JP2002214791A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate excellent in development latitude without lowering the developability of a non-image area. SOLUTION: The photosensitive planographic printing plate has a photosensitive layer containing an o-quinonediazido compound on a surface-roughened and anodically oxidized aluminum substrate and has a continuous layer containing a water-soluble copolymer having a fluoroaliphatic group and a poly(oxyalkylene) group on the photosensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive lithographic printing plate, and more particularly to a positive photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Conventionally, a positive photosensitive lithographic printing plate, which has been widely used, generally has an exposed portion of a photosensitive layer dissolved and removed with an alkali developing solution to expose a support layer and receive water. It is a non-image area that tends to repel oil-based ink. On the other hand, the unexposed part remains on the plate as it is because it is insoluble in the alkali developing solution, and becomes an image part which repels water and easily receives oily ink.

[0003] However, if there is an excessive replenishment of the alkali developing replenisher or the like, the unexposed portion of the photosensitive layer, which is supposed to be an image portion, may be easily dissolved by the alkali developing solution. When such a phenomenon occurs, there is a problem that the film thickness of the image portion after the alkali development is reduced, resulting in unevenness of the ink density on the printed matter or reduction of the image area.

On the other hand, if the solubility of the photosensitive layer in an alkali developing solution is reduced in order to increase the resistance to a slight increase in alkali strength (hereinafter referred to as development latitude), the photosensitive layer is exposed to non-image areas. There is a problem that the layer remains and stains occur. In order to solve this problem, attempts have been made to make the vicinity of the surface of the photosensitive layer difficult to dissolve in a developing solution that is an alkaline aqueous solution. For example, a method of including a hardly soluble substance having a surface orientation in the photosensitive layer is used. Have been. However, in this method, since a solvent in which the lower layer is dissolved is used, there is a problem that a poorly soluble substance enters not only on the surface but also inside the photosensitive layer, thereby impairing the developability of the non-image area.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive lithographic printing plate having a developing latitude without deteriorating the developability of a non-image area. Another object of the present invention is to provide a photosensitive lithographic printing plate having a good development latitude even when developed using a developer containing no silicate.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have solved the above object by the following photosensitive lithographic printing plate. That is, the present invention has a photosensitive layer containing an o-quinonediazide compound on an aluminum support that has been subjected to surface roughening and anodizing, and a fluoroaliphatic group and a poly (oxyalkylene) group are provided on the photosensitive layer. A photosensitive lithographic printing plate having a continuous layer containing a water-soluble copolymer having the formula:

[0007] The inventors have tried to add various hardly soluble substances having a surface orientation to the photosensitive layer, but did not obtain satisfactory results. Further, an attempt was made to provide an upper layer using an organic solvent on the surface of the photosensitive layer, but it was mixed with the components of the lower layer, and a sufficient effect was not obtained.

On the other hand, a photosensitive layer containing an o-quinonediazide compound is provided on a roughened and anodized aluminum support, and a fluoroaliphatic group and a poly (oxyalkylene) are provided on the photosensitive layer. ) It is clear that the photosensitive lithographic printing plate obtained by providing a continuous layer containing a water-soluble copolymer having a group greatly improves the development latitude while maintaining the developability of the non-image area. became. That is, they found that a water-soluble copolymer having a fluoroaliphatic group and a poly (oxyalkylene) group was sparingly soluble in an aqueous alkaline developer, and this water-soluble copolymer was used on a photosensitive layer using water as a solvent. By coating on the photosensitive layer, it was possible to form a layer which is hardly soluble in an alkaline aqueous developer on the surface of the photosensitive layer so as not to be mixed with the photosensitive layer, and it was revealed that the development latitude was greatly improved.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION <Continuous layer containing water-soluble copolymer having fluoroaliphatic group and poly (oxyalkylene) group> First, a fluoroaliphatic group and a poly (oxyalkylene) used in the present invention are used. ) The water-soluble copolymer compound having a group will be described in detail. The water-soluble copolymer compound having a fluoroaliphatic group and a poly (oxyalkylene) group in the present invention is preferably a copolymer of a fluoroaliphatic group-containing monomer and a poly (oxyalkylene) group-containing monomer. .

The term "fluoroaliphatic group" means a saturated and generally monovalent or divalent aliphatic group usually having a fluorine atom. This includes linear, branched or cyclic. The fluoroaliphatic group is 3 to 20, preferably 6 to 20 in order to exert a sufficient effect for the purpose of the present invention.
The ratio of fluorine to the total amount of hydrogen and fluorine having 12 carbon atoms and bonded to carbon is preferably 20 mol%, more preferably 35 mol% or more. Suitable fluoro-aliphatic _{groups, C n F 2n + 1 -} (n is 1 or more, preferably an integer of 3 or more) substantially completely or fully fluorinated perfluoro aliphatic group such as (hereinafter, Rf).

If the fluorine atom in the Rf group is less than 20 mol%, the object of the present invention cannot be sufficiently achieved. The effect is greater when the fluorine atom is localized at the terminal of the Rf group. R
If the number of carbon atoms in the f group is 2 or less, the fluorine content can be increased, but the total amount of fluorine atoms becomes insufficient, and the effect is weak. Even if the fluorine content in the copolymer is increased by increasing the ratio of the fully fluorinated Rf group-containing monomer having 2 or less carbon atoms to the copolymer, the fluorine atoms are localized. Therefore, a sufficient effect cannot be obtained. On the other hand, when the number of carbon atoms of the Rf group is 21 or more, if the fluorine content is high, the solubility of the obtained copolymer in a solvent is low, and if the fluorine content is low, the fluorine atoms are sufficiently localized. Disappears, and a sufficient effect cannot be obtained.

As the addition-polymerizable monomer part in the addition-polymerizable monomer having an Rf group, a vinyl monomer having a radically polymerizable unsaturated group is preferably used. Of these vinyl monomers, particularly preferred are acrylate, methacrylate, acrylamide, methacrylamide, styrene and vinyl.
Specific examples of acrylates and methacrylates to which a fluoroaliphatic group is bonded include, for example, Rf-R'-OOC-
C (R ″) ＝ CH ₂ (where R ′ is, for example, a single bond, alkylene, sulfonamidoalkylene, or carbonamidoalkylene, and R ″ is a hydrogen atom, a methyl group,
A halogen atom or a perfluoroaliphatic group).

Examples of these are, for example, US Pat. Nos. 2,803,615, 2,642,416, 2,826,564, 3,102,103, and 3 No. 3,282,905, and No. 3,304,278, JP-A-4-106180, JP-A-6-256289,
JP-A-7-72936, JP-A-62-1116, JP-A-62-48772, JP-A-63-77574,
Examples thereof include those described in JP-A-62-36657 and those described in The Chemical Society of Japan, 1985 (No. 10), pages 1884-1888. In addition to these fluoroaliphatic group-bonded monomers, Reports Res. La
b. Macromers to which a fluoroaliphatic group described in Asahi Glass Co., Ltd. 34, 1984, pp. 27-34 can also be used. Further, as the fluoroaliphatic group-bonding monomer, a mixture having different lengths of perfluoroalkyl groups as shown in the following structural formula can be used.

