JPH10115931A - Positive type photosensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent dissolution of an anodized film and to relieve or eliminate occurrence of scum and stains caused when being left, by forming a layer containing a specified polymer compound on an Al plate subjected to a roughing treatment, and an anodizing treatment, and turned to be hydrophilic. SOLUTION: The layer formed on the Al plate subjected to the roughing treatment and the anodizing treatment and the hydrophilicness enhancing treatment contains repeating units represented sented by formula I and those represented by formula II as the copolymer components. In formulae I and II, R1 is an H or halogen atom or an alkyl group; each of R2 and R3 is an H or halogen atom, or a hydroxy, optionally substituted alkyl, aromatic, heterocyclic, -OR4 , -COOR5 , -CONHR6 , or -COR7 group; each of R4 -R7 is an alkyl or aromatic group; X is H or a metal atom; (n) is 1, 2, or 3; each of R12 and R13 is H or a halogen atom or an alkyl group; and Y is a divalent organic group.

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 feeling has been widely used.
Optical lithographic printing plates require a fine roughening treatment as a support.
Performed, and in some cases the surface by alkali etching
After cleaning, the anodic oxide film on the aluminum plate
Comprising an o-quinonediazide compound thereon
It is provided with a photosensitive layer. o-Quinonediazide compound
Is known to be converted to carboxylic acid by UV exposure
Therefore, if this is developed with an aqueous alkaline solution,
Only the exposed portions of the photosensitive layer are removed to expose the support surface.
You. Since the surface of the aluminum support is hydrophilic,
The part where the surface of the holding body is exposed (non-image part) retains water
Repels oil-based inks. On the other hand, development of the photosensitive layer
The areas that were not removed (image area) are lipophilic and
Repels and accepts ink. Such a positive photosensitive lithographic plate
The alkaline aqueous solution used as the developer for the printing plate
Known, but most commonly used
Are aqueous silicate solutions such as sodium silicate and potassium silicate
It is. The reason is that silicon oxide SiO which is a component of silicate
_TwoAnd alkali metal oxide M_TwoO ratio (generally [Si
O _Two] / [M_TwoO]) and the concentration of both in the liquid
It is possible to adjust developability to some extent by changing
That's because.

However, in the developing solution mainly composed of silicate described above, although the increased development stability and increase the SiO ₂ concentration, easily solids due to SiO ₂ is deposited, the automatic developing machine of the nozzle It is known that problems such as clogging and contamination of the device due to adhered matter are difficult to be solved by washing with water, and that development stability is also lacking.
In addition, when the developer is subjected to the neutralization treatment during the waste liquid treatment, the solution is liable to gel due to SiO ₂ , which tends to cause inconveniences such as clogging of the piping system. A developer which can avoid these inconveniences contains, as a development stabilizer, at least one compound selected from saccharides, oximes, phenols, and fluorinated alcohols in an amount of 0.01 mol / L or more, and an alkali. A developer containing an agent, that is, a silicate-free developer can be considered,
When trying to develop a conventional positive-type photosensitive lithographic printing plate, the anodic oxide film on the aluminum support is dissolved with a developer,
There are other disadvantages, such as accumulation in the developing solution, forming scum and sludge, deteriorating the washing performance of the automatic developing machine, and causing clogging of the spray.

[0004] Further, silicate-free pH 10-13.
When the substrate subjected to the anodic oxide film treatment is developed with about two developers, there is also a problem that the non-image area becomes white due to dissolution of the anodic oxide film during development. In addition, there is a problem that leaving the plate during printing makes it more difficult to remove ink. Such a phenomenon is referred to as standing stain. Further, even in a developing solution containing silicate, a substance contained in the photosensitive layer is irreversibly adsorbed on the non-image portion of the lithographic printing plate obtained by development, and the so-called residual color is contaminated. As a result, there is also a problem that it is difficult to distinguish the image part from the non-image part. Conventionally, various treatments for an anodized film of a support have been proposed. Although steam treatment, which is said to have a dissolution preventing ability during development, can prevent whitening of non-image areas, it has not been able to solve the problem of standing stains. On the other hand, the silicate treatment of the anodized film can solve the problem of whitening of the non-image area and the stain on standing, but has the disadvantage that the printing durability is deteriorated.

In order to solve the above problems, US Pat. No. 3,136,636 proposes to provide an intermediate layer of a water-soluble polymer such as polyacrylic acid and carboxymethylhydroxyethylcellulose. However, it was still unsatisfactory in terms of printing durability.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to prevent the anodic oxide film from being dissolved at the time of development, and to reduce or eliminate the generation of scum and standing stains without whitening the non-image area. It is another object of the present invention to provide a photosensitive lithographic printing plate capable of achieving high sensitivity and excellent printing durability.
Another object of the present invention is to provide a photosensitive lithographic printing plate in which residual colors are reduced or eliminated.

[0007]

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, in the present invention, a structural unit represented by the following general formula (1) and a structural unit represented by the general formula (2) are copolymerized on an aluminum plate which has been subjected to a surface roughening treatment, an anodic oxidation treatment, and a hydrophilic treatment. This is achieved by a positive photosensitive lithographic printing plate characterized in that a photosensitive layer is provided after a layer containing a polymer compound as a component is provided. General formula (1)

[0008]

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(R ₁ represents a hydrogen atom, a halogen atom or an alkyl group. R ₂ and R ₃ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a substituted alkyl group, an aromatic group, a substituted aromatic group. Group, —OR ₄ , —COOR ₅ ,
Represents -CONHR ₆ , -COR ₇ or -CN,
Alternatively, R ₂ and R ₃ may combine to form a ring. R ₄ ~
R ₇ represents an alkyl group or an aromatic group. X represents a hydrogen atom, a metal atom, NR ₈ R ₉ R ₁₀ R ₁₁ . R ₈ ~
R ₁₁ each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aromatic group, or a substituted aromatic group, or R ₈ and R ₉ may combine to form a ring. n is 1 to 3
Represents an integer. R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a halogen atom or an alkyl group. Y represents a divalent organic group. )

