JPS62251743A - Photosensitive compositions and photosensitive lithographic plate - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to enlarge development allowance by incorporating a compound to be allowed to produce an acid by radiation of actinic rays and a compound having in the main chain at least one carbonate ester group decomposable with an acid. CONSTITUTION:The photosensitive composition contains the compound to be allowed to produce an acid by radiation of actinic rays in a proper amount of 0.1-50wt%, preferably, 0.2-10wt% of the total solids of the photosensitive composition, and the compound having in the main chain at least one carbonate ester group represented by formula I decomposable with an acid, preferably, in an amount of 5-70wt%, especially, 10-50wt% of the total solids of the photosensitive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive lithographic printing plate and a photosensitive composition used in the printing plate.

[Conventional technology]

BACKGROUND ART Orthoquinonediazide compounds are conventionally known as photosensitive substances in photosensitive compositions used in photosensitive lithographic printing plates. The composition has been widely used for lithographic printing plates, photoresists for photoetching, and the like. Examples of this stronger orthoquinone diazide compound include JP-A Nos. 47-5303, 4B-63802, and 4B-
No. 63803, No. 49-3870j, No. 56-104
No. 4, No. 56-1045, Special Publication No. 4J-11222, No. 43-28403, No. 45-9610, No. 49
-17481 publications, U.S. Patent No. 2,797,21
No. 5, No. 3,046,120, Same! 1,188.2
No. 10, No. 3.454,400, No. 3,544,32
No. 3, No. 3.573,917, No. 5,674,49
No. 5, No. 3,785,825, British Patent No. 1,27
No. 7,602, No. 1 and 2 color No. 1,345, No. 1 and 2
No. 67,005, No. 1,529,888, No. 1,
Examples include those described in various specifications such as No. 550,932 and German Patent No. 854,890.

The above-mentioned orthoquinone diazide compounds are partially decomposed by irradiation with actinic rays and made soluble in a developer for photosensitive planographic printing plates, but all of them have the drawback of low sensitivity. .

As a method of increasing the sensitivity of photosensitive substances used in photosensitive compositions, there is a method of causing a second reaction using the acid generated by photolysis, and as a result, the area exposed to actinic rays is solubilized. A photosensitive substance is used that has a positive effect. Specifically, it is a photosensitive composition consisting of a combination of an at-generated compound by photolysis and a compound decomposable by a nucleic acid. 5
There is a compound having a carboxylic acid ester group described in Japanese Patent No. 625.

However, although these compounds generally exhibit high sensitivity as well as the above-mentioned orthoquinonediazide compounds, the sensitivity and development tolerance during development are not sufficient, and they are not satisfactory for actual use.

Further, a compound having a carbonate group in a side chain that can be cleaved by an acid is described in JP-A-59-45459. Even in photosensitive lithographic printing plates using this compound in the photosensitive layer, the sensitivity and development tolerance during development were not satisfactory for actual use.

[Problem that the invention seeks to solve]

Therefore, there has been a demand for a high-performance photosensitive composition with improved overall performance as a photosensitive composition for use in a photosensitive layer of a photosensitive lithographic printing plate.

An object of the present invention is to provide a novel photosensitive composition that has high sensitivity and wide development tolerance. Another object of the present invention is to provide a photosensitive lithographic printing plate having a photosensitive layer formed from a photosensitive composition having high sensitivity and wide development tolerance.

[Means for solving problems]

To summarize the present invention, the first invention of the present invention relates to a photosensitive composition, which comprises a compound capable of generating an acid upon irradiation with actinic rays and at least one component in the main chain capable of being decomposed by the acid. It is characterized by containing a compound having two carbonate ester groups.

The second invention of the present invention relates to a photosensitive lithographic printing plate, and is characterized by having a photosensitive layer formed from the photosensitive composition of the first invention on a support.

As a result of intensive research, the present inventors have discovered that a photosensitive composition having high sensitivity and wide development tolerance can be obtained by using a compound having a carbonate group in the main chain that can be partially decomposed by an acid, and The present inventors have discovered that a photosensitive lithographic printing plate using a photosensitive composition in a photosensitive layer can be put to practical use, and has accomplished the present invention.