[0014]

Embedded image

Next, the monomer having a poly (oxyalkylene) group in the water-soluble copolymer compound will be described. Poly
An (oxyalkylene) group is represented by-(OR) _X- . Here, R is preferably an alkylene group having 2 to 4 carbon atoms,
For _{example, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - C
_{H (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3)
-, And the like. X represents the number of oxyalkylene units, and is usually 2 to 60, preferably 5 to 40.

The above-mentioned poly (oxyalkylene) chain may be composed entirely of the same oxyalkylene unit like a poly (oxypropylene) chain, or two or more different types of oxyalkylene may be bonded irregularly. May be done. Also, poly (oxyalkylene)
The chain may be composed of a linear oxyalkylene unit (for example, an oxyethylene unit) or a branched oxyalkylene unit (for example, an oxypropylene unit). Oxypropylene units may be combined. Furthermore, poly (oxyalkylene)
The chains may be linked via one or more linking groups. If there are three or more linking groups, three or more poly (oxyalkylene) chains can be bonded to the linking groups. In this case, a (meth) acrylate having a plurality of poly (oxyalkylene) chains bonded via a linking group is obtained, and has a poly (oxyalkylene) chain which is a copolymer component of the fluoroaliphatic group-containing compound ( It can be used as (meth) acrylate.

The preferred molecular weight of the poly (oxyalkylene) group is 250-3000, more preferably 60
0 to 2500. Other poly (oxyalkylene)
For the synthesis method and specific examples of the (meth) acrylate having a group, the description of JP-A-62-227140 is further referred to in the present specification.

As the above-mentioned poly (oxyalkylene) (meth) acrylate, commercially available hydroxy poly (oxyalkylene) material, for example, trade name "Pluronic" (Plulro)
nic, Asahi Denka Kogyo Co., Ltd.), Adeka polyether (Asahi Denka Kogyo Co., Ltd.), "Carbowax" (Carbowax,
Glyco Products), "Triton" (Toriton, Rohm and Haas) and P.I. E. FIG. G (Daiichi Kogyo Pharmaceutical)
(Manufactured by K.K.) can be produced by reacting with a known method with acrylic acid, methacrylic acid, acryl chloride or acrylic acid anhydride.

The water-soluble copolymer having a fluoroaliphatic group and a poly (oxyalkylene) group of the present invention is produced from the above fluoroaliphatic group-containing monomer and poly (oxyalkylene) group-containing monomer by a known and conventional method. be able to. For example, (meth) acrylate having a fluoroaliphatic group and poly (oxyalkylene) (meth) acrylate can be produced by adding a general-purpose radical polymerization initiator in an organic solvent and thermally polymerizing the same. Alternatively, the compound can be produced in the same manner as described above, if necessary, by adding another addition-polymerizable unsaturated compound.

The molecular weight of the polyacrylate oligomer is
It can be adjusted by adjusting the concentration and activity of the initiator, the concentration of the monomer and the polymerization reaction temperature, and by adding a chain transfer agent such as a thiol such as n-octyl mercaptan. Fluoroaliphatic groups of the invention and poly
Examples of the water-soluble copolymer having an (oxyalkylene) group include acrylates containing a fluoroaliphatic group, Rf-R '
—OOC—C (R ″) ＝ CH ₂ is converted to poly (oxyalkylene) monoacrylate CH ₂ ＣＨCHC (O) (OR)
The copolymer obtained by copolymerizing with xOCH ₃ is shown below.

[0021]

Embedded image

Further, preferred examples of the water-soluble copolymer of the present invention include copolymers obtained by polymerizing monomers represented by the following general formulas (I) and (II).

[0023]

Embedded image

In the formula (I), R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, d is an integer of 1 to 5, and n is 6 to Indicates an integer of 12. In the formula (II), R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a, b and c each represent 0 or an integer of 1 to 55. a +
The sum of b + c is preferably 10 or more, and more preferably 30 or more. If the sum of a + b + c is less than 10, the solubility of the obtained copolymer in a coating solvent (water) becomes poor, which is not preferable.

The method for producing the water-soluble copolymer is described in JP-A-62-227140, which is incorporated herein by reference. Still more specific examples of the water-soluble copolymer of the present invention include the following compounds.

[0026]

Embedded image

The molecular weight of the water-soluble copolymer in the present invention is such that the weight average molecular weight (Mw) calculated from the integrated intensity ratio of the terminal group to the side chain functional group in NMR measurement is 3,000-2.
00,000, preferably between 4,000 and 100,0
00 range. If it is less than 3,000, the effect of preventing the penetration of the developer becomes weak, and if it exceeds 200,000, the solubility of the developer deteriorates and the photosensitive layer residue in the non-image area cannot be sufficiently removed. Not suitable. Here, the weight average molecular weight is measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard substance, and is a so-called polystyrene equivalent weight average molecular weight.

In the water-soluble copolymer of the present invention, the ratio of the fluoroaliphatic group-containing monomer to the poly (oxyalkylene) group-containing monomer is preferably in the range of 2: 8 to 7: 3. If the amount of the fluoroaliphatic group-containing monomer used is small, the effect of preventing the penetration of the developer becomes weak, and if it is too large, the monomer is not dissolved in the coating solution (water).

The water-soluble copolymer in the present invention includes a block copolymer, a random copolymer, a graft copolymer and the like, and is not limited to a copolymer having a specific bonding mode. The amount of the unreacted monomer contained in the polymer may be wide, but is preferably 20% by mass or less, and more preferably 10% by mass or less.

A polymer having a molecular weight within the above range can also be obtained by adjusting the amounts of a polymerization initiator and a chain transfer agent when copolymerizing a corresponding monomer. Note that a chain transfer agent refers to a substance that moves an active site of a reaction by a chain transfer reaction in a polymerization reaction, and the likelihood of the transfer reaction occurring is represented by a chain transfer constant Cs.

The chain transfer constant Cs × 10 ⁴ (60 ° C.) of the chain transfer agent used in the present invention is preferably 0.01 or more, more preferably 0.1 or more, and 1 or more.
It is particularly preferable that the above is satisfied. As the polymerization initiator,
In general, peroxides, azo compounds, and redox initiators commonly used in radical polymerization can be used as they are. Of these, azo compounds are particularly preferred.

Specific examples of the chain transfer agent include halogen compounds such as carbon tetrachloride and carbon tetrabromide; alcohols such as isopropyl alcohol and isobutyl alcohol;
Olefins such as -methyl-1-butene, 2,4-diphenyl-4-methyl-1-pentene, ethanethiol,
Butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyl disulfide, sec-butyl disulfide, 2-hydroxyethyl disulfide, thiosalicylic acid, thiophenol, Examples include sulfur-containing compounds such as thiocresol, benzyl mercaptan, and phenethyl mercaptan, but are not limited thereto.

More preferably, ethanethiol, butanethiol, dodecanethiol, mercaptoethanol,
Mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyl disulfide, se
c-butyl sulfide, 2-hydroxyethyl disulfide, thiosalicylic acid, thiophenol, thiocresol, benzyl mercaptan, and phenethyl mercaptan, particularly preferably ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptopropionic acid Methyl, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyl disulfide, sec-
Butyl disulfide and 2-hydroxyethyl disulfide.

The water-soluble copolymer compound is used in an amount of 0.1 to 2
A continuous layer that is hardly soluble in an alkaline water developer over the entire surface of the photosensitive layer is formed by dissolving the polymer in a water having a concentration of 0% by mass in water as a coating solvent, applying the solution on a photosensitive layer described below, and then drying. Can be done. The coating can be performed in the same manner as the coating of the photosensitive layer. The coating concentration after drying is preferably from ¹ to 500 mg / m ² .