In the present invention, the dissolution of the anodic oxide film during development, the whitening of the non-image area, the generation of scum, and the stain on standing can be effectively prevented by performing the hydrophilic treatment. It is characterized in that a polymer compound having a structural unit represented by the formula (2) and a structural unit represented by the general formula (2) as a copolymer component is used for an undercoat layer. That is, by using the bifunctional structural unit represented by the general formula (2), it is possible to obtain a network polymer having a higher molecular weight and a three-dimensional spread than the chain polymer compound. -Like polymer compound has high sensitivity and excellent mark-proof performance by effectively coating the surface of the aluminum plate which has been subjected to surface roughening treatment, anodizing treatment and further hydrophilization treatment, and the residual color has been reduced. A positive photosensitive lithographic printing plate can be provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) of the present invention will be described in detail below. In the structural unit represented by the general formula (1), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group or a substituted alkyl group, and is preferably a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms. Represents Particularly preferably, it represents a hydrogen atom or a methyl group. R ₂ and R ₃ 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, -R 4, -COOR 5, -CONHR} 6, -
It may represent COR ₇ or —CN, or R ₂ and R ₃ may combine to form a ring. Here, R _{4 to} R ₇ each represent an alkyl group or an aromatic group. More preferred R ₂ and R
₃ are each independently a hydrogen atom, a hydroxyl group, a chlorine atom, alkyl group having 1 to 4 carbon atoms, a phenyl group, -R _4, -C
_{OOR 5, -CONHR 6, -COR 7} , is a -CN,
Here, R _{4 to} R ₇ are an alkyl group having 1 to 4 carbon atoms or a phenyl group. Particularly preferred R ₂ and R ₃ are each independently a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group. X represents a hydrogen atom, a metal atom, NR ₈ R ₉ R ₁₀ R ₁₁ , wherein R _{8 to} R ₁₁ each independently represent a hydrogen atom,
It may represent an alkyl group, a substituted alkyl group, an aromatic group or a substituted aromatic group, or R ₈ and R ₉ may combine to form a ring. More preferred X is a hydrogen atom, a monovalent metal atom, N
R ₈ R ₉ R ₁₀ R ₁₁ , wherein R _{8 to} R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Particularly preferred X represents a hydrogen atom, sodium, potassium, or _{NR 8 R 9 R 10 R 11} , wherein, R ₈ to R ₁₁ are each independently a hydrogen atom, a methyl group, an ethyl group. n represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1. R
Examples of the substituent in the substituted alkyl group of ₁ , R ₂ and R ₃ and R _{8 to} R ₁₁ include a halogen atom, a hydroxyl group, an aryl group,
Examples thereof include an alkoxy group, an alkoxycarbonyl group, and an acyl group. Preferably, a hydroxyl group, a methoxy group, an acetyl group, and a methoxycarbonyl group are used. Examples of the substituent in the substituted aromatic group represented by R ₂ and R ₃ and R _{8 to} R ₁₁ include a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group and an acyl group, and preferably a hydroxyl group or a methyl group. , An ethyl group, a methoxy group, an acetyl group, and a methoxycarbonyl group.

In the structural unit represented by the general formula (2),
And R₁₂, R₁₃Are each independently a hydrogen atom, a halogen
Represents an atom or an alkyl or substituted alkyl group
Is preferably a hydrogen atom, a chlorine atom or a group having 1 to 4 carbon atoms.
Represents an alkyl group. Particularly preferably, a hydrogen atom or methyl
Represents a radical. R₁₂, R₁₃Is a substituted alkyl group of R₁, R
_TwoAnd R_ThreeAnd R₈~ R₁₁Substituents on the substituted alkyl groups of
And may be substituted with the same substituents as described above. Y is divalent
Represents a functional group, preferably a phenylene group or an alkylene
Group, -CO _TwoCH_Two-, -CH_TwoOCOOCH_Two-, -CH
_TwoNHCH_Two-, -CH_TwoOCH_Two-, -CH_TwoNHCON
HCH_Two-, -OCOCH_TwoCH_TwoCO_Two-, -CH_TwoC₆H
_FourCH _Two-, -CH_TwoOCOC₆H_FourCO_TwoCH_TwoRepresents-
And particularly preferably a phenylene group and an alkyl having 1 to 4 carbon atoms.
Kylene group, -CO_TwoCH_Two-, -OCOCH_TwoCH_TwoCO_Two
-, -CH_TwoOCOC₆H_FourCO_TwoCH_Two-, -CH_TwoC₆H_Four
CH_TwoRepresents-.

Specific examples of the monomer of the structural unit represented by the general formula (1) are shown below. However, the present invention is not limited to this specific example.

[0014]

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[0015]

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It is to be noted that the mixture used as a raw material of the polymer compound used here may contain the structural unit represented by the general formula (1) in an amount of 20% or more, preferably 40% or more. Also,
The structural units represented by the general formula (1) may be used alone or in combination of two or more. Next, specific examples of the monomer of the structural unit represented by the general formula (2) are shown below. However,
The present invention is not limited to this specific example.

[0017]

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[0018]

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The mixture used as the raw material of the polymer compound used here preferably contains the structural unit represented by the general formula (2) in the following range. It is preferable that 0% <(molar fraction of the structural unit represented by the general formula (2)) ≦ 30%, and 0% <(molar fraction of the structural unit represented by the general formula (2)) ≦ More preferably, it is in the range of 20%. The polymer compound according to the present invention is generally
It can be manufactured using a radical chain polymerization method ("T
extbook of Polymer Science "3rd ed, (1984) FWBil
lmeyer, A Wiley-Interscience Publication). The molecular weight of the high molecular compound having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) as a copolymer component may be in a wide range, but gel permeation chromatography is performed using polystyrene as a standard. The weight average molecular weight (Mw) is 500 to 2.0 when measured using
It is preferably 00,000 and 5,000 to
More preferably, it is in the range of 500,000.

