JPS62133451A - Photosensitive composition and photosensitive lithographic plate material - Google Patents

Abstract

PURPOSE:To improve the inking performance of a printing ink and printing resistance and to prevent stains due to rapid development or the like by using a polymer having phenolic hydroxyl groups and alcoholic hydroxyl groups each in a specified range. CONSTITUTION:The polymer to be used has in the molecular structure, repeating units derived from a monomer having phenolic hydroxyl groups, preferably, embodied by N-(4-hydroxyphenyl)-(meth)acrylamide, preferably, in an amount of 6-15mol%, a monomer having alcoholic hydroxyl groups, preferably, embodied by 2-hydroxyethyl (meth)-acrylate, preferably, in an amount of 15-60mol%, and a monomer having cyano groups on the side chains, preferably, such as acrylonitrile or methacrylonitrile.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a diazo photosensitive composition and a printing plate material thereof, and more particularly, to a diazo photosensitive composition and a printing plate material thereof. The present invention relates to a type diazo photosensitive composition and its printing plate material.

[Conventional technology]

Conventionally, a photosensitive plate obtained by coating a thin film of a photosensitive substance on a support is exposed to light through a transparent image to create a difference in solubility between exposed and unexposed areas, and then developed with an appropriate solvent and exposed to light. Various techniques have been devised for forming relief images on 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.

Furthermore, as a polymer compound used in combination with a diazo compound, a polymer compound having a functional group such as a hydroxyl group, an amino group, a cyano group, or a urethane group in its molecule is effective. Phenolic hydroxyl group, for example, p-
Polymer compound containing hydroxyphenyl (meth)acrylamide, etc., Japanese Patent Publication No. 7364/1986, Japanese Patent Publication No. 52-7364, Japanese Patent Publication No. 52-7364
Alcoholic hydroxyl groups of polymer compounds containing 2-oxydialkyl (meth)acrylate monomers and diazo compounds and polymer compounds containing 2-oxydialkyl (meth)acrylate monomers and acrylonitrile monomers described in JP 5-34929. Polymer compounds having a structural unit having this structure are known.

[Problem that the invention seeks to solve]

However, when a photosensitive composition containing these polymer compounds used in combination with a diazo compound is coated on a metal plate, such as an aluminum plate, and used as a lithographic printing plate material, the photosensitive composition contains phenolic groups as hydroxyl groups. If a polymer compound containing only hydroxyl groups is used, the resist strength unique to aromatic rings, such as improved printing durability, strong affinity for printing inks, and resist strength against various printing processing chemicals, cannot be achieved. However, due to poor solubility in the developer, it has the disadvantage of easily carrying over development defects. In particular, this drawback has been a major problem in rapid development processing, which is one of the labor-saving measures in the plate-making process.

On the other hand, when a polymer compound having only alcoholic hydroxyl groups is used, although the developability is good, it is easily scratched due to poor physical strength and is weak against impact force, so it is particularly resistant to high-speed printing such as off-the-shelf export. Problems include poor printing, erosion of the resist by processing chemicals during printing, and poor inking at the start of printing due to poor affinity for ink.

Therefore, the object of the present invention is to prevent poor ink adhesion caused by poor gum removal especially in the early stages of printing when the printing ink is coated on a support and used as a photosensitive lithographic printing plate material. The object of the present invention is to provide a photosensitive lithographic printing plate material which has good developability, rapid development, etc., is free from stains, and has good printing durability.

Another object of the present invention is to provide a photosensitive lithographic printing plate material that is highly resistant to various processing chemicals when coated on a support and used as a photosensitive lithographic printing plate material. be.

Still another object of the present invention is to provide a photosensitive composition with good exposure visible image properties (printed images).

[Means for solving problems]

As a result of extensive research to achieve the above objectives, the present inventors discovered that extremely good performance is achieved when phenolic hydroxyl groups and alcoholic hydroxyl groups are contained within a specific range, leading to the present invention. It is something.

That is, in the photosensitive composition according to the present invention, which contains an azo compound and a polymer compound, the polymer compound contains 6 to 40 mol% of monomer units having a phenolic hydroxyl group in its molecular structure. It is characterized by containing 6 to 60 mol% of monomer units having alcoholic hydroxyl groups and monomer units having cyano groups in side chains.

