JPH10339953A - Support for lithographic printing plate, photosensitive lithographic printing plate and manufacture of support for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance adhesion the a photosensitive layer and to improve printing resistance and to reduce the occurrence of sludge in development and to eliminate residual films and dyes in development. SOLUTION: This support to be used for the lithographic printing plate is obtained by roughening an aluminum plate on the surface and treating it by an anodic oxidation process and further treating the surface with an aqueous solution of a metal silicate and an aqueous solution of a zirconium potassium fluoride so as to control it to an amount of 10-100 mg Si in terms of SiO2 , 0.01-15 mg F, and 5-50 mg Zr each per 1 m<2> of the surface of the support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate support used for a photosensitive lithographic printing plate and a method for producing the lithographic printing plate support.

[0002]

BACKGROUND OF THE INVENTION A photosensitive lithographic printing plate has a photosensitive layer provided on a hydrophilic support, and is provided with a layer of a positive photosensitive composition on the support. There is a negative-working photosensitive lithographic printing plate in which a layer of a negative-working photosensitive composition is provided on a support.

[0003] Conventionally, the support used in these photosensitive lithographic printing plates has, after anodizing treatment, control of adhesiveness to a photosensitive layer and control of dissolution of an anodized film in a developing solution during development (dissolution). It has been proposed to perform various surface treatments such as sealing treatment and post-treatment for the purpose of improving stains at the time of printing or the like, if the amount is large.

For example, Japanese Patent Application Laid-Open No. 55-81346 discloses that a hydrophilic polymer compound layer containing colloidal silica dispersed therein is provided after a silicate aqueous solution treatment, thereby eliminating stains on a non-image area. Japanese Patent Application Laid-Open No. 63-99992 proposes that, after silicate post-treatment, by treating with steam or a dilute alkali solution at 60 to 100 ° C., the stain on the non-image area is not reduced without reducing the printing durability. It has been proposed to eliminate.

[0005] However, when a positive photosensitive lithographic printing plate is prepared on the support subjected to these treatments, the amount of the anodic oxide film dissolved in the developer is reduced, and the generation of sludge is reduced. There is a problem that the photosensitive layer is left later, or a dye remains, which causes stain. Further, the adhesiveness of the photosensitive layer to the support was reduced, and the printing durability was insufficient. Further, there was also a problem that the anodic oxide film was corroded and whitened by cleaning with a plate cleaner containing an acid, and the printing durability was further reduced.

Japanese Patent Publication No. 53-131102 discloses that the hydrophilicity and printing durability of the non-image area can be improved by treating with an aqueous solution of potassium zirconium fluoride and then with an aqueous solution of sodium silicate. As suggested in Example 1, after treatment with a 1% aqueous solution of potassium zirconium fluoride at 76.7 ° C. for 30 seconds, 56.7 ° C.
% Sodium silicate aqueous solution for 30 seconds, the surface of the anodic oxide film is coated with a large amount of potassium zirconium fluoride. Also, when a photosensitive lithographic printing plate prepared using the support is developed with a developer containing a silicate, the adsorption of silicic acid does not similarly occur, so that the hydrophilicity of the grain surface is increased. The property is reduced, and it becomes easy to become dirty.

Japanese Patent Publication No. 53-131102 discloses Example 4
In the case where the above processing order is reversed, that is, 76.7
After treatment with a 5% aqueous sodium silicate solution at 60 ° C for 60 seconds, a 7% aqueous 1% potassium zirconium fluoride solution at 76.7 ° C
It is described that, when treated for 60 seconds, a photosensitive lithographic printing plate prepared using the support is inferior in sensitivity stability and printing durability over time.

The inventors of the present invention have studied the reason why the photosensitive lithographic printing plate prepared using the above-mentioned support is inferior in sensitivity stability and printing durability over time, and found that the addition of silicic acid by treatment with an aqueous solution of sodium silicate. It was found that the amount and the amount of fluorine and zirconium by the treatment with the aqueous potassium zirconium fluoride solution were not within the appropriate ranges.

[0009] Therefore, when the support subjected to the anodizing treatment is treated with an aqueous silicate solution, and further treated with an aqueous potassium zirconium fluoride solution to obtain a support for a photosensitive lithographic printing plate, the silicate aqueous treatment is used. Of the amount of SiO ₂ and the amount of fluorine and zirconium in the aqueous solution of potassium zirconium fluoride in water treatment, a high hydrophilicity was imparted to the support by using these specific amounts. In addition to improving stains in printing, excellent adhesion with the photosensitive layer, excellent printing durability, less sludge in development, no residual film / dye in development, In addition, a support for a photosensitive lithographic printing plate having excellent plate cleaner resistance was obtained, and it was found that the above problem could be solved.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to impart high hydrophilicity to a support, improve stains in printing, and have excellent adhesion to a photosensitive layer, good printing durability, and good development. A photosensitive lithographic printing plate support capable of obtaining a photosensitive lithographic printing plate having a low occurrence of sludge, having no residual film and no dye residue during development, and having excellent plate cleaner resistance, and a method for producing the same. To provide.

[0011]

The objects of the present invention are as follows: (1) A flat aluminum plate having a roughened surface and anodized
A support for a printing plate, wherein the surface of the support has a silicon content.
Is SiO_Two10mg / m in conversion^TwoAbove, 100mg / m^TwoBelow, fluorine
The amount is 0.01mg / m^TwoMore than 15mg / m^TwoBelow, the amount of zirconium
5mg / m^TwoMore than 50mg / m^TwoIs processed to be
A support for a lithographic printing plate. (2) A photosensitive layer is provided on the lithographic printing plate support described in (1) above.
A photosensitive lithographic printing plate characterized by being provided. (3) Roughening the aluminum plate, anodizing it,
Treatment with an aqueous solution of metal silicate,
In the method of treating with an aqueous solution of potassium ruconium,
The amount of silicon on the surface of the carrier is SiO _Two10mg / m in conversion^TwoAbove, 1
00mg / m^TwoBelow, the amount of fluorine is 0.01 mg / m^TwoMore than 15mg / m^TwoLess than
Below, the amount of zirconium is 5mg / m^TwoMore than 50mg / m^TwoBelow
As in metal silicate aqueous treatment and zirconium fluoride
The above-mentioned, characterized in that an aqueous solution of potassium potassium is performed.
The method for producing a lithographic printing plate support according to (1). (4) Roughening the aluminum plate, anodizing it,
Treatment with an aqueous solution of metal silicate,
Treatment with aqueous potassium ruconium solution, then acid or
In the method of treating with an aqueous alkali solution,
Silicon content is SiO _Two10mg / m in conversion^TwoAbove, 100mg / m^TwoLess than
Below, the amount of fluorine is 0.01mg / m^TwoMore than 15mg / m^TwoBelow, zircon
The amount of nickel is 5mg / m^TwoMore than 50mg / m^TwoSo that
Metal silicate aqueous solution treatment, potassium zirconium fluoride
Perform aqueous solution treatment and acid or alkali aqueous solution treatment.
The support for a lithographic printing plate as described in (1) above,
Manufacturing method. (5) Immediately before the anodic oxidation treatment, perform a dissolution treatment with alkali.
The flat panel according to the above (3) or (4),
A method for producing a printing plate support. (6) In the dissolution treatment with alkali just before anodic oxidation
1.0 to 3.0 g / m^TwoIs characterized by
The method for producing a lithographic printing plate support according to the above (5). To
Is achieved.