Next, the positive photosensitive lithographic printing plate of the present invention will be described in detail in the order of the support, the photosensitive composition and the developing treatment.

<Support> The support used in the photosensitive lithographic printing plate of the present invention and the processing thereof will be described below. (Aluminum plate) The aluminum plate used in the present invention is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a trace amount of a different atom. The hetero atoms include silicon, iron, manganese, body, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The alloy composition has an atomic content of 10% by mass or less. Aluminum that is suitable for the present invention is pure aluminum, but it is preferable that completely pure aluminum contains as little foreign atoms as possible because it is difficult to produce due to refining technology. Further, any aluminum alloy having a different atomic content of the above-described level can be said to be a material that can be used in the present invention. As described above, the composition of the aluminum plate used in the present invention is not particularly limited, and any of conventionally known and publicly available materials can be appropriately used. Preferred materials include JISA 1050,
1100, 1200, 3003, 3103, and 3005 materials. The aluminum plate used in the present invention is optionally subjected to a degreasing treatment for removing rolling oil on the surface, for example, by treating with a surfactant or an alkaline aqueous solution.

(Roughening treatment and anodizing treatment) The surface treatment of the aluminum plate is carried out by mechanically roughening the surface, electrochemically dissolving and roughening the surface, and There is a method of chemically dissolving the surface selectively.
As a mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. In addition, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment in order to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film. In general, 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 the electrolyte.

Since the anodizing treatment varies depending on the electrolyte used, it cannot be specified unconditionally. Generally, however, the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5%.
It is suitable if it is within the range of 60 A / dm ² , voltage of 1 to 100 V, and electrolysis time of 10 seconds to 5 minutes. The amount of the anodic oxide film is preferably 1.0 g / m ² or more, more preferably 2.0 to 2.0 g / m ^2.
It is in the range of 6.0 g / m ² . 1.0 g of anodic oxide film
If it is less than / m ² , the printing durability is insufficient, the non-image portion of the lithographic printing plate is easily scratched, and so-called “scratch stain” in which ink adheres to the scratched portion during printing is likely to occur. Become. Incidentally, such an anodizing treatment is performed on the surface used for printing of the lithographic printing support, but an anodized film of 0.01 to 3 g / m ² is also formed on the back surface due to the back of the lines of electric force. It is generally done.

(Hydrophilic treatment) After the above-mentioned treatment, a hydrophilic treatment may be performed. As the hydrophilic treatment at this time, a conventionally known hydrophilic treatment is used. As such a hydrophilizing treatment, US Pat. No. 2,714,06
No. 6, No. 3,181,461, No. 3,280,734,
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in 3,902,734.
In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. Alternatively, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461, and 4,689,272 are disclosed. A method of treating with such polyvinyl phosphonic acid is used. Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

(Silica treatment) The anodic oxide film of the aluminum plate subjected to the above treatment was treated with an alkali metal silicate of 0.001 to 30% by mass, preferably 0.05 to 10% by mass, at 25 ° C. To an aqueous solution with a pH of 9-13,
For example, it can be immersed at 5-80 ° C. for 0.5-120 seconds. If the pH of the alkali metal silicate aqueous solution is lower than 9, the solution will gel, and if it is higher than 13.0, the oxide film will be dissolved. As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used for increasing the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide.

Incidentally, an alkaline earth metal salt or a Group IVB salt may be added to the above-mentioned processing solution. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. No. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium potassium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like. Can be.

The alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.10 to 1
0% by mass, and a more preferred range is 0.05 to 5.0% by mass. By the silicate treatment, the hydrophilicity on the aluminum plate surface is further improved, so that the ink does not easily adhere to the non-image area during printing, and the stain performance is improved.

(Undercoat layer) It is preferable to provide an organic undercoat layer on the photosensitive lithographic printing plate of the present invention before coating the photosensitive layer in order to reduce the remaining photosensitive layer in the non-image area. Examples of the organic compound used in the organic undercoat layer include carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, and naphthyl. Organic phosphonic acids such as phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid, and ethylenediphosphonic acid; Phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine Hydroxy Although selected from such as hydrochloric acid salt of an amine having a group,
You may mix and use 2 or more types.

Further, at least one compound selected from a group of high molecular compounds having a structural unit represented by the following general formula [IV] in a molecule, such as poly (p-vinylbenzoic acid), can be used.

[0046]

Embedded image

In the general formula [A], R ₄₁ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms. Particularly preferably, it represents a hydrogen atom or a methyl group. R ₄₂ and R ₄₃ are each independently a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a substituted alkyl group, an aromatic group, substituted aromatic group, -OR _44, -COOR _45, -CO
It may represent NHR ₄₆ , —COR ₄₇ or —CN, or R ₄₂ and R ₄₃ may combine to form a ring. Where R ₄₄
To R ₄₇ each represents an alkyl group or an aromatic group. More preferred R ₄₂ and R ₄₃ are each independently a hydrogen atom, a hydroxyl group, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, -OR ₄₄ , -COOR ₄₅ , -CONHR ₄₆ , -CO
R ₄₇ and —CN, wherein R _{44 to} R _{47 each} have 1 to 4 carbon atoms.
Alkyl groups or phenyl groups. Particularly preferred R ₄₂ and R ₄₃ are each independently a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group.

M is a hydrogen atom, a metal atom, NR₄₈R₄₉R₅₀
R₅₁Where R₄₈~ R₅₁Are each independently water
Element atom, alkyl group, substituted alkyl group, aromatic group, substitution
Represents an aromatic group, or R₄₈And R₄₉Combine to form a ring
You can do it. More preferred X is a hydrogen atom, monovalent gold
Genus atom, NR₄₈R₄₉R₅₀R₅₁Where R₄₈~ R
₅₁Are each independently a hydrogen atom, an alkyl having 1 to 4 carbons.
It is a kill group or a phenyl group. Particularly preferred X is water
Elementary atom, sodium, potassium or NR₄₈R ₄₉R₅₀R
₅₁Where R₄₈~ R₅₁Is each independently hydrogen
Represents an atom, a methyl group, or an ethyl group. p is an integer from 1 to 3
Represents, preferably represents 1 or 2, more preferably
Represents 1.

A polymer compound having a component having an onium group in addition to the component represented by the general formula [A] may be used. In a polymer compound having a monomer having an onium group as a polymerization component, onium groups are preferably onium groups consisting of Group V or Group VI of the periodic table, more preferably nitrogen atoms, phosphorus atoms or An onium group consisting of a sulfur atom, particularly preferably an onium group consisting of a nitrogen atom.

The molecular weight of the polymer compound may be in a wide range, but when measured by a light scattering method, the weight average molecular weight (Mw) is preferably from 500 to 2,000,000, more preferably from 1,000 to 600,000. More preferably, there is. Further, a number average molecular weight (Mn) calculated from an integrated intensity ratio between a terminal group and a side chain functional group in NMR measurement.
Is preferably 300 to 500,000, and 500
More preferably, it is で 100,000. When the molecular weight is smaller than the above range, the adhesion to the substrate is weakened, and the printing durability is deteriorated. On the other hand, if the molecular weight is larger than the above range, the amount of adhesion to the substrate becomes too strong, and the developability decreases.

This organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, etc. A solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof is immersed in an aluminum plate to adsorb the organic compound, and thereafter, washed with water or the like and dried to form an organic undercoat layer. Is the way. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by mass can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by mass, preferably 0.05 to 20% by mass.
The immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C, and the immersion time is 0.1 to 20 minutes, preferably 2 to 1 minute.

The pH of the solution used is adjusted by adjusting the pH with a basic substance such as ammonia, triethylamine or potassium hydroxide or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be used in the range of ~ 12. Further, a yellow dye can be added for improving the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the organic undercoat layer after drying is 1-2.
00 mg / m ² is suitable, preferably ^{2 to} 100 mg / m ²
It is. If the coating amount is less than 1 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² .

(Backcoat) On the back surface of the support, a backcoat is provided if necessary. Such a back coat comprises an organic polymer compound described in JP-A-5-45885 and a metal oxide obtained by hydrolyzing and polycondensing an organic or inorganic metal compound described in JP-A-6-35174. A coating layer is preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si
(OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) ₄
Such a silicon alkoxy compound is inexpensive and easily available, and a metal oxide coating layer provided therefrom is particularly preferable because of its excellent development resistance.

<Photosensitive composition> Next, the photosensitive composition used in the photosensitive lithographic printing plate of the present invention will be described in detail.
The photosensitive composition used in the present invention is an o-quinonediazide compound. A typical example thereof is an o-naphthoquinonediazide compound. The o-naphthoquinonediazide compound is preferably an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403.

Other suitable o-quinonediazide compounds include US Pat. Nos. 3,046,120 and 3.1.
There is an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and phenol-formaldehyde resin described in U.S. Pat.

Other useful o-naphthoquinone diad compounds include those reported and known in numerous patents. For example, JP-A-47-5303,
No. 48-63802, No. 48-63803, No. 48
Nos. -96575, 49-38701, 48-13
No. 354, Japanese Patent Publication No. 37-18015, and No. 41-112
No. 22, No. 45-9610, No. 49-17481,
JP-A-5-11444, JP-A-5-19477, JP-A-5-19478, JP-A-5-107755, U.S. Pat. Nos. 2,797,213 and 3,454,400
No. 3,544,323 and No. 3,573,917
No. 3,674,495, No. 3,785,825
No. 1,227,602, UK Patent No. 1,251,3
No. 45, No. 1,267,005, No. 1,329,88
No. 8, No. 1,330,932, German Patent No. 854,
890 and the like can be mentioned.

As other o-quinonediazide compounds, o-naphthoquinonediazide compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride can be used. . For example, JP-A-51-139402
No. 58-150948, No. 58-203434
No., 59-165053, 60-12445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
Nos. 2-178562, 64-76047, U.S. Patent Nos. 3,102,809, 3,126,281, 3,130,047, 3,148,983, and Nos. 3,184,310, 3,188,210, and 4,639,406, etc., which are described in public relations or specifications.

In synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound.
More preferably, the reaction is performed in an amount of from 0.3 to 1.0 equivalent.
As the 1,2-diazonaphthoquinonesulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferred, but 1,2-diazonaphthoquinone-4-chloride is preferred.
Sulfonyl chloride can also be used. The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and amounts of introduction, but all the hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid ester. The ratio of the compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%. The amount of these positive-acting photosensitive compounds (including the above combinations) occupying in the photosensitive composition of the present invention is suitably from 1 to 50% by mass, more preferably from 10 to 40% by mass. It is.

Of the above-mentioned positive-acting photosensitive compounds, especially the o-quinonediazide compound alone can constitute the photosensitive layer. However, when any of the photosensitive compounds is used, the binder (binder) is used. It is preferable to use together with a resin soluble in alkaline water as (-). Such resins soluble in alkaline water include novolak resins having this property, for example, phenol-formaldehyde resin, m-cresol-formaldehyde resin,
p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o- or m- / p- / o-mixed ) Crezo-such as mixed formaldehyde resin
And formaldehyde resin. These alkali-soluble polymer compounds have a weight average molecular weight of 500
~ 100,000 are preferred.

In addition, a resole type phenol resin is also preferably used, and phenol / cresol (m-, p-
-, O- or m- / p- / o-mixtures). A mixed formaldehyde resin is preferred.
Phenol resins described in Japanese Patent No. 217034 are preferred.

Further, a phenol-modified xylene resin, polyhydroxyethylene, polyhalogenated hydroxystyrene, an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, and JP-A-2-866. JP-A-7-28244, a vinyl resin or urethane resin having a sulfonamide group described in
JP-A-7-36184, JP-A-7-36185
JP-A-7-248628, JP-A-7-26139
No. 4, JP-A-7-333839, etc., various alkali-soluble polymer compounds such as vinyl resins having a structural unit can be contained. In particular, in the case of a vinyl resin, a film-forming resin having as a polymerization component at least one selected from the following alkali-soluble group-containing monomers (1) to (4) is preferable.

(1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o -Or m-chloro-p-hydroxystyrene, o
-, Acrylamides having an aromatic acid group such as m- or p-hydroxyphenyl acrylate or methacrylate, methacrylamides, acrylates,
Methacrylates and hydroxy styrenes,
(2) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and its half ester, itaconic acid, itaconic anhydride and its half ester

(3) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) Naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (paminosulfonylphenyl ) Methacrylamides such as methacrylamide, N- [1 (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate and m-aminosulfonyl phenyl Sulfonyl acrylate, p-
Unsaturated sulfonamides such as acrylate acid such as aminisulfonylphenyl acrylate, 1- (3-aminosulfonylphenylnaphthyl) acrylate, o
Unsaturated sulfonamides such as methacrylic acid esters such as -aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate;

(4) phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide;
And phenylsulfonyl methacrylamide which may have a substituent such as tosyl methacrylamide. Further, in addition to these alkali-soluble group-containing monomers, a film-forming resin obtained by copolymerizing the following monomers (5) to (14) is preferably used. (5) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate,

(6) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2 (Substituted) acrylates such as -chloroethyl, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (7) methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloromethyl methacrylate, 4-hydroxybutyl methacrylate (Substituted) methacrylates such as, gillsyl methacrylate, N-dimethylaminoethyl methacrylate,

(8) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N
-Phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N
-Nitrophenyl methacrylamide, N-ethyl-N-
Acrylamide or methacrylamide such as phenylacrylamide and N-ethyl-N-phenylmethacrylamide, (9) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as octyl vinyl ether and phenyl vinyl ether,

(10) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate; (11) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and (12) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; (13) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; (14) N-vinyl pyrrolidone, N-vinyl carbazole; 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

These alkali-soluble polymer compounds are
Those having a weight average molecular weight of 500 to 500,000 are preferred. Such alkali-soluble polymer compounds may be used alone or in combination of two or more, and are used in an amount of 99% by mass or less, preferably 98% by mass or less of the total composition. Further, in a photosensitive lithographic printing plate which is not exposed to infrared light to near infrared light, a more preferable additive range of the alkali-soluble polymer compound as described above is 30 to 80% by mass of the whole composition. . This range is preferred from the viewpoint of developability and printing durability.

Further, as described in US Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin, is used. O of the condensate with phenol formaldehyde
It is preferable to use a naphthoquinonediazidesulfonic acid ester (for example, one described in JP-A-61-243446) in order to improve the oil sensitivity of an image.