The photosensitive composition of the present invention comprises a compound that can generate an acid upon irradiation with actinic rays (hereinafter referred to as an acid-generating compound) and a carbonate group-containing compound that can be partially decomposed by an acid (hereinafter referred to as an acid-decomposable compound). Contains.

The acid-decomposable compound is a compound containing in its main chain at least one carbonate group that can be decomposed by an acid represented by the following general formula: % formula % (1).

Further, the carbonate ester group I has the following general formula (1): (in the formula R1
and R1 represents a substituted or unsubstituted alkylene group, arylene group, alkenylene group, aralkylene group, or alkyleneoxy group.

R3, the formulas may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, an aralkyl group, and the above alkyl group includes a straight chain, branched, or cyclic group. The number of carbon atoms is 1 to 12, more preferably 1 to 6.

Furthermore, R and R4 may be bonded to each other to form a ring. Further, as the above-mentioned substituent group, a monocyclic one such as a phenyl group is suitable, and it may have a substituent.

It is preferable that Shima and & do not become hydrogen atoms at the same time, and more preferably Karasu and Yama are alkyl groups or aryl groups that may have substituents.

xl and XI may be the same or different and each represents a bond or a hydrogen atom) A structure represented by the following is preferable because it shows particularly excellent performance.

The above-mentioned compound containing a carbonate ester group may be a low-molecular compound in which Xi%XI is hydrogen, or a high-molecular compound in which xi and X are bonds and contain general formula l as a repeating unit, but preferably is a compound containing three or more of the above carbonate ester groups t- in its main chain.

In the case of polymer compounds, the number average molecular weight is approximately 5.
A range of 00 to 120,000 is appropriate, preferably 1000
~50,000.

The molecular weight is measured by gel permeation chromatography (hereinafter abbreviated as GPC).

Calculation of number average molecular weight was done by Morio Takuue, Tatsuya Miyabayashi, and Masayuki Tanaka.”
The peaks of the oligomer region are averaged by the method described in "Journal of the Chemical Society of Japan," pages 800 to 805 (1972).
This method shall be used to connect the center of the peak and the center of the valley. Further, in the case of a polymer compound, the content t of the carbonate ester groups represented by the general formula (2) is preferably 10% or more, more preferably 25% or more of the total carbonate ester groups.

These acid-decomposable compounds can be prepared by reacting iodides such as alkyl iodides corresponding to silver carbonate using known methods;
Alternatively, a method in which a compound having an alcoholic OH group and/or a phenolic OH group (hereinafter referred to as an OH group-containing compound 5) corresponding to the corresponding chloroformide ester is reacted by a known method, diphenyl carbonate, diethyl carbonate, etc. It can be synthesized by subjecting a low-molecular carbonate compound and an OH group-containing compound to an ester conversion reaction using a known method, or by reacting an OH group-containing compound corresponding to phosgene using a known method. For the synthesis of a compound having three or more carbonate ester groups, a method of transesterification or a method of reacting an OH group-containing compound corresponding to phosgene is preferred.

The above reaction using phosgene is, for example, Otsu-related,
“Experimental Methods of Polymer Synthesis” by Masayoshi Kinoshita (Kagaku Doujin) 323
A method similar to or similar to the method described on pages 324 to 324 can be used.

Examples of the OH group-containing compounds include monohydric alcohols, dihydric alcohols, trihydric or higher alcohols, monohydric phenolic compounds, divalent phenolic compounds,
Phenolic compounds with a higher value or phenolic O
Examples include compounds having both an H group and an alcoholic OH group.

Commercial products can be used for these OE (group-containing compounds), but in some cases they can also be synthesized by ordinary synthesis methods. For example, Jikken Kagaku Koza, Vol. 19, p.
It can be synthesized by a method similar to or similar to the method described on page 176.

Specific examples of the acid-decomposable compound of the present invention having at least one carbonate ester group are shown below.