Hereinafter, the present invention will be described in detail.

First, the aluminum plate used in the present invention will be described.

The aluminum plate used in the present invention includes:
Not only a pure aluminum plate but also a plate made of an aluminum alloy is included. Various aluminum alloys 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, or iron is used.

The aluminum plate is preferably subjected to a degreasing treatment prior to roughening to remove rolling oil and the like on the aluminum surface. Examples of the degreasing treatment include a degreasing treatment using a solvent such as trichlene and thinner, and an emulsion degreasing treatment using an emulsion such as kesilon and triethanol. In the degreasing treatment, an aqueous solution of an alkali such as caustic soda can be used. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide films that cannot be removed by the above degreasing treatment alone can also be removed.

When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is preferable to immerse it in an acid such as phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, chromic acid, or a mixed acid thereof to perform a neutralization treatment. When performing electrochemical surface roughening after the neutralization treatment, it is particularly preferable to match the acid used for neutralization with the acid used for electrochemical surface roughening.

Various methods are used for the surface roughening of the support, and the type of the surface roughening method is not limited.
A chemical surface roughening method, a mechanical surface roughening method, an electrochemical surface roughening method, and these surface roughening methods can be appropriately combined and used.

In the chemical surface roughening method, an aqueous solution of an alkali such as caustic soda can be used. After chemical surface roughening using an aqueous alkali solution, phosphoric acid, nitric acid,
It is preferable to immerse in an acid such as hydrochloric acid, sulfuric acid, and chromic acid, or a mixed acid thereof to perform neutralization. When electrochemical surface roughening is further performed after the neutralization treatment, it is particularly preferable to match the acid used for neutralization with the acid used for electrochemical surface roughening.

Various methods are used for the mechanical surface roughening method and are not particularly limited, but brush polishing and honing polishing are preferred. The surface roughening by brush polishing is performed, for example, with a hair diameter of 0.
Rotate a cylindrical brush with 2 to 1 mm brush bristles,
This is performed by pressing against the surface of the support while supplying a slurry in which the abrasive is dispersed in water to the contact surface. The surface roughening by the honing polishing is performed, for example, by injecting a slurry in which an abrasive is dispersed in water by applying pressure from a nozzle and colliding the surface of the support obliquely. Examples of abrasives used in these surface roughening methods include those commonly used for polishing, such as volcanic ash, alumina, and silicon carbide. The abrasive usually has a particle size of # 200 to # 2000, but preferably has a particle size of # 400 to # 800.

When the surface is mechanically roughened, it is immersed in an aqueous solution of an acid or alkali to remove abrasives and aluminum debris that have penetrated the surface of the aluminum plate and to control the pit shape. Preferably, the surface is etched. As the acid, for example, sulfuric acid,
Persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like are used, and as the base, for example, sodium hydroxide, potassium hydroxide and the like are used. Among these, it is preferable to use an aqueous alkali solution.

When the above treatment is carried out by immersion in an aqueous alkali solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid or chromic acid, or a mixed acid thereof. After the neutralization treatment, when performing electrochemical surface roughening, it is particularly preferable to match the acid used for the neutralization with the acid used for the electrochemical surface roughening, and after the neutralization treatment, When performing anodizing treatment, it is particularly preferable to match the acid used for neutralization with the acid used for the anodizing treatment.

As the electrochemical surface roughening method, a commonly used method of roughening the surface using an alternating current in an acidic electrolyte can be used. In the present invention, as the acidic electrolytic solution, an acidic electrolytic solution usually used for an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. For the electrochemical surface roughening method, various current waveforms, for example, a rectangular wave, a trapezoidal wave, a sawtooth wave, and the like can be used, but a sine wave is preferably used. The electrochemical surface roughening treatment may be performed by continuously supplying the entire amount of electricity required for the treatment in one step. The processing may be divided into several times with a delay in the progress of the processing. If you want to split and perform electrochemical surface roughening,
The amount of positive electricity in one divided process should be 100 C / dm ² or less,
In addition, it is preferable to set the pause time or the time for delaying the progress of the electrolytic treatment to 0.6 to 5 seconds. In the case of performing electrochemical surface roughening by dividing, it is preferable to use a hydrochloric acid-based electrolytic solution, whereby uniform grain can be formed.

The voltage applied in the electrochemical graining using a nitric acid-based electrolyte is preferably 1 to 50 V,
~ 30V is more preferred. Current density (peak value) is 10 ~
200 A / dm ² is preferred, and 20 to 150 A / dm ² is more preferred. The amount of electricity is 100 to 2000 C / d in total for all processing steps.
m ² , preferably 200 to 1500 C / dm ² , more preferably 200
10001000 C / dm ² . The temperature is preferably from 10 to 50 ° C, 1
5-45C is more preferred. The nitric acid concentration is preferably 0.1 to 5% by weight, particularly preferably 0.5 to 2.0% by weight.

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.

The voltage applied in the electrochemical graining using a hydrochloric acid-based electrolyte is preferably 1 to 50 V,
~ 30V is more preferred. Current density (peak value) is 10 ~
200 A / dm ² is preferred, and 20 to 150 A / dm ² is more preferred. The amount of electricity is 100 to 2000 C / dm ^{2 in} total for all processing steps.
Is preferable, and 200 to 1000 C / dm ² is more preferable. The temperature is preferably from 10 to 50C, more preferably from 15 to 45C. The hydrochloric acid concentration is preferably from 0.1 to 5% by weight, particularly preferably from 0.5 to 2.0% by weight.

If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, etc. can be added to the electrolytic solution.
It is particularly preferred to add ~ 5% by weight.

The surface of an electrochemically roughened support is immersed in an acid or alkali aqueous solution to remove the surface smut and the like and control the pit shape, and the surface is etched. Is preferred. As the acid, for example, sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like are used, and as the base, for example, sodium hydroxide, potassium hydroxide and the like are used. Among these, it is preferable to use an aqueous alkali solution.

The amount of etching is particularly preferably 1.0 to 3.0 g / m ^{2 in} terms of weight loss including smut. When the above treatment is performed by dipping in an aqueous alkali solution, it is preferable to perform a neutralization treatment by dipping in an acid such as phosphoric acid, nitric acid, sulfuric acid, or chromic acid, or a mixed acid thereof. When anodizing is performed after the neutralization, it is particularly preferable that the acid used for the neutralization is matched with the acid used for the anodization.

After the surface roughening treatment, the aluminum plate is subjected to anodizing treatment to form an anodized film.

The method of the anodic oxidation treatment used in the present invention is not particularly limited, and a known method can be used. An oxide film is formed on the support by the anodic oxidation treatment.
The anodizing treatment is generally performed by direct current electrolysis using sulfuric acid or phosphoric acid or a mixed aqueous solution of both as an electrolytic solution. In the present invention, the anodic oxidation treatment is preferably performed using sulfuric acid as the electrolytic solution. The concentration of sulfuric acid is preferably 5 to 50% by weight, particularly preferably 15 to 35% by weight. The temperature is preferably from 10 to 50 ° C. The processing voltage is
The voltage is preferably 18 V or more, more preferably 20 V or more. The current density is preferably 1 to 30 A / dm ² .
The quantity of electricity is preferably 100 to 300 C / dm ² .