Further, the photosensitive lithographic printing plate may be subjected to a burning treatment in order to improve printing durability, chemical resistance, or suitability for special inks. A phenol compound can be added therein. Specific examples of phenols include phenol, catechol, resorcinol, pyrogallol, phloroglysin, aminophenol, and 2,4-
Dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,4-dihydroxybenzophenone,
Examples include a hydroxymethylphenol compound described in JP-A-157385 and a phenol compound containing a methoxymethyl group described in JP-A-7-17888.

(Development Accelerator) In the photosensitive composition of the present invention, it is preferable to add cyclic acid anhydrides, phenols and organic acids in order to increase sensitivity and improve developability. As the cyclic acid anhydride, US Pat.
No. 5,128, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
3,6-Endoxy- △ 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4-trihydroxybenzophenone, 2,3,4-hydroxy-4-hydroxybenzophenone, 4,4,4-trihydroxy-
Examples include triphenylmethane, 4,4,3,4-tetrahydroxy-3,5,3,5-tetramethyltriphenylmethane.

Further, as the organic acids, JP-A-60-8
No. 8942, JP-A-2-96755 and the like, there are sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters and carboxylic acids, and specifically, p-toluene sulfone Acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid,
Examples thereof include 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The proportion of the above cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is as follows:
0.05 to 15% is preferable, and 0.1 to 5% is more preferable.
% By mass.

(Development Stabilizer) In the photosensitive composition of the present invention, JP-A-62-2517 is used in order to increase the stability of processing under development conditions (so-called development tolerance).
Non-ionic surfactants described in JP-A No. 40 and JP-A-4-68355, JP-A-59-1210
No. 44 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, and polyoxyethylene nonyl phenyl ether.

Specific examples of the double-sided surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N , N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and alkylimidazoline type (for example, trade name Levon 15, manufactured by Sanyo Chemical Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably from 0.05 to 15% by mass, more preferably from 0.1 to 5% by mass.

(Print-out Agent, Dye, Others) In the photosensitive composition of the present invention, a print-out agent for obtaining a visible image immediately after exposure, and a dye or other filler as an image colorant are added. be able to. As the dye that can be used in the present invention, a cation having a basic dye skeleton described in JP-A-5-313359 and a sulfonic acid group as the only exchange group, and having 1 to 3 hydroxyl groups A basic dye comprising a salt with an organic anion having 10 or more carbon atoms can be used. The amount of addition is 0.2 to 5% by mass of the entire photosensitive composition.

Also, compounds described in the above-mentioned JP-A-5-313359 which generate photo-decomposition products which interact with the dyes to change the color tone, for example, JP-A-50-36209 (US Pat. No. 3,969,118) -)-Naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-53-3
No. 6223 (U.S. Pat. No. 4,160,671) describes trihalomethyl-2-pyrone and trihalomethyltricidin, and JP-A-55-62444 (U.S. Pat. No. 2,038,8).
01), various o-naphthoquinonediazide compounds described in JP-A-55-77742 (U.S. Pat. No. 4,279,9).
82) -trihalomethyl-5-aryl-
A 1,3,4-oxadiazole compound or the like can be added. Among these compounds, compounds having absorption at 400 nm may be used as a yellow dye described later.

As a colorant for an image, the above-mentioned JP-A-5-313 is used.
Other dyes can be used in addition to the dyes described in JP-A-359-359. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes. Specifically, Oil Green BG, Oil Blue BOS, Oil Blue # 6
03, (above, manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue BOH, Victoria Pure Blue N
APS, ethyl violet 6HNAPS [or more, manufactured by Hodogaya Chemical Industry Co., Ltd.], rhodamine B (C145170)
B), malachite green (C142000), methylene blue (C1520195) and the like.

Further, in the photosensitive composition of the present invention,
The following yellow dyes can be added. 417 nm represented by the general formula (i), (ii) or (iii)
A yellow dye having an absorbance of 70% or more of the absorbance at 436 nm;

[0079]

Embedded image

In the formula (i), R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkenyl group. R ₂₁ and R ₂₂ may form a ring. R ₂₃ , R ₂₄ and R ₂₅ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. G ₁ and G ₂ each independently represent an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group,
It represents an arylsulfonyl group or a fluoroalkylsulfonyl group. G ₁ and G ₂ may form a ring. Further, at least one of R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , G ₁ and G ₂ has at least one sulfonic acid group, carboxyl group, sulfonamide group, imide group, N-sulfonylamido group A phenolic hydroxyl group, a sulfonimide group, or a metal salt thereof,
Has inorganic or organic ammonium salts. Y is O, S, N
R (R is a hydrogen atom or an alkyl group or an aryl group), Se, -C (CH ₃ ) _2- , or a divalent atomic group selected from -CH = CH-, and n1 is 0 or 1.

[0081]

Embedded image

In the formula (ii), R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, a substituted heterocyclic group, an allyl group or a substituted allyl group. And R ₂₆ and R ₂₇ may together form a ring with the carbon atom to which they are attached. n2 represents 0, 1 or 2. G ₃ and G ₄ are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, an arylcarbonyl group, a substituted arylcarbonyl Group, alkylthio group, arylthio group,
Represents an alkylsulfonyl group, an arylsulfonyl group, or a fluoroalkylsulfonyl group. However, G ₃ and G ₄ are not simultaneously hydrogen atoms. Further, G ₃ and G ₄ may form a ring composed of a nonmetallic atom together with the carbon atom to which they are bonded. Further, at least one of R ₂₆ , R ₂₇ , G ₃ and G ₄ has at least one sulfonic acid group, carboxyl group, sulfonamide group, imide group, N-sulfonylamide group, phenolic hydroxyl group, sulfonimide group, Or a metal salt, an inorganic or organic ammonium salt thereof.

[0083]

Embedded image

In the formula (iii), R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ ,
R ₃₂ and R ₃₃ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a hydroxyl group, an acyl group, a cyano group, an alkoxycarbonyl group, an aryloxy group. Represents carbonyl, nitro, carboxyl, chloro, and bromo groups.

The photosensitive lithographic printing plate of the present invention can be obtained by dissolving the above-mentioned components of the photosensitive composition in a solvent capable of dissolving the components and coating the solution on a support. The solvent is selected so as not to dissolve the polymer compound containing an acid group and an onium group contained in the intermediate layer of the present invention. Specifically, for example, γ-butyrolactone, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ethyl, 2-methoxyethyl acetate,
-Methoxy-2-propanol, 1-methoxy-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, Diacetone alcohol, methanol, ethanol,
It can be appropriately selected and used from isopropanol, diethylene glycol dimethyl ether and a mixture of these solvents.

The concentration (solid content) of the above components is suitably from 2 to 50% by mass. The coating amount is 0.5 g / m ² to 4.
0 g / m ² is preferred. If the amount is less than 0.5 g / m ² , the printing durability will deteriorate. When the amount is more than 4.0 g / m ² , the printing durability is improved, but the sensitivity is lowered.

The photosensitive composition according to the present invention may contain a surfactant for improving a coating method, for example, JP-A-62-1.
A fluorine-based surfactant as described in JP-A-70950 can be added. A preferable addition amount is 0.01 to 20% by mass of the total photosensitive composition in combination with the fluorine-containing polymer compound of the present invention, and more preferably 0.0 to 20% by mass.
5 to 10% by mass. With the lithographic printing plate obtained as described above, a printed matter faithful to the original film can be obtained, but the print blurring and the roughness of the printed matter are poor.
As a method of improving the burn blur, there is a method of making the surface of the photosensitive amount provided in this way uneven. For example, as described in Japanese Patent Application Laid-Open No. 61-258255, there is a method in which particles of several μm are added to a photosensitive solution and the particles are applied. Is not improved at all.

