JPS6295533A - Photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE:To prevent staining and the thickening of dots in a photomechanical process by specifying the amount of an anodic oxide film on the grain parts of an Al plate and the amount of diazo resin in a photosensitive composition and using PF6<-> or BF4<-> as anions in the diazo resin. CONSTITUTION:A layer of a photosensitive composition contg. diazo resin and a high molecular compound having carboxyl groups is formed on a grained and anodically oxidized Al plate to obtain a photosensitive lithographic printing plate. At this time, the amount of the anodic oxide film on the grain parts of the Al plate is regulated to 0.2-1.8g/m<2>, the amount of the diazo resin in the photosensitive composition is regulated to 10-60wt% and PF6<-> and BF4<-> is used used as anions in the diazo resin. An Al plate is anodically oxidized by supplying electric current to the plate as the anode in an aqueous soln. of an inorg. acid such as phosphoric acid, chromic acid boric acid or sulfuric acid, an org. acid such as oxalic acid or a mixture of two or more kinds of such acids, preferably in an aqueous soln. of phosphoric acid or a mixture of the acid with sulfuric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate, and more particularly to a diazo photosensitive lithographic printing plate used in offset printing and the like.

[Background of the invention] Conventionally, a photosensitive material is coated in a thin film on a support and then exposed to light through a transparent image on a photosensitive plate. Current value with solvent! C,
Various techniques have been proposed for forming relief images on photosensitive plates. Conventionally, as a photosensitive composition used for such a purpose, a combination of a diazo compound and a polymer compound is well known in the case of a negative planographic printing plate.

On the other hand, a grained aluminum plate is used as a lithographic printing plate, and in order to further improve printing durability, the grained surface is oxidized (approximately 2 g/f) (especially to improve printing durability). If necessary, it is known to cover by about 3 to 5 g/f).

However, the anodized grained surface has a strong effect of reflecting ultraviolet light during exposure, and especially when used as a negative lithographic printing plate, the print may have streaks of fill lX original). 1 is reproduced above (from now on point fat effect ■l
(abbreviated as), seal (ii from the 11th edition to the year of the seal!I','i
In the middle-aged 1J song, which is the final song of the Song Doka r, the final song, the point fat effect on J, 'S:Reshu is a
3 and there are many inconveniences.

As a photosensitive planographic printing plate that overcomes these drawbacks,
A photosensitive lithographic printing plate using a photopolymer type as a photosensitive composition, for example, printing in which a compound having α, β unsaturated ketones in the main chain described in JP-A-55-40415 is developed with a solvent. Examples include a method for producing a plate, or a photosensitive lithographic printing plate in which a diazo resin is a main component of a resist as a photosensitive composition.

However, in the photosensitive lithographic printing plates mentioned above,
Aqueous development: development cannot be done with liquid, stains occur with rapid development, etc.Furthermore, although development is possible with aqueous developer, developing problems may occur especially with a tired developer; There are many problems such as poor storage stability, and the current situation is that there is no photosensitive lithographic printing plate that satisfies all the performance requirements.

In order to improve these shortcomings, the present inventors created a polymer with diazo resin, d3, and carboxyl groups on an aluminum plate-F that was grained and anodized as a result of stacking fine holes. The anodic oxide coating 1 on the grained portion of the aluminum plate is set to a certain range, and the content of the diazo resin in the photosensitive composition is set to a certain range, and the diazo C1 It has been discovered that the above-mentioned problems can be solved by employing a photosensitive lithographic printing plate in which fat anions are specific anions.

[Objective of the Invention] That is, the object of the present invention is to enable development with an aqueous developer, and which does not cause stains even when developed with a fatigued developer or is subjected to rapid processing (l!). To provide a photosensitive lithographic printing plate in which halftone dots are small in thickness during plate making.

Another purpose is to ensure that the resist is hardly immersed even in the case of rubbing development, and to prevent stains of 11f even in the case of developing with fatigue developer 61 solution or rapid development.
The photosensitive ↑11 resin printing plate is 1, H (11).

Furthermore, another purpose is to have a high printing durability and a plate making iJj.
, J: Sign 11: An object of the present invention is to provide a photosensitive lithographic printing plate in which halftone dots at the time of printing are small in thickness.

Another object of the present invention is to provide a photosensitive lithographic printing plate with good exposure and visible image properties.

Furthermore, another object is to provide a photosensitive lithographic printing plate which has good storage stability and has small halftone dots during plate making.

