JPH10161314A - Photosensitive resin composition and photosensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing plate having high sensitivity and excellent durability against a cleaner and to prevent damages by a ball-point pen and remaining of an ink of a ball-point pen by incorporating a vinyl polymer having a specified or more molar ratio of structural units containing cyclic hydrocarbon groups selected from specified compds. into a photosensitive resin layer. SOLUTION: A photosensitive resin compsn. containing a compd. which produces radicals by light, active rays, electron beams or acid is applied on one surface of a base body, and the photosensitive resin layer contains a vinyl polymer having >=75mol% structural units containing cyclic hydrocarbon groups. The structural units containing cyclic hydrocarbon groups consist of at least one structural unit selected from compds. expressed by formula 1 to formula III. In formulae I to III, R<1> to R<12> are independently hydrogen atoms, alkyl groups, etc., and R<1> to R<3> are hydrogen atoms or 1 to 4C alkyl groups, R<4> to R<12> are independently hydrogen atoms or 1 to 6C alkyl groups or phenyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition containing a compound capable of generating an acid or a radical by light, actinic radiation or an electron beam, and a high molecular compound, and a photosensitive composition comprising the photosensitive composition as a photosensitive layer. Regarding lithographic printing plates.

[0002]

2. Description of the Related Art Lithographic printing is a printing method that skillfully utilizes the property that water and oil are not essentially mixed. In this lithographic printing, printing is usually performed while cleaning the plate surface with various cleaners for the purpose of cleaning the plate surface.
Therefore, a lithographic printing plate is required to have both sensitivity, which is a general performance, and resistance to a cleaner.

In recent years, for lithographic printing plates, it has been desired to reduce processing waste liquids for rapid processing and environmental protection. Conventionally, as one technique for this purpose, it has been known to make the photosensitive layer thinner, thereby enabling reduction in the amount of sludge and processing waste liquid and the cost.

[0004] On the other hand, during plate-making work, a mark is often made on the plate for registration and marking with a ballpoint pen. The exposed part of the inscribed part must of course be developed and hydrophilic. However, the ballpoint pen ink does not become hydrophilic because it remains on the surface of the support, resulting in printing stains. Further, the portion of the photosensitive layer which is drawn with the ballpoint pen ink is eroded with the ink.

[0005] As described above, it is desired that the printing plate has improved sensitivity, resistance to a cleaner, and suitability for a ballpoint pen ink.

However, if the photosensitive layer is made thinner for rapid processing and environmental protection, it becomes more difficult to balance sensitivity, resistance to cleaners, suitability for ballpoint pen ink, etc., and impair printing durability and chemical resistance. There is a limit to thinning because it comes out.

Conventionally, various proposals have been made as a countermeasure against the ink of the ballpoint pen, for example, Japanese Patent Application Laid-Open No. 61-205933 using a specific novolak resin is disclosed.

[0008] However, these prior arts did not satisfy all of the above requirements and required further development.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive resin composition and a lithographic printing plate having high sensitivity and excellent cleaner resistance and having no residual ball-point pen ink after being removed. .

[0010]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
The problem has been solved by the following configuration.

A. In a photosensitive resin composition containing a compound that generates an acid or a radical by light, actinic radiation, or an electron beam on one surface of a support, the photosensitive resin layer contains 75 mol of a structural unit containing a cyclic hydrocarbon group. % Of a vinyl polymer containing at least 1% by weight of a photosensitive resin composition.

B. The photosensitive resin composition according to the above item a, wherein the structural unit containing a cyclic hydrocarbon group contains an aromatic ring.

C. In a photosensitive lithographic printing plate containing a compound that generates an acid or a radical by light, actinic radiation, or an electron beam on one surface of the support, the photosensitive resin layer contains 75 mol of a structural unit containing a cyclic hydrocarbon group. % Of a photosensitive lithographic printing plate comprising a vinyl polymer containing at least 10% by weight.

D. The photosensitive lithographic printing plate according to claim c, wherein the structural unit containing a cyclic hydrocarbon group contains an aromatic ring.

E. The photosensitivity described in the above item a, wherein the structural unit containing a cyclic hydrocarbon group is at least one structural unit selected from the compounds represented by the following general formulas (1), (2) and (3). Resin composition.

[0016]

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(Wherein, R ^{1 to} R ¹² each represent a hydrogen atom,
Represents an alkyl group, an aryl group, an alkylene group, a cycloalkyl group, a cycloalkylene group or an aralkyl group, an arylene group or an aralkylene group. F). In the above general formulas (1), (2) and (3), R ¹ , R ² and R ³ each represent a hydrogen atom or a carbon atom
The photosensitive resin composition according to item e above, wherein each of R ^{4 to} R ¹² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.

G. In a photosensitive resin composition containing a compound that generates an acid or a radical by light, actinic radiation, or an electron beam on one surface of a support, the photosensitive layer has a structural unit represented by the following general formula (4). A photosensitive resin composition comprising a polymer having at least 40 mol% of

[0019]

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(X represents a —CHO, —COCH ₃ , —NO ₂ or —CN group) h. The photosensitive resin layer contains 7 structural units containing a cyclic hydrocarbon group.
The photosensitive resin composition according to the above item g, comprising a polymer having 5 mol% or more.

I. X in the above general formula (4) is -CN
The photosensitive resin composition according to the above item g or h, which is a group.

J Any one of the above items g to i, wherein the structural unit represented by the general formula (4) is a structural unit selected from the following general formulas (A) to (C). 1
Item 6. The photosensitive resin composition according to item 1.

[0023]

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(Wherein, R ^{13 to} R ²¹ each represent a hydrogen atom,
Represents an alkyl group, a phenyl group, an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group. X represents -CHO, -COCH _3, -NO ₂ or -CN group. Hereinafter, the present invention will be described in detail.

The present invention relates to a photosensitive resin composition and a photosensitive lithographic printing plate. The resin composition having a photosensitive layer according to the present invention and the photosensitive lithographic printing plate each include a structural unit containing a cyclic hydrocarbon group. Is contained in a vinyl polymer containing at least 75 mol%. The vinyl polymer is preferably contained in an amount of 80 mol% or more, more preferably 85 mol% or more.

Further, the structural unit containing preferably at least 50 mol% of a cyclic hydrocarbon group contains an aromatic ring.

The vinyl polymer containing a cyclic hydrocarbon group referred to herein includes, for example, a vinyl polymer containing an aromatic ring, and the aromatic ring includes a monocyclic or condensed cyclic aromatic ring.