Next, a synthesis example of a polymer compound having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) of the present invention as a copolymer component will be described. [Synthesis Example 1] Synthesis of polymer compound (P-1) 68.2 g (0.46 mol) of p-vinylbenzoic acid, 5.0 g (0.04 mol) of allyl methacrylate, and 171 g of 1-methoxy-2-propanol were used. Take in a 500 ml three-necked flask and heat with stirring under a stream of nitrogen.
C. Next, 1.15 g (5 mmol) of dimethyl 2,2'-azobis (isobutyrate) was added, and stirring was continued. Two hours later, 1.15 g (5 mmol) of dimethyl 2,2'-azobis (isobutyrate) was added. After another two hours, dimethyl 2,2'-azobis (isobutyrate) 1.15
g (5 mmol) was added. After stirring for 2 hours,
171 g of methoxy-2-propanol was added, and the mixture was allowed to cool to room temperature. The reaction was poured into 7.5 liters of water with stirring. The precipitated solid was collected by filtration and dried. The yield is 7
0.3 g. As a result of measuring the molecular weight of the obtained solid by GPC (eluent: tetrahydrofuran), the weight average molecular weight (Mw) was 79,000 in terms of polystyrene. [Synthesis Example 2] Synthesis of polymer compound (P-2) 73.9 g (0.499 mol) of p-vinylbenzoic acid,
The same operation as in the above [Synthesis Example 1] was performed except that 0.13 g (1 mmol) of divinylbenzene and 173 g of 1-methoxy-2-propanol were used. The yield of the obtained solid was 69.7 g, and the weight average molecular weight (Mw) was 85,000 in terms of polystyrene. Other general formula (1)
A polymer having the structural unit represented by the general formula (2) and the structural unit represented by the general formula (2) as a copolymer component is also synthesized in the same manner.

Next, the positive photosensitive lithographic printing plate of the present invention will be described in detail. In the present invention, the photosensitive lithographic printing plate may be a PS plate. [Support] <Aluminum plate and its surface roughening treatment, anodizing treatment,
Hydrophilic treatment> (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, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The alloy composition has a different atomic content of 10% by weight or less. Aluminum which is suitable for the present invention is pure aluminum. However, since pure aluminum is difficult to produce due to refining technology, it is preferable that aluminum contains as little foreign atoms as possible. In addition, any aluminum alloy having the above-described heteroatom content 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 conventionally known and publicly available materials can be appropriately used. Preferred materials include JIS A 10
50, 1100, 1200, 3003, 310
3, the same 3005 materials are included. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm. Prior to the surface roughening treatment of the aluminum plate, a degreasing treatment for removing a rolling oil on the surface, for example, a treatment with a surfactant or an alkaline aqueous solution is performed as necessary.

(Roughening and Anodizing) The surface of the aluminum plate may be roughened mechanically, electrochemically dissolved and roughened, and chemically. There is a method of selectively dissolving the surface. 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. Further, 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 as required, 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. Anodizing treatment conditions vary depending on the electrolyte used, and thus cannot be specified unconditionally. In general, the concentration of the electrolyte is a 1-80% solution, and the liquid temperature is 5-7.
0 ° C., current density 5-60 A / dm ² , voltage 1-100 V,
An electrolysis time of 10 seconds to 5 minutes is appropriate. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily scratched,
So-called "scratch stains" in which ink adheres to scratches during printing are likely to occur. In addition, such an anodizing treatment is performed on the surface used for printing on the support of the lithographic printing plate, and the back surface of the electric force lines causes a 0.01 to 3 g / m ² anodic oxide film on the back surface. It is generally formed.

(Hydrophilization treatment) As the hydrophilization treatment used after the above-mentioned treatment, there is conventionally known:
A hydrophilic treatment is used. Examples of such a hydrophilic treatment include U.S. Pat. Nos. 2,714,066 and 3,181.
No. 461, No. 3,280,734, No. 3,902,7
No. 34 discloses an alkali metal silicate (for example, sodium silicate aqueous solution) method. In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. Alternatively, Japanese Patent Publication No. 36-22
No. 063, and potassium fluoride zirconate disclosed in U.S. Pat. Nos. 3,276,868 and 4,153.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in U.S. Pat. No. 461 and 4,689,272 is used. Among these, a particularly preferred hydrophilization treatment is an alkali metal silicate treatment.

(Alkali metal silicate treatment) The anodic oxide film on the aluminum plate which has been treated as described above is coated with an alkali metal silicate of 0.1 to 30% by weight, preferably 0.5 to 30% by weight.
It is immersed in an aqueous solution of 10% by weight and having a pH of 10 to 13 at 25 ° C., for example, at 15 to 80 ° C. for 0.5 to 120 seconds. If the pH of the alkali metal silicate aqueous solution is lower than 10, 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 to increase the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide and lithium hydroxide. In addition, an alkaline earth metal salt or IVB
A group metal salt may be blended. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. No. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like. Can be. 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 0.01 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight.

[Organic (undercoat) layer] After these hydrophilic treatments, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) are formed on an aluminum plate by various methods described below. An organic layer containing a polymer compound having a copolymer component is provided.

This organic undercoat layer can be provided by the following method. A solution in which a high molecular compound having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) as a copolymer component is dissolved in water or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof. Is applied on an aluminum plate and dried, and the organic compound is dissolved in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof. This is a method in which a compound is adsorbed, followed by washing with water or the like and drying to provide an organic undercoat layer. In the former method, 0.005 to 1 of the above organic compound is used.
A solution with a concentration of 0% by weight can be applied in various ways. 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 weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20 to 9%.
0 ° C., preferably 25-50 ° C .;
It is 1 second to 20 minutes, preferably 2 seconds to 1 minute. The pH of the above solution is adjusted with a basic substance such as ammonia, triethylamine or potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
5 can be used. 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 2 to 10
0 mg / m ² are suitable, preferably from 5 to 50 mg / m ^2. If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true when the amount is more than 100 mg / m ² .