[Structure 1 of the Invention The above object of the present invention is to provide a photosensitive planographic plate comprising a grained and anodized aluminum plate provided with a photosensitive composition layer containing a diazo resin and a polymer compound having a carboxyl group. In the printing plate, the anodic oxide film thickness of the grained portion of the aluminum plate is 0.2 to 1.8 (]/n
', and the content of the diazo resin in the photosensitive composition is from 10% by weight to 60% by weight, and
This is achieved using a photosensitive lithographic printing plate in which the anion of the diazo resin is PF et al. or BF4.

[Specific Structure of the Invention] The photosensitive diazo resin used in the present invention includes a diazo resin represented by a condensate of an aromatic diazonium salt and an active carbonyl-containing compound, particularly formaldehyde, among which Diazo resins soluble in organic solvents are preferred.

The diazo resin used in the present invention is, for example, a diazo resin which is an organic solvent-soluble reaction product of a condensate of p-diazodipenylamine and formaldehyde or acetaldehyde, and hexafluorophosphate or tetrafluoroborous Fl salt. Resin inorganic salts are preferably used.

A more preferable example of the diazo resin used in the present invention is one represented by the following general formula [I].

General formula [I] (wherein R+, R2, and R3 are hydrogen atoms, alkyl groups, or alkoxy groups, such as methyl groups, ethyl groups,
Represents an xy group or an ethoxy group, R is a hydrogen atom,
represents an alkyl group, such as a methyl group, an ethyl group or a propyl group, or a phenyl group, and X 1. lLP F
s or B1:4, and n is a number from 1 to 200), and contains 20 mol% or more, preferably 20 to 60 mol%, of a resin in which n in the formula is 5 or more. It is.

The photosensitive composition used in the present invention contains the diazo resin and a polymer compound having a 7J ruboxy group, which will be described in detail below, but the content of the diazo resin in the photosensitive composition is as follows:
10 weight percent to 60 weight percent, preferably 12 weight percent to 40 weight percent, more preferably 15,000 weight percent to 3041 weight percent. One of the features of the present invention is that the content of diazo resin in the photosensitive composition is 1! Furthermore, the effect of the present invention was exhibited by the combination of the content of the diazo(go-1 fat), a specific polymer compound, and a specific aluminum grain plate. , which should be really rough.

The polymer compound having all carboxyl groups according to the present invention is a vinyl type or condensation type polymer compound containing an aromatic carboxylic acid or an aliphatic carboxylic acid in its molecule.

Specific examples of the monomer unit having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid and its anhydride, phosphoric acid, maleic acid and its anhydride, vinyl benzoate, etc. It will be done. Preferred are acrylic acid and methacrylic acid.

The proportion of the monomer contained in the polymer compound is 2
It is characterized in that the effect is greatly exhibited at mole % or more. Preferably it is 2 to 20 mol%, more preferably 5 to 15 mol%.

The polymer compound having a carboxyl group according to the present invention includes, in addition to one unit of a monomer containing a carboxyl group, one unit of a monomer containing an alcoholic hydroxyl group and/or phenolic water. Who is my partner?Q
Used wisely.

Specific examples of hydrants having an alcoholic hydroxyl group include (meth)acrylic acid esters of compounds shown in the following general formula [■] as described in Japanese Patent Publication No. 52-73G4, and acrylamides. is mentioned.

General formula [U] R4 (wherein R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom, a methyl group, an ethyl group, or a chloromethyl group, and n is an integer from 1 to 10), for example, 2- Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate-1-, 2- and droxypentyl (meth)acrylate, etc., and examples of acrylamides include N-methylol (meth)acrylamide, N- Examples include hydroxyethyl (meth)acrylamide. Good J
, L <l; L 2-hydroxyethyl (meth)acrylate.

In addition, examples of monomers having an aromatic hydroxyl group include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(2-hydroxyphenyl)-(meth)acrylamide, N-(4-hydroxyethyl )-(meth)acrylamide, monomers of (meth)acrylamides such as 0-lm- or p-hydroxyphenyl (meth)acrylate monomers, such as 0-1-
or p-hydroxystyrene monomer.

Preferably N-(4-hydroxyphenyl)-(meth)
It is acrylamide.

The υJ content of the monomer having an alcoholic hydroxyl group in its polymer molecule is preferably from 1 to 80 mol%, more preferably from 30 to 60 mol%. On the other hand, the proportion of the monomer having an aromatic hydroxyl group in the polymer molecule is preferably 1 to 80 mol%, and J is more preferable (
It is 12 to 40 mol%. Furthermore, it is also possible to mix and use both of these hydroxyl group-containing compounds in the same molecule. The 1-1 tal content m is preferably above 1''UU, more preferably 31-90 mol%.