In addition, the photosensitive lithographic printing plate material related to this cicada is on a support,
In a photosensitive lithographic printing plate material provided with a photosensitive layer containing a diazo compound and a polymer compound as main components, the polymer compound contains 6 to 40 mol% of monomer units having a phenolic hydroxyl group in its molecular structure, It is characterized by containing 6 to 60 mol% of monomer units having alcoholic hydroxyl groups and monomer units having cyano groups in side chains.

The present invention will be explained in detail below.

Examples of the monomer having a phenolic hydroxyl group constituting the polymer compound used in the present invention include N-(4-
Hydroxyphenyl)-(meth)acrylamide, N-
Monomers of (meth)acrylamides such as (2-hydroxyphenyl)-(meth)acrylamide and N-(4-hydroxynaphthyl)-(meth)acrylamide: 0-
1Ill- or p-hydroxyphenyl (meth)acrylate monomers: 0-lm- or p-hydroxystyrene monomers and the like. Preferably they are 0-11- or p-hydroxyphenyl (meth)acrylate monomers, N-(4-hydroxyphenyl)-(meth)acrylamide monomers, and more preferably N-(4-
Hydroxyphenyl)-(meth)acrylamide monomer.

The proportion of the monomer having a phenolic hydroxyl group in the molecule of the polymer compound is, compared to the conventionally known content,
A relatively small amount is preferred, the content being 6 to 40 mol%, preferably 6 to 30 mol%, more preferably 6 to 15 mol%.

Specific examples of monomers having an alcoholic hydroxyl group include (meth)acrylic acid esters and acrylamides such as the compounds shown in the following general formula CI) as described in Japanese Patent Publication No. 52-7364. .

In the formula, R1 is a hydrogen atom or a methyl group, R8 is a hydrogen atom,
Methyl group, ethyl group or chloromethyl group, and n is 1
Indicates an integer between ~10.

Examples of (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, and examples of acrylamides include N -Methylol (meth)acrylamide, N
-Hydroxyethyl (meth)acrylamide and the like. Preferably it is 2-hydroxyethyl (meth)acrylate.

The proportion of the monomer having an alcoholic hydroxyl group in the molecule of the polymer compound is 6 to 60 mol%, more preferably 15 to 60 mol%. It is preferable to contain.

On the other hand, examples of monomers having a cyano group in the side chain constituting the polymer compound used in the present invention include acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-
Examples include methyl-3-butenenitrile, 2-cyanoethyl acrylate, O+, l-1p-cyanostyrene, and the like. Preferred are acrylonitrile and methacrylonitrile.

The proportion of the monomer having a cyano group in the side chain in the molecule of the polymer compound is 1 to 40 mol%, preferably 10 to 30 mol%.

These monomers having a phenolic hydroxyl group, monomers having an alcoholic hydroxyl group, and monomers having a cyano group in the side chain are effective when copolymerized with other monomers. Monomers to be copolymerized include (1) monomers having a carboxyl group in the side chain such as (meth)acrylic acid, itaconic acid and its anhydride, maleic acid and its anhydride, and phosphoric acid, preferably methacrylic acid; It is acrylic acid.

(2) Methyl (meth)acrylate, ethyl (meth)acrylate, methyl α-ethyl acrylate, ethyl α-ethyl acrylate, n-propyl (meth)acrylate, l-propyl (meth)acrylate, n-butyl (meth)acrylate, ) acrylate, i-butyl (meth)acrylate,
t-Butyl (meth)acrylate, 8-butyl (meth)
Acrylate, n-pentyl (meth)acrylate, i
-pentyl (meth)acrylate, n-hexyl (meth)acrylate, t-hexyl (meth)acrylate,
Examples include heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. Preferred are methyl (meth)acrylate and ethyl (meth)acrylate. More preferred is ethyl acrylate.

(3) (Meth)acrylamides such as (meth)acrylamide, N-ethylacrylamide, N-hexylacrylamide, N-phenylacrylamide, etc. (4) Vinyl ethers such as propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (5) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate (6) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene (7) Methyl vinyl ketone, ethyl vinyl ketone, Vinyl ketones such as propyl vinyl ketone and phenyl vinyl ketone (8) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc. may be any monomer that can be copolymerized with a monomer having alcoholic and phenolic hydroxyl groups and a monomer having a cyano group in the side chain.