<Backcoat> A backcoat is provided on the back surface of the support, if necessary. Examples of the back coat include a coating comprising a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. Layers are 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 )
Silicon alkoxy compounds such as ₄ are inexpensive and easily available,
A coating layer of a metal oxide provided therefrom is particularly preferred because of its excellent development resistance.

Next, the photosensitive layer, its components, development processing and the like in the photosensitive lithographic printing plate of the present invention will be described. [Photosensitive layer] On the support obtained as described above, a photosensitive layer made of a known positive photosensitive composition is provided to obtain a photosensitive lithographic printing plate. As the composition for the photosensitive layer, any composition can be used as long as its solubility or swelling property in a developer changes before and after exposure. Hereinafter, typical ones will be described. <O-quinonediazide compound> Examples of the photosensitive compound of the positive photosensitive composition include o-quinonediazide compounds, and representative examples thereof include o-naphthoquinonediazide compounds. 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 orthoquinonediazide compounds include 1,2,3,2,3,4,5,6,7,8,7,8,7,8,7,8,7,8,7,8
-Diazonaphthoquinone-5-sulfonic acid chloride and an ester of phenol-formaldehyde resin, described in JP-A-2-96163, JP-A-2-96165, and JP-A-2-96661.
There are esters of 2-diazonaphthoquinone-4-sulfonic acid chloride with phenol-formaldehyde resin.
Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303 and JP-A-48-5303
63802, 48-63803, 48-965
No. 75, No. 49-38701, No. 48-13354
No., JP-B-37-18015, 41-11222
No. 45-9610, No. 49-17481,
U.S. Pat. Nos. 2,797,213 and 3,454,4
No. 00, No. 3,544,323, No. 3,573
No. 917, No. 3,674,495, No. 3,78
5,825, British Patent Nos. 1,227,602, 1,251,345, 1,267,005, 1,329,888, and 1,330,932 ,
Those described in the specification such as German Patent No. 854,890 can be mentioned.

Examples of other o-naphthoquinonediazide compounds include compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride. Specific examples of such compounds are described in JP-A-51-139402 and JP-A-5-139402.
8-150948, 58-203434, 59
-165053, 60-12445, 60-
No. 134235, No. 60-163430, No. 61-1
No. 18744, No. 62-10645, No. 62-106
No. 46, No. 62-153950, No. 62-17856
2, No. 64-76047, U.S. Pat.
No. 809, No. 3,126,281, No. 3,13
No. 0,047, No. 3,148,983, No. 3,1
No. 84,310, No. 3,188,210, No. 4,
No. 639, 406 and the like, and those described in each gazette or specification.

Particularly preferred o-naphthoquinonediazide compounds include o-quinonediazidesulfonic acid esters of polyhydroxy compounds having a weight average molecular weight of 2,000 or more. Examples of the polyhydroxy compound include pyrogallol / acetone resin, phenol-formaldehyde resin, cresol formaldehyde resin, hydroxystyrene resin, and halogenated hydroxystyrene resin. When the molecular weight of the o-naphthoquinonediazide compound is 2,000 or more, better image intensity can be obtained as compared with the case where the molecular weight is 2,000 or less.

When 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 0.3 to 1.0 equivalent.
As the 1,2-diazonaphthoquinonesulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride can be used. The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduced amounts.
The proportion of the compound converted with 2-diazonaphthoquinone sulfonic acid ester in this mixture (the content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%. It is. The amount of these o-quinonediazide compounds in the photosensitive composition of the present invention is suitably from 10 to 50% by weight, and more preferably from 15 to 40% by weight. The above molecular weight 2,
An o-naphthoquinonediazide compound having a molecular weight of 2,000 or more and an o-naphthoquinonediazide compound having a molecular weight of less than 2,000 can be used in combination. In this case, the ratio of the latter o-quinonediazide compound is preferably 50% by weight or less, more preferably 30% by weight or less, based on all the o-quinonediazide compounds.

<Polymer Binder> Although the o-quinonediazide compound alone forms the photosensitive layer, a resin soluble in alkaline water is preferably used together with this kind of resin as a binder. As such a resin soluble in alkaline water, there is a novolak resin having this property, for example, a phenol formaldehyde resin,
m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o- or m
-/ P- or m- / o-mixture) and cresol formaldehyde resins such as mixed formaldehyde resins. In addition, resol type phenol resins are also preferably used, and phenol / cresol (m
-, P-, o- or m- / p-, m- / o-).
Particularly, phenol resins described in JP-A-61-217034 are preferred.

Also, a phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, and JP-A-2-866. Various alkali-soluble polymer compounds such as an acrylic resin having a sulfonamide group described in (1) and a urethane resin can also be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
0 to 20,000 and number average molecular weight of 200 to 60,00
0 is preferred. Such alkali-soluble polymer compounds may be used alone or in combination of two or more, and generally used in an amount of 80% by weight or less of the total composition. Further, as described in U.S. Pat. No. 4,123,279, a phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. It is preferable to use a condensate with the above in view of improving the oil sensitivity of the image.

Particularly preferred as the polymer binder for the photosensitive layer provided on the support for the photosensitive lithographic printing plate of the present invention is that the content of the component having three or more aromatic groups in one molecule is 90% by weight or more. And a weight average molecular weight of 10,000
There are zero or more novolak-type phenol-formaldehyde resins. Hereinafter, in the present specification, the component having three or more aromatic groups in one molecule of the polymer binder is referred to as a trinuclear or higher component. Here, the weight average molecular weight is defined as a value in terms of polystyrene measured by gel permeation chromatography (GPC). Such a phenol-formaldehyde resin is synthesized by condensing phenol with an aldehyde such as formaldehyde or paraformaldehyde using an acidic catalyst. In particular, the weight average molecular weight used in the present invention is 10,0.
In order to obtain a phenol-formaldehyde resin of not less than 00, it is preferable to use 0.7 to 0.9 mol of aldehyde per 1 mol of phenol. If the aldehyde content is 0.7 mol or less, a sufficient molecular weight cannot be obtained,
If it exceeds 9 mol, a gel is easily formed, which is not preferable. As the acidic catalyst used in the condensation reaction, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, and the like can be used, and oxalic acid is preferable.

