JPH09300838A - Substrate for photosensitive lithographic printing plate and its manufacture, and photosensitive lithographic printing plate and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the bonding properties with a photosensitive layer and superior resistance to printing by specifying respectively the anode oxide film amount and the relation between the depth of sealing and the depth of the whole film in a photosensitive lithographic printing plate substrate provided by making the surface of an aluminum plate rough to form an anodic oxide film and then sealing. SOLUTION: In a photosensitive lithographic printing plate substrate, the surface of an aluminum plate 1 is made rough to form an anodic oxide film 2 and sealed films 4 are formed on pores 3, the anodic oxide film amount is set as 1g/m<2> or more. The depth of sealing and the depth of the whole film are formed to satisfy the relation of (depth of sealing/depth of whole film) × 100<25, and the unsealed surface areas and the sealed surface areas are formed to satisfy the relation of [(unsealed surface areas-sealed surface areas)/unsealed surface areas] × 100<40. Also the unsealed pore aperture areas and the sealed pore aperture areas are formed to satisfy the relation of [(unsealed pore aperture areas-sealed pore aperture areas)/unsealed pore aperture areas 9147/28} μ 100<50.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION A photosensitive lithographic printing plate is a positive lithographic printing plate having a photosensitive layer provided on a support, and a positive photosensitive composition layer provided on the support. There is a negative-working photosensitive lithographic printing plate having a negative-working photosensitive composition layer provided thereon.

Conventionally, the support of these photosensitive lithographic printing plates has been subjected to surface roughening treatment, anodizing treatment, sealing treatment and the like in view of printability.

For the surface roughening treatment, mechanical surface roughening methods such as ball polishing, brush polishing, blast polishing, buff polishing, honing polishing, etc., and the surface of the support by AC or DC in an acidic electrolytic solution such as hydrochloric acid or nitric acid. Electrochemical surface-roughening methods and the like for electrolytic treatment of are known.

Since the surface of the support grained by these methods is soft and easily abraded as it is, it is then anodized to form a hard oxide film on the surface to obtain abrasion resistance.

The anodized support is subjected to a sealing treatment. For these sealing treatments, hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment and the like are used. The sealing treatment is a treatment for improving the characteristics of the photosensitive lithographic printing plate by closing the pores formed in the oxide film formed by the anodic oxidation treatment with a metal oxide, a hydroxide or the like.

Attempts have been made to improve the performance of the photosensitive lithographic printing plate by sealing the support.

For example, Japanese Patent Application No. 7-77391 discloses that a support having a sealing treatment has a pore diameter of 6 nm or more and a pore opening area of 1.5% or more so that printability and dot gain during printing can be improved. Have been proposed to improve. In Japanese Patent Publication No. 57-7427, [SiO ₂ ] / [M] ([SiO ₂ ] represents the molar concentration of the SiO ₂ component in the developing solution for the development treatment of the photosensitive lithographic printing plate, M] represents the molar concentration of the alkali metal component.) It is proposed to use a developer having a molar ratio of 0.5 or more and 0.8 or less to suppress the developability and the generation of dust in the developer.

Further, in Japanese Patent Laid-Open No. 1-150583, in a support subjected to a sealing treatment, the sealing depth / total coating depth × 100
By setting it to 25 or more, it is possible to prevent contamination of the non-image area, scratches and abrasion of the non-image area, ink stain recovery, and easy balance of water and ink. A plate can be obtained according to Japanese Patent Application Laid-Open No. 4-1766.
No. 90 discloses that in a support subjected to a sealing treatment, (unsealed surface area-surface area after sealing) / unsealed surface area × 100 is 40 to 95.
By that, it has been proposed to obtain a support for a lithographic printing plate suitable for producing a photosensitive lithographic printing plate having excellent strength and corrosion resistance in the non-image area, the support is a photosensitive layer and However, there was a problem in the adhesiveness, the developability of the obtained photosensitive lithographic printing plate, and the printing durability of the obtained lithographic printing plate.

Therefore, the inventors of the present invention investigated the sealing treatment of the photosensitive lithographic printing plate support obtained by roughening an aluminum plate, forming an anodized film and then sealing treatment.
Excellent development by making the depth of the sealing and the total film depth, the surface area of the unsealed and the surface after the sealing, the pore opening area of the unsealed and the pore opening area after the sealing specific Has sex
It was also found that a photosensitive lithographic printing plate having excellent printing durability was obtained.

[0011]

It is a first object of the present invention to provide a photosensitive lithographic printing plate which has excellent adhesion to a photosensitive layer, excellent printing durability in printing and excellent developability. It is to provide a support for a lithographic printing plate.