It is also effective to copolymerize these enomer units having carboxyl groups and monomer units having alcoholic water 111 and/or phenolic water ul with other monomers.

Other copolymerizable monomers include (1) (meth)acrylic esters, such as methyl (
meth)acrylate, ethyl(meth)acrylate-1~,
Methyl α-ethyl acrylate, ethyl α-ethyl allylate, n-propyl (meth)acrylate-h, 1-propyl (meth)acrylate, n-butyl (meth)acrylate, 1-butyl (meth)acrylate, [-butyl (meth)acrylate, S-butyl (meth)acrylate,
n-benzyl(meth)acryle-1-1I-pentyl (
meth)acrylate, n-hexyl(meth)acrylate, i-hexyl(meth)acrylate, heptyl(
meth)acrylate, octyl(meth)acrylate,
Examples include nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. Preferably it is ethyl (meth)acrylate-1-.

(2) Acryloni 1 heliyl, methacrylonitrile, (3
) (meth)acrylamides such as (meth)acrylamide, N-ethylacrylamide, N-hexylacrylamide, and N-phenylacrylamide; (4) vinyl ethers such as propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (5) Vinyl esters such as vinyl acedate, vinyl chloroacetate, vinyl butyrate, etc. (6) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, etc. (7) Medyl vinyl ketone, ethyl vinyl ketone, propylene Vinyl ethers such as bilvinyl lactone and phenylvinylene, (8) Olefins such as 1-dylene, propylene, isobutylene, butadiene and isoprene, N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine etc., but other monomers that can be copolymerized with a monomer having an alcoholic or aromatic hydroxyl group, a monomer having a carboxyl group, and a (meth)acrylic acid ester monomer may be used.

As a method for synthesizing the polymer compound in the photosensitive composition used in the present invention, a generally known radical polymerization method or the like is used to synthesize an initiator (0 , 1 to 4.0 mol %) by a solution method.

The molecule ω of the polymer compound is the weight average molecule ♀ (hereinafter abbreviated as MW), which is the standard polystyrene comparison molecular weight determined by the gel permeation chromatography method (hereinafter abbreviated as GPC method) known to -FQ. 5. QOX10 to 7.00 x104 is preferable, more preferably 1
．． 00 XIO to 5.9 (lxlo), and preferably has a relatively low molecular diameter.

On the other hand, the molecule a dispersion ratio (representing the value obtained by dividing the m8 average molecular weight by the average molecular weight; hereinafter abbreviated as dispersion ratio) is preferably 5.0 or less, more preferably 4.0 or less.

The content of the polymer compound in the photosensitive composition is preferably 30 to 99% by weight, more preferably 40 to 97% by weight, based on the total composition.

Further, as an additive that can be used in the present invention, there is a dye. This is for the purpose of visualizing images, and includes acridine dye, cyanine dye, styryl dye,
Pigments such as triphenylmethane dyes and phthalocyanines,
Further, a photochromic substance (azide compound, spiropyran compound) for the purpose of visualizing images by exposure to light may be added. For example, Victoria Pure Blue BOH, Victoria Blue Base F-4R, Crystal Violet, Victoria Blue, Meguru Buy A Lettu 1, Oil Blue 603, Roglin Blue B Conch, Dark Acrylic Super Black, etc. The dye is usually contained in the photosensitive composition in an amount of about 0.5 to about 10% by weight, preferably about 1 to 5% by weight.

Various additives can be further added to the photosensitive composition of the present invention.

For example, alkyl ethers (
(e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, nonionic surfactants (e.g., Pluronic L-64 (manufactured by Asahi Denka Corporation)), plasticizers to impart flexibility and abrasion resistance to the coating film. agents (e.g. butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, diptyl phthalate, dihexyl phthalate, dioctyl phthalate, R + -ricrezyl phosphate, tribugyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic) (oligomer of acid or methacrylic acid) 1 Liposensitizing agent for improving the oil sensitivity of the image area (for example, a hafesterized product of styrene-maleic anhydride copolymer with alcohol described in JP-A No. 55-527) , stabilizers [e.g. polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, organic acid acrylic acid,
methacrylic acid, citric acid, oxalic acid, benzenesulfonic acid, butthalenesulfonic acid, 4-methoxy-2-arsenic acid, roxybenzophenone-5-sulfonic acid, etc.). The amount of addition of these additives varies depending on the purpose of use and τ, but in general, the amount of addition is 0.01 to τ based on the total solid content.
30IQ%.