When the phenol / formaldehyde resin thus obtained contains 10% by weight or more of a dinuclear component, the low molecular weight component is removed by a method such as fractional precipitation, fractional dissolution, column chromatography, etc. The following components need to be reduced to 10% by weight or less. A phenol-formaldehyde resin containing 10% by weight or more of a binuclear or less component has high solubility and is inferior in chemical resistance, and a phenol-formaldehyde resin having a weight-average molecular weight of less than 10,000 has a printing resistance (chemical resistance). Sex). In addition, a cresol / formaldehyde resin used as a binder for a conventional positive photosensitive lithographic printing plate has a pH of 12.5.
It cannot be developed with the following developers. Thus, the content of the component having three or more aromatic groups in one molecule is 90% by weight.
By using a novolak-type phenol / formaldehyde resin having a weight average molecular weight of 10,000 or more, development can be performed with a developer having a relatively low pH, and sufficient printing durability (chemical resistance) can be obtained. Can be provided. The molecular weight of the photosensitive composition is 10.0 or less.
The amount of the phenol-formaldehyde resin of 00 or more is 30 to 90% by weight, more preferably 40 to 70% by weight.

The photosensitive composition may optionally contain an alkali-soluble resin other than the above-mentioned novolak-type phenol / formaldehyde resin. In particular, when a developer having a relatively low pH is used as such an alkali-soluble resin, it is soluble in alkaline water having a pH of 12.5 [where the resin soluble in alkaline water having a pH of 12.5 is 0.11 mol of sodium hydroxide and 0.4 mol of potassium chloride were dissolved in water to make 1 liter of an aqueous solution (p
(12.5 liters of an alkaline aqueous solution of H12.5), and 30.0 g of the resin is added thereto, and the mixture is stirred and dissolved in 30 minutes.] And the weight average molecular weight is 10,000.
00 to 100,000, and the following (1) to
A film-forming resin having at least one or more selected from the alkali-soluble group-containing monomers (4) as a polymerization component 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,
acrylamides having an aromatic hydroxyl group such as o-, m- or p-hydroxyphenyl acrylate or methacrylate, methacrylamides, acrylates, methacrylates and hydroxystyrenes, (2) acrylic acid, methacrylic acid, maleic acid Acid, maleic anhydride and its half ester, itaconic acid,
Unsaturated carboxylic acids such as itaconic anhydride and its half esters,

(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- (p-aminosulfonyl) Phenyl)
Methacrylamides such as methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate and m-aminosulfonylphenyl Acrylate, p
-Aminosulfonylphenyl acrylate, 1- (3-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenylnaphthyl) acrylate;
unsaturated sulfonamides such as methacrylates such as o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate;
(4) Phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide, and phenylsulfonylmethacrylamide which may have a substituent such as tosylmethacrylamide.

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, 2-chloroethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate,
(Substituted) such as N-dimethylaminoethyl acrylate
Acrylic acid ester, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, octyl methacrylate,
(Substituted) methacrylates such as phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate,

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

(10) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate; (11) styrenes such as styrene, α-methyl styrene, methyl styrene and chloromethyl styrene; 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-vinylpyrrolidone, N-vinylcarbazole; 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. Such alkali-soluble film-forming resins can be used alone or in combination of two or more.
It is used in a weight% addition amount. In addition to the above copolymer, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, and the like are also used.

<Degreasing agent> Further, US Pat.
As described in the specification of Japanese Patent No. 3,279, a condensate of phenol having an alkyl group having 3 to 8 carbon atoms as a substituent and formaldehyde, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, is used in combination. Is preferred for improving the oil sensitivity of the image.

<Development Accelerator> In the photosensitive composition, it is preferable to add a cyclic acid anhydride, a phenol or an organic acid in order to increase the sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy- △ ⁴ -tetrahydrophthalic anhydride described in U.S. Pat. No. 4,115,128. Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. As phenols, bisphenol A,
p-nitrophenol, p-ethoxyphenol, 2,
4,4'-trihydroxybenzophenone, 2,3,4
-Trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxy-triphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetra Methyltriphenylmethane and the like can be mentioned.

Further, as 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, carboxylic acids, and the like. Sulfonic 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,
3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid,
Erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned. The proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably from 0.05 to 15% by weight, more preferably from 0.1 to 5% by weight.

<Development Stabilizer> Further, in the photosensitive composition, Japanese Patent Application Laid-Open Nos. 62-251740 and 4-68355 disclose a method for expanding the stability of processing under development conditions (so-called development latitude). And amphoteric surfactants described in JP-A-59-121044 and JP-A-4-13149. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric 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 Co., Ltd.) and alkyl imidazoline type (for example, trade name Levon 15, manufactured by Sanyo Chemical Co., Ltd.) and the like.
The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

<Print-Out Agent and Dye> A print-out agent for obtaining a visible image immediately after exposure, and a dye or pigment as an image colorant can be added to the photosensitive composition. Representative examples of the printing-out agent include a combination of a compound that releases an acid upon exposure (photoacid releasing agent) and an organic dye that can form a salt. More specifically,
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-36209 and JP-A-53-8128,
No. 36223, No. 54-74728, No. 60-362
No. 6, No. 61-143748, No. 61-151644
And combinations of a trihalomethyl compound and a salt-forming organic dye described in JP-A-63-58440 and JP-A-63-58440. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the salt-forming organic dyes described above. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS,
Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, Japanese Unexamined Patent Publication No. Sho 62-2
The dyes described in JP 93247 A are particularly preferred.