A second object of the present invention is to provide a photosensitive lithographic printing plate which has excellent adhesion to the photosensitive layer, excellent printing durability in printing, and excellent developability.

A third object of the present invention is to provide a method for treating a photosensitive lithographic printing plate excellent in printing durability and developability.

[0014]

The above objects of the present invention are as follows: (1) In a photosensitive lithographic printing plate support obtained by roughening an aluminum plate, forming an anodized film and then sealing the plate, the amount of the anodized film is 1 g / A support for a photosensitive lithographic printing plate, which has a pore size of m ² or more and a sealing depth and a total coating depth that satisfy the following formula 1.

[0015]

(Equation 7) (2) The aluminum plate is roughened so that the amount of anodized film is 1
After anodizing treatment so that it becomes g / m ² or more, the sealing depth and the total coating depth are such that the sealing depth and the total coating depth satisfy the formula 1 below. And a method for producing a photosensitive lithographic printing plate support.

[0016]

(Equation 8) (3) In a photosensitive lithographic printing plate support obtained by roughening an aluminum plate to form an anodized film and then sealing the plate, the amount of the anodized film is 1 g / m ² or more, A support for a photosensitive lithographic printing plate, wherein the surface area and the surface area after sealing are the unsealed surface area and the surface area after sealing that satisfy the following formula 2.

[0017]

[Equation 9] (4) The aluminum plate is roughened so that the amount of anodized film is 1
After anodic oxidation treatment so that the amount of g / m ² or more, the unsealed surface area and the unsealed surface area satisfy the following formula 2 so that the unsealed surface area and the unsealed surface area satisfy the following formula 2. A method for producing a support for a photosensitive lithographic printing plate, which comprises treating.

[0018]

(Equation 10) (5) In a photosensitive lithographic printing plate support obtained by roughening an aluminum plate to form an anodized film and then sealing the plate, the amount of the anodized film is 1 g / m ² or more, and the unsealed A photosensitive lithographic printing plate support, wherein the pore opening area and the pore opening area after sealing are the unopened pore opening area and the pore opening area after sealing, which satisfy the following formula 3. .

[0019]

[Equation 11] (6) The aluminum plate is roughened so that the amount of anodized film is 1
After anodizing treatment so that the pore opening amount becomes g / m ² or more, the unsealed pore opening area and the unsealed pore opening area satisfy the following formula 3 below. A method for producing a photosensitive lithographic printing plate support, which comprises performing a sealing treatment so as to have an opening area.

[0020]

(Equation 12) (7) A photosensitive lithographic printing plate comprising a support for the photosensitive lithographic printing plate described in (1), (3) or (5) above, and a layer of a photosensitive composition provided thereon. (8) After exposing the photosensitive lithographic printing plate described in (7) above to imagewise exposure, [SiO ₂ ] / [M] ([SiO ₂ ] is S in the developing solution).
It represents the molar concentration of the iO ₂ component, and [M] represents the molar concentration of the alkali metal component. ) Is 1.0 or less, and the development treatment is carried out with a developing solution consisting of an aqueous solution of an alkali metal silicate. Is achieved by

Hereinafter, the present invention will be described in detail.

The aluminum plate used for the support of the photosensitive lithographic printing plate of the present invention includes a pure aluminum plate and an aluminum alloy plate (hereinafter collectively referred to as an aluminum plate). Various aluminum alloys 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.

In the present invention, the aluminum plate is preferably subjected to a degreasing treatment in order to remove oil and oily substances adhering to the surface before roughening. As the degreasing treatment, solvent degreasing with trichlene, thinner or the like, emulsion degreasing treatment with an emulsion of kerosene or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used to remove stains and natural oxide films that 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, acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof is used. It is preferable to carry out desmutting by dipping.

After the pretreatment as described above is performed, a roughening treatment is performed. The roughening treatment is not particularly limited, but as the roughening method, a mechanical method for mechanically roughening the surface, a method for electrochemically roughening the surface, an alkali or an acid or those There is a chemical roughening method in which the surface is roughened with an etching agent composed of a mixture of

In the present invention, the above methods can be used alone or in combination to carry out the surface roughening treatment.

The mechanical surface roughening method that can be used is not particularly limited, but examples of the mechanical surface roughening method that can be used include ball polishing, brush polishing, blast polishing, and the like. The buff polishing method and the honing polishing method can be used. Among these, the brush polishing method and the honing polishing method are preferable. Further, it is also possible to carry out roughening by laminating a sheet that has been roughened in advance on the surface of the support and applying pressure to transfer the roughened pattern. The mechanical surface roughening method can be performed alone or in combination of two or more.

