JPH08258445A - Support for lithographic printing plate and manufacture thereof, and photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE: To provide a support for a lithographic printing plate with good printability in terms of a hydrophilic property, water retentivity, and adhesion to a photosensitive layer, the manufacturing method of the support, and a photosensitive lithographic printing plate. CONSTITUTION: A support for a lithographic printing plate which has a smooth surface 3μm or less in Rmax and grain structure in which the opening diameter of micropores is 8nm or more and the depth is 800nm or more. A manufacturing method for the support in which the surface of an aluminum plate, after being roughened, is subjected to chemical treatment to dissolve a sharp part of the roughened surface for smoothing so that Rz/Ra is 95% or less in comparison with that before the treatment. A photosensitive lithographic printing plate in which a photosensitive layer is formed on the support.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a support for a lithographic printing plate, a method for producing the same, and a photosensitive lithographic printing plate. Particularly, from the viewpoint of printability, hydrophilicity, water retention and adhesiveness with a photosensitive layer are provided. And a method for producing the same, and a photosensitive lithographic printing plate.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a support used for a photosensitive lithographic printing plate is required to have excellent hydrophilicity, water retention, adhesiveness to a photosensitive layer, etc. from the viewpoint of printability. Therefore, a support obtained by hydrophilically treating an aluminum plate that has been roughened and anodized is usually used.

[0003]

PRIOR ART AND OBJECT OF THE INVENTION US Pat. No. 3,861,9
No. 17 defines the depth of rough surfaces, German Patent No. 1,81
No. 3,443 defines the height difference of a rough surface and is disclosed in Japanese Patent Laid-Open No. 55-1.
32294 defines the average depth, U.S. Pat. No. 1,412,768 anodizes in sulfuric acid at high current density, U.S. Pat. No. 3,511,661 anodizes in phosphoric acid. Japanese Patent Application Laid-Open No. 3-253596 discloses anodizing method after the treatment.

According to the research conducted by the present inventors, a large amount of water retention by roughening the grain surface is effective for tone reproduction and easy printing at the time of printing. It was also found that in a grain structure having sharp edges, ink particles are caught and the photosensitive layer does not come off easily during development, which causes stains.

Therefore, in relation to claims 1 to 4, an object of the present invention is to provide a support for a lithographic printing plate which is less likely to cause stains such as stop stains, has no residual film, and has water squeezed during printing. A method for producing the same and a photosensitive lithographic printing plate are provided.

On the other hand, the lithographic printing method is a printing method utilizing the fact that water and oil are essentially immiscible, and the printing plate surface receives a non-image area which receives water and repels ink, and water. An image portion that repels and receives the ink is formed, water and ink are supplied from the printing machine, and only the ink received in the image portion is transferred to the paper. A printing machine generally uses an offset printing method in which the ink received in the image area on the printing plate surface is once transferred to a rubber blanket and then transferred to paper. Normal,
As the number of printed sheets increases, the non-image area on the blanket also becomes soiled with ink, but if the degree of soiling is large, it becomes difficult to wash, and if the stain becomes remarkable, the non-image area on the paper surface becomes soiled. It becomes a problem of coming.

Conventionally, a support used for a photosensitive lithographic printing plate is required to have excellent hydrophilicity, water retention and adhesiveness with a photosensitive layer from the viewpoint of printability, and from such a viewpoint, a normal surface is required. An aluminum plate that has been subjected to a roughening treatment called graining is used. The surface roughening treatment is performed by mechanical surface roughening such as ball polishing, brush polishing, blast polishing, buff polishing, honing polishing, etc., and electrolytic treatment of the surface of the support by alternating current or direct current in an acidic electrolytic solution such as hydrochloric acid or nitric acid. There are known electrochemical roughening methods and the like. The aluminum plate that has been grained by such a method is relatively soft and easily abraded as it is, so an oxide film is formed by anodizing the aluminum plate. The surface of the aluminum plate thus treated is hard and has excellent wear resistance.

However, even under the various printing conditions, the aluminum plate which has been subjected to such a treatment stains the non-image area,
It is insufficient to satisfy the printing durability. In order to solve such a problem, in order to improve the stain on the non-image area, a hydrophilic treatment is performed after the anodizing treatment. JP-A-56-21126 discloses a method of forming an undercoat layer comprising a hydrophilic resin and a water-soluble salt, and JP-A-64-14090 discloses a method of providing an undercoat layer comprising a carboxylate.
No. 130391, a method of providing a hydrophilic layer comprising at least one selected from inorganic hydrochloric acid and organic hydrochloric acid of a compound having at least one amino group and at least one group selected from a carboxyl group and a sulfo group, Japanese Patent Laid-Open No. 63-165183 proposes a method of providing a hydrophilic layer containing at least one amino group and a phosphonic group or a salt of a phosphonic group, but the printing durability is deteriorated only by subjecting these to hydrophilic treatment. It was not enough to improve the stain resistance. In addition, after the printing machine was stopped for a while at the time of printing, such as during examinations and breaks, fine dot-like stains that occurred when printing was resumed were not improved. Further, regarding the rough surface shape, in US Pat. No. 4,301,229, the cumulative frequency distribution of the pit diameter and the center line average roughness are defined, and in US Pat. No. 3,861,917, the depth of the rough surface is defined, Canadian Patent No. 955,449 defines the height and diameter of the rough surface peaks, German Patent No. 1,813,443 defines the height difference of the rough surfaces, and JP-A-55-132294 defines the average depth. JP-A-5-24376 proposes that the pit diameter and the maximum depth in the direction perpendicular to the diameter be specified, but even with these shapes, printing durability and stain resistance of non-image areas, especially printing restart It was not sufficient for minute spot-like stains. In addition, special fair 2
No. 12752 proposes a method of electrolytically roughening in a nitric acid-based electrolytic solution and then performing alkali etching. However, with this alone, the non-image area is less likely to become dirty and the printing durability is good. The stain resistance was insufficient.

In view of the above, the object of the present invention is to provide a planographic printing plate excellent in stain resistance of the non-image area and printing durability, excellent in stain resistance of the blanket, and excellent in tone reproduction. It is to provide a method for manufacturing a printing plate support.

[0010]

OBJECTS OF THE INVENTION A common object of the present invention is to provide a lithographic printing plate support having good hydrophilicity, water retention and adhesiveness to a photosensitive layer from the viewpoint of printability, a method for producing the same, and a photosensitive lithographic printing plate. Is to provide.

[0011]

SUMMARY OF THE INVENTION The above object of the present invention is to roughen the surface of an aluminum plate and then chemically treat the surface of the aluminum plate to melt and smooth sharp parts of the roughened surface to obtain Rz /
A method for producing a lithographic printing plate support, characterized in that Ra is 95% or less compared to that before treatment, Rmax has a smooth surface of 3 μm or less, and the opening diameter of the micropores is 8 nm or more and the depth is Has a grain structure of 800 nm or more, and the surface of the lithographic printing plate support and aluminum plate is roughened, and then chemically treated to dissolve and smooth the sharpened portion of the roughened surface. The photosensitive lithographic printing plate is characterized by comprising a photosensitive layer on a support whose Rz / Ra is 95% or less compared to that before treatment, and has a smooth surface with Rmax of 3 μm or less. ,
Moreover, the opening diameter of the micropore is 8 nm or more and the depth is 80.
A photosensitive lithographic printing plate comprising a support having a grain structure of 0 nm or more and a photosensitive layer provided on the support, a roughened, anodized aluminum plate,
The roughening is performed a) electrochemically in a nitric acid-based electrolytic solution to a diameter of 8
Pits of 0.00 to 2000 nm are formed, and b) chemical etching is performed in an alkaline aqueous solution so that the dissolution amount of aluminum is 4
To 6 g / m ² , and c) a desmut treatment with an acid, a method for producing a lithographic printing plate support, and a roughened and anodized aluminum plate, Roughening a) electrochemically produces pits having a diameter of 7 to 25 μm in a hydrochloric acid-based electrolytic solution, and b) electrochemically produces pits having a diameter of 600 to 1000 nm in a nitric acid-based electrolytic solution, and c). A method for producing a lithographic printing plate support, which comprises chemically etching in an alkaline aqueous solution so that the amount of aluminum dissolved is 3 to 5 g / m ² and d) desmutting treatment, hydrochloric acid-based After producing pits electrochemically in an electrolytic solution, the method for producing a lithographic printing plate support as described above, characterized by comprising a step of chemically etching with an acid or alkali aqueous solution, roughening ,anodization In the treated aluminum plate, the roughening is performed a) mechanically with a length of 30 to 50 μm.
m, width of 5 to 15 μm, center interval 50 to 200 μm
And b) electrochemically in a hydrochloric acid-based electrolytic solution with a diameter of 7
.About.25 .mu.m pits are generated, c) electrochemically pits having a diameter of 600 to 1000 nm are generated in a nitric acid-based electrolytic solution, and d) chemical etching is performed in an alkaline aqueous solution so that the amount of aluminum dissolved is 3 to 5 g / m. Do so as to be ² ,
e) A method for producing a lithographic printing plate support, which comprises performing desmutting treatment with an acid, after mechanically forming recesses, and after electrochemically forming pits in a hydrochloric acid-based electrolytic solution, the acid Alternatively, it is achieved by each of the above-mentioned methods for producing a lithographic printing plate support, which comprises a step of chemically etching with an alkaline aqueous solution.