In the present invention, the vinyl polymer contained in the photosensitive layer has a structural unit containing a cyclic hydrocarbon group selected from the compounds represented by formulas (1), (2) and (3). Preferably, the vinyl polymer has at least one structural unit, wherein R ^{1 to} R ¹² are each a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl , Butyl, pentyl, heptyl, octyl group, etc.), alkylene group (eg, methylene, ethylene, butylene, propylene, etc.), cycloalkyl group (eg, cyclohexyl group, etc.), aryl group (eg, phenyl group, etc.) or aralkyl group (eg, benzyl group) Group) cycloalkylene group,
Represents an arylene group or an aralkylene group.

In the present invention, a vinyl polymer having at least one structural unit whose structural unit containing a cyclic hydrocarbon group is selected from the compounds represented by formulas (1), (2) and (3) is used. But the general formula (1)
In the structural units represented by (2) and (3), R ¹ ,
R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{4 to} R ¹² are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or a phenyl group. Good effects of the invention can be achieved.

In particular, R ¹ , R ² and R ³ are each a hydrogen atom or a methyl group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
^It is preferred that ¹⁰ , R ¹¹ and R ¹² are each a hydrogen atom.

Further, a vinyl polymer containing at least 20 mol%, preferably at least 30 mol%, more preferably at least 40 mol% of the structural units represented by the above general formulas (1), (2) and (3) The purpose and effect of the present invention can be favorably exhibited.

In the photosensitive resin composition of the present invention, the photosensitive layer contains a polymer having a structural unit represented by the general formula (4) and having a structural unit content of 40 mol% or more.

The structural unit represented by the general formula (4) is represented by 4
A vinyl polymer containing at least 5 mol%, more preferably at least 50 mol% is preferred.

Further, the polymer having the structural unit represented by the general formula (4) according to the present invention contains the structural unit containing a cyclic hydrocarbon group in an amount of 75 mol% or more, preferably 80 mol% or more. Is preferred. In the general formula (4),
X is -CHO, -COCH _3, represents a -No ₂ or -CN group, and more preferably a -CN group.

In the present invention, the structural unit represented by the general formula (4) is more preferably a structural unit selected from the general formulas (A) to (C). In the general formulas (A) to (C), R ^{13 to} R ²¹ are each a hydrogen atom or an alkyl group, an alkylene group, a cycloalkyl group, an aryl group or an aralkyl represented by the general formulas (1) to (3). Represents a group having the same meaning as the group, cycloalkylene group, arylene group or aralkylene group. R ¹³ ,
R ^14, R ¹⁹ is preferably a hydrogen atom or a methyl group, R ¹⁵ ~
R ¹⁸ , R ²⁰ and R ²¹ are preferably hydrogen atoms.

Hereinafter, specific examples of the polymer compound which is a vinyl polymer containing a cyclic hydrocarbon group according to the present invention will be shown.
The present invention is not limited to this.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The above-mentioned polymer compound (vinyl polymer) can be synthesized by a known method, and the numbers described in the lower part of the structural formula represent the respective molar ratios.

The polymer compound according to the present invention is added to a layer containing the photosensitive resin composition of the present invention. The amount of addition may be arbitrary, but may be 2 to 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 25% by weight based on the total weight of the binder.

The photosensitive resin composition according to the present invention can use any support. The aluminum support includes a support made of pure aluminum and an aluminum alloy. Various aluminum alloys can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, and iron is used.

Prior to roughening, the aluminum support is preferably subjected to a degreasing treatment in order to remove grease, rust, dust and the like on the aluminum surface. As the degreasing treatment, solvent degreasing using a solvent such as trichlene or thinner, emulsion degreasing treatment using an emulsion of kerosene, triethanol or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used to remove stains and natural oxide films that cannot be removed only by the above degreasing treatment.

When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, a smut is formed on the surface of the support. In this case, an acid such as phosphoric acid, nitric acid, sulfuric acid or chromic acid is used.
Alternatively, it is preferable to perform a desmut treatment by immersing in a mixed acid thereof.

Prior to such a degreasing treatment, mechanical roughening may be performed. The mechanical surface roughening method is not particularly limited, but brush polishing and honing polishing are preferable. In brush polishing, for example, a cylindrical brush on which bristles having a bristle diameter of 0.2 to 1 mm are planted is rotated, and a slurry in which an abrasive is dispersed in water is supplied to a contact surface and pressed against a surface of a support to roughen the surface. I do. In the honing polishing, a slurry in which an abrasive is dispersed in water is ejected under pressure from a nozzle and collides obliquely with the surface of a support to roughen the surface.

Further, mechanical roughening can be carried out by bonding a previously roughened sheet to the surface of the support and applying a pressure to transfer the rough surface pattern.

After performing the desmutting treatment, the surface of the aluminum support is electrolytically roughened in an acidic electrolytic solution by using an alternating current. Hydrochloric acid, nitric acid or the like is used as the electrolytic solution at this time, but hydrochloric acid is more preferable. The electrolyte may contain nitrates, chlorides, amines, aldehydes, phosphoric acid,
Chromic acid, boric acid, acetic acid, oxalic acid and the like can be added.

The electrolytic surface roughening treatment is described in, for example, Japanese Patent Publication No. 48-28123, British Patent No. 896563, Japanese Patent Application Laid-Open No. 53-67507, and Japanese Patent Application No. 8-15036. Although these methods can be used, the method of Japanese Patent Application No. 8-151,036 is more preferable.

The voltage applied in the electrochemical graining is preferably 1 to 50 V, more preferably 5 to 30 V. The current density is preferably 10 to 200 A / dm ² ,
0 to 150 A / dm ² is more preferable. Electricity is 100
２０００2000 C / dm ² , preferably 200 to 1500 C
/ Dm ² , more preferably 200 to 1000 C /
dm ² . The temperature is preferably from 10 to 50 ° C, and from 15 to 50 ° C.
45 ° C is more preferred.

The current waveform used for the electrolysis is appropriately selected depending on the roughened shape to be obtained, such as a sine wave, a rectangular wave, a trapezoidal wave, and a sawtooth wave, and a sine wave is particularly preferable.

The support having been subjected to the electrolytic surface roughening treatment is immersed in an aqueous alkali solution to remove the smut and the like of the surface and to control the pit shape of the rough surface, and the surface is etched. Examples of the alkaline agent include sodium hydroxide, potassium hydroxide and the like. As these alkaline aqueous solutions, 0.05 to 40% aqueous solutions are used.
The treatment is performed at a liquid temperature of 0 to 90 ° C for 5 seconds to 5 minutes.