<Coating Solvent> The photosensitive composition is dissolved in a solvent that dissolves the above-mentioned components, and is coated on an aluminum plate as a support. The solvent used here is disclosed in
Organic solvents described in 1-95463 are used alone or in combination. The photosensitive composition of the present invention is dissolved and dispersed at a solid content concentration of 2 to 50% by weight, coated on a support and dried. <Coating Amount> The coating amount of the layer of the photosensitive composition (photosensitive layer) applied on the support varies depending on the application, but is generally 0.3 to 4.0 g / dry weight. m ² is preferred. As the amount of coating decreases, the amount of exposure for obtaining an image may be small, but the film strength is reduced. As the coating amount increases, the exposure amount is required, but the photosensitive film becomes strong. For example, when used as a printing plate, a printing plate having a high printable number (high printing durability) can be obtained.

<Improvement of coating surface quality> In the photosensitive composition,
A surfactant for improving the coating surface quality, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added. The preferable addition amount is 0.001 to 1.0% by weight of the total photosensitive composition, and more preferably 0.005 to 0.5% by weight. <Matte layer> On the surface of the photosensitive layer provided as described above, a mat layer is provided in order to shorten the evacuation time in the close contact exposure using the vacuum printing frame and to prevent printing blur. Is preferred. Specifically, JP-A-50-1258
No. 05, Japanese Patent Publication No. 57-6582, No. 61-28986
And a method in which a solid powder is thermally melted as described in JP-B-62-62337.

[Development treatment] The PS plate thus obtained is exposed through a transparent original image with a light beam using a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp or the like as a light source, and then developed. <Developer main agent> The pH of the developer is about 10.0 to 13.5, and a developer having a relatively low pH may be used.
For example, a developer containing no silicate and having a pH of 10.0 to 12.7, more preferably a pH of 11.0 to 12.5, can be used. As such a developing solution and a developing replenishing solution, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, lithium silicate,
Tribasic sodium, potassium, ammonium,
Dibasic sodium, potassium, ammonium,
Sodium bicarbonate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium And the like. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine,
Diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylbutylammonium hydroxide, etc. Are also used.

A developer containing an alkali silicate such as potassium silicate, lithium silicate or sodium silicate has the advantage that stains during printing hardly occur, and the alkali silicate has a composition of [SiO ₂ ] / [ M] = 0.5 to 2.5
(Where [SiO ₂ [M] indicates the molar concentration of SiO _{2 and} the molar concentration of total alkali metal, respectively), and a developer containing 0.8 to 8% by weight of SiO ₂ is preferably used. . In addition, water-soluble sulfites such as sodium sulfite, potassium sulfite, and magnesium sulfite, resorcin, methylresorcin, hydroquinone, and thiosalicylic acid can be added to the developer. The content of these compounds in the developer is preferably 0.002 to 4% by weight, and more preferably 0.01 to 1% by weight.
% By weight.

Further, a preferable developer main agent is pH
An alkaline solution containing a compound having a buffer action of 10 or more can be used. As the compound having such a buffering action, one having an acid dissociation constant (pKa) of 10.0 to 13.2 is preferable, and IONISATION CONST issued by pergamon Press.
Selected from those described in ANTS OF ORGANIC ACIDS IN AQUEOUS SOLUTION etc., for example, 2,2,3,3-
Tetrafluoropropanol-1 (pKa 12.7
4), alcohols such as trifluoroethanol (12.37) and trichloroethanol (12.24), pyridine-2-aldehyde (12.68), pyridine-4-aldehyde (12.05) and the like Aldehydes, sorbitol (13.0), saccharose (12.7), 2-deoxyribose (12.61),
2-deoxyglucose (12.51), glucose (12.46), galactose (12.35), arabinose (12.34), xylose (12.2)
9), fructose (12.27), ribose (1)
2.22), saccharides such as mannose (12.08), L-ascorbic acid (11.34), salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (1)
2.84), 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 (11.56), pyrogallol (Id. 11.34),
Phenol (10.0), o-cresol (10.
33), resorcinol (11.27), p-cresol (10.27), m-cresol (10.0)
Compounds having a phenolic hydroxyl group such as 9),

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 (11.37).
Oximes such as 35) and adenosine (12.5
6), inosine (12.5) and guanine (12.
3), cytosine (12.2), hypoxanthine (1)
2.1), nucleic acid-related substances such as xanthine (11.9), and diethylaminomethylphosphonic acid (12.
32), amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1-ethylidene diphosphonic acid (1)
1.54), 1-hydroxy 1,1-ethylidene diphosphonic acid (11.52), benzimidazole (1
2.86), thiobenzamide (12.8), picoline thioamide (12.55), barbituric acid (1.
2.5) and the like. These compounds having a buffering action can be appropriately used at an appropriate pH, for example, pH 10.0 to 1 by using in combination with the above-mentioned alkaline agent.
It can be adjusted to 2.7 and used. Further, these compounds having a buffering action and alkali agents can be used alone or in combination of two or more. Preferred among these alkaline buffers are combinations of non-reducing sugars such as sulfosalicylic acid, salicylic acid, or saccharose and sorbitol with sodium hydroxide and potassium hydroxide. Further, two or more compounds each having the above-mentioned buffer action and alkali agent may be used as a mixture.