The electrochemical surface-roughening method that can be used is not particularly limited, but the electrochemical surface-roughening method that can be used includes, for example, acidic electrolysis containing hydrochloric acid or nitric acid. A method of electrolytically treating the surface with alternating current or direct current in a liquid can be mentioned. The electrochemical surface roughening method can be performed alone or in combination of two or more kinds.

The electrochemical graining treatment is described, for example, in Japanese Patent Publication No. 48-28123, British Patent No. 896563, and Japanese Patent Laid-Open No. 53-67507. In the present invention, These methods can be used.

When the surface is roughened by the electrochemical surface roughening method, the applied voltage is preferably 1 to 50 volts, and 2 to
30 volts is more preferred. Current density is 10 to 150 A / dm ²
Is preferred, and 20-100 A / dm ² is more preferred. The amount of electricity is 50 to 5000 coulombs / dm ² , preferably 100 to 1000 coulombs / dm ² , and more preferably 200 to 800 coulombs / dm ² . The temperature of the electrolytic solution is preferably 10 to 50 ° C, more preferably 15 to 45 ° C. The concentration of hydrochloric acid or nitric acid in the electrolyte is 0.
01 to 5% by weight is preferable, and a nitric acid-based electrolytic solution is preferable as the electrolytic solution.

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.

When two or more surface-roughening treatment methods are combined, it is preferable to perform chemical etching treatment by immersing the surface-roughening treatment in an aqueous solution of acid or alkali.
As the acid, for example, sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid or hydrochloric acid can be used, and as the alkali, for example, sodium hydroxide or potassium hydroxide can be used. Among these, it is preferable to use an alkaline aqueous solution for the chemical etching treatment. The chemical etching treatment can be performed by using an aqueous solution of 0.05 to 40% by weight of acid or alkali at a liquid temperature of 40 to 100 ° C. for 5 to 300 seconds.

When the above chemical etching treatment is carried out using an aqueous alkali solution, smut is formed on the surface of the support, so that it is dipped in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof, It is preferable to apply a desmut treatment.

Subsequent to the surface roughening treatment, anodizing treatment is preferably carried out in order to improve the water retention, the adhesion to the photosensitive layer and the strength of the non-image area surface.

The method of anodizing treatment that can be used in the present invention is not particularly limited, and a known method can be used. By carrying out the anodizing treatment, an oxide film is formed on the support.

As the electrolytic solution used for the anodizing treatment, any one can be used as long as it can form a porous oxide film, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, sulfamic acid, benzene sulfone. An acid or a mixed acid in which two or more kinds thereof are combined is used.

The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolytic solution used, but generally, the concentration of the electrolytic solution is 1 to 80% by weight, and the temperature of the electrolytic solution is 5 to 70%.
° C., a current density of 0.5 to 60 A / dm ^2, voltage 1 to 100 V, the electrolysis time of 10 seconds to 5 minutes is suitable.

A preferred anodizing treatment is a method of using a sulfuric acid aqueous solution as an electrolytic solution and treating with a direct current, but an alternating current can also be used. The concentration of sulfuric acid is preferably 5 to 45% by weight, and electrolytic treatment is preferably performed at a temperature of the electrolytic solution of 20 to 50 ° C. and a current density of 0.5 to 20 A / dm ² for ²⁰ to 250 seconds.

In the present invention, the amount of the anodized film formed by the anodizing treatment must be 1 g / m ² or more.

The pores formed on the roughened and anodized aluminum plate are sealed. The sealing treatment is carried out by using a known method such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment, and electrodeposition sealing treatment. be able to.

The sealing treatment film is formed, for example, from the bottom of the pore when the electrodeposition sealing treatment is performed, and from the upper portion of the pore when the steam sealing treatment is performed. Although the method of forming the sealing treatment film differs depending on the method, in any of the sealing treatments, in the present invention, the depth of the sealing hole and the total coating depth, the surface area of the unsealed surface and The pore-sealing treatment is carried out so that a support satisfying any of the following requirements for the surface area of, the pore-opening area of unsealed pores, and the pore-opening area after sealing is obtained. (1) Let the sealing depth and the total coating depth be the sealing depth and the total coating depth that satisfy the following formula 1.

[0042]

(Equation 13)

(2) Let the unsealed surface area and the unsealed surface area be the unsealed surface area and the unsealed surface area that satisfy the following formula 2.

[0044]

[Equation 14]

(3) The unopened pore opening area and the unopened pore opening area are defined as the unopened pore opening area and the unsealed pore opening area satisfying the following expression (3).

[0046]

(Equation 15)

In the present invention, the "sealing depth" and the "total film depth" in the formula 1 are defined as follows: after the support sample is sufficiently cooled in liquid nitrogen, both ends of the support sample are pulled. It can be determined by dividing the sample and observing the pores of the rough surface of the support appearing on the fracture surface using a high resolution electron microscope.