After the surface is etched with an aqueous alkali solution, the surface is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof to perform a neutralization treatment. When anodizing treatment is performed after the neutralization treatment, it is particularly preferable to match the acid used for the neutralization with the acid used for the anodization treatment. After the neutralization treatment, water washing is performed, and then anodization treatment is further performed. As the electrolyte used for the anodic oxidation treatment, any electrolyte can be used as long as it forms a porous oxide film. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, sulfamic acid, benzenesulfonic acid, etc., or a mixture thereof.
A mixed acid of a combination of two or more types is used. Anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be specified unconditionally. However, generally, the concentration of the electrolytic solution is 1 to 80.
% By weight, temperature 5 to 70 ° C, current density 1 to 60 A / d
m ² , a voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are appropriate. Preferred is a sulfuric acid method, which is usually treated with a direct current, but an alternating current can also be used.

The concentration of sulfuric acid is 10 to 50% by weight and the temperature is 20
The electrolytic treatment is preferably performed at 〜50 ° C. and a current density of 1-20 A / dm ² for 10 seconds to 5 minutes. Preferably, the electrolyte contains aluminum ions.

The anodized aluminum support may be subjected to a sealing treatment as required. The sealing treatment can be performed by a known method such as a hot water treatment, a boiling water treatment, a steam treatment, a sodium silicate treatment, a dichromate aqueous solution treatment, a nitrite treatment, and an ammonium acetate treatment. The aluminum support having been subjected to the sealing treatment may be provided with a hydrophilic layer. For the formation of the hydrophilic layer, US Pat.
81,461, the hydrophilic metal cellulose described in U.S. Pat. No. 1,860,426, the amino acids described in JP-B-6-94234, JP-A-6-2436, etc., or the salt thereof. Amines having a hydroxyl group and salts thereof described in JP-A-5-32238.
Phosphate described in 19494 and polymer compounds containing a monomer unit having a sulfo group described in 59-101651 can be used.

The support of the present invention may further comprise, for example, JP-A No. 5-225059, in order to prevent abrasion on the photosensitive layer when the photosensitive lithographic printing plates are overlaid, or to prevent elution of the aluminum component into the developing solution during development. Showa 50-151136, 57-6
No. 3293, No. 60-73538, No. 61-6786
No. 3, JP-A-6-35174 and the like, a process of providing a protective layer on the back surface of the support can be performed.

In the present invention, the other conditions of the photosensitive substance used in the photosensitive layer are not particularly limited, and various kinds of substances which are usually used for a positive photosensitive lithographic printing plate are used. be able to. Hereinafter, this point will be described.

(Photosensitive composition containing o-quinonediazide compound) The o-quinonediazide compound used in the present invention is a compound having an o-quinonediazide compound in a molecule. Examples of the o-quinonediazide compound include ester compounds of o-quinonediazidesulfonic acid with various aromatic polyhydroxy compounds or polycondensation resins of phenols and aldehydes or ketones.

Examples of the phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol, thymol, and divalent such as catechol, resorcin, and hydroquinone. Examples include trihydric phenols such as phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcinol / benzaldehyde resin, pyrogallol / acetone resin and the like. Can be

The condensation rate of o-quinonediazidesulfonic acid with respect to the OH groups of the phenols of the o-quinonediazide compound (reaction rate per OH group) is preferably 5 to 80%, more preferably 10 to 45%. is there.

As the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can be used.

For example, known 1,2-benzoquinonediazidosulfonic acid esters, 1,2-naphthoquinonediazidosulfonic acid esters, 1,2-benzoquinonediazidosulfonic acid amides, and 1,2-naphthoquinonediazidosulfonic acid amides are known. -Quinonediazide compounds, specifically "Light-Sensitive Systems" by J. Kosar (Light-Sens)
active Systems) pp. 339-352 (1
965), John Willie and Sons (Jo)
hn Willey & Sons, Inc. (New York) and W.S.D.Forest (WSD)
e Forest), "Photoresist" (Photo)
resist, vol. 50 (1975), 1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di-, described in McGraw Hill (New York).
(Benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4-
(N-ethyl-N-β-naphthyl) -sulfonamide,
1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-5-sulfonyl) -3,5-dimethylpyrazole,
1,2-naphthoquinonediazide-5-sulfone-4'-
Hydroxydiphenyl-4'-azo-β-naphthol-
Ester, N, N-di- (1,2-naphthoquinonediazido-5-sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2- Naphthoquinonediazide-5-sulfone-2,4-dihydroxybenzophenone ester, 1,2-naphthoquino, diazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid Condensation product of 2 mol of chloride and 1 mol of 4,4'-diaminobenzophenone, 1,2-naphthoquinonediazide
A condensate of 2 mol of 5-sulfonic acid chloride and 1 mol of 4,4'-dihydroxy-1,1'-diphenylsulfone,
Condensate of 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride with 1 mol of purprogalin, 1,2-
Examples thereof include 1,2-quinonediazide compounds such as naphthoquinonediazide-5- (N-dihydroabiethyl) -sulfonamide. In addition, Japanese Patent Publication No. 37-195
No. 3, No. 37-3627, No. 37-13109, No. 40-26126, No. 40-3801, No. 45-5
No. 604, No. 45-27345, No. 51-13013
JP-A-48-96575 and JP-A-48-63802.
And 1,2-quinonediazide compounds described in JP-A-48-63803 and the like.

Of the above o-quinonediazide compounds,
An o-quinonediazide ester compound obtained by reacting 1,2-benzoquinonediazidosulfonyl chloride or 1,2-naphthoquinonediazidosulfonylchloride with a pyrogallol-acetone condensed resin or 2,3,4-trihydroxybenzophenone is particularly preferred. As the o-quinonediazide compound used in the present invention, the above compounds may be used alone or in combination of two or more.

The proportion of the o-quinonediazide compound in the photosensitive composition is preferably from 6 to 60% by weight, particularly preferably from 10 to 50% by weight.

(Clathrate compound) The photosensitive composition of the present invention may contain a clathrate compound. The clathrate compound is not particularly limited as long as it is a compound that can take in (clathrate) a chemical species, but an organic compound soluble in a solvent used for preparing the composition is preferable. Examples of such organic compounds include, for example, “host guest chemistry”
(Michio Hiraoka et al., Kodansha, 1984, Tokyo) and other books and "Tetrahedron Report" (No. 226 (198
7) P5725A. Collet et al.), "Chemical Industry April Issue" ((1991) P278 Shinkai et al.), And "Chemical Industry April Issue" ((1991) P288 Hiraoka et al.).

Examples of the inclusion compound that can be preferably used in the present invention include cyclic D-glucans, cyclophanes, neutral polyligands, cyclic polyanions, cyclic polycations, cyclic peptides, SPHERANDS, Cavitand (CAVITA
NDS) and their acyclic analogs. Among these, cyclic D-glucans and their non-cyclic analogs, cyclophanes, and neutral polyligands are more preferred.

The cyclic D-glucans and non-cyclic analogs thereof include, for example, compounds in which α-D-glucopyranose is linked by a glycooxide bond.