[0012]

According to the first to fourth aspects of the present invention, the sharp edges are melted and rounded to eliminate the catching of the ink particles, improve the removability of the photosensitive layer, and do not affect the water retention amount. Was created. By making Rmax small, eliminating the sticking of ink particles, improving the removability of the photosensitive layer, and making the micropores large and deep in order to supplement the printing performance by the water retention amount, it is difficult to get out once the dampening water enters It has a grain structure, which improves the ease of printing because the water is squeezed during printing and the tone reproduction.

Further, according to claims 5 to 9 of the present invention, there is provided a photosensitive lithographic printing plate which is compatible with stain resistance of a non-image area and printing durability, and is excellent in stain resistance of a blanket and tone reproducibility. I was able to provide it.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. First, claims 1 to 4 will be described. The aluminum support used in the present invention includes a support made of pure aluminum and an aluminum alloy. Various aluminum alloys can be used, such as silicon, copper, manganese, magnesium, chromium, zinc, lead,
An alloy of a metal such as bismuth, nickel, titanium, sodium and iron and aluminum is used.

The aluminum support is preferably subjected to a degreasing treatment in order to remove rolling oil on the aluminum surface prior to roughening. As degreasing treatment, trichlene,
A degreasing treatment using a solvent such as thinner or an emulsion degreasing treatment using an emulsion such as kerosene and 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.

As a graining treatment method carried out for improving the adhesion to the photosensitive layer and improving the water retention,
There are a so-called mechanical surface-roughening method for mechanically roughening the surface and a so-called electrochemical surface-roughening method for electrochemically roughening the surface. Examples of the mechanical surface roughening method include ball polishing, brush polishing, blast polishing, buff polishing and the like. The electrochemical surface roughening method includes, for example, a method of electrolytically treating the support with an alternating current or a direct current in an electrolytic solution containing hydrochloric acid, nitric acid, or the like. One of these
One or a combination of two or more methods makes it possible to grain the support. Regarding the electrolytic surface roughening treatment, for example, Japanese Examined Patent Publication (Kokoku) No. 48-28123, British Patent No. 896563, and Japanese Patent Laid-Open No. 53-67507.
These methods can be used in the present invention.

In the case of the invention described in claim 1, the voltage applied in the electrolytic surface roughening is preferably 1 to 50 V,
2-30 volts is more preferred. Current density is 10-1
50 A / dm ² is preferable, and 20-100 A / dm ² is more preferable. The amount of electricity is 100 to 20000 c / dm
^2, preferably 100~10000c / dm ^2, more preferably 200~5000c / dm ^2. The temperature is
10-50 degreeC is preferable and 15-45 degreeC is more preferable. The nitric acid concentration is preferably 0.01 to 5% by weight. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, etc. can be added to the electrolytic solution.

At this time, in the case of the invention described in claim 2, Rm
More preferably, the applied voltage is 1 to 20 V and the current density is 10 to 70 A / dm in order to set ax to 3 μm or more.
² , the amount of electricity is 100 to 3000 c / dm ² , and the temperature is 10
˜30 ° C., concentration 0.01˜2.0 wt%.

Next, as described in the invention of claim 1, it is preferable to perform the following chemical treatment so that Rz / Ra becomes 95% or less. It is preferable that the surface of the aluminum plate is chemically treated with an acid or alkali aqueous solution for the purpose of smoothing and homogenizing the grained aluminum plate. Specific examples of the acid or alkaline aqueous solution include acids such as hydrofluoric acid, zirconic acid fluoride, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid, and sodium hydroxide, potassium hydroxide, sodium triphosphate, sodium aluminate, silicic acid. An alkaline aqueous solution such as sodium or sodium carbonate is used. These acid or alkaline aqueous solutions may be used alone or in combination of two or more. The chemical treatment is carried out using a 0.05 to 40% by weight aqueous solution of these acids or alkalis at a liquid temperature of 40 to 100 ° C for 5 to 3
Process for 00 seconds.

Particularly preferred are aqueous sodium hydroxide and sulfuric acid solutions, having a concentration of 5 to 30% by weight and a temperature of 70 to 10
The invention of claim 1 is satisfied when the treatment is carried out under the condition of 0 ° C.

Since smut is generated on the surface of the support obtained by the roughening treatment and the chemical treatment, a treatment such as washing with water or alkali etching is appropriately performed to remove the smut. Is generally preferred. As such processing, for example, Japanese Patent Publication No. 48-2812
Treatment methods such as the alkali etching method described in JP-A No. 3 and the sulfuric acid desmutting method described in JP-A No. 53-12739 are mentioned.

Further, an anodizing treatment is carried out in order to improve water retention and wear resistance of the surface. As the electrolyte used for anodizing the aluminum plate, any electrolyte that forms a porous oxide film can be used, and generally sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but generally, the concentration of the electrolyte is 1 to 80 wt% solution,
The liquid temperature is appropriately 1 to 70 ° C., the current density is 1 to 60 A / dm ² , the voltage is 1 to 100 V, and the electrolysis time is 10 seconds to 5 minutes. In the particularly preferred sulfuric acid method, the treatment is usually performed with a direct current, but an alternating current can be used. The sulfuric acid is used at a concentration of 5 to 30%, and is electrolyzed at a temperature range of 20 to 60 ° C. for 5 to 250 seconds. The electrolytic solution preferably contains aluminum ions. Further, the current density at this time is preferably 1 to 20 A / dm ² .

At this time, in the case of the invention described in claim 2, it is more preferable to use sulfuric acid, the concentration is 5 to 50% by weight, the temperature is 30 to 60 ° C., the current density is 15 to 60 A / dm ² ,
The voltage is 20 to 100V.

Next, claims 5 to 9 will be described. The aluminum support used in the present invention includes a support made of pure aluminum and an aluminum alloy. Various types of aluminum alloy can be used,
For example, an alloy of aluminum and a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium and iron is used.

The aluminum support is preferably subjected to a degreasing treatment in order to remove rolling oil on the aluminum surface prior to roughening. As degreasing treatment, trichlene,
A degreasing treatment using a solvent such as thinner, an emulsion degreasing treatment using an emulsion such as kerosene or triethanol, and the like are used. Further, 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, therefore, an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof is used. It is preferable to perform immersion and desmut treatment.

In the present invention, a roughening process is next performed. Mechanically, a concave portion having a length of 30 to 50 μm and a width of 5 to 15 μm is 100
Generate at intervals of ˜200 μm. If these recesses are too small, the dampening water will not easily evaporate uniformly, and if they are too large, the dampening water will not spread uniformly. Similarly, if the intervals are sparse, it is difficult for the dampening water to evaporate uniformly, and if it is too dense, it is difficult for the dampening water to spread uniformly.

