretreatment of the support is used.
It was found that when a compound having an amino group was contained in the PVPA bath during the treatment, the above compound was amine-added to the PVPA polymer to easily introduce a reactive group into the polymer, and the PVPA itself or the above compound itself Paying attention to the reactivity with the support and the reactivity between the reactive group newly added to PVPA and the photopolymerizable layer, high adhesion between the support and the photopolymerizable layer, and storage stains etc. do not occur. The present invention has been accomplished by finding new processing.

Further, according to the present invention, as is conventionally done,
A three-layer coating type production line of intermediate layer / photopolymerizable layer (photosensitive layer) / overcoat layer (oxygen barrier layer) is not necessarily required, and a so-called ordinary PVPA pretreatment bath and a photosensitive layer / oxygen barrier layer are coated. Since it can be constructed, it is very cost effective.

The present invention can provide a printing plate having high resolution, high printing durability, and good stains on non-image areas at low cost.

(Metal Support) The metal support according to the present invention (hereinafter also referred to as a support) has, as its base, a metal plate made of, for example, aluminum, stainless steel, chromium, nickel, a polyester film, a polyethylene film, A film obtained by laminating or vapor-depositing the above-mentioned metal thin film on a plastic film such as a polypropylene film can be used, and a polyester film, a vinyl chloride film, a film such as a nylon film having a hydrophilic treatment can be used. An aluminum support is preferably used, in which case it may be pure aluminum or an aluminum alloy.

As the aluminum alloy for the support, various materials can be used. For example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium and iron. Etc. are used.

The support according to the present invention is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface before roughening (graining treatment). As the degreasing treatment, degreasing treatment using a solvent such as trichlene and thinner, kesilon,
Emulsion degreasing treatment using an emulsion such as triethanol is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films which cannot be removed only by the above degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is formed on the surface of the support. In this case, dip it in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof to desmut it. It is preferable to apply a treatment.

Examples of the roughening method in the present invention include mechanical methods and electrochemical methods.
It is preferable to electrochemically roughen the surface in an acidic medium,
In this case, a method of mechanically roughening may be combined.

The method of electrochemically roughening the surface is not particularly limited, but a method of electrochemically roughening in an acidic medium, that is, an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical graining method can be used, but it is preferable to use a hydrochloric acid-based or nitric acid-based electrolytic solution. Regarding the electrochemical graining method, for example, Japanese Patent Publication No. 48-28123, British Patent No. 896,563, and Japanese Patent Laid-Open No. 53-67507.
The method described in the publication can be used.

This roughening method can be generally carried out by applying a voltage in the range of 1 to 50 V, but it is preferable to set the voltage in the range of 10 to 30 V.

The current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The amount of electricity is 100-500
A range of 0 c / dm ² can be used, but 100 to
It is preferable to select from the range of 2000 c / dm ² .

The temperature for carrying out this roughening method is 10 to 50 ° C.
However, it is preferable to select from the range of 15 to 45 ° C.

Electrification using a nitric acid-based electrolytic solution as the electrolytic solution
When performing a surface roughening, a range of 1 to 50 volts is generally used.
Can be done by applying a voltage of
It is preferable to select from the range of 10 to 30 volts. Current density
10 to 200 A / dm ²The range of
Can, but 20-100A / dm²It is preferable to choose from the range
Good Electricity is 100-5000c / dm²Range of
Can be used, but 100 to 2000 c / dm²
It is preferable to select from the range. Performs an electrochemical roughening method
The heating temperature may be in the range of 10 to 50 ° C.
Is preferably selected from the range of 15 to 45 ° C. Electrolyte
The nitric acid concentration in is preferably 0.1 to 5 mass%. electrolytic
The solution should contain nitrates, chlorides, amines, and
Luthedes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid
Etc. can be added.

When a hydrochloric acid-based electrolyte is used as the electrolyte,
Generally, it can be performed by applying a voltage in the range of 1 to 50 V, but it is preferable to select from the range of 2 to 30 V. Current density is 10-200A /
A range of dm ² can be used, but 50 to 150 A
It is preferable to select from the range of / dm ² . Electricity is 10
The range of 0 to 5000 c / dm ² can be used, but 100 to 2000 c / dm ² , and further 200 to 10
It is preferable to select from the range of 00c / dm ² . The temperature for carrying out the electrochemical graining method may be in the range of 10 to 50 ° C, but is preferably selected in the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added to the electrolytic solution.

After the surface is roughened by the above-mentioned electrochemical surface roughening method, it is preferable to immerse it in an aqueous solution of acid or alkali in order to remove aluminum dust and the like on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and examples of the base include sodium hydroxide, potassium hydroxide and the like. Among these, it is preferable to use an aqueous solution of alkali. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . Further, it is preferable that after the dipping treatment is carried out with an alkaline aqueous solution, the dipping treatment is carried out by dipping in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The mechanical roughening method according to the present invention is not particularly limited, but a brush polishing method and a honing polishing method are preferable. Roughening by a brush polishing method is performed by, for example, rotating a rotary brush using brush bristles having a diameter of 0.2 to 0.8 mm, and, for example, particles of volcanic ash having a particle diameter of 10 to 100 μm in water. It can be performed by pressing a brush while supplying the uniformly dispersed slurry. Roughening by honing polishing is, for example,
Particles of volcanic ash having a particle size of 10 to 100 μm can be uniformly dispersed in water, pressure is applied from a nozzle to eject, and the surface of the support can be obliquely collided for roughening. Further, for example, abrasive particles having a particle size of 10 to 100 μm are provided on the surface of the support at 2.5 × 10 ³ to 1 at intervals of 100 to 200 μm.
It is also possible to carry out roughening by laminating sheets applied so as to have a density of 0 × 10 ³ pieces / cm ² and applying pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the above method, it is preferable to immerse it in an aqueous solution of an acid or an alkali in order to remove the abrasive, the aluminum scraps and the like that have invaded the surface of the support. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid,
Phosphoric acid, nitric acid, hydrochloric acid or the like is used, and as the base, for example, sodium hydroxide, potassium hydroxide or the like is used. Among these, it is preferable to use an alkaline aqueous solution such as sodium hydroxide. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . It is preferable to carry out the neutralization treatment by immersing in an alkaline aqueous solution and then immersing it in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The above-described mechanical surface roughening treatment method and electrochemical surface roughening method may be used alone for surface roughening, or may be combined for surface roughening, but they may be used in combination. The method of roughening is preferred.

Next, the support can be subjected to anodizing treatment. The method of anodizing treatment that can be used in the present invention is not particularly limited, and a known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. The anodizing treatment includes
A method in which an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% is used as an electrolytic solution and electrolysis is performed at a current density of 1 to 10 A / dm ² is preferably used. In addition, US Pat. No. 1,412,768 is used. The method of electrolyzing in sulfuric acid at a high current density described in Japanese Patent No. 3,511,661, the method of electrolysis using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, oxalic acid, malonic acid, etc. Examples include a method of using a solution containing one kind or two or more kinds. The formed anodic oxide coating amount is appropriately 1 to 50 mg / dm ² , and preferably 10 to 40 mg / dm ² . The amount of anodized coating is
For example, an aluminum plate is treated with a chromic acid phosphoric acid solution (phosphoric acid 85%
Liquid: 35 ml, chromium oxide (IV): 20 g is dissolved in 1 L of water) to dissolve the oxide film, and the mass change before and after dissolution of the coating on the plate is measured.