FIG. 1 shows the pores appearing in the fractured surface, which was broken in the above-described manner, on a support which had been subjected to a sealing treatment in which a sealing treatment film was formed from the bottom of the pores, for example, an electrodeposition sealing treatment. FIG. 2 schematically shows the pores appearing on the fractured surface, which has been subjected to a sealing treatment in which a sealing treatment film is formed from the surface of the pores, for example, a water vapor sealing treatment, which is broken as described above. It is a thing. In FIGS. 1 and 2, 1 is an aluminum support, 2 is an anodized film, 3 is a pore, and 4 is a sealing treatment film. The aluminum support is first roughened, and then anodized to form an anodized film 2 having pores 3 formed therein. Further, the sealing treatment film 4 is formed by the sealing treatment.

The depth of the pores is the depth in which the pores are filled by the pore-sealing treatment, and is represented by a shown in FIG. The total coating depth is the depth of the pores before the sealing treatment coating 4 is formed by the sealing treatment, and is represented by b shown in FIG.

In equation 1

[0051]

(Equation 16) The value of is the average value of the values obtained by the depth of each sealing hole and the total film depth obtained in the randomly selected measurement area as described above.

In the present invention, the "surface area of unsealed pores" and "surface area after sealing" in the formula 2 are the surface area of the unsealed support surface and the surface area of the support surface after sealing, which is determined by the simple BET method. It is the value measured in.

In equation 2

[0054]

[Equation 17] The value of is determined by the surface area of the unsealed holes and the surface area after the closed holes, which are obtained as described above.

In the present invention, the "open area of unsealed pores" and "area of open pores after sealing" in the formula 3 are random for the surface of the unsealed support and the surface of the support after sealing. Observe the measurement area selected for using a high resolution electron microscope,
It can be obtained by image processing.

The opening of the pore after sealing means the opening of the pore obtained after filling by the sealing treatment, and is indicated by d shown in FIG. Further, the opening of the unsealed pore means the opening of the pore before being filled by the sealing treatment, and is indicated by c shown in FIG.

The opening area of the unsealed pores is calculated by adding up the areas of the openings of the unsealed pores, and the pore opening area after sealing is the opening area of the pores after sealing. It is calculated by adding up the area of.

In Equation 3

[0059]

(Equation 18) The value of is determined by the pore opening area of the unsealed pore and the pore opening area after the sealing, which are obtained as described above.

The sealing conditions for obtaining the support satisfying the above requirements can be determined by conducting a simple experiment.

A hydrophilic layer may then be provided on the sealed aluminum plate. The formation of the hydrophilic layer, the alkali metal silicate described in U.S. Pat.No. 3,181,461, the hydrophilic cellulose described in U.S. Pat.No. 1,860,426, JP-B 6-94234, JP-B 6-2436. Amino acids and salts thereof described in JP-B-5-32238, amines having hydroxyl groups and salts thereof described in JP-B-5-32238,
The phosphates described in JP-A-19494 and the polymer compounds containing a monomer unit having a sulfo group described in JP-A-59-101651 can be used.

The photosensitive composition for forming the layer of the photosensitive composition in the photosensitive lithographic printing plate of the present invention is not particularly limited, and it is usually the photosensitive composition used in the photosensitive lithographic printing plate. Can be used.

Examples of the photosensitive composition that can be used in the present invention include the followings. 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.

[0064]

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, a composition containing methyl methacrylate, polymethyl methacrylate and polyethylene glycol methacrylate monomers. , A photopolymerizable composition such as a composition containing methyl methacrylate, an alkyd resin and a polyethylene glycol dimethacrylate monomer.

These photopolymerizable photosensitive resin compositions include photopolymerization initiators commonly known in the art (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 linear polyurethane resins described in No. 1,257, phthalated resins of polyvinyl alcohol, epoxy resins which are condensates of bisphenol A and epichlorohydrin, and cellulose derivatives such as cellulose acetate and cellulose acetate phthalate. 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 phenols in the polycondensation resin with the above-mentioned phenols and aldehydes or ketones include 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 resin, m-cresol-formaldehyde resin, m- and p-mixed cresol-formaldehyde resin, resorcin-benzaldehyde resin, Examples include pyrogallol / acetone resin.

In the o-naphthoquinonediazide compound, the condensation rate of o-naphthoquinonediazidesulfonic acid with respect to the hydroxyl groups of phenols (reaction rate with respect to one hydroxyl group) is preferably 15% to 80%, 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 mentioned. 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-
A 1,2-quinonediazide compound such as naphthoquinonediazide-5- (N-dihydroabietyl) -sulfonamide can be exemplified. 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 kinds.