Rumor! Spray g ;z
; z; to Otsuh's
04 4
A4 The content of the acid-decomposable compound of the present invention is preferably 5 to 70% by weight, particularly preferably 10 to 70% by weight, based on the total solid content of the photosensitive composition of the present invention.
It is 50% by weight.

Further, the acid-decomposable compounds of the present invention may be used alone or in combination of two or more. When the composite of acid-decomposable compounds of the present invention is obtained as a mixture of several, the mixture may be used as it is or may be used after being separated. The photosensitive composition of the present invention further includes: It is essential to contain an acid generating compound.

The acid generating compound of the present invention includes various known compounds and mixtures. For example, diazonium salts, phosphonium salts, sulfonium salts, and iodonium BF4
″″, PF, -1Sl)F, ″″, 5IF6-″″, c
Salts such as to4-, organohalogen compounds, orthoquinone-diazide sulfonic acid chloride, and organometallic/organohalogen compounds are also active element radiation-sensitive components that form or separate acids upon irradiation with actinic light. It can be used as an acid generating compound of the invention. All organic halogen compounds, which are known in principle as free-radical-forming photoinitiators, are compounds which form hydrohalic acids and can be used as acid-generating compounds according to the invention.

Examples of compounds forming the aforementioned hydrohalic acids are described in U.S. Pat. No. 3,515,552, U.S. Pat. .243,621, and for example, West German Patent Publication No. 2.610,
Compounds that generate acids upon photolysis as described in No. 842 can also be used.

Furthermore, JP-A-54-74728 and JP-A-55-2411
No. 5, No. 55-77742, No. 6cm 5626, No. 60-1! 2-halomethyl-i, 3,4-oxadiazole compounds described in each publication No. 18539 can also be used.

Specific examples of the acid generating compound of the present invention include JP-A-56-
The following can be mentioned as described in Japanese Patent No. 17345.

4-(n-flobylamino)-benzenediazonium tetrafluoroboret), '-p-tolylumercapto 2,5-diethoxybenzenediazonicum hexafluorophosphate and tetrafluoroborate, diphenylamine-4-diazonium sulfate , 4-methyl-6-dolichloromethyl-2-pyrone, 4
-(3,4,5-trimethoxy-steryl)-6-dolichloromethyl-2-pyrone, 4-(4-methoxy-styryl)-6-(5,3,5-trichloro-propenyl)
-2-? quinolone, 2-trichloromethyl-benzimidazole, 2-tribromomethyl-quinolone, 2,4-
Dimethyl-1-tribromoacetyl-benzene, 6-nitro-1-tribromoacetyl-benzene, 4-dibromoacetyl-benzoic acid, 1,4-bis-dibromomethylbenze/, tris-dibromomethyl-θ-triazine, 2-(6-methoxynaphth-2-yl)-12-(
naphth-1-yl)-12-(naphth-2-yl)-1
2-(4-ethoxyethyl-naphth-1-yl)-12
-(benzopyrani-3-yl)-12-(4-methoxy-anthracy-1-yl)- and 2-(phenanthi-9
-yl)-4,6-bis-trichloromethyl-8-triazine, and also 0-naphthoquinonediazide-4-sulfonic acid halide described in JP-A-50-56209 can also be used.

Furthermore, in addition to the compound having a halomethyl group described above in combination with a suitable dye, 0-naphthoquinonediazide-4
-Sulfonic acid halide or JP-A-55-6244
When used in combination with the 0-su7toquinone diazide compound described in Japanese Patent Application Laid-open No. 59-218442, a clear visible light with good stability over time is created between the unexposed area and the exposed area. Provides contrast.

The acid-generating compound of the present invention can vary widely depending on its chemical properties and the composition or physical properties of the photosensitive composition of the present invention, but is approximately [A range of L1 to about 50% by weight is suitable, preferably a range of 12 to 10% by weight.

In addition to the acid-generating compound of the present invention and the acid-decomposable compound of the present invention, the photosensitive composition of the present invention further contains a water-soluble resin, an alkali-soluble resin, or an organic solvent-soluble resin. It is preferable to use it. Among these, alkali-soluble resins are particularly preferred, and suitable alkali-soluble resins include phenol, 0-cresol,
At least one of m-cresol and p-cresol
Examples include novolak resin consisting of 1111 class and formaldehyde.