The support subjected to the anodizing treatment may be subjected to a sealing treatment if necessary. These sealing treatments can be performed by using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment and ammonium acetate treatment.

For the support which has been subjected to anodizing treatment or, if necessary, sealing treatment, it is preferable that the surface of the support is treated with an aqueous solvent containing PVPA after the treatment, and the aqueous solvent is an aqueous solution. Is preferred.

An aqueous solution containing PVPA means PVPA
Is preferably an aqueous solution containing 0.01 to 30%, and particularly preferably an aqueous solution of 0.05 to 10%. If the content concentration is lower than the above range, the effect of the present invention is small, and if the content concentration is higher than the above range, the liquid viscosity may be high and handling may be difficult.

Further, it is preferable that the above-mentioned aqueous solution further contains a compound other than PVPA. As the compound to be contained, conventionally known water-soluble resin, water-dispersible inorganic fine particles,
Examples thereof include acids and bases.

Specifically, as the water-soluble resin, as the hydrophilic resin, for example, polyvinyl alcohol,
Polysaccharide, polyvinylpyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, sucrose octaacetate, ammonium alginate, sodium alginate, polyvinylamine, polyallylamine, polystyrene sulfonic acid, polyacrylic Examples thereof include acids, water-soluble polyamides and maleic anhydride copolymers.

Examples of the water-dispersible inorganic fine particles include colloidal silica and necklace-shaped colloidal silica described in JP-A-2001-232746.

The acids include phosphoric acid, sulfuric acid, nitric acid,
Hydrochloric acid, other strong acids or salts thereof may be mentioned.

Examples of the bases include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide.

In the present invention, the compound that can be used together with these PVPAs is preferably 0 to 40%, more preferably 0 to 20% as the concentration in the aqueous solution.

The treatment time with the aqueous solution containing PVPA according to the present invention is preferably 0.5 seconds to 3 minutes, more preferably 1 second to 1 minute, and particularly 2 seconds to 30 seconds. Is preferred. If it is less than this range, the effect of the present invention may be reduced, and if it is more than this range, the productivity is inferior, so the above range is preferable.

The treatment temperature during the treatment with the above-mentioned aqueous solution is 40 to 100 depending on the temperature of the aqueous solution and the substrate to be treated.
It is preferably in the range of ℃, more preferably 50 ~
90 ° C, particularly 60 to 80 ° C is preferable. At lower temperatures, the effect of the present invention may be small, and at higher temperatures, the above range is preferable from the viewpoint of production stability.

The PVPA treatment according to the present invention is as follows, but the above-mentioned PVPA treatment is carried out as necessary.
Performed on the support that has been subjected to PA treatment. That is, the PVPA treatment of the present invention is performed by treating the surface of the support with: A) PVPA
And B) an aqueous solvent containing a compound having an amino group,
: C) an aqueous solvent containing a compound having an ethylenic addition-polymerizable group, and: an aqueous solvent containing a reaction product of a reaction between PVPA and a compound having an amino group,
Treatment with at least one of the above is preferable, and the aqueous solvent is preferably water.

The compound having the above amino group is
A compound having an amino group and an ethylenic addition-polymerizable group can be mentioned as a preferred embodiment in the present invention.

The aqueous solvent in the present invention means a solvent containing water as a main component, and the mass% of water in the solvent is preferably 50% or more, more preferably 70% or more. In addition, the aqueous solvent is preferably an aqueous solution of the above PVPA and each compound (the compound contained in the above).

Further, in the present invention, P of the above-mentioned present invention is used.
It is more preferable to perform the VPA treatment and the above-mentioned PVPA treatment in combination.

The aqueous solution used for the PVPA treatment of the present invention is preferably an aqueous solution containing PVPA as a main component. The ratio in the liquid is preferably 99.99: 0.01 to 30:70 by mass of PVPA and each compound described above (the sum thereof when a plurality of types are mixed),
More preferably, it is in the range of 99.9: 0.1 to 50:50.

The PVPA referred to in the present invention refers to a polymer having a vinyl phosphonic acid skeleton, and it is preferable that the repeating units of vinyl phosphonic acid have 50% or more, more preferably 70% or more of all the repeating units.

The PVPA has a molecular weight Mw of preferably from 1,000 to 1,000,000, more preferably from 2,000 to 500,000.

The pH of the aqueous solution of PVPA (concentration 10%) is preferably in the range of 1 to 4, more preferably 1.2 to.
A range of 2.5 is especially preferred.

Other solvents can be used in combination with water in the aqueous solution used for the PVPA treatment of the present invention. The solvent that can be used is not particularly limited as long as it is a water-based organic solvent, but alcohol-based, glycol-based, and ether-based solvents are preferable, and alcohol-based solvents are particularly preferable.

Further, in the present invention, it is also possible to preferably use a pH adjuster using an acid such as acetic acid / hydrochloric acid or a base such as ammonia / sodium hydroxide.

(Compound Having Amino Group) The compound having an amino group according to the present invention is incorporated into the polymer chain by reacting with the hydroxyl group of PVPA, and is dissolved as the reaction progresses due to the water solubility of the polymer. , A certain amount or more P
When it reacts with the hydroxyl group of VPA, the water solubility of PVPA deteriorates, the reactivity with the support decreases, and the stability of the treatment solution decreases, which is disadvantageous.
The addition ratio of the compound having an amino group to the repeating unit A is preferably in the range of 0.01 to 50 mol%. More preferably, it is 0.05 to 45 mol%, especially 0.1 to 40.
A range of mol% is preferred. The addition rate can be analyzed by NMR (nuclear magnetic resonance analysis), IR (infrared analysis), or the like.

From this point of view, it is preferable that the water-solubility of the compound having an amino group is high, and it is particularly preferable that the compound which dissolves in pure water at atmospheric pressure and 25 ° C. in an amount of 1% by mass or more within 24 hours. .

The amino group of the compound having an amino group according to the present invention may be a primary, secondary, tertiary or quaternary amino group, but a primary or secondary amino group is preferred. .

As the compound having an amino group according to the present invention, a compound having an amino group and an ethylenic addition-polymerizable group can be preferably used.

(Compound Having Amino Group and Ethylenic Addition Polymerizable Group) The amino group of the compound having an amino group and an ethylenic addition polymerizable group according to the present invention is a primary, secondary or
It may be either a tertiary or quaternary amino group, but 1
A primary or secondary amino group is preferred. The compound having an amino group and an ethylenic addition-polymerizable group in one molecule is preferably a compound represented by the following formula, but is not limited thereto.