The thickness of the formed anodic oxide film is 0.5 to
5.0 μm is preferred, and 1.5 to 3.5 μm is more preferred. Micropores are generated in the anodized film, and the density of the micropores is preferably 400 to 700 / μm ² , and 400 to 600
Particles / μm ² are more preferred.

The support for a lithographic printing plate of the present invention has a surface S
i amount is 10 mg / m ² or more and 100 mg / m ² or less in terms of SiO ₂ ,
The amount is 0.01 mg / m ² or more and 15 mg / m ² or less, and the Zr amount is 5 mg / m ²
As described above, the dose is 50 mg / m ² or less.

The amount of Si on the surface of the lithographic printing plate support was determined as SiO
10 mg / m ² or more, 100 mg / m ² or less in ₂ conversion, F content 0.01 mg / m ²
m ² or more, 15 mg / m ² or less, Zr amount 5 mg / m ² or more, 50 mg /
In order to make m ² or less, the roughened and anodically oxidized aluminum plate finally has a Si content of 10 mg in terms of SiO _2.
/ M ² or more and 100 mg / m ² or less, for example, a treatment with an aqueous silicate solution, and then the amount of F is reduced to 0.01 mg / m ^2.
Above, 15 mg / m ² or less, Zr amount 5 mg / m ² or more, 50 mg / m ²
The following treatment, for example, treatment with an aqueous solution of potassium zirconium fluoride is performed.

By treating the aluminum plate having the anodic oxide film formed thereon with an aqueous silicate solution, SiO ₂ is adsorbed on the anodic oxide film to impart hydrophilicity and alkali resistance.

Finally, the amount of Si was converted to 10 mg / SiO ₂ equivalent.
In order to make the amount of m ² or more and 100 mg / m ² or less, the amount of Si adsorbed by the treatment with the silicate aqueous solution is 1 in terms of SiO _{2 in} consideration of the amount of Si removed by the next treatment.
It is preferable to set it to 5 to 105 mg / m ² . However, a more preferred range is 35-105 mg / m ² , even more preferably 55-105 mg / m ² . The Si adsorbed in the first treatment with the silicate aqueous solution reduces the amount of F subsequently performed to 0.01 mg /
m ² or more, 15 mg / m ² or less, Zr amount 5 mg / m ² or more, 50 mg /
It is partially removed by appropriately performing the second processing to reduce the size to m ² or less. Normally, the amount of Si removed is about 5 mg / m ² .

Examples of the silicate used in the treatment include sodium silicate, for example, sodium orthosilicate, sodium metasilicate, sodium silicate No. 1, sodium silicate No. 3, sodium silicate No. 3, sodium silicate No. 4, and sodium silicate. Mixtures of two or more of these, potassium silicate, for example, 2K potassium silicate, potassium A silicate, potassium B silicate, potassium C silicate, 1K potassium silicate, and a mixture of two or more of these. Further, a mixture of the above sodium silicate and potassium silicate can also be used.

As the silicate, silicates other than the above-mentioned sodium silicate and potassium silicate can be used. Examples of these silicates include barium silicate, lithium silicate and silicate. Stolonium is mentioned.

The concentration of the aqueous silicate solution used is
0.05 to 5.0% by weight is preferred, and more preferably 0.5 to 2.
0% by weight. The pH of the aqueous silicate solution is 10 to 1
3 is preferred, and more preferably 11-13.

The treatment with the silicate aqueous solution is preferably performed at 10 to 90 ° C., more preferably at 30 to 70 ° C. The processing time is preferably from 1 to 120 seconds.

The treatment of the grain surface with the silicate aqueous solution is not limited to the treatment under the above-mentioned treatment conditions, but a method capable of treating the grain surface such that the silicon amount on the grain surface is within the range of the present invention. Then, any processing method can be used.

If the amount of Si adsorbed by the treatment with the aqueous silicate solution is less than 15 mg / m ^{2 in} terms of SiO ₂ , assuming that the treatment with the aqueous solution of potassium zirconium fluoride is performed next, potassium zirconium fluoride The treatment with the aqueous solution removes SiO ₂ , and the amount of Si becomes less than 10 mg / m ^{2 in} terms of SiO ₂ , resulting in insufficient hydrophilicity. In addition, 105mg in terms of SiO ₂ /
high concentration in an attempt to adsorb many SiO ₂ than m ^2,
When treated at high temperature and high pH, the dissolution amount of the anodic oxide film during the treatment is large, the micropore diameter of the anodic oxide film is widened, the voids are increased, and the anodic oxide film becomes soft and easily wears. Not only is the printing durability reduced, but printing stains are more likely to occur during printing.

In the case where the roughened surface has complicated sharp irregularities or the specific surface area of the anodic oxide film is extremely high due to the high pore density of the anodic oxide film, the relative surface area is relatively small. be treated with a weak process conditions, there is a case where SiO ₂ adsorption amount is more than 105 mg / m ² in terms of SiO _2, in this case, the ink adheres to the excessive unevenness of the support surface during printing It causes printing stains. Further, a high pore density means that there are many voids in the anodic oxide film, and the anodic oxide film is soft, easily worn, and deteriorates printing durability.

In order to avoid the above-mentioned problems caused when the pore density of the anodic oxide film is high or the specific surface area of the anodic oxide film is extremely high, it is necessary to use an alkaline agent before the anodizing treatment, for example, The surface dissolution amount (dissolution amount including smut, if smut is present) is 1.0 to 3.0 g / m ²
The surface may be smoothed by treating so that excessive and complicated irregularities on the surface are formed into appropriate irregularities and have an appropriate specific surface area.

The pore density of the anodic oxide film is 400 to 700 / pore.
μm ² is appropriate. This pore density can be obtained by using an electrolytic solution mainly containing sulfuric acid and performing anodizing treatment by controlling the voltage in DC electrolysis to be 18 V or more, preferably 20 V or more.

If the support provided with the anodized film is simply treated with an aqueous silicate solution, the adhesion to the positive photosensitive layer is poor, and only low printing durability can be obtained. In addition, despite the poor adhesion to the photosensitive layer, a residual film or a dye residue occurs during development, and the adhesion balance is poor. Furthermore, there is no resistance to a plate cleaner solution containing an acid.

Therefore, in the present invention, the amount of F is 0.01 mg
/ M ² or more, 15 mg / m ² or less, Zr content 5 mg / m ² or more, 50 mg
/ M ² or less is performed.

For the above treatment, an aqueous solution of potassium zirconium fluoride (K ₂ ZrF ₆ ) can be used. At present, it is not clear how F and Zr are adsorbed to the anodic oxide film by the treatment with the potassium zirconium fluoride aqueous solution.

In the aqueous solution of potassium zirconium fluoride,
Acids such as sulfuric acid, acetic acid and phosphoric acid can be added.

The concentration of the treating agent used is from 0.01 to 0.1.
Preferably 2% by weight, more preferably 0.02 to 0.1% by weight
It is. The pH of the treating agent is preferably from 3 to 5.

The treatment is preferably performed at 10 to 90 ° C., more preferably at 30 to 70 ° C. The processing time is preferably from 1 to 120 seconds.