In order to layer such a 4T photosensitive composition on a support, the above-mentioned diazo resin, polymer compound and, if necessary, a predetermined matrix of various additives are mixed in a suitable solvent (methyl cellosolve, ethyl cellosolve, methyl Prepare a photosensitive solution by dissolving it in cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water, or a mixture thereof, etc., apply it onto a support, and dry it. The concentration of the photosensitive composition is preferably in the range of 1 to 50% by weight.

In this case, the coating skewer for the photosensitive composition weighs approximately 02 to 10 g.
/v' or 1° is sufficient.

A typical example of an aluminum plate used in the present invention that is grained and further anodized in a specific range is shown below.

The method of graining is to degrease the surface of the aluminum plate (including laminates) with an alkaline agent, trichloride, etc.
A brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, a honing method, or a combination of these methods may be used.

Preferably, a brush polishing method, an electrolytic etching method, a honing method, or a combination thereof is used.

Furthermore, after applying desmut treatment with caustic soda etc.
Lii3FM oxidation treatment, which is one of the features of the present invention, is performed. For example, anodizing treatment is performed using inorganic salts such as phosphoric acid, chromic acid, boric acid, sulfuric acid, or organic acids such as oxalic acid alone.
Alternatively, the treatment is carried out in an aqueous solution containing a mixture of two or more of these acids, preferably in an aqueous solution of phosphoric acid or sulfuric acid, and more preferably in an aqueous solution of phosphoric acid, by passing an electric current through an aluminum plate as an anode.

For example, in a 10-50% phosphoric acid or sulfuric acid aqueous solution, preferably in a phosphoric acid aqueous solution, at 10-50°C.
, preferably at a current density of 0.2-8A/at 25-45°C.
dm', preferably from 0.5 to 5 A/di', for a period of from 5 seconds to 8 minutes, preferably from 30 seconds to 2 minutes.

The amount of anodic oxide film is one of the features of the present invention, and is 0.2j
l/v2 to 1.8 (1/u person, preferably 0.3
Q/v' ~ 1.3 (1/+') The anodic oxide film m can be easily measured by a known method. For example, phosphoric acid chromic acid solution (85% phosphoric acid solution 351Q 60 to 9 in fermented chromium (Vl) (20a dissolved in 1y of water)
After soaking at 0° C. for 5 to 30 minutes, the anodic oxide film h1 is measured gravimetrically. Furthermore, generally known puncture treatment is preferably used for the aluminum plate of the present invention.

The preferred puncture treatment applied to the present invention is an aqueous p1-silicate solution, a concentration of 0.1 to 3%, and a temperature of 80 to 95'CT.
l' Soak for 10 seconds to 2 minutes, t, L/T fi wat
L, J, I:) 11F, j: L < 1. i After that, it is treated by immersing it in water at 40-95°C for 10 seconds to 2 minutes.

The photosensitive lithographic printing plate having the photosensitive composition coated on the support can be prepared by conventional methods.

That is, by exposing to light through a transparent original having line images, halftone images, etc., and then developing with an aqueous developer,
A negative relief image is obtained for the original image. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

The aqueous developer used in the development of the photosensitive lithographic printing plate according to the present invention may be any known aqueous developer, but
The following are preferable. That is, the developer for developing the photosensitive lithographic printing plate according to the present invention contains a specific organic solvent, an alkaline agent, and water as essential components. Here, the specific primary solvent is one that can dissolve or swell the non-exposed area (non-image area) of the above-mentioned photosensitive composition layer when contained in the developer, and that is A solvent having a solubility in water of 10% by weight or less is 9% or less. Such FT machine solvents only need to have the above-mentioned properties, and are not limited to the following, examples of which include ethyl acetate, propyl acetate, Butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate,
Carboxylic acid esters such as butyl lactate, butyl levulinate; ethyl butyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone: ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinols; alkyl-substituted aromatic hydrocarbons such as xylene;
These include halogenated hydrocarbons such as dichlorobenzene, dichlorobenzene, and monochlorobenzene.

One or more of these solvents may be used. Among these solvents, nibolengelicol nanof]nyl ether and benzyl alcohol are particularly effective. J: The content of these organic solvents in the developer is approximately 1 to 2.
More preferable results are obtained when the content is 0 weight percent, and particularly from 2 to 10 weight percent.

On the other hand, the alkaline agent contained in the developer includes (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium salt of dibasic or tertiary phosphoric acid; Inorganic alkaline agents such as sodium metasilicate, sodium carbonate, ammonia, etc. (B) Mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-
Examples include organic amine compounds such as butylamine, mono-, di-, or triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, and ethylenediamine.