As a method for synthesizing the polymer compound in the composition of the present invention, a generally known radical polymerization method or the like may be used, for example, using an initiator such as azobisisobutyronitrile or benzoyl peroxide (0.1 to 4.0 mol %). ) is easily synthesized by solution polymerization method.

The molecular weight of the polymer compound is a weight average molecular weight of 5, based on a standard polystyrene comparison molecular weight determined by the generally known gel permeation chromatography method (GPC method).
．． 00X 103 to 2.0OX 10' is preferable, and more preferably 1.00X 10' to 8.00X 10'
, particularly preferably 1.50X 1G' to 5.90X 1
G' and preferably has a relatively low molecular weight.

On the other hand, its molecular weight dispersion ratio (the value obtained by removing the weight average molecule m M w by the number average molecule ffi M n
represents.

The dispersion ratio (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 30 to 99% by weight, preferably 40 to 97% by weight, based on the total composition.

The photosensitive diazo compounds used in the present invention include diazo resins represented by condensates of aromatic diazonium salts and, for example, active carbonyl-containing compounds, especially formaldehyde, and among these, organic solvent-soluble diazo resins are preferred. .

Examples of the diazo resin include diazo resin inorganic salts which are organic solvent-soluble reaction products of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, and hexafluorophosphate or tetrafluoroborate;
Further, as described in U.S. Pat. Examples include organic solvent-soluble diazo resin organic acid salts which are reaction products such as 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, or salts thereof.

A preferred example is one containing 20 mol % or more, preferably 20 to 60 mol %, of a resin represented by the following general formula (1), where n in the chain formula is 5 or more.

In the formula, R3, R4 and R8 represent a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, etc.) or an alkoxy group (e.g. methoxy group, ethoxy group, etc.), and R' is a hydrogen atom,
represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) or a phenyl group, and X is PF,
or BF, and n represents a number from 1 to 200.

The content of diazo resin in the photosensitive composition according to the present invention is
Preferably 1 to 70% by weight, more preferably 3 to 60% by weight
Weight%.

In addition to the above-mentioned materials, dyes, pigments, coating properties improvers, plasticizers, etc. can be added to the photosensitive composition of the present invention, if necessary.

Examples of the dyes include Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet, Brilliant Green, Ethyl Violet, Triphenylmethane represented by methyl green, erythrosin B, pesic fuchsin, malachite green, oil red, m-cresol purple, rhodamine B1 auramine, 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc. type, diphenylmethane type, oxazine type, xanthine type,
Examples include iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes.

The dye is usually present in the photosensitive composition in an amount of about 0.5% to about 10% by weight.
, preferably about 1 to 5% by weight.

Examples of coating property improvers include alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, and nonionic surfactants (e.g., Pluronic L-64 (manufactured by Asahi Denka)). Examples of plasticizers for imparting flexibility and wear resistance include butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, and tributyl phosphate. , trioctyl phosphate, tetrahydrofurfuryl oleate, and oligomers of acrylic acid or methacrylic acid. Examples of the oil-sensitizing agent for improving the oil-sensitivity of the image area include JP-A-55-527.
Examples of stabilizers include polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, organic acids (acrylic acid, methacrylic acid, Citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5
-sulfonic acid, etc.). The amount of these additives added varies depending on the purpose for which they are used, but is generally between o and oi and 30% by weight based on the total solid content.

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above-mentioned components, and by coating and drying it on the surface of a support, for example, a photosensitive lithographic printing plate material or a photoresist (
For example, resin letterpress materials, printed wiring boards, etc.) can be formed.

The present invention is characterized not only by the photosensitive composition itself, but also by the lithographic printing plate material obtained using the photosensitive composition.

The case where a lithographic printing plate material is obtained using the photosensitive composition of the present invention will be described below.

Examples of solvents that can be used include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents may be used alone or in combination.
Use by mixing more than one species.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. The coating amount varies depending on the application, but for photosensitive lithographic printing plate materials, the solid content is preferably 0.2 to 109/m''.

In the photosensitive lithographic printing plate material using the photosensitive composition of the present invention, the support may be a metal plate such as aluminum, zinc, steel, or steel, or plated or plated with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include vapor-deposited metal plates, paper, plastic films, glass plates, resin-coated paper, paper covered with metal foil such as aluminum, and hydrophilic-treated PlusDeck film. Among these, aluminum plates are preferred. When an aluminum plate is used as a support for a photosensitive lithographic printing plate material, it is preferably subjected to surface treatments such as grain treatment, anodization treatment, and if necessary, pore sealing treatment.