Examples of the compound include carbohydrates composed of D-glucopyranose groups such as starch, amylose and amylopecton, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and polymerization of D-glucopyranose groups. A cyclodextrin having a degree of 9 or more, such as cyclodextrin, and SO ₃ C ₆ H ₄ CH ₂ C ₆ H ₄ S
O ₃ group, NHCH ₂ CH ₂ NH group, NHCH ₂ CH ₂ NHC
H ₂ CH ₂ NH group, SC ₆ H ₅ group, N ₃ group, NH ₂ group, NEt
₂ groups, SC (NH ₂ ⁺ ) NH ₂ group, SH group, SCH ₂ CH ₂ N
Modified D-glucans into which substituents such as an H ₂ group, an imidazole group, and an ethylenediamine group have been introduced.
Further, a cyclodextrin derivative, a branched cyclodextrin, a cyclodextrin polymer, and the like are also included.

The term "branched cyclodextrin" refers to a known cyclodextrin in which a water-soluble substance such as a monosaccharide or disaccharide such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine is branched or added. Preferably, maltosyl cyclodextrin in which maltose is bonded to cyclodextrin (the number of bonded molecules of maltose may be one, two, or three), or glucosylcyclodextrin (glucose in which glucose is bonded to cyclodextrin) May be any one molecule, two molecules, or three molecules).

Cyclophanes are cyclic compounds having a structure in which aromatic rings are connected by various bonds, and many compounds are known.
These known compounds can be mentioned.

The neutral polyligand includes crown compounds, cryptands, cyclic polyamines and their non-cyclic analogs. The compound is known to effectively incorporate metal ions, but can also effectively incorporate cationic organic molecules.

Other clathrates include urea, thiourea, deoxycholic acid, dinitrodiphenyl, hydroquinone, o-trithymotide, oxyflavan, dicyanamine nickel, dioxytriphenylmethane, triphenylmethane, methylnaphthalene, spirochroman, Examples include perhydrotriphenylene, clay mineral, graphite, zeolite (faujasite, chabazite, mordenite, levynite, montmorillonite, halosite, etc.), cellulose, amylose, protein and the like.

These clathrates may be added as a simple substance. However, the clathrate itself or the clathrate containing the molecule incorporated therein may be improved in solubility in a solvent and compatibility with other additives. For this purpose, a polymer in which a substituent having an inclusion function is suspended as a pendant substituent on the polymer may be added together.

Among the above inclusion compounds, cyclic and acyclic D-
Glucans, cyclophanes, and acyclic cyclophane analogs are preferred. More specifically, cyclodextrin, calixarene, resorcinol-aldehyde cyclic oligomer, and para-substituted phenols acyclic oligomer are preferred. Most preferred are cyclodextrin and its derivatives, and among them, β-cyclodextrin and its derivatives are more preferred. The ratio of these clathrates to the photosensitive composition is 0.01%.
-10% by weight is preferred, and 0.1-5% by weight is more preferred.

(Alkali-Soluble Resin) Examples of the alkali-soluble resin include novolak resins, acrylic polymers, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. .

The novolak resin used in the present invention includes, for example, phenol / formaldehyde resin, cresol / formaldehyde resin, and JP-A-55-5784.
No. 1 phenol-cresol-formaldehyde copolymer resin disclosed in JP-A-55-12
And a copolymer resin of p-substituted phenol and phenol or cresol and formaldehyde as described in No. 7553.

The molecular weight (polystyrene standard) of the novolak resin is preferably such that the number average molecular weight Mn is 3.00 ×
10 ^{2 to} 7.50 × 10 ³ , weight average molecular weight Mw of 1.0
0 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn is 5.00 × 10 ^{2 to} 4.00 × 10 ³ and Mw is 3.00 ×
10 ^{3 to} 2.00 × 10 ⁴ .

The above novolak resins may be used alone or in combination of two or more. The proportion of the novolak resin in the photosensitive composition is preferably from 5 to 95% by weight.

(Acrylic Polymer) The acrylic polymer that can be used in the present invention is a polymer obtained by polymerizing acrylic acid and its derivative, and the polymer includes other than acrylic acid and its derivative. It includes those obtained by copolymerizing monomers.

Examples of acrylic acid and its derivatives include acrylic acids such as acrylic acid, methacrylic acid and α-chloroacrylic acid; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylate,
Esters of acrylic acid such as p-aminosulfonylphenyl methacrylate; nitriles such as acrylonitrile and methacrylonitrile; acrylamide; N- (p-
Aminosulfonylphenyl) methacrylamide, N-
Amides such as (p-methylaminosulfonylphenyl) methacrylamide; anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide; and p-aminosulfonylphenyl methacrylate. .

The monomers other than acrylic acid and its derivatives used as the copolymerization component include unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride; monomethyl itaconate, dimethyl maleate, and the like. Esters of unsaturated aliphatic dicarboxylic acids such as diethyl maleate; ethylene, propylene, isobutylene,
Ethylenically unsaturated olefins such as butadiene and isoprene; styrenes such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene; imides such as N-phenylmaleimide; vinyl acetate, vinyl propionate and benzoate Vinyl esters such as vinyl acrylate and vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and β-chloroethyl vinyl ether; vinyl chloride; vinylidene chloride; vinylidene cyanide; 1-methyl-
1-methoxyethylene, 1,1-dimethoxyethylene,
Ethylene derivatives such as 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene; N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, And vinyl monomers such as N-vinyl compounds such as N-vinylpyrrolidone. These vinyl monomers have a structure in which the unsaturated double bond is cleaved and are present in the polymer compound.

The monomers other than acrylic acid and its derivatives used as acrylic acid and its derivatives and copolymerization components may be bonded to the above-mentioned polymer compound in either a block or random state.

The above polymers may be used alone or in combination of two or more. It can also be used in combination with other polymer compounds and the like.

As the acrylic polymer, an acrylic polymer having a phenolic hydroxyl group is preferable.

(Vinyl copolymer having a phenolic hydroxyl group) In the acrylic polymer having a phenolic hydroxyl group, the phenolic hydroxyl group is represented by the following general formula (I):
It is preferably contained as a structural unit represented by [VI].

[0090]

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In the general formulas [I] to [VI], R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ is a hydrogen atom,
Represents an alkyl group, an aryl group or an aralkyl group, and preferably represents a hydrogen atom. A represents an alkylene group which may have a substituent linking a nitrogen atom or an oxygen atom to an aromatic carbon atom, m represents an integer of 0 to 10, and B may have a substituent. It represents a good phenylene group or a naphthylene group which may have a substituent.

In the present invention, among these, a copolymer containing at least one structural unit represented by the general formula [II] is preferable.