Specifically, for example, m-cresol, p-cresol,
Formaldehyde/novolak resin or phenol/m-cresol/p-/resol/formaldehyde/novolak resin may be used.

The above novolac resin may be used alone, or two
A mixture of more than one species may be used.

The molecular weight of the novolac resin is (polystyrene standard measurement) number average molecular weight Mn xoox1os~Z50x1''
% Weight average molecule 11Mw1)E 1. OOX10
m~50OX104 is suitable, preferably Mn
is 5.0OX10"~4.0OX10"SMy is 500X 103 S2.00 X 104T6.

The molecular weight of the novolak resin is measured by GPC method. Calculation of Mn and Mw is based on the above-mentioned 1 Journal of the Chemical Society of Japan” 8.
By the method described on pages 00 to 805 (1972),
Assumed to be performed.

Further, the content of these novolac resins in the photosensitive composition of the present invention is preferably 30 to 95% by weight, more preferably 50 to 90% by weight.

The photosensitive composition of the present invention contains the above-mentioned acid-generating compound of the present invention, acid-decomposable compound of the present invention, soluble resin, etc., as well as pigments such as dyes and pigments, and plasticizers as necessary. Furthermore, if necessary depending on the purpose of use, a sensitizer (a compound that increases the acid generation efficiency of the acid generation compound of the present invention) and the like may be added.

Examples of pigments such as dyes and pigments used in the photosensitive composition of the present invention include Victoria Pure Blue BOH (Odugaya Chemical Co., Ltd.), Oil Blue φ6OS (Orient Chemical Co., Ltd.), Patent Pure Blue [Sumitomo Mikuni Chemical Co., Ltd.], Crystal Violet, Brilliant green, ethyl violet, methyl green, -erythrosin B1 basic tsuksin, malachite green, oil red, m
-Cresol Purple, Rhodamine B1 Auramine, 4
Examples include -p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc., and examples include lutriphenylmethane type, diphenylmethane type, oxazine type, xanthine type, iminonaphthoquinone type, azomethine type, and anthraquinone type.

In addition, examples of plasticizers include phthalate esters, triphenyl phosphates, and maleate esters, and coating properties improvers include surfactants such as fluorine-based surfactants, nonionic active agents such as ethylcellulose polyalkylene ether, etc. Agents, etc. can be mentioned.

Furthermore, a lipophilic resin can be completely added to the photosensitive composition of the present invention in order to improve the oil sensitivity of the photosensitive composition.

Examples of the lipophilic resin (hereinafter referred to as a liposensitizing agent) include phenols substituted with an alkyl group having 5 to 15 carbon atoms, as described in JP-A-50-125806. and an aldehyde condensate, specifically t
- Butylphenol formaldehyde resin etc. can be added. Furthermore, a photosensitive resin obtained by condensing a lipophilic substituted phenol formaldehyde resin with a sulfonic acid chloride of 0-quinonediazide can also be added. These sensitizers are preferably contained in the photosensitive composition of the present invention in an amount of 1 to 5% by weight. A photosensitive layer is provided by coating and drying these on the surface of a suitable support, and a photosensitive lithographic printing plate made of the photosensitive composition of the present invention (hereinafter referred to as a photosensitive lithographic printing plate of the present invention) is prepared. Solvents that can be used to dissolve each component of the photosensitive composition of the present invention include cellosolves such as metelcerone rub, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate; Examples include dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone, and the like. These solvents may be used alone or in combination of two or more.

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 example, for photosensitive planographic printing plates, the solid content is 05 to 5.017 m.
is preferred.

The support provided with the photosensitive layer using the photosensitive composition of the present invention may be a metal plate made of aluminum, zinc, steel, copper, etc., or a support plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include metal plates, paper, plastic films, glass plates, paper coated with resin, paper covered with metal foil such as aluminum, and plastic films treated to make them hydrophilic. Among these, aluminum plates are preferred. As the support for the photosensitive lithographic printing plate of the present invention, it is more preferable to use an aluminum plate that has been subjected to surface treatments such as graining, anodizing, and, if necessary, sealing.