The treatment for adsorbing F and Zr on the grain surface is not limited to the treatment under the above treatment conditions.
Any treatment method can be used as long as it can be treated so that the F content and the Zr content of the grain surface are within the range of the present invention.

When the F content of the anodic oxide film is 0.01 mg / m ² or more,
mg / m ² or less, a Zr amount 5 mg / m ² or more, by a 50 mg / m ² or less, balance between adhesiveness is improved, without causing residual film and the dye-remaining during development, adhesion of the photosensitive layer Properties such as improved printability and improved printing durability. Further, resistance to a plate cleaner solution containing an acid is also provided.

In the present invention, the amount of F on the surface of the support is 0.1%.
01mg / m ² or more, 15 mg / m ² or less, Zr amount is 5 mg / m ² or more,
Although it is 50 mg / m ² or less, preferably, the amount of F is 0.01 mg / m ^2.
m ² or more, 10 mg / m ² or less, Zr amount is 5 mg / m ² or more, 20 mg /
m ² or less. F content is less than 0.01 mg / m ² or Zr
When the amount is less than 5 mg / m ² , the effect of improving the residual film and the residual dye is not obtained, and the printing durability and the plate cleaning resistance are not improved. When the amount of F exceeds 15 mg / m ² or the amount of Zr exceeds 50 mg / m ² , the residual film and the dye residue are improved, and plate cleaner resistance can be imparted. Adhesion decreases and printing durability decreases. Further, 10 mg of the Si content in terms of SiO ₂ / m ²
As described above, the hydrophilicity provided by setting the content to 100 mg / m ² or less is also impaired, and printing stains are likely to occur during printing.

In the second treatment for adsorbing F and Zr, when the F amount of the anodic oxide film exceeds 15 mg / m ² and the Zr amount exceeds 50 mg / m ² , the alkali or acid is then added. If the excess amount of F and Zr is removed by performing the surface cleaning treatment according to (1) and the amount of adsorption is within the range of the present invention, the effect of the present invention can be exhibited.

F, Z in the second F, Zr adsorption process
The adsorption amount of Zr is affected by the specific surface area of the anodic oxide film as in the case of the SiO ₂ amount, but when the adsorption amount of F and Zr exceeds the upper limit of the range of the present invention due to the large specific surface area, , For the same reason as above,
Alternatively, the coating is liable to be worn and the printing durability is reduced.

In the photosensitive lithographic printing plate of the present invention, a photosensitive layer made of a photosensitive composition is provided on the support obtained as described above.

The photosensitive composition used in the present invention is not particularly limited. In the present invention, a photosensitive composition usually used for a photosensitive lithographic printing plate can be used. Examples of the photosensitive composition that can be used in the present invention include the following. 1) Photocrosslinkable photosensitive resin composition The photosensitive component in the photocrosslinkable photosensitive resin composition comprises a photosensitive resin having an unsaturated double bond in a molecule,
For example, U.S. Pat.Nos. 3,030,208 and 3,435,237
No. 3,622,320, etc., as a photosensitive group in the polymer main chain.

[0058]

Embedded image And polyvinyl cinnamate having a photosensitive group on the side chain of the polymer. 2) Photopolymerizable photosensitive resin composition A photopolymerizable composition containing an addition-polymerizable unsaturated compound, comprising a monomer having a double bond or a monomer having a double bond, and a polymer binder. Representative examples of such a composition are described in, for example, US Pat. Nos. 2,760,863 and 2,791,504.

Examples of the photopolymerizable composition include a composition containing methyl methacrylate, a composition containing methyl methacrylate and polymethyl methacrylate, and a composition containing methyl methacrylate, polymethyl methacrylate and a polyethylene glycol methacrylate monomer. And a photopolymerizable composition such as a composition containing methyl methacrylate, an alkyd resin and a polyethylene glycol dimethacrylate monomer.

These photopolymerizable photosensitive resin compositions contain a photopolymerization initiator generally known in this technical field (for example,
Benzoin derivatives such as benzoin methyl ether, benzophenone derivatives such as benzophenone, thioxanthone derivatives, anthraquinone derivatives, acridone derivatives, etc.)
Is added. 3) Photosensitive composition containing diazo compound Preferred examples of the diazo compound used in the photosensitive composition include diazo resins represented by condensates of an aromatic diazonium salt with formaldehyde or acetaldehyde. Particularly preferably, a salt of a condensate of p-diazophenylamine with formaldehyde or acetaldehyde, for example, a reaction product of the above condensate with hexafluorophosphate, tetrafluoroborate, perchlorate or periodate. Diazo resin inorganic salts, and diazo resin organic salts, which are reaction products of the condensate and sulfonic acids described in US Pat. No. 3,300,309.

The diazo resin is preferably used with a binder. As such a binder, various polymer compounds can be used, and preferably, a polymer is disclosed in JP-A-54-98613.
Monomer having an aromatic hydroxyl group, for example, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene , O
-, A copolymer of m- or p-hydroxyphenyl methacrylate and the like and another monomer, a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit described in U.S. Pat.No. 4,123,276 as a main repeating unit Containing polymers, natural resins such as shellac, rosin, polyvinyl alcohol, U.S. Pat.
Examples thereof include a linear polyurethane resin, a phthalated resin of polyvinyl alcohol, an epoxy resin which is a condensate of bisphenol A and epichlorohydrin, and cellulose derivatives such as cellulose acetate and cellulose acetate phthalate described in 1,257. 4) Photosensitive composition containing o-quinonediazide compound The o-quinonediazide compound is a compound having an o-quinonediazide group in a molecule. Examples of the o-quinonediazide compound that can be used in the present invention include: o-Naphthoquinonediazide compounds, for example, ester compounds of o-naphthoquinonediazidesulfonic acid with phenols and polycondensation resins with aldehydes or ketones.

Examples of the phenol in the polycondensation resin with the phenol and aldehyde or ketone include, for example, phenol, o-cresol, m-cresol,
Examples include monohydric phenols such as p-cresol, 3,5-xylenol, carvacrol, and thymol; dihydric phenols such as catechol, resorcinol, and hydroquinone; and trihydric phenols such as pyrogallol and phloroglucin. As the aldehyde, for example, formaldehyde,
Examples include benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Preferred among these are formaldehyde and benzaldehyde. Examples of the ketone include acetone, methyl ethyl ketone, and the like.

Specific examples of polycondensation resins with phenols and aldehydes or ketones include phenol-formaldehyde resins, m-cresol-formaldehyde resins, m-, p-mixed cresol-formaldehyde resins, resorcin-benzaldehyde resins, Pyrogallol / acetone resin;

In the above-mentioned o-naphthoquinonediazide compound, the condensation rate of o-naphthoquinonediazidesulfonic acid to OH groups of phenols (reaction rate for one OH group) is preferably 15% to 80%, more preferably 20%. ~
45%.