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

An alkali-soluble resin is preferably added to the photosensitive composition containing the o-quinonediazide compound.

In the present invention, the alkali-soluble resin which is preferably used in combination with the o-quinonediazide compound is, for example, a novolac resin, a vinyl polymer having a phenolic hydroxyl group, or JP-A-55-57841. Examples thereof include condensation resins of polyphenols with aldehydes or ketones.

Examples of the novolak resin include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde copolymer resin as described in JP-A-55-57841, and JP-A-55. 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 is preferably 3.00 × 10 ^{2 to} 7.5 in terms of number average molecular weight Mn.
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 kinds.

When a novolak resin is used in combination, it is preferable that the novolac resin is 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 is represented by the following general formula [I] to
A polymer containing at least one structural unit represented by [V] is preferable.

[0082]

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 structural units represented by the above general formulas [I] to [V]. Examples of the monomer to be copolymerized include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene, α-methylstyrene, p
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.

Of the above monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention.

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 vinyl polymer having a phenolic hydroxyl group is preferably contained in the photosensitive composition in an amount of 0.5 to 70% by weight.

As the vinyl polymer having a phenolic hydroxyl group, 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.

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.

Further, an inclusion compound can be added to the photosensitive composition.

The inclusion compound that can be used in the present invention is, so to speak, a host compound capable of incorporating (inclusion) a chemical species such as sodium ion or potassium ion into the inclusion compound as a guest molecule. There is no particular limitation so long as it is an organic compound soluble in the solvent used for preparing the photosensitive composition. Examples of such organic compounds include, for example, books such as "Host Guest Chemistry" (Michio Hiraoka, Kodansha, 1984, Tokyo) and "Tetrahedron Report" (No.226 (1987) P5).
725A. Collet et al., “Chemical Industry April Issue” ((1991) P278
Shinkai et al.), “Chemical Industry April Issue” ((1991) P288 Hiraoka et al.)
And the like are listed.

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

Examples of the cyclic D-glucans and acyclic analogs thereof include compounds in which α-D-glucopyranose is linked by a glycoloxide bond.

Examples of the compound include sugars such as starch, amylose and amylopectin, which are composed of D-glucopyranose groups, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and D-glucopyranose polymerization. Cyclodextrins such as cyclodextrin having a degree of 9 or more, 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.

[0095]

Embedded image And modified D-glucans. Moreover, the cyclodextrin derivative represented by the following general formula [IX] and general formula [X], a branched cyclodextrin, a cyclodextrin polymer, etc. are also mentioned.

[0096]

Embedded imageIn the general formula [IX], R₁~ R_ThreeAre the same
May be different, hydrogen atom, alkyl group or substituted
Represents an alkyl group. In particular, R ₁~ R_ThreeIs a hydrogen atom or
Hydroxyethyl group, hydroxypropyl group
Is preferred, and the content of substituted alkyl groups in one molecule is 15%.
It is more preferably about 50%. n_TwoIs positive from 4 to 10
Represents an integer.

[0097]

Embedded imageIn the general formula [X], R is a hydrogen atom, -R^Two -CO_Two
H, -R^Two -SO_ThreeH, -R^Two-NH_TwoOr -N-
(R^Three)_Two(R^TwoIs a straight or branched chain having 1 to 5 carbon atoms.
Represents an alkylene group, R^ThreeIs a straight chain having 1 to 5 carbon atoms or
Represents a branched chain alkyl group.

An example of the production of cyclodextrin is "Jo
unal of the American Chemical Society, Vol. 71, No. 3
P. 54, 1949, "Cheimish Berichte", vol. 90, p. 2561
1957, Vol. 90, page 2572, 1957, but is not of course 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,
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 in, for example, Starch Kagaku, 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 branched cyclodextrin preferably used include the following specific exemplified compounds.

[Exemplified Compounds] D-1 α-Cyclodextrin with one molecule of maltose bonded D-2 β-Cyclodextrin with one molecule of maltose D-3 γ-Cyclodextrin with one molecule of maltose D-4 Malto Α-Cyclodextrin with two molecules of D-sulfate D-5 β-Cyclodextrin with two molecules of maltose D-6 γ-Cyclodextrin with two molecules of maltose D-7 α-Cyclodextrin with three molecules of maltose D-8 β-Cyclodextrin with 3 molecules of maltose D-9 γ-Cyclodextrin with 3 molecules of maltose D-10 α-Cyclodextrin with 1 molecule of glucose D-11 β-with 1 molecule of glucose bonded Cyclodextrin D-12 1 molecule of 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

The structures of these branched cyclodextrins are analyzed by HPLC, NMR, TLC (thin layer chromatography), IN
EPT method (Insensitive nuclei enhanced by polarization
transfer) has been studied in various ways,
Even with the current science and technology, it has not yet been finalized and is in the stage of an estimated structure. However, each monosaccharide or 2
The fact that sugars and the like are bound to cyclodextrin is correct in the above measurement method. Therefore, in the present invention, when the monosaccharide or disaccharide polymolecule is bound to cyclodextrin, for example, when individually bound to each glucose of cyclodextrin as shown below, or It includes both those linearly linked to one glucose.