<Surfactant> In the developer and the replenisher,
Various surfactants and organic solvents can be added, if necessary, for the purpose of promoting developability, dispersing developed scum, and increasing the ink affinity of the printing plate image area. Preferred surfactants include
Examples include anionic, cationic, nonionic and amphoteric surfactants. 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, sorbitan fatty acid partial esters, pentaerythritol fatty acid Esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylene Castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bi Non-ionic surfactants such as 2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts , Dialkyl sulfosuccinate salts, linear alkyl benzene sulfonates, branched chain alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfo phenyl ether salts,

N-methyl-N-oleyltaurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, fatty acid alkyl ester sulfates, alkyl sulfates, polyoxy Ethylene alkyl ether sulfates, fatty acid monoglyceride sulfates,
Polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / anhydrous Anionic surfactants such as partially saponified maleic acid copolymers, partially saponified olefin / maleic anhydride copolymers, naphthalenesulfonate formalin condensates, alkylamine salts,
Quaternary ammonium salts such as tetrabutylammonium bromide, cationic surfactants such as polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, imidazolines, etc. Amphoteric surfactants. Among the surfactants mentioned above, the term "polyoxyethylene" can be read as a polyoxyalkylene such as polyoxymethylene, polyoxypropylene, or polyoxybutylene, and these surfactants are also included.

Further 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 and hydrophilic groups,
Non-ionic forms 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. 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 weight, more preferably 0.01 to 5% by weight.

<Development Stabilizer> Various development stabilizers are used in the developer and the replenisher. 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 or amphoteric surfactants described in JP-A-50-51324,
There is a water-soluble cationic polymer described in JP-A-95946 and a water-soluble amphoteric polymer electrolyte described in JP-A-56-142528. Further, JP-A-59-
No. 84241, an organoboron compound to which an alkylene glycol is added, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-11246, JP-A-60-12975.
Japanese Patent Application Laid-open No. 01-286, Japanese Patent Application Laid-Open No. 61-2
No. 15554, polyethylene glycol having a weight average molecular weight of 300 or more, a fluorinated surfactant having a cationic group described in JP-A-63-175858, and at least 4 mol of an acid or alcohol described in JP-A-2-39157. A water-soluble ethylene oxide addition compound obtained by adding ethylene oxide, a water-soluble polyalkylene compound, and the like can be given.

<Organic Solvent> An organic solvent is further added to the developing solution and the developing replenisher, if necessary. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight 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-phenoxyethanol, Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples include amines and N-phenyldiethanolamine. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the used solution. The amount used is closely related to the amount of surfactant used, and as the amount of organic solvent increases,
Preferably, the amount of surfactant is increased. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

<Reducing Agent> A reducing agent is further added to the developer and the replenisher. This is to prevent stains on 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 phenolic compounds such as thiosalicylic acid, hydroquinone, methol, methoxyquinone, resorcin, and 2-methylresorcin; and amine compounds such as phenylenediamine and phenylhydrazine. More preferred inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, bisulfite, diphosphite, thiosulfate and dithionite. Salts and the like can be mentioned. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by weight with respect to the developing solution at the time of use.

<Organic carboxylic acid> An organic carboxylic acid can be further added to the developer and the replenisher. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are those having 8 carbon atoms.
~ 12 alkanoic acids. 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 carboxyl group is substituted on a benzene ring, a naphthalene ring, an anthracene ring, or the like. 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 Acid, a few
-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 enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if the content is less than 0.1% by weight, the effect is not sufficient, and if it is 10% by weight or more, the effect cannot be further improved. In addition, dissolution may be hindered when another additive is used in combination. Therefore, the preferred amount is 0.1 to 10% by weight, more preferably 0.5 to 4% by weight, based on the amount of the developing solution used.

<Others> The developer and the replenisher may further contain an antifoaming agent and a water softener, 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 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 (methylene Phosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

The optimum value of such a water softener varies depending on its chelating power, the hardness of the hard water used and the amount of the hard water. 0.01 to 5% by weight, more preferably 0.01 to 5% by weight
It is in the range of 0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, an adverse effect on an image portion such as color omission appears. The remaining component of the developer and replenisher is water,
Further, if necessary, various additives known in the art can be contained. It is advantageous from the viewpoint of transportation that the developing solution and the replenishing solution are concentrated solutions having a smaller water content than when used, and are diluted with water when used.
The degree of concentration in this case is suitably such that each component does not cause separation or precipitation.

[Post-processing] The PS plate developed with the above-mentioned developer is rinsed with washing water, a surfactant and the like,
Post-treatment is performed with a finisher or a protective gum solution containing arabic gum or a starch derivative as a main component. These processes can be used in various combinations for the post-processing of the PS plate. In recent years, in the plate making and printing industries, automatic developing machines for PS plates have been widely used in order to streamline and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for horizontally transporting a PS plate, each processing solution tank and a spray device, and horizontally transports an exposed PS plate. Meanwhile, the developing solution and the post-processing are performed by spraying the processing solution pumped up by a pump from a spray nozzle. Recently, a PS plate has been immersed in a processing solution tank filled with a processing solution by a guide roll or the like and transported to carry out development processing, or a certain 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 automatic processing, processing can be performed while replenishing each processing solution with a replenisher in accordance with the processing amount, 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.

[0064]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following, all percentages are by weight unless otherwise specified. (Examples 1 and 2, Comparative Examples 1 to 5) JI having a thickness of 0.24 mm
The surface of the SA1050 aluminum plate was grained using a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, then neutralized with 20% HNO ₃ , and washed with water. This is V _A
The electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution at an anode electricity of 160 coulomb / dm ² using a sine wave alternating current under the condition of = 12.7 V. When the surface roughness was measured, it was 0.6 μm (Ra display). Subsequently, after immersing in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, the current density was 14% in a 20% H ₂ SO ₄ aqueous solution.
A / dm ² , anodized so that the amount of the anodic oxide film was equivalent to 2.5 g / m ² , and washed with water to prepare a substrate [A].