Well-known methods can be applied to these treatments.

Examples of the graining treatment include a mechanical method and an electrolytic etching method.

Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing. The various methods described above can be used alone or in combination depending on the composition of the aluminum material.

Electrolytic etching is carried out in a bath containing inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, etc. alone or in a mixture of 2 W or more.

After the graining process, desmutting is performed using an alkali or acid aqueous solution as necessary to neutralize the material, followed by washing with water.

The anodic oxidation treatment is carried out by using an electrolytic solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc., and using an aluminum plate as an anode. The amount of anodic oxide film formed is 1 to 50 m9/
da” is appropriate, preferably 10 to 40 ta9/
da”, particularly preferably 25 to 40 m9/
The amount of anodized film is, for example, an aluminum plate coated with a phosphoric acid chromic acid solution (phosphoric acid 85% solution: 35 m (2
, chromium oxide (Vl): 20y dissolved in 172 water) to dissolve the oxide film, and it is determined by measuring the change in weight of the plate before and after the film is dissolved.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

In addition, when contact-baking a film original onto a photosensitive lithographic printing plate material, the printing frame is generally vacuumed, but a method for improving this vacuum adhesion is also photosensitive lithographic printing using the photosensitive composition of the present invention. It can be applied to plate materials. Methods for improving vacuum adhesion include mechanically creating unevenness on the surface of the photosensitive layer, scattering solid powder on the surface of the photosensitive layer,
A method of providing a matte layer on the surface of a photosensitive layer as described in JP-A-50-125805, and JP-A-55
Examples include a method of heat-sealing a solid powder onto the surface of a photosensitive layer, as described in Japanese Patent No. 12974.

The photosensitive lithographic printing plate material coated on the support can be prepared by conventional methods. That is, by exposing a transparent original image having a line image, a halftone image, etc. to light, and then developing it with an aqueous developer, a negative relief image can be obtained with respect to the original image. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

The developer used in the development of the photosensitive lithographic printing plate material of the present invention may be any known developer, but the following are preferred. That is, the developer for developing the photosensitive lithographic printing plate material of the present invention contains a specific organic solvent, an alkaline agent, and water as essential components. Here, the specific organic 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 resistant to water at room temperature (20°C). refers to an organic solvent with a solubility of 10% by weight or less. Such organic solvents only need to have the above-mentioned characteristics, and are not limited to the following, examples of which include ethyl acetate,
Carboxylic acid esters such as propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone; ethylene glycol monobutyl ether , ethylene glycol benzyl ether,
Alcohols such as ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; such as methylene dichloride, ethylene dichloride, monochlorobenzene Examples include halogenated hydrocarbons. One or more of these organic solvents may be used.

Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective.

Further, the content of these organic solvents in the developer is approximately 1 to 20ilff1%, and particularly preferable results are obtained when the content is 2 to 10% by weight.

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

Preferred are (A) potassium silicate, sodium silicate, and CB) organic amine compounds, particularly preferred are (A) potassium silicate, (B) glue, or triethanolamine.

The content of these alkaline agents in the phenomenon liquid is usually 0,
05 to 8% by weight, preferably 0.5 to 6% by weight.

Furthermore, in order to further enhance storage stability, printing durability, etc., it is preferable to include a water-soluble sulfite in the developer as necessary. Such water-soluble sulfites are preferably alkali or alkaline earth metal salts of sulfite, such as sodium sulfite, potassium sulfite, lithium sulfite, magnesium sulfite, and the like. The content of these sulfites in the developer composition is usually 0.05 to 4% by weight, preferably 0.11 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 that are more easily soluble in water than the organic solvent used. Furthermore, anionic activators, amphoteric activators, etc. can also be used. Examples of such alcohols and ketones include methanol, ethanol, propatool, butanol, acetone,
Methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-methoxy-
Preferably, methylbutanol, N-methylpyrrolidone, etc. are 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 used, but it is generally preferred that the amount is about 30% by weight or less based on the entire developer.

After the photosensitive lithographic printing plate material of the present invention is imagewise exposed, if it is brought into contact with the above-mentioned developer or rubbed, the photosensitive layer will be formed after 10 to 60 seconds at about 10 to 40 degrees Celsius. The photosensitive composition in the non-exposed areas is completely removed without adversely affecting the exposed areas.