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 buffing. The various methods described above can be used alone or in combination depending on the composition of the aluminum material.

To perform electrolytic etching, use phosphoric acid, sulfuric acid, hydrochloric acid,
This is carried out using a bath containing one or a mixture of two or more inorganic acids such as nitric acid. 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 performed by electrolyzing using an aluminum plate as an anode using a solution containing 1 m or more of sulfuric acid, chromic acid, succinic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The amount of the anodic oxide film formed is suitably 1 to 5 (19/d-), preferably 10 to 4011 M1/dm", particularly preferably 25 to 40 η/dmz. The amount of the anodic oxide film is For example, an aluminum plate is heated in a phosphoric acid chromic acid solution (phosphoric acid 85% solution: 55 ml, chromium oxide (Vl
): 209 is dissolved in 1 ton of 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, the printing frame is generally vacuumed when contact-baking a film roll onto a photosensitive lithographic printing plate, and a method for improving this vacuum adhesion is also applicable to photosensitive lithographic printing using the photosensitive composition of the present invention. Can be applied to any version. Methods for improving vacuum adhesion include a method of mechanically creating unevenness on the surface of the photosensitive layer, a method of scattering solid powder on the surface of the photosensitive layer, and a method of spreading solid powder on the surface of the photosensitive layer.
A method of providing an i-t layer on the surface of a photosensitive layer as described in Japanese Patent Application Laid-Open No. 125-129-1982
Examples include a method of heat-sealing a solid powder onto the surface of a photosensitive layer as described in Japanese Patent No. 74.

The photosensitive lithographic printing plate of the present invention can be exposed and baked in the same manner as conventionally used ones. As an exposure means, for example, a transparent positive film is exposed to light using a light source such as an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, or scanning exposure is performed using a laser beam, and then the film is developed with a developer, and only the unexposed areas are exposed. However, a positive-positive relief image is formed on the surface of the support.

As the developer used for developing the photosensitive lithographic printing plate of the present invention, an aqueous alkaline developer is suitable. Examples include aqueous solutions of alkali metal salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium tertiary phosphate. The concentration of the alkali metal salt is preferably 105 to 20% by weight, more preferably 1 to 10% by weight CL.

Anionic surfactants, amphoteric surfactants, and organic solvents such as alcohols can be added to the developer of the present invention, if necessary.

Ethylene glycol monophenyl ether, benzyl alcohol, n-propyl alcohol, etc. are useful as organic solvents. The content of the organic solvent in the developer is preferably 15 to 15% by weight, and more preferably 1 to 5% by weight.

〔Example〕

Hereinafter, the photosensitive composition of the present invention and the photosensitive lithographic printing plate of the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (Synthesis of Exemplary Compounds No. 2) Hydroquinone [Tokyo Kasei Kogyo Co., Ltd., Tokyo Kasei Standards]
grade) 5.5f (5 moles of CLO), a,a'-dihydroxy-p-diinpropylbenzene [manufactured by Tokyo Chemical Industry Co., Ltd., Tokyo Chemical Standards grade] 29t ((Ll,, 5 moles of diphenyl carbonate [ Tokyo Chemical Industry Co., Ltd., Tokyo Chemical Standard Special Grade 342.8? ((L2 mol) and p-toluenesulfonic acid 30 mol) Gradually heat to 180° C. while stirring.

After stirring at 180° C. for 5 hours, the phenol produced at that temperature is distilled off under reduced pressure. After the formation of phenol is complete, the mixture is heated to 180° C. for an additional hour. After cooling, 350 g of tetrahydrofuran was added to the reaction product, followed by 1.5 f of anhydrous potassium carbonate, stirred, and then filtered.

The solvent was distilled off from the r liquid under reduced pressure to obtain a white, slightly viscous solid 20f.