[0068]

[Chemical 1]

In the formula, R ₁ represents an organic group having a monovalent ethylenic addition-polymerizable group, and examples thereof include an acryloyl group, a methacryloyl group and a vinyl group, and an acryloyl group or a methacryloyl group is particularly preferable. Y represents a divalent linking group having 1 to 10 carbon atoms, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, -SO
_{2 -, - SO -, -} O -, - S -, - N (R 10) -, -
(C = O)-, -COO-,-(P = O)-, -CON
Examples thereof include a divalent linking group composed of groups such as H- alone or in combination. However, R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Among the above, an alkylene group, -O-,-(C = O)-,-
A divalent linking group composed of a group represented by COO- or -CONH- alone or in combination is preferable.

R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocycle, and preferably a hydrogen atom or an alkyl group. Represents a group or a heterocycle. Examples of the ethylenic addition-polymerizable group include known groups described below.

Specific examples of the compound having an amino group and an ethylenic addition-polymerizable group in one molecule according to the present invention include N, N-dimethylaminoethyl acrylate,
N, N-diethylaminoethyl acrylate, N, N-
Dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminobutyl acrylate, N, N-diethylaminobutyl acrylate and N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N -Dimethylaminopropyl methacrylate,
N, N-diethylaminopropyl methacrylate, N,
N-dimethylaminobutyl methacrylate, N, N-diethylaminobutyl methacrylate, N, N-dimethylaminoethyl acrylamide, N, N-diethylaminopropyl acrylamide, N, N-dimethylaminoethyl methacrylamide, N, N-dimethylaminopropyl methacryl Examples thereof include amide, N, N-diethylaminoethylmethacrylamide, N, N-diethylaminopropylmethacrylamide, 2-vinylpyridine, 4-vinylpyridine, allylamine, 2-methylallylamine, and diallylamine, but are not particularly limited thereto. However, from the viewpoint of photoreactivity, an amino compound having an acrylic group or a methacrylic group as an unsaturated group is desirable.

The following compounds can also be preferably used in the present invention.

[0073]

[Chemical 2]

(Compound Having Two or More Amino Groups in One Molecule) As the compound having an amino group according to the present invention, a compound having two or more amino groups in one molecule can also be preferably used. The amino group in this compound may be a primary, secondary, tertiary or quaternary amino group, but a primary or secondary amino group is preferred.
The preferred amino group is a compound represented by the following formula, but is not limited thereto.

[0075]

[Chemical 3]

In the formula, R ₄ is a divalent organic group having 1 to 22 carbon atoms (preferably an alkylene group, an arylene group, an alkenylene group, an alkynylene group, —SO ₂ —, —SO—,
-O -, - S -, - N (R 10) -, - (C = O) -, -
Examples thereof include a divalent linking group composed of groups such as COO-,-(P = O)-, and -CONH- alone or in combination, or a divalent group having a siloxane bond. However, R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

Of these, preferred are alkylene groups, arylene groups, -O-,-(C = O)-, -COO.
It is a divalent linking group composed of groups such as-and -CONH- alone or in combination.

Specifically, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2- (3,3'-diaminodiphenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2- (4,4′-Diaminodiphenyl) propane, 2,2- (3,3′-diaminodiphenyl) hexafluoropropane, 2,2- (3
4'-diaminodiphenyl) hexafluoropropane,
2,2- (4,4'-diaminodiphenyl) hexafluoropropane, 3,3'-oxydianiline, 3,4 '
-Oxydianiline, 4,4'-oxydianiline,
3,3'-diaminodiphenyl sulfide, 3,4'-
Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,
4'-diaminodiphenyl sulfone, 1,3-bis [1
-(3-Aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-
Methylethyl] benzene, 1,4-bis [1- (3-aminophenyl)] benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy)
Benzene, 3,3'-bis (3-aminophenoxy) diphenyl ether, 3,3'-bis (4-aminophenoxy) diphenyl ether, 3,4'-bis (3-aminophenoxy) diphenyl ether, 3,4'-bis (4-aminophenoxy) diphenyl ether, 4,
4'-bis (3-aminophenoxy) diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenyl ether, 1,4-bis [1- (4-aminophenyl) -1-methylethyl-bis (3- Aminophenoxy)] biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 3,4'-bis (3-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl, 4, 4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) Phenyl] sulfone, 2,2-bis [3- (3
-Aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3
-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy)
Phenyl] hexafluoropropane, 9,9-bis (3
-Aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, methylenediamine, hexamethylenediamine, dodecamethylenediamine and the like can be mentioned. ) Or a divalent group having a siloxane bond.

Specific examples include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone and 4,4 '.
-Diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3'-dimethylbenzidine, 3,3 '. -Dimethoxybenzidine, o-tolidine,
4,4 "-diaminoterphenyl, 1,5-diaminonaphthalene, 2,5-diaminopyridine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4 '
-Bis (p-aminophenoxy) biphenyl, 2,2-
Examples thereof include bis [4- (p-aminophenoxy) phenyl] propane and hexahydro-4,7-methanoindanylene dimethylenediamine, but are not particularly limited thereto. Moreover, it is preferable to use siloxane diamine in order to improve the adhesiveness to the inorganic substrate. A siloxane diamine represented by the following formula is preferably used.

[0080]

[Chemical 4]

In the formula, R ₅ is a divalent organic group having 1 to 10 carbon atoms (preferably an alkylene group, an arylene group, an alkenylene group, an alkynylene group, —SO ₂ —, —SO—,
-O -, - S -, - N (R 10) -, - (C = O) -, -
Examples of the divalent linking group include groups such as COO-,-(P = O)-, and -CONH- alone or in combination. However, R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. m represents an integer of 1 to 10.

Of these, a divalent linking group composed of an alkylene group or an arylene group alone or in combination is preferable.

R ₆ , R ₇ , R ₈ or R ₉ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocycle. . Of these, preferred is a hydrogen atom or an alkyl group.

When used in the present invention, the siloxane diamine is preferably used in the range of 1 to 20 mol% of the compound having two or more amino groups in one molecule according to the present invention. This is preferable because the effect of improving the adhesiveness is exhibited and the heat resistance is also good.

Specific examples of the siloxane diamine include bis (3-aminopropyl) tetramethyldisiloxane,
Examples thereof include bis (10-aminodecamethylene) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramers, octamers, and bis (3-aminophenoxymethyl) tetramethyldisiloxane. In the present invention, one of these compounds having two or more amino groups in one molecule is
One kind or two or more kinds can be used.

Preferred specific examples of the compound having two or more amino groups in one molecule according to the present invention are:
The following can be mentioned.