Further, as the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can be exemplified. That is, for example,
-Benzoquinonediazidesulfonic acid ester, 1,2-
Known 1,2- such as naphthoquinonediazidosulfonic acid ester, 1,2-benzoquinonediazidosulfonic acid amide, and 1,2-naphthoquinonediazidosulfonic acid amide
Quinonediazide compounds, more specifically, "Light-Sensitive Systems" by J. Kosar, 339-352 (1965)
Year), John Wille and Sands
y & Sons, Inc. (New York) and WSDe Forest, Photoresist, Vol. 50 (1975); McGraw Hill, New York 1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4- (N- Ethyl-N-β-naphthyl) -sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-5-sulfonyl) -3,5-dimethylpyrazole, 2-Naphthoquinonediazide-5-sulfonic acid-4'-hydroxydiphenyl-4'-azo-β-naphthol Tel,
N, N-di- (1,2-naphthoquinonediazido-5-sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-
Anthraquinone, 1,2-naphthoquinonediazide-5
Sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 mol and 4 mol Condensate with 1 mol of 4,4'-diaminobenzophenone, 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-dihydroxy-
A condensate with 1 mol of 1,1'-diphenylsulfonic acid,
Condensate of 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride with 1 mol of purprogalin, 1,2-
Examples thereof include 1,2-quinonediazide compounds such as naphthoquinonediazide-5- (N-dihydroabiethyl) -sulfonamide. In addition, Japanese Patent Publication No. 37-1953
Nos. 37-3627, 37-13109, 40-26126, 40-
No. 3801, No. 45-5604, No. 45-27345, No. 51-13013,
1,2-quinonediazide compounds described in JP-A-48-96575, JP-A-48-63802, and JP-A-48-63803 can also be mentioned.

Of the above o-quinonediazide compounds,
An o-quinonediazide ester compound obtained by reacting 1,2-benzoquinonediazidosulfonyl chloride or 1,2-naphthoquinonediazidosulfonylchloride with a pyrogallol-acetone condensed resin or 2,3,4-trihydroxybenzophenone is particularly preferred.

In the present invention, as the o-quinonediazide compound, the above compounds may be used alone or in combination of two or more.

The proportion of the o-quinonediazide compound in the photosensitive composition is preferably from 5 to 60% by weight, particularly preferably from 10 to 50% by weight.

It is preferable to further add an alkali-soluble resin to the photosensitive composition containing the o-quinonediazide compound.

In the present invention, examples of the alkali-soluble resin which is preferably used in combination with the o-quinonediazide compound include, for example, a novolak resin, a vinyl polymer having a phenolic hydroxyl group, and those described in JP-A-55-57841. And condensation resins of polyhydric phenols and aldehydes or ketones.

Examples of the novolak resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolymer resin described in JP-A-55-57841, and JP-A-55-57841. And copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A-127553.

The molecular weight (polystyrene standard) of the novolak resin preferably has a number average molecular weight Mn of 3.00 × 10 ^{2 to} 7.5.
0 × 10 ³ , weight average molecular weight Mw is 1.00 × 10 ^{3 to} 3.00 × 10 ⁴ ,
More preferably, Mn is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.
00 × 10 ^{3 to} 2.00 × 10 ⁴ .

The above novolak resins may be used alone or in combination of two or more.

When a novolak resin is used in combination, it is preferred that the novolak resin be contained in the photosensitive composition in an amount of 5 to 95% by weight.

The vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and has the following general formula [I] to
A polymer containing at least one structural unit represented by [V] is preferable.

[0076]

Embedded image

In the general formulas [I] to [V], R
₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R
₃ represents a hydrogen atom, a halogen atom or an alkyl group,
Preferred is a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and are preferably a hydrogen atom. A represents an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom to an aromatic carbon atom, m represents an integer of 0 to 10, and B represents a substituent. Represents a phenylene group which may be substituted or a naphthylene group which may have a substituent.

The vinyl polymer having a phenolic hydroxyl group used in the present invention preferably has a copolymer type structure having the structural units represented by the general formulas [I] to [V]. Examples of the monomer to be copolymerized include, for example, ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene, α-methylstyrene,
Styrenes such as -methylstyrene and p-chlorostyrene; for example, acrylic acids such as acrylic acid and methacrylic acid; for example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride; for example, methyl acrylate , Ethyl acrylate, n-butyl acrylate,
Esters of α-methylene aliphatic monocarboxylic acids such as isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate For example, nitriles such as acrylonitrile and methacrylonitrile, for example, amides such as acrylamide, for example, anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, and m-methoxyacrylanilide, for example, acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate, and vinyl acetate, for example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and β-chloroethyl vinyl ether , Vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1- Ethylene derivatives such as nitroethylene, for example, N-vinylpyrrole,
N-vinyl carbazole, N-vinyl indole, N-
There are N-vinyl monomers such as vinylpyrrolidene and N-vinylpyrrolidone. These monomers are present in the polymer compound in a structure in which the unsaturated double bond is cleaved.

Among the above-mentioned monomers, esters and nitriles of aliphatic monocarboxylic acids exhibit excellent performance for the purpose of the present invention and are preferred.

These monomers may be bonded to the polymer used in the present invention in either a block or random state.

When a vinyl polymer having a phenolic hydroxyl group is used in combination, the content of the vinyl polymer having a phenolic hydroxyl group is preferably 0.5 to 70% by weight in the photosensitive composition.

As the vinyl polymer having a phenolic hydroxyl group, the above polymers may be used alone or in combination of two or more. Further, it can be used in combination with another polymer compound or the like.

When an alkali-soluble resin is used in combination, o-
The proportion of the quinonediazide compound in the photosensitive composition is preferably 5 to 60% by weight, particularly preferably 10 to 60% by weight.
50% by weight.

It is preferable to further add an inclusion compound to the photosensitive composition containing the o-quinonediazide compound.

The clathrate compound is not particularly limited as long as it is a compound that can take in (clathrate) a chemical species.
Organic compounds soluble in the solvent used for preparing the composition are preferred. Examples of such organic compounds include, for example,
"Host Guest Chemistry" (Michio Hiraoka et al., Kodansha
1984, Tokyo) and "Tetrahedron Report" (No.226 (1987) P5725A. Collet et al.), "Chemical Industry April Issue" ((1991) P278 Shinkai et al.), "Chemical Industry April Issue" (1991) P288 Hiraoka et al.).

The inclusion compounds preferably used in the present invention include, for example, cyclic D-glucans, cyclophanes, neutral polyligands, cyclic polyanions, cyclic polycations, cyclic peptides, SPHERANDS, CAVITANDS and their acyclic analogs. Among these, cyclic D-glucans and their non-cyclic analogs, cyclophanes, and neutral polyligands are more preferred.

The cyclic D-glucans and non-cyclic analogs thereof include, for example, compounds in which α-D-glucopyranose is linked by a glycooxide bond.

Examples of the compound include carbohydrates composed of D-glucopyranose groups such as starch, amylose and amylopectin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and polymerization of D-glucopyranose groups. Cyclodextrin having a degree of 9 or more, such as cyclodextrin, and SO ₃ C ₆ H ₄ CH ₂ C ₆ H ₄
SO ₃ group, NHCH ₂ CH ₂ NH group, NHCH ₂ CH ₂ NH
CH ₂ CH ₂ NH group, SC ₆ H ₅ group, N ₃ group, NH ₂ group, NE
t ₂ group, SC (NH ⁺ ₂ ) NH ₂ group, SH group, SCH ₂ CH
_{2 The following} formula introducing a substituent such as NH ₂ group, imidazole group, ethylenediamine group, etc.