Preferred are the right-type amine compounds (B), and particularly preferred are di- or triethanolamine.

The content R of these alkaline agents in the developing solution is usually 0.05 to 4% by weight, preferably 0.5 to 2% by weight.

Further, in order to further improve storage stability, rigidity resistance, etc., it is preferable to include a water-soluble sulfite in the developer. Such water-soluble sulfites are preferably alkali or alkaline earth metal salts of sulfite, such as 1-lium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite. The content of these sulfites in the developer composition is usually 5 to 4% by weight, preferably 0.1 to 1% by weight.

Certain solubilizers may also be included to aid in the dissolution of the organic solvents mentioned above in water.

As such a solubilizing agent, in order to achieve the desired effects of the present invention, it is preferable to use alcohols and ketones of low molecular weight and more easily soluble in water than the d-containing solvent used. Furthermore, anionic activators, amphoteric activators, etc. can also be used. Examples of such alcohols and ketones include methanol, ethanol, propatool, butanol, aretone,
Methyl ederketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methane
-xybutanol, ethoxybutanol, 4-methoxy-4-methylbutanol, N-methylpyrrolidone, etc. are preferably used. Preferred examples of the activator include sodium isopropylnaphthalene sulfonate, sodium n-butylnaphthalene sulfonate, sodium N-methyl-N-pentadecylaminoacetate, and sodium lauryl sulfate. There is no particular restriction on the amount of solubilizers such as alcohols and ketones to be used, but it is generally preferred that the amount be about 30% by weight or less based on the entire developer.

After imagewise exposure, the photosensitive lithographic printing plate of the present invention can be brought into contact with the above-mentioned developer, or after 10 to 60 seconds at about 10°C to 40°C. , the photosensitive composition in the non-exposed areas of the photosensitive composition layer is completely removed without adversely affecting the exposed areas of the photosensitive composition layer.

Next, present invention 1: 1.1. Polymer compound used
:Synthesis examples of typical diazo resins are shown below.

Polymer compound synthesis example 1 N-(4-hydroxyphenyl)methacrylamide 17
．． 9i; I, 16.10 parts of acrylonitrile, 74.4 g of ethyl acrylate, and 8.7 g of methacrylic R (respective molar ratio 8:24:60:8) were mixed with 1 part of distilled acetone.
80iQ was dissolved in 180% distilled methanol (total monomer concentration: 35 mol/y), 6.20 (3 mol%) of azobisisobutyronitrile was added, and the polymerization reaction was carried out under reflux in a nitrogen stream for 8 hours. went.

After the reaction was completed, the reaction solution was concentrated and poured into a large volume of water with stirring, and the resulting white precipitate was collected by filtration and dried.
I got 09.

Measurements were made under the GPC conditions shown below, and the results were listed below.

Mw: 3.90XIQ, dispersion ratio: 1.9
8GPC measurement conditions GPC equipment '11: Hitachi 635-GPC equipment column
: Shogatsukusu^802x A303x A304 flow Weight; Tetrahydrofuran 151Q 7 minutes Molecule conversion: Standard polystyrene equivalent [Toyo Soda ■ Manufactured] Polymer compound synthesis example 2 The amount of azobisisobutyronitrile in polymer compound synthesis example 1 was 6 All treatments were carried out in the same manner except that 3.5 g was added instead of .2 g to obtain 115 g of Copolymer-2. G
The results of the PC measurement were as follows.

Mw: 5.70 X10, dispersion ratio +1.
48 Polymer compound synthesis example 3 N-(4-hydroxyphenyl) methacrylamide 49
．． 6 g, acrylonitrile 36.19, ethyl acrylate 84 g, methacrylic 117.2 g (respective molar ratio 14:34:42:10) were distilled to 190 g acetone.
The mixture was dissolved in 190 g of distilled methanol (total monomer concentration = 5.3 ° C. l/l), and azobisisobutyronitrile 12 (3.7 mol %) was added in a nitrogen stream.
The polymerization reaction was carried out for 8 hours in a flowing state. After the reaction was completed, the mixture was poured into water and separated in the same manner as in Synthesis Example 1. A white resin (copolymer-3) of 168q was obtained. The molecular seedlings were measured as in the previous example and are shown below.