[0087]

[Chemical 5]

(Compound Having Ethylenic Addition-Polymerizable Group) As the compound having an ethylenic addition-polymerizable group used in the present invention, a known monomer (hereinafter sometimes referred to simply as "monomer") may be mentioned. Specific examples thereof include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, and tetrahydrofuryl. Furyloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid ester such as 1,3-dioxolane acrylate, or acryl thereof Methacrylate, itaconate, crotonate, methacrylate was replaced with maleate,
Itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol diacrylate, polytetramethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neo Pentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol hydroxy pivalate diacrylate, neopentyl glycol adipate diacrylate, di-acrylate of neopentyl glycol hydroxypivalate ε-caprolactone adduct, 2- (2- Hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-
1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6
-Difunctional acrylic acid esters such as diacrylates of diglycidyl ether of hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester such as methacrylic acid, itaconate, crotonate, maleate in which these acrylates are replaced by trimethylol Propane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate ε-caprolactone adduct, pyrogallol triacrylate, Propionate - dipentaerythritol triacrylate, propionic acid - dipentaerythritol tetraacrylate, polyfunctional acrylic acid ester acids such as hydroxypivalic valyl-modified dimethylolpropane triacrylate or methacrylate these acrylate, itaconate, crotonate,
Methacrylic acid instead of maleate, itaconic acid, crotonic acid, maleic acid ester and the like can be mentioned, and oligomers thereof can also be used.

Also, a prepolymer of the above-mentioned monomer can be used in the same manner as above. Examples of the prepolymer include compounds such as those described below,
A prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerization property can also be suitably used. These prepolymers may be one type or two types.
One or more kinds may be used in combination, or may be used as a mixture with the above-mentioned monomer and / or oligomer.

Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, Polybasic acids such as pimelic acid, sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin (Meth) acrylic acid was introduced into a polyester obtained by binding a polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, and 1,2,6-hexanetriol. Li ester acrylates, such as bisphenol A- epichlorohydrin - (meth)
Epoxy acrylates such as acrylic acid, phenol novolac-epichlorohydrin- (meth) acrylic acid in which (meth) acrylic acid is introduced into an epoxy resin, for example, ethylene glycol-adipic acid-tolylene diisocyanate-2-hydroxyethyl acrylate, polyethylene Glycol-tolylene diisocyanate-2
-Hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate-xylene diisocyanate,
Urethane acrylate obtained by introducing (meth) acrylic acid into urethane resin, such as 1,2-polybutadiene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate and trimethylolpropane-propylene glycol-tolylene diisocyanate-2-hydroxyethyl acrylate. For example, silicone resin acrylates such as polysiloxane acrylate and polysiloxane-diisocyanate-2-hydroxyethyl acrylate, and other alkyd-modified acrylates obtained by introducing a (meth) acryloyl group into an oil-modified alkyd resin,
Examples include prepolymers such as spirane resin acrylates.

The above-mentioned compound having an ethylenic addition polymerizable group can also be applied to the photopolymerizable layer (also referred to as a photosensitive layer) of the photosensitive lithographic printing plate material according to the present invention.

The photosensitive layer according to the present invention also comprises a phosphazene monomer, triethylene glycol, isocyanuric acid ethylene oxide (EO) modified diacrylate,
Monomers such as isocyanuric acid EO-modified triacrylate, dimethyloltricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, alkylene glycol type acrylic acid-modified, urethane-modified acrylate and the like, and a structure formed from the monomers Addition-polymerizable oligomers and prepolymers having units can be contained.

Examples of the monomers preferably used in the present invention include phosphoric acid ester compounds having at least one ethylenic double bond group. The compound is a compound in which at least a part of hydroxyl groups of phosphoric acid is esterified, and may have an ethylenic double bond in the molecule,
Particularly preferred is a compound having a (meth) acryloyl group.

In addition to these, Japanese Patent Laid-Open Nos. 58-212994, 61-6649, 62-46688, 62-48589 and 62-173295.
No. 62-187092 and No. 63-671.
89, Japanese Patent Application Laid-Open No. 1-244891, and the like, and the like. Further, "11290 chemical products", Chemical Industry Daily, p. 286-p. 294, the compound described in "UV / EB curing handbook (raw material)", Polymer Publishing Association, p. The compounds described in 11 to 65 and the like can also be preferably used in the present invention. Of these, compounds having two or more acryl groups or methacryl groups in the molecule are preferred in the present invention, and further, the compounds have a molecular weight of 10,000 or less, more preferably 5,000.
Those of 0 or less are preferable.

For the photosensitive layer according to the present invention, 1.0 to 80.0 of the above-mentioned monomer is added to the photosensitive composition for coating the photosensitive layer.
The content is preferably in the range of mass%, and more preferably in the range of 3.0 to 70.0 mass%.

(Polymer Binder) The photosensitive layer according to the present invention preferably contains a polymer binder. The polymer binder preferably contains a vinyl-based copolymer composed of at least one of the monomers (monomers) described in (1) to (17) below.

(1) A monomer having an aromatic hydroxyl group, for example, o- (or p-, m-) hydroxystyrene, o
-(Or p-, m-) hydroxyphenyl acrylate and the like.

(2) Monomers having aliphatic hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5 -Hydroxypentyl methacrylate, 6-
Hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

(3) A monomer having an aminosulfonyl group, for example, m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like.

(4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide and N- (p-toluenesulfonyl) methacrylamide.

(5) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride.

(6) Substituted or unsubstituted alkyl acrylates such as methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, acrylic acid 2-chloroethyl, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.

(7) Substituted or unsubstituted alkyl methacrylate, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.

(8) Acrylamide or methacrylamide, such as acrylamide, methacrylamide, N
-Ethyl acrylamide, N-hexyl acrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N-phenyl acrylamide, N
-(4-hydroxyphenyl) acrylamide, N-
(4-hydroxyphenyl) methacrylamide and the like.

(9) Monomers containing a fluorinated alkyl group such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl. Methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

(10) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether,
Propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc.

(11) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(12) Styrenes such as styrene, methylstyrene, chloromethylstyrene and the like.

(13) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(14) Olefins such as ethylene,
Propylene, i-butylene, butadiene, isoprene and the like.

(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

(16) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene. etc.

(17) A monomer having an amino group, for example, N, N-diethylaminoethyl methacrylate, N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethyl acrylamide, acryloyl morpholine, N-i-propyl acrylamide, N, N- Diethyl acrylamide etc.

The polymer binder may be any other polymer binder such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, natural resin, etc. You may use together with the vinyl-type copolymer which concerns on this invention.

The content of the above-mentioned polymer binder in the composition for coating the photosensitive layer according to the present invention is 1 for the photosensitive layer.
The range of 0 to 90 mass% is preferable, the range of 15 to 70 mass% is more preferable, and the use of 20 to 50 mass% is particularly preferable from the viewpoint of sensitivity. Further, the above vinyl-based copolymer has a content of 50 to 10 in the polymer binder.
It is preferably 0% by mass, and more preferably 100% by mass.

The acid value of the polymer contained in the polymer binder according to the present invention is preferably in the range of 10 to 150, more preferably 30 to 120, and more preferably 50.
It is particularly preferable to use it in the range of from 90 to 90 from the viewpoint of balancing the polarities of the entire photosensitive layer, and this can prevent aggregation of the pigment in the photosensitive layer coating liquid.