Examples of the copolymerizable components of the acrylic polymer having the structural units represented by the general formulas [I] to [VI] include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. Styrenes such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene; acrylic acids such as acrylic acid and methacrylic acid; for example, itaconic acid and maleic acid;
Unsaturated aliphatic dicarboxylic acids such as maleic anhydride, for example, methyl acrylate, ethyl acrylate, acrylic acid-
α- such as n-butyl, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate
Esters of methylene aliphatic monocarboxylic acid, for example, nitriles such as acrylonitrile and methacrylonitrile, for example, amides such as acrylamide and methacrylamide, for example, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacryl Anilides such as anilides, for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and β-chloroethyl vinyl ether; vinyl chloride; Vinylidene, vinylidene cyanide such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-
Ethylene derivatives such as dimethoxycarbonyl ethylene and 1-methyl-1-nitroethylene, for example, N-vinyl based compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene, N-vinyl pyrrolidone Monomers.

Among the above-mentioned monomers, acrylic acid, methacrylic acid, aliphatic monocarboxylic acid and the like may be used as copolymerization components of the acrylic polymer having the structural units represented by the general formulas [I] to [VI]. Acid esters and nitriles are preferred because they exhibit excellent overall performance. More preferred are methacrylic acids, methyl methacrylate, acrylonitrile, ethyl acrylate and the like.

Formulas (I) to (A) in an acrylic resin
The content of the structural unit represented by each of (VI) is 5 to
70 mol% is preferable, and especially 10 to 40 mol% is preferable.

The proportion of the acrylic polymer in the photosensitive composition is preferably from 5 to 95% by weight.

(Ultraviolet Absorbing Dye) The photosensitive composition of the present invention may contain an ultraviolet absorbing dye in order to prevent halation.

Examples of such compounds include Diaresin Brilliant, Yellow 6G, Dialesin Yellow 3G, Dialesin Yellow F, Dialesin Red Z, Dialesin Yellow H2G, manufactured by Mitsubishi Kasei Corporation.
Dialegin Yellow HG, Dialegin Yellow HC, Dialegin Yellow HL, Dialegin Orange HS, Dialegin Orange G, Dialegin Red GG, Dialegin Yellow GR, Dialegin Red S, Dialegin Red HS, Dialegin Red A, Diaresin Red H, Diacid Ride Yellow 2G, Nippon Kayaku Kaya Set
Yellow K-RL, Kayaset Yellow K-CL, Kayaset Yellow EG, Kayaset Yellow E-
AR, Kayaset Yellow AG, Kayaset Yellow GN, Kayaset Yellow 2G, Kayaset Yellow SF-G, Kayaset Orange K-RL, Kayaset Orange G, Kayaset Orange A-N, Kayaset Orange SF- R, Kayaset Flavin F
N, Kayaset Flavin FG, Kayaset Red K
-BL, Kayacryl Golden Yellow
yellow or orange dyes such as wGL-ED.

The content of the ultraviolet absorbing dye is preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight in the photosensitive composition. Further, within the above range, two or more kinds can be used in combination.

(Organic acid / inorganic acid / acid anhydride) The photosensitive composition of the present invention may contain an organic acid / inorganic acid / acid anhydride. Examples of the acid used in the present invention include an organic acid described in JP-A-60-88942 and JP-A-2-137850, and a new edition of Chemical Handbook, edited by The Chemical Society of Japan (Maruzen Publishing), pp. 92-158. And the inorganic acids described in (1). Examples of organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, m
Sulfonic acids such as benzenedisulfonic acid, sulfinic acids such as p-toluenesulfinic acid, benzylsulfinic acid and methanesulfinic acid, phosphonic acids such as phenylphosphonic acid, methylphosphonic acid and chloromethylphosphonic acid, formic acid, acetic acid, propionic acid and butyric acid , Isobutyric acid, pentanoic acid, hexanoic acid, aliphatic monocarboxylic acids such as heptanoic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, o-, m-, p-hydroxybenzoic acid,
o-, m-, p-methoxybenzoic acid, o-, m-, p-
Aromatic monocarboxylic acids such as methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid, and 3,5-dimethylbenzoic acid. Also,
Saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, itaconic acid, malic acid, and tetrahydro Phthalic acid, 1,1-cyclobutanedicarboxylic acid,
1,1-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
-Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid.

Among the above organic acids, more preferred are p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Sulfonic acids such as mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and m-benzenedisulfonic acid; cis-1,2-cyclohexanedicarboxylic acid; and syringic acid.

Examples of inorganic acids include nitric acid, sulfuric acid, hydrochloric acid,
Examples thereof include silicic acid and phosphoric acid, and more preferably sulfuric acid and phosphoric acid.

When an acid anhydride is used, the type of the acid anhydride is also arbitrary, and those derived from aliphatic / aromatic monocarboxylic acids such as acetic anhydride, propionic anhydride and benzoic anhydride, and succinic anhydride , Maleic anhydride, glutaric anhydride, phthalic anhydride, etc., and those derived from aliphatic / aromatic dicarboxylic acids. Preferred acid anhydrides are glutaric anhydride and phthalic anhydride. These compounds can be used alone or in combination of two or more.

The content of these acids is generally from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, based on the total solids of the entire photosensitive composition. It is.

(Surfactant) The photosensitive composition of the present invention may contain a surfactant. As the surfactant, an amphoteric surfactant, an anionic surfactant, a cationic surfactant,
Nonionic surfactants, fluorinated surfactants and the like can be mentioned.

Examples of the amphoteric surfactant include lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl, imidazolinium betaine and the like.

Examples of the anionic surfactant include fatty acid salts,
Alkyl sulfate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl allyl sulfate, naphthalene Sulfonic acid formalin condensate,
And polyoxyethylene alkyl phosphates.

Examples of the cationic surfactant include an alkylamine salt, a quaternary ammonium salt, and an alkyl betaine.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene. Examples include sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, alkylalkanolamides, and the like.

Examples of the fluorine-based surfactant include acrylate or methacrylate containing a fluoroaliphatic group and a copolymer of (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate. For example, JP-A-62-170950 and JP-A-62-2
No. 26143, U.S. Pat. No. 3,787,351 (for example, Megafac F-171,173,1)
77, Defensor MCF300, 312, 313 (all manufactured by Dainippon Ink and Chemicals, Inc.), Modiper F-10
0, 102, 110 (manufactured by NOF CORPORATION) and the like. These compounds can be used alone or in combination of two or more. The proportion occupying in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

(Printout Material) A printout material for forming a visible image upon exposure can be added to the photosensitive composition of the present invention. The printout material is composed of an organic dye that changes its color tone by interacting with a compound that generates an acid or a free radical upon exposure. O-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-36209, o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-53-36223, and phenols having an electron-withdrawing substituent Or an ester compound or an amide compound with aniline acid, a halomethylvinyloxadiazole compound and a diazonium salt described in JP-A-55-77742 and JP-A-57-148784.