[0089]

Embedded image And modified D-glucans. Further, there may be mentioned cyclodextrin derivatives, branched cyclodextrins, and cyclodextrin polymers represented by the following general formulas [VI] and [VII].

[0090]

Embedded image

In the general formula [VI], R₁~ R_ThreeIs
Each of which may be the same or different, a hydrogen atom, an alkyl
Or a substituted alkyl group. In particular, R ₁~ R_ThreeBut water
Atom or hydroxyethyl group, hydroxypropyl
Preferably a substituted alkyl group in one molecule
Is more preferably 15% to 50%.
n_TwoRepresents a positive integer of 4 to 10.

[0092]

Embedded image

In the general formula [VII], R represents a hydrogen atom
Child, -R^Two -CO_TwoH, -R^Two -SO_ThreeH, -R^Two-NH_TwoMa
Or -N- (R^Three)_Two(R^TwoIs a straight chain having 1 to 5 carbon atoms or
Represents a branched alkylene group;^ThreeHas 1 to 5 carbon atoms
Represents a linear or branched alkyl group.

The production example of cyclodextrin is described in "Jo
unal of the American Chemical Society, Vol. 71, No. 3
Page 54 1949, `` Cheimish Berichte '' Vol. 90, No. 2561
P. 1949, vol. 90, p. 2561, p. 1957, but of course is not limited thereto.

The term "branched cyclodextrin" used in the present invention means that a water-soluble substance such as a monosaccharide or disaccharide such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine is added or bound to a known cyclodextrin. And preferably,
Maltosylcyclodextrin in which maltose is bound to cyclodextrin (the number of molecules bound to maltose may be one, two or three) or glucosylcyclodextrin in which glucose is bound to cyclodextrin (the number of molecules bound to glucose) Is one molecule, two molecules,
Or any of three molecules).

Specific methods for synthesizing these branched cyclodextrins are described, for example, in Starch Chemistry, Vol. 33, No. 2, 119
-126 (1986), 127-132 (1986), starch chemistry,
Vol. 30, No. 2, pp. 231-239 (1983), etc., and can be synthesized with reference to these known methods. For example, maltosyl cyclodextrin can be prepared by using cyclodextrin and maltose as raw materials. And maltose by cyclodextrin using an enzyme such as isoamylase or pullulanase. Glucosylcyclodextrin can be produced in a similar manner.

In the present invention, examples of the preferably used branched cyclodextrin include the following specific compounds.

[Exemplary Compounds] D-1 α-cyclodextrin having one molecule bonded with maltose D-2 β-cyclodextrin having one molecule bonded with maltose D-3 γ-cyclodextrin D-4 having one molecule bonded with maltose Α-cyclodextrin D-5 in which two molecules of maltose are bound β-cyclodextrin D-5 in which two molecules of maltose are bound D-6 γ-cyclodextrin in which two molecules of maltose are bound D-7 α-cyclodextrin in which three molecules of maltose are bound D-8 β-cyclodextrin in which three molecules of maltose are bound D-9 γ-cyclodextrin in which three molecules of maltose are bound D-10 α-cyclodextrin in which one molecule of glucose is bound D-11 β-in which one molecule of glucose is bound One molecule of cyclodextrin D-12 glucose bound γ-cyclodextrin D-13 α-cyclodextrin with two glucose molecules bonded D-14 β-cyclodextrin with two glucose molecules bonded D-15 Gamma-cyclodextrin with two glucose molecules bonded D-16 glucose three molecules Α-cyclodextrin D-17 bound to β-cyclodextrin with three molecules of glucose D-18 γ-cyclodextrin bound to three molecules of glucose

Regarding the structure of these branched cyclodextrins, HPLC, NMR, TLC (thin layer chromatography), INEPT method (Insensitive nuclei enhance)
Various methods such as d bypolarization transfer have been studied, but they have not yet been determined even with the current technology, and are in the stage of estimation structure. However, the fact that each monosaccharide or disaccharide or the like is bound to cyclodextrin is that there is no error in the above measurement method. Therefore, in the present invention, when multiple molecules of monosaccharides and disaccharides are bonded to cyclodextrin, for example, as shown in the following figure, when they are individually bonded to each glucose of cyclodextrin, It includes both those linked linearly to one glucose.

[0100]

Embedded image

In these branched cyclodextrins,
Since the ring structure of the existing cyclodextrin is kept as it is, it shows the same inclusion function as the existing cyclodextrin, and the addition of highly water-soluble maltose or glucose dramatically increases the solubility in water. The feature is that it has improved.

[0102] The branched cyclodextrin used in the present invention can be obtained as a commercial product. For example, maltosyl cyclodextrin is commercially available as Isoelite (registered trademark) manufactured by Shimizu Minato Seika.

Next, the cyclodextrin polymer used in the present invention will be described.

The cyclodextrin polymer used in the present invention is preferably a polymer represented by the following general formula [VIII].

[0105]

Embedded image The cyclodextrin polymer used in the present invention can be produced by subjecting cyclodextrin to a cross-linking polymerization with, for example, epichlorohydrin.

The cyclodextrin polymer preferably has a water solubility, that is, a solubility in water of 20 g or more per 100 ml of water at 25 ° C., and for this purpose, the polymerization degree n ₂ in the general formula [VIII] is 3 to 3.
The water solubility of the cyclodextrin polymer itself and the effect of solubilizing the substance are higher as this value is smaller.

These cyclodextrin polymers are described, for example, in JP-A-61-97025 and German Patent No. 3,544,842.
It can be synthesized by a general method described in the specification and the like.

The cyclodextrin polymer may be used as an inclusion compound of the cyclodextrin polymer as described above.

Cyclophanes are cyclic compounds having a structure in which aromatic rings are linked by various bonds, and many compounds are known. Examples of cyclophanes include these known compounds. it can.

Examples of the bond connecting the aromatic rings include a single bond,-(CR ₁ R ₂ ) _m -bond, -O (CR ₁ R ₂ ) _m O-bond, and -NH (CR ₁ R ₂ ) _m NH. -Bond,-(CR ₁ R ₂ ) _p
NR ₃ (CR ₄ R ₅ ) _q -bond,-(CR ₁ R ₂ ) _p N ⁺ R ₃ R ₄
(CR ₅ R ₆ ) _q -bond,-(CR ₁ R ₂ ) _p S ⁺ R ₃ (CR ₄
R ₅ ) _q -bond, -CO ₂ -bond, -CONR-bond (where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and a hydrogen atom Or an alkyl group having 1 to 3 carbon atoms, and m, p and q may be the same or different, and represent an integer of 1 to 4).

As the compound, for example, the following formula:

[0112]

Embedded image The following formula represented by paracyclophanes, tri-o-tymotide, and cycloriveratrilene represented by

[0113]

Embedded image The following formula represented by orthocyclophanes, metacyclophphane, calixarene, resorcinol-aldehyde cyclic oligomers represented by

[0114]

Embedded image Metacyclophanes represented by

[0115]

Embedded image Para-substituted phenolic acyclic oligomers represented by

The neutral polyligand includes crown compounds, cryptands, cyclic polyamines and their non-cyclic analogs. The compound is known to effectively incorporate metal ions, but can also effectively incorporate cationic organic molecules.