〔Effect of the invention〕

As is clear from the above and later examples, the present invention has excellent strong and weak alkali developability, particularly rapid and fatigue developability, good ink receptivity, and excellent stiffness resistance. A photosensitive lithographic printing plate material can be provided.

〔Example〕

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Synthesis example! N-(4-hydroxyphenyl)methacrylamide (H
ypMA)l 5.69.2-hydroxyethyl methacrylate (HEMA) 40.19, acrylonitrile (
AN) 4.679, ethyl acrylate (EA) 35.
29 methacrylic acid (MAA) 3.799% was dissolved in distilled acetone 84-1 distilled methanol 84m4, azobisisobutyronitrile (AIBN) 2°899% was added, heated under a nitrogen stream, and brought to reflux. The polymerization reaction was carried out for 8 hours.

The above preparation conditions are shown below.

[Charge monomer molar ratio]

11ypMA:HEMA:AN:EA:MAA=10
:35:10:40:5 [Total monomer concentration: CM)]
・・・・・・・・・・・・ 5.25 mol/Q [initiator molar concentration: CI)] ・・・・・・・・・・・・
After the completion of the 2 mol% reaction, the reaction solution was poured into a large amount of water with stirring, and the resulting white precipitate was filtered and dried.
I got 9. It was measured under the following GPC conditions and the results are shown in Table 1.

My: 5.61Xl, 04 Dispersion ratio (Mw/Mn) + 1.89 GPC measurement conditions GPC device: Hitachi 635 type GPC device Column: Shodex (Showa Denko): A30
2 XA803 ), and copolymers 2 to 7 were synthesized by changing the yield, weight average molecular weight ffl (Mw), and molecular weight dispersion as shown in Table 1.

Comparative Synthesis Examples 1 to 9 The monomer charging ratio, weight ratio, total monomer concentration CM), initiator molar concentration (1), yield, weight average molecular it (Mw), and molecular weight dispersion of Synthesis Example 1 were as shown in Table 2. Comparative copolymers 1 to 9 were synthesized with various changes.

Comparative copolymer 6 was prepared using copolymer-1 described in Example 1 of JP-A No. 59-78340, and comparative copolymer-7 was prepared using Example 1 of JP-A No. 57-4: (890). It was synthesized in the same manner as the copolymer described above.

Example! An aluminum plate with a thickness of 0.24 mm was degreased by immersing it in a 3% aqueous sodium hydroxide solution, and after washing with water, it was soaked in 1% hydrochloric acid and 1% sodium hydroxide.
% boric acid aqueous solution at 25°C for 5 minutes and washed with water.Next, it was immersed in a 0.9% sodium hydroxide aqueous solution, washed with water, and etched in a 40% sulfuric acid aqueous solution at 30°C for 5 minutes.
．． It was anodized at 5A/da' for 2 minutes and washed with water. Furthermore, 9
It was treated with a 1% sodium metasilicate solution at 0°C for 30 seconds, then washed with water and dried to produce a grained aluminum plate.

Next, a photosensitive liquid having the following composition was applied to the aluminum plate using a Whaler. Further at 100℃ 2
Drying was carried out for a minute to obtain a photosensitive lithographic printing plate material.

(Photosensitive coating liquid composition) Copolymer 1 6.09 p-
Hexa-711, ffl ++ -) lhI4i (A-+-7k
+ ILJ-σ)-# ++ Fring body GP
According to C analysis, 31 mol% of general formula (It) is ≧5) Mw: 2400 Dispersion ratio: 1.5 0.489・Jerimar AC-1OL (manufactured by Nippon Pure Chemical Industries, Ltd.) 0.369・
Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.099 methyl cellosolve LOOmQ, the coating amount after drying was l', 69/m''.

Next, the photosensitive lithographic printing plate material was exposed to light under the conditions shown below, and after observing the exposed visible image properties, running development was performed using developer-1.

Furthermore, the obtained lithographic printing plate was printed on an off-wheel printing machine “System 35”.
”, and observed the number of sheets torn at the start, stains in non-image areas, and ``collapse'' on the wires.Next, print was carried out until the ink became difficult to adhere to the image areas, and the number of sheets was measured. The results are shown in Table 3.