(Compound that Generates Acid or Free Radical by Exposure) Examples of the compound that generates an acid or free radical upon exposure include a halomethyloxadiazole compound and a halomethyl-s-triazine compound.

A halomethyloxadiazole compound is
Oxadiazoles are compounds having a halomethyl group, preferably a trichloromethyl group.

These compounds are known, for example, JP-B-57-6096 and JP-B-61-51788.
JP-B-1-28369, JP-A-60-13853
No. 9, No. 60-177340, No. 60-24
No. 1049, for example.

The halomethyl-s-triazine compound is a compound having at least one halomethyl group, preferably a trichloromethyl group, on the s-triazine ring.

The amount of the compound capable of forming an acid or a free radical upon exposure to light in the photosensitive composition is from 0.01 to 3
It is preferably 0% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.2 to 3% by weight.

These compounds can be used alone or in combination of two or more.

(Dye) Dye is used for the purpose of obtaining a visible image by exposure (exposure visible image) and a visible image after development.

As the dye, those which change color tone by reacting with a free radical or acid can be preferably used.
Here, "change in color tone" includes both a change from colorless to a color tone and a change from color to colorless or a different color tone. Preferred dyes are those that form a salt with an acid to change the color tone. For example, Victoria Pure Blue BOH (made by Hodogaya Chemical Co., Ltd.), Oil Blue #
603 (manufactured by Orient Chemical Industries), patent pure blue (manufactured by Sumitomo Mikuni Chemicals), crystal violet,
Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Paysic Fuchsin, Malachite Green, Oil Red, m
-Cresol purple, rhodamine B, auramine,
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes represented by 4-p-diethylaminophenyliminaphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. are colored to colorless Alternatively, it is mentioned as an example of a color changing agent that changes to a different color tone.

On the other hand, examples of the color changing agent that changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p '-Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p',
p "-tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, Primary or secondary arylamine dyes represented by p ', p "-triaminotriphenylmethane are exemplified.

The proportion of the above color changing agent in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.02 to 5% by weight.

These compounds can be used alone or in combination of two or more. Particularly preferred dyes are Victoria Pure Blue BOH and Oil Blue # 603.

(Oil Sensitizing Agent) An oil sensitizing agent for improving the oil sensitivity of an image area (for example, a half-esterified product of a styrene-maleic anhydride copolymer with an alcohol described in JP-A-55-527). , Pt-butylphenol-
Novolak resins such as formaldehyde resins, or partially esterified products thereof with o-quinonediazide compounds, fluorine surfactants, p-hydroxystyrene
0% fatty acid ester) is preferably used. The amount of these additives varies depending on the object and purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.

Each of these components was dissolved in the following solvent,
The photosensitive lithographic printing plate of the present invention can be produced by providing a photosensitive layer by coating and drying the surface of the support. There is no particular limitation on the usage of the solvent.

(Solvent) Solvents usable for dissolving the photosensitive composition of the present invention include fatty acids such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol. Aliphatic alcohols, allyl alcohol, benzyl alcohol, anisole, phenetole, n-hexane, cyclohexane, heptane, octane, nonane, hydrocarbons such as decane, diacetone alcohol, 3-methoxy-1-butanol, 4-methoxy-1 -Butanol, 3-ethoxy-
1-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-ethyl-1-pentanol-4-ethoxy-1-pentanol, 5-methoxy-
1-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methylhexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone,
γ-butyrolactone, 3-hydroxy-2-butanone,
4-hydroxy-2-butanone, 4-hydroxy-2-
Pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol Propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol alkyl ethers and their acetates (MC, EC, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether,
Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, MC acetate, EC acetate), diethylene glycol monoalkyl ethers and their acetates (diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, diethylene glycol monomethyl ether acetate, etc.), Diethylene glycol dialkyl ethers (DMDG, DEDG, DBD
G, MEDG), triethylene glycol alkyl ethers (monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, etc.), propylene glycol alkyl ethers and their acetates (monomethyl ether, monoethyl ether, n-propyl ether) , Monobutyl ether, dimethyl ether, diethyl ether, monomethyl ether acetate, monoethyl ether acetate, etc.), dipropylene glycol alkyl ethers (monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether, diethyl ether), ethyl formate , Propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Methyl propionate, carboxylic acid esters such as ethyl propionate, methyl butyrate, ethyl butyrate, etc., dimethylformamide, dimethyl sulfoxide,
Dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

The solvent that can be used when dissolving the photosensitive composition preferably contains at least one solvent selected from propylene glycol monomethyl ether, methyl ethyl ketone, methyl lactate, and diethyl carbitol.

(Coating) As a method for applying the photosensitive substance according to the present invention, conventionally known methods, for example, die coater coating, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating And methods such as electrostatic air spray coating, roll coating, blade coating, and curtain coating.

[0128] While the photosensitive layer thickness is not particularly limited, is preferably in the range of 5 to 30 mg / dm ² in total thickness, more preferably 20 mg / dm ² or less in total thickness as shown in claim 5, It is more preferably in the range of 5 to ²⁰ mg / dm ² , and particularly preferably in the range of 8 to 16 mg / dm ² .

(Coating Layer) In the photosensitive lithographic printing plate according to the present invention, a coating layer composed of a water-insoluble organic solvent-soluble polymer compound having a film-forming ability can be formed on the photosensitive layer.

As a method for applying the coating layer, a conventionally known coating method is used in the same manner as the application of the photosensitive composition layer.

(Mat Agent) It is preferable to further provide a mat layer on the surface of the photosensitive layer provided as described above. The mat layer shortens the time of evacuation during contact exposure using a vacuum printing frame, and prevents crushing of fine halftone dots at the time of exposure due to poor adhesion and blurring. Specifically, JP-A-50-125805, JP-B-57-6582,
Examples thereof include a method of providing a mat layer as described in JP-A-61-28986 and a method of thermally fusing a solid powder as described in JP-B-62-62337.

The purpose of the mat layer is to improve the vacuum adhesion between the image film and the photosensitive lithographic printing plate in the contact exposure, thereby shortening the evacuation time, and further reducing the loss of fine halftone dots during exposure due to poor adhesion. It is to prevent. As a method for applying the mat layer, a method of thermally fusing powdered solid powder described in JP-A-55-12974, and a method of spraying polymer-containing water described in JP-A-58-182636, are used. There is a method of drying the mat layer, and any method may be used. However, it is preferable that the mat layer itself is dissolved in the alkali developer or can be removed by this.