[0104]

[Chemical 6]

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.

The branched cyclodextrin used in the present invention can be obtained as a commercial product. For example, maltosyl cyclodextrin is commercially available as Isoeryte (registered trademark) manufactured by Shimizu Minato Seito Co., Ltd.

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

As the cyclodextrin polymer used in the present invention, those represented by the following general formula [XI] are preferable.

[0109]

[Chemical 7] [In formula, n < ₂ > is a polymerization degree and represents 3-4. ]

The cyclodextrin polymer used in the present invention can be produced by crosslinking cyclodextrin with, for example, epichlorohydrin to form a crosslinked polymer.

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., for that purpose, the degree of polymerization n ₂ in the above general formula [XI] is 3 to 3. The lower the value, the higher the water solubility of the cyclodextrin polymer itself and the solubilizing effect of the substance.

These cyclodextrin polymers are disclosed, for example, in JP-A-61-97025 and German Patent 3,544,842.
It can be synthesized by a general method described in the specification and the like.

The cyclodextrin polymer may also 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 connected by various bonds, and many compounds are known. Examples of cyclophanes include these known compounds. it can.

[0115] As the bond connecting an aromatic ring, for example, a single _{bond, - (CR 1 R 2)} m - _{bond, -O (CR 1 R 2)} m O- _{bond, -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).

Examples of the compound include compounds represented by the following formulas:

[0117]

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

[0118]

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

[0119]

Embedded image Metacyclophanes represented by

[0120]

Embedded image Para-substituted phenolic acyclic oligomers represented by

Neutral polyligands include crown compounds, cryptands, cyclic polyamines and acyclic analogs thereof. The compound is known to effectively incorporate metal ions, but can also effectively incorporate cationic organic molecules.

Other inclusion compounds include urea, thiourea, deoxycholic acid, dinitrodiphenyl, hydroquinone, o-trithymotide, oxyflavan, dicyanoamminenickel, dioxytriphenylmethane, triphenylmethane, methylnaphthalene, spirochroman, Examples include perhydrotriphenylene, clay minerals, graphite, zeolites (faujasite, chabazite, mordenite, levinite, montmorillonite, halosite, etc.), cellulose, amylose, proteins and the like.

These clathrate compounds may be added as a simple substance, but they improve the solubility of the clathrate compound itself or the clathrate compound incorporating the molecule in a solvent and the compatibility with other additives. For this reason, a polymer in which a substituent having an inclusion ability is suspended as a pendant substituent may be added together with the polymer.

Examples of the polymer include those disclosed in JP-A-3-221501, JP-A-3-221502, and 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.

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

Cyclodextrin and its derivatives are most preferred, and β-cyclodextrin and its derivatives are more preferred.

Further, a printout material capable of 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,
An ester compound or amide compound of o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-55-6244 and a phenol or aniline having an electron-withdrawing substituent, JP-A-55-77742, JP-A-57-1
Examples of the halomethyl vinyl oxadiazole compound and diazonium salt described in JP 48784 publication,
Examples of organic dyes include Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Patent Pure Blue (Sumitomo Mikuni Chemical Co., Ltd.), and Oil Blue #.
603 (manufactured by Orient Chemical Industry Co., Ltd.), Sudan Blue I
I (manufactured by BASF), crystal violet, malachite green, fuchsin, methyl violet, ethyl violet, methyl orange, brilliant green,
Examples thereof include Congo Red, Eosin, Rhodamine 66 and the like.

In addition to the above-mentioned materials, the photosensitive composition of the present invention may optionally contain 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, the photosensitive composition of the present invention contains, 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.

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

Examples of the solvent 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, propylic acid 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.

The coating method used for coating the surface of the support with the photosensitive composition is a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, 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 application, but for example, a coating amount of 0.05 to 5.0 g / m ² as a solid content is preferable.

The photosensitive lithographic printing plate of the present invention can be made into a plate by exposing and developing it in a usual manner. 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.

Suitable light sources 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.

The photosensitive lithographic printing plate of the present invention comprises [Si
Excellent developability can be obtained by performing development processing with a developer comprising an aqueous solution of an alkali metal silicate having O ₂ ] / [M] of 1.0 or less, preferably 0.5 or more and 0.8 or less.