Molecular weight was measured using GPC. GPC measurement conditions are:
The following is a common practice. Equipment: Hitachi Risakusho Ura 635 model, separation column: Showa Denko M Shodex (5hodex)
) A 802, A 805 and A304 are connected directly, temperature: room temperature, solvent: tetrahydrofuran,
Flow rate: 1.5 d/min. A calibration curve was prepared using polystyrene as a standard.

Calculation of number average molecule i1Mn and weight average molecular weight My,
When carried out using the method described above, Mw=3,300, Mn=
1,100, and the degree of dispersion Mw/Mn = IO.

(Preparation of Photosensitive Planographic Printing Plate Sample 1) After degreasing an aluminum plate (material: 1050, tempering: H16) with a thickness of A24 m+ in 5 ml of caustic soda aqueous solution at 60°C for 1 minute, Temperature: 250% in aqueous solution, flow density: 60A/am'', processing time;
Make sure to perform the electrolytic etching process for 30 seconds. Next, after desmutting in a 5% caustic soda aqueous solution at 60°C for 10 seconds, the temperature was reduced to 20°C in a 20% sulfuric acid solution.
The anodic oxidation treatment was performed under the following conditions: current density: 3 k/dm2, treatment time: 1 minute. Furthermore, a hot water sealing treatment was performed with hot water at 50° C. for 20 seconds to produce an aluminum plate as a support for a lithographic printing plate material.

Next, a photosensitive composition coating solution having the following composition was applied to this aluminum plate using a rotary coater and dried at 90° C. for 4 minutes to obtain positive photosensitive lithographic printing plate sample 1.

Photosensitive composition coating liquid composition> Compound obtained by synthesis of exemplified compound NO12
2-149 Sensitivity measurement step tablet (Eastman Kodak gNo.
2. Density difference (gray scale of 21 steps in each L15), 2 kW metal halide lamp [Iwasaki Electric ((translated)) Idol Fin 20001 as a light source 6
A sample was prepared that was exposed for 50 seconds from a distance of 0. Next, this sample was developed by diluting SDP-1 (Konishi Roku Photo Industry Co., Ltd.) nine times with water and using a developer solution for 60 seconds at 25°C.

When the sensitivity was measured using the gray scale of the step tablet, it was found that the fifth stage was completely developed (became clear).

Comparative Example 1 The aluminum support prepared in Example 1 was coated with polyester (described in Synthesis Example 1 of JP-A-60-3625) in place of Exemplified Compound N092 in the photosensitive composition coating solution of Example 1. α,α′-dihydroxy-p-
Photosensitive lithographic printing plate sample 3 was obtained in the same manner as in Example 1, except that a dehydration condensation product of diisopropylbenzene and terephthalic acid (Mn=1,200) was used.

The coating type t after drying was approximately 20 M9/dm2.

Next, using this photosensitive lithographic printing plate sample 3, Example 1
When exposure and development were carried out in the same manner as above, and the sensitivity was determined, it was found that the 21/2 step was completely developed (clear) on the gray scale of the step tablet.

Comparative Example 2 Poly(p-tert-butoxycarbonyloxy-α-methylstyrene) ( Synthesized by the method described in the Examples of JP-A No. 59-45459, Mn=
A photolithographic printing plate sample 5 was obtained in the same manner as in Example 1 except that 2QOOO) was used.

The coating weight after drying is about 20M? /am”.

Next, using this photosensitive lithographic printing plate sample 5, Example 1
When I developed it in the same manner as above and determined the sensitivity, it was found that the second stage was completely developed (clear) in the gray scale of the step tablet.

Example 2 (Synthesis of Exemplified Compound NO63) Hydroquinone 5.5f (105 mol), α,α'-dihydroxy-p-diisopropylbenzene 29f (Q, 15 mol) in the synthesis of Exemplified Compound N002 of Example 1
As a substitute, tetramethylene glycol [manufactured by Tokyo Kasei Kogyo Co., Ltd., Tokyo Kasei Standard Special Grade 19.0f (CL 1 mol), α
, α′-cyhitroxy-p-diisopropylbenzene (
The synthesis and post-treatment were carried out in the same manner, except that 19.4f (used in Example 1) (1 mol of cL) was used.