Other clathrate compounds include urea, thiourea, deoxycholic acid, dinitrodiphenyl, hydroquinone, o-trithymotide, oxyflavan, dicyanamine nickel, dioxytriphenylmethane, triphenylmethane, methylnaphthalene, spirochroman, Perhydrotriphenylene, viscous mineral, graphite, zeolite (faujasite, chabazite, mordenite, levynite, montmorillonite, halosite, etc.), cellulose, amylose, protein and the like.

These clathrates may be added as a simple substance. However, the solubility of the clathrate itself or the clathrate containing the molecule into the solvent and the compatibility with other additives are improved. For this purpose, a polymer in which a substituent having an inclusion function is suspended as a pendant substituent on the polymer may be added together.

The polymer is described, for example, in JP-A-3-221501, JP-A-3-221502, JP-A-3-221503,
It can be easily obtained by using a method as disclosed in JP-A-3-221504 and JP-A-3-221505.

Among the above inclusion compounds, cyclic and non-cyclic D-glucans, cyclophanes, and non-cyclic cyclophan analogs are preferable. More specifically, cyclodextrin, calixarene, resorcinol-aldehyde cyclic oligomer, and para-substituted phenols acyclic oligomer are preferred.

The most preferred are cyclodextrin and its derivatives, among which β-cyclodextrin and its derivatives are more preferred.

The ratio of these clathrates to the photosensitive composition is preferably 0.01 to 10% by weight, and 0.1% to 5% by weight.
Is more preferred.

Further, a printout material for forming a visible image upon exposure can be added to the photosensitive composition of the present invention. Printout materials consist of a compound that generates an acid or a free radical upon exposure to light and an organic dye that changes its color by interacting with the generated acid or a free radical. As the compound, for example, JP-A-50-36209
O-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-53-36223, trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-53-36223,
JP-A 55-67772 discloses an ester compound or amide compound of o-naphthoquinonediazide-4-sulfonic acid chloride and a phenol or aniline having an electron-withdrawing substituent described in JP-A-55-6777. Examples thereof include halomethylvinyloxadiazole compounds and diazonium salts described in JP-A-57-148784 and the like. Organic dyes include, for example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) , Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Industries, Ltd.), Sudan Blue II (manufactured by BASF), Crystal Violet,
Malachite green, fuchsin, methyl violet,
Ethyl violet, methyl orange, brilliant green, congo red, eosin, rhodamine 66 and the like can be mentioned.

Further, in addition to the above-mentioned materials, a plasticizer, a surfactant, an organic acid,
Acid anhydrides and the like can be added.

Further, in order to improve the oil sensitivity of the photosensitive composition, for example, p-
tert-butylphenol formaldehyde resin, pn
Octylphenol formaldehyde resins or resins in which these resins are partially esterified with an o-quinonediazide compound can also be added.

A matting agent can be added to the photosensitive composition as needed.

The photosensitive layer of the present invention can be formed by applying a coating solution obtained by dissolving or dispersing a photosensitive composition comprising each of these components in a solvent on a support and drying the coating.

Solvents that can be used when dissolving the photosensitive composition include, for example, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, ethyl formate, propyl formate , Butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate,
Examples include ethyl butyrate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, diacetone alcohol, acetylacetone, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

As the coating method used for coating the photosensitive composition on the surface of the support, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, and the like can be used. Methods such as electrostatic air spray coating, roll coating, blade coating, and curtain coating are used. In this case the coating amount varies depending on the use, for example, preferably the coating amount of 0.05 to 5.0 g / m ² by dry weight, more preferably 0.8~1.8g / m ^2, in particular the 1.2~1.6g / m ² that Is preferred.

Further, in order to prevent the photosensitive layer from being scratched when the photosensitive lithographic printing plates are superimposed,
In order to prevent the elution of the aluminum component into the developer, on the back surface of the support, JP-A-50-151136, JP-A-57-151136
No. 63293, JP-A-60-73538, JP-A-61-67863
And a process of providing a protective layer described in JP-A-6-35174.

The photosensitive lithographic printing plate of the present invention can be made by exposing and developing by a usual method. For example, a transparent original image having a line image, a halftone image or the like is brought into close contact with a photosensitive surface and exposed, and then the photosensitive layer is removed using an appropriate developing solution to obtain a relief image.

Light sources suitable for exposure include mercury lamps, metal halide lamps, xenon lamps, chemical lamps,
And carbon arc lamps. Further, as the developer used for development, for example, sodium silicate, alkali metal silicate such as potassium silicate, sodium hydroxide,
An alkaline aqueous solution such as an aqueous solution of potassium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate and the like can be used. The concentration of the aqueous alkali solution at this time varies depending on the type of the photosensitive composition and the alkali, but is generally in the range of 0.1 to 10% by weight. Further, an organic solvent such as a surfactant or alcohol can be added to the aqueous alkali solution as needed.

[0133]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 << Preparation of Aluminum Plates 1 to 9 >> (1) Aluminum plate having a thickness of 0.24 mm (material 1050, temper H
16), the following pretreatment was performed as shown in Table 1. Alkali treatment (referred to as pretreatment A) An aluminum plate was immersed in a 1% aqueous sodium hydroxide solution kept at 50 ° C., subjected to a dissolution treatment so that the dissolution amount was 2 g / m ² , washed with water, and then washed with water. Was immersed for 10 seconds in a treatment solution having the same composition as the electrolyte used for the electrolytic surface roughening treatment and kept at 25 ° C. for neutralization, and then washed with water. Brush polishing (referred to as pre-treatment B) An aluminum plate was polished with a 15% by weight slurry of # 800 alumina and a cylindrical rotating nylon brush, and then 1% sodium hydroxide kept at 50 ° C. After being immersed in an aqueous solution and subjected to a dissolution treatment so that the dissolution amount becomes 5 g / m ² and washed with water, a treatment solution maintained at 25 ° C. having the same composition as the electrolyte solution used for the next electrolytic surface roughening treatment For 10 seconds to neutralize, and then washed with water. (2) Table 1 shows the quantity of electricity used for one electrolytic surface-roughening treatment of the obtained aluminum plate using an electrolytic solution having the electrolytic solution composition shown in Table 1 at the current density shown in Table 1. The electrolytic surface roughening treatment was performed the number of times shown in Table 1 with the indicated amount of electricity. At this time, the distance between the electrode and the surface of the aluminum plate was 10 mm.

After the electrolytic surface roughening treatment, it was immersed in a 1% aqueous solution of sodium hydroxide maintained at 50 ° C., and the amount of dissolution including the smut of the roughened surface was reduced to the amount shown in Table 1. Alkaline etching, and then kept at 25 ° C.
After immersion in a 10% aqueous sulfuric acid solution for 10 seconds for neutralization, the substrate was washed with water. (3) Next, anodizing was performed in a 20% sulfuric acid aqueous solution under a constant voltage condition of 20 V so that the amount of electricity became 150 C / dm ^2, and aluminum plates 1 to 9 were obtained.