The method for applying the mat layer is the same as the method for applying the photosensitive composition layer by a conventionally known method.

(Exposure) In the use of the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original having a line image, a halftone dot image or the like is applied to the photosensitive surface. Exposure is performed in close contact, and then the photosensitive layer is removed from the non-image area using a suitable developer to obtain a relief image. As a light source suitable for exposure, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp and the like are used.

(Processing) In the present invention, both the developing solution and the developing replenisher used for the development of the photosensitive lithographic printing plate contain an alkali metal silicate. As alkali metals of alkali metal silicate, lithium, sodium,
Potassium is included, of which potassium is most preferred. At the time of development, it is preferable that a development replenisher is appropriately replenished in accordance with the development processing amount of the photosensitive lithographic printing plate.

Preferred developers and replenishers are [SiO
₂ ] / [M] (where [SiO ₂ ] represents the molar concentration of SiO ₂ and [M] represents the molar concentration of the alkali metal) is from 0.15 to 1.0, and the SiO ₂ concentration is It is an aqueous solution of an alkali metal silicate that is 0.5 to 5.0% by weight based on the total weight. Particularly preferably, [SiO 2
₂ ] / [M] is 0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, and [SiO ₂ ] /
[M] is 0.15 to 0.5, and the SiO ₂ concentration is 1.
0 to 3.0% by weight.

The above-mentioned developing solutions and developing replenishers can contain water-soluble or alkali-soluble organic and inorganic reducing agents.

Examples of the organic reducing agent include phenol compounds such as hydroquinone, methol, and methoxyquinone, and amine compounds such as phenylenediamine and phenylhydrazine. Examples of the inorganic reducing agent include:
For example, sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, sulfites such as potassium bisulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite,
Examples thereof include phosphites such as sodium dihydrogen phosphite and potassium dihydrogen phosphite, hydrazine, sodium thiosulfate, and sodium dithionite.

These water-soluble or alkali-soluble reducing agents are preferably contained in the developing solution and the developing replenisher at 0.05 to 10% by weight. The developing solution and the developing replenisher may contain an organic acid carboxylic acid. These organic carboxylic acids include aliphatic carboxylic acids having 6 to 20 carbon atoms and aromatic carboxylic acids in which a benzene ring or a naphthalene ring is substituted with a carboxyl group.

The aliphatic carboxylic acids include those having 6 to 2 carbon atoms.
The alkanoic acid of 0 is preferable, and specific examples thereof include caproic acid, enantiic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mystyric acid, palmitic acid,
Stearic acid and the like are particularly preferable.
~ 12 alkanoic acids. Further, the aliphatic carboxylic acid may be a fatty acid having a double bond in a carbon chain or a fatty acid having a branched carbon chain. The aliphatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

Specific examples of aromatic carboxylic acids include benzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, gallic acid, 1-hydroxy-
2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2
-Hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-
Naphthoic acid and the like.

The aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt. The content of the aliphatic carboxylic acid or aromatic carboxylic acid can be at least 0.1 to 30% by weight.

The developer and the developing replenisher can contain various anionic, nonionic and cationic surfactants and organic solvents.

Further, known additives can be added to the developing solution and the developing replenisher.

[0145]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Support) An aluminum plate (material: 1050, tempered H16) having a thickness of 0.3 mm was degreased in a 5% aqueous sodium hydroxide solution kept at 65 ° C. for 1 minute. Thereafter, the plate was washed with water, immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 1 minute, neutralized, and further washed with water.

This aluminum plate was immersed in a 1.0 wt% hydrochloric acid aqueous solution at a temperature of 25 ° C. and a current density of 100 A / dm.
^2. Electrolytic surface roughening was performed with an alternating current under the conditions of a treatment time of 60 seconds. Then in a 5% aqueous sodium hydroxide solution
Desmut treatment at 10 ℃ for 10 seconds, then 20%
Anodizing was performed in a sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² and a processing time of 1 minute.

Thereafter, it was immersed in a 1% aqueous solution of sodium nitrite kept at 80 ° C. for 30 seconds, washed with water and dried at 80 ° C. for 3 minutes. Further, the substrate was immersed in an aqueous solution of carboxymethylcellulose (concentration: 0.1 Wt%) maintained at 85 ° C. for 30 seconds, and dried at 80 ° C. for 5 minutes to prepare a support.

Next, a photosensitive solution having the following composition was applied on the above support using a die coater and dried at 80 ° C. to prepare a photosensitive lithographic printing plate sample. The coating amount is 1.4 g / m ²
Met.

(Photosensitive Liquid) Novolak resin (molar ratio of phenol: m-cresol: p-cresol: 10:54:36, weight average molecular weight 4000) 6.7 g pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinone Condensate of diazide-5-sulfonyl chloride (esterification ratio 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co.) 0.08 g 2,4-bis (trichloromethyl) -6 -(P-methoxystyryl) -s-triazine 0.15 g FC-430 (manufactured by Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g cyclohexanone: methyl ethyl ketone = 70: 30 100 ml polymer compound 1 0.5g Example 2 Example 1 There the 0.5g of the polymer compound 1 was except for using 0.5g of polymer compound-2 in the same manner as in Example 1 to prepare a sample.

Example 3 A sample was prepared in the same manner as in Example 1, except that 0.5 g of polymer compound-1 was changed to 0.5 g of polymer compound-3.

Example 4 A sample was prepared in the same manner as in Example 1 except that 0.5 g of the polymer compound-1 was changed to 0.5 g of the polymer compound-4.

Example 5 A sample was prepared in the same manner as in Example 1, except that 0.5 g of polymer compound-1 was changed to 0.5 g of polymer compound-5.

Example 6 A sample was prepared in the same manner as in Example 1 except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound-6.

Example 7 A sample was prepared in the same manner as in Example 1, except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound-7.

Example 8 A sample was prepared in the same manner as in Example 1, except that 0.5 g of polymer compound-1 was changed to 0.5 g of polymer compound-8.

Example 9 A sample was prepared in the same manner as in Example 1 except that 0.5 g of the polymer compound-1 was changed to 0.5 g of the polymer compound-9.

Example 10 A sample was prepared in the same manner as in Example 1 except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound-10.

Example 11 A sample was prepared in the same manner as in Example 1, except that 0.5 g of polymer compound-1 was changed to 0.5 g of polymer compound-11.

Example 12 A sample was prepared in the same manner as in Example 1, except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound-12.

Example 13 A sample was prepared in the same manner as in Example 1, except that 0.5 g of the polymer compound-1 was changed to 0.5 g of the polymer compound-13.

Example 14 A sample was prepared in the same manner as in Example 1, except that 0.5 g of the polymer compound-1 was changed to 0.5 g of the polymer compound-14.