However, for example, Japanese Patent Application Laid-Open No. 50-12580
No. 5, JP-B-57-6582, JP-B-61-28986
And Japanese Patent Application Laid-Open No. 62-62337, a method of forming a component having irregularities on the surface of a photosensitive layer is used to improve bokeh blur and improve the roughness of printed matter. Further, as described in JP-A-55-30619, when a light absorbing agent having absorption in the photosensitive wavelength region of the photosensitive material is contained in the mat layer, the burning blur and the roughness are further improved. In addition, an original film having a line number of 300 lines or more per inch and an original film obtained by FM screening, which is more easily burned and blurred than an original film having a line number of 175 lines per inch and which tends to give a sense of roughness to the printed matter, is used. Thus, a good printed matter can be obtained. As described above, the following fine patterns are preferably provided on the surface of the photosensitive layer of the photosensitive printing plate. That is, the height of the coated portion is preferably in the range of 1 to 40 μm, particularly 2 to 20 μm, and the size (width) is 10 to 10000 μm, especially
The range of 0 to 200 μm is preferred. The amount is 1 to 100
The range is 0 / m ² .

<Developing Process> Next, the developing process of the photosensitive lithographic printing plate of the present invention will be described. (Exposure) The photosensitive lithographic printing plate of the present invention is developed after being subjected to image exposure. As a light source for actinic rays for image exposure, there are a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, a chemical lamp and the like. Radiation includes electron beam, X-ray, ion beam,
There are far infrared rays. Also, g-line, i-line, Deep-U
V light and a high-density energy beam (laser beam) are also used. Laser beams include helium-neon laser, argon laser, krypton laser, helium, cadmium laser, KrF excimer laser,
Examples include a semiconductor laser and a YAG laser.

(Developer) A preferable developer for the photosensitive printing plate of the present invention is an alkaline aqueous solution containing substantially no organic solvent. Specifically, sodium silicate, potassium silicate, NaOH, KOH, LiOH,
Aqueous solutions such as sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, aqueous ammonia and the like are suitable.
More preferably, the developer contains (a) at least one saccharide selected from non-reducing sugars and (b) at least one base and has a pH in the range of 9.0 to 13.5.
Hereinafter, the developer will be described in detail. In the present specification, unless otherwise specified, the developing solution means a developing solution (a developing solution in a narrow sense) and a developing replenisher.

(Non-Reducing Sugar and Base) This developer comprises at least one compound whose main components are selected from non-reducing sugars and at least one base, and has a pH of 9.0.
〜13.5. Such non-reducing sugars are saccharides having no free aldehyde group or ketone group and exhibiting no reducibility, trehalose-type oligosaccharides in which reducing groups are bonded to each other, glycosides in which the reducing groups of saccharides are bonded to non-saccharides. It is classified as a sugar alcohol reduced by hydrogenation of a body and a saccharide, and both are suitably used. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. As sugar alcohols, D, L-arabit, ribit, xylit, D, L-sorbit, D, L-mannit, D, L-idit, D, L-idit
L-talit, durisit, allozursit and the like.

Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Among these, particularly preferred non-reducing sugars are sugar alcohols and saccharose. D-sorbitol, saccharose and reduced starch syrup are particularly preferred because they have a buffering action in an appropriate pH range and are inexpensive. These non-reducing sugars can be used alone or in combination of two or more kinds, and their ratio in the developer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations above this range,
It is difficult to achieve high concentration and the problem of cost increase comes up.
When a reduction or the like is used in combination with a base, there is a problem that the color changes to brown over time, the pH gradually decreases, and the developability decreases.

As the base to be combined with the non-reducing sugar, a conventionally known alkali agent can be used. For example, sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium, disodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, Same ammonium, sodium borate,
Inorganic alkali agents such as potassium and ammonium are exemplified. Also, monomethylamine, dimethylamine,
Trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc. Organic alkaline agents are also used.

These alkaline agents are used alone or in combination of two or more. Of these, sodium hydroxide and potassium hydroxide are preferred. The reason is that by adjusting these amounts with respect to the non-reducing sugar, the pH can be adjusted in a wide pH range. Trisodium phosphate, potassium phosphate, sodium carbonate, potassium phosphate and the like are also preferable because they themselves have a buffering action. These alkaline agents raise the pH of the developer to 9.0 to 9.0.
It is added so as to be in the range of 13.5, and the addition amount is determined by the desired pH and the addition amount of the non-reducing sugar, but the more preferable pH range is 10.0 to 13.2.

Further, an alkaline buffer consisting of a weak acid other than saccharides and a strong base can be used in combination with the developer. As a weak acid used as such a buffer, pKa is 10.0-1.
3.2 are preferred. Such weak acids include Per
IONISATION CONSTANTS OF ORGANIC published by gamon Press
Selected from those described in ACIDS IN AQUEOUS SOLUTION and the like, for example, 2,2,3,3-tetrafluoropropanol-1 (pKa 12.74), trifluoroethanol (12.37),
Alcohols such as 2.24), aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05), and salicylic acid (13.68).
0), 3-hydroxy-2-naphthoic acid (12.8
4), catechol (12.6), gallic acid (12.
4), sulfosalicylic acid (11.7), 3,4-dihydroxysulfonic acid (12.2), 3,4-dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene ( 11.82), hydroquinone (11.5)
6), pyrogallol (11.34), o-cresol (10.33), resorcinol (11.27), p
-Cresol, (10.27), m-cresol (1
0.09) and other compounds having a phenolic hydroxyl group,

2-butanone oxime (12.45);
Acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.3)
Oximes such as 5), adenosine (12.56),
Nucleic acid-related substances such as inosine (12.5), guanine (12.3), cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), and diethylamino Methylphosphonic acid (id. 12.32), 1-
Amino-3,3,3-trifluorobenzoic acid (12.2.
9), isopropylidene diphosphonic acid (12.1)
0) 1,1-ethylidene diphosphonic acid (11.5)
4) 1-hydroxy 1,1-ethylidene diphosphonic acid (11.52), benzimidazole (12.8)
6), thiobenzamide (12.8), picoline thioamide (12.8), picoline thioamide (12.5)
5) and weak acids such as barbituric acid (12.5).

Preferred among these weak acids are sulfosalicylic acid and salicylic acid. As a base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.
These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH within a preferred range depending on the concentration and combination.

(Surfactant) To the developer, various surfactants and organic solvents can be added as necessary for the purpose of accelerating the developability, dispersing the development residue, and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic,
Cationic, nonionic and amphoteric surfactants are included. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, and sorbitan. Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylene Castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-
Non-ionic surfactants such as bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides;

Fatty acid salts, abietic salts, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, straight-chain alkylbenzenesulfonates, branched-chain alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypoly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, alkyl sulfate esters, polyoxy Ethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphorus Ester salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphoric acid ester salts,
Partially saponified styrene / maleic anhydride copolymers,
Partially saponified olefin / maleic anhydride copolymers, anionic surfactants such as naphthalene sulfonate formalin condensates, quaternary ammonium salts such as alkylamine salts, tetrabutylammonium bromide, and polyoxyethylene alkylamine salts And cationic surfactants such as polyethylene polyamine derivatives, and amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. Among the above-listed surfactants, polyoxyethylene and polyoxymethylene, polyoxypropylene, poly (oxyalkylene) such as polyoxybutylene can also be read,
Those surfactants are also included.

More preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anionic type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine,
Cationic and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups,
Non-ionic types such as oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, and urethanes containing perfluoroalkyl groups and lipophilic groups are included. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

(Development Stabilizer) Various development stabilizers are used in the developer. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. Salts are mentioned as preferred examples. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946,
There is a water-soluble amphoteric polymer electrolyte described in 142,528.

Further, an organic boron compound to which an alkylene glycol has been added described in JP-A-59-84241, and a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-111246. JP-A-60-129750, polyoxyethylene / polyoxypropylene-substituted alkylenediamine compounds, JP-A-61-215554, polyethylene glycol having a weight average molecular weight of 300 or more, JP-A-63-175858. JP-A-2-39157 discloses a fluorine-containing surfactant having a cationic group, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol, and a water-soluble polyalkylene compound. No.

(Organic Solvent) The developer of the present invention does not substantially contain an organic solvent, but an organic solvent is added if necessary. As such an organic solvent, one having a solubility in water of about 10% by mass or less is suitable, and is preferably selected from those having a solubility of 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol,
4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m
-Methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N
-Phenylethanolamine and N-phenyldiethanolamine. "Substantially free of an organic solvent" in the developer of the present invention means that the content of the organic solvent is 5% by mass or less based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because if the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent does not completely dissolve, and therefore, it is impossible to expect good developability.

(Reducing Agent) A reducing agent can be further added to the developer. This prevents contamination of the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferred organic reducing agents include thiosalicylic acid, hydroquinone, methol, methoxyquinone, resorcinol, phenol compounds such as 2-methylresorcinol, phenylenediamine,
Amine compounds such as phenylhydrazine;
More preferred inorganic reducing agents include sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrophosphite,
Examples thereof include sodium salts, potassium salts, and ammonium salts of inorganic acids such as thiosulfuric acid and dithionous acid. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in the developer in use in the range of 0.05 to 5% by mass.

(Organic carboxylic acid) An organic carboxylic acid can be further added to the developer. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acids include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used.

The aromatic carboxylic acid is a compound in which a benzene ring, a naphthalene ring, an anthracene ring or the like is substituted with a carboxyl group, specifically, o-chlorobenzoic acid,
p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6- Dihydroxybenzoic acid, 2,3
-Dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-
There are hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid and 2-naphthoic acid, and hydroxynaphthoic acid is particularly effective.

The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to increase the water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is lower than 0.1% by mass, the effect is not sufficient,
If it exceeds 0% by mass, not only the effect cannot be further improved but also dissolution may be hindered when another additive is used in combination. Therefore, the preferred amount of addition is 0.1 to 10% by mass, more preferably 0.5% by mass, based on the developer used.
４4% by mass.

(Others) The developer may further contain a preservative, a coloring agent, a thickener, an antifoaming agent, a water softener and the like, if necessary. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and the like. Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts;
Aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-
Examples include hydroxyethane-1,1-diphosphonic acid and their sodium, potassium and ammonium salts.

The optimal value of such a water softener varies depending on the chelating power, the hardness of the hard water used and the amount of the hard water. 01 to 5% by mass, more preferably 0.01 to 0.1% by mass.
The range is 5% by mass. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is more than this range, adverse effects on the image area such as color omission appear. The remaining component of the developer is water. It is advantageous from the viewpoint of transportation that the developing solution is a concentrated solution in which the content of water is smaller than that at the time of use and is diluted with water at the time of use. In this case, the degree of concentration is appropriately such that each component does not cause separation or precipitation.

As the developer for the photosensitive lithographic printing plate of the present invention, the developer described in JP-A-6-282079 can also be used. This is because an alkali metal silicate having a SiO ₂ / M ₂ O (M represents an alkali metal) molar ratio of 0.5 to 2.0 and a sugar alcohol having 4 or more hydroxyl groups are added with 5 mol or more of ethylene oxide. Is a developer containing a water-soluble ethylene oxide addition compound obtained by the above method. Sugar alcohol is a polyhydric alcohol corresponding to one obtained by reducing an aldehyde group and a ketone group of a sugar to form primary and secondary alcohol groups, respectively. Specific examples of sugar alcohols include D, L-trait, erythritol, D, L-arabit, ribit, xylit, D, L-sorbit, D, L
L-mannit, D, L-id, D, L-tallit,
Dulcit, allodulcit, and di-, tri-, tetra-, penta-, and hexaglycerin obtained by condensing a sugar alcohol. The water-soluble ethylene oxide adduct is obtained by adding 5 mol or more of ethylene oxide to 1 mol of the sugar alcohol. Further, propylene oxide may be block-copolymerized with the ethylene oxide-added compound, if necessary, as long as the solubility is acceptable. These ethylene oxide addition compounds may be used alone or in combination of two or more.

The amount of addition of these water-soluble ethylene oxide addition compounds is 0.001 to 5 with respect to the developer (working solution).
% Is suitable, more preferably 0.001 to 2% by weight. The above-mentioned various surfactants and organic solvents can be further added to this developer, if necessary, for the purpose of promoting the developability, dispersing the development residue, and increasing the ink affinity of the printing plate image area.

(Development and Post-processing) A PS plate developed with a developer having such a composition may be washed with water, a rinsing solution containing a surfactant or the like, a finisher or a protective gum mainly composed of gum arabic or a starch derivative. The liquid is post-treated.
These processes can be used in various combinations for the post-processing of the PS plate of the present invention.

In recent years, in the plate making / printing industry, automatic developing machines for PS plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a PS plate, each processing solution tank and a spray device, and pumps the exposed PS plate horizontally while pumping it. Each processing liquid is sprayed from a spray nozzle to perform development and post-processing. Recently, a PS plate is immersed and transported by a submerged guide roll or the like in a processing solution tank filled with a processing solution to carry out development processing, or a fixed amount of small amount of washing water is supplied to the plate surface after development for washing. There is also known a method of reusing the waste water as dilution water of a developer undiluted solution.

In such an automatic processing, the processing can be performed while replenishing each processing liquid with the respective replenisher in accordance with the processing amount, the operating time and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets.

[0115]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In addition, all percentages in the following examples are mass% unless otherwise specified.

(Examples 1 to 8 and Comparative Examples 1 to 6) (a) The surface of a JIS A1050 aluminum plate having a thickness of 0.24 mm was sand-grained with a nylon brush and an aqueous suspension of pumice stone of 400 mesh. Washed well with water. (b) The aluminum plate is spray-etched at a caustic soda concentration of 2.6 wt%, an aluminum ion concentration of 6.5 wt%, and a temperature of 70 ° C., and the aluminum plate is 7 g.
/ M ² dissolved. Thereafter, washing with water was performed by spraying. (c) Desmut treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid (containing 0.5% by weight of aluminum ions) at a temperature of 30 ° C., followed by washing with a spray. As the nitric acid aqueous solution used for the desmutting, a waste liquid from a step of performing electrochemical surface roughening using an alternating current in a nitric acid aqueous solution was used.