[0136]

[Table 1] << Preparation of Supports 1 to 25 >> Using the aluminum plates 1 to 9 shown in Table 2, the treatment agent, concentration, and pH shown in Table 2 (pH
Was adjusted with NaOH. Table 2
The first treatment was carried out at the temperature and time shown in Table 2, and then the second treatment was carried out at the temperature and time shown in Table 2 using the treatment solution and the treatment liquid having the concentration shown in Table 2. Next, washing was performed as shown in Table 2 to prepare Supports 1 to 25.

The following supports 1 to 25 were obtained.
SiO 2 on the surface of the support by the method _TwoSi amount converted to F
The amount and Zr amount were measured. Table 2 shows the measurement results. <SiO_TwoOf F, F and Zr> by X-ray fluorescence measurement
I went.

Using a sample coated with a fixed amount of sodium silicate and a sample coated with a fixed amount of potassium zirconium fluoride, the relationship between the amount of Si, F, and Zr on the surface and the measured intensity in the fluorescent X-ray measurement was determined. To create a calibration curve. From the measured intensity of each support in the fluorescent X-ray measurement, the Si
The amount, F amount, and Zr amount were calculated.

[0139]

[Table 2]

<< Preparation of photosensitive lithographic printing plates 1 to 25 >> A coating solution of a photosensitive composition having the following composition was applied to the obtained support using a wire bar, dried at 80 ° C., and subjected to photosensitive lithographic printing. Got a version. At this time, the coating amount of the photosensitive composition coating solution,
The dry weight was adjusted to 1.6 g / m ² .

<Photosensitive Composition Coating Solution> 6.70 g of pyrogallol acetone resin (Mw: 3000) and novolak resin (the molar ratio of phenol / m-cresol / p-cresol is 10/54/36 and Mw is 4000) Condensate of naphthoquinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6 -(P-methoxystyryl) -s-triazine 0.15 g FC-430 (manufactured by Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.02 g methyl cellosolve 100 ml <residual film, plate cleaner resistance, halftone dot The difficulty of karami,
Evaluation of printing durability> A positive original film having a halftone dot and a fine line is adhered to each of the obtained photosensitive lithographic printing plates,
8mW using 4kW metal halide lamp as light source
/ Cm ² for 60 seconds. The exposed photosensitive lithographic printing plate is converted to a commercially available developer (S
DR-1, manufactured by Konica Corporation, diluted 6 times, development time 20
For 2 seconds at a developing temperature of 27 ° C.). The lithographic printing plate thus obtained was evaluated for residual film, plate cleaner resistance, halftone dot blemishes, and printing durability by the following methods. Table 3 shows the obtained results.

-Residual film The ultraviolet reflection intensity of the surface of the support after development was measured by Spectrophotome.
ter U-3210 (manufactured by Hitachi, Ltd.). The measured values (abs) at 280 nm and 500 nm were determined, and Δabs = [measured value at 280 nm] − [measured value at 500 nm] was calculated, and the obtained value (Δabs) was used as an index of the degree of residual film. The smaller this value is, the smaller the remaining film is. If this value is 0.05 or less, there is no problem.

Plate Cleaner Resistance The image was immersed in an ultraplate cleaner solution for 10 minutes, and the degree of whitening on the surface of the image was visually observed to evaluate good or bad.

-Difficulty of halftone dot coloration The obtained lithographic printing plate was used with a printing machine (D made by Mitsubishi Heavy Industries, Ltd.).
AIYA1F-1), and printing is performed using coated paper, dampening solution (etching liquid SG-51, Tokyo Ink Co., Ltd., concentration 1.5%), and ink (Hyplus M Moku, manufactured by Toyo Ink Mfg. Co., Ltd.). Then, the color of the printed matter in the 70% halftone dot portion was visually evaluated, and good or bad was judged.

Evaluation of Printing Durability The obtained lithographic printing plate was placed on a printing machine (D manufactured by Mitsubishi Heavy Industries, Ltd.).
AIYA1F-1), and printing was performed using coated paper, fountain solution (Tokyo Ink Co., Ltd. etch solution SG-51 concentration 1.5%), and ink (Toyo Ink Mfg. Co., Ltd., Hiplus M Red). Printing was performed until ink deposition failure appeared in the image area of the printed matter or ink adhered to the non-image area, and the number of printed sheets up to that time was obtained to evaluate the printing durability.

・ Sludge suitability in development (alkali resistance)
With respect to the obtained supports 1 to 25, a 5-fold concentrated developer was dropped on the support surface. Good and poor sludge suitability were evaluated based on the degree of bubble generation. Table 3 shows the obtained results.

[0147]

[Table 3]

[0148]

The present invention provides a support with high hydrophilicity,
Along with improving the stain on printing, the adhesiveness with the photosensitive layer is excellent, the printing durability is good, the occurrence of sludge in development is small, and the photosensitive lithographic printing plate using the support of the present invention is There is no residual film and no dye remaining during development and the plate cleaner resistance is excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C25D 11/04 C25D 11/04 Z 11/16 301 11/16 301 11/18 11/18 A G03F 7/00 503 G03F 7 / 00 503

Claims (6)

[Claims] 1. A lithographic printing plate support obtained by roughening an aluminum plate and subjecting the plate to anodization treatment, wherein the surface of the support has a silicon content of 10 mg / m ² or more and 100 mg / m ² or less in terms of SiO ₂ . A lithographic printing plate support characterized in that it has been treated so that the amount of fluorine is 0.01 mg / m ² or more and 15 mg / m ² or less, and the amount of zirconium is 5 mg / m ² or more and 50 mg / m ² or less. 2. A photosensitive lithographic printing plate comprising a support for a lithographic printing plate according to claim 1 and a photosensitive layer provided thereon. 3. An aluminum plate is roughened and anodized.
And then treated with an aqueous solution of a metal silicate,
Treatment with aqueous potassium zirconium fluoride solution
And the amount of silicon on the surface of the support is SiO _Two10mg / m in conversion
^TwoAbove, 100mg / m^TwoBelow, the amount of fluorine is 0.01 mg / m^TwoOver 15
mg / m^TwoHereinafter, the amount of zirconium is 5 mg / m^TwoMore than 50mg / m^Two
Treatment with metal silicate aqueous solution and
It is characterized by performing potassium zirconium fluoride aqueous solution treatment
The method for producing a lithographic printing plate support according to claim 1. 4. An aluminum plate is roughened and anodized.
And then treated with an aqueous solution of a metal silicate,
Treated with an aqueous solution of potassium zirconium fluoride, and then
In the method of treating with an acid or alkali aqueous solution,
The amount of silicon on the body surface is SiO _Two10mg / m in conversion^TwoMore than 100
mg / m^TwoBelow, the amount of fluorine is 0.01 mg / m^TwoMore than 15mg / m^TwoLess than
Below, the amount of zirconium is 5mg / m^TwoMore than 50mg / m^TwoBelow
As in metal silicate aqueous treatment, zirconium fluoride
Potassium aqueous solution treatment and acid or alkali aqueous solution treatment
Lithographic printing plate according to claim 1, wherein
Of manufacturing a support for a vehicle. 5. The method for producing a lithographic printing plate support according to claim 3, wherein a dissolution treatment with an alkali is performed immediately before the anodic oxidation treatment. 6. The method for producing a lithographic printing plate support according to claim 5, wherein the amount of surface dissolution in the dissolution treatment with an alkali immediately before anodic oxidation is 1.0 to 3.0 g / m ^2. .