(Compound that Generates Radicals by Actinic Rays) It is preferable to use a compound that generates radicals by actinic rays (hereinafter, also referred to as a photopolymerization initiator) in the photopolymerizable layer (photosensitive layer) according to the present invention. Those which can be preferably used as the photopolymerization initiator are described in, for example, J. Carbonyl compounds, as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar,
Examples thereof include organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, and photoreducible dyes, and the compounds disclosed in British Patent 1,459,563 are also preferable.

Specifically, the following examples can be given, but the invention is not limited thereto. That is, benzoin methyl ether, benzoin-i-propyl ether,
Benzoin derivatives such as α, α′-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate,
Benzophenone derivatives such as 4,4′-bis (dimethylamino) benzophenone; 2-chlorothioxanthone, 2
Thioxanthone derivatives such as i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; acridone derivatives such as N-methylacridone and N-butylacridone; α,
In addition to α'-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, JP-B-59-
1281 and 61-9621 and the triazine derivatives described in JP-A-60-60104; the organic peroxides described in JP-A-59-1504 and JP-A-61-243807; 43-23684, 44-6413, 44-6413, 47-1604 and U.S. Pat. No. 3,56.
Diazonium compounds described in 7,453; organic azide compounds described in U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853; JP-B-36-22062; 37-13109, 38-18015 and 45-9610.
O-quinonediazides described in Japanese Patent Publication No. 55-3
9162, JP-A-59-14023, and "Macromolecules".
s) ”, various onium compounds described in Vol. 10, p. 1307 (1977); azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109, 851 and 126. , 712 and "Journal of Imaging Science (J.
Imag. Sci. ), 30, 174 (1986)
Year)); (oxo) sulfonium organic boron complexes described in JP-A-5-213861 and JP-A-5-255347; JP-A-59-152396 and JP-A-61-151197. Titanocenes;
"Coordination Chemistry Review (Co
coordination Chemistry Revi
ew) "84, 85-277 (1988), and transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; JP-A-3-2094.
2,4,5-triarylimidazole dimer described in JP-A-77; carbon tetrabromide; organic halogen compounds described in JP-A-59-107344.

Among them, titanocenes are preferable. Specific examples of titanocenes include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4. , 5,6-Pentafluorophen-1-yl, di-cyclopentadienyl-Ti
-Bis-2,3,5,6-tetrafluorophenyl-1-
Il, di-cyclopentadienyl-Ti-bis-2,
4,6-Trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-
2,4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-
Pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2, 4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrid-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals) and the like can be mentioned. However, the present invention is not limited to this.

When laser light is used as the light source, it is preferable to add a sensitizing dye to the photosensitive layer.

Examples of the compound for wavelength sensitizing from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, flugide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane. , Triphenylmethane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyrromethene compounds,
Examples thereof include pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, and thiobarbituric acid derivatives, and further, European Patent No. 568,993, US Patent Nos. 4,508,811, and 5,227,227.
No. 2001-125255, 11-2.
The compounds described in 71969, etc. are also used.

In the present invention, a preferable specific example of the combination of the above-mentioned photopolymerization initiator and sensitizing dye is described in JP-A-200
The combination described in JP-A No. 1-125255 and JP-A No. 11-271969 can be mentioned.

The content of these polymerization initiators in the photosensitive layer is not particularly limited, but is 0.1 to 20 relative to 100 parts by mass of the compound having an ethylenic addition polymerizable group according to the present invention.
Parts by mass are preferred. The mixing ratio of the photopolymerization initiator and the sensitizing dye is 1: 100 to 100: 1 in terms of molar ratio.
preferable.

(Various Additives) In addition to the above-mentioned components, the coating composition for the photopolymerizable photosensitive layer according to the present invention contains an ethylenic non-polymerizable polymerizable compound during the production or storage of the photosensitive lithographic printing plate material. It is desirable to add a polymerization inhibitor in order to prevent unnecessary polymerization of the saturated double bond monomer. Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-.
Thiobis (3-methyl-6-t-butylphenol),
2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate and the like can be mentioned.

The addition amount of the polymerization inhibitor is preferably 0.01 to 5% with respect to the mass of the total solid content of the above composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, or may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably 0.5% to 10% of the total composition.

Further, a coloring agent can also be used, and conventionally known coloring agents can be suitably used including commercially available coloring agents. For example, those described in the revised new edition "Pigment Handbook", edited by Japan Pigment Technology Association (Seibundo Shinkosha), Color Index Handbook, etc. may be mentioned.

Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, metal powder pigment and the like. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium and calcium, etc.) and organic pigments (azo, thioindigo) Pigments, anthraquinone pigments, anthanthrone pigments, triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and their derivatives, quinacridone pigments, etc.).

Of these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength range of the spectral sensitizing dye corresponding to the exposure laser used, and in this case, the pigment at the laser wavelength used is selected. The reflection absorption of the pigment using the integrating sphere is preferably 0.05 or less. The amount of the pigment added is 0.1 with respect to the solid content of the composition.
-10 mass% is preferred, and more preferably 0.2-5 mass%.

As an exposure light source, an argon laser (48
8nm) or SHG-YAG laser (532nm)
In the case of using a violet pigment, a violet pigment or a blue pigment is preferably used from the viewpoint of the absorption of the pigment in the above-mentioned photosensitive wavelength region and the visibility of the image after development. Examples of such substances include cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue fast sky blue, indanthrene blue, indico, dioxane violet, iso Examples thereof include biolanthrone violet, indanthrone blue, and indanthrone BC. Among these, phthalocyanine blue and dioxane violet are more preferable.

Further, the above composition may contain a surfactant as a coatability improving agent within a range not impairing the performance of the present invention. Among them, the fluorine-based surfactant is preferable.

Further, in order to improve the physical properties of the cured film, an additive such as an inorganic filler or a plasticizer such as dioctyl phthalate, dimethyl phthalate or tricresyl phosphate may be added. The addition amount of these is preferably 10% or less of the total solid content.

(Coating) Examples of the solvent used in preparing the coating composition for the photosensitive layer and the intermediate layer according to the present invention include alcohols: polyhydric alcohol derivatives, and
ec-butanol, isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,
5-Pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, lactic acid Butyl, diethyl oxalate, methyl benzoate and the like are preferred.

The prepared coating composition (layer coating solution) can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material. Examples of the coating method of the coating liquid include an air doctor coater method, a blade coater method, a wire bar method, a knife coater method, a dip coater method, a reverse roll coater method, a gravure coater method, a cast coating method, a curtain coater method and an extrusion coater method. Can be mentioned.

When the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained, and when it is too high, not only Marangoni occurs but also fog in non-image area occurs. As a preferable drying temperature range, a range of 60 to 160 ° C is preferable, a range of 80 to 140 ° C is more preferable, and a range of 90 to 120 ° C is particularly preferable.

(Overcoat Layer) It is preferable to provide an overcoat layer (also referred to as a protective layer or an oxygen barrier layer) on the upper side of the photosensitive layer according to the present invention. The layer preferably has high solubility in a developing solution (generally an alkaline aqueous solution) described below.