MW: 2.50xlo, dispersion ratio: 3.3 Polymer compound synthesis example 4 2-hydroxyethyl methacrylate 1509, acrylonitrile 60g, methyl methacrylate 79.5Q
, 10.5 g of methacrylic'M (the molar ratio of each is 3
7:35:24:4) distilled dioxane 70
09 (total monomer concentration = 4.6 mol/
e) Benzoyl peroxide 15[] (2 mol %) was gradually added, and a polymerization reaction was carried out under reflux in a nitrogen stream for 8 hours. After the reaction was completed, 0.5 g of hydroquinone was added,
The solvent was distilled off under reduced pressure, and when the viscosity had decreased, it was poured onto a stainless steel plate and vacuum dried. 270g
A plate-shaped resin (copolymer-4) was obtained. GPC measurement values are shown below.

Mw: 4.80 xlo, dispersion ratio: 2.2 Polymer Compound Synthesis Example 5 The same procedure as in Polymer Synthesis Example 1 except that 1.5 g of a′i of azobitub 10 nidotrile was added instead of 6.2 g. After treatment, 1 osg of copolymer-5 was obtained. G
The results of the PC measurement were as follows.

Mw: 7.50 x 10, dispersion ratio = 2.5 Comparative polymer synthesis example-1 27 g of butanediol and 1 part of chlorobenzene were added, and after replacing with nitrogen, 50 g of hexamethylene diisocyanate 1 0.52 of chlorobenzene was heated under distant flow, and half of it was heated. Add the mushrooms all at once and stir vigorously, then drip the rest over the course of 3 hours.

Continue to swim for another hour.

After the reaction is completed, it is separated and redeposited with dimethylformamide-methanol. Comparative copolymer-1,639 was obtained. The GPC results are shown below.

MW: 2.9X10, dispersion ratio: 3.4 Diazo resin synthesis example 1 p-diazodiphenylamine sulfate IL5 (1 (50 mmol)) was dissolved in 40.9 (L @1Ililic acid) under water cooling. This reaction 1.35g (45 mmol) in liquid
of rose formaldehyde was slowly added dropwise. On this occasion,
The addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued for 2 hours under water cooling.

This reaction mixture was added dropwise to 500 mQ of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 m12 of pure water, and 6
．． 8 g of zinc chloride was dissolved and a cold concentrated aqueous solution of IC was added.

The resulting precipitate was filtered, washed with ethanol, and
Dissolved in 50-year pure water. A cold aqueous solution containing 8 g of ammonium hexafluoroline dissolved therein was added to this solution. The resulting precipitate was collected by filtration, washed with water, and then dried at 30° C. for one day and night to obtain diazo resin-1.

As a result of measuring the β-naph 1--luka-tubbling product of the synthesized diazo resin-1 using the same GPC device as in Polymer Compound Synthesis Example 1, it was found that n≧5 was 30 mol%, and Mw = 2
,400. Mw/Mn = 2.11.

Below is a blank space [Structural formula Kodiazo Resin Synthesis Example 2.3 In the above Diazo Resin Synthesis Example 1, the molar ratio of paraform charged was reduced by 15% (Diazo Resin Synthesis Example 2) and increased by 20% (Diazo Resin Synthesis Example 3). A similar synthesis was performed. The analytical data is described below.

Diazo resin-20≧5 is 23 mol%.

Mw =2,000. Mw/Mro = 2.3
1 Diazo resin-3n≧5 is 45 mol%.

Mw = 3jOO, Mw /Mn = 4.
Comparative Synthesis Example 1 of 52 Diazo Resin Exactly the same as in Diazo Resin Synthesis Example 1 except that 115 g of 2-hydroxy-4-methybenzophenone-5-sulfone was used instead of ammonium hexafluorophosphate. I went to

The analytical values are shown below.

Comparative diazo resin - 10≧5 is 30T nyl%.

Mw =2,450. Mw /Mn -2,12 Next, an example of manufacturing an aluminum grained plate serving as a support is shown below.

Manufacturing Example of Support Support-1 An aluminum plate was electrolytically polished in a 17 g/ffi hydrochloric acid bath at a bath temperature of 25°C and 50 A/dn' for 25 seconds to form a grained plate with a maximum roughness of 4 μm. Obtained. The grained board was placed in a 40ffiffi% phosphoric acid bath at a bath temperature of 35°C.
Anodizing was performed at 3.2 A/df for 20 seconds. Next, in order to measure the anodic oxide film content, a vinyl tape was pasted on the back side of the aluminum, and a phosphoric acid solution (35 moles of 85% phosphoric acid solution and 20 g of chromium oxide (Vl)
was immersed in solution 82) dissolved in water 12 at 75° C. for 10 minutes, and the anodic oxide film (hereinafter abbreviated as ADfm) was calculated by the Coerli method.