The mechanical surface roughening method is not particularly limited, but brush polishing and honing polishing are preferable. In brush polishing, for example, the wire diameter is 5 to 15 μm, and the interval is 100 to 200 μm.
The roll brush with the bristles of No. 2 is rotated and pressed against the surface of the support to roughen the surface. In the honing polishing, for example, Al ₂ O ₃ particles having a particle size of 5 to 15 μm are uniformly dispersed in water, pressure is applied from a nozzle to eject the particles, and the particles are collided with the support surface from an oblique angle to roughen the surface. In addition, particles having a length of 30 to 50 μm and a width of 5 to 15 μm were previously prepared as 100
It is also possible to carry out roughening by laminating a sheet applied so as to have a spacing of ˜200 μm on the surface of the support and applying pressure to transfer the rough surface pattern.

The mechanically roughened support is then electrochemically roughened, but prior to this, the abrasive, aluminum debris, which has eroded into the surface of the mechanically roughened support. In order to remove the above, it is preferable to perform a chemical etching treatment by immersing in an aqueous solution of acid or alkali. 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,
Includes potassium hydroxide and the like. Among these, it is preferable to use an aqueous solution of alkali. 40 to 100 using 0.05 to 40% by weight aqueous solution of these acids or alkalis
The treatment is performed at a liquid temperature of ° C for 5 to 300 seconds.

When the above is immersed in an aqueous alkali solution, smut is formed on the surface of the support. In this case, therefore, acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof is used. It is preferable to carry out an immersion desmut treatment.

The voltage applied in the electrochemical surface roughening using a hydrochloric acid-based electrolytic solution is preferably 1 to 50 V, more preferably 2 to 30 V. Current density is 10
~ 200 A / dm ² is preferred, 50-150 A / dm
² is more preferable. Electricity is 100 to 20000c /
dm ² is preferable, and 100 to 10000 c / dm ² is more preferable. The temperature is preferably 10 to 50 ° C. and 15 to 50 ° C.
45 ° C is more preferable. The hydrochloric acid concentration is preferably 0.1 to 5% by weight. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, etc. can be added to the electrolytic solution.

By combining these conditions, a diameter of 7 to 25 μm is electrochemically measured in a hydrochloric acid-based electrolytic solution.
Can generate pits. The voltage applied in the electrochemical roughening using a nitric acid-based electrolytic solution is preferably 1 to 50 V, more preferably 2 to 30 V. The current density is preferably 10 to 150 A / dm ² , and 20 to 10 A / dm ^2.
0 A / dm ² is more preferable. The amount of electricity is 100 to 10
000 c / dm ² , preferably 200 to 5000
c / dm ² , more preferably 500 to 3000 c / dm
It is ² . The temperature is preferably 10 to 50 ° C., and 15 to 4
5 ° C is more preferable. The nitric acid concentration is preferably 0.1 to 2% by weight. The electrolytic solution may contain nitrates, chlorides, and
Amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added.

By combining these conditions, a diameter of 800 to 20 is electrochemically applied in a nitric acid-based electrolytic solution.
00 nm pits and 600-1000 nm diameter pits can be generated.

When the surface is electrochemically roughened in a hydrochloric acid-based electrolytic solution and then electrochemically roughened in a nitric acid-based electrolytic solution, a chemical etching treatment is performed during which it is immersed in an acid or alkali aqueous solution. Is preferably performed. 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. 40 to 100 ° C. using 0.05 to 40% by weight aqueous solution of these acids or alkalis
At the liquid temperature of 5 to 300 seconds. When the above is immersed in an aqueous solution of alkali, smut is generated on the surface of the support. In this case, phosphoric acid, nitric acid,
Desmutting is preferably performed by immersing in an acid such as sulfuric acid or chromic acid, or a mixed acid thereof.

The electrochemically roughened support is then chemically etched in an aqueous alkaline solution. As the alkaline aqueous solution used for the chemical etching, sodium hydroxide, potassium hydroxide, sodium triphosphate, potassium triphosphate, sodium aluminate, sodium metasilicate, sodium carbonate, etc. are used, and the amount is 5 to 40% by weight.
The treatment is performed with an aqueous solution at a liquid temperature of 20 to 80 ° C. for 1 to 60 seconds. By combining these conditions,
The amount of aluminum dissolved is 4 to 6 g / m ² , or 3 to 5
Chemical etching treatment is performed with an alkaline aqueous solution so as to obtain g / m ² . Since smut is formed on the surface of the support which has been chemically etched with an alkaline aqueous solution, it is desmutted by immersing it in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof. After the roughening process,
Anodizing treatment may be performed, followed by sealing treatment and hydrophilic treatment. The above-mentioned treatments can be applied to the anodizing treatment, the sealing treatment and the hydrophilic treatment.

Further, in order to prevent scratches on the photosensitive layer when the photosensitive lithographic printing plates are superposed, and to prevent the elution of the aluminum component into the developing solution at the time of development, JP-A-50-50
-151136, 57-63293, 60-7.
No. 3538, No. 61-67863, JP-A-6-351.
The treatment of providing a protective layer on the back surface of the support described in No. 74 can be performed. The length, width, depth, or pit diameter of the concave portion of the present invention may be 200 to 100 at a photographing magnification.
It can be measured using an electron micrograph taken at 00 times.

The support preferably used in the present invention may be subjected to a sealing treatment after the anodizing treatment. Examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment. Further, the support preferably used in the present invention may be provided with a hydrophilic undercoat layer. Examples of the hydrophilic undercoat layer include alkali metal silicates described in US Pat. No. 3,181,461 and US Pat. No. 1,860,426.
Hydrophilic cellulose described in JP-A-60-14
9491 and 63-165183, amino acids and salts thereof, hydroxyl group-containing amines and salts thereof described in JP-A-60-232998, JP-A-6-62.
Phosphates described in JP-A-2-19494, JP-A-59-1
Examples thereof include polymer compounds containing a monomer unit having a sulfo group described in JP-A No. 01651.

Next, a photosensitive layer containing the photosensitive composition is applied onto the surface-treated support to obtain a photosensitive lithographic printing plate preferably used in the present invention. The photosensitive substance used in this photosensitive layer is not particularly limited, and various substances usually used in photosensitive lithographic printing plates can be used. Hereinafter, this point will be described.

(Photosensitive layer) The photosensitive lithographic printing plate of the present invention can be obtained by coating the surface-treated support of the present invention with a photosensitive layer of a photosensitive composition. The photosensitive substance used in this photosensitive layer is not particularly limited as long as it is an o-quinonediazide compound when a positive photosensitive lithographic printing plate is to be obtained, and usually, for example, various kinds of compounds such as those described below are used. Stuff used.

(Photosensitive composition containing o-quinonediazide compound) In the photosensitive composition containing an o-quinonediazide compound used, an o-quinonediazide compound and an alkali-soluble resin are used in combination. Examples of the o-quinonediazide compound include ester compounds of o-naphthoquinonediazidesulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the above-mentioned phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, and dihydric compounds such as catechol, resorcinol and hydroquinone. Examples include trihydric phenols such as phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred of these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin. To be OH of phenols of the o-naphthoquinonediazide compound
The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the group (reaction rate with respect to one OH group) is preferably 15 to 80%, and more preferably 20 to 45%.

Further, as the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, 1, 2
-Benzoquinone diazide sulfonate, 1,2-
Known 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, etc.
Quinone diazide compounds, more specifically J. Kosar "Light-Sensitive Systems" (Light-Sensitive System)
ems) pp. 339-352 (1965), John.
Willie & Sons (John Willey &
Sons, Inc. (New York) and W. S. De Forest, "Photoresist", Volume 50 (1975), McGraw H
ill) (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-M-β-
Naphthyl) -sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1-
(1,2-naphthoquinonediazide-5-sulfonyl)-
3,5-Dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfone-4'-hydroxydiphenyl-
4'-azo-β-naphthol-ester, N, N-di-
(1,2-naphthoquinonediazide-5-sulfonyl)-
Aniline, 2 '-(1,2-naphthoquinonediazide-5
-Sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-5-sulfone-
2,4-dihydroxybenzophenone ester, 1,2
-Naphthoquinonodiazide-5-sulfonic acid-2,3,4
-Trihydroxybenzophenone ester, a condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4'-diaminobenzophenone,
Condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4′-dihydroxy-1,1′-diphenylsulfone, 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride Examples thereof include a 1,2-quinonediazide compound such as a condensate of 1 mol of purpurogallin and 1,2-naphthoquinonediazide-5- (N-dihydroabietyl) -sulfonamide. In addition, Japanese Examined Patent Publications No. 37-1953 and 37-3627
Nos. 37-13109, 40-26126, 40-3801, 45-5604, 45-27.
No. 345, No. 51-13013, JP-A-48-965.
The 1,2-quinonediazide compounds described in JP-A No. 75, 48-63802 and 48-63803 can also be mentioned.