Preferred examples of the material forming the protective layer include polyvinyl alcohol, polysaccharides, polyvinylpyrrolidone, polyethylene glycol, gelatin,
Glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate,
Examples thereof include polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide and the like. These compounds can be used alone or in combination of two or more to form a coating composition. A particularly preferable compound is polyvinyl alcohol.

To prepare the protective layer coating composition, the above materials can be dissolved in a suitable solvent to prepare a coating solution.
This coating solution is coated on the photopolymerizable photosensitive layer according to the present invention,
The protective layer can be formed by drying. The thickness of the protective layer is preferably 0.1 to 5.0 μm, and particularly preferably 0.5 to 3.0 μm for the photosensitive lithographic printing plate material.
The protective layer may further contain a surfactant, a matting agent, etc., if necessary.

As the coating method of the protective layer, the known methods mentioned in the above examples can be preferably used. The drying temperature of the protective layer is more preferably lower than the drying temperature of the photosensitive layer. The difference from the drying temperature of the photosensitive layer is preferably 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit in that case is preferably about 50 ° C. at most.

The drying temperature of the protective layer is preferably lower than the glass transition temperature (Tg) of the binder contained in the photosensitive layer. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or more, more preferably 40 ° C. or more, and the upper limit of the difference is at most about 60 ° C. Is preferred.

(Manufacturing Method) The photosensitive lithographic printing plate material according to the present invention is preferably manufactured by the following manufacturing method. That is, a photopolymerizable layer containing the above-mentioned compound having an ethylenic addition-polymerizable group and a compound capable of generating radicals by actinic rays is coated and formed on the roughened metal support as described above. Is more preferable, and further, a manufacturing method having the following steps from a to d is more preferable. a) a step of electrochemically roughening the metal support in an acidic medium b) the surface of the metal support is: A) an aqueous solvent containing PVPA and B) a compound having an amino group,
And C) an aqueous solvent containing a compound having an ethylenic addition-polymerizable group, and an aqueous solvent containing a reaction product obtained by reacting PVPA with a compound having an amino group, and step c of treating with at least one of the above ) Step of providing a photopolymerizable layer containing a compound having an ethylenic addition-polymerizable group and a compound capable of generating radicals by actinic rays d) Step of providing an overcoat layer. Further, in the plurality of steps, In the present invention, it is preferable to have a step of mechanically roughening the surface of the metal support, and it is preferable in the present invention to have a step of treating with a water-based solvent containing PVPA before the step b).

(Image forming method) As a light source for imagewise exposing the photosensitive lithographic printing plate material of the present invention, for example, a laser,
Examples thereof include a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a high pressure mercury lamp, and an electrodeless light source. Xenon lamp, halogen lamp,
A carbon arc lamp, a metal halide lamp, a tungsten lamp, a high pressure mercury lamp, an electrodeless light source and the like can be preferably used.

In the case of collective exposure, a mask material having a desired exposure image pattern formed of a light-shielding material may be superposed on the photosensitive lithographic printing plate material and the entire surface may be exposed.

When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp or a tungsten lamp is exposed and controlled by an optical shutter material such as liquid crystal or PLZT, an image signal is used. It is possible and preferable to perform appropriate digital exposure. In this case, direct writing can be performed without using a mask material.

The laser exposure is suitable for direct writing without using a mask material, because light can be focused into a beam and scanning exposure can be performed according to image data. Further, when a laser is used as a light source, it is easy to reduce the exposure area to a minute size, and high-resolution image formation becomes possible.

As the laser light source, an argon laser, a He-Ne gas laser, a YAG laser, a semiconductor laser or the like can be preferably used.
Laser scanning methods include cylinder outer surface scanning, cylinder inner surface scanning, and plane scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum having a recording material wound on the outer surface, and rotation of the drum is main scanning and movement of laser light is sub scanning. In the cylinder inner surface scanning, the recording material is fixed on the inner surface of the drum, and the laser beam is irradiated from the inside.
Main scanning is performed in the circumferential direction by rotating part or all of the optical system, and sub-scanning is performed in the axial direction by linearly moving part or all of the optical system parallel to the axis of the drum. In planar scanning, a polygon mirror or galvanometer mirror and an fθ lens are combined to perform main scanning of laser light,
Sub-scanning is performed by moving the recording medium. The scanning of the outer surface of the cylinder and the scanning of the inner surface of the cylinder make it easier to increase the accuracy of the optical system and are suitable for high-density recording.

(Developer) The exposed portion of the photopolymerizable photosensitive layer which is imagewise exposed is cured. By developing this with an alkaline developing solution, the unexposed portion is removed and image formation becomes possible. As such a developing solution, a conventionally known alkaline aqueous solution can be used. For example sodium silicate,
Same potassium, same ammonium; dibasic sodium phosphate, same potassium, same ammonium; sodium bicarbonate, same potassium, same ammonium; sodium carbonate, same potassium,
Examples thereof include alkaline developing solutions using inorganic alkali agents such as ammonium ammonium; sodium hydrogen carbonate, potassium hydrogen, ammonium hydrogen carbonate; sodium borate, potassium potassium, ammonium hydrogen carbonate; sodium hydroxide; potassium hydroxide;

Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine,
Di-i-propylamine, tri-i-propylamine,
Organic alkali agents such as butylamine, monoethanolamine, diethanolamine, triethanolamine, mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine and pyridine can also be used.

These alkaline agents may be used alone or in combination of two or more. If necessary, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer.

In the development according to the present invention, it is preferable to develop with a developing solution containing an alkali silicate and having a pH of less than 12.5, more preferably in the range of pH 10.5 to 12.4.

[0150]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. In addition, "part" in an Example represents a "mass part" unless there is particular notice.

Example 1 (Synthesis of Binder) In a three-necked flask under a nitrogen stream,
Add 12 parts of methacrylic acid, 70 parts of methyl methacrylate, 8 parts of acrylonitrile, 10 parts of ethyl methacrylate, 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile, and put in an oil bath at 80 ° C in a nitrogen stream. The reaction was carried out for 6 hours. Then, 3 parts of triethylammonium chloride and 2 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The mass average molecular weight measured by GPC (gel permeation chromatography) was about 50,000, and the glass transition temperature (Tg) measured by DSC (differential thermal analysis) was about 85 ° C.

(Preparation of Support 1) An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution kept at 65 ° C. and degreasing treatment was carried out for 1 minute. And then washed with water. This degreased aluminum plate was immersed in a 10% hydrochloric acid aqueous solution kept at 25 ° C. for 1 minute for neutralization, and then washed with water. Then, this aluminum plate was treated with an alternating current in an aqueous solution of 0.3% by mass of nitric acid at 25 ° C. and a current density of 100 A / dm ^{2 by} an alternating current.
After electrolytic surface-roughening for 10 seconds, desmut treatment was performed for 10 seconds in a 5% sodium hydroxide aqueous solution kept at 60 ° C. The desmutted roughened aluminum plate is placed in a 15% sulfuric acid solution at 25 ° C. and a current density of 10 A / d.
Anodizing treatment was performed for 1 minute under conditions of m ² and voltage of 15V. At this time, the center line average roughness (Ra) of the surface is 0.65.
was μm.