As a result, the ADI was 1!11/112. Next, the anodized aluminum plate was immersed in a 1% by weight solution of sodium metasilicate at 90"C for 30 seconds to perform a sealing treatment. Thereafter, it was washed with water and dried, and then formed into Support-1. did.

Supports-2 and -3 Under the manufacturing conditions of Support-1, the current value for anodic oxidation was set to 3.2.
A/df to 2.9A/dt2 (support-2), 2
, OA/di' (Support-3), but a support was produced under exactly the same conditions. ADfi is 0.5 (]/i' (support-2), (1,3(]/
12 (Support-3).

Support-4 Under the manufacturing conditions of Support-1, the anodic bath was changed from phosphoric acid to sulfuric acid, and the current value was changed from 3.2 A/dt2 to 2.8.
Production was carried out under exactly the same conditions except that it was reduced to A/dt'. ADffl was 1 g/12.

Support-5 An aluminum plate was brushed in advance with a nylon brush in a v220 g/l nitric acid bath at a bath temperature of 25°C.
Electrolytic polishing was performed at 55 A/dv12 for 30 seconds to obtain a grained plate with a maximum roughness of 4.5 μm.

Next, the same anodic oxidation treatment as for Support-4 was performed in a sulfuric acid bath. ADiTz was 1 g/l'.

Comparative Support-1 Under the manufacturing conditions of Support-1, the current value for anodic oxidation was set to 3.
A support was manufactured under exactly the same manufacturing conditions except that the value was increased from 2A/d1' to 4.3Δ/d12. The AD amount is 2.
It was 3(]/l'.

Comparative Support-2 Under the manufacturing conditions of Support-1, the current value for anodic oxidation was set to 3.
2A/dn' to 0.5A/dw', time 20
A support was produced under exactly the same conditions except that the time was changed from seconds to 10 seconds. ADfi was 0.1 a/df.

[Examples] The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples.

Example 1 The following photosensitive composition liquid 1 was applied to the grains of the support 1 using a Whaler. Further, drying was performed at 90° C. for 4 minutes to obtain a photosensitive planographic printing plate.

[1 photosensitive composition liquid 16.0 g of the above copolymer 11.18 g of the above diazo resin Jurimer AC-1OL 0.36 (1
(Manufactured by Japan side 11 J old) Victoria Pure Blue 5o)-10,09i7 (Manufactured by Hodogaya Chemical 01) Methyl cellosolve 1001. p (Nembutsu of diazo resin 15.5% market weight 1-) The coating film weight after drying was 17 mg/d, t.

Next, the photosensitive lithographic printing plate was exposed under the conditions shown below,
The printed images were visually judged. Furthermore, development processing was performed under various development conditions shown below.

In addition, for printing plates that have been subjected to standard development processing, the value at which the halftone dots (49.1% of the halftone dots in 150 lines) of the film original are recirculated in the printing plate is determined by "Sakura Area Duck 1000" (Konishiroku Photo Industry K K ) was used to measure and calculate. Furthermore, this plate was printed under the printing conditions shown below, and the printing durability (the point where the solid area becomes defective) and the halftone dot area on the printed matter (using Sakura Area Duck 1000'') were evaluated. Ta.

On the other hand, photosensitive lithographic printing plates stored at 55° C. for 9 days were developed under the same developing conditions and the presence or absence of stains was determined. The results are shown in Table 1.

Exposure conditions> Exposure machine: Metal halide lamp “Idol Fin 2000” (manufactured by Iwasaki Electric KK)
Distance: 1f Time: 30 seconds Film original: Halftone chart, Kodak Step Tablet, film original with solid area.Development conditions> Developer phenyl cellosolve 480g Jetanolamine (80%) 159 (1I413N to J Pionin) Genuine oil (made by KK) 180q water

12p Kozuri Development A commercially available paper "Kimwipe" (manufactured by Jujo Kimberly KK) was immersed in the above developer and rubbed strongly by hand about 10 times to observe the presence or absence of scratches on the image area.

The above developer was placed in a standard development Sakura PS plate automatic processor "PSP-8f30" (Konishi Roku Photo Industries KKfJ) and development was carried out at 25° C. for 45 seconds.

rapid development Development processing was performed using a standard development time of 20 seconds.

For fatigue, an unexposed negative PS plate “SWN-N” (manufactured by Konishiroku Photo Industry KK) was repeatedly developed and fatigued (15
i'/ff1) solution under the above two conditions, and the presence or absence of stains on non-images was mainly observed.