The substrate [A] was made of sodium silicate 2.5 wt%.
The substrate [B] was prepared by treating with an aqueous solution at 30 ° C. for 20 seconds and washing with water. The undercoat liquid (I) having the following composition was applied to the surface of the substrate [B] treated in this manner, and dried at 70 ° C. for 10 seconds. The coating amount after drying was 15 mg / m ² .・ ・
(Example 1) (I) P-1 0.3 g Methanol 100 g Water 1 g Similarly, instead of P-1 of the undercoat liquid (I), P-
Substrate B was prepared by applying the undercoating liquid using 2 (Example 2) to 15 mg / m ² substrate B. On the other hand, for comparison, a support (Comparative Example 1) in which the undercoat liquid was not applied to the substrate [B] was prepared. In addition, a support (Comparative Example 2) was prepared in which the substrate [B] was coated with polyacrylic acid described in US Pat. No. 3,136,636 instead of P-1 of the undercoat liquid (I). Further, P-3 (polymer compound obtained from a mixture containing no structural unit represented by the general formula (2)) synthesized in the following synthesis example instead of P-1 of the undercoat liquid (I) on the substrate [B] A support (Comparative Example 3) coated with was prepared. Finally, for comparison, a support (Comparative Example 4) in which the undercoat liquid (I) was not applied to the substrate A subjected to the anodizing treatment and a support in which the undercoat liquid (I) was applied were also prepared (Comparative Example 5).

Synthesis of Comparative Polymer Compound (P-3) 74.1 g (0.5 mol) of p-vinylbenzoic acid, 1-
The same operation as in the above [Synthesis Example 1] was performed except that 173 g of methoxy-2-propanol was used. The yield of the obtained solid was 71.2 g, and the weight average molecular weight (Mw)
Was 31,000 in terms of polystyrene.

The following photosensitive solution was applied to the substrate thus produced. Photosensitive solution Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (weight average molecular weight 2,500) 45 parts by weight Phenol formaldehyde novolak resin (weight average molecular weight 11,000 80 parts by weight p-toluenesulfonyl methacrylamide (28 mol%): acrylonitrile (21 mol%): ethyl acrylate (51 mol%) copolymer 20 parts by weight 2- (p-methoxyphenyl)- 4,6-bis (trichloromethyl) -s-triazine 2 parts by weight Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 1 part by weight Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc.) Activator) 0.4 parts by weight Methyl ethyl ketone 1000 parts by weight Propylene glycol Glycol monomethyl ether 1000 parts by weight

The PS plate thus obtained was exposed through a manuscript film for 60 seconds from a distance of 1 m using a 3 kW metal halide lamp. Thereafter, a commercially available automatic developing machine PS-900 having an immersion type developing tank with the following developing solution.
V (manufactured by Fuji Photo Film Co., Ltd.). Developer Salicylic acid 0.1 mol / L Saccharose 0.1 mol / L Tetrabutylammonium bromide 0.001 mol / L NaOH (Adjust the solution pH to 12.5)

The observation of whitening of the non-image area during development was performed as follows. After the development, the solid portion and the non-image portion were erased with an erasing liquid RP-1 manufactured by Fuji Photo Film Co., Ltd. and washed with water, and then the solid erased portion and the non-image portion were visually evaluated as follows. …: No difference in color between solid portion and non-image portion ×: Non-image portion is clearly whiter than solid erasure portion After printing 2,000 sheets with the SOR-M printing machine, printing is stopped and left for 40 minutes. After that, the sheet was mounted on the printing machine again and printed 100 sheets. At this time, the manner in which the ink was removed from the non-image area was observed and evaluated as follows. ○: The ink is dispensed quickly ×: The ink is dispensed slowly (easy to stain) In order to compare the printing durability, print a large number of sheets according to the usual method and measure the number of printable sheets. Judged. Evaluation of scum and sludge was performed as follows. After processing 1 m ² of the plate with 1 liter of the developing solution, the degree of dissolution of the oxide film in the alkali developing solution at this time was determined based on the state of the residue remaining in the developing solution. …: No scum or sludge is generated. ×: Large amounts of scum and sludge are generated. For the residual color, the difference between the density of the non-image area after development and the density of the support before coating was indicated by (ΔD). A smaller value indicates that the residual color is reduced. The sensitivity was determined by exposing and developing a step wedge manufactured by Fuji Photo Film Co., Ltd. (each step having a density difference of 0.15) by the above-described method, and indicating the number of clear steps. The higher the number of stages, the higher the sensitivity. Table 1 shows the above results.

[0070]

[Table 1]

[0071]

The positive photosensitive lithographic printing plate of the present invention can prevent the dissolution of the anodic oxide film at the time of development as compared with conventional ones, and thus can prevent the whitening of the non-image area at the time of development, and reduce the generation of sludge gas. It has the remarkable effects of preventing generation, reducing stains on standing, reducing residual colors, and exhibiting high sensitivity and excellent printing durability.

Continued on the front page (72) Inventor Keisa Akiyama 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd.

Claims (1)

[Claims] 1. A structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) are copolymerized on an aluminum plate which has been subjected to a surface roughening treatment, an anodizing treatment and a hydrophilic treatment. A positive-type photosensitive lithographic printing plate characterized in that a photosensitive layer is provided after a layer containing a polymer compound having a component is provided. Embedded image (R ₁ represents a hydrogen atom, a halogen atom or an alkyl group. R ₂ and R ₃ each independently represent a hydrogen atom, a hydroxyl group,
Halogen atom, alkyl group, aromatic group, -OR ₄ , -C
OOR ₅ , —CONHR ₆ , —COR _7, or —CN, or R ₂ and R ₃ may combine to form a ring. R _{4 to} R ₇ each represent an alkyl group or an aromatic group.
X represents a hydrogen atom, a metal atom, NR ₈ R ₉ R ₁₀ R ₁₁ .
R _{8 to} R ₁₁ each independently represent a hydrogen atom, an alkyl group, or an aromatic group, or R ₈ and R ₉ may combine to form a ring. n represents an integer of 1 to 3. R ₁₂ , R
₁₃ each independently represents a hydrogen atom, a halogen atom or an alkyl group. Y represents a divalent organic group. )