After the above treatment, the treatment was carried out by immersing in the following aqueous solution and conditions. <Aqueous solution temperature> 80 ° C. <Aqueous solution> Vinylphosphonic acid 0.2 parts PVPA [Homopolymer] Concentration shown in Table 1 Compound containing amino group Compound shown in Table 1 and concentration Table showing compound having ethylenic addition polymerizable group Compound shown in 1 and concentration Compound having cyclic amino group and ethylenic addition-polymerizable group Compound shown in Table 1 and concentration Ion-exchanged water 100 parts An aluminum plate was passed through the above solution for 30 seconds and dried.

[0154]

[Chemical 6]

(Preparation of photosensitive lithographic printing plate material) A photopolymerizable photosensitive layer coating solution having the following composition was coated on the above-mentioned support with a wire bar so as to have a dry weight of 1.4 g / m ^2.
Dry at 1.5 ° C for 1.5 minutes. After that, further on the photosensitive layer,
2.0 g of dry coating solution for overcoat layer
It was coated with an applicator so as to have a surface area of m ² and dried at 75 ° C. for 1.5 minutes to prepare a planographic printing plate material having an overcoat layer on the photosensitive layer.

[0156]   <Photosensitive layer coating liquid>   Acrylic copolymer 1 (synthetic binder, molecular weight Mw = 50,000) 35.0 parts   Spectral sensitizing dye 1 2.0 parts   Spectral sensitizing dye 2 2.0 parts   IRGACURE 784 (manufactured by Ciba Specialty Chemicals) 4.0 parts   EO-modified tris (acryloxyethyl) isocyanuric acid                   (Aronix M-315: manufactured by Toagosei Co., Ltd.) 35.0 parts   Polytetramethylene glycol diacrylate                   (PTMGA-250: Kyoeisha Chemical Co., Ltd.) 10.0 parts   Polyfunctional urethane acrylate                 (U-15HA: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5.0 parts   Phthalocyanine pigment (MHI454: manufactured by Mikuni dye company) 6.0 parts   2-t-butyl-6- (3-t-butyl-2-hydroxy             -5-Methylbenzyl) -4-methylphenyl acrylate                 (Sumilizer GS: Sumitomo 3M) 0.5 parts   Fluorine-based surfactant (FC-431; manufactured by Sumitomo 3M Limited) 0.5 part   Methyl ethyl ketone (boiling point = 79.6 ° C.) 80 parts   Cyclopentanone (boiling point = 129 ° C.) 820 parts   <Overcoat layer coating liquid>   Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Industry) 89 parts   Water-soluble polyamide (P-70: manufactured by Toray) 10 parts   Surfactant (F1405: manufactured by Dainippon Ink and Chemicals, Inc.) 0.5 part   900 parts of water

[0157]

[Chemical 7]

(Image formation) With respect to the photosensitive lithographic printing plate material prepared as described above, 2540 dpi (dpi is 2.40) using a CTP exposure device (Tigercat: manufactured by ECRM) equipped with an FD-YAG laser light source. 54c
Image exposure was performed at a resolution of (representing the number of dots per m). Next, a pre-washing part for removing the overcoat layer before development, a developing part filled with a developing solution having the following composition, a washing part for removing the developing solution adhering to the plate surface, and a gum solution for protecting the image area (GW-3 : CTP automatic developing machine (PHW32-V: Technig) equipped with Mitsubishi Chemical's two-fold dilution)
Preheating (100 ° C., 10 seconds) / development treatment was carried out by Raph Co., Ltd. to obtain a lithographic printing plate.

<Developer composition> (Aqueous solution containing the following additives) A Potassium silicate 8.0 mass% Perex NBL: Kao Corporation 3.0 mass% Caustic potassium pH = 12.3 Addition amount ( Evaluation of lithographic printing plate) The lithographic printing plate obtained as described above was evaluated as follows, and the results are shown in Table 1.
The results are shown in Table 2 in the same manner as in Example 2 and the following.

<< Sensitivity >> No film loss in the image area was observed, and the halftone dot exposure area of 175 lines and 50% was twice as light as the exposure quantity that could be reproduced to 50% on the prepared lithographic printing plate surface. It was drawn and used as sensitivity.

<Printing durability> A lithographic printing plate produced by exposing and developing a 175-line image with an appropriate exposure amount was coated with a printing paper (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink ( Toyo Ink Co., Ltd. Toyo King High Echo M Beni and dampening water (Tokyo Ink Co., Ltd. H liquid SG-51)
Printing was performed using a density of 1.5%), and after continuous printing of 1000 sheets, the plate surface was wiped with a cleaner, the number of prints at which highlight spots were thinned and shadow portions were entangled was used as an index of printing durability. One press life refers to the work of wiping with a cleaner after continuous printing of 1000 sheets. The larger the number, the better the printing durability.

<Stain recovery> After continuous printing of 1000 sheets, wipe with a cleaner and restart printing after 15 minutes, and set the number of sheets where non-image area scumming disappears. The smaller the number, the better.

<< 90% Halftone Reproduction >> Halftone dots are drawn with the above laser writing power without linearity correction, and the halftone dot area that should be reproduced to 90% is photographed with a 500 × optical microscope and 2 mm × 2 mm. The area of the image portion of the range is calculated and shown as a dot percentage.

[0164]

[Table 1]

As described above, the photosensitive lithographic printing plate material of the present invention is excellent in the performance of sensitivity, printing durability, stain recovery and linearity, and when it is used in combination with a compound having an ethylenic addition polymerizable group, It can be seen that when a compound having an amino group and an ethylenic addition-polymerizable group is used, more preferable performance is exhibited.

Example 2 The following mixed solution of PVPA and dimethylaminoethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light ester DM) was adjusted by changing the addition ratio to prepare a PVPA-modified product.
The addition rate of the light ester to the PVPA repeating unit was the amount shown in Table 2.

<Solution temperature> 80 ° C. Vinyl phosphonic acid 0.2 parts by mass PVPA 1.5 parts by mass Dimethylaminoethyl methacrylate Concentration shown in Table 2 Diluting solvent 100 parts by mass (kind shown in Table 2) Aluminum in the above solution The plate was passed for 30 seconds to dry.

In addition to the above evaluations, the following evaluations were carried out. << Solubility >> Dissolving solvent of the obtained modified product (solvents shown in Table 2. MEK represents methyl ethyl ketone)
On the other hand, the solubility% was confirmed under environmental stirring at 25 ° C.

<< Addition Rate >> Calculated by the ratio of the acid value of the PVPA homopolymer and the acid value of the PVPA ester.

[0170]

[Table 2]

From the above results, it can be seen that all of them show preferable performance, but when the addition rate is 50 mol% or less, the performance of stain recovery and linearity is excellent.