Exposure conditions〉 Exposure machine: Metal halide lamp “Idol 2000”
Manufactured by Koji Denkisha] Distance: 1 m Time: 30 seconds Film original: Kodak Step Tablet No. 12
Developing conditions for a 150-line halftone original with 150-line dots pasted -1> Developer solution-1 -Phenyl cellosolve 480g・Jetanolamine (80%) 1599・Pionin A4413 (manufactured by Takemoto Yushi Co., Ltd.) 1809・Water
11 Automatic processor: Sakura PS version automatic processor “PSP-860” (manufactured by Konishiroku Photo Industry Co., Ltd.) (Brush pressure +7ffII11) Gum: Scw-2 (manufactured by Konishiroku Photo Industry Co., Ltd.) Development temperature: 25°C Development time: 15 seconds to 45 seconds Running conditions: Unexposed negative 28 plate “5WN-N” (
The development process was repeated using Kikuzen size (manufactured by Konishiroku Photo Industry Co., Ltd.).

Printing conditions〉 Off-line printing machine: “System 35” (manufactured by Kokai Printing Machinery Co., Ltd.)
Paper: Page paper Ink: “Fine News Z” (manufactured by Dainippon Ink Co., Ltd.) Blank: “Kinyo Air Plan” (manufactured by Kanebe Co., Ltd.) Printing speed: 30,000 sheets/hour Then, similarly under the following developing conditions -2 The exposed photosensitive lithographic printing plate material was developed and the developability was mainly evaluated.

Development conditions-2> Developer solution-2 Potassium metasilicate 4809 water
12
12 Developer: Sakura PS plate automatic processor “PSP-860” (
Gum: Scw-1 (manufactured by Konishiroku Photo Industries, Ltd.) Development temperature: 25°C Development time: 15 seconds to 45 seconds Examples 2 to 7 In the photosensitive solution used in Example 1 Similar experiments were conducted using copolymers 2 to 7 (corresponding to Examples 2 to 7) instead of copolymer 1. The results are shown in Table 3.

Comparative Examples 1 to 7 Similar experiments were conducted using Comparative Copolymers 1 to 7 (corresponding to Comparative Examples i to 7) used in place of Copolymer 1 in the photosensitive solution used in Example 1. . The results are shown in Table 3.

Comparative Example 8 In the photosensitive solution used in Example 1, p-diazine' phenylamine and paraformaldehyde (molar ratio 1:0.9
) in place of the hexafluorophosphate of the condensation resin with p-
A similar experiment was conducted using 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, which is a condensation resin of diazodiphenylamine and paraformaldehyde (molar ratio 1:0.9). The results are shown in Table 3.

Comparative Example 9 In the photosensitive solution used in Example 1, p-diazodiphenylamine was used instead of hexafluorophosphate of the condensation resin of p-diazophenylamine and paraformaldehyde (molar ratio 1:0.9). Paraformaldehyde (molar ratio 1:
Hexafluorophosphate (β-
A similar experiment was conducted using a compound of general formula (n) in which n≧5 was 15% based on GPC analysis of a coupled product with naphthol. The results are shown in Table 3.

Comparative Examples to, tt A similar experiment was conducted using Comparative Copolymer 8.9 (corresponding to Comparative Examples to, tt) instead of Copolymer 1 in the photosensitive solution used in Example 1. The results are shown in Table 3.

As is clear from the results in Table 3, strong alkali It can be seen that we have succeeded in developing a photosensitive lithographic printing plate material that has excellent weak alkaline developability, particularly rapid and fatigue developability, good ink receptivity, and excellent printing durability.

Claims (2)

[Claims] (1) In a photosensitive composition containing a diazo compound and a polymer compound, the polymer compound contains 6 to 40 mol% of monomer units having a phenolic hydroxyl group in its molecular structure and a monomer having an alcoholic hydroxyl group. A photosensitive composition comprising 6 to 60 mol% of units and a monomer unit having a cyano group in a side chain. (2) In a photosensitive lithographic printing plate material comprising a photosensitive layer containing a diazo compound and a polymer compound as main components on a support, the polymer compound is a monomer having a phenolic hydroxyl group in its molecular structure. 6 to 40 mol% of units, and 6 to 6 monomer units having alcoholic hydroxyl groups.
1. A photosensitive lithographic printing plate material containing 0 mol % and a monomer unit having a cyano group in a side chain.