Example 15 A sample was prepared in the same manner as in Example 1, except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound-15.

Example 16 A sample was prepared in the same manner as in Example 1, except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound-16.

Comparative Example 1 A sample was prepared in the same manner as in Example 1, except that 0.5 g of polymer compound-1 was changed to 0.5 g of polymer compound-17.

Comparative Example 2 A sample was prepared in the same manner as in Example 1, except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound-18.

Comparative Example 3 A sample was prepared in the same manner as in Example 1, except that 0.5 g of the polymer compound-1 was changed to 0.5 g of the polymer compound-19.

Comparative Example 4 A sample was prepared in the same manner as in Example 1, except that 0.5 g of Polymer Compound-1 was changed to 0.5 g of Polymer Compound 20.

Comparative Example 5 A sample was prepared in the same manner as in Example 1, except that 0.5 g of the polymer compound-1 was changed to 0.5 g of the polymer compound 21.

<Performance Evaluation> (Sensitivity) A step tablet for sensitivity measurement (No. 2, manufactured by Eastman Kodak Co., Ltd., gray scale of 21 steps with a density difference of 0.15) was closely attached to the sample, and a 4 kw metal halide lamp (Dainippon) Screen Quick Co., Ltd.
Exposure was performed from a distance of 90 cm using k) as a light source. Next, this sample was developed by diluting a developing solution SDR-1 (manufactured by Konica Corporation) 6 times with water and developing at 27 ° C. for 20 seconds.

The sensitivity was defined as the exposure time at which 3.0 steps of the step tablet were completely cleared. The smaller the value, the better the sensitivity.

(Cleaner resistance) A step tablet for sensitivity measurement (same as described above) was closely attached to the sample and exposed and developed in the same manner. The obtained lithographic printing plate is applied to a printing machine GTO manufactured by Heidelberg Co., Ltd., and coated paper, printing ink (New Bright Red manufactured by Toyo Ink Mfg. Co., Ltd.) and fountain solution (SEU-3 manufactured by Konica K.K .; 2.5% ) Was used for printing.

Every 500 printed sheets were washed with an ultra plate cleaner (Dainichi Seika Co., Ltd.). Printing was continued until an inking failure appeared on the solid portion of the image of the printed matter or ink was deposited on the non-image portion, and the number of printed sheets at that time was counted.

(Ball Pen Pen Larre) A sample is drawn with an oil ballpoint pen (manufactured by a pilot) while applying a load of 50 g to the sample.

Thereafter, this sample was developed at 27 ° C. for 20 seconds by diluting the SDR-1 developer 4 times with water. The resulting sample was visually evaluated for the vignetting condition of the photosensitive layer with a ballpoint pen ink in the following four ranks.

◎: The photosensitive layer is not vignetted. わ ず か: Grain is slightly exposed. Δ: Grain is partially exposed. ×: Grain is completely exposed. Draw over 50 g using an oil-based ballpoint pen (made by pilot).

Thereafter, exposure was performed from a distance of 90 cm using a 4 kw metal halide lamp (bio Quick manufactured by Dainippon Screen Co., Ltd.) as a light source. Next, this sample was developed at 27 ° C. for 20 seconds by diluting the developing solution SDR-1 6-fold with water. The remaining state of the ballpoint pen ink of the obtained sample was visually evaluated in the following four ranks.

A: Ballpoint pen ink is not completely left. O: Ballpoint pen ink is left slightly .: Ballpoint pen ink remains in some places. X: Ballpoint pen ink is completely left.

[0179]

[Table 1]

As is clear from the table, according to the present invention, a printing plate having high sensitivity and excellent cleaner resistance was obtained. Further, it can be seen that a lithographic printing plate having ball-point pen ink resistance, that is, a lithographic printing plate free from ink residue and ink residue can be obtained.

According to the present invention, it was found that when the dry thickness of the photosensitive layer was 1.8 g / m ² or less, preferably 1.6 g / m ² or less, the effect of the present invention was remarkably exhibited.

[0182]

As demonstrated in the examples, according to the present invention, it is possible to obtain a lithographic printing plate having high sensitivity with improved cleaner resistance and improved ballpoint pen ink resistance.

Claims (10)

[Claims] Claims: 1. A light, actinic radiation,
A photosensitive resin composition containing a compound that generates an acid or a radical by an electron beam, wherein the photosensitive resin layer contains a vinyl polymer containing at least 75 mol% of a structural unit containing a cyclic hydrocarbon group. A photosensitive resin composition. 2. The photosensitive resin composition according to claim 1, wherein the structural unit containing a cyclic hydrocarbon group contains an aromatic ring. 3. A light, actinic radiation,
A photosensitive lithographic printing plate containing a compound that generates an acid or a radical by an electron beam, wherein the photosensitive layer contains a vinyl polymer containing at least 75 mol% of a structural unit containing a cyclic hydrocarbon group. Photosensitive lithographic printing plate. 4. The photosensitive lithographic printing plate according to claim 3, wherein the structural unit containing a cyclic hydrocarbon group contains an aromatic ring. 5. The structural unit containing a cyclic hydrocarbon group is at least one structural unit selected from compounds represented by the following general formulas (1), (2) and (3). 2. The photosensitive resin composition according to item 1. Embedded image (Wherein, R ^{1 to} R ¹² each represent a hydrogen atom, an alkyl group,
Represents an aryl group, an alkylene group, a cycloalkyl group, a cycloalkylene group or an aralkyl group, an arylene group or an aralkylene group. ) 6. In the general formulas (1), (2) and (3), R ¹ , R ² and R ³ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{4 to} R ¹² Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, respectively. 7. A light, actinic radiation,
In a photosensitive resin composition containing a compound that generates an acid or a radical by an electron beam, the photosensitive resin layer contains a polymer having a structural unit represented by the following general formula (4) in an amount of 40 mol% or more. A photosensitive resin composition comprising: Embedded image (X represents -CHO, -COCH _3, -NO ₂ or -CN group.) 8. The photosensitive resin composition according to claim 7, wherein the photosensitive resin layer contains a polymer having 75 mol% or more of a structural unit containing a cyclic hydrocarbon group. 9. The photosensitive resin composition according to claim 7, wherein X in the general formula (4) is a —CN group. 10. The structural unit represented by the general formula (4) is a structural unit selected from the following general formulas (A), (B) and (C). The photosensitive resin composition according to any one of the above. Embedded image (Wherein, R ^{13 to} R ²¹ each represent a hydrogen atom, an alkyl group,
Represents an aryl group, an alkylene group, a cycloalkyl group, a cycloalkylene group, an arylene group or an aralkyl group, or an aralkylene group. X is -CHO, -COCH _3, -NO ₂
Or a -CN group. )