Example 3 (Production of support 2) Aluminum plate having a thickness of 0.24 mm
(Material 1050, temper H16) kept at 65 ° C 5%
Immerse in sodium hydroxide aqueous solution and degrease for 1 minute
After that, it was washed with water. Polish this degreased aluminum plate
Fine-grade alumina as a medium (average particle size ~ 5 Miku
Ron) and fine grade quartz (up to 5 microns) (aluminum
Na to quartz 70:30 weight ratio) with a solid content of 15%
Use rally at 250 rpm in the opposite direction to the web
Brushing with a single rotating 54.8 cm diameter brush
After mechanically roughening the surface by heat treatment, keep it at 25 ° C.
After immersing in 10% hydrochloric acid aqueous solution for 1 minute to neutralize,
Washed Then, this aluminum plate is 0.3% by mass
In nitric acid aqueous solution of 25 ℃, current density 100A / dm²
Electrolytic surface roughening for 60 seconds with AC current under the conditions
In a 5% aqueous sodium hydroxide solution kept at 60 ° C
Desmut treatment was performed for 10 seconds. Desmut treatment
The roughened aluminum plate subjected to the
At 25 ° C and current density of 10 A / dm ², Voltage of 15V
Anodizing treatment was performed for 1 minute under the conditions. At this time, inside the surface
The average core roughness (Ra) was 0.75 μm. This way
For the support 2 and the support 1 obtained above, PV
PA treatment was performed. The PVPA treatment is as follows:
(PVPA treatment 1 or 2).

[0173]   <Solution temperature> 80 ° C   <PVPA treatment 1>   Vinyl phosphonic acid 0.2 parts by mass   PVPA 1.5 parts by mass   Ion-exchanged water 100 parts by mass   <PVPA treatment 2>   Vinyl phosphonic acid 0.2 parts by mass   PVPA 1.5 parts by mass   Dimethylaminoethyl methacrylate 0.5 parts by mass   Ion-exchanged water 100 parts by mass The support was immersed in the above solution for 20 seconds and dried.

In Example 3, as Samples 1 to 3,
The above-mentioned supports 1 and 2 and PVPA treatments 1 and 2 were treated in the following combinations. Regarding the photosensitive layer and the overcoat layer, a photosensitive lithographic printing plate material was prepared in the same manner as in Example 1.

Sample 1: Support 1 is subjected to PVPA treatment 2. Sample 2: Support 2 is subjected to PVPA treatment 2.

Sample 3: PVPA treatments 1 and 2 on support 2
Give. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

[0177]

[Table 3]

According to the production method of the present invention, good performance can be obtained, but high printing durability can be obtained particularly on a support subjected to mechanical surface roughening and electrochemical surface roughening. . In addition, by using PVPA treatments 1 and 2 together,
It can be seen that favorable soil recovery performance is obtained.

[0179]

INDUSTRIAL APPLICABILITY The present invention has excellent adhesion between the photopolymerizable layer and the support, can achieve both printing durability and improvement of stains in non-image areas, and further has high resolution and good storability. A support for a photosensitive lithographic printing plate material capable of obtaining a printing plate, a photosensitive lithographic printing plate material, and a method for producing the same can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA02 AA14 AB03 AC01 AC08                       AD01 BC32 BC42 BC51 CA01                       CA14 CA23 CA25 CA30 CA39                       CA41 CA50 CB13 CB14 DA18                       DA20 DA35 FA03 FA17                 2H096 AA07 BA05 BA20 CA03 CA05                       EA02 EA04 GA08

Claims (13)

[Claims] 1. A photosensitive material which is a roughened metal support and is treated with an aqueous solvent containing at least A) polyvinyl phosphonic acid and B) a compound containing an amino group. Support for lithographic printing plate material. 2. The support for a photosensitive lithographic printing plate material according to claim 1, wherein the aqueous solvent further contains C) a compound having an ethylenic addition polymerizable group. 3. The support for a photosensitive lithographic printing plate material according to claim 1, wherein the compound having an amino group is D) a compound having an amino group and an ethylenic addition-polymerizable group. 4. A roughened metal support treated with an aqueous solvent containing at least a reaction product of a reaction between polyvinyl phosphonic acid and a compound having an amino group. A support for a photosensitive lithographic printing plate material. 5. The addition ratio of the compound having an amino group to the repeating unit of polyvinyl phosphonic acid is 0.
The support for the photosensitive lithographic printing plate material according to claim 4, which is from 01 to 50 mol%. 6. A photosensitive lithographic printing plate material having, on a roughened metal support, a photopolymerizable layer containing a compound having an ethylenic addition-polymerizable group and a compound capable of generating radicals by actinic rays. And the metal support is:
A) an aqueous solvent containing polyvinyl phosphonic acid and B) a compound having an amino group, and C: an aqueous solvent further containing a compound having an ethylenic addition-polymerizable group, and: having polyvinyl phosphonic acid and an amino group A photosensitive lithographic printing plate material, which is treated with at least one selected from an aqueous solvent containing a reaction product obtained by reacting a compound. 7. The reaction product obtained by reacting the polyvinyl phosphonic acid with the compound having an amino group has an addition ratio of the compound having an amino group to the repeating unit of polyvinyl phosphonic acid of 0.01 to 50 mol%. 7. The photosensitive lithographic printing plate material according to claim 6, which is in the range. 8. A photosensitive lithographic printing plate material having a photopolymerizable layer containing, on a roughened metal support, a compound having an ethylenic addition-polymerizable group and a compound capable of generating radicals by actinic rays. A method for producing a photosensitive lithographic printing plate material, which comprises the following steps a to d. a) a step of electrochemically roughening the metal support in an acidic medium b) the surface of the metal support is: A) an aqueous solvent containing polyvinyl phosphonic acid and B) a compound having an amino group: And C) an aqueous solvent containing a compound having an ethylenic addition-polymerizable group; and an aqueous solvent containing a reaction product of a reaction between polyvinyl phosphonic acid and a compound having an amino group, treated with at least one of the above Step c) Step of providing a photopolymerizable layer containing a compound having an ethylenic addition-polymerizable group and a compound capable of generating radicals by actinic rays d) Step of providing an overcoat layer 9. The method for producing a photosensitive lithographic printing plate material according to claim 8, wherein the steps a to d further include a step of mechanically roughening the surface of the metal support. 10. The method for producing a photosensitive lithographic printing plate material according to claim 8, further comprising a step of treating with an aqueous solvent containing polyvinyl phosphonic acid before the step b). 11. The photosensitive lithographic printing plate material according to claim 1, wherein the amino group of the compound having an amino group is a primary or secondary amino group. Support. 12. The photosensitive lithographic printing plate material according to claim 6, wherein the amino group of the compound having an amino group is a primary or secondary amino group. 13. The photosensitive lithographic printing plate material according to claim 8, wherein the amino group of the compound having an amino group is a primary or secondary amino group. Manufacturing method.