A white, slightly viscous solid 21F was obtained.

() When the molecular weight was measured in the same manner by PC, M
y = 4.200, Mn == 1,500, My/
Mn=2.8.

In the preparation of photosensitive lithographic printing plate sample 1 of Example 1, exemplified compound No. 2 was replaced with exemplified compound N obtained above.
Using o, 3, phenol, m-cresol and p-
A photosensitive lithographic printing plate sample 2 was prepared in the same manner as Example 1 except that a copolycondensation resin of m-cresol, p-cresol, and formaldehyde was used instead of a copolycondensation resin of cresol and formaldehyde. When exposure and development were carried out in the same manner as above, and the sensitivity was determined, it was found that the fifth stage of the step tablet's gray scale was completely developed (clear).

Comparative Example 3 Polyester (as described in Synthesis Example 2 of JP-A-60-3625) was added to the aluminum support prepared in Example 2 in place of Exemplified Compound No. 5 in the photosensitive composition coating solution of Example 2. By the method described, α,α′-dihydroxy-p
A photosensitive lithographic printing plate sample 4 was obtained in the same manner as in Example 2 except that a dehydration condensation product of diisopropylbenzene and adipine rIl, Mn=1,200)t- was used.

The coating weight after drying is approximately 20 M'l/dm".

Next, using this photosensitive lithographic printing plate sample 4t, it was exposed and developed in the same manner as in Example 2, and the sensitivity was determined.The third stage was completely developed (clear) on the gray scale of the step tablet. )there was.

Example 3 Development acceptability was examined using photosensitive lithographic printing plate samples 1.2.3.5 and 4 obtained in Example 1.2 and Comparative Example 1.2.3.

As a method for examining development acceptability, a developer solution with a diluted alkali concentration and a developer solution with a higher alkali concentration are prepared respectively, and the photosensitive lithographic printing plate sample 1 is prepared.
A positive original film was placed on ~5 and exposed for 30 seconds. Using 9 samples, the number of clear stages when developed with a developer with reduced developing ability and the number of clear stages when developed with a developer with excessive developing ability. We calculated the difference in the number of steps cleared.

The results are shown in Table 1.

The smaller the difference between the number of clear stages when developed with a developer with reduced developing ability and the number of clear stages when developed with a developer with excessive developing ability, the better the development acceptability is.

Table 1 From the above results, the photosensitive lithographic printing plates of the present invention having the photosensitive composition of the present invention on the support were Samples 1 and 2 of Examples 1 and 2 and Sample 3 of Comparative Examples 1.2 and 3. The photosensitive planographic printing plate samples 1 and 4 of the present invention have higher sensitivity than those seen in the comparison with .5 and 4, and can be sufficiently developed for practical use. Comparative Examples 1.2 and 3 show that Comparative Examples 1.2 and 3, Samples 5.5 and 4, show that development can be carried out in a wide range of dilution ratios of the developer used, and that development tolerance is extremely high. It turns out that it is in good condition.

Overall, it is clear that the photosensitive lithographic printing plate of the present invention is a photosensitive lithographic printing plate with improved overall performance.

〔Effect of the invention〕

As explained above, the photosensitive composition of the present invention has high sensitivity and wide development tolerance, and the photosensitive lithographic printing plate of the present invention having the composition as a photosensitive layer has a high overall performance. It has all the remarkable effects of improved high performance.

Patent applicant Konishiroku Photo Industry Co., Ltd. Same Mitsubishi Chemical Industries, Ltd.

Claims (1)

[Scope of Claims] 1. A photosensitive composition containing a compound capable of generating an acid upon irradiation with actinic rays and a compound having at least one carbonate ester group in its main chain that can be decomposed by an acid. . 2. A photosensitive composition formed from a photosensitive composition containing, on a support, a compound capable of generating an acid upon irradiation with actinic rays and a compound having at least one carbonate ester group in its main chain that can be decomposed by an acid. 1. A photosensitive lithographic printing plate characterized by having a transparent layer.