<Printing conditions> Ink WII machine: Heidel GT○ Printing ink: Ushi 1 to Raking Red "Toyo Ingi KK So" Printing paper: Coated paper Dampening water: 40 times diluted solution of 5EU-1 Blanket: Air Bran (Fujikura Industries) KK> Printing speed: 5000 rpm Example 2 Support-2 was used instead of support-1 used in Example 1.
Diazo resin-3 was used instead of diazo resin-1, and diazo-containing M
20% by weight instead of 15.5% by weight, copolymer-1
An experiment was conducted in exactly the same manner as in Example 1, except that Copolymer-2 was used instead of. The results are shown in Table 1.

Example 3 An experiment was conducted in exactly the same manner as in Example 1, except that Diazo Resin-2 was used in place of Diazo Resin-1 used in Example 1. The results are shown in Table 1.

Example 4 Diazo S9 of Example 1 from 15.5 weight Φ% to 38 weight G%
The experiment was carried out in exactly the same manner as in Example 1, except that the animals were housed in different locations.

The results are shown in Table 1.

Example 5 The same experiment as in Example 1 was conducted except that Copolymer-5 was used instead of Copolymer-1 in Example 1. The results are shown in Table 1.

Example 6 An experiment was conducted in exactly the same manner as in Example 1, except that Copolymer-3 was used instead of Copolymer-1 in Example 1. The results are shown in Table 1.

Example 7 The same experiment as in Example 1 was conducted except that Copolymer-4 was used instead of Copolymer-1 in Example 1. The results are shown in Table 1.

Example 8 An experiment was carried out in exactly the same manner as in Example 1, except that Support-4 was used instead of Support-1 in Example 1.

The results are shown in Table 1.

Example 9 An experiment was carried out in exactly the same manner as in Example 1, except that Support-5 was used instead of Support-1 in Example 1.

The results are shown in Table 1.

Example 10 An experiment was carried out in exactly the same manner as in Example 1, except that Support-3 was used instead of Support-1 in Example 1.

The results are shown in Table 1.

Comparative Example 1 The diazo-containing ω of Example 1 was reduced by 15.5% by weight to 7.
The experiment was conducted in exactly the same manner as in Example 1, except that 51ff1% was used. The results are shown in Table 1.

Comparative Example 2 An experiment was conducted in exactly the same manner as in Example 1, except that Comparative Support-1 was used instead of Support-1 in Example 1. The results are shown in Table 1.

Comparative Example 3 Comparative diazo resin-1 was used instead of diazo resin-1 of Example 1.
The experiment was conducted in exactly the same manner as in Example 1, except that Example 1 was used.

The results are shown in Table 1.

Comparative Example 4 An experiment was conducted in exactly the same manner as in Example 1, except that the diazo resin content in Example 1 was increased from 15.5% by weight to 65% by weight. The results are shown in Table 1.

Comparative Example 5 An experiment was conducted in exactly the same manner as in Example 1, except that Comparative Support-2 was used instead of Support-1 in Example 1. The results are shown in Table 1.

Comparative Example 6 An experiment was conducted in exactly the same manner as in Example 1, except that Comparative Copolymer-1 was used instead of Copolymer-1 in Example 1. After exposure, the resulting photosensitive lithographic printing plate produced a clear visible image as in Example 1, but could not be developed at all with the developer used in Example 1.

As is clear from Table 1 below, the present invention is characterized in that a specific diazo resin is present in a photosensitive composition in a certain range, and that a suitable anodic oxide film with an aluminum grain of the support is formed, and
This is an interesting fact because the characteristics of the present invention were achieved for the first time in combination with a polymer compound having a specific functional group.

Example 11 In place of the developer used in Example 1, a practical test was carried out using the following developer, and the results were exactly the same.

Developer solution Benzyl alcohol 360g Sodium sulfite 36 (11~Reethanolamine 24o9 Pelex N B 1
360 (1 (1-bublnaphthalenesulfone sodium flower air 1-las K K =>

Claims (1)

[Claims] In a photosensitive lithographic printing plate, in which a photosensitive composition layer containing a diazo resin and a polymer compound having a carboxyl group is provided on a grained and anodized aluminum plate, the grained portion of the aluminum plate is The amount of anodized film is 0.2 to 1.8 g/m^2, the content of the diazo resin in the photosensitive composition is 10 to 60 weight percent, and the anion of the diazo resin is PF_6. A photosensitive lithographic printing plate characterized by being ^- or BF_4^-.