[0136]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example Graining an aluminum sheet with a rotating brush,
After washing with water, it was immersed in a 10 wt% caustic soda aqueous solution kept at 70 ° C., etched so that the amount of aluminum dissolved was 7 g / m ^2, and then washed with water.

Then, it was immersed in a 10% aqueous solution of sulfuric acid for 20 seconds to be neutralized and washed with water. Then, using a 1.5% nitric acid aqueous solution heated to 40 ° C as the electrolytic solution, electrolytic etching is performed for 30 seconds, immersed in a 10% caustic soda aqueous solution at 50 ° C for 10 seconds, and then immersed in a 20% sulfuric acid aqueous solution to clean the surface. After washing, it was washed with water.

Further, the amount of anodic oxide film was 2 g / m ² in a 30 wt% sulfuric acid aqueous solution kept at 30 ° C. for 2 minutes using direct current.
Anodizing treatment was performed so that

Then, electrodeposition sealing treatment was performed under the conditions shown in Table 1 in a 4% ammonium borate electrolytic solution at 30 ° C. to prepare Support Samples 1 to 8.

Support samples 9 to 16 were prepared by steam sealing under the conditions shown in Table 2 in a saturated steam chamber at 1 atm and 100 ° C.

With respect to the obtained support samples 1 to 8,

[0142]

[Equation 19] (Hereinafter, referred to as a sealing rate A) was obtained.

Regarding the obtained support samples 9 to 16,

[0144]

(Equation 20) (Hereinafter, referred to as a sealing rate B.)

[0145]

(Equation 21) (Hereinafter, referred to as a sealing rate C) was obtained.

The method of obtaining the sealing rate A, the sealing rate B, and the sealing rate C will be specifically described below.

<Porosity A> After sufficiently cooling the support sample in liquid nitrogen, both ends of the support sample are pulled and divided, and the fracture surface is subjected to high resolution SEM (S-5000 manufactured by Hitachi Ltd.).
H), acceleration voltage: 1.5 KV, observation magnification 5000-100
The observation area (2μ
The depth of each sealing hole shown in FIG. 1 and the total coating depth in m) were measured, and the sealing rate A as an average value was obtained.

<Sealing rate B> The surface area of the unsealed support surface and the surface surface of the support surface after sealing were measured using QUANTASORB (manufactured by Yuasa Ionics Co., Ltd.) for determining the surface area by the simple BET method. Then, the sealing rate B was obtained.

<Sealing rate C> The surface of the unsealed support and the surface of the support after sealing were subjected to high resolution SEM (S manufactured by Hitachi Ltd.).
-5000H), acceleration voltage: 1.5KV, observation magnification 100
Dot analyzer by observing under the condition of 000 to 200,000 times
Image processing using DA-5000 (Shin Oji Paper Co., Ltd.)
Figure 1 for a randomly selected observation area (500 mm x 500 mm)
The pore opening area of the unsealed hole and the pore opening area after the sealing as shown in (3) were calculated to determine the sealing rate C.

The obtained results are shown in Tables 1 and 2.

[0151]

[Table 1]

[0152]

[Table 2]

On the obtained support, a photosensitive composition having the following composition was added.
Apply the coating solution using a wire bar and then at 80 ℃ for 2 minutes
After drying, photosensitive lithographic printing plate samples 1 to 16 were prepared. Feeling
The coating amount of the coating composition for the light-sensitive composition is 2.0 g / m 2 as a dry weight.
^Two It was made to become.

<Photosensitive Composition Coating Liquid> Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw: 4000) 6.70 g Pyrogallol acetone resin (weight average molecular weight 3000) and o -Condensation product of 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 Fluorosurfactant FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl cellosolve 100 ml

A positive original film having halftone dots and fine lines was adhered to the obtained photosensitive lithographic printing plate samples 1 to 15 and a 2 kw metal halide lamp was used as a light source at 8 mW / cm ² .
It was exposed by irradiation for 60 seconds.

Samples 1 to 1 of the exposed photosensitive lithographic printing plate
15 is A potassium silicate (manufactured by Nippon Kagaku Co., Ltd.) and caustic potassium, and the following [SiO ₂ ] / [M] ([SiO ₂ ] represents the molar concentration of the SiO ₂ component in the developer, and [M] is The developing treatment was performed with a developer having a molar concentration of an alkali metal component. The developers shown in Table 3 were used as the developers for developing the photosensitive lithographic printing plate samples.

Developer A [SiO ₂ ] / [M] = 0.6 Developer B [SiO ₂ ] / [M] = 0.8 Developer C [SiO ₂ ] / [M] = 1.2 Using the planographic printing plate obtained Then, by the following evaluation method,
The printing durability was evaluated. Further, the developability was evaluated by the following evaluation method. Table 3 shows the obtained results.