(D) Electrochemical surface roughening treatment was continuously performed using an AC voltage of 60 Hz. At this time, the electrolytic solution was a 1 wt% aqueous solution of nitric acid (containing 0.5 wt% of aluminum ions and 0.007 wt% of ammonium ions) at a temperature of 50 ° C. The AC power supply waveform was subjected to electrochemical surface roughening treatment using a trapezoidal rectangular wave AC with a time TP until the current value reaches a peak from zero to a peak of 2 msec, a duty ratio of 1: 1 and a carbon electrode as a counter electrode. . Ferrite was used for the auxiliary anode. The current density was 30 A / peak at the current peak value.
dm ² , and the amount of electricity was 230 c / dm ² in total of the amount of electricity when the aluminum plate was an anode. 5% of the current flowing from the power supply was diverted to the auxiliary anode. Thereafter, water washing by spraying was performed.

(E) The aluminum plate was treated with a caustic soda concentration of 26.
When etching is performed by spraying at 70 ° C. by spraying at an aluminum ion concentration of 6.5 wt% at 70 ° C., and dissolving the aluminum plate at 0.2 g / m ² , and performing electrochemical surface roughening using a preceding alternating current. The smut component mainly composed of aluminum hydroxide formed was removed, and the edge portion of the generated pit was dissolved to smooth the edge portion. Thereafter, washing with water was performed by spraying. (f) A desmut treatment was performed by spraying with a 25% by weight aqueous solution of sulfuric acid having a concentration of 60 ° C. (containing 0.5% by weight of aluminum ions), followed by washing with water by spraying. (g) Using an anodizing apparatus, sulfuric acid concentration of 170 g / l (including 0.5 wt% of aluminum ions), temperature of 30 ° C., 20 A /
Anodizing treatment was performed so that the dm ² and the amount of the anodic oxide film corresponded to 2.4 g / m ² , and then the substrate was washed with water by spraying to prepare a substrate [A]. When the surface roughness was measured, it was 0.55 μm (Ra display). (h) Next, the substrate [A] was treated with a 0.1% aqueous solution of No. 3 sodium silicate at 20 ° C. for 10 seconds, and then washed with spray water to prepare a substrate [B].

The undercoat liquid [A] was applied to the substrate [B] and dried at 90 ° C. for 10 seconds. The coating amount after drying was 5 mg / m ² for the undercoat liquid [A].

Undercoating liquid [A] Polymer compound described in JP-A-10-301262 0.1 g (the structural formula is shown below) Methanol 100 g Water 0 g Undercoating liquid [B] β-alanine 0.2 g Methanol 100 g Water 1g

[0121]

Embedded image

In addition, other substrate [A] / undercoat [A], substrate [A] / undercoat [B] (coating amount: 10 mg
/ M ² ), the photosensitive layer and the upper layer were coated in the same manner, exposed and developed, and the development tolerance was evaluated. And there was almost no difference due to the combination of the substrate and the undercoat.

The following photosensitive solution A was applied to an undercoated substrate (substrate [B] / undercoat [A]) and dried to form a photosensitive layer. The photosensitive layer coating amount after drying was 1.3 g /
m ² .

[Photosensitive solution A] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709). 0.7g ・ Binder Cresol novolak (meta-para ratio 6: 4, weight average molecular weight 4000) 1.60g Phenol novolak (weight average molecular weight 12000) 0.3g ・ p-octylphenol-formaldehyde resin (US Patent No. 4) 0.01 g, naphthoquinone-1,2-diazido-4-sulfonic acid chloride 0.02 g, tetrahydrophthalic anhydride 0.02 g, pyrogallol 0.02 g, benzoic acid 0.02 g 4- [p-N, N-bis (ethoxycarbonylmethyl) aminopheni 0.05 g of -2,6-bis (trichloromethyl) -S-triazine 0.10 g of Victoria Pure Blue BOH (a dye manufactured by Hodogaya Chemical Co., Ltd. in which the counter anion is changed to 1-naphthalenesulfonic acid) F176PF (fluorinated surfactant, manufactured by Dainippon Ink and Chemicals, Inc.) 0.06 g methyl ethyl ketone 30.0 g 1-methoxy-2-propanol 10.0 g

On the photosensitive layer, an upper layer coating solution having the following composition was uniformly applied by a coater, and then dried at 120 ° C. for 10 seconds to form an upper layer.

(Upper Layer Coating Solution) 0.5 g of high molecular compound represented by the following structural formula (1) (see Table 1 for m, n, ac): 250.0 g of pure water

[0127]

Embedded image

Finally, in order to shorten the vacuum and adhesion time,
A photosensitive lithographic printing plate was prepared by forming a mat layer by the method described in JP-B-61-28986.

Comparative Example 1 A photosensitive lithographic printing plate of a comparative example was prepared in the same manner as in Example 1 except that the upper layer was not provided. The photosensitive lithographic printing plate thus prepared was image-exposed for 1 minute with a 3 kW metal halide lamp from a distance of 1 m through a step wedge P manufactured by Fuji Photo Film Co., Ltd. (each step having a density difference of 0.15). Photo film PS processor 90
Developed for 12 seconds at 30 ° C. using 0 VR. The developer used was adjusted as follows.

First, developing solutions A and B shown below were prepared. The pH of each developer was 13.0. For each developer A and B, the pH of developer A and B
The pH was increased or decreased by 0.2, respectively, based on
Types of liquids (A1 (-0.2), A2 (+0.2), B1
(−0.2), B2 (+0.2)) were prepared.

Exposure and development processing are similarly performed on the four kinds of developing solutions thus adjusted, and the difference in the number of solid steps (the smallest number of step wedges remaining after development) (A2 and A1 and the difference between B2 and B1). It can be said that the smaller the change in the number of solid steps, the better the development tolerance.

Developer A: D-sorbitol 5.1 parts by mass Sodium hydroxide 1.1 parts by mass Triethanolamine / ethylene oxide adduct (30 mol) 0.03 parts by mass Water 93.8 parts by mass Developer B: [SiO ₂ ] / [Na ₂ O] molar ratio 1.2, SiO ₂ 1.4 mass% sodium silicate aqueous solution 100 mass parts ethylenediamine / ethylene oxide adduct (30 mol) 0.03 mass parts

Table 1 shows the evaluation results of the compounds of Examples 1 to 6 and Comparative Examples 1 to 3 and the photosensitive lithographic printing plates using these compounds.

[0134]

[Table 1]

As is clear from the above table, the provision of the upper layer of the present invention provided a photosensitive lithographic printing plate having excellent development tolerance (Examples 1 to 6). A photosensitive lithographic printing plate inferior in development tolerance was obtained (Comparative Example 1).

[0136]

As described above, according to the present invention, a photosensitive lithographic printing plate having a good development latitude can be provided. Further, according to the present invention, even when development is performed using a developer containing no silicate, that is, even when the non-image area is not hydrophilized by the developer, a positive photosensitive lithographic plate having a good development latitude can be obtained. Printing plate can be provided.

Claims (1)

[Claims] A photosensitive layer containing an o-quinonediazide compound is provided on an aluminum support which has been subjected to surface roughening and anodizing treatment, and a fluoroaliphatic group and a poly (oxyalkylene) group are provided on the photosensitive layer. A photosensitive lithographic printing plate having a continuous layer containing a water-soluble copolymer.