Of the above o-quinonediazide compounds,
An o-quinone diazide ester compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable. As the o-quinonediazide compound used in the present invention, the above compounds may be used alone or in combination of two or more kinds. The proportion of the o-quinonediazide compound in the photosensitive composition is preferably 6 to 60% by weight, and particularly preferably 10 to 50% by weight.

(Diazo Compound) On the other hand, when a negative photosensitive lithographic printing plate is to be obtained, a known photosensitive composition containing a diazo compound may be used. The diazo compound in this photosensitive composition is, for example, preferably a diazo resin represented by a condensation product of an aromatic diazonium salt and formaldehyde or acetaldehyde. Particularly preferably, p
A salt of a condensate of diazophenylamine with formaldehyde or acetaldehyde, for example a diazo resin which is the reaction product of a hexafluoroborophosphate, tetrafluoroborate, perchlorate or periodate with said condensate. Examples thereof include inorganic salts and organic salts of diazo resins, which are reaction products of the condensates and sulfonic acids as described in US Pat. No. 3,300,309. Furthermore, diazo resins are preferably used with binders. As the binder, various polymer compounds can be used, but preferably JP-A-54-986.
No. 13, a monomer having an aromatic hydroxyl group, for example, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p. -Hydroxystyrene, o-, m-, or p-hydroxyphenylmethacrylate copolymers with other monomers, US Pat.
123,276, polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units, natural resins such as shellac and rosin, polyvinyl alcohol, US Pat. No. 3,751, No. 257, linear polyurethane resins, polyvinyl alcohol phthalated resins, epoxy resins condensed from bisphenol A and epichlorohydrin, and cellulose derivatives such as cellulose acetate and cellulose acetate phthalate.

In addition to the above, the following photosensitive composition may be used. 1) Photocrosslinking-type photosensitive resin composition The photosensitive component in the photocrosslinking-type photosensitive resin composition is composed of a photosensitive resin having an unsaturated double bond in the molecule. For example, US Pat. No. 3,030, No. 208, 3,43
Nos. 5,237, 3,622,320 and the like have a photosensitive group in the polymer main chain.

[0047]

Embedded image And a 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, which comprises a monomer having a double bond or a monomer having a double bond. A typical example of such a composition comprising a polymer binder is disclosed in, for example, US Pat. No. 2,760,8.
63 and 2,791,504, JP-A-59-42684, JP-B-6-76444, JP-A-5-85562 and the like.

As an example, a composition containing methylmethacrylate, a composition containing methylmethacrylate and polymethylmethacrylate, a composition containing methylmethacrylate, polymethylmethacrylate and polyethyleneglycolmethacrylate monomers, methylmethacrylate, an alkyd resin. A photopolymerizable composition such as a composition containing a polyethylene glycol dimethacrylate monomer is used.
This photopolymerization type photosensitive resin composition includes a photopolymerization initiator usually known in this technical field (for example, benzoin derivative such as benzoin methyl ether, benzophenone derivative such as benzophenone, thioxanthone derivative, anthraquinone derivative, acridone derivative, etc. ) Is added.

(Alkali-Soluble Resin) As the alkali-soluble resin, a novolac resin, a vinyl polymer having a phenolic hydroxyl group, a condensation of a polyhydric phenol with an aldehyde or a ketone described in JP-A-55-57841. Resin etc. are mentioned.

Examples of the novolac resin used in the present invention include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-57841.
Phenol-cresol-formaldehyde copolymer resin as described in JP-A-55-127
Examples thereof include copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in Japanese Patent No. 553.

The novolak resin preferably has a number average molecular weight Mn of 3.00 × (polystyrene standard).
10 ^{2 to} 7.50 × 10 ³ , and the 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 3.0.
It is 0 × 10 ^{3 to} 2.00 × 10 ⁴ . The above novolak resins may be used alone or in combination of two or more.

The ratio of the novolak resin in the photosensitive composition is preferably 5 to 95% by weight. Further, the vinyl copolymer having a phenolic hydroxyl group preferably used in the present invention is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and has the following general formula [I]
Polymers containing at least one structural unit of [V] are preferred.

[0054]

Embedded image

[In the formula, 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, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents
Represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ]

As the polymer used in the present invention, those having a copolymer type structure are preferable, and the above-mentioned general formula [I] is used.
~ Examples of the monomer unit that can be used in combination with the structural unit represented by the general formula [V] include ethylenically unsaturated offylenes such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene and α-. Styrenes such as methylstyrene, p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, and unsaturated aliphatic dicarboxylic acids such as itacone, maleic acid and maleic anhydride,
For example, methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, Α such as ethyl methacrylate
-Esters of methylene aliphatic monocarboxylic acid, for example, nitriles such as acrylonitrile, methacrylonitrile, etc., amides such as acrylamide, such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc. Anilides such as vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl benzoate and vinyl acetate,
For example, methyl vinyl ether, ethyl vinyl ether,
Isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1 -Dimethoxycarbonylethylene, ethylene derivatives such as 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N
There are N-vinyl type monomers such as -vinylcarbazole, N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles exhibit excellent performance for the purpose of the present invention and are preferred. These monomers may be bound to the polymer used in the present invention in either a block or random state.

The proportion of the vinyl polymer used in the present invention in the photosensitive composition is preferably 0.5 to 70% by weight. As the vinyl polymer, the above polymers may be used alone or in combination of two or more kinds.
It can also be used in combination with other polymer compounds.

(Organic Acid / Inorganic Acid / Acid Anhydride) The photosensitive composition of the present invention may contain an organic acid / inorganic acid / anhydride. Examples of the acid used in the present invention include organic acids described in JP-A No. 60-88942 and Japanese Patent Application No. 63-293107, and "Chemical Handbook New Edition" edited by The Chemical Society of Japan, No. 92-158. The inorganic acids described on the page can be mentioned.
Examples of organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzensulfonic acid,
Sulfonic acids such as m-benzenedisulfonic acid, sulfinic acids such as p-toluenesulfinic acid, benzylsulfinic acid and methanesulfinic acid, phosphonic acids such as phenylphosphonic acid, methylphosphonic acid and chloromethylphosphonic acid,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid and heptanoic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, o-, m-, p -Hydroxybenzoic acid,
o-, m-, p-methoxybenzoic acid, o-, m-, p-
Aromatic monocarboxylic acids such as methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid and 3,5-dimethylbenzoic acid can be mentioned. Also,
Saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, itaconic acid, malic acid, tetrahydro Phthalic acid, 1,1-cyclobutanedicarboxylic acid,
1,1-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

Among the above organic acids, more preferable one is p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Examples include sulfonic acid such as mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzensulfonic acid, and m-benzenedisulfonic acid, cis-1,2-cyclohexanedicarboxylic acid, and syringic acid. Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, silicic acid, phosphoric acid and the like, more preferably sulfuric acid and phosphoric acid.

When an acid anhydride is used, the type of acid anhydride is also arbitrary, and those derived from aliphatic / aromatic monocarboxylic acids such as acetic anhydride, propionic anhydride, benzoic anhydride, and succinic anhydride. , Maleic anhydride, glutaric anhydride, phthalic anhydride, and the like, and the like derived from aliphatic / aromatic dicarboxylic acids. Preferred acid anhydrides are glutaric anhydride and phthalic anhydride. These compounds may be used alone or in combination of two or more. The content of these acids is generally 0.05 to 5% by weight, and preferably 0.1 to 3% by weight, based on the total solid content of the entire photosensitive composition.

(Surfactant) The photosensitive composition of the present invention may contain a surfactant. As the surfactant, an amphoteric surfactant, an anionic surfactant, a cationic surfactant,
Nonionic surfactants, fluorine-based surfactants and the like can be mentioned.

Examples of the amphoteric surfactant include lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl, imidazolinium betaine and the like.
As the anionic surfactant, a fatty acid salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, an alkylsulfosuccinate,
Examples thereof include alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate ester salt, polyoxyethylene alkyl allyl sulfate ester salt, naphthalene sulfonic acid formalin condensate, and polyoxyethylene alkyl phosphate ester. Examples of cationic surfactants include alkylamine salts, quaternary ammonium salts, and alkyl betaines.

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene. There are sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide and the like.

Examples of the fluorinated surfactants include copolymers of acrylates or methacrylates containing a fluoroaliphatic group and (polyoxyalkylene) acrylates or (polyoxyalkylene) methacrylates. These compounds may be used alone or in combination of two or more. Particularly preferably FC-430
(Sumitomo 3M Co., Ltd.) Fluorine-based polyethylene glycol # -2000 (Kanto Chemical Co., Inc.). The proportion in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

(Printout Material) A printout material capable of forming a visible image by exposure can be added to the photosensitive composition. The printout material comprises an organic dye which changes its color tone by interacting with a compound which forms an acid or a free radical upon exposure. Examples of the compound which forms an acid or a free radical upon exposure include, for example, JP-A-50- O described in Japanese Patent No. 36209
-Naphthoquinonediazide-4-sulfonic acid halogenide,
An ester compound or amide compound of o-naphthoquinonediazide-4-sulfonic acid chloride and an electron-withdrawing substituent phenol or aniline acid described in JP-A-53-36223, JP-A-55-
Examples thereof include halomethylvinyloxadiazole compounds and diazonium salts described in JP-A 77742, JP-A-57-148784 and the like.

(Compound which produces an acid or a free radical upon exposure to light) As a compound which can be used in the photosensitive composition of the present invention to produce an acid or a free radical upon exposure, for example, a halomethyloxadiazole compound, A halomethyl-s-triazine compound or the like is used. The halomethyl oxadiazole compound is a compound having halomethyl group, preferably trichloromethyl group, in oxadiazoles.

These compounds are known, for example, Japanese Patent Publication Nos. 57-6096 and 61-51788,
Japanese Patent Publication No. 1-28369, JP-A-60-13853
No. 9, JP 60-177340, and JP 60-24.
It is described in Japanese Patent No. 1049. In addition, the halomethyl-s-triazine compound is a compound having one or more halomethyl groups, preferably a trichloromethyl group, in the s-triazine ring.

In the photosensitive composition of the present invention, the addition amount of the compound which forms an acid or a free radical upon exposure to light is 0.
01 to 10% by weight is preferable, and 0.1 is more preferable.
˜30 wt%, and particularly preferably 0.2 to 3 wt%. These compounds may be used alone or in combination of two or more.

(Dye) A dye may be further used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development.

As the dye, those which change color tone by reacting with free radical or acid can be preferably used.
Here, "the color tone changes" includes both a change from colorless to a color tone, and a change from a colored to a colorless or different color tone. Preferred dyes are those which form a salt with an acid to change the color tone. For example, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue #
603 (manufactured by Orient Chemical Industry Co., Ltd.), patent pure blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), crystal violet,
Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Pesic Fuchsin, Malachite Green, Oil Red, m
-Cresol purple, rhodamine B, auramine,
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes such as 4-p-diethylaminophenyliminaquinoquine and cyano-p-diethylaminophenylacetanilide are colored to colorless. Alternatively, it may be mentioned as an example of a color changing agent that changes to a different color tone.

On the other hand, examples of the discoloring agent that changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p. ′ -Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ′,
p ″ -tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p, Examples thereof include primary or secondary arylamine dyes represented by p ′, p ″ -triaminotriphenylmethane. The proportion of the above-mentioned discoloring agent in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.02 to
Used at 5% by weight. These compounds may be used alone or in combination of two or more. Particularly preferred dyes are Victoria Pure Blue BOH and Oil Blue # 6.
It is 03.

(Oil Sensitizer) An oil sensitizer for improving the oil sensitivity of the image area (for example, a half-esterified product of an alcohol of a styrene-maleic anhydride copolymer described in JP-A-55-527). , Pt-butylphenol-
Novolak resins such as formaldehyde resins, or partial esterification products of these with o-quinonediazide compounds, fluorine-based surfactants, p-hydroxystyrene 5
0% fatty acid ester, etc.) are preferably used. The amount of these additives added varies depending on the object of use and purpose, but is generally 0.01 to 30% by weight based on the total solid content.

(Inclusion Compound) The inclusion compound that can be used in the present invention is not particularly limited as long as it is a compound that can include water or an organic molecule, but it is soluble in the solvent used for preparing the composition. Organic compounds are preferred. Examples of such organic compounds include, for example, “Host Guest Chemistry” (Michio Hiraoka et al., Kodansha 1984).
Years, Tokyo) etc. and "Tetrahedron Report"
(No. 226 (1987) P5725A. Colle
t), "Chemical industry April issue" ((1991) P278 Shinkai et al.), "Chemical industry April issue ((1991) P288 Hiraoka et al.), and the like.

The inclusion compounds which can be preferably used in the present invention include, for example, cyclic D-glucans, cyclophanes, neutral polyligands, cyclic polyanions, cyclic polycations, cyclic peptides and SPHERANDS, CAVITAND
NDS) and their acyclic analogs. Among these, cyclic D-glucans and non-cyclic analogs thereof, cyclophanes, and neutral polyligands are more preferable.

Examples of the cyclic D-glucans and their non-cyclic analogs include compounds in which α-D-glucopyranose is linked by a glycolide bond. Examples of the compound include sugars such as starch, amylose, and amylopectone, which are composed of D-glucopyranose groups, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and D-glucopyranose having a polymerization degree of 9 Cyclodextrins such as the above cyclodextrin and SO ₃ C ₆ H ₄ CH ₂ C ₆ H ₄ SO
₃ groups, 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, NEt ₂ group, SC (NH ₂ ⁺ ) NH ₂ group, SH group,
SCH ₂ CH ₂ NH ₂ group, the following formula in which a substituent such as an imidazole group or an ethylenediamine group is introduced.

[0077]

Embedded image

Examples include modified D-glucans represented by: Further, the following general formula [VI] and general formula [VI
And a branched cyclodextrin, a cyclodextrin polymer, etc.

[0079]

[Chemical 4]

In the general formula [VI], R _{1 to} R ₃ are
They may be the same or different and each represents a hydrogen atom, an alkyl group or a substituted alkyl group. In particular, those in which R _{1 to} R ₃ are a hydrogen atom or a hydroxyethyl group or a hydroxypropyl group are preferable, and those in which the content of the substituted alkyl group in one molecule is 15% to 50% are more preferable. n ₂ represents a positive integer of 4 to 10.

[0081]

Embedded image

[0082] In the general formula [VII], R represents a hydrogen ^{_{atom, -R 2 -CO 2 H, -R}} 2 -SO 3 H, -R 2 -N
H ₂ or ^{_{-N- (R 3) 2 (R}} 2 represents a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms, ^{R 3} is linear or branched alkyl having 1 to 5 carbon atoms Represents a group.

An example of the production of cyclodextrin is "J
ounal of the American Che
"Mical Society" Vol. 71, pp. 354 1
949, "Cheimish Berichte", Volume 90, page 2561, 1949, Volume 90, volume 256
The first page is described in 1957, but is not limited to these.

The branched cyclodextrin used in the present invention is a known cyclodextrin in which a water-soluble substance such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine, or a water-soluble substance such as disaccharide is branched or added. And preferably,
Maltosyl cyclodextrin in which maltose is bound to cyclodextrin (the number of bound molecules in maltose may be 1, 2, 3 or the like) or glucosyl cyclodextrin in which glucose is bound to cyclodextrin (number of bound molecules in glucose Is 1 molecule, 2 molecules,
3 molecules or the like may be used).

Specific methods for synthesizing these branched cyclodextrins include, for example, Starch Chemistry, Vol. 33, No. 2, 1
Pp. 19-126 (1986), pp. 127-132 (1)
986), Starch Chemistry, Volume 30, No. 2, 231-23.
9 (1983) and the like, and can be synthesized by referring to these known methods. For example, maltosyl cyclodextrin uses cyclodextrin and maltose as raw materials and uses enzymes such as isoamylase and pullulanase. Then, it can be produced by a method of binding maltose to cyclodextrin. Glucosylcyclodextrin can be produced in the same manner. These clathrate compounds may be added as a simple substance, but in order to improve the solubility of the clathrate compound itself or the clathrate compound incorporating the molecule in the solvent and the compatibility with other additives, Polymers with pendant substituents attached to them as pendant substituents may also be added together.

Each of these components was dissolved in the following solvent,
By coating and drying the support surface according to the present invention,
By providing a photosensitive layer, the photosensitive lithographic printing plate of the present invention can be manufactured.

(Solvent) As a solvent which can be used when the photosensitive composition used in the present invention is dissolved, methanol,
Ethanol, n-propanol, i-propanol, n
-Aliphatic alcohols such as butanol, n-pentanol and hexanol, allyl alcohol, benzyl alcohol, anisole, phenetole, n-hexane, cyclohexane, heptane, hydrocarbons such as octane, nonane and decane, diacetone alcohol, 3 -Methoxy-1
-Butanol, 4-methoxy-1-butanol, 3-ethoxy-1-butanol, 3-methoxy-3-methyl-
1-butanol, 3-methoxy-3-ethyl-1-1-pentanol-4-ethoxy-1-pentanol, 5-methoxy-1-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, Methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-butanone, 4-hydroxy-2- Pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-
Pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol alkyl ethers and their acetates (MC, EC , Butyl cellosolve,
Phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, MC acetate, EC acetate), diethylene glycol monoalkyl ethers and their acetates (diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, Diethylene glycol monomethyl ether acetate, etc.), diethylene glycol dialkyl ethers (DMDG, DEDG, D
BDG, MEDG), triethylene glycol alkyl ethers (monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, etc.), propylene glycol alkyl ethers and their acetates (monomethyl ether, monoethyl ether, n-propyl ether) , Monobutyl ether, dimethyl ether, diethyl ether, monomethyl ether acetate, monoethyl ether acetate, etc.), dipropylene glycol alkyl ethers (monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether, diethyl ether), ethyl formate , Propyl formate,
Carboxylic esters such as butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, methyl lactate ,
Examples thereof include ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

(Coating Layer) In the photosensitive lithographic printing plate according to the present invention, a coating layer made of a water-insoluble organic solvent-soluble polymer compound capable of forming a film can be formed on the photosensitive layer.

On the surface of the photosensitive layer provided as described above, a mat layer is provided in order to shorten the vacuuming time in contact exposure using a vacuum baking frame and prevent baking blur. preferable. Specifically, JP-A-50-1258
No. 05, Japanese Patent Publication No. 57-6582, No. 61-28986.
The method of providing a mat layer as described in each of the publications, the method of heat-bonding a solid powder as described in JP-B-62-62337 and the like can be mentioned.

(Mat agent) The purpose of the matte layer is to improve the vacuum adhesion between the image film and the photosensitive lithographic printing plate during contact exposure, thereby shortening the vacuuming time, and further reducing the fine network during exposure due to poor adhesion. It is to prevent the dots from collapsing. As a coating method of the matte layer, there is disclosed in Japanese Patent Laid-Open No. 55-
No. 12974 includes a method of heat-sealing powdered solid powder and a method of spraying polymer-containing water described in JP-A No. 58-182636 and drying, and any method may be used. It is desirable that the matte layer itself be soluble in an alkaline developer or be removable by this.

(Coating) The coating method used for coating the photosensitive composition on the surface of the support is a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air coating. Spray application,
Methods such as electrostatic air spray coating, roll coating, blade coating and curtain coating are used. At this time, the coating amount varies depending on the use, but, for example, as solid content is 0.05 to
A coating amount of 5.0 g / m ² is preferred.

(Exposure) In using the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original image having a line image, a halftone image or the like can be applied to the photosensitive surface. A relief image is obtained by exposing the film in close contact with it and then removing the photosensitive layer in the non-image area with a suitable developing solution. Suitable light sources for exposure include mercury lamps, metal halide lamps, xenon lamps,
Chemical lamps, carbon arc lamps, etc. are used.

(Treatment) The negative-working or positive-working developer used in the present invention may be any one as long as it comprises an alkali metal silicate solution containing water as a main solvent. For example, an alkaline agent, an organic solvent, an anionic surfactant, a water-soluble reducing agent and a nonionic surfactant and /
Alternatively, it contains a cationic surfactant. In the developer composition, silicate [SiO ₂ ] / alkali metal oxide [M
₂ O] ratio (provided that silicate [SiO ₂ ] and alkali metal oxide [M ₂ O] indicate a molar concentration) is 0.5 to 2.
For the other alkali metal silicates, additives, etc., conventional development processing agents can be used.

[0094]

EXAMPLES The present invention will be described more specifically with reference to the following examples. First, claims 1 to 4 will be described. Examples 1 to 6 (Production of grain) Six types of aluminum supports having different surface roughening conditions, chemical treatment conditions, and anodic oxidation conditions were produced.
The manufacturing conditions and the shape of the obtained grain are shown in Table 1 below. After all the roughening, chemical treatment and anodic oxidation treatment, all the sands were immersed in a 1.0% ammonium acetate solution at 85 ° C. for 30 seconds, and then in a 0.1% aqueous solution of carboxymethylcellulose. Soak for 30 seconds at ℃, 8
A support was prepared by drying at 0 ° C for 5 minutes.

[0095]

[Table 1]

A photosensitive composition coating solution having the following composition was applied to the obtained support using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate. At this time, the coating amount of the photosensitive composition coating liquid was 2.0 g / m ² as a dry weight.
It was made to become.

<Photosensitive Composition Coating Liquid> Novolak resin (phenol / m-cresol / p-cresol molar ratio of 10/54/36 and Mw of 4000) 6.70 g of pyrogallolacetone resin (Mw: 3000) Condensate with o-naphthoquinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (Trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorine-based surfactant FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0 0.02 g Methyl Cellosolve 100 ml The resulting photosensitive lithographic printing plate had halftone dots and fine lines. Closely the Rupoji original film, using a 2kw metal halide lamp as a light source and exposed by irradiation with 8 mW / cm ² 60 sec. This exposed photosensitive lithographic printing plate was used as a commercially available developer (SDR-1, Konica Corporation).
Development, 6 times dilution, development time 20 seconds, development temperature 27 ° C.).

Printing is carried out using the lithographic printing plate thus obtained,
Water width, dirt, residual film, and stop dirt were evaluated by the following evaluation methods. The obtained results are shown in Table 2.

[0099]

[Table 2]

Dirt during printing is treated with 300 m ² and then
A printing plate was prepared and printed on a printing machine GTO manufactured by Heidelberg Co., Ltd., and the presence or absence of stains was visually evaluated according to the following criteria. [Evaluation of stains during printing] ⊚: No stains ◯: Slight stains are observed, but there is no problem in practical use ×: Very stains

[Evaluation of Contamination by Residual Film] Five sensitivity measuring step tablets (No. 2, Eastman Kodak Co., 21-step gray scale with a density difference of 0.15 each) were brought into close contact with the sample, and the printing plate was attached. It was created. Erasing liquid for 5 image areas formed on the printing plate (SIR-15, made by Konica)
The image area was erased by. The erasing time is divided into 5 levels, and fringe stains caused by the erasing at that time are removed by the developing ink (SPO).
-1, made by Konica) and confirmed. ◯: Good Δ: Erasure marks appear (ink does not adhere, but residual film can be visually confirmed) ×: Stain (ink adheres)

[Evaluation of Water Width] While keeping the ink amount dial constant and changing the water amount dial, the dial value of the water amount at which the non-image area starts to become dirty or the flat mesh portion starts to become entangled and the ink density at the image area The dial value of the decreasing amount of water was obtained and the difference was taken as the water width. A: Difference is 18 or more in dial value O: Difference is 14 or more and less than 18 in dial value X: Difference is less than 14 in dial value

[Evaluation of Stop Contamination] After printing 3000 sheets by a printing machine GTO manufactured by Heidelberg, the printing machine was stopped and the number of fine dot-like contaminations generated when printing was started again was evaluated.

⊚: No emission at all ∘: Slight emission but no problem in practical use x: Substantial emission

Next, claims 5 to 9 will be described. Examples 11 to 13 An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was immersed in a 10% sodium hydroxide aqueous solution kept at 85 ° C., degreased for 1 minute, and then washed with water. did. This degreased aluminum plate was immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, desmutted, and washed with water. Then, this aluminum plate is 1.0%
In a nitric acid aqueous solution at a temperature of 30 ° C. and a current density of 80 A
Electrolytic surface roughening was performed for 30 seconds with an alternating current under the condition of / dm ² . Then, chemical etching was performed in a 10% sodium hydroxide aqueous solution kept at 70 ° C. so that the amount of aluminum dissolved was 5 g / m ² . Then, it was immersed in a 10% nitric acid aqueous solution kept at 25 ° C. for 10 seconds, desmutted, and washed with water. Then, anodization treatment was performed in a 20% aqueous sulfuric acid solution at a temperature of 35 ° C. and a current density of 3 A / dm ² for 1 minute. Then, the aluminum support 11 was dipped in a 0.1% ammonium acetate aqueous solution kept at 80 ° C. for 30 seconds for sealing treatment and dried at 80 ° C. for 5 minutes.
I got

When the surface of the obtained aluminum support was photographed and observed by an electron microscope at a magnification of 10,000 times by a conventional method, it was confirmed that the diameter of the pits formed by the nitric acid electrolytic surface roughening was 1200 to 1500 nm. It was Next, a photosensitive composition coating liquid having the following composition was applied using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate. At this time, the dry weight of the photosensitive composition coating liquid was set to 2.0 g / m ² .

Novolak resin (phenol / m-cresol / p-cresol molar ratio of 10/54/36 and Mw of 4000) 6.70 g Pyrogallolacetone resin (Mw: 3000) and o-naphthoquinonediazide-5-sulfonyl Condensate with chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.02 g Methyl cellosolve 100 ml was obtained. 4Kw metal halide lamp as a light source And use, was exposed by irradiation with 8 mW / cm ² 60 sec. This exposed photosensitive lithographic printing plate was used as a commercially available developer (SDR-1, manufactured by Konica Corporation, diluted 6 times, developed time 20 seconds, developed temperature 27).
Development). When the lithographic printing plate thus obtained was printed, the results shown in Table 4 were obtained.

Example 12 An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was dipped in a 10% sodium hydroxide aqueous solution kept at 85 ° C. and degreased for 1 minute. Washed with water. The degreased aluminum plate was immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, desmutted, and washed with water. Then, this aluminum plate is
% Nitric acid aqueous solution, temperature 30 ℃, current density 13
Electrolytic roughening was performed for 60 seconds with an alternating current under the condition of 0 A / dm ² . Then, it was dipped in a 10% aqueous sodium hydroxide solution kept at 70 ° C. for 10 seconds, then dipped in a 10% aqueous nitric acid solution kept at 25 ° C. for 10 seconds, desmutted, and washed with water. Then, this aluminum plate,
In a 0.5% aqueous nitric acid solution, electrolytic surface roughening was performed for 30 seconds with an alternating current under the conditions of a temperature of 30 ° C. and a current density of 40 A / dm ² . Then, in a 10% aqueous sodium hydroxide solution kept at 70 ° C., the amount of aluminum dissolved was 4 g / m 2.
Chemical etching was performed so as to be ² . Then 25
It was immersed for 10 seconds in a 10% nitric acid aqueous solution kept at 0 ° C., desmutted, and washed with water. Then, in a 20% aqueous solution of sulfuric acid, the temperature was 35 ° C. and the current density was 3 A / dm ^{2 under} the conditions of 1
Anodizing treatment was performed for a minute. Then, the aluminum support 12 was obtained by immersing in a 0.1% ammonium acetate aqueous solution kept at 80 ° C. for 30 seconds for sealing treatment, and drying at 80 ° C. for 5 minutes.

The surface of the obtained aluminum support was photographed and observed with an electron microscope at a magnification of 1000 times according to a conventional method. As a result, the pits formed by hydrochloric acid electrolytic surface roughening had a diameter of 1
It was confirmed to be 0 to 15 μm. Magnification 10000
As a result of photographing and observing with a magnification, it was confirmed that the diameter of the pit formed by nitric acid electrolytic surface roughening was 700 to 900 nm. A photosensitive composition was applied in the same manner as in Example 11, exposed and developed, and printed.

Example 13 An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was immersed in a 10% aqueous sodium hydroxide solution kept at 85 ° C. and degreased for 1 minute. Washed with water. The degreased aluminum plate was immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, desmutted, and washed with water. Then, a dispersion liquid in which Al ₂ O ₃ particles having an average particle diameter of 10 μm were mixed with water so that the volume ratio was 10 parts and uniformly dispersed with a stirrer,
6 kg / c pressure from 60 nozzles with a diameter of 2 mm
It was injected at m ^2, 100 mm relative to the surface of the aluminum plate
From the distance of 30 degrees. Then 70
It was dipped in a 10% sodium hydroxide aqueous solution kept at 0 ° C for 10 seconds, then dipped in a 10% sulfuric acid aqueous solution kept at 25 ° C for 10 seconds, desmutted, and washed with water.
Next, this aluminum plate was electrolytically roughened in an aqueous 2.0% hydrochloric acid solution for 60 seconds by an alternating current under the conditions of a temperature of 30 ° C. and a current density of 130 A / dm ² . afterwards,
1 in 10% sodium hydroxide solution kept at 70 ° C
It was dipped for 0 seconds, then dipped in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 10 seconds, desmutted, and washed with water. Next, this aluminum plate was electrolytically surface-roughened for 30 seconds by an alternating current in a 0.5% aqueous nitric acid solution at a temperature of 30 ° C. and a current density of 40 A / dm ² . Then, chemical etching was performed in a 10% sodium hydroxide aqueous solution kept at 70 ° C. so that the amount of aluminum dissolved was 4 g / m ² . Then 10% kept at 25 ° C
It was immersed in an aqueous solution of sulfuric acid for 10 seconds, desmutted, and washed with water. Then, in a 20% aqueous solution of sulfuric acid, a temperature of 35
Anodizing treatment was performed for 1 minute under conditions of a temperature of 3 ° C. and a current density of 3 A / dm ² . Then, it is immersed in a 0.1% ammonium acetate aqueous solution kept at 80 ° C. for 30 seconds for sealing treatment,
Aluminum support 13 was obtained by drying at 80 ° C. for 5 minutes.

When the surface of the obtained aluminum support was photographed and observed by an electron microscope at a magnification of 200 by an ordinary method, it was confirmed that the recesses had a length of 32 to 40 μm, a width of 8 to 10 μm, and an interval of 150 to 180 μm. Was done. Magnification 10
When photographed and observed at 00 times, it was confirmed that the diameter of the pit formed by the electrolytic electrolytic surface roughening was 10 to 15 μm. When photographed and observed at a magnification of 10,000 times, the diameter of the pits formed by the electrolytic surface roughening of nitric acid is 700 to 9
It was confirmed to be 00 nm. A photosensitive composition was applied in the same manner as in Example 11, exposed and developed, and printed.

Comparative Example 11 Aluminum support was carried out in the same manner as in Example 11 except that chemical etching was performed in a 10% sodium hydroxide aqueous solution maintained at 70 ° C. so that the amount of aluminum dissolved was 2 g / m ^2. I got body 4. A photosensitive composition was applied in the same manner as in Example 11, exposed and developed, and printed.

Comparative Example 12 Aluminum support was carried out in the same manner as in Example 12 except that chemical etching was performed in a 10% sodium hydroxide aqueous solution kept at 70 ° C. so that the amount of aluminum dissolved was 2 g / m ^2. I got body 5. A photosensitive composition was applied in the same manner as in Example 11, exposed and developed, and printed.

Comparative Example 13 Aluminum support was carried out in the same manner as in Example 13 except that chemical etching was carried out in a 10% sodium hydroxide aqueous solution kept at 70 ° C. so that the amount of aluminum dissolved was 2 g / m ^2. I got body 6. A photosensitive composition was applied in the same manner as in Example 11, exposed and developed, and printed.

Comparative Example 14 Instead of electrolytically surface-roughening for 30 seconds with an alternating current in a 1.0% aqueous nitric acid solution at a temperature of 30 ° C. and a current density of 80 A / dm ² , a 2.0% aqueous hydrochloric acid solution was used. Example 11 except that electrolytic surface roughening was performed for 60 seconds with an alternating current under the conditions of a temperature of 30 ° C. and a current density of 130 A / dm ^2.
An aluminum support 7 was obtained in the same manner as in. Example 11
The photosensitive composition was applied in the same manner as above, exposed, developed and printed.

Comparative Example 15 In a 2.0% aqueous nitric acid solution, electrolytic surface roughening was carried out for 60 seconds with an alternating current under the conditions of a temperature of 30 ° C. and a current density of 130 A / dm ² , followed by holding at 70 ° C. % Sodium hydroxide aqueous solution for 10 seconds and then 10% aqueous nitric acid solution kept at 25 ° C. for 10 seconds Desmut treatment and water washing were not performed.
An aluminum support 8 was obtained in the same manner as in 3. Example 1
In the same manner as in 1, the photosensitive composition was applied, exposed, developed, and printed.

Comparative Example 16 After electrolytic surface roughening in a hydrochloric acid aqueous solution, soaking in a 10% sodium hydroxide aqueous solution kept at 70 ° C. for 10 seconds, and then 10% sulfuric acid kept at 25 ° C. 10 in aqueous solution
Desmut treatment of dipping for 2 seconds and washing with water, and 0.
In a 5% nitric acid aqueous solution, the temperature is 30 ° C. and the current density is 4
An aluminum support 9 was obtained in the same manner as in Example 13 except that the electrolytic surface roughening treatment with an alternating current for 30 seconds was not performed under the condition of 0 A / dm ² . A photosensitive composition was applied in the same manner as in Example 11, exposed and developed, and printed.

[0118]

[Table 3]

[0119]

[Table 4]

<Evaluation Method> Evaluation of Printing Durability The lithographic printing plate thus obtained was printed on a printing machine (manufactured by Mitsubishi Heavy Industries Ltd. D
AIYA1F-1) coated paper, dampening water (Tokyo Ink Co., Ltd. etchant SG-51, concentration 1.5%), ink (Toyo Ink Co., Ltd. high plus M red) printing Printing was performed until defective ink deposition appeared in the image area of the printed matter or ink adhered to the non-image area. The number of printed sheets at that time was determined and the printing durability was evaluated.

-Recovery property of entire surface stain Under the same printing condition, after the entire surface was stained with ink and printing was started, printing was started and the number of sheets where a clean and complete image was obtained was evaluated.

[0122] - in the fine point-like stains similar printing conditions, to stop once the printing press at the time of smoked 5,000 sheets, and after allowing to stand for one hour, to begin printing, in a fine point-like dirt that occurred 100cm ² The number of samples was evaluated.

Dot gain: Under the same printing conditions, the density of the image area is set to 1.6, and the number of screen lines on the printed matter is 150 line when printing is performed.
The area of 50% halftone dots of / inch is measured and 5 on the printing plate
The amount of gain was evaluated from the area of 0% halftone dots. The area was measured with a Macbeth densitometer.

K value 150 lines of screen ruling on the printed matter when printing is performed with the density of the image part set to 1.6 under the same printing condition.
The density of 80% halftone dots of / inch was measured and evaluated using the following formula. The concentration was measured with a Macbeth densitometer.

K value = (image portion density-80% halftone dot density) / image portion density The larger the K value, the better the reproducibility of the high density halftone dot portion.

Water width Under the same printing conditions, keeping the ink amount dial constant and changing the water amount dial, the dial value of the water amount at which the non-image area starts to become dirty or the flat mesh portion starts to entangle, and the image area The dial value of the amount of water at which the ink concentration decreased was determined, and the difference was defined as the water width.

-Blanket Contamination Under the same printing conditions, the printing machine was stopped at the time when 10,000 sheets were printed, and the degree of ink stain on the non-image area on the blanket was visually evaluated. ○: Almost no dirt ×: Very dirty

Example 14 The same experiment as in Example 3 was carried out except that the following negative type photosensitive composition coating liquid was used in place of the positive type photosensitive composition coating liquid in Example 3, and the same effect as that of Example 3 was obtained. was gotten.

<Negative-type photosensitive composition coating liquid> Copolymer (p-hydroxyphenylmethacrylamide / acrylonitrile / ethyl acrylate / methacrylic acid = 10/25/57/8 Mw = 60,000) 5.0 g diazo resin (Shown below) 0.5g

[0130]

[Chemical 6] Julimer AC-10L (manufactured by Nippon Pure Chemical Industries, Ltd.) 0.05 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.1 g Methyl Cellosolve 100.0 ml

[0131]

INDUSTRIAL APPLICABILITY According to the present invention, a lithographic printing plate support having good hydrophilicity, water retention and adhesiveness to a photosensitive layer from the viewpoint of printability, a method for producing the same, and a photosensitive lithographic printing plate are provided. it can.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shinichi Matsubara 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company

Claims (9)

[Claims] 1. Rz / Ra is 95% of that before treatment by roughening the surface of an aluminum plate and then chemically treating it to dissolve and smooth sharp parts of the roughened surface.
A method for producing a support for a lithographic printing plate, comprising: 2. A lithographic printing plate support having a smooth surface having an Rmax of 3 μm or less and a grain structure having an opening diameter of micropores of 8 nm or more and a depth of 800 nm or more. . 3. Rz / Ra is 95% of that before treatment by roughening the surface of an aluminum plate and then chemically treating it to dissolve and smooth sharp parts of the roughened surface.
A photosensitive lithographic printing plate comprising the following support and a photosensitive layer provided thereon. 4. A photosensitive layer is provided on a support having a smooth surface with Rmax of 3 μm or less and having a grain structure with an opening diameter of micropores of 8 nm or more and a depth of 800 nm or more. A photosensitive lithographic printing plate characterized by: 5. A surface-roughened and anodized aluminum plate is electrochemically formed into a pit having a diameter of 800 to 2000 nm in a nitric acid-based electrolytic solution, and b) an alkali. Chemical etching is performed in an aqueous solution so that the amount of aluminum dissolved becomes ⁴ to 6 g / m ² ,
c) A method for producing a lithographic printing plate support, which comprises performing desmut treatment with an acid. 6. A surface-roughened and anodized aluminum plate is prepared by electrochemically forming a) pits having a diameter of 7 to 25 μm electrochemically in a hydrochloric acid-based electrolytic solution, and b) nitric acid. Electrochemically in a system electrolyte solution with a diameter of 600-1000n
A lithographic printing plate characterized by producing pits of m, c) chemical etching in an alkaline aqueous solution so that the amount of aluminum dissolved is 3 to 5 g / m ² , and d) desmutting treatment with acid. For manufacturing a support for use. 7. The method according to claim 6, further comprising the step of chemically forming a pit in a hydrochloric acid-based electrolytic solution and then chemically etching it with an acid or alkali aqueous solution.
A method for producing the lithographic printing plate support described. 8. A roughened and anodized aluminum plate, wherein the roughened surface is a) mechanically 30 to 5 in length.
0 μm, width of 5 to 15 μm, center interval 50 to 200
the pits having a diameter of 7 to 25 μm electrochemically in a hydrochloric acid-based electrolytic solution and c) the pits having a diameter of 600 to 1000 nm electrochemically in a nitric acid-based electrolytic solution; ) A method for producing a lithographic printing plate support, which comprises chemically etching in an alkaline aqueous solution so that the amount of aluminum dissolved is 3 to 5 g / m ² and e) performing desmut treatment with an acid. 9. A method comprising a step of chemically etching with an aqueous acid or alkali solution after mechanically forming a recess and electrochemically forming a pit in a hydrochloric acid-based electrolytic solution. The method for producing a lithographic printing plate support according to claim 8.