<Evaluation of Printing Durability> The lithographic printing plate thus obtained was set on a printer GTO manufactured by Heidelberg Co., Ltd., and coated paper printing ink (High Plus Red manufactured by Toyo Ink Mfg. Co., Ltd.) and a fountain solution ( Printing is performed using Konica Corporation SEU-3: 2.5%), and printing is continued until defective solidification appears in the solid part of the image part of the printed matter or ink is inked in the non-image part, at which time The printing durability was evaluated by counting the number of printed sheets.

<Evaluation of developability> The reflection optical density (Δ ₂ ) of the non-image area after development and the reflection optical density (Δ ₁ ) of the surface of the support immediately before coating the photosensitive layer were determined, and the difference (ΔD) Was evaluated according to the following evaluation criteria. (Evaluation Criteria) ○ ... ΔD <0.02 △ ... 0.02 ≦ ΔD ≦ 0.05 × ... 0.05 <ΔD

[0160]

[Table 3]

From Table 3, the photosensitive lithographic printing plate using the support of the present invention has excellent printing durability, and [Si
It can be seen that excellent developability can be obtained when developed with a developer comprising an aqueous solution of an alkali metal silicate having O ₂ ] / [M] of 1.0 or less.

[0162]

The photosensitive lithographic printing plate support of the present invention comprises:
It is possible to obtain a photosensitive lithographic printing plate having excellent printing durability and developability.

[Brief description of drawings]

FIG. 1 is a schematic view showing a pore that has been subjected to a sealing treatment formed on a fractured surface of a support.

FIG. 2 is another schematic view showing the pores subjected to the sealing treatment formed on the fractured surface of the support.

[Explanation of symbols]

 1 Aluminum support 2 Anodized film 3 Pore 4 Sealing treatment film

Front page continuation (72) Inventor Takahiro Mori 1st Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Kimi Kojima 1st Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Kazuyuki Nishio No. 1 Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (8)

[Claims] 1. A photosensitive lithographic printing plate support obtained by roughening an aluminum plate to form an anodized film and then sealing the plate, wherein the amount of the anodized film is 1 g / m ² or more, and the hole is sealed. And the total film depth are defined as the sealing depth and the total film depth that satisfy the following formula 1. A photosensitive lithographic printing plate support. [Equation 1] 2. An aluminum plate is roughened and anodized so that the amount of anodized film becomes 1 g / m ² or more,
A method for producing a photosensitive lithographic printing plate support, which comprises performing a sealing treatment so that the depth of the sealing hole and the total coating depth satisfy the following formula (1). [Equation 2] 3. A photosensitive lithographic printing plate support obtained by roughening an aluminum plate to form an anodized film and then sealing the plate, wherein the anodized film amount is 1 g / m ² or more and is unsealed. The surface area of the pores and the surface area after sealing are calculated by the following formula 2
A support for a photosensitive lithographic printing plate, characterized in that it has an unsealed surface area satisfying the conditions and a surface area after sealing. (Equation 3) 4. An aluminum plate is roughened and anodized so that the amount of anodized film becomes 1 g / m ² or more,
A support for a photosensitive lithographic printing plate, which is subjected to a sealing treatment so that the unsealed surface area and the surface area after the sealing satisfy the following formula 2 Manufacturing method. (Equation 4) 5. A photosensitive lithographic printing plate support obtained by roughening an aluminum plate, forming an anodized film, and then sealing the plate, wherein the amount of the anodized film is 1 g / m ² or more and is unsealed. For a photosensitive lithographic printing plate, wherein the pore opening area of the hole and the pore opening area after sealing are the unopened pore opening area satisfying the following formula 3 and the pore opening area after sealing. Support. (Equation 5) 6. An aluminum plate is roughened and anodized so that the amount of anodized film is 1 g / m ² or more,
The sealing treatment is performed so that the unsealed pore opening area and the unsealed pore opening area are the unsealed pore opening area and the unsealed pore opening area that satisfy the following Expression 3. A method for producing a photosensitive lithographic printing plate support. (Equation 6) 7. A photosensitive lithographic printing plate comprising a support for a photosensitive lithographic printing plate according to claim 1, 3 or 5 on which a layer of a photosensitive composition is provided. 8. The photosensitive lithographic printing plate according to claim 7, after imagewise exposure, [SiO ₂ ] / [M] ([SiO ₂ ] represents the molar concentration of the SiO ₂ component in the developer, and [M 2 ] Represents the molar concentration of the alkali metal component.) Is 1.0 or less, and the development treatment is carried out with a developing solution composed of an aqueous solution of an